The method of purification of ethyl synthetic industrial alcohol from impurities of aldehydes and ketones
(57) Abstract:The invention relates to the field of technology organic chemistry, and in particular to methods of cleaning ethyl synthetic industrial alcohol from impurities of aldehydes and ketones. Cleaning lead processing ethyl synthetic industrial alcohol reagent and caustic alkali, with a reagent selected from a number of: resorcinol, urea, hydroxylamine sulfate, hydrazinehydrate, hydrazine sulfate, sodium sulfite, dymadon, soybean oil, sunflower oil at a ratio of reagent is caustic alkali, followed by boiling and distillation. Purified ethyl synthetic industrial alcohol suitable for use in aerosol preparations. table 2. The invention relates to the technology of organic chemistry and relates to methods of cleaning ethyl synthetic industrial alcohol (ESTs) from impurities of aldehydes and ketones.According to the technical requirements in force in Russia (THE 38.402-62-117-90), ESTs may contain not more than 0,7 0,9% volume fraction of acetaldehyde and not more than 0.2% volume fraction of crotonic aldehyde. The content of ketones is not standardized.A known method of purification of synthetic ethyl flavors  the disadvantages of this method include the high cost and lack of efficiency of treatment of the alcohol of the proposed method.A known method for separating ethanol from water-alcohol solutions, obtained as a waste product in the production of silicon dioxide, processing of 0.8-1.0% per 1 l of a solution of hydrochloric acid hydroxylamine and 3% on 1 l of calcium chloride solution or dilute sulfuric acid of at least 10 g per 1 l of solution, followed by distillation. The disadvantages of this method are the need to use a very large number of reagents, as well as noticeable residual presence in the rectified acetaldehyde 
The known method of separation of individual products in the manufacture of synthetic ethanol treatment by sodium bisulfite and sodium hydroxide , followed by distillation. The disadvantages of this technical solution should include a high residual content (0.05%) of acetaldehyde in the final technical ethanol.There is also known a method of rectification of the crude alcohol, which consists in the processing of raw alcohol with a mixture of alkali (caustic soda), potassium manganese acid or bicarbonate of sodium  the Composition and amount of the mixture varies depending on the presence and amount of certain impurities. The disadvantages of this method will otnositsa insufficient cleaning efficiency is the reception and is a prototype.The purpose of the present invention is perhaps more thorough cleaning (the acetic aldehyde and acetone not more than 0.01% volume fraction, the Croton th aldehyde absence) of ESTs according to chromatographic analysis.This goal is achieved by processing ESTs (specifications 38.402-62-117-90) with a maximum content of impurities with a reagent selected from the range: resorcinol, urea, hydroxylamine sulfate, hydrazinehydrate or hydrazine sulfate, sodium sulfite, dymadon, soybean oil or sunflower oil, hydrate of sodium oxide or potassium and subsequent rectification when the ratio of the alkali reagent (g/DM3ESTS):
resorcinol alkali(2,0-10,0) (1,0-5,0),
urea alkali(1,0-5,0) (0,5-2,5),
hydroxylamine sulfate alkali(1,0-5,0) (0,5-2,5),
the alkali hydrazinehydrate(0,5-2,5) (0,5-2,5),
hydrazine sulfate alkali(0,5-2,5) (0,5-2,5),
sodium sulfite lye(1,0-5,0) (1,0-3,0)
the alkali dimedone(2,0-10,0) (1,0-3,5),
soybean oil lye(2,0-10,0) (1,0-3,5),
sunflower oil lye(2,0-10,0) (1,0-3,5).Reagent selected from the above range, add these amounts together with the alkali in the untreated ESTs, subjected to boiling for 4 hours and then distilled processed alcohol.The proposed solution is illustrated by examples of specific performance.Example 1. In a round bottom glass flask with a capacity of 1.5 liters, equipped with a reverse refrigerator and thermometer, is placed 1 DM3Acts above THE indicators:
mass concentration of acids in terms of acetic acid, mg/DM36,5
the volume fraction of acetaldehyde, 0,52
the volume fraction of crotonic aldehyde, 0,16
the volume fraction of ethyl ether, and 0.8
mass concentration of solids, mg/DM34,5
the volume fraction of polymers of ethylene, no
