Dispersible granules gas soot

 

(57) Abstract:

The invention is intended to obtain pellets of a gas soot, uterine mixtures or concentrates based on them. Gas soot has an absorbance value of n-dibutyl phthalate in loose soot equal to or less than 92 cm3/100 g carbon black. Organic compound or mixture of organic compounds has a melting point at least 25oC, decomposes at the temperature of sintering is less than 5% has a viscosity at the temperature of sintering below 2 Pas at shear rate 10 s-1and wets gas soot. Aglomerados gas soot and organic compound or mixture of organic compounds in the absence of water. Get a pellet gas soot. These granules can be used for uterine mixtures or concentrates for introducing gas of carbon black in the polymer environment. The result of the invention: preparation of solid non-dusting, abrasion resistant granules gas soot. 3 S. and 12 C.p. f-crystals, 8 PL.

The scope of the invention

This invention relates to the production of granules gas soot with the molten organic compound or mixture of organic compounds. These products can be used in many applications and is especially useful only elastomeric environment.

Art

When getting gas soot using powdered materials with bulk densities in the range of from about 0.02 to 0.1 g/cm3called loose Sagami. Because of their low density and large surface area of friable products are cohesive, have very poor transport characteristics and much dust. However, they are dispersible. Due to inconvenient technological qualities in many applications cannot take advantage of their excellent dispersive ability of the pigment. For example, a porous soot cannot be loaded in a controlled manner in a standard dispersing devices such as Banbury mixers, twin screw extruders and the like.

To improve the processing characteristics of loose products condense. For the grade of soot technological characteristics tend to improve with increasing degree of compaction. On the other hand, with increasing degree of compaction gradually deteriorates the dispersibility. Thus, improving volumetric technological characteristics receive lower dispersive ability of the pigment. For this reason, the degree of compaction and the means used to seal the t three basic ways to achieve the seal. These methods in order to ensure a high degree of compaction of the following: mixing or vacuum loose product, dry granulation and wet granulation. Since in many applications the characteristic gas soot depends on the achieved degree of dispersion, a suitable degree obtained seal depends on the consumers equipment for dispersion and, mainly, from the generated shear stresses. As a result of the mixing process or the vacuum processing to produce a powder, which cannot be processed in a large volume and which only comes Packed in bags. However, due to the fact that this form of product is much more dispersibility as compared with the more dense counterparts, it is used where required is a slight dispersion.

Dry granulation carried out in rotating drums. Industrial drums have diameters from 6 to 10 feet (1.8 to 3 m) and a length of from 20 to 40 feet (6 to 12 m) and rotate at speeds from 5 to 20 rpm Friable product is continuously loaded from one end of this drum. Tumbling dry soot leads to the formation of small kruglyhin part of the obtained granules, which recycle the boot end of the drum. Usually obtained in the dry drums products have a relatively low density and, therefore, are relatively weak and have low resistance to abrasion. As a result, the granules can be damaged during transportation, which leads to deterioration of their bulk technological characteristics. There are many ways to increase the strength of the granules. These methods include Supplement small amounts of oils and binders.

The wet granulation process is carried out in a pin grainers. Such installations consist of a cylinder with a diameter of from 0.4 to 1.5 m and a length of from 3 to 4 m Along the axis of the installation is spinning rod equipped with a variety of pins, usually arranged in the form of spirals with pins, almost reaching to the wall of the cylinder. The speed of rotation of the rod depends on the diameter of the installation and the required degree (intensity) of the granulation. Speed of rotation can be changed in the range from 300 to 1500 rpm In the installation continuously served the loose soot and water. The combination of capillary forces generated by the water, in a mixture of soot - water and mechanical action of the pins leads to the formation of spherical wet granules, benefits depends on the structure of soot and in many cases is 1:1. Leaving the granulator wet granules are then dried in a rotary drier. Because of the high moisture content in the granules drying is an expensive operation.

Despite a decrease in the dispersive ability of the pigment granules and associated cost of drying, pin granulation is widely used because it gives a more dense, abrasion-resistant granules than the dry method. In addition to water for granulation can easily add a binder, such as lignosulfonate, sugar or molasses, as well as additives such as polyoxyethylene non-ionic surfactants, substituted polyethylene glycol and so on, This serves to increase the strength or, when using surface-active substances, increase strength and improve the dispersive ability of the pigment dried granules.

The industry is also trying to improve the ratio between the increased strength of granules and decrease the dispersive ability of the pigment, receiving pellets not containing moisture and including oil. Without changing the classification of risk, it is possible to prevent the oil content in the soot with a maximum of 8 wt.%. Oil can easily enter in soot by dry granulation. When the oil content of more than about 15 wt.% granules are characterized by Ko, in various mixers using aqueous emulsions of the oil. It can be expected that in most cases the drying will result in the loss of oil through the method of steam distillation and the need for additional process steps.

Pin granulation can also be carried out using pure oil instead of emulsion water/oil. In these cases, does not require drying to remove the water and therefore causes no loss of oil. However, for the formation of pellets oil content in the granules will be much more than 8 wt.%, what needs to change their classification risk.

Another approach to improve the ratio between the increased strength of granules and reduced dispersibility, is the pelleting of carbon black in the aqueous medium containing latexes, compatible with rubber. Found that the resulting composition pellets after drying, have excellent qualities for processing and excellent dispersibility for use in rubber. As described in U.S. Patent N 4,569,834, other researchers granularit gas soot when using aqueous dispersions of waxy polyalkyl, such as polyethylene waxes, and also found that the dried granules are superior influence of water it is therefore necessary to include expensive surgery drying. In aqueous emulsion or dispersion should also include, or be formed in them, additives. In addition, they must be thermally stable at the maximum temperature of drying is achieved in industrial rotary dryers. These factors limit the class of materials that can be used in the operation of granulation. An additional limitation is that the additive must be compatible with the environment in which it is used. However, such compositions of granules obtained by a pin granulation gas soot when using aqueous emulsions and dispersions of various substances are useful.

Other researchers have developed an improved method of agglomeration, in which the aqueous suspension of gas soot mixed with oil, with a softening temperature above about 100oC.

To increase the strength of the granules obtained by the dry method, Coppersmiths and others have used up to 5 wt.% molten high density polyethylene with a melting point of 125 - 135oC. Description of the method proposed in this work Mednikov M. M., Osipov V. M., I. G. Zaidman, Ivanovskii, V. I., Oreklov S. V. and Ryabinkov A. I., "The Use of PE in Dry Pelletization of Carbon Black", Internati shear rate of 10 sec-1at 190oC. These researchers injected solid polyethylene portable air loose gas soot temperature from 180 to 210oC. the Authors claim that the polymer is melted and then is adsorbed on the surface of carbon black. After that soot granularit dry method (temperature not specified), receiving the pellets, which have a bulk resistance of granules in 2 - 5 kg higher than the corresponding values for the granules obtained in the absence of polyethylene (approximately 8 kg).

While the method Mednikova, etc. gives a slight increase in the strength of the granules made the winning strength is relatively small. In addition, the examples above descriptions appeared in the East German Patent N 133,442, which declared this technology. It should be noted that in the Example 1 of the said Patent is established that the polyethylene has a molecular weight of 2600. This is not consistent with the established range of molecular weights from 15,000 to 150,000, suitable, as has been said, for practical application of the invention. In addition, as noted in this Patent, the molten polyethylene is used as the location for the formation of agglomerates (by adhesion of soot on its surface). This suggests that melted the em into the pores within the aggregates. Therefore, it should be clear that specified in Example 1, the molecular weight of the polyethylene is not the correct value. This statement is confirmed by the data of this application, where it is established that increase strength does not occur when using low melt viscosity, at the level specified in the Patent in Eastern Germany 133,442.

In U.S. Patent N 3,429,958 (Wallcott) use a different approach to education dispersible granules with good surround technological characteristics. Wallcott granulosum gas soot, using melted paraffin in a pin mixer. Received the cooled granules containing about 50 wt. % paraffin, are slobodetski (not dusty) and was found to have greater dispersibility in an ink environment than granules, obtained from a conventional wet method. In this work, as examples of furnace soot Wallcott used HAF carbon black (DBP = 102 cm3/100 g), SAF (DBP = 113 cm3/100 g) and ISAF (DBP = 114 cm3/100 g). Wallcott indicates that the furnace shed the weight ratio of the gas soot : paraffin should be about 50:50 and declares that this ratio is in the range from 50:50 to 30: 70. Thus, this method requires a relatively high content of Paralia many applications used Wallcott paraffin content is excessive. In many cases (for example, lubricity, release forms, glamour, high impact resistance and so on) there is a preferred paraffin content, above which deteriorate technical characteristics of the product. Often preferred is smaller in comparison with the loading of carbon black paraffin content. According to this, the use of pellets containing 50% or more wax to achieve a desired loading of soot will inevitably lead to the addition of wax more than the required level, leading to poor performance and increased value. In some applications, it is preferable that the paraffin content in the pellets was always less than 48 wt.%. In addition, as will be further described, the method pin granulation gradually becomes more complicated with increasing content of liquid paraffin and for many soot becomes impossible when the content of 48%.

