Method of tall oil resin application

FIELD: chemistry.

SUBSTANCE: invention relates to a method of processing tall oil resin. The method of processing tall oil resin, which contains sterol alcohols, and, possibly, wood alcohols of fatty acids and resin acids, the source of which is tall oil, is characterised by the fact that, at least, a part of the fatty acids and resin acids is released from sterol ethers and ethers of wood alcohols and converted into lower alkyl ethers; alkyl ethers, obtained in he said way, are extracted by evaporation from resin, then condensed, with the further hydration of the obtained condensate. The product, obtained by the claimed method and the application of the method for fuel production are also claimed.

EFFECT: application of tall oil resin, which usually represents a waste product, for obtaining fuel or a fuel component.

17 cl, 1 dwg

 

The present invention relates to a method for the treatment of tall oil resin, characterized in restrictive part of claim 1 of the attached claims.

In this method, the processing composition contains Stereolove esters of fatty acids and resin acids derived from tall oil and, possibly, other esters of wood spirits.

The present invention also relates to the product in accordance with paragraph 14 and to its use in accordance with paragraph 16 of the attached claims.

Tall oil is a renewable organic natural product, obtained as a by-product in the pulp industry. It is widely known that tall oil contains resin acids, fatty acids, sterols, and other wood alcohols, and small amounts of inorganic compounds, such as Na2S04, which is the residual products remaining after pulping. Furthermore, tall oil contains cations of metals, wood and fertilizers, obtained, for example, of the following elements: Ca, Fe, Mg, P, Al, Zn, Mn, V, As, and Si. Tall oil may also contain other inorganic compounds. Most often they have the form of resinates and/or salts of fatty acids. Their percentage is usually from 140 to 280 ppm (ppm). This means that they bind the material the molecular weight of which is approximately 6.7-7.5 times greater than their molecular weight. Depending on the concentration of the materials in question is associated, for example, resin acids from 900 to 1900 ppm = maximum of 0.2 wt.% in a crude tall oil and about 0.6% in the resin remaining after purification of tall oil.

Resin tall oil, which is a residual product purification by distillation is usually burned in a mixture with the head distillate purification of tall oil. Resin tall oil contains about 13 per cent of free resin acids, from about 3% to 8% of free fatty acids, about 1% of free sterols and approximately 12% related sterols and approximately 60% of esters of fatty acids and fatty acid esters of wood-based alcohols. In addition, the resin contains a small amount of lignin molecular weight is usually more than 1000, and dimers and oligomers of the resin acids.

If the resin is to obtain motor fuel from fatty acids and resin acids contained in the resin, the remains of metal to remove.

Fuel containing residues of metals, unsuitable for use in cars; in addition, these residues become catalyst poisons in the process of hydrogenation, which is carried out in the manufacture and�mobilnih fuels to stabilize the fuel and prevent its oxidation and to lower the point of freezing.

In accordance with the decision described in published patent application WO 2009131510, the removal of these cations is carried out by processing with the use of sulfuric acid and phosphoric acid followed by filtration through a filter <10 μm. In accordance with this patent application used for processing crude tall oil (STM).

However, processing the known method does not ensure complete removal of the zinc, vanadium and arsenic. The removal of each metal by means of a separate acid treatment allows to obtain a substantially complete precipitation, but this method is expensive and complicated. Thus, for the processing of STM in accordance with a known solution required processing large amounts of material. This treatment does not remove lignin and increases its solubility.

In the patent US 4426322 described used before distillation processing processing STM by means of water under pressure, which removes from tall oil soluble salts, mainly Na2SO4preferably at a temperature of 130°C. However, this treatment does not remove cations associated with resin acids and fatty acids, and fibers contained in the suspension.

In accordance with the patent US 4248769 sulphate soap before acidification was washed with a solution of concentrated Na2SO4that p�allows to remove approximately 50% of salts of lignins i.e. lignans.

In published patent application US 2009/0217573 A1 describes the preparation of crude tall oil fuel for internal combustion engines. In accordance with this application form crude tall oil esterified with alcohol (C1-C8), water and alcohol are separated, the remaining dry ether, the mixture is separated by distillation into two fractions, and reduce the amount of sulfur compounds by removing them by distillation at different stages.

