The method of purification of terpene hydrocarbons sulfur from


C09F3/02 - as a by-product in the paper-pulping process

 

(57) Abstract:

Usage: chemical and pulp and paper industry. Essence: terpene hydrocarbons is treated with 1.0 to 10% aqueous solutions of N-golodnikov acids with a ratio of the oxidizer solution: terpene hydrocarbons from 0.1:1 to 1:1, at pH from 1 to 12. As the oxidant used the hydrated sodium salt of chloramide paratoluenesulfonyl, the crystalline sodium salt of chloramide parachlorobenzotrifluoride, N-chloramide acetic acid, N,N-dichloroethene. The technical result improved method of purification of terpene hydrocarbons to the total sulfur content less than 0.005% and increase the yield of the target product. 5 C.p. f-crystals, 1 table.

The invention relates to a method of purification of terpene hydrocarbons from sulfur and can be used in the chemical and pulp and paper industry.

It is known that sulphate turpentine and received on the basis of individual terpene hydrocarbons ( -pinene, Delta-three Karen, dipentene, and others) contain up to 0.03% (in terms of sulfur) of organic sulfur compounds. For this reason, they have limited scope, primarily due ASS="ptx2">

Global practice shows that sulphate turpentine and obtained on its basis terpene hydrocarbons are not limited in application in that case, if the mass fraction of organic sulfur compounds in them does not exceed 50 PPT (0,0050%) in terms of sulphur. Therefore, sulphate turpentine or terpene hydrocarbons are subjected to purification from sulfur.

Most widely for treatment of terpene hydrocarbons sulfur or sulfate turpentine is used the way they handle various oxidants, which typically use oxygen, peroxide, hypochlorite. There is a method in which the cleaning sulfate turpentine carried out with the help of hydroperoxides terpene compounds: p-Mentana, pinane, meta-pinane. The advantage of such hydroperoxides that, after reaction, they remain as terpene alcohols, without reducing consumer properties of turpentine. The process is carried out at a temperature of about 100oC, flow rate of gidroperekisi 3 - 10 g per 100 g of turpentine, followed by distillation fractions boiling at a temperature of 100 - 160oC, washing with distilled water (20 - 25 g). After decanting, the organic phase is used as the finished product. The degree of purification of the finished product from zerostart lsemaj hydroperoxides, their high flow, high temperature process, which leads to oxidation contained in turpentine terpenes reduce their output /PL 124833, A, 25.07.85/.

Also known purification method sulfate turpentine from sulfur compounds by treating it with an alkaline solution of hydrochloride sodium containing 150 g/l of active chlorine. After separation of the solution of sodium hypochlorite turpentine washed with water, and then treated with 15% sulfuric acid and again washed with water. The main disadvantage of this method is the high content of sulfur compounds in purified turpentine is 0.04%. In addition, the disadvantages of this method are that a significant amount of wastewater generated by repeated leaching of the product, and the use of sulfuric acid at one stage of the process /AT 241965, A, 25.08.65/.

Another known method of cleaning turpentine also perform the processing solution of sodium hypochlorite, but in an acidic environment (pH 3.5 to 5.0) at a temperature of 10 - 40oC for 20 to 50 minutes Then the turpentine is neutralized with alkali solution and washed with water /SU 332115, A, 14.03.72/.

The chemical composition of turpentine does not change. However, this method does not allow to obtain a product of desired quality at containing what adowanie large volume of wastewater, while carrying out the process in an acidic environment increases the corrosion of the equipment.

The closest attainable degree of purification from sulfur is a known method, where the oxidant use oxygen (prototype). Sulfate turpentine purge air for 35 minutes at a temperature of 110oC in the reactor with a ratio of length to diameter of 3.5. A reactor equipped with a heating element, the air is fed through a ceramic filter cartridge located in the bottom of the reactor. The interface 30 DM3/l, the path of the gas exchange 400 mm. the result turpentine, with a mass fraction of sulfur 0,008%. (D 148637A, 10.01.80).

However, this method is not without drawbacks, chief among which is the inability to achieve the required quality of purified turpentine, total sulfur mass fraction is not more than 0.005%, and a high content of peroxide compounds, which significantly limits the scope of its application. In addition, in this way arises the need for capture and purification of gas emissions resulting from the processing of turpentine air and reduces the yield of the target product by the partial oxidation of terpene hydrocarbons contained Cai terpene hydrocarbons to the mass fraction of total sulfur not more than 0.005% and increase the yield of the target product.