The difficulties encountered while processing granules gas soot, and when the dispersion of the granules have formed the basis for the business for the production of concentrated dispersions of gas soot in aqueous and nonaqueous media (often referred to as uterine mixtures or concentrates). Particularly important is proizvodi viscous thermoplastic material, such as polyethylene, polypropylene, Acrylonitrile-butadiene-styrene copolymer, ethylene vinyl acetate and other Dispersion is carried out in standard equipment for dispersion, such as a Bunbury mixer or twin screw extruders or similar. To obtain a suitable uterine mixtures particularly important is the formation of dispersions of good quality. Upon completion of the process dispersion uterine mixture is subjected to, for example, extrusion and then cut into pellets for shipment to the consumer.

Download black carbon in the pellets is, as implied by the term "concentrate" the best and will depend on the structure of carbon black. Gas soot consists of units consisting of partially connected initial particles. The space between the primary particles form vnutriigrovaya voids or porosity. Shows the structure establishes a relationship of the average number of primary particles per aggregate. It is established in the work of A. I. Medalia "Morphology of Aggregates: 6. Effective Volume of Aggregates of Carbon Black From Electron Microscopy: Application to Vehicle Absorption and to Die Swell in Filled Rubber", J. Colloid and Interface Science, 32, 115 (1970). The value of this volume can be determined by evaluating the absorbance of n-dibutyl phthalate (DBP) soot and by procedure ASTM D 2414. This value represents the capillary state. Consider that the units of soot in the gas mixture soot-DBP in the capillary near their fractions with maximum packing.

For economic reasons, preferred are a large loading of carbon black in masterbatches or concentrates. However, for a quick introduction during thinning, the viscosity of the concentrate should not be very different from the viscosity of the medium in which it is dispersed. The viscosity of the concentrate increases with the loading of pigment and coming to a high value when the content of solids approaches the value required to make the pigment has reached its maximum compacted faction. According this to obtain acceptable viscosities loading of soot and masterbatches should be less than the amount at which it reaches the maximum compacted faction, and therefore contains little air, or does not contain it at all. In other words, the loading of carbon black is less than that required to achieve the capillary state.

Unlike regular uterine mixtures of granules of this invention are obtained when downloads soot, exceeding the capillary state, so that they contained the air. As a result, they may seem more westemeyer, as the applied high pressure can reduce the volume of voids between the aggregates of carbon black. Medalia and Sawyer showed that the gas soot are highly compressible. This is discussed in the work Medalia, A. I. and R. L. Sawyer "Compressibility of Carbon Black, Proc. Fifth Carbon Conference, 1961", Pergammon Press, NY, 1963, p. 563.

The criterion that the granules of the present invention receive the "dry" side of the capillary state (that is, they contain air) for agglomeration of molten organic compounds in the absence of water, can be used to distinguish them from normal uterine mixtures, such as those described in the literature and usually get "wet" side of the capillary state (i.e. granules masterbatches essentially contain no voids). The expression "dry" and "wet" side of the capillary state is used only to specify, contain or do not contain the air in the granules comprising a mixture of soot and organic compounds.

The maximum content of carbon black in normal uterine mixtures depends on the maximum acceptable viscosity. For such reason, the amount of polymer masterbatches essentially more necessary to achieve capillary sostoyanie land surfaces download, that can be achieved increases with the decrease in soot DBP.

The dispersibility of carbon black decreases with increasing surface area of carbon black and/or by reducing the content of DBP. Owing to occur when the variance of the difficulties (and depending on the application) to obtain master batches rarely use carbon black with a low DBP and very large surface area. For example, for use where necessary black or protection from UV radiation, soot must have a minimum surface area. To obtain suitable concentrates with carbon black having a large surface area, you can often use a product with a high content of DBP. Thus, for practical reasons, upon receipt of the fallopian mixtures find a compromise between loading of soot and dispersion quality. Therefore, in the production of master batches soot rarely use carbon black with the lowest possible content of DBP.

Despite the cost of concentrates or masterbatches find a significant market, because the resulting products do not contain dust, easy to transport and much easier dispersed in a compatible thermoplastic environment than carbon black, granular, normal is the group or mixture of organic compounds, when ambient temperatures are solid, can be used instead concentrates without significant loss of performance.

Description of the invention

The present invention relates to the receipt and use of Svobodnaya (not dusty), resistant to abrasion, dispersible granules gas soot. Taking advantage of such properties, these products can be used instead of the usual gas pellets of carbon black in such areas as:

1) preparation of master batches, Laden gas with soot;

2) the achievement of a higher downloads soot in normal uterine mixtures by using the soot with a lower structure (i.e. with a lower content of DBP), without increasing their viscosity or without destroying the state of dispersion, which is achieved by the use of products with a higher structure (i.e. with a higher content DBP);

3) use instead of the normal uterine mixtures for introducing gas of carbon black in the polymer environment.

According to this first embodiment, the present invention provides a granule gas soot containing gas soot from 10 to less than 48 wt.% organic compounds or mixture of organic compounds, and pointed to by the si organic compounds in the absence of water, when this organic compound or mixture of organic compounds has the following characteristics:

a) the melting point at least 25oC and preferably above 45oC;

b) in the molten state and when used temperature sintering demonstrates the decomposition or destruction is less than 5%;

C) in the molten state and when used temperature sintering demonstrates a viscosity below 2 Apiaries at the shear rate of 10 sec-1;

g) in the molten state wets gas soot.

Used for granule formation method of agglomeration is preferably a dry granulation or pin granulation. Organic compound or mixture of organic compounds preferably represents at least one of: polimernoe organic compound, organic thermoplastic homopolymer, organic thermoplastic copolymer and paraffin wax.

The present invention also provides a method of applying granules according to the invention in the form of masterbatches or concentrates.

Additional features and advantages of the present invention described in the detailed opisannogo of the invention are implemented and achieved in different ways, described in the detailed description, and indicated in the claims.

The best ways to implement this invention

The granules of this invention can be obtained by agglomeration or in conditions of intense mixing as in a typical continuous pin graining, or in milder conditions, such as in dry drums. According to this, since the degree of mixing in most granulating devices, such as disk granulators, installation for briquetting, roller compactors, shear mixers, etc. are intermediate between the corresponding values for dry drums and pin granulators, in the practice of the present invention will be most acceptable device for sintering under suitable conditions. For example, in the case of pin granulation and, as shown Wallcott, paraffin instead of water, traditionally used as a cohesive liquid holding together moistened pellets, you can use the molten organic compound or mixture of organic compounds. The liquid is wetting, when the angle of its interaction with firm connection is less than 90oC. In the case granulirovannym currently used method of introducing oils. However, the contents of the drum must be maintained at temperatures above the melting point melting compounds or mixtures of compounds.

Organic compound or mixture of compounds used in the granulation process, pre-chosen in such a way that they are compatible with the environment in which is dispersed the granulated product. Compatible is a compound which is soluble in the medium or mixed with it at least in the quantities in which it is applied, more preferably has an essentially higher solubility or Miscibility than the quantity.

When unused the temperature of the granulating molten organic compound or mixture of organic compounds must be resistant to degradation or destruction. Suitable are organic compounds or mixture of organic compounds which have less than 5% decomposition or destruction in the molten state and at a temperature of agglomeration.

Organic compound or mixture of organic compounds suitable for use in obtaining a granulated product of the present invention must meet the abode/transportation/storage of gas soot. Thus, they should be solid at temperatures at least 25oC, and more preferably above 45oC;

2) in the molten state and when used temperature granulation they show the decomposition or destruction of fewer than 5%;

3) in the molten state and at a temperature granulation they show relatively low viscosity below about 2 Apiaries at the shear rate of 10 sec-1so that they can be dispersed or transformed into small droplets;

4) they moisten gas soot.

It is preferable that the organic compound or mixture of organic compounds were compatible with the implied application.