In an article published in the journal Energy & Fuels (2001, 15, 1166-1172) described the conversion of the resin fractions of crude tall oil into motor fuel. In accordance with this article, first remove the group-COOH by converting them into alcohols or hydrocarbons, applying thermal cleavage for removal of CO2. This requires a temperature of approximately 400°C, and the catalyst Ni-Mo. In accordance with the same article possible hydrogenation directly resin acids at a temperature of from 350 to 400°C and a hydrogen pressure of 100 bar with the use of Ni-Mo oxide catalyst on the surface of aluminum oxide. This allows you to get cycloalkanes and hydrogenated aromatic compounds.

The experiments described in this publication is interesting because they used pure pitch fraction (Unitol NCY/Arizona Chemical). The boiling point of the main part poluchennogo� product was approximately 320°C at normal pressure.

In the patent US 5705722 proposed hydrogenation of tall oil, essentially not containing ash (distilled product, CC balance which is resin tall oil), Hz at a pressure of 4 MPa and a temperature of from 370°C to 450°C. Indicated that the cetane number of the thus prepared product is good enough to apply this product as an additive in low-grade diesel fuel, which is a petrochemical product.

In the above-described patent documents systematically used fractions, of which removed chemicals with a high molecular weight, or, according to some publications, laboratory tests carried out with the use of "pure" chemicals. Tall oil and, in particular, its resin contain a large number of cations, which are catalytic poisons. Consequently, the methods based on hydrogenation pure chemical agents, no industrial application.

The object of the present invention is to eliminate at least some of the problems associated with known technology, and providing a completely new method of processing of tall oil resin, in particular machining to get out of it fuel or additive to the fuel.

The present invention is based on the su� first resin and release fatty acids from their esters, contained in the resin. This can be accomplished, for example, using water hydrolysis or transesterification, or combinations thereof, wherein the transesterification is essentially carried out using low molecular weight alcohol. After that fatty acids liberated from esters of high molecular mass, or their lower alkyl esters, is removed from the resin by distillation or preferably by evaporation. The steam is condensed and separated.

It was found that the evaporation is preferably carried out with the aid of the device in which the resin is treated in such a way that it essentially boils on the surface evaporation. In accordance with one of preferred embodiments of the invention, this device is an evaporator with a small distance between the surface evaporation and surface condensation (from the English. short path evaporator), i.e. a device in which to be heating surface and a cooling surface disposed close to each other and in which the gas stream is separated from the vaporized fluid is very slow due to the large size of the heating surfaces and condensation. When using such a device, the number of droplets and other particles entrained with the gas stream is minimal.

Possible hydrogenation products prepared in the described way in which �idresource, i.e. saturated, the double bond of alkyl esters of fatty acids, and the group-COOH or -- COOCH3fatty acids are converted to carbon dioxide and methane or ethane. With alkyl esters of resin acids similar, with the difference that their ring structure at least partially opens. With this method formed biocomponent, suitable for use as an automotive fuel, for example diesel fuel.

More specifically, the method in accordance with the present invention is mainly characterized in restrictive part of claim 1 of the attached claims.

The product in accordance with the present invention described in claim 14, and used in accordance with the present invention described in claim 16 of the attached claims.

The present invention provides significant advantages. So, it can significantly increase the economic value of the components of tall oil resin compared with that obtained from its combustion.

After separation of the main part of the esters of fatty and resin acids and free fatty and resin acids by evaporation in the resin remain sterols, which are also separated and which are even more valuable than fatty acids.

Of those present in tall oil metals Zn, As, Fe, Si and Pb, and, according to some �of experts, also Na and Sa are harmful to catalytic poisons, since they clog the pores of the catalyst carrier, such as activated carbon and Al2O3. The first five metals in this list, i.e., Zn, As, Fe, Si and Pb, are catalytic poisons during hydrogenation. In addition, the metals together, for example, with phosphorus present in automotive fuels are catalytic poisons in catalytic Converter of exhaust gases, among which the most harmful is the lead. In jet fuels, the maximum permissible total amount of metals is from 5 to 98 ppb (billion part) (0,001 ppm), depending on published sources.

In turn, copper is the most harmful metal impurities in commodity fuel with high octane components. Already when the content of 25 mg/l it causes oligomeric molecules (caldesmon).

Consequently, the metals must be thoroughly removed from fatty and resin acids, which are formed of resin tall oil, and basically form a fuel derived from tall oil products.

In patent publication WO 2010/003504 described method of adsorption and absorption of metals from diesel fuel. This decision relates to the removal of cations of Cu, Pb and Zn by applying a fatty acid (R2COOH), which are applied to the powder medium.

Clean and n� containing metal fatty acids and resin acids or their esters, which can be obtained by using the present invention, the most popular, when they are used as fuel for internal combustion engines. You can hydrate fatty acids, also together with resin acids, even for fuel for a gas turbine engine.