This goal is achieved by the fact that as oxidizers use N-halogenide acids, in particular, the most accessible of them:

the crystalline sodium salt of chloramide benzosulfimide (chloramine B);

the crystalline sodium salt of chloramide parachlorobenzotrifluoride (chloramine HB);

the crystalline sodium salt of chloramide paratoluenesulfonyl (chloramine-T).

- N-chloramide acetic acid,

- N,N-dichloroethene.

Terpene hydrocarbons or turpentine treated with 0.1 to 10% aqueous solution of oxidizer within 3 hours. The ratio of terpene hydrocarbons: oxidizer solution 1: 0.1 to 1. The reaction can be conducted in a neutral, acidic or alkaline environments. It is preferable in an alkaline environment, because in this case improves the process of separation of the reaction mass, reduces the corrosion of the equipment.

After separation of the oxidizer solution of terpene fraction is subjected to vacuum distillation or distillation under reduced pressure.

The oxidizer solution used for cleaning terpene hydrocarbons repeatedly.

In the proposed method used oxidizing agents do not interact with terpene hydrocarbons is="ptx2">

For a better understanding of the process provides the following example.

Example. In a reactor equipped with a stirrer, reflux condenser and thermometer, load 100 g of sulfate-pinene (mass fraction-pinene 98%; total sulfur mass fraction of 0.03%), 100 g of an aqueous solution of chloramine B (mass fraction of chloramine-B in aqueous solution of 2.5%) and 3 g of sodium hydroxide (pH of the medium 12). The mixture was thoroughly stirred for 3 hours at a temperature of 50oC. Then turn off the mixer, defend the reaction mass is separated organic fraction and chased her under reduced pressure. Get 98 g-pinene, yield 98%.

The product obtained has the following physico-chemical characteristics:

Mass fraction of the main substances - 98%

The refractive index at 20oC - 1,4658

Density at 20oC - 0,867 g/cm3< / BR>
Mass fraction of total sulfur - 0,0035%

Mass fraction of residue from evaporation to 0.08%

To obtain comparative data was conducted experiments with various oxidants, changed mass fraction of oxidant in aqueous solution, the ratio of the aqueous solution of oxidizing agent: terpene hydrocarbons, reaction temperature, pH of the medium, as well as raw materials. The data are summarized in table.

As you can see from the data is from sulfur, reaction conditions do not have a significant impact on yield and quality of the target product and can vary depending on the equipment used.

The advantage of this method is that used as oxidant N-golodnikov acids allows to obtain purified from sulfur-terpene hydrocarbons, with a mass fraction of sulphur, not more than 0.005%. The proposed oxidants do not interact with terpene hydrocarbons that contribute to the high yield of the target products. Exclusion from the process air oxygen reduces fire and explosion hazards, resulting in no formation of gas emissions. The reusability of the oxidizer solution allows you to process virtually no waste water generation. All these circumstances allow for the first time to organize an environmentally friendly cleaning process terpene hydrocarbons from sulfur.

The proposed method does not require non-standard equipment and can be easily implemented in an industrial environment. Used as oxidant compounds are not scarce, produced by domestic industry.

1. The method of purification of terpene hydrocarbons from sulfur, vclab, characterized in that the oxidizing agent used is 1.0 to 10% aqueous solutions of N-golodnikov acids with a ratio of the oxidizer solution : terpene hydrocarbons from 0.1 : 1 to 1 : 1, when the pH of the medium from 1 to 12.

2. The method according to p. 1, characterized in that the oxidant is used, the crystalline sodium salt of chloramide benzosulfimide.

3. The method according to p. 1, characterized in that the oxidant is used, the crystalline sodium salt of chloramide paratoluenesulfonyl.

4. The method according to p. 1, characterized in that the oxidant is used, the crystalline sodium salt of chloramide parachlorobenzotrifluoride.