Examples of suitable substances include, but are not limited to, simple organic compounds, polymeric materials, a mixture of simple organic compounds, thermoplastic homopolymers and copolymers, mixtures of Homo - or copolymers, and a mixture of simple organic compounds with copolymer materials. Granular products after cooling to a temperature below the melting point organic compounds (compounds) consist of a dispersible, free current (Nepal and words, essentially improved exchange between improved technological characteristics and deterioration of the dispersive ability of the pigment. In many cases, the granulated products of this invention can be used either in the form of concentrates or more predominantly right instead concentrates for introducing gas of carbon black in the polymer environment.

In a preferred embodiment, the organic compound or mixture of organic compounds are polymeric wax such as polyethylene wax, ethylene-vinyl acetate wax and the like, and mixtures of these waxes. Such proposed for the application of waxes are well known in the art and are sold by various companies, including Allied Signal, under the trademark A-CRpolyethylene and A-CRcopolymers, BASF Corp., under the trademarks LUWAXRand Montan Waxes, and Eastman Kodak under the trademark EPOLENE Waxes. The waxes used in rubbers, plastics and coatings as agents for release from molds and/or lubricants. In addition, they act as pigment dispersing agents and are often used in conventional compositions uterine mixtures of soot. Use them sparingly, because when the content is more optimal level, they can be adversely affected by the recalls soot significantly more than paraffin. Below are discussed more fully organic compounds or mixture of organic compounds.

The present invention includes obtaining and applying a hard, non-dusting, abrasion resistant granules gas soot. They can be used for many purposes, such as obtaining concentrates, or to use instead of the usual concentrates for injection up to 5 wt.% gas carbon black in the coating and thermoplastic polymer environment. Granules of the present invention receive through agglomeration, it is most convenient, in a conventional pin tumbler pellet continuous action and dry drums using molten organic compound or mixture of organic compounds as a cohesive liquid that holds the pellets together, in the absence of water. To avoid the introduction of undesirable quantities of organic compounds (compounds) in the intended application, the granules include gas soot and from 10 to less than 50 wt.% organic compounds (compounds).

The volume of liquid (water, oil or molten organic compounds) used in the granulation, has an important effect on the strength of wet granules. Ayala and others distinguish fitt G. D. "The Relevance of Powder/Liquid Wettabilityto the Cohesiveness of Carbon Black Agglomerates", Part. Caract., 3, 26 - 31 (1986). These compounds are: 1) the condition of dry granules; 2) the state of the pendulum, when the voids in the grains partially filled with fluid that forms bridges between adjacent units; 3) funicular state, when the neighboring region pendulum connected in continuous fluid system included with scattered pockets of air; 4) the capillary state, when the liquid just fills all the voids in the granules, so that the meniscus on the surface of the granules provide maximum pressure capillary suction; and 5) the suspension, when the fluid exceeds the amount needed for the liquid state. Cohesive force provided by the fluid that wets soot increases with increasing liquid content and reaches its maximum value when the capillary state. For capillary state occurs a rapid decrease in cohesion with a slight increase in liquid content. The stability of the moistened granules increases with increasing cohesion.

Due to the fact that the nature of the sealing forces involved in the post-pelleting, granular the uh processes can vary. Fluid requirement for these two operations, as well as other devices for agglomeration are discussed sequentially.

Pin granulation

When the pin granulation mechanical action of fast-moving pins is used for orientation of soot aggregates in close proximity, while the liquid provides the necessary grip for holding the units together in the pellet. In the absence of a minimum amount of liquid, the force of the blows of fast-moving pins with existing granules leads to fragmentation of the granules. In other words, the minimum degree of cohesion is necessary for successful granulation pin in the granulator. Sufficient cohesion gas soot is achieved when the liquid content in the granules is between the value needed to achieve the state of the pendulum and the capillary state. On the other hand, when the content liquid is essentially exceeds the amount needed to achieve the capillary state, is formed soaked coherent mass, which slows down the formation of granules and unloading of product from the granulator. In addition, the level of productivity and the (capillary) while reduced quality paged granules, in terms of their sphericity and homogeneity.

According to this granulating pin in the pellet volume is added to the soot liquid must be greater than the amount needed for the early formation of significant relationships pendulum, and less than the number required to achieve the capillary state. Preferably the granulation in the state of the pendulum and/or in the funicular state, when the resulting granules contain air voids.

A correct estimate of the amount of fluid required to achieve the capillary state, can be obtained from the evaluation of DBP in loose soot (marked FDBP). This quantity provides a measure of the amount of DBP necessary to achieve the capillary state in a mixture of soot-DBP, and comparable in magnitude with the amount of fluid required to achieve the capillary state in the pellet. According to this mass% of the liquid content in the granules, leaving a pin pelletizer, Wliq,maxmust be less than the number

< / BR>
where FDBP expressed in cm3/100 g carbon black andliqis the density of molten compounds (compounds) in g/snse 48% always reach, when the degree pin pelleting of carbon black with FDBP equal to or less than 92 cm3/100 g

The beginning of education a significant ties pendulum occurs when all vnutriigrovaya pores filled in and between units gas soot immediately begins to form a large number of bridges from the liquid. The unit is the smallest dispersible unit gas soot. It consists of linked (coupled) of the primary particles. For non-porous primary particle size of the primary particles is inversely proportional to the surface area of soot. Between the primary particles forming the aggregate, are voids or pores. As vnutriigrovaya pores are the least of those present in the granules, they first filled with the wetting liquid. Only after will be filled volume vnutriarterialnah then (also called the absorbed amount), can form a large number of cohesive megalightning links pendulum.

Medalia have developed a procedure for estimating the absorbed amount of DBP values. This is described in the work of A. I. Medalia "Effective Degree of Immobilization of Rubber Occluded within Carbon Black Aggregates", Rubber Chemistry & Technology, 45, (5), 1172 (1972). The amount of the absorbed volume, in cm3/g gas soot, can paravane, will depend on the intensity of the granulating process and will be between the values of FDBP and crushed DBP, CDBP. CDBP determined by procedure ASTM D 3493-93. Usually the value of the CDBP is 15 - 25% (say 20%) less than the value of FDBP. Thus, the minimum absorbed amount of gain, using equation (2) the amount of CDBP instead DBP

= [(CDBP)of-21.5]/127,0.

So as to ensure that the clutch needed to hold the granules together in a pin granulator, requires communication pendulum, the minimum percentage of liquid Wliq,minneeded to pin granulation, can be expressed as

Wliq,minliq(100)/(1+aliq) (3)

Thus, for example, carbon black, with a value of FDBP 92 cm3/100 g carbon black minimum calculated content of molten organic compounds necessary for the formation of granules (assuming thatliq= 1.0 g/cm3and CDBP 73,6 cm3/100 g gas soot) is equal to 29.1%. In accordance with this soot with a value of FDBP 92 cm3/100 g carbon black content of organic compounds is in the range from 29.1 to 48%, and in terms of practical granulation (when granules contain some amount of postgame, decreasing the value of FDBP products will contain a smaller amount of organic matter.

Dry granulating

As already noted, the granules are produced in a dry drum in much less stringent conditions than in the pin pelletizer. As a consequence, the value of FDBP is slightly reduced. In addition, the granules may be formed in the absence of cohesion of the liquid. However, the resulting granules have a low density and fragile. The increase in strength can be achieved by adding a certain minimum quantity of molten organic compound or mixture of organic compounds. The degree of the achieved increase strength depends on the amount of added organic compound or mixture of organic compounds. At low concentrations of melt liquid mass moves to vnutrikarernym zones, thus attain a small increase in strength. If the amount added of the molten organic compound or mixture of organic compounds increase, despite the incomplete filling vnutriarterialnah then, get some increase in strength. This increase in strength is due to the fact that some units, the image of the AK will be displayed, a slight increase in the strength of the granules may occur when the content of the molten organic additive is below 10 wt.%. The preferred method of carrying out the dry granulation is, first of all, obtaining a homogeneous mixture of loose soot with the necessary molten organic compound (compounds). Such mixtures can be obtained, for example, by a continuous supply of loose soot and melted organic material in apparatus for grinding or other efficient chopping device. More preferably, when the content of molten compounds (compounds) are lower than necessary to achieve the state of the pendulum, loose soot and sprayed molten material may be mixed in a conventional pin tumbler granulator continuous action. After that, the mixture of loose soot and organic compounds can be served in a hot dryer together with recycled granules of the product.

Periodic methods of granulation

As noted earlier, for the production of products of this invention can be used periodically methods of granulation. The only limitation is that the granulation produced in the absence of the speaker.% the weight of the granular composition. Particularly preferred periodic granulation method includes the use of a disc granulators and one of various devices for sealing.

Suitable melting compounds

Organic compounds or mixture of compounds suitable for use in obtaining products of this invention should have the following characteristics:

1) They are solid at temperatures normally encountered during shipping/handling/transportation/storage of gas soot. Thus, they should be solid at temperatures at least 25oC and more preferably above 45oC.