The present invention will be described in detail below using the accompanying drawing.

The drawing shows a block diagram of the technological process in accordance with one embodiment of the present invention.

In General, the present invention includes the following:

- the major part of the fatty acids and resin acids release from their stalowych esters and possibly other esters of wood-based alcohols;

preferably they can be converted to esters of methanol or ethanol or the like lower alkyl esters;

- inter-esterified products are removed from the resin by evaporation and then condensed, preferably directly, and

- condensate obtained is hydrogenated.

Under the "main part" here means that at least about 50 mol. %, more preferably at least 70 mol. %, especially at least 80 mol. % fatty acids and resin acids contained in the resin, a release from their esters with sterols and wood alcohols, and is converted into lower alkyl� esters.

Under "lower alcohol" in this context means the alcohol C1-4, preferably methanol or ethanol.

In accordance with this invention there are at least two ways (see Fig.1), depending on how fatty acids and resin acids release from stalowych esters and, possibly, other esters of wood-based alcohols. It is also possible the combination of these two methods.

In accordance with the first method, indicated in the drawing Alt. 1, the process begins with a water hydrolysis, which is preferably a hydrolysis in acidic medium. In the drawing, the reference position 1 designates a hydrolysis step. Soluble salts and at least part of the cations associated with resin acids, dissolved in water, which is removed after hydrolysis by decantation. Position 2 indicated the stage of drying.

Preferably, the hydrolysis is carried out at a temperature of approximately 250°C to 360°C respectively and at a pressure of from 40 to 86 bar, and, in addition, clarification is carried out at a temperature of approximately 95°C. it is also Possible the implementation of the hydrolysis at a temperature of approximately 220°C to 280°C respectively and at a pressure of from 25 to 65 bar.

At this stage, the soluble salts and at least some of the salts dissolved due to the acidity, Esch� are in the aqueous phase.

As described above the aqueous hydrolysis may partially or fully be a water rinse. It is important that the largest possible number of stages as many metals, phosphorus, and the solid phase was removed from fatty acids, resin acids and/or their lower alkyl esters (methyl or ethyl esters that are separated from the resin. After any treatment with water a mixture of fatty acids that is subject to esterification, must be thoroughly dried. If the mixture is not subjected to esterification, and is separated into parts is hydrogenated and after the split on the place of distillation or in any other place, the removal of the metals is just as important.

A special property of water of hydrolysis is that dissolved salts are removed along with the excess water, taking into account that before the evaporation of the water at least most of the water is decanted to remove organic materials. It should be understood that in the context of the invention under aqueous hydrolysis or by hydrolysis of steam pre-processing means possible before esterification of alcohols.

Instead of water the hydrolysis of 1 is possible to carry out washing with water, drying and transesterification. This way you can remove the bulk of salts (Na2SO4).

In addition, in the aqueous hydrolysis is possible to use methanol or ethanol, which improves RA�salanie emulsions and promotes transesterification (J. Am. Chem. Soc, 2001, 123 (41) pp.10101-10102).

Then carry out the transesterification 3 using a lower alcohol, typically C1-4such as methanol or ethanol, after drying the reaction mixture.

In accordance with another preferred embodiment of the invention the transesterification carried out using the lower alcohol, such as methanol or ethanol, is used directly (this solution is designated in the drawing by the position of Alt.2). In this case also used acid catalyst, which simplifies the separation of metals in a water phase is removed by decantation, or centrifugation, or by evaporation.

The pressure and temperature of the transesterification is selected depending on the amount of alcohol dissolved in the resin, and pressure of steam in the mixture. Usually the pressure is chosen so that the alcohol could evaporate at the selected temperature. Thus, temperature is usually from 25°C to 300°C, for example from about 50°C to 250°C and the pressure is normal atmospheric pressure or above, for example, maximum 150 bar (abs.), more preferably maximum 100 bar (abs.), for example, from about 2 to 90 bar (abs.).

The most transesterification is preferably carried out using methanol or ethanol using an acid catalyst, for example sulfuric acid or sour�ing ion exchange resin.

These transesterification and subsequent drying and evaporation 5 always performed immediately after each other.

To maximize the use of resin, for example, in the manufacture of automotive fuels fatty acids due to the release of esters separated by distillation 6.

There are many methods of separation, e.g., using a fractionating column, which usually contains a return, or simply using the "Stripping-distillation", in which the column does not contain a return, but contains some plates, or thin-film evaporator, or the evaporator with a small distance between the surface evaporation and surface condensation.