5. The method according to p. 1, characterized in that the oxidizing agent used is N-chloramide acetic acid.

6. The method according to p. 1, characterized in that the oxidizing agent used is N, N-dichloroethene.

 

Same patents:

The invention relates to methods of cleaning sulfate turpentine raw from sulfur compounds

The invention relates to a method of purification of crude sulfate turpentine from sulfur compounds

The invention relates to a technology for production of alkyl benzenes in the presence of a catalyst in the form of an ORGANOMETALLIC complex of aluminium chloride and can be used in the washing of the catalyst, the decomposition of chlorinated organic compounds and neutralizing alkylates

The invention relates to a method of separation of isobutene from a hydrocarbon fractions by treating them with water in the presence of an acid catalyst with the formation of tertiary butyl alcohol, which is then subjected to decomposition with obtaining isobutylene or used as a commercial product
The invention relates to the field of allocation of tertiary olefins from mixtures of hydrocarbons of varying degrees of saturation and can be used in the production of monomers for IC
The invention relates to the separation of tertiary olefins from mixtures of hydrocarbons of varying degrees of saturation and can be used in industry to obtain monomers for IC

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: crude alpha-olefin is heated, raw vinylidene olefins are isomerized in the presence of catalyst and alpha-olefin is separated from isomerized vinylidene olefin by rectification. Separation of alpha-olefin is carried out for at least two successive steps at similar temperatures on top of vat and reducing pressure of rectifying column at each following step. Condensed phase removing from top of the rectifying column at previous step is fed to feeding zone of the following step and the rectifying column at top and vat section is sprayed. For spraying the top section of column the condensed phase removing from the top of rectifying column at the same step is used and for spraying the vat section of column the vat liquid of rectifying column at the same step is used. Separated alpha-olefin is purified additionally from oxygen-containing impurities by adsorption up to polymerization degree of purity. Raw heating, isomerization, separation and adsorption are carried out in atmosphere in inert gas. The unit used for treatment of alpha-olefin includes reactor for isomerization of vinylidene olefins in raw, rectifying column wherein feeding zone is joined with reactor outlet and wherein alpha-olefin of high purity degree is removed from the column top. The unit includes also at least one rectifying column for additional treatment of alpha-olefin of high purity from isomerized vinylidene olefins and adsorption column for separation of oxygen-containing impurities in alpha-olefin of high purity wherein the column inlet is joined with the top outlet of the last rectifying column used for additional treatment of alpha-olefin of high purity and outlet is used for removing alpha-olefin of the polymerization purity degree. Invention provides enhancing quality of the end product.

EFFECT: improved method for treatment.

8 cl, 1 dwg, 1 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to treatment of C5-hydrocarbons in order to remove cyclopentadiene impurities, which process may be, in particular, used in rubber production industry when producing hydrocarbon monomers applicable in stereospecific polymerization processes. Treatment of hydrocarbons is accomplished with cyclohexane in presence of organic solvent and alkali catalyst, after which C5-hydrocarbons are separated from reaction products via rectification. Organic solvent is selected from alkylene glycol monoalkyl ethers including their mixtures taken in amounts 0.5 to 5.0 wt % based on C5-hydrocarbons.

EFFECT: increased degree of cyclopentadiene extraction at lower reagent consumption.

8 cl, 1 tbl, 23 ex

FIELD: organic chemistry.

SUBSTANCE: invention refers to enhanced method of propane and/or butanes flow separation from original hydrocarbons containing alkylmercaptan impurities by means of fractional distillation resulted in liquid phase and separated flow from column head at pressure providing that separated flow from column head containing propane and/or butanes has temperature within 50 to 100°C, including (i) addition to specified origin hydrocarbons an amount of oxygen sufficient for mercaptan oxidation, (ii) fractional distillation of produced mixture containing at least one catalyst layer oxidising mercaptans to sulphur compounds with higher boiling temperatures and (iii) separation of sulphur compounds with higher boiling temperatures as portion of distillation liquid phase.

EFFECT: improved method of propane and/or butanes flow separation from of original hydrocarbons by means of fractional distillation resulted in liquid phase and separated flow.

8 cl, 2 tbl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention is referred to the area of hydrocarbons preparation by catalytical hydrodeoxygenation of products of fast pyrolysis of a biomass and working out of the catalyst for this process. The catalyst of oxygen-organic products hydrodeoxygenation of fast pyrolysis of lignocellulose biomasses, containing either precious metal in amount of no more 5.0 wt % or containing nickel, or copper; either iron, or their combination in a non-sulphide restored shape in amount of not more than 40 wt % and transitive metals in a non-sulphide shape in amount of not more than 40 wt %, carrying agent - the rest, is described. Three variants of the catalyst preparation method, providing application of transition metals on the carrying agent by a method of impregnation of the carrying agent solutions of metal compounds are described, or simultaneous sedimentation of hydroxides or carbonates of transition metals in the presence of the stabilising carrier, or the catalyst is formed by joint alloying/decomposition of crystalline hydrate nitrates of transition metals together with stabilising components of zirconium nitrate type. The process of oxygen-organic products hydrodeoxygenation of a biomass fast pyrolysis is performed using the above described catalyst in one stage at pressure of hydrogen less than 3.0 MPa, temperature 250-320°C.

