Volume-growing graphite intercalates with controlled initial temperature

FIELD: carbon materials.

SUBSTANCE: invention relates to graphite intercalates, which can be used as safe supplement in preparation of fireproofing compositions. Volume-growing graphite intercalates contain, as intercalated constituents, at least one intercalated Lewis acid selected from aluminum, antimony, zinc, yttrium, chromium, nickel, and/or iron chlorides and, if necessary, in combination with solvent(s) used in preparation thereof, and at least one organic compound.

EFFECT: enabled purposeful setting of initial temperatures of graphite intercalates within a wide range.

13 cl, 1 dwg, 2 tbl, 6 ex

 

The object of the invention are increasing in volume intercalates of graphite with controlled initial temperature, which can be used as intumescent fireproof additive to obtain a flame-retardant compositions, in particular intumescent masses for fireproof sealing of the through holes, for isolation of inputs (pins) and other holes in the walls, grounds and/or ceilings of buildings, as well as the way they are received.

Increasing in volume intercalates of graphite known as porous graphite and available in the industry. We are talking about the connections between layers of the graphite lattice layer contain foreign parts (intercalates). Such increases in volume intercalates of graphite are obtained usually in such a way that the graphite particles dispersed in the solution which contains an oxidizing agent and want to enable the guest connection. Commonly used oxidizing agents are nitric acid, potassium chlorate, chromic acid, potassium permanganate and the like compounds. As the subject of the inclusion compound is used, for example, concentrated sulphuric acid, when this interaction occurs at temperatures from 60 to 130°over time up to four hours (see, for example, European application paten the ER-IN-0085121). Alternatively, it is possible to include in the graphite metal chlorides in the presence of, for example, chlorine in the form of a gas (E. Stumpp, Physica (1981), 9-16).

Increasing in volume intercalates of graphite or porous graphite when heated to temperatures above the so-called initial temperature greatly increase in volume (the ratio of the increase in volume more than 200)that is caused by the fact that intercalates embedded in a layered structure of graphite, due to the rapid heating to the indicated temperature, decomposed with formation of gaseous substances, resulting in the graphite particles increase in volume in the direction perpendicular to the plane of the layer, or swell (European patent application EP-IN-0085121). This property greatly increase in volume is used in the intumescent masses, which are for example used for fireproof sealing of inputs (outputs) of cable and pipes and other holes through walls and ceilings of buildings. In case of fire after the initial temperature there is an increase in the volume of the graphite particles and thereby intumescent masses, sealing the input (output), so that after separation of the cable and/or plastic tube that is threaded through the hole, the breakout of fire through the input (output) will be prevented or slowed down.

The initial temperature is defined as the temperature at Kotor is th begins the process of thermal increase in the amount of intumescent systems, in this case, the increase in volume of intercalated graphite, that is, the temperature of the beginning of the process of increasing in volume. Traditional and produced for sale types of porous graphite have only a very limited initial temperature: about 150°With around 160°and about 200°C. to have the flexibility to respond to special requirements for the materials for fireproof masses about the behaviour of the wall, it is desirable to use increasing in volume intercalates of graphite, which have a broader scope of variation in relation to their initial temperature.

The task underlying the presented invention is to create increasing in volume intercalates of graphite, the initial temperature can be set purposefully over a wide area.

Strikingly, it was found that due to deintercalation intercalibrated of Lewis acids, which are indicated as well as the acceptors, and intercalibrated organic compounds, which are referred to as base Lewis or donors, that is, by introducing as internalional a Lewis acid and an organic compound, it becomes possible depending embedded in graphite intercalation purposefully to achieve that corresponds to the result set, the initial temperature in the range from 44 to 233°C.

The above problem can be solved by increasing the volume of intercalated graphite according to claim 1. The following paragraphs relate to preferred forms of embodiment of the specified object of the invention, the method of obtaining the above intercalated graphite and their application.

The object of the invention is therefore increasing in volume intercalates of graphite with controlled initial temperature, which differ in that they contain as intercalated composite parts, at least one intercalated a Lewis acid, which optionally is combined with the solvent(s)used(I) when received, in particular by nitromethane, and at least one organic compound. Through the appearance of this intercalate, namely organic compounds, it is possible according to the invention to control the initial temperature.

According to the invention as internalional Lewis acid is preferably used a metal halide, in particular chloride of a metal, such as AlCl3, SbCl5, ZnCl2, YCl3, CrCl3, NiCl2and/or FeCl3.

As organic compounds claimed intercalates of graphite preferably contain compounds from the group comprising halides karbonovy the acids, dehalogenated dicarboxylic acids, alkylhalogenide, aryl halides, alkylhalogenide, arylalkylamine, aliphatic or aromatic alcohols, dialkyl ethers, dearlove esters, arylalkyl ethers, aliphatic or aromatic glycol ethers, esters of carboxylic acids, esters of dicarboxylic acids, alkenes, 1,3-diketones and organic complexing agents.

