The method of obtaining epoxydecane vegetable oils
(57) Abstract:The invention relates to a method for epoxydecane vegetable oils, which are used as plasticizers stabilizers of polyvinyl chloride, various polymer non-toxic compositions. Describes how to obtain epoxydecane vegetable oils by oxidation, and the oxidation of oils or waste carried out in air with UV light for 6 h with simultaneous cooling to 6 to 10oC. the Technical result in the use of this invention is to simplify the process, the absence of expensive and hazardous reagents, lack of wastewater. table 2. The invention relates to methods for epoxydecane vegetable oils used as plasticizers and stabilizers of polyvinyl chloride, various polymer non-toxic compositions.Known epoxidation of vegetable oils held peracetic or naturalyou acids in two ways. One of these methods at the beginning of the organic acid or its anhydride and 30% hydrogen peroxide are nagkalat, then it is used for epoxidation vegetable oil epoxidised nagkalat at the time of its formation /A. C. Danyushevsky, A. F. Vorob'ev, A. N. Sergeeva research in the field of stabilization of polyvinyl chloride", "Plastic" N 11, S. 20-23, 1960/.The obstacles to achieve the desired technical result is that required large quantities of such chemicals as hydrogen peroxide, formic or acetic acid, and then after the epoxidation reaction, the washing water received product from nagkalat.A method of obtaining epoxydecane esters of fatty acids by epoxidation of esters of unsaturated fatty acids in the environment plasticizers mixture of formic acid and hydrogen peroxide at 70-75oC /A. S. USSR N 794009, MKI 07 D 301/12, From 08 To 5/15, 1981/. The obstacles to achieve the desired technical result is that epoxydecane soybean oil contains dioctylphthalate. Total time epoxidation is very significant - 12 hours, the temperature of the epoxidation is 70 - 75oC. For epoxidation used significant quantities of expensive reagents. 300 kg of soybean oil using 150 g of dioctylphthalate, 380 kg of hydrogen peroxide (30%), 60 kg of formic acid (85%). After carrying out epoxidation produce a assertion re the organic layer is then reloaded in the vacuum evaporation apparatus and distilled impurities and filtered from mechanical impurities. Thus, this method is multistage and costly reagents and, therefore, ethnological.A known method of producing epoxypolyester epoxidation of vegetable oils organic nagkakamali in the moment of their formation of organic acids and hydrogen peroxide in the presence of a catalyst is sulfuric acid in the medium of organic solvent. /A. S. USSR N 1068432, MKI 07 D 301/16, C 07 D 303/16, 1984). The obstacles to achieve the desired technical result is that the multi-stage process: after receiving epoxyether raw, it is washed with water, then carry out the neutralization of the aqueous alkali solution followed by rinsing with water and distilled off the solvent (benzene), water, filtered with the separation of the target product. The distillation of the solvent and water are in the presence of 0.1 to 5.0% (wt.) from the mass of epoxyether raw mixture of soda ash and montmorillonite clay at a ratio of 1:(1-10) and accordingly the temperature of 130-170oC and the pressure 20-760 mm RT.article This process also uses a large number of reagents: 200 g of soybean oil, 200 g of benzene, 35,52 g of acetic acid, 181,9 g hydrogen peroxide (30%) with 1 g of the stabilizer of trinatriyfosfat, 2,55 g Catania epoxidation. The total duration of 15 hours. In addition, the implementation of this method is accompanied by large quantities of wastewater. Thus the disadvantages of this method is the complexity of the process due to its mnogostadiinost and duration.Closest to the claimed is a method for epoxydecane vegetable oils or peracetic naturalyou acids /M. F., Sorokin, H. A. Kochneva, L., soda