10 g of resorcinol, 5.0 g of caustic soda, boil the reaction mixture for 4 hours, replace the reflux condenser on Christmas reflux condenser with a length of 25 cm and a downward refrigerator, distilled 10 ml Pradhana that drop, 975 ml of the main fraction is purified acts with the indicators shown in the table. 2. In the flask remains about 25 ml of the cubic residue containing acetic aldehyde-resorcinol the resin oligomers of resorcinol, alkaline condensate crotonic aldehyde and the one hydroxide 3.0 g, potassium manganese acid of 2.0, the Results of the analysis are given in table. 2.Examples 3 20. In the conditions of example 1, the reactants and their number is listed in the table. 1. The results of the tests cleared ESTs are given in table. 2.Example 21. In the reactor of stainless steel with a volume of 5 m3fitted with mechanical stirrer, jacketed for heating steam and cooling water, temperature sensors, pressure, upper and lower levels, the pipes for loading, distillation and plum alcohol and VAT residue, heat exchanger and system for collecting Pradhana, the main fraction and VAT residue, download 3750 l ESTs include the stirrer and heating, water flow in the heat exchanger, heating the mass to about 40-50oC and through the loading hatch load 35 kg of resorcinol and 5.0 kg of caustic soda. Hermetically close the hatch reactor and bring the reaction mixture to a boil. The reactor mode "on" works 4 hours.After 4 hours of boiling in the mode of returning the condensate to the reactor mode ("on") through the sampler will take a sample of the distillate analyzed by chromatograph on the indicators specified in the table. 2. If satisfactory results of the analysis of the reactor is switched to the mode of distillation, which opens the valve of the distillation of alcohol and C is the frame acts. In the reactor remains 150 l VAT residue, which is sent to the tank bottoms and further burning. Cleaned ESTs from collection direct to the consumer.This demonstrates the practical utility and industrial applicability of the proposed technical solutions.From the above examples should the possibility of chemical cleaning acts with extreme amounts of impurities in industrial scale.All reagents used for this purpose are available tonnage industry of Russia.Quality cleaned ESTs meets the requirements of ethyl alcohol used in the manufacture of aerosol products.Thus, the use of the reagent of the above number to clear ESTs raw, in contrast to the method according to the prototype, allows you to brush up on alcohol high degree of purification, providing novelty and usefulness of the proposed solutions (inventive step). One of the main advantages of the present invention is maloothodnoj for all types of waste sent less than 7% by weight of the distilled spirits, while when using the cleaning rectification losses are bol the impurities of aldehydes and ketones by treatment with a reagent and a caustic alkali, boiling for 4 h and subsequent partition, characterized in that the reagent is used substances selected from the range: resorcinol, urea, hydroxylamine sulfate, hydrazine hydrate, hydrazine sulfate, sodium sulfite, dymadon, soybean oil, sunflower oil, and as the caustic alkali is caustic soda or caustic potash in the following ratio reagent caustic alkali, g/DM3ethyl alcohol:
resorcinol alkali 2,0 10,0 1,0 5,0;
urea alkali 1,0 5,0 1,0 3,5;
hydroxylamine sulfate alkali 1,0 5,0 0,5 2,5;
hydrazine hydrate alkali 0,5 2,5 0,5 2,5;
hydrazin sulfate alkali 0,5 2,5 0,5 2,5;
sodium sulfite lye 1,0 1,0 3,0 5,0;
dymadon alkali 2,0 10,0 1,0 3,5;
soybean oil alkali 2,0 10,0 1,0 3,5;
sunflower oil alkali 2,0 10,0 1,0 3,5.
FIELD: chemical technology.
SUBSTANCE: invention relates to removing impurities, such as aldehydes, from ethylene glycol aqueous solutions by treatment with bisulfite-treated strong-base anion-exchange resin. Invention describes a method for reducing the content of aldehydes in ethylene glycol aqueous solution containing about from 0.2 wt.-% to 20 wt.-% of ethylene glycol containing about from 80 wt.-% to 99.7 wt.-% of water and about from 100 mln-1 (mas.) to 0.1 wt.-% of aldehydes. Method involves contacting indicated solution with bisulfite-treated solid strong-base anion-exchange resin that before treatment with bisulfite comprises quaternary ammonium functional groups in hydroxide form. Invention provides the improvement in removing impurities, such as aldehydes, from flows of ethylene glycol aqueous solutions.
EFFECT: improved method for treatment.
2 cl, 1 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for treatment of aluminum alcoholates. Method involves passing aluminum alcoholates through a column filled with extrudates of aluminum oxide in γ-form with pore volume from 0.4 to 0.8 cm3/g prepared by preliminary hydrolysis of aluminum alcoholates, molding the prepared aluminum oxide to extrudates with diameter from 1.6 to 3 mm and length 3-4 mm and their following purification by calcinations at temperature 400-500°C. As a rule, the treatment of alcoholates is carried out at temperature 20-150°C in column for 1-5 h. Method provides the development of simple and available technology for treatment of aluminum alcoholates with hydrocarbon chain length from C3 to C6 and above from impurities up to the level 10-3-10-4 wt.-%.