When fatty acids or their esters evaporate, it is important that they evaporate without boiling. For this you may use a thin film evaporator, but, in particular, used evaporator is the evaporator with a small distance between the surface evaporation and surface condensation that contains the droplet separator.

In the evaporator with a small distance between the surface evaporation and surface condensation surface condensation and surface evaporation are in the same space and are of approximately equal size. Gases move for a short distance at low speed. Thus, the metal ions are not moved over�spine of heat on the surface of condensation. When the pure esters of fatty acids thus formed, easy to carry out the hydrogenation, since catalysts are not poisoned by metals.

The use of the evaporator with a small distance between the surface of the evaporation and condensation surface is preferred because in this case, if a certain amount of metal is moved in the distillate or the evaporite, this quantity is minimal. This is important because, when alkyl esters (usually methyl esters) of fatty acids or resin acids, thus separated, is used for the manufacture of diesel fuel by hydrogenation, the hydrogenation catalysts are not contaminated. You can apply these esters along with petrochemical raw materials directly for further processing at the plant for the refining of petroleum.

In both cases, the water and the excess alcohol from the first transesterification should be removed in a separate node 4, and only after that methyl esters of fatty acids and resin acids are separated in a high vacuum from other components of the resin.

In accordance with one of preferred embodiments of the present invention after removal of the esters of fatty acids and resin acids by evaporation Stereolove compounds vaporize at stage 6, with significantly reduced pressure. Another possi�the third way is after evaporation of the released acids bottoms resin is dissolved in a lower alcohol, in particular C1or C2and the separated alcohol phase is evaporated, and the sterols isolated for further purification.

In both cases, sterols distilled or evaporated under still lower pressure than fatty acids (T, essentially, about 225°C, p is from 0.01 to 3.5 mbar).

Educated alkyl ether evaporated condenses most preferably directly after evaporation. Usually the time between the evaporation and subsequent condensation is from about 1 to 60 minutes, preferably from about 1 to 10 minutes.

In accordance with another preferred embodiment of the invention method is that the product in which the fatty acids and resin acids are not bound in high molecular weight esters, dried to remove water from it (after decanting) and then evaporated, preferably in two stages.

In this case, the composition of the methyl ester of fatty acid and methyl ester of resin acid formed in the condensate evaporator in the first stage 5, and staronova composition is formed in the following step 6. The residue contains neutral materials and oligomers having a high boiling point. The balance also includes the metal resinates.

In the first phase, the working� pressure is from about 3 to 15 mbar (abs.), and operating temperature 220°C, and in the second stage, as indicated above, the working temperature is more preferably approximately 225°C and working pressure from 0.01 to 3.5 mbar (abs.).

Thus, it is possible to provide approximately 60% to 70% of a resin component containing no metal salts.

Although you can successfully use methyl esters without further purification as fuel for diesel engines (Bioresource Technology, Volume 98, issue 2 Jan. 2007 pp.241-246), the product is susceptible to oxidation and oligomerization.

Consequently, the fraction of alkyl esters of fatty and resin acids optionally is hydrogenated catalytically and isomerized to improve cetane number. Using hydrogenation can be dicarboxylate acid and saturate double bonds.

If at this stage requires the allocation stealaway fractions for final purification, it is separated by evaporation under reduced pressure. The hydrogenation can be carried out in a known essentially by the method, for example described in the publication Petroleum and Science and Technology 16 (5&6), 597-609 (1998).

After evaporation of the remaining resin (in the drawing, a residual resin") containing dimeric resin acids, oligomers, lycopene and wood-based alcohols, such as lutein and neoxanthin, etc., and metal salts of resin acids are burned or used as raw material for adhesives.

In stat�e in the journal of Petroleum and Science and Technology 16 (5& 6), 597-609 (1998) described the conversion by hydrogenation of tall oil, from which the removed resin (DPTO - from the English. "Depitched Tall Oil), in excellent improver cetane number of diesel oil. In particular, the article investigates the poisoning of catalysts. It is clear that the poisoning of the catalysts is significantly more likely when working with the resin than with tall oil, from which is removed the resin, and this poisoning is caused by relatively higher contents of metals.

The above-described method yields a composition in which the total metal content is less than 50 mg/litre, and, in addition, the maximum total content (Cu+Pb+Zn) is 300 micrograms/liter.

You should make a few remarks on the application of the present invention in the plant for the purification of tall oil.