2) In the molten state and when the temperature of the granulation they demonstrate the decomposition or destruction in the amount of less than 5%.

3) In the molten state and when the temperature of the granulation they show relatively low viscosity below about 2 Apiaries, at the shear rate of 10 sec-1so they can be sprayed or converted into small droplets.

4) They moisten gas soot.

Preferably, the organic compound or mixture of organic compounds were also some organic compounds, polymeric materials, a mixture of simple organic compounds, thermoplastic homopolymers and copolymers, mixtures of Homo - and copolymers, and a mixture of simple organic compounds with polymeric materials and mixtures thereof. Preferred polymeric compounds are:

1) Homopolymers or copolymers of ethylene with at least one of the monomers consisting of butene, hexene, octene, norbornene, vinyl acetate, acrylic acid (present in the form of acid or ionomer), methacrylic acid (present in the form of acid or ionomer), alkyl(C1-C9)acrylate, maleic anhydride, complex monoether maleic acid and carbon monoxide.

2) Homopolymers (atactic, isotactic and syndiotactic form) of propylene and copolymers with ethylene; polynorbornene; paleochannel.

3) Homopolymers of styrene or copolymers with at least one of the following connections: -methylsterol, vinyltoluene, Acrylonitrile, butadiene, maleic anhydride, inden, kumaran and alkylacrylate.

4) Glycols; homopolymers of ethylene oxide and propylene oxide and static or block copolymers; ethoxylated or ethoxylated/propoxycarbazone phenols, Ltd and polyamine.

5) the Resin obtained by the esterification of extraction of rosin, gum rosin, rosin from tall oil (tall oil rosin), abietinus acid (or its hydrogenated derivatives) with a polyhydric alcohol selected from ethylene glycol, glycerol or pentaerythritol.

6) condensation Products of dimeric acid with diola or diamine; polycaprolactone or polycaprolactam.

Particularly preferred are polymeric materials with relatively low molecular weights, which melt and form a liquid with low viscosity at moderate temperatures, such as commercially available polyethylene, polyethylene-polybutene, ethylene-acrylic acid and ethylene-vinyl acetate waxes. Organic compounds may also contain small amounts of additives such as dispersing agents, UV stabilizers and antioxidants. At room temperature these additives can be solid or liquid up until all used in the granulation composition has the appropriate characteristics. The potential number of organic compounds or mixtures of compounds that meet the specified characteristics, large.

Agglomeration or granulirovanii:

1) Installation provided with a device for melting and the introduction of the necessary molten compound or mixture of compounds or a block used for its uniform distribution on the loose soot, or granulator.

2) the temperature of the carbon black is equal to or above the melting point of an organic compound or mixture of organic compounds.

3) the Contents of the granulator support at a temperature equal to or above the melting point of an organic compound or mixture of organic compounds.

4) the plant is equipped with devices for cooling the agglomerated or granulated product to a temperature below the temperature of solidification of the molten material.

Agglomerated or granulated product after cooling to a temperature below the melting point of an organic compound or mixture of organic compounds comprises dispersible, freely running, hard, abrasion-resistant, non-dusting granules, the preferred sizes are in the range of from 0.2 to 6.0 mm, the Increase in strength is due to the fact that the pendular and funicular connection harden and form a solid mazarakata bridges.

Lucah more durable, what bridges the liquid present in the granules containing oil.

The following examples are intended to illustrate the present invention but do not restrict it.

Experimental part

Periodic pin granulation

Sample preparation is carried out in a pin granulator periodic action with a diameter of 8 inches (0.2 m) and a length of 8 inches (0.2 m). The Central rod is equipped with fourteen pins with a diameter of 0.5 inch (0,013 m), which almost reach the cylinder wall. The speed of rotation of the rod can be varied from 100 to about 1700 rpm. Cylindrical wall installation can be heated electrically to temperatures up to 300oC.

Granulation is carried out, putting in a pellet mill known quantity of carbon (usually 400 grams). Then usually add fluid when the rotor speeds ranging from 50 to 100 revolutions per minute. If cohesion liquid is water, it injections into the granulator through a nozzle. If cohesion liquid is molten organic compound or mixture of compounds, it is poured into a preheated pellet mill (the wall temperature from 200 to 300oC) when temima be noted, that in pellet periodic operation temperature of soot should not be equal to or higher than a melting temperature of molten compounds (compounds). In the presence of this compound and used the high temperatures of the pellet mill, the temperature of the mixture rises rapidly to a value above the melting point organic compounds (compounds). After adding the molten material, the speed of rotation of the granulator is brought to the desired value. Typically, the formation of granules of organic liquids occurs within 3 minutes and with water for 3 to 10 minutes.

Continuous pin granulation

Hot loose carbon black having a surface area of 43 m2/g and FDBP 135 cm3/100 g, served with a speed of about 180 pounds per hour (0.02 kg/s) in a pellet with a diameter of 10 inches (0.25 m) and a length of 61 inches (1.54 m). Molten paraffin at a temperature of 175oC simultaneously added to the granulator through a spray under pressure. The temperature of the walls of the granulator support 175oC. Rotor, equipped with approximately 120 pins arranged in the form of a double helix that rotates at a certain speed.

Granulation in a dry drum

Granular is up to 35 revolutions per minute. The temperature of the drum support from 55 to 65oC. the Required amount of molten organic substance mixed with loose soot in the mixer. Received heated powder containing 300 g gas soot, add approximately 45 minutes to 200 g of the seed layer of granules in a rotating drum. The granulation process is completed in approximately four hours. In the initial stage of seed granules consisted of granules obtained in the pin pelletizer. In the second cycle granulation as the seed granules use the product of the first cycle. And finally, in the third cycle granulation diluted use the product from the second cycle. Under these conditions, the final product (third cycle) contains only 6.4% of the original seed material.

Product evaluation

Assessment of the durability of the pellets are tests on bulk granule strength (ASTM D1937-93), the crushing strength of individual granules (ASTM D3313-92) and the abrasion resistance of the granules (use a modification of the procedure of ASTM D4324). Modification of ASTM test D4324 consisted of the determination of total dust formed after shaking the sample for 5 and 20 minutes, as required by the test there is no difference in kolichestvo (by weight) number of granules, sifted to a narrow distribution in size, in a graduated cylinder and utrata then the sample to constant volume.

The dispersibility was evaluated as in the environment of plastic (ABS) and in liquid medium. Details of the procedures used below.

A copolymer of Acrylonitrile-butadiene-styrene (ABS) represented GPM 5600-0000 manufactured by GE Plastics, received from Polimerland Inc. Masterbatches for gas soot in ABS mixed in a Banbury mixer with a capacity of 1.6 liters when the download gas soot from 20 to 50 wt.%. Seemingly the melt viscosity determined using Monsanto Processibility Tester (MPT) with a capillary having a ratio of length to diameter of 20:1 and a diameter of 1.5 mm, an Apparent viscosity measured at a shear rate of 600 s-1and a temperature of 230oC.

Masterbatches and granules containing paraffin, thin on the injection moulding machine Battenfeld BA 500 E to 1% loading of carbon black in ABS. The color of the fundamental tone (the value of L*) dilution determined using a Hunter LabScan, (0,45) degree geometry, 10 degree surveillance, CIElab and light D65. The value of L*decreases with increasing black (the degree of blackness).

Determination of impact strength Izod carried out according to ASTM D256. The estimated dispersion define S-131. In this procedure, evaluate liquefaction at 100-fold increased, and the size and number redispersion units visually compared with the data of the standard map. Dimensions redispersion units increases with the value of the evaluation (from 1 to 6), and their number gradually increases from A to F. in the Examples below, given the experimental details.

Examples

Experiments are conducted to demonstrate that the gas soot with different structural level (determined by the value of FDBP) and different surface areas can be easily pelletized with a variety of molten organic compounds or mixtures of organic compounds that satisfy the conditions above. These studies are carried out in a heated pin granulator periodic action. Unless otherwise stated, in the operation of granulation using 400 g of loose soot. FDBP and square surfaces used soot, the composition and amount of organic compounds, the conditions applied and the agglomeration soot pellets are listed below.

Examples 1-6: Obtaining pellets of the gas carbon black

Used in these examples, the carbon black has an area of the surface of the melting points of about 100oC, at 500 rpm for 3 minutes, receiving granules containing a 61.5 wt.% carbon black.

Example 2. Soot granularit with 325 g of AC-6 polyethylene wax, melting point about 100oC, at 500 rpm for 3 minutes, receiving granules containing 55.2 wt.% carbon black.