According to the invention, the preferred halides of carboxylic acids correspond to the General formula (I)

,

in which R denotes hydrogen or alkyl, alkenylphenol, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms and X means a halogen atom, preferably a chlorine atom or a bromine atom. Especially preferred halides of carboxylic acids are acetylchloride, hexanoate, octanoate, palmitoylated, benzoyl chloride, phenylacetylene, 2-phenylpropionitrile and the acid chloride pavlinovoi acid.

According to the invention preferred dehalogenated dicarboxylic acids correspond to the General formula (II)

,

in which n denotes an integer with a value from 1 to 30, preferably from 1 to 18, and X means a halogen atom, preferably a chlorine atom or a bromine atom. According to the finding is particularly preferred dehalogenated dicarboxylic acids are oxalicacid, dichlorohydrin malonic acid, dichlorohydrin succinic acid, dichlorohydrin glutaric acid and dichlorohydrin adipic acid.

Intercalates of graphite, is presented in the invention contain as alkylhalogenide, aryl halides, arylalkylamine or alkylhalogenide preferably compounds of General formula (III)

,

in which R denotes alkyl, alkenylphenol, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms and X means a halogen atom, preferably a chlorine atom or a bromine atom. Preferred representatives of these halogenated compounds are phenylcarbamate, 2-Phenoxyethanol and 2-phenylethylene.

According to another preferred form of execution of the inventive intercalates of graphite as aliphatic or aromatic alcohols containing a compound of General formula (IV)

,

in which R denotes alkyl, alkenylphenol, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms. According to the invention, the preferred alcohols are methanol, ethanol, 1,3-propandiol, 1,4-butanediol and benzyl alcohol.

According to the invention preferred dialkylamide and dearlove esters suitable for the Ute of General formula (V)

,

in which R, independently of one another, denote alkyl, alkeline, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms. Preferred representatives of this group are diethyl ether and diphenyl ether.

According to another preferred form of execution of the inventive intercalates of graphite as organic compounds containing aliphatic or aromatic glycol ethers of the General formula (VI)

,

in which n denotes an integer with a value from 1 to 30, preferably from 1 to 18, and R, independently of one another, denote alkyl, alkeline, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms. A particularly preferred representative of this group is dimethyl ether of ethylene glycol.

As esters of carboxylic acids according to the invention preferred are compounds of General formula (VII)

,

in which R denotes hydrogen or alkyl, alkenylphenol, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms and R1means an alkyl group with 1-8, preferably 1-6, carbon atoms. A particularly preferred representative of what the group is ethyl acetate.

In addition, according to the invention as the organic compounds in graphite can be activated esters of dicarboxylic acids of the formula (VIII)

,

in which n denotes an integer with a value from 1 to 30, preferably from 1 to 18, and R, independently of one another, denote alkyl, alkeline, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms.

As alkenes are preferred, in particular, compounds of General formula (IX)

,

in which R, independently of one another, denote hydrogen atoms, alkyl, alkeline, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms, according to the invention in the preferred embodiment, is used styrene.

According to the invention the preferred 1,3-diketones correspond to the General formula (X):

,

in which n denotes an integer with a value from 1 to 30, preferably from 1 to 18, and R, independently of one another, denote alkyl, alkeline, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms.

According to the invention in graphite blocks as organic complexing agents preferably include atiende misteriously acid, nitrilotriethanol acid, pendantry-triphosphate and/or triethanolamine.

Alkyl and alkeneamine groups defined in the above groups R and R1contain from 1 to 30, preferably from 1 to 18 and more preferably from 1 to 8 carbon atoms. Preferred aryl groups are phenyl and naftalina group, while the preferred arylalkyl group is a benzyl group.

The invention also relates to a method for obtaining defined above intercalated graphite by deintercalation intercalibrated chlorides of metals and organic compounds or by subsequent intercalation of organic compounds in the intercalates, which are intermediate products and received by the inclusion internalional Lewis acid in graphite.

The preferred method of the invention is that graphite and internalional the Lewis acid is subjected to interaction in a sealed tube or in an appropriate solvent and then the resulting intercalate of graphite and a Lewis acid which is an intermediate product, if necessary, after prior separation, purification and drying, is subjected to the interaction with the organic compound and the reaction product out, cleaned and dried.

In this way the first stage of interaction is the major graphite with internalional Lewis acid can be carried out in a sealed tube (quartz tube), which is heated after deposition of graphite and internalional a Lewis acid or a suitable solvent.

Although the interaction is preferably in the solvent, because it can be conducted at lower temperatures than solid-phase reaction of metal chloride with graphite in a sealed quartz tube, have significant restrictions in respect of the used solvent, which should dissolve the chloride of the metal, and to contribute directly or indirectly to the electron transfer between the graphite and the metal chloride. Used for this purpose solvents are, for example, nitroalkanes General formula CH3(CH2)nNO2where n denotes an integer with a value from 0 to 10, and their structural isomers, in particular nitromethane, nitroethane, 1-nitropropane, carbon tetrachloride and thionyl chloride.