In principle, you can use the installation for the purification of tall oil for reactions and physical separation described above. If you do not have evaporators with small distance between the surface of the evaporation and condensation surface, apply a thin film evaporator is a droplet separator and a distillation column, which has a low coefficient of delegatie separates the spray metal resinates. However, the benefits of the use of the evaporator with a small distance between the surface evaporation and surface �ondensate are small pressure drop and a lower surface temperature of evaporation.

Conventional distillation system for tall oil, the capacity of which is, for example, 150,000 tons/year of fatty acids and resin acids, produces approximately 60,000 tonnes/year of tall oil resin. When processing the resin on one of the specified distillation setup when the applied bottom boilers are thin-film evaporators or evaporators falling film, and they work with much lower bandwidth, surface boiling is so small that hardly any unwanted metal compounds into the distillate.

Material transfer from the heating surface to the condensing almost exclusively limited to the evaporation of molecules in the application of the evaporator with a small distance between the surface of the evaporation and condensation surface, or one of the more conventional evaporators such as thin-film evaporator and a falling film evaporator, at a much lower bandwidth than thermal conductivity on which they are calculated.

In accordance with another preferred embodiment of the invention, the evaporation is performed in a thin-film evaporator at a bandwidth comprised between 1/3 to 1/2 of the original bandwidth, which is calculated for the evaporator.

1. �] processing of tall oil resin, containing Stereolove alcohols and possibly wood alcohols, fatty acids and resin acids of the tall oil, characterized in that:
at least part of the fatty acids and resin acids release from stalowych ethers and esters of wood-based alcohols and converted to lower alkyl esters;
- the thus obtained alkyl esters are removed by evaporation from the resin and then condense, and
- condensate obtained is hydrogenated.

2. A method according to claim 1, characterized in that the fatty acids and resin acids first release at least a part of stalowych ethers or esters of wood alcohols, and these esters typically have high molecular weight, with the use of water hydrolysis.

3. A method according to claim 1, characterized in that the fatty acid and resin acid release from stalowych ethers or esters of wood-based alcohols, usually having a high molecular weight, subjecting them to the reaction of transesterification with lower alcohols.

4. A method according to claim 1, characterized in that the resin is treated in such a way that it essentially boils on the surface evaporation.

5. A method according to claim 1, characterized in that the treatment is performed in an evaporator with a small distance between the surface evaporation and surface condensation.

6. A method according to claim 1, characterized in that the processing of OS�of Directors carries out in the falling film evaporator with bandwidth equal to 1/3 to 1/2 of the original bandwidth, which is calculated for the evaporator.

7. A method according to claim 1, characterized in that the processing is performed in a thin-film evaporator at a bandwidth equal to 1/3 to 1/2 of the original bandwidth, which is calculated for the evaporator.

8. A method according to claim 1, characterized in that after removal of the esters of fatty acids and resin acids by evaporation Stereolove compounds vaporize at a much lower pressure.

9. A method according to claim 1, characterized in that the bottoms of the resin remaining after evaporation of the released acid, dissolved in a lower alcohol, and the separated alcohol phase is evaporated, and the sterols isolated for further purification.

10. A method according to claim 1, characterized in that the acid and esters decarboxylase by hydrogenation of the condensate and saturate double bonds.

11. A method according to any one of claims.1-10, characterized in that the alkyl ether is condensed directly after evaporation, and the time between the evaporation and subsequent condensation is generally from about 1 to 60 minutes, preferably from about 1 to 10 minutes.

12. A method according to any one of claims.1-10, characterized in that at least about 50 mol.%, more preferably at least 70 mol.%, in particular at least 80 mol.% fatty acids and resin keys�from, contained in the tall oil resin, a release from their esters with sterols and wood alcohols and converted to lower alkyl esters.

13. A method according to claim 11, characterized in that at least about 50 mol.%, more preferably at least 70 mol.%, in particular at least 80 mol.% fatty acids and resin acids contained in the tall oil resin, a release from their esters with sterols and wood alcohols and converted to lower alkyl esters.

14. A method according to claim 1, characterized in that the lower alkyl esters are prepared from the alcohol (C1-4preferably from methanol or ethanol.

15. The product obtained by the method according to any one of claims.1-14.

16. The product according to claim 15, characterized in that prior to hydrogenation, the total content of the metal is less than 50 mg/liter, the total maximum content (Cu+Pb+Zn) is not more than 300 micrograms/liter.

17. The application of the method according to any one of claims.1-14 for fuel, particularly automotive fuels such as diesel fuel.