Example 3. Soot granularit with a mixture of 245 g AC-6 polyethylene wax and 25 g of liquid surfactants of polyisobutenylsuccinic (Lubrizol L2165), melting point 90oC, at 500 rpm for 3 minutes, receiving granules containing 59,7 wt.% carbon black.

Example 4. Soot granularit with a mixture of 293 g AC-6 polyethylene wax and 32 g of liquid surfactants of polyisobutenylsuccinic (Lubrizol L2165), melting point 90oC, at 500 rpm for 2.5 minutes, receiving granules containing 55.2 wt.% carbon black.

Example 5. Soot granularit with 300 g of paraffin wax (Aldrich), the melting point of 53 to 56oC, at 500 rpm for 5 minutes, receiving granules containing 57,1 wt.% carbon black.

Example 6. Soot granularit with 375 g of paraffin wax (Aldrich), the melting point of 53 to 56oC, at 500 rpm for 1 minute, receiving the pellets, containing of 51.6 wt.% carbon black.

Examples 7-9: Obtaining pellets of the gas carbon black

Used Wu granularit with 180 g of AC-6 polyethylene wax, melting point about 100oC at 800 rpm for 3 minutes, receiving granules containing 69,0 wt.% carbon black.

Example 8: Soot granularit with 216 g of AC-6 polyethylene wax, melting point about 100oC at 800 rpm for 3 minutes, receiving granules containing 64,9 wt.% carbon black.

Example 9: Soot granularit with a mixture of 195 g AC-6 polyethylene wax and 21 g of liquid surfactants of polyisobutenylsuccinic (Lubrizol L2165), melting point 90oC, at 500 rpm for 2 minutes, obtaining granules containing 64,9 wt.% carbon black.

Examples 10-14: Obtaining pellets of the gas carbon black

Used in these examples, the carbon black has a surface area of 220 m2/g and FDBP 100 cm3/100 g carbon black.

Example 10: Soot granularit with 375 g of CARBOWAXRpolyethylene glycol with molecular weight of approximately 1000 (PEG 1000, Union Carbide), a melting point of about 38oC, at 500 rpm for 3 minutes, receiving granules containing 51,6 wt.% carbon.

Example 11: Soot granularit with a mixture of 135 g of CARBOWAXRPEG1000, polyethylene glycol with a molecular weight of about 1000, and 240 g of TERGITOLRXD, surface-active substances on the basis of a copolymer of ethylene oxide and propylene (Union Carbide), melting point about 30<'s granularit with a mixture of 135 g of CARBOWAXRPEG1000, polyethylene glycol with a molecular weight of about 1000, and 240 g of TERGITOLRXH, surface-active substances on the basis of a copolymer of ethylene oxide and propylene (Union Carbide), melting point about 30oC, at 500 rpm for 3 minutes, receiving granules containing 51,6 wt.% carbon.

Example 13: Soot granularit with a mixture of 135 g of CARBOWAXRPEG1000, polyethylene glycol with a molecular weight of about 1000, and 240 g of TERGITOLRXJ, surface-active substances on the basis of a copolymer of ethylene oxide and propylene (Union Carbide), melting point about 30oC, at 500 rpm for 3 minutes, receiving granules containing 51,6 wt.% carbon.

Example 14: Soot granularit with a mixture of 375 g of TERGITOLRXD, surface-active substances on the basis of a copolymer of ethylene oxide and propylene (Union Carbide), melting point about 30oC, at 500 rpm for 3 minutes, receiving granules containing 51,6 wt.% carbon.

Examples 15-16: Obtaining pellets of the gas carbon black

Used in these examples, the carbon black has a surface area of 42 m2/g and FDBP about 124 cm3/100 g carbon black. The pellet is placed 350 g of loose soot.

Example 15: Soot granularit with a mixture of 330 g of polyethylene and polybutene paraffins (15 and aluca granules containing 51,5 wt.% carbon black.

Example 16: Soot granularit with 348 g of stearic acid, melting point of about 71oC at 800 rpm for 6 minutes, receiving granules containing 50,1 wt.% carbon black.

Example 17-18: Obtaining pellets of the gas carbon black

Used in these examples, the carbon black has a surface area of 42 m2/g and FDBP about 124 cm3/100 g carbon black.

Example 17: Soot granularit with a mixture of hydrocarbon polymers: 85 g PICCOVAR L-30 and 85 g PICCO 6100, obtained from Hercules, and having a melting point of about 120oC, at 500 rpm for 2 minutes, obtaining granules containing 70,2 wt.% carbon black.

Example 18: Soot granularit with a mixture of hydrocarbon polymers: 100 g PICCOVAR L-30 and 100 g PICCO 6100, obtained from Hercules, and having a melting point of about 120oC, at 500 rpm for 1.3 minutes, receiving granules containing 66,7 wt.% carbon black.

As shown by Equation (1), all granules of the above Examples are obtained on the "dry" side of the capillary state, this means that they contain air.

Examples 19-22: determination of the quantity of granules

To further confirm the assertion that the granules contain air (i.e. emptiness), conducted studies of chutney of the present invention contain air and therefore, founded on the "dry" side of the capillary state. Granules for these studies receive a pin granulator periodic operation, using either polyethylene wax (PE), Examples 19 and 20, or ethylene-vinyl acetate wax (EVA), Examples 21 and 22. In all cases, the granules are obtained at 500 rpm using carbon black having a loose DPB 74 cm3/100 g and a surface area of 210 m2/year Used in the study of Parametrii sifted granules have a size of more than about 300 microns.

The volume of voids within the granules get, determining the pore volume occupied by mercury at pressures penetration in the range from 24 up to 33,000 pounds per square inch (0,165 - 228 MPa), which corresponds to a pore size from 8900 (8.9 microns) to 6.5 nm. As the granules have sizes that are significantly larger than the pore size of the considered range, and because a significant introduction of mercury occurs at lower pressures penetration, it is likely that the actual volume of the pores within the granules few large values. Calculate the volume, soot, taking her skeletal density equal to 1.86 g/cm3, paraffin, taking its density is equal to 0.92 g/cm3and air in the granules. The obtained results bring the stand.

Examples 23-26: Continuous pin granulation

Loose soot from FDBP 140 cm3/100 g and a surface area of 46 m2/g granularit with EVA paraffin in the granulator continuous operation at multiple speeds of rotation of the rotor. The samples characterized from the point of view of the content of the wax (thermogravimetric analysis), density (tap densities), medium size (by manual sieving), the mass strength of granules, strength crush strength and attrition. Granules are strong enough so that exceed the measuring ability of the instruments: 90 pounds for a test mass granule strength (MPS) and 160 g to test the strength of the pellet crush strength (PCS). The results obtained are presented in Table 2.

Results Table. 2 shows that by increasing the speed of rotation of the rotor soot content in the granules and the density of the party tend to increase. This means that the paraffin content and density of the granules can be varied by changing the stiffness of the conditions of operation of the granulation. In all cases receive granules with high resistance to abrasion (as demonstrated small or a significant increase in dust from 5 to 20 m is the level of paraffin, necessary to maintain the granules in the state of the pendulum and funicular state. With further increase of the rotor speed to 1150 rpm while maintaining the speed of adding wax on about the same level as in Example 26, the granulation is carried out on the "wet" side of the capillary state. In the operation of the granulation becomes unstable at the initial stage rather unload lumps than the granules, the increasing demand for automatic loading and, finally, this leads to a shutdown of the granulator. Thus, the operation of the granulator on the "wet" side of the capillary state is impossible.

Examples 27-32: Granulation in the drum

Experiments are conducted to show that it is possible to achieve a significant increase strength by granulation gas soot in the presence of molten compounds in the dry drum. For convenience, the molten liquid is chosen lauric alcohol, as it has a low melting point 25oC and, therefore, it is easy to hold in the molten state during the operation of the granulation in the drum. Then before you get the product features, it is translated into a solid with m2/,

For soot FDBP 74 cm3/100 g for liquids with density of 0.82 g/cm3(the density of lauric alcohol) calculations according to equation (2) using FDBP instead of DBP by the equation (3) shows that the state of the pendulum reaches, when the pellets contain about 25 wt.% lauric alcohol. The research process in a dry drum carried out by adding lauric alcohol, processed loose soot (300 g of carbon black plus different amounts of alcohol), to 200 g of seed granules (for more details see experimental part). Loose soot contains 0, 9,1, 16,7, 23,1 and 28.6 wt.% the alcohol. As original as the seed material used dried granules obtained by wet method, and does not contain lauric alcohol, calculated content of lauric alcohol in the granules after three cycles of the drum is 0, 8,6, 15,9, 22,2 and 27.6 wt.% alcohol, respectively. Thus higher used alcohol just exceeds the amount needed to achieve the state of the pendulum.