In the case of solvents contained in the obtained intermediate product, representing intercalate of graphite and acid Lewis, This intermediate product, if necessary, can be isolated, purified and dried, and the treatment is carried out, for example, so that an intermediate product is washed with solvent and then dried.

In the interaction of graphite with internalional Lewis acid process conduct a closed tube pre is respectfully at a temperature of from 200 to 800° S, more preferably from 250 to 600°when duration time from 3 minutes to 72 hours, preferably from 10 to 24 hours, particularly preferably from 12 to 18 hours.

Finally, the intermediate product, representing intercalate of graphite and a Lewis acid is subjected to interaction with the organic compound, the organic compound is introduced into the reaction or in liquid or molten form, or in a suitable solvent.

According to another form of execution of the invention intercalation internalional Lewis acid and organic compounds occurs at the same time, through deintercalation. This method consists in the fact that graphite, internalarray the Lewis acid and the organic compound are simultaneously subjected to the interaction of organic compounds in liquid or molten form, or in a suitable reaction solvent. Used solvent should dissolve the chloride of the metal and the organic compound, and to promote the electron transfer between the graphite and subject to the inclusion of a metal chloride and an organic compound.

After the interaction, the resulting reaction product is isolated and purified in the usual manner, for example by washing with solvent, and dried.

Declare intercalation (introduction) the authority shall ical connection occurs or in the received first by intercalation intermediate product, which contains graphite, intercalated a Lewis acid and, if necessary, a solvent, preferably nitromethane, or occurs within deintercalation, preferably by means of interaction of participants of the reaction, if necessary, in a solvent, at a temperature in the region of from 10 to 100°C, preferably at a temperature of from 10 to 50°With, mainly at room temperature, duration time from 3 minutes to 48 hours, preferably from 30 minutes to 24 hours.

When interacting internalarray the Lewis acid is used preferably in an amount of from 0.02 to 20 moles, preferably from 0.05 to 10 moles, per mole of graphite, while the organic compound is used in an amount of from 0.75 to 1000 wt.%, preferably from 2 to 800 wt.%, in calculating the amount of the graphite and the Lewis acid or the weight of the intermediate product, representing intercalate of graphite and of a Lewis acid and, if necessary, intercalated solvent, preferably nitromethane.

The next object of the invention is the use of the above intercalated graphite as porous graphite as intumescent fireproof additive to obtain a flame-retardant compositions, in particular to obtain swellable mass for fire-resistant door seals buds, wadowita and other openings in walls, the grounds and/or ceilings of buildings.

Discussed above and shown in the following examples, the initial temperature of the claimed intercalated graphite measured by thermomechanical analysis by changing the size of the material depending on the temperature. For this purpose, the sample is placed in a holder, which is equipped with a measuring probe, and contribute to the furnace, which is heated using a suitable temperature profile within a predefined temperature range. The probe may optionally be loaded with variable load. When this dimension positive change size is measured as the increase in volume and a negative change in size as shrinkage.

To determine the increase in volume of the proposed intercalated graphite powder sample contribute in a corundum crucible and covered with a steel crucible. Steel crucible ensures the increase in the volume of the sample transfer changes the size of the sample on the probe without a jolt. This system crucibles are placed in a sample holder device for thermo-mechanical analysis and contribute in the oven.

As a result of such thermo-mechanical analysis of the gain curve, as it is represented in the drawing, which caused an increase in the material volume in percent as a linear shift of the steel crucible Rel is increased by temperature.

The initial temperature of swellable material is defined mathematically as the point of intersection of the continued baseline before the increase in the volume of the sample and the tangent at the inflection point on the curve increasing in volume.

Given this definition, the initial temperatures were following conditions are met:

Temperature program:dynamic fashion (with upstream isothermal phase for 5 minutes at 25°)
Heating rate:10°C/10 min
Temperature area:from 25 to 500°With (partly from 25 to 1100°)
Gas analysis:Synthetic air
The flow speed:50 ml/min
Load:0,06 N
Vessel for samples:150 μl corundum crucible+150 μl steel crucible (as cap)

The following examples serve to further disclosure of the invention.

Example 1

Getting FeCl3-graphite-intercalate in nitromethane as an intermediate product (FeCl3/CH3NO2-graphite)

In a round bottom flask of 100 ml dissolve 11,68 g (0.07 mol) FeCl3in 15 ml of nitromethane. Then add 5 g (0.42 mol) of graphite and mix in ECENA 18 hours at room temperature. The material is washed with nitromethane as solvent, sucked off and dried.

The obtained intermediate product contains FeCl3and nitromethane as intercalation and has an initial temperature 148°C.