 

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FIELD: chemistry.

SUBSTANCE: invention relates to an improved method for reesterification of at least one compound containing at least one ester functional group with at least one compound containing at least one hydroxyl group, in which red mud, formed during production of aluminium through a Bayer process, is used as a reaction-accelerating compound.

EFFECT: method allows for maximum utilisation of wastes - red mud, both in storage and annually formed.

27 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an integrated method of producing jatropha methyl ester (JME) and by-products from encapsulated seeds of jatropha containing 1.06% of free fatty acids (FFA), said method comprising the steps of: (i) mechanically removing the shells of the jatropha seeds in a shell-removal machine to obtain jatropha shells and jatropha seeds; (ii) squeezing out jatropha oil, obtaining jatropha oil cake containing 4-6% nitrogen and waste oil sludge from the jatropha seeds obtained at step (i), using an oil press; (iii) neutralising jatropha oil obtained at step (ii) with a base; (iv) transesterifying one part of neutralised jatropha oil obtained at step (iii) with an alcohol and a base with stirring for 10-20 minutes and separating the crude glycerol layer GL1 and crude jatropha methyl ester (JME); (v) washing crude JME obtained at step (iv) three times with the pure glycerol layer to separate three impure glycerol layers GL2, GL3 and GL4 containing methanol and KOH to obtain glycerol-washed JME (JME-G3W); (vi) purifying JME-G3W obtained at step (v) to remove alkali metal impurities; (vii) treating part of remaining neutralised oil obtained at step (iii) with glycerol layers GL5 (GL1+GL2+GL3) obtained at steps (iv) and (v) to obtain JME and glycerol layer GL6; (viii) separating JME and glycerol layer GL6 obtained at step (vii); (ix) treating glycerol layer GL6 obtained at step (viii) with remaining part of neutralised oil for removing methanol to obtain JME and glycerol layer GL7; (x) separating JME and glycerol layer GL7 obtained at step (ix); (xi) using glycerol layer GL7 as obtained at step (x) directly for the production of polyhydroxyalkanoates (PHAs) or for the neutralisation of alkali with sulphuric acid to obtain pure glycerol and still bottom GL8; (xii) combining JME-G3W obtained at step (vi) and JME obtained at steps (viii) and (x) to obtain combined methyl ester; and (xiii) transesterifying combined methyl ester obtained at step (xii) with methanolic KOH to obtain pure jatropha methyl ester (biodiesel) having total glycerol content of 0.088% and free glycerol of 0.005%. The invention also relates to an integrated method of producing JME and byproducts from jatropha seeds, the method including steps of: a) carrying out said steps (i) and (ii); b) briquetting the jatropha shells obtained at step (i) in a briquetting machine with the addition of waste oil sludge obtained at step (ii) to obtain jatropha briquettes with density of 1.05-1.10 g/cm3 as a by-product; c) hydrolysing jatropha oil cake having 4-6% nitrogen obtained at step (ii) with H3PO4, H2SO4 to obtain jatropha oil cake hydrolysate (JOCH) as a by-product; and d) carrying out steps (iii)-(xiii).

EFFECT: invention provides a simpler and more energy-efficient method of producing fatty acid methyl ester (biodiesel) which is integrated with beneficial recycling of by-products such as seed shells, deoiled cake and crude glycerol stream.

13 cl, 7 dwg, 7 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: method comprises the following basic operations. a) producing mixtures of fatty acid alkyl esters and glycerine by trans- esterification, starting from lipid-based vegetable or animal materials and from lower alcohols or bioalcohols in excess; b) separating the mixtures obtained from the said operation a) of trans-esterification into a phase based on raw glycerine and a phase containing said mixtures of fatty acid alkyl esters and the excess amount of lower alcohols or bioalcohols; the method being characterised by that said starting lipid-based vegetable or animal materials include one or more of the following ingredients: i) raw vegetable oil; ii) refined vegetable oil; iii) used edible oil and/or animal fats and by that said ingredients undergo the following preliminary treatment steps before said operation a) of transesterification: 1) said ingredient i), raw vegetable oil, is subjected to preliminary cleaning and refinement in order to remove impurities and to neutralise and fractionate the oil by cooling, and then drying the refined oil thus obtained; 2) said ingredient ii), refined vegetable oil, is subjected to preliminary drying; 3) said ingredient iii), used edible oil and/or animal fats, is subjected to a preliminary cleaning, drying and then esterification of the free fatty acids contained therein, by addition of lower alcohols or bioalcohols; the obtained product based on fatty acid alkyl esters is mixed in a proportion of not more than 20% with dried refined oil obtained from treatments 1) or 2) above. Said preliminary treatments are performed in corresponding three sections for preliminary treatment of material, said sections being used together or alternatively to each other. The invention also relates to a biofuel or biofuel mixture.