The granules obtained after three cycles of granulation characterized with respect to their medium size, density, mass and individual processional carbon granules, carbon density in the pellets. In conclusion, also determine the comparative properties of the granules obtained pin granulation and used at the initial stage as the seed material (Example 32). The results are shown in Table 3.

Results Table. 3 show that at low concentrations of lauric alcohol, below about 8.6 wt.%, products granulation in the drum have low strength pellets. With the increasing content in the granules lauric alcohol more than about 10 wt.% there is a gradual increase in the strength of the granules. When you reach the state of the pendulum (to 25.3 wt.% lauric alcohol) and pass it strength products, granulated in the drum exceeds the strength of the product, granulated wet (Example 32), even though the density of the soot in the granules on the basis of free of alcohol is less than the corresponding values for the granules obtained by the method pin granulation. These results indicate that to increase the durability of the pellets can be used molten material, even when using fewer connections than necessary to achieve the state of the pendulum.


The comparative experiments carried out to determine the influence of soot loading in normal uterine mixes the technical characteristics of liquefaction. In these examples, the soot off FDBP 114 cm3/100 g of carbon black with a surface area of 140 m2/g granularit with water in a pin granulator, dried and then get masterbatches (ABS) with loadings of carbon black 20, 30 and 40%. Estimate the viscosity of the fallopian mixtures. The apparent viscosity of the polymer without filler is 269 Apiaries. Then dilute to 1% loading of carbon black and evaluate black, impact strength and dispersion quality of the final products. The results obtained are summarized in Table 5 and show that the viscosity of the fallopian mixtures increases with the loading of the gas soot. When the viscosity increase uterine mixtures deteriorate technical characteristics of the product, especially at 40% load, from the point of view of blackness, estimate the variance and impact strength.

Examples 36-37: the Study of the dispersive ability of the pigment

In order to show that the products of the present invention are dispersible, compare the achieved quality of the dispersions some of them about the quality of the dispersion obtained using conventional masterbatches. For these purposes balooga actions using the soot of the same model, as in Examples 1-6 and Examples 33-35. Control granules obtained by granulating 400 g of carbon black in pin granulator periodic action. To obtain pellets using the following quantities of liquids:

Example 36: 350 g of water and 40 g of isopropanol (add additional wetting soot).

Example 37: 400 g of water and 40 g of isopropanol.

Granules of Examples 36 and 37, containing 49,4 and 52.4 wt.% a mixture of water/isopropanol, respectively, dried at 150oC. each dried product get uterine mixture containing 20 wt.% download soot. The samples obtained is extruded, cut into pellets and designated as Example 36A (derived granules of Example 36) and 37A (derived granules of Example 37). These granules masterbatches, as well as granules of Examples 1-5, obtained using PE wax or PE wax in polyisobutylene-succinimide, or paraffin with the same loose soot, diluting the ABS, reaching the soot loading of 1%. The achieved characteristics of black, impact strength and the estimated dispersion are presented in Table 6.

The data of Table 6 show that the best characteristics of viscous product from the point of view of black (Naiman (20% loading of carbon black) Royal mixtures (Examples 36A and 37A). The results obtained are essentially identical to the results presented in Table 5, with the same download master batches. According to this expect that the technical characteristics of liquefied products that will be found for the most highly loaded (and more applicable in practice) master batches must follow the trends shown in Table 5.

Specifications liquefied drugs with pure PE wax, especially for a product with a smaller load (Example 2), approaching the characteristics obtained when the normal 20% load master batches and, apparently, must surpass characteristics obtained at 30% load (see Table 5). In addition, the apparent viscosity of the samples of Examples 1 and 2 exceed 2100 and 860 Apiaries, respectively. These results demonstrate that the granules with relatively large seemingly viscosities (compared with normal uterine mixtures - see Table 5) can be used for use in liquefied drugs. Thus, these results show that the products obtained in the "dry" side of the capillary state, can act as concentrates with appropriate technical characteristics of liquefaction.

Tehnicheskaya (Examples 3 and 4), quite similar to the characteristics found when using pure PE paraffin at comparable loadings of carbon black. Despite the relatively large number used to obtain pellets of wax, specifications liquefied products of Examples 5 and 6 below characteristics defined for other examples.

Example 38

Factory method are the pellets formed from the gas soot with a value of FDBP 70 cm3/100 g and a surface area of 230 m2/, Granules are produced in a continuous way pin granulation using water as the cohesion of the liquid, and then dried them in the factory, obtaining a granulated product with DBP 64 cm3/100 g (Example 38). This product was dispersed in ABS with the formation of masterbatches containing 20 wt.% carbon black (Example 38A).

The technological characteristics of the liquefied product of Example 38A are compared with the corresponding characteristics of Examples 7, 8 and 9 in Table 7. All products receive, using as raw materials of comparative loose soot.

Black, impact strength and the estimated dispersion for liquefied products obtained from the pellets of the present invention, close to cosultancy assume also the technical characteristics of the granules is improved with the increase in the number of PE wax, used in the operation of granulation.

The amount of molten organic compounds used in the operation of granulation soot Tables 6 and 7, comprise less than 50 wt.% within the range bounded by the values of Wliq,maxand Wliq,min. In addition, as mentioned previously and is consistent with these findings, the amount required for the granulation of the material decreases with decreasing patterns of soot.

Examples 39-40

Explore granulation with water-soluble molten liquids, which are surface-active agents. In these studies, the dispersive ability of the pigment products of Examples 10-14 are compared with the corresponding quantities of loose predecessor used to obtain granules (Example 39) and product pin granulation with water (Example 40). In the latter case, the wet granules containing 50 wt.% moisture, dried at 150oC.

As described below, used molten liquid composed of polyethylene glycol and various surfactants on the basis of copolymers of ethylene oxide and propylene. Used carbon black has Lena temperature below the 50oC and are used mainly in the form of mixtures with product PEG 1000, melting at a higher temperature. All mixes contain 60 parts surfactant and 40 parts of PEG 1000. The molten products form a single phase.

To evaluate the dispersive ability of the pigment products of Examples 10-14, along with loose smut (Example 39) and soot, granulated conventional pin method (Example 40), is dispersed in an aqueous medium containing a surfactant and ethanol. Practice shows that the dispersed soot stable in this environment. In all cases, 0.08 g of carbon black added to 200 ml of water environment. Each suspension is subjected to the same dispersion conditions, first stirring by a magnetic stirrer and then providing acoustic effects within 1, 5 and 15 minutes. At each stage of dispersion assess the state of dispersion in suspension by determining their optical density (O. D.) after dilution suspendida environment. The optical density of the suspensions, standardized relatively constant dilution of 0.25 parts of suspension and 8 parts suspendida environment, are summarized in Table 8.

The results of Table 8 show that through NY are comparable magnitudes. This means that the sample is completely dispersed. After 5 minutes of acoustic impact friable product (Example 39), and samples containing surfactants (Examples 11, 12, 13 and 14), have the same optical density, comparable with the optical densities of the suspensions after a 15-minute acoustic impact. Therefore, these products are fully dispergirovannykh after 5 minutes of acoustic stimuli. On the other hand, the sample granulated in the presence of water (Example 40), has the lowest optical density and, therefore, is the least well-dispersed product. The dispersibility of the sample, granulated with PEG (Example 10), is intermediate between despergiruemaya sample, granulated with water, and pellets containing surfactant. The optical density of samples in a shorter time dispersion are consistent with the view that the dispersible granules containing surfactant TERGITOL XD (Example 14), significantly better than the loose carbon black (Example 39). In addition, the optical density of the products of Examples 11, 12 and 13 are comparable to an optical density of loose product. These results indicated the practical characteristics and dispersibility, equal to or better than the dispersibility of loose product.

1. Pellet gas soot containing gas soot and organic compound or mixture of organic compounds in the absence of water, characterized in that the gas soot has an absorbance value of n-dibutyl phthalate in loose soot FDBP, determined according to ASTM D2414 equal to or less than 92 cm3/100 g carbon black, and the pellet contains from 10 to less than 48 wt.% organic compounds or mixtures of organic compounds and is formed by sintering at a temperature above the melting point of an organic compound or mixture of organic compounds, with organic compound or mixture of organic compounds has the following characteristics: (a) a melting point at least 25oWith; (b) in the molten state and at a temperature of agglomeration shows less than 5% decomposition or destruction; C) in the molten state and at a temperature sintering exhibits a viscosity below 2 PA c with a shear rate of 10-1and g) in the molten state wets the gas phase.