Example 2

Getting FeCl3-graphite-intercalate as an intermediate product by means of solid-phase reactions

Mix 2.25 g (to 0.19 mol) of graphite and 2.25 g (0.01 mol) FeCl3and melt the mixture in a quartz tube. Then melted in a quartz tube, the reaction mixture was incubated for 17 hours at 300°C. After cooling, washed with a small amount of water, sucked off and dried.

The initial temperature of the obtained intermediate product is 314°C.

Example 3

Intercalation (introduction) organic compounds in the intermediate product, representing FeCl3/CH3NO2-graphite-intercalate

Mix 1 g (84 mmol) of the intermediate product, representing FeCl3/CH3NO2-graphite-intercalate obtained according to example 1 in 3 ml (0.03 mmol) of Propionaldehyde for 24 hours at room temperature. The material is then sucked off, washed with a small amount of diethyl ether and dried.

The initial temperature of the obtained product is 132°C.

Example 4

Intercalation of organic compounds in the product, representing FeO3-graphite-intercalate

Mix 0.5 g (42 mmol) of the intermediate product, representing FeCl3-graphite-intercalate obtained according to example 2 in 3 ml (0.03 mmol) of Propionaldehyde for 24 hours at room temperature. The material is then sucked off, washed with a small amount of diethyl ether and dried.

The initial temperature of the material is 152°C.

Example 5

Repeat the technology of the process according to example 3 using intermediate product, representing FeCl3/CH3NO2-graphite-intercalate example 1, and the organic compounds listed in table I, and receive the products from the initial temperature specified in the same table.

Nitrilotriacetate acid
Table I
Organic compoundInitial temperature (°)
Oxalicacid44
Dichlorohydrin malonic acid114
Dichlorohydrin succinic acid150
Dichlorohydrin glutaric acid133
Dichlorohydrin adipic acid138
Acetylchloride114
Propionyl is lorid 132
Hexanoate154
Octanolwater156
Palmitoylated146
The benzoyl chloride150
Phenylacetylene157
3-Phenylpropionylamino153
The acid chloride pavlinovoi acid150
The acid chloride of acrylic acid156
Methanol152
Ethanol152
1,3-Propandiol152
1,4-Butanediol134
Benzyl alcohol : 129
Phenylcarbamate159
2-Phenoxyethane156
2-Phenylethylene159
The ethyl acetate155
Diethyl ether153
Dimethyl ether of ethylene glycol158
Diphenyl ether156
Styrene139
Acetoacetic ester140
The acetylacetone154
Benzoylacetone155
Add156
155
Pendantry-trisphosphate159
Triethanolamine156

From table I it is easy to see that by appropriate selection of used organic compounds the initial temperature obtained uvelichivajushejsja in the amount of intercalate graphite can be purposefully increase in area from 44 to 159°C.

Example 6

Repeat the methods of example 4, using intermediate product, representing FeCl3-graphite-intercalate from example 2, the compounds listed in table II. Table II shows the initial temperature of the products obtained.

Table II
Organic compoundInitial temperature (°)
Acetylchloride172
Hexanoate167
Octanolwater157
Palmitoylated144
The benzoyl chloride147
Phenylacetylene118
3-Phenylpropionylamino137
The acid chloride pavlinovoi acid100
Oxalicacid/td> 57
Dichlorohydrin malonic acid106
Dichlorohydrin succinic acid173
Dichlorohydrin glutaric acid147
Dichlorohydrin adipic acid146
Methanol124
Ethanol164
1,3-Propandiol171
1,4-Butanediol187
Benzyl alcohol : 159
Phenylcarbamate164
2-Phenoxyethane233
2-Phenylethylene142
The ethyl acetate153
Diethyl ether174
Dimethyl ether of ethylene glycol133
Diphenyl ether150
Acetoacetic ester151
The acetylacetone169
Benzoylacetone158
Add120
Nitrilotriacetate acid139
Pendantry-trisphosphate205
Triethanolamine164

From table II it is easy to see that is even appropriate to use organic compounds the initial temperature obtained uvelichivajushejsja in the amount of intercalate graphite purposefully can be set in the range from 57 to 233° C.

1. Increasing in volume intercalates of graphite with controlled initial temperature to obtain a flame-retardant compositions containing as intercalated composite parts, at least one intercalated a Lewis acid selected from the AlCl3, SbCl5, ZnCl2, YCl3, CrCl3, NiCl2and/or FeCl3if necessary, in combination with the solvent(s)used(I) when received, and at least one organic compound.

2. Intercalates of graphite according to claim 1, characterized in that the organic compound is selected from the group comprising halides of carboxylic acids, dehalogenated dicarboxylic acids, alkylhalogenide, aryl halides, alkylhalogenide, arylalkylamine, aliphatic or aromatic alcohols, dialkyl ethers, dearlove esters, arylalkyl ethers, aliphatic or aromatic glycol ethers, esters of carboxylic acids, esters of dicarboxylic acids, alkenes, 1,3-diketones and organic complexing agents.