EFFECT: improved treatment method.
2 cl, 5 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for preparing alkaline- and thermostable composition based on sugar alcohols of the optical density less or equal to 0.100 in S-test. Method involves treatment of sugar-base composition with strong-base anion-exchange resin in hydroxide form at temperature 30-100°C. Method provides decreasing consumption of chemical reagents and providing carrying out the combined a single-step process for alkaline stabilization and decolorizing.
EFFECT: improved preparing method.
18 cl, 7 tbl, 8 ex
SUBSTANCE: claimed invention relates to method of methanol recuperation from mixtures which contain it and water. Method lies in the following: a) carried out is multi-step evaporation in at least two steps of evaporation, each of which includes evaporator, with consecutive reduction of pressure with transition from each previous step of evaporation to each further step of evaporation and with heating of evaporators of second step of evaporation and each further step of evaporation with vapour-like main product from corresponding previous step of evaporation, and also b) carried out is multi-step distillation in at least two steps of distillation, in each of which distillation column and evaporator are included, with supply into each following distillation step of bottom product from corresponding previous distillation step and with consecutive pressure increase with transition from each previous distillation step to further distillation step, as well as with heating of evaporator at each distillation step, excluding last distillation step, with vapour-like main product from distillation column corresponding to following distillation step, obtained during evaporation at last step of multi-step evaporation (a) product is supplied for distillation into first step of multi-step distillation (b).
EFFECT: method allows to reduce consumption of energy used for methanol recuperation.
8 cl, 1 dwg, 1 ex
SUBSTANCE: present invention relates to a method for synthesis of pentaerythritol and dipentaerythritol, involving reaction of acetaldehyde with formaldehyde in the presence of sodium hydroxide, purification of the reaction solution through distillation of excess formaldehyde, evaporation and crystallisation of technical pentaerythritol, washing the residue, recrystallisation of technical pentaerythritol, separation of the residue from the solution and drying commercial-grade pentaerythritol and treatment of the product after drying. After drying the product is treated through separation, thereby extracting the pentaerythritol fractions most contaminated with non-volatile impurities of dipentaerythritol and cyclic formalin, and the extracted fractions are processed by leaching pentaerythritol with demineralised water at 10-80°C and ratio of liquid phase to solid phase equal to (5.5-8)/1, and subsequent separation of the formed pentaerythritol solution and dipentaerythritol precipitate and taking the pentaerythritol solution to the technical pentaerythritol recrystallisation step.
EFFECT: method enables to obtain pentaerythritol with low content of dipentaerythritol and cyclic formalin impurities, as well as recycling of dipentaerythritol.
6 cl, 1 tbl, 7 ex
SUBSTANCE: present invention relates to a method of processing alcohol production wastes: concentrate of head impurities of ethyl alcohol (CHI) and an intermediate fraction of ethyl alcohol (IFEA). The method involves obtaining a water-alcohol solution of CHI or IFEA with density (0.837-0.940) g/cm3 (I) and conducting continuous extraction of impurities (C3-C5 alcohols, esters, carbonyl compounds) in a packed column with a mixture of aromatic hydrocarbons (II) or a mixture of aromatic and aliphatic hydrocarbons (III) with ratio of volume flow I: II or, respectively, I : III, equal to 1:(1-4) (preferably 1:1.2). To intensify mass exchange into solution (I), (0.1-0.5) wt % mixture (IV) of anionic alkyl sulphates and noionic oxyethylated alkyl phenols in ratio (25-20):(70-75) wt% (IV). The desired processing products: raffinate - aqueous of ethanol with weight ratio of the latter equal to (80-20) wt % can be used to obtain high-purity edible ethyl alcohol and as an anti-icing agent for glass used on cars, and extract - solution of alcohol and esters in a mixture of hydrocarbons is used to prepare mixed solvents for the paint industry.
EFFECT: high efficiency of the method of processing alcohol production wastes.