EFFECT: increase stability in processing processes of oxygen-containing organic raw materials with the low content of sulphur, and also soft conditions of process realisation.

10 cl, 12 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to the method of purification of paraffin hydrocarbons from methanol admixtures. The said purification is carried out in the presence of hydrogen on the catalyst containing one of the metal selected from Ni and Pd applied on the inert carrier at temperature 30-100°C, mole excess hydrogen : methanol in the range (5-50): 1 and volume hydrocarbons feed rate 1-6 hrs.-1.

EFFECT: simplifying and cheapening of the process.

1 cl, 9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of extracting isobutylene from an isobutylene containing fraction through hydration of the isobutylene containing fraction, obtaining a tert-butanol containing fraction and its subsequent dehydration. The method is characterised by that, dehydration is done in two stages. At the first stage, temperature is kept at 90-120°C and pressure at 1-3 kgf/cm2 and concentrated isobutylene and an aqueous solution of tert-butyl and sec-butyl alcohol are extracted, from which concentrated sec-butyl alcohol and an isobutylene containing fraction, which is taken for hydration, are extracted at the second stage. Process at the second stage is carried out at temperature 100-130°C and pressure 2-6 kgf/cm2.

EFFECT: use of the given method allows for extracting isobutylene without butene or butadiene impurities, and reduction of tert-butyl alcohol loss.

1 cl, 1 tbl, 8 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: C10+ fraction of alpha-olefins contaminated with aromatic C9+ compounds is extracted from the main product stream and fed into a conversion reactor where C10+ alpha olefins and aromatic C9+ components react in the presence of a Friedel-Crafts alkylation catalyst to form aromatic C19+ compounds, and the obtained aromatic C19+ compounds are separated from unreacted C10+ alpha olefins in or after the conversion reactor.

EFFECT: method simplifies removal of by-products.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing pure 1-butene from C4 hydrocarbon fractions primarily containing 1-butene, 2-butene, and butane(s) with a 1,3-butadiene and isobutene impurity, involving preparation of a mixture primarily containing 2-butenes via rectification, catalytic isomerisation of 2-butenes into 1-butene and extraction of 1-butene via rectification, characterised by that at least catalysed isomerisation of 1-butene into 2-butene in said fraction is carried out at temperature lower than 120°C, as well as rectification with continuous removal of isobutane, isobutene and 1,3-butadiene in the distillate and obtaining a residual stream primarily containing 2-butene and n-butane, in which rectification conditions are maintained such that concentration of 1,3-butadiene and isobutene with respect to the sum of 2-butene is not higher than standard limits in the desired 1-butene. A large portion of n-butane is separated from the residual stream via extractive rectification with a polar agent and catalysed isomerisation of 2-butenes to 1-butene is carried out at temperature higher than 120°C, while continuously extracting the formed 1-butene via rectification.

EFFECT: high efficiency of the method.

14 cl, 5 ex, 4 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to developing a catalyst and a process for obtaining hydrocarbons via catalytic hydrodeoxygenation of products of processing plant biomass. The invention describes a catalyst for hydrodeoxygenation of organooxygen products of processing plant biomass, which is a complex composite containing transition metals and is a mixed oxide of the following type: where Mi is a transition metal in oxide form, other than nickel or boron, 2≤n≤5, with atomic ratio from 0.01-99, mainly from 7 to 99, and a stabilising additive in amount of not more than 30 wt %. The invention also describes a process for hydrodeoxygenation of organooxygen products of processing plant biomass, which is carried out in a single step at hydrogen pressure 0.5-20 MPa, temperature 250-320°C in the presence of the catalyst described above.

EFFECT: high activity of the disclosed non-sulphided catalysts, which enable to conduct a process for hydro-deoxygenation of oxygen-containing compounds - model compounds of products of processing plant biomass at high substrate/catalyst ratios.

4 cl, 24 ex, 3 tbl

Up!