3. Intercalates of graphite according to claim 2, characterized in that as gelegenheid carboxylic acids they contain a compound of General formula (I)

,

in which R denotes hydrogen or alkyl group, aryl group, arylalkyl group or alcylaryl group is 1-30, preferably with 1 to 18, carbon atoms, and X means a halogen atom, preferably a chlorine atom or a bromine atom.

4. Intercalates of graphite according to claim 2, characterized in that as dehalogenated dicarboxylic acid they contain a compound of General formula (II)

,

in which n denotes an integer with a value from 1 to 30, preferably from 1 to 18, and X means a halogen atom, preferably a chlorine atom or a bromine atom.

5. Intercalates of graphite according to claim 2, characterized in that as alkylhalogenide, arylalkenes, arylalkylamine or alkylhalogenide they contain a compound of General formula (III)

R-X (III)

in which R denotes alkyl, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms, and X means a halogen atom, preferably a chlorine atom or a bromine atom.

6. Intercalates of graphite according to claim 2, characterized in that as aliphatic or aromatic alcohol they contain a compound of General formula (IV)

R-OH (IV)

in which R denotes alkyl, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms.

7. Intercalates of graphite according to claim 2, characterized in that as dialkylamide ether, dietilovogo ether or arylalkyl ether they contain is at the compound of General formula (V)

,

in which R, independently of one another, denote alkyl, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms.

8. Intercalates of graphite according to claim 2, characterized in that as aliphatic or aromatic glycol ether they contain a compound of General formula (VI)

,

in which n denotes an integer with a value from 1 to 30, preferably from 1 to 18, and R, independently of one another, denote alkyl, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms.

9. Intercalates of graphite according to claim 2, characterized in that as a complex ether carboxylic acids they contain a compound of General formula (VII)

,

in which R denotes hydrogen or alkyl, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms, and R1means an alkyl group with 1-8, preferably 1-6, carbon atoms.

10. Intercalates of graphite according to claim 2, characterized in that as a complex ester of dicarboxylic acid they contain a compound of General formula (VIII)

,

in which n denotes an integer with a value from 1 to 30, preference is sustained fashion from 1 to 18, and R, independently of one another, denote alkyl, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms.

11. Intercalates of graphite according to claim 2, characterized in that as alkene they contain a compound of General formula (IX)

,

in which R, independently of one another, denote hydrogen atoms or alkyl, aryl, arylalkyl or alcylaryl group with 1-30 carbon atoms, preferably 1-18 carbon atoms.

12. Intercalates of graphite according to claim 2, characterized in that as a 1,3-diketone they contain a compound of General formula (X)

,

in which n denotes an integer with a value from 1 to 30, preferably from 1 to 18, and R, independently of one another, denote alkyl, aryl, arylalkyl or alcylaryl group with 1-30, preferably 1 to 18, carbon atoms.

13. Intercalates of graphite according to claim 2, characterized in that the organic complexing agents they contain ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriethanol acid, pendantry-triphosphate and/or triethanolamine.



 

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11 cl, 1 dwg, 4 ex

FIELD: metallurgy; semiconductor and aeronautical engineering; manufacture of electrodes, seals for aircraft engines and super clean articles.

SUBSTANCE: coke at yield of volatile agents of 4.0-12.0 mass-% in which fraction of size lesser than 0.09 mm is no less than 97 mass-% and fraction of size lesser than 0.045 mm is no less than 91 mass-% is mixed with 30-40 mass-% of coal-tar pitch, 0.015-2.0 mass-% of sterically hindered phenols and/or phenyl phosphites and 0.015-2.0 mass-% of stearic acid. Mass ratio of stearic acid to sterically hindered phenols and/or phenyl phosphites ranges from 1:1 to 2:1. Mixing with coal-tar pitch is performed at temperature of 110-160°C. Mass thus obtained is cooled to room temperature, crushed, ground and blanks at density of 1.01-1.25 g/cm3 are molded and roasted at 1000°C. Roasted blanks are graphitized at temperature rise by the following scheme: to 800°C, 30-60°C/h; to 1500, 5-25°C/h; to 2200°C, 15045°C/h. Holding time at each stage is equal to 3/7 h. Material thus obtained has apparent density of 1650-1870 kg/m3 at compressive strength of 103-160 Mpa and bending strength of 81-88 Mpa.

EFFECT: enhanced efficiency.

2 tbl, 1 ex

FIELD: production of sorbent on base of thermally expanded graphite used for extraction of water-insoluble compounds from water, soil and hard surfaces; gathering concentrated acids.

SUBSTANCE: proposed plant includes loading bin, proportioner, branch pipe for delivery of carrier gas, branch pipe for delivery of starting raw material (oxidized graphite), expansion chamber, separator with vertical partition and receiving bin. Proposed plant is also provided with ejector and tangential flow swirler combined with it; branch pipe for delivery of starting raw material is provided with external envelope for passing the coolant; ejector is mounted at expansion chamber inlet under outlet hole of starting material delivery branch pipe.