4 cl, 8 ex, 1 tbl, 2 dwg
SUBSTANCE: present invention relates to a method of producing dehydrated ethyl alcohol, which can be used in chemical, electronic and pharmaceutical industry. The method involves feeding crude alcohol or a water-alcohol solution into a preliminary dehydration column operating under a vacuum to obtain a distillate which is fed into a final dehydration column operating at excess pressure, where dehydrated alcohol is collected in form of a residue and the distillate is fed into the preliminary dehydration column in form of reflux. The distillation process in the preliminary dehydration column takes place at absolute pressure of 8.0-13.3 kPa to obtain a distillate with alcohol content 98.2-98.9 vol. %, and the distillation process in the final dehydration column takes place at absolute pressure 0.1-0.5 MPa and alcohol content in the reflux of 96.5-97.2 vol. %.
EFFECT: method enables to obtain an end product of high quality using an improved an improved process scheme.
1 tbl, 1 dwg, 2 ex
SUBSTANCE: invention relates to cleaning of ethanol used as solvent for optical measurements. Proposed method consists in processing ethanol by oxidiser and base with subsequent rectification. Note here that iodine in concentration of, at least, 0.0125 wt % is used as oxidiser. Note also that processing by iodine and base is performed in boiling.
EFFECT: lower costs, translucent (up to 210 nm) ethanol.
SUBSTANCE: present invention relates to a method of separating liquid phase by-products of Fischer-Tropsch synthesis, which involves the following steps: a) feeding the liquid phase by-products into a standard fractionation column (1) in its middle part with output of a portion of the stream I, having a boiling point range from 50 to 120°C, as a side cut to obtain light components having boiling point below 50°C from the top of the column, and heavy components, having boiling point higher than 120°C from the bottom of the column; b) feeding the stream I into a column (2) for separating acetic acid in its middle part to obtain a stream of aqueous solution II, containing alcohols and ketones, having boiling point range from 50 to 100°C from the top of the column, and a stream III of aqueous solution of acetic acid from the bottom of the column; and c) feeding the stream II into a column (3) for separating ethanol in its middle part to obtain a stream IV of a mixture of methanol and acetone from the top of the column and a stream V of aqueous solution of ethanol and n-propanol from the bottom of the column (see dwg 3).
EFFECT: high efficiency of the process.
9 cl, 4 dwg, 30 tbl, 30 ex
SUBSTANCE: invention relates to improved method of obtaining polyols, which includes the following stages: a) oxidation of unsaturated natural fats, unsaturated natural fatty acids and/or esters of fatty acids with dinitrogen oxide; b) interaction of the product, obtained at stage a), with hydrating reagent in presence of catalyst, which contains, at least, one transition metal from groups from 6 to 11; c) interaction of the reaction product from stage b) with alkylene oxides in presence of multimetalcyanide catalyst. Invention also relates to method of obtaining polyurethanes, which includes oxidation of unsaturated natural fats, unsaturated natural fatty acids and/or esters of fatty acids with dinitrogen oxide, interaction of the obtained product with hydrating reagent in presence of catalyst, which contains, at least, one transition metal from groups from 6 to 11, interaction of the reaction product with alkylene oxides in presence of multimetalcyanide catalyst with obtaining polyols, interaction of polyisocyanates with polyols as compounds, which have two hydrogen atoms, reactionable with respect to isocyanate groups.
EFFECT: simple methods make it possible to obtain wide spectrum of products without application of expensive initial reagents.
10 cl, 8 ex
FIELD: distillery industry; production of a dehydrated ethyl alcohol.
SUBSTANCE: the invention is pertaining to the field of distillery industry, in particular, to the methods of production of a dehydrated ethyl alcohol. The method provides for concentration of the water-alcohol solution purified from impurities by a rectification, its dehydration by adsorption through the molecular sieves and its regeneration by a desorption. Concentration of the water-alcohol solution and its dehydration by adsorption are conducted at the pressure of 105-350 kPa. A part of the formed during the concentration vapors is once more heated up to the temperature of 96-150°C and feed to the stage of desorption, which is realized at the pressure of 5-60 kPa. The rest part of the vapor from the stage of adsorption and a desorption is subjected to condensation and the water-alcohol liquid is fed to the stage of the alcohol concentration with withdrawal of the water from the process. The invention allows to intensify the process of dehydration and to reduce consumption of the heat-power input.
EFFECT: the invention allows to intensify the process of dehydration and to reduce the heat and power inputs.
FIELD: method for production of alcohol-containing solvents based on waste from ethanol production from food-grade raw materials.
SUBSTANCE: claimed method includes reprocessing of etheraldehyde fraction of concentrate containing ethanol main admixtures from starch- and/or sugar-containing raw materials. Process is carried out in rectifier at vapor phase temperature in still of 60-90°C. Nitrosolvent is obtained by mixture sampling at 60-70°C. Degreasing solvent is obtained by mixture sampling at starting temperature in column top of 73°C or more when ethers are detected in distillate. Claimed nitrosolvent (degreasing solvent) contain (mass %): acetate-type ethers 10-30 (0.8-2.9); aliphatic alcohols 51-74 (87-89); acetaldehyde 5-9 (0.2-1.5), and water 8-10 (8-10).