EFFECT: method is extremely flexible with respect to providing raw material and provides high flexibility with respect to applicability of the obtained product.

15 cl, 1 ex, 1 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of processing fat and fat-containing biomass. The method can be used in producing fuel and intermediate products for organic synthesis. The method is carried out via simultaneous exposure to ionising radiation and temperature of fatty material at normal or low pressure in a fluidised bed to obtain commercially valuable radiolysis products, which are a fuel (primarily diesel fuel) and intermediate products for organic synthesis. The material is exposed to an electron beam with energy of 0.1-8 MeV with dose rate higher than 0.05 kGy/s while heating below the dry distillation (pyrolysis) onset temperature. Alkanising the starting mass, use of catalysts and/or ultrasound can be additional controlling factors depending on composition of the starting material.

EFFECT: high degree of recycling material and output of valuable fractions of fuel hydrocarbons and intermediate products for heavy organic synthesis.

6 cl, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to mixtures of alkyl ethers of fatty acids for use as raw material for producing biofuel which contains at least 50 wt % alkyl ethers of saturated fatty acids containing 6-14 carbon atoms, alkyl ether of myristoleic acid and alkyl ethers of monounsaturated fatty acids containing more than 14 carbon atoms, less than 10 wt % alkyl ether of myristic acid and alkyl ethers of saturated fatty acids containing more than 18 carbon atoms. 1) said alkyl ethers of fatty acids contain alkyl ether of lauric acid (C12:0), said alkyl ether of lauric acid makes up 5-20 wt % of the mixture; or 2) said mixture contains 15-40% alkyl ethers of fatty acids containing 6-14 carbon atoms and 60-85% alkyl ethers of monounsaturated fatty acids containing more than 18 carbon atoms. The invention also relates to a method of producing said mixture.

EFFECT: invention provides a fuel mixture which is less likely to freeze in cold climate conditions.

27 cl, 13 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing fatty acid esters, which are used as diesel biofuel, from whole oilseeds, involving the following consecutive steps: a) preheating unhulled and cleaned whole seeds; b) squashing the oilseeds together with their shells; c) drying the squashed seeds until achieving water and volatile substance content of 0.5-2.5%; d) re-esterification by bringing the squashed seeds into contact with an alcohol medium in the presence of a catalyst; e) separating the liquid and solid phases obtained from re-esterification; f) neutralising the liquid phase obtained at step (e); and g) removing alcohol and separating glycerol from fatty acid esters, which are then purified. The invention also relates to a method of producing an oil cake, meant for use as animal feed, from the obtained solid phase, which involves the following steps: 1) removing alcohol from said solid phase; and 2) adding glycerol obtained at step (g) of the method on any of the previous claims.

EFFECT: method of obtaining fatty acid esters from squashed oilseeds.

25 cl, 12 tbl, 19 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing organic carbonates and carbamates. Described is an alcoholysis method, involving: feeding reactants and a trace amount of a soluble organometallic compound, which is soluble in the reactants, into a reactor containing a solid alcoholysis catalyst, wherein the trace amount ranges from about 1 ppm to about 3000 ppm with respect to total mass of the added reactants; where the soluble organometallic compound and the solid alcoholysis catalyst each independently contains a Group II to Group VI element. Described is a method of producing dialkylcarbonates, involving: feeding an alcohol and an alcoholysis reactant, containing at least one compound from urea, organic carbamate and cyclic carbonate, in the presence of the catalyst system described above. Described is a method of producing diarylcarbonate, involving: feeding an aromatic hydroxy compound and dialkylcarbonate in the presence of the catalyst system described above. Described is a method of producing alkylarylcarbonate, involving: feeding an aromatic hydroxy compound and dialkylcarbonate in the presence of the catalyst system described above. Described is a method of producing biodiesel, involving: feeding an alcohol and glycerine in the presence of the catalyst system described above The methods described above involve reaction of a spent solid alcoholysis catalyst, involving: removal of polymer materials deposited on the catalyst; and redeposition of catalytically active metals on the solid catalyst.

EFFECT: longer duration of the cycle of the alcoholysis method.

36 cl, 7 tbl, 18 dwg, 14 ex

FIELD: medicine.