EFFECT: reduced power requirements with no reduction in productivity; improved quality of sorbent.

4 cl, 3 dwg, 1 tbl

FIELD: atomic industry; chemical industry; metallurgy; heat-and-power engineering; production of the oxidized black lead.

SUBSTANCE: the invention may be used is pertaining to the methods of production of the oxidized black lead and may be used in atomic industry, chemical industry, metallurgy, heat-and-power engineering at production of heat-insulating and refractory materials, a flexible graphite foil, sorbents. Prepare a non-laminated, having electronic conductivity suspension of black lead in 70-98 % H2SO4. The suspension may be further added with H3PO4 orCH3COOH. The gained suspension is fed into to the reactor 1 of the hopper 12 through a branch-pipe 3 by means of a piston 13. In the reaction chamber 9 it is moved by gravity flow along the hollow perforated cathode 7 and gets in contact with the anode 5. The anodic oxidation of the black lead conduct without its prepressing to the anode in absence of a free electrolyte with production of the electrical power in amount of no less than 30 A·h/kg of black lead at a constant value of the electric current or at a constant anode potential. Excess of an acid passes through a separator made out of a filtering fabric 8 and enters in the internal cavity of the cathode 7, one end 11 of which is open and then - into a collector 17. The ionic bond between the cathode 7 and the anode 8 is conducted through the separator 8, preventing an occurrence of a possible short circuit. The ring-type design of the reaction chamber 9 ensures uniformity of treatment of the anode and the least hydraulic resistance. The oxidized black lead is discharged through a branch-pipe 4, hydrolyzed, flushed, filtered and dried. The invention allows to boost productivity and to produce a foam-graphite after its frothing at the temperature of 900°C with a high degree uniformity and a bulk density of 1.5-3.2 g/l.

EFFECT: the invention ensures an increased productivity and production of a foam-graphite with a high degree uniformity and a good bulk density.

22 cl, 4 dwg, 2 tbl, 2 ex

FIELD: manufacture of articles from carbon materials, electrodes for example.

SUBSTANCE: articles made from carbon materials are heated in electrical furnace and are held to preset degree of graphitization. During heating and holding at heat, present magnitudes of temperature of characteristic point of articles located in end face of blank in center section of upper row is recorded. Moment of discontinuation of holding at heat and switching-off electric power is found from the following formula: : where γ is degree of graphitization; τ12 is time interval where graphitization takes place, h; F is function characterizing the time dependence of isothermal holding, h required for obtaining preset degree of graphitization versus graphitization temperature; T (τ) is present temperature of characteristic point of articles, °C; is present time, h.

EFFECT: reduced power requirements down to 5% at scheduled graphitization and down to 13% at forced graphitization.

1 ex

FIELD: atomic industry; chemical industry; metallurgy; heat-and-power engineering; a method and a device for production of the oxygenated graphite.

SUBSTANCE: the invention presents a method of production of the oxygenated graphite and a device for its realization and may be used in atomic, a chemical industry, in metallurgy and heat power engineering at production of a flexible graphite foil, heat-insulating and fire-proof materials, sorbents. Graphite suspension is prepared in 30-98 % sulfuric acid or nitric acid. The ratio of the electroconductivities of the suspension and each acid exceeds 1. The suspension may additionally contain H3POorCH3COOH. The produced suspension is continuously or discretely is discharged through a branch pipe 3 in the reaction chambers 11 of the merry-go-round type reactor 1 with a cylindrical body 2, an annular anode 6 made in the form of a chute and cathodes 10 made the form of vanes. The anode 6 is mounted in the body 2 coaxially with it and is supplied with a jacket of chilling 7. Cathodes 10 are supplied with the separation casings and fixed to a bracket 9 fixed on the shaft 8 of the rotary drives. Anodic oxidizing of graphite conduct without compacting of the anode 6 in absence of the free electrolyte at a constant value of the electric current or at a constant potential of the anode with a message confirming that the current value in both cases is no less than 30 A·h/kg graphite. Cathodes 10 transfer the suspension by a chute of the anode 6. The formed compound of implantation is unloaded through a branch pipe 4, hydrolyzed, flushed, filtered and dried. The invention allows to increase productivity and to produce a foamed graphite after dilatation at 900°C with a high degree of homogeneity and bulk density of 1.1-3.4 g/dm3.

EFFECT: the invention ensures increased productivity and production of the foamed graphite with a high degree homogeneity and good bulk density.

17 cl, 2 dwg, 3 tbl, 5 ex

FIELD: chemical industry branches, special technical equipment, possibly manufacture of different articles and heat exchanging systems.