2. Pellet gas soot under item 1, characterized in that the melting point of an organic compound or mixture of organic compounds exceeds 45oC.

3. Pellet get polimernoe organic compound, organic thermoplastic homopolymer, organic thermoplastic copolymer and/or paraffin.

4. Pellet gas carbon black according to any one of p. 1, 2 or 3, characterized in that the minimum percentage of organic matter in a granule (Wliq,min) is equal to or exceeds the amount defined by the following equation:

Wliq,min>liq(100f)/(1+aliq)

where = [(CDBP) - 21,5]/127,0;

liqis the density of molten compounds, g/cm3;

CDBP represents the amount of absorption of dibutyl phthalate shredded gas soot, determined according to ASTM D 3494-93.

5. Pellet gas soot under item 1, characterized in that the organic compound is a homopolymer or copolymer of ethylene, in which at least one monomer is a butene, hexene, octene, norbornene, vinyl acetate, acrylic acid, methacrylic acid, C1- C9-alkylacrylate, maleic anhydride or complex monoether maleic acid and carbon monoxide, a homopolymer of propylene or a copolymer of propylene with ethylene, polynorbornene, paleochannel, a homopolymer or copolymer of styrene, vinyltoluene, Acrylonitrile, butadiene, maleic anhydride, inden, kumaran, or the fraternal connection is the polymer of ethylene oxide and propylene oxide, ethoxylated or ethoxylated/propoxycarbonyl phenol, alkyl phenol, aliphatic amine, aliphatic amide, a polyhydric alcohol, an ester of a polyhydric alcohol or polyamine.

7. Pellet gas soot under item 1, characterized in that the said organic compound is a resin obtained by the esterification of the extraction of rosin, gum rosin, rosin from tall oil, abietinus acid or its hydrogenated derivative with a polyhydric alcohol selected from ethylene glycol, glycerol or pentaerythritol.

8. Pellet gas soot under item 1, characterized in that the organic compound is a product of condensation of a dimer acid with diola or diamine, polycaprolactone or polycaprolactam.

9. Royal blend or concentrate containing granules gas carbon black according to any one of paragraphs.1 - 8.

10. A method of producing granules gas soot, comprising agglomerating gas carbon black, characterized in that the gas soot has an absorbance value of n-dibutyl phthalate in loose soot FDBP, determined according to ASTM D 2414 equal to or less than 92 cm3/100 g carbon black, and the pellet contains from 10 to less than 48 wt.% organic compounds or mixtures organize carried out at a temperature above the melting point of an organic compound or mixture of organic compounds in the absence of water, where the organic compound or mixture of organic compounds has the following characteristics: (a) a melting point at least 25oWith; (b) in the molten state and at a temperature of agglomerating shows less than 5% decomposition or destruction; C) in the molten state and at a temperature of agglomerating exhibits a viscosity below 2 PA s at a shear rate of 10-1.

11. The method according to p. 10, characterized in that the melting point of an organic compound or mixture of organic compounds exceeds 45oC.

12. The method according to p. 10 or 11, characterized in that the organic compound or mixture of organic compounds comprises polimernoe organic compound, organic thermoplastic homopolymer, organic thermoplastic copolymer and/or paraffin.

13. The method according to any of paragraphs.10, 11 or 12, characterized in that the agglomerating realized by means of dry granulation.

14. The method according to any of paragraphs.10, 11 or 12, characterized in that the agglomerating spend way pin granulation.

15. The method according to p. 14, characterized in that the minimum percentage of organic matter in a granule (Wliq,min) is equal to or exceeds the number
liqis the density of molten compounds, g/cm3;

CDBP represents the amount of absorption of dibutyl phthalate shredded gas soot, determined according to ASTM D 3494-93.

Priority points:

12.07.94 - PP.1 - 15;

16.03.95 - PP.1 - 15 (clarification of signs).

 

Same patents:

The invention relates to the field of hardening of products and batch preparation, in particular to the preparation of the charge in the scheme of acceptance of metallurgical raw materials and its delivery to the smelter in the form of granules, pellets or pelletized material

The invention relates to the processing of material in the form of liquid particles in a fluidized bed, in particular to a device for processing material in the form of particles containing a binder liquid fluidized bed

The invention relates to the production of mineral fertilizers, suitable for bulk transport and storage in bulk
The invention relates to chemical technology of organic silicon compounds, and in particular to methods of solid waste synthesis organochlorosilanes, which can be used, for example, in metallurgy

The invention relates to a structure-forming additive for detergent compositions formed by an aqueous solution of alkali metal silicate, such as sodium or potassium, with a molar ratio of SiO2/M2O 1.6 - 4, and inorganic product, inert with respect to the silicate, and the above-mentioned inorganic product is 5 to less than 55% by weight, based on dry weight, and the weight ratio, residual water associated with the silicate/silicate, calculated on the dry weight above or equal to 33/100, preferably 36/100

FIELD: mineral fertilizers.

SUBSTANCE: invention relates to granulated mineral fertilizers containing ammonium phosphates modified by surfactants and powdering substances, which do not lose their physicochemical properties during transportation and storage. Manufacture process comprises granulation of ammonium phosphate pulp, drying of granules, sorting and selection of commercial fraction, cooling and addition of modifying supplements. The latter are added in the cooling stage into zone with bed temperature by 5-10°C exceeding temperature of cooled product. Conditioning additives utilized can be either only liquid or the same mixed with dry powdering substances.

EFFECT: improved quality of surface coverage and simplified process.

2 cl, 3 ex

FIELD: inorganic substances technology.

SUBSTANCE: invention relates to production of granulated potassium sulfate appropriate for use in chemical industry for manufacturing mineral fertilizers and in agriculture as chlorine-free potassium-containing fertilizer. Process according to invention comprises spraying binding component onto dry potassium sulfate powder while simultaneously mixing materials in granulator mixer followed by drying thus formed granules to residual moisture not exceeding 1%. As binding component, liquid potassium soap or 50% solution thereof is used on the basis of 8 g binder per 100 g potassium sulfate. Once spraying of binding component ended, dry potassium sulfate is supplied through screw feeder to support growth of granules.

EFFECT: enabled production of granulated potassium sulfate in the form of non-caked and non-dusting product with stable granulometric composition and loose density, which contains high amount of basal substance (at least 51% K2O).

2 cl, 2 tbl

FIELD: manufacture of fertilizers; equipment for production of granulated carbamide.

SUBSTANCE: proposed method of production of granulated carbamide includes spraying its melt in granulation zone at contact with cooling air flow, hardening of drops of melt in free fall, treatment of granules with modifying agent- mixture of surfactant with film-forming agent in aqueous medium in the course of free fall at temperature of from 80 to 110°C and cooling of granules thus formed. Mixture is used in the amount of 0.01-0.16% of carbamide mass in terms of dry residual. Use may be made of ionogenic and nonionogenic agents. Film-forming agent may be selected from group containing amino-formaldehyde and epoxy resins, polyvinyl acetate and animal glues. Granulation tower has hollow housing with melt sprayer in upper part and apparatus for cooling the granules in fluidized layer in lower part, as well as injectors for spraying modifying agent which are located over circumference in lower part of tower above cooling apparatus.

EFFECT: enhanced strength of granules.

3 cl, 1 dwg, 10 ex

FIELD: chemical industry; methods of production of the granulated carbamide.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the granulated carbamide and may be used at the enterprises of the nitrogen production branch of industry producing carbamide as fertilizers. The method of production of the granulated carbamide provides for the crystalline carbamide melting, introduction of the modifying agent into the melt of the carbamide and granulation. In the capacity of the modifying agent they use the sediment of magnesium-ammonium-phosphate produced at the sewage purification from ions of ammonium or from phosphate ions, which is introduced into the carbamide melt in the form of the water suspension the finely dispersed magnesium-ammonium-phosphate with the content of water including crystallization water, of no more than 14 kg per 1 ton of the carbamide melt or in the form of the dry finely dispersed magnesium-ammonium-phosphate in amount of 5 - 10 kg per 1 ton of the carbamide melt. The technical result of the invention is the increased strength of the carbamide granules at the simultaneous improvement of the agrochemical efficiency of the fertilizers.

EFFECT: the invention ensures the increased strength of the carbamide granules at the simultaneous improvement of the agrochemical efficiency of the fertilizers.

8 ex, 1 tbl

FIELD: agriculture; chemical industry; other industries; methods of conditioning of the granulated fertilizers.