EFFECT: simplified and economy method for reprocessing of waste from ethanol production; enhanced assortment of alcohol-containing solvents.
3 cl, 1 dwg, 3 ex, 3 tbl
FIELD: alcohol production.
SUBSTANCE: method comprises direct distillation of concentrate of top ethyl alcohol impurities or rectification of intermediate ethyl alcohol fraction in presence of an alkali agent selected from sodium and potassium oxide, carbonate, and bicarbonate hydrates, and aqueous ammonia in case of top ethyl alcohol impurities processing and selected from sodium and potassium oxide, carbonate, and bicarbonate hydrates, calcium oxide, and aqueous ammonia in case of intermediate ethyl alcohol fraction rectification at alkali agent concentration 0.01 to 3.0 wt % and vat temperature 80-86°C. Desired processing product is commonly used as a binary mixture component and vat residue obtained in distillation and rectification operation is commonly used as additional component of fuel oil.
EFFECT: achieved wasteless processing of alcohol production wastes and utilization of all processing products.
FIELD: industrial organic synthesis and chemical engineering .
SUBSTANCE: invention relates to a process of producing liquid oxygenates, including methanol, C2-C4-alcohols, formaldehyde, lower organic acids, or mixtures thereof, and to installation for implementation the process. Process comprises successively supplying natural gas from complex gas preparation plant to a series of "gas-gas" heat exchangers and into annular space of at least one tubular reaction zone of reactor, wherein natural gas is heated to temperature of the beginning of reaction, whereupon heated gas is passed to the entry of the tubular reaction zone mixer, into which compressed air or oxygen is also injected to provide gas-phase oxidation in reaction zone of reactor. Resulting reaction mixture is discharged from reactor into a series of "gas-liquid" and "gas-gas" heat exchangers, wherein reaction mixture is cooled to ambient temperature and sent to separator, wherefrom liquid phase is passed through lower carboxylic acid recovery vessel to the system of rectification columns to isolate the rest of mixture components, whereas leaving gas is recycled to complex gas preparation plant. More specifically, oxidation is carried out within temperature range 240 to 450°C and pressure from 2 to 10 MPa at residence time of reaction mixture in reactor 2-6 sec and oxidant concentration 2 to 15 wt %. In reactor having mixers hollow and at least one tubular reaction zones, required temperature is maintained constant throughout all length of tubular reaction zone and at entries for compressed air or oxygen in mixers of each of tubular reaction zones and hollow reaction zone. Liquid oxygenate production plant is composed of aforesaid complex gas preparation plant, a series of "gas-gas" heat exchanger to heat natural gas, reactor, a series of "gas-liquid" and "gas-gas" heat exchangers to cool reaction mixture obtained in reactor, gas-liquid separator, lower carboxylic acid recovery vessel, and system of rectification columns to isolate the rest of products.
EFFECT: enabled implementation of the process directly near gas and gas condensate deposits, increased conversion of methane per one passage through reactor, and increased yield of oxygenates due to improved design of plant.
6 cl, 1 dwg, 1 tbl
SUBSTANCE: invention pertains to the method of oxidation of hydrocarbons using oxygen in trifluoroacetic acid and can be used particularly for oxidation of alkanes, cycloalkanes, alkylaromatic hydrocarbons, alkenes, cycloalkenes. The method involves saturation of trifluoroacetic acid with oxygen, after which, the initial hydrocarbon is added to the obtained reaction medium and is kept until depletion of bound oxygen with obtaining the corresponding oxygen containing compound.
EFFECT: invention allows carrying out a process of selective partial catalytic oxidation of hydrocarbons with obtaining different oxygen containing organic compounds without use of high temperature and traditional catalyst systems based on transition metals.
1 tbl, 5 ex
FIELD: food products; alcoholic beverages.
SUBSTANCE: according to the method, initial flow is supplied to the first distillation steam-stripping column while its distillate is passed to the second distillation rectifying column. Initial flow is refined using first membrane separation method. Obtained concentrate is passed to the first distillation column and derived permeate is supplied to the second distillation column. Distillate from the second distillation column is refined using second membrane separation method.
EFFECT: increasing pureness of obtained ethanol.
16 cl, 2 dwg, 2 tbl