SUBSTANCE: process comprises manufacture of preliminarily prepared coke-filler of green or baked petroleum coke by performing steps of disintegrating till fraction 90 micrometers at content of fraction 20 -50 micrometers no less than 60 -65 %, mixing it with coal cake in relation 5.0 - 2.0 respectively; heating up to 1100 -1300°C; cooling, disintegrating till fraction no more than 90 micrometers; using prepared coke-filler for making molding mass of articles; pressing articles, firing them and graphitizating. Steps of mixing disintegrated coke with cake at relation 5.0 - 2.0, heating mixture, cooling it and again disintegrating may be repeated twice. Density of articles 1.78 - 1.80 g/cm3, compression strength 67.0 - 72.0 MPa.

EFFECT: enhanced quality of articles having no surface flaws.

2 cl, 2 ex

FIELD: nonferrous metallurgy and precision engineering.

SUBSTANCE: invention is intended for use in manufacturing production accessories and tools for electronic treatment. Calcined coke is ground to average particle size between 2 and 20 μm and mixed with medium-temperature coal pitch taken in excess from 3 to 10% of the weight of composition relative to content of pitch providing maximum density and strength of graphite blanks without thermal-vacuum treatment. Resulting mix is subjected to thermal-vacuum treatment under pressure 80-320 hPa and temperature 250-320°C during 1 to 10 h. Thereafter, coke-pitch composition is ground to produce molding powder, from which blanks are pressed. Resulting blanks are fired at 1000-1300°C and graphitized at 2600-3000°C. Fine-grain graphite shows compaction strength 80-120 MPa, density 1.75-1.85 g/cm3, and density variations not exceeding ±0.1 g/cm3.

EFFECT: improved performance characteristics of product.

3 cl, 3 tbl, 22 ex

FIELD: manufacture of updated gasket materials from graphite tape, foil, strips or sheets.

SUBSTANCE: thermally expanded graphite powder is rolled into cloth, 0.1-10 mm thick. In the course of rolling, cloth is subjected to nondestructive testing by means of one or several pairs of measuring sensors placed along its width; each pair of sensors includes transmitting and receiving sensors which are placed on either side of cloth; They are subjected to electromagnetic radiation at frequency of 103-106 Hz and phase shift angle relative to phase of oscillations of wave falling on specimen is measured. Frequency of oscillations is fixed. For obtaining enhanced accuracy of measurements, correcting pair of sensors may be mounted in parallel with measuring sensors. Present density of material is determined by calibration graph of material density versus phase shift angle which is plotted before measurements. At plotting the graph, density of material is determined by direct weight method. Thus, rolling parameters are corrected according to results of determination of present density.

EFFECT: improved quality of flexible material; immediate elimination technological malfunction.

6 cl, 3 dwg, 1 ex

FIELD: chemical industry and special-purpose technique; manufacture of large-sized blanks of shaped articles for chemical and heat-exchange apparatus.

SUBSTANCE: starting coke-filler is mixed with coal-tar pitch and is impregnated with it; then mixture is calcined at temperature of 1100°C and ground to size not exceeding 1.25 mm at content of particles of no more than 0.07 mm in the amount not exceeding 50%. For obtaining fine-grained materials, grinding is continued till particles of 0.5 mm have been obtained. Powder thus obtained is mixed with pitch and blanks are molded from hot coke-pitch mass by extrusion through tip or in mold, after which blanks are subjected to roasting and graphitization. After roasting and graphitization, blanks may be again impregnated with coal-tar pitch and subjected to repeated roasting. Density of material thus made ranges from 1.65 to 1.78 g/cm3, compressive strength ranges from 30.0 to 51.3 Mpa and bending strength ranges from 16 to 26.4 Mpa.

EFFECT: avoidance of rejects.

3 cl, 3 ex

FIELD: atomic industry; chemical industry; metallurgy; heat-and-power engineering; a method and a device for production of the oxygenated graphite.

SUBSTANCE: the invention presents a method of production of the oxygenated graphite and a device for its realization and may be used in atomic, a chemical industry, in metallurgy and heat power engineering at production of a flexible graphite foil, heat-insulating and fire-proof materials, sorbents. Graphite suspension is prepared in 30-98 % sulfuric acid or nitric acid. The ratio of the electroconductivities of the suspension and each acid exceeds 1. The suspension may additionally contain H3POorCH3COOH. The produced suspension is continuously or discretely is discharged through a branch pipe 3 in the reaction chambers 11 of the merry-go-round type reactor 1 with a cylindrical body 2, an annular anode 6 made in the form of a chute and cathodes 10 made the form of vanes. The anode 6 is mounted in the body 2 coaxially with it and is supplied with a jacket of chilling 7. Cathodes 10 are supplied with the separation casings and fixed to a bracket 9 fixed on the shaft 8 of the rotary drives. Anodic oxidizing of graphite conduct without compacting of the anode 6 in absence of the free electrolyte at a constant value of the electric current or at a constant potential of the anode with a message confirming that the current value in both cases is no less than 30 A·h/kg graphite. Cathodes 10 transfer the suspension by a chute of the anode 6. The formed compound of implantation is unloaded through a branch pipe 4, hydrolyzed, flushed, filtered and dried. The invention allows to increase productivity and to produce a foamed graphite after dilatation at 900°C with a high degree of homogeneity and bulk density of 1.1-3.4 g/dm3.