SUBSTANCE: invention refers to new compounds of formula (I) where X is carboxylic acid, carboxylates, carboxylic anhydride, diglyceride, triglyceride, phospholipid, or carboxamides, or to any their pharmaceutically acceptable salt. The invention particularly refers to (4Z, 7Z, 10Z, 13Z, 16Z, 19Z)-ethyl 2-ethyldocosa-4,7,10,13,16,19-hexanoate. The invention also refers to a food lipid composition and to a composition for diabetes, for reducing insulin, blood glucose, plasma triglyceride, for dislipidemia, for reducing blood cholesterol, body weight and for peripheral insulin resistance, including such compounds. Besides, the invention refers to methods for treating and/or preventing diabetes, dislipidemia, peripheral insulin resistance, body weight reduction and/or weight gain prevention, insulin, blood cholesterol, blood glucose and/or plasma triglyceride reduction.

EFFECT: higher clinical effectiveness.

61 cl, 4 tbl, 16 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a product used in chocolate, margarine or shortening, obtained by melting a mixture of components (a) and (b), where component (a) contains triglyceride of disaturated medium-chain fatty acids and monosaturated long-chain fatty acid and (b) contains triglyceride of 1,3-disaturated long-chain fattya cids and 2-monosaturated long-chain fatty acid, wherein the bond length determined through X-ray diffraction, measured in the product is equal to greater than 65 Å, where the medium-chain fatty acid(s) contain(s) 6-12 carbon atoms, and the long-chain fatty acid(s) contain(s) 14-24 carbon atoms.

EFFECT: owing to formation of intramolecular compounds, fats and oil contain a larger amount of symmetrical triglycerides such as cocoa oil, and contain medium-chain fatty acids which do not form separate crystals and can endow the product with a smooth texture and prevent turbidity.

8 cl, 9 dwg, 17 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing carboxylic esters via esterification of carboxylic acids and/or re-esterification of carboxylic esters with methanol or ethanol in the presence of a metallic catalyst, in which the reaction takes place at temperature higher than 150°C, said metallic catalyst is an alkali-earth metal salt and an aliphatic carboxylic acid containing 10-24 carbon atoms, and at the end of esterification or re-esterification, respectively, the metallic catalyst is extracted and then reused as a liquid catalyst in the method of producing carboxylic esters via esterification of carboxylic acids and/or re-esterification of carboxylic esters with methanol or ethanol in the presence of a catalyst. The advantage of the method lies in that, in the initial mixture, free fatty acids can be present in any concentrations. These free fatty acids are also esterified in the said reaction to fatty acid alkyl esters. Hence, low-quality fat/oil can be processed. Another advantage of the method is that, the esterification/re-esterification reaction can also take place in the presence of water. Thus, water-containing material, particularly hydrous alcohol, can also be used. Unreacted free fatty acids or glycerides are returned for esterification/re-esterification, owing to which no losses occur. In contrast to processes without catalysts, the disclosed method has an advantage in that, the reaction can take place with amounts of alcohol which are a little higher than stoichiometric amounts, which markedly increases profitability of the method.

EFFECT: improved method of producing carboxylic esters.

5 cl, 4 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: method of alkyl ester obtainment involves, for instance: mixing of triglyceride-containing oil source with primary alcohol or secondary alcohol in organic solvent to obtain a solution; where each organic solvent molecule includes 4-8 carbon atoms and heteroatom; triglyceride reaction with primary alcohol or secondary alcohol in the presence of lipase immobilised on a carrier, to obtain alkyl ester, where solution does not undergo phase separation in the course of reaction, and glycerin is produced as a by-product; and obtainment of alkyl ester by phase separation in alkyl ester and glycerin after extraction of organic solvent and unreacted primary or secondary alcohol by condensation.

EFFECT: obtainment of mix with high content of high-purity alkyl esters.

46 cl, 8 ex

FIELD: food industry.

SUBSTANCE: invention relates to fat-and-oil industry. The deoxidising agent for food oils containing particles of magnesium hydroxide containing carbonate groups, represented by the following formula (1) and having specific surface area equal to 80 - 400 m2/g determined by the BET method, or their baked particles; and a method for regeneration of used food oil by way of deoxidising agent usage: Mg(OH)2-x(CO3)0.5x·mH2O (1) where x fulfils the condition 0.02≤x≤0.7 while m fulfils the condition 0≤m≤1.

EFFECT: invention allows to enhance oil deoxidising capability.

11 cl, 3 dwg, 10 tbl, 1 ex

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