SUBSTANCE: the invention is pertaining to the technology of production of the mineralfertilizers with the improved physical properties slowly variable at transportations and storing. For mitigation of the blocking property of the fertilizers the granules after cooling are coated with the conditioning additivess in the separate apparatus. The method includes granulation of the pulp of ammonium phosphates, drying of the granules, their cooling with introduction at this stage by the sprinkling method of the liquid conditioning additives in the section with the temperature of the layer exceeding by 5-10°С the temperature of the being cooled product. The fluid additive is injected several times distributing it across the section of sprinkling in the form of drips with the varying dimensions. The dimension of the drips change within the limits of ddr/dgr equal to (0.05-0.15): 1). At that the dimension of the drips is increasing with the increase of the difference of the temperatures of the additive and the layer of the granules in the place of the injection. The temperature of the liquid additive is kept within the limits of 70-90°С. The treated granules of the fertilizer have obtained the qualitative coating reducing the blocking property of the fertilizer.

EFFECT: theinvention ensures, that the treated granules of the fertilizer have obtained the qualitative coating reducing the blocking property of the fertilizer.

2 cl, 2 ex

FIELD: coal industry; municipal services; other industries; methods and devices for production of the grained solid fuel.

SUBSTANCE: the invention is pertaining to the process of production of the grained composite fuel, which is intended for usage in the communal heating supply systems or in the household purposes. The method of production of the grained solid fuel with the help of the installation includes grinding of the coal fines, introduction in the composition of the fuel of the ground vegetable additive (for example, the sawdust or the beet press), their joint grinding in the rotary roller mill, sending of the part of the produced mixture in the volume near to 1/3 to mixing with the binder and formation of the seed grains in the turbo-blade mixer. Further route the received mass of seed grains and the remaining part of the mixture in the volume near 2/3 from the mixer for granulation into the plate granulator. The binding is also routed in the granulator to form the seed grains. The produced granules of the spherical shape in the narrow range of the dimensions within 15-30 mm are dried and cooled in the sectional dryer and packed by means of the weighing-and-filling machine into the tare having the form of the cardboard boxes of the different dimensions intended for usage in the capacity of artificial fuel wood. The technical result of the invention consists in the reduced power input for the production process, simplification of the production process, improvement of ecology, the increased efficiency of production of the final product.

EFFECT: the invention ensures the reduced power input for the production process, simplification of the production process, improvement of ecology, the increased efficiency of production of the final product.

5 cl, 1 tbl, 1 dwg, 8 ex

FIELD: technological processes; construction.

SUBSTANCE: invention solves problem of how to involve mass industrial waste phosphogypsum into production cycle as analog of construction material of natural origin. Method for preparation of granulated phosphogypsum includes mixing of initial phosphogypsum with binder and further rolling of mixture, at that binder used is return powder of phosphogypsum produced in mode of granulated material thermal treatment at the temperature of 170-200°C and its further crushing, at that portion of material recycle makes mostly up to 0.5 of total flow.

EFFECT: reduction of expenses in process of granulated phosphogypsum production.

4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing moulded titanium-containing zeolite. Powdered titanium-containing zeolite is moulded with binding material in form of a basic salt of aluminium 5,6-oxynitrate. The granules undergo drying at room temperature and at temperature 100-150°C, and are annealed at temperature 250-350°C.

EFFECT: high strength of zeolite granules and low power consumption.

5 ex

FIELD: biotechnologies.

SUBSTANCE: method involves advance preparation of dry raw material components containing a matrix and biologically active components; micronising of prepared dry components is performed till 5-150 mcm particle size. Micronised components are supplied to a drying microgranulator in which a fluidised bed is formed and mixing of granulated raw material components is performed with further microgranulation of the obtained mixture and its drying. Microgranulation and drying stages include stable toroidal movement of fluidised bed granules. Microgranulation stage involves addition to the mixture of soluble micro- and ultramicrocomponents by fine atomisation through an atomiser together with a binding agent solution at microgranule formation stage. Addition rate is 0.02-0.04 g/min per gramme of initial dry mixture; after stable toroidal movement of fluidised bed granules is formed, binding agent feed rate is increased up to 0.04-0.08 g/min per gramme of initial dry mixture. With that, granule test sampling is performed from time to time. After granules with size of 0.8-1.0 mm are formed, binding agent feed rate is decreased to 0.01-0.03 g/min per gramme of initial dry mixture and drying is performed at the temperature of 35-55°C.

EFFECT: method ensures uniform distribution of microelements by weight of microgranules, reduction of losses of microelements at their formation and reduction of dust formation at use of premix.

9 cl, 5 dwg, 1 tbl, 3 ex

FIELD: automation of chemical technological processes; control of water-stream soot granulation process.

SUBSTANCE: proposed method includes stabilization of power consumed by electric motor of granulator rotor drive by change of flow rate of water to granulator and stabilization of smoothed present magnitude of water flow rate through change of revolutions of sluice-type feeder supplying soot to granulator.

EFFECT: improved quality of soot granulation; enhanced stability of temperature conditions in drying moist granules.

3 dwg, 1 tbl, 2 ex

FIELD: organic chemistry.

SUBSTANCE: invention refers to granular carbon black production process. Produced granular carbon black contains mainly large-spherical granules and can be applied as intensifying extender of elastomers, as well as source material for sorbents and catalyst carriers. Method of carbon black granules production implies consecutive mixing of carbon black flow moving horizontally and rotating with line speed 5-12 m/s and solution of various concentration of bonding additive - molasses - in two zones until granules are formed. Then granules are dried. Molasses amount placed into first zone is 77-80% of required granules amount, the rest of molasses solution 20-23% is introduces to second zone. Invention provides granules production of 3-8 mm.

EFFECT: production of large-spherical carbon black granules.

11 ex, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention is intended for chemical industry and can be applied in production of varnishes, paints, pigments and polymer compositions, such as rubber mixes. Non-granulated carbon-black is charged into rapid granulation machine, carbon-black amount maintained at constant level. Water under pressure of 3-5 bar is injected through nozzles attached in pairs to two holders positioned as close to granulation machine as possible. Water jet cones dispersed by nozzles are oriented along carbon-black flow direction at an angle of 10 to 90° to it. In one version, granulated carbon-black has oil absorption power over 100 ml per 100 g and over 78 ml per 100 g after pressing, and includes less than 3.5 wt % of granule fraction of over 2.5 mm diametre, and over 22 wt % of granule fraction of 0.71 to 1.0 mm diameter. Hardness of single granules of 0.71 to 1.0 mm diameter fraction comprises 7.0 to 25.0 g. In another version, granulated carbon-black has oil absorption power under 90 ml per 100 g and under 78 ml per 100 g after pressing, and includes less than 30 wt % of granule fraction of of 0.71 to 1.0 mm diameter. Hardness of single granules of 0.71 to 1.0 mm diameter fraction comprises 7.0 to 25.0 g.

EFFECT: obtaining carbon-black with oil absorption power under 90 ml per 100 g and less than 30 wt % of granules with diameter of 0.71 to 1.0 mm.

5 cl, 3 tbl, 10 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: method of producing granular modified soot involves mixing, while heating, powder thereof with a water-soluble modifying agent - polyether with molecular weight between 290 and 3000 with hydroxyl number between 50 and 800 mg KOH/g in amount of 1.0-5.0% of the weight of the soot, granulation of the mixture followed by drying the wet granules at 285-320°C for a period of time which is 5-30% longer than needed to achieve moisture content of 0.5%. The obtained granular soot contains 2-8% volatile substances, where the content of oxygen in the volatile substances is not less than 71%, and content of oxygen in quinine and phenol groups is not less than 74%.

EFFECT: polymer compositions based on said soot have high resistance to UV radiation, which allows their use in making articles in contact with drinking water and food products.

6 cl, 6 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: method of producing microspherical granules of soot involves mixing soot with a granulating liquid and drying the obtained wet granules. The granulating liquid used is aqueous solution of furfuryl alcohol with concentration 20-30%. The weight ratio of granulating liquid to soot is equal to (1.07-1.12):1.

EFFECT: method enables to obtain small-sized microspherical granules of soot with high output.

1 tbl, 10 ex

FIELD: process engineering.

SUBSTANCE: invention may be used for cleaning effluents formed in production of acetylene. For this, soot particles agglomerated to 1 mm-size are subjected to concentration of solid substances by sedimentation. Soot slime obtained in sedimentation is dehydrated at pressure. In compliance with preferable version, primary particles of soot are agglomerated to 0.001-0.05 mm-size. Immediately before sedimentation, water solution containing organic flocculant, preferably, anionic flocculant, is added to effluents. To improve wetting of floating soot particles surfactants are added before sedimentation. Besides, before filtration, water solution containing organic flocculant, preferably, anionic flocculant, is added to effluents.

EFFECT: efficient and simple process.

10 cl, 2 ex

Up!