EFFECT: the invention ensures increased productivity and production of the foamed graphite with a high degree homogeneity and good bulk density.

17 cl, 2 dwg, 3 tbl, 5 ex

FIELD: manufacture of articles from carbon materials, electrodes for example.

SUBSTANCE: articles made from carbon materials are heated in electrical furnace and are held to preset degree of graphitization. During heating and holding at heat, present magnitudes of temperature of characteristic point of articles located in end face of blank in center section of upper row is recorded. Moment of discontinuation of holding at heat and switching-off electric power is found from the following formula: : where γ is degree of graphitization; τ12 is time interval where graphitization takes place, h; F is function characterizing the time dependence of isothermal holding, h required for obtaining preset degree of graphitization versus graphitization temperature; T (τ) is present temperature of characteristic point of articles, °C; is present time, h.

EFFECT: reduced power requirements down to 5% at scheduled graphitization and down to 13% at forced graphitization.

1 ex

FIELD: atomic industry; chemical industry; metallurgy; heat-and-power engineering; production of the oxidized black lead.

SUBSTANCE: the invention may be used is pertaining to the methods of production of the oxidized black lead and may be used in atomic industry, chemical industry, metallurgy, heat-and-power engineering at production of heat-insulating and refractory materials, a flexible graphite foil, sorbents. Prepare a non-laminated, having electronic conductivity suspension of black lead in 70-98 % H2SO4. The suspension may be further added with H3PO4 orCH3COOH. The gained suspension is fed into to the reactor 1 of the hopper 12 through a branch-pipe 3 by means of a piston 13. In the reaction chamber 9 it is moved by gravity flow along the hollow perforated cathode 7 and gets in contact with the anode 5. The anodic oxidation of the black lead conduct without its prepressing to the anode in absence of a free electrolyte with production of the electrical power in amount of no less than 30 A·h/kg of black lead at a constant value of the electric current or at a constant anode potential. Excess of an acid passes through a separator made out of a filtering fabric 8 and enters in the internal cavity of the cathode 7, one end 11 of which is open and then - into a collector 17. The ionic bond between the cathode 7 and the anode 8 is conducted through the separator 8, preventing an occurrence of a possible short circuit. The ring-type design of the reaction chamber 9 ensures uniformity of treatment of the anode and the least hydraulic resistance. The oxidized black lead is discharged through a branch-pipe 4, hydrolyzed, flushed, filtered and dried. The invention allows to boost productivity and to produce a foam-graphite after its frothing at the temperature of 900°C with a high degree uniformity and a bulk density of 1.5-3.2 g/l.

EFFECT: the invention ensures an increased productivity and production of a foam-graphite with a high degree uniformity and a good bulk density.

22 cl, 4 dwg, 2 tbl, 2 ex

FIELD: production of sorbent on base of thermally expanded graphite used for extraction of water-insoluble compounds from water, soil and hard surfaces; gathering concentrated acids.

SUBSTANCE: proposed plant includes loading bin, proportioner, branch pipe for delivery of carrier gas, branch pipe for delivery of starting raw material (oxidized graphite), expansion chamber, separator with vertical partition and receiving bin. Proposed plant is also provided with ejector and tangential flow swirler combined with it; branch pipe for delivery of starting raw material is provided with external envelope for passing the coolant; ejector is mounted at expansion chamber inlet under outlet hole of starting material delivery branch pipe.

EFFECT: reduced power requirements with no reduction in productivity; improved quality of sorbent.

4 cl, 3 dwg, 1 tbl

FIELD: metallurgy; semiconductor and aeronautical engineering; manufacture of electrodes, seals for aircraft engines and super clean articles.

SUBSTANCE: coke at yield of volatile agents of 4.0-12.0 mass-% in which fraction of size lesser than 0.09 mm is no less than 97 mass-% and fraction of size lesser than 0.045 mm is no less than 91 mass-% is mixed with 30-40 mass-% of coal-tar pitch, 0.015-2.0 mass-% of sterically hindered phenols and/or phenyl phosphites and 0.015-2.0 mass-% of stearic acid. Mass ratio of stearic acid to sterically hindered phenols and/or phenyl phosphites ranges from 1:1 to 2:1. Mixing with coal-tar pitch is performed at temperature of 110-160°C. Mass thus obtained is cooled to room temperature, crushed, ground and blanks at density of 1.01-1.25 g/cm3 are molded and roasted at 1000°C. Roasted blanks are graphitized at temperature rise by the following scheme: to 800°C, 30-60°C/h; to 1500, 5-25°C/h; to 2200°C, 15045°C/h. Holding time at each stage is equal to 3/7 h. Material thus obtained has apparent density of 1650-1870 kg/m3 at compressive strength of 103-160 Mpa and bending strength of 81-88 Mpa.

EFFECT: enhanced efficiency.

2 tbl, 1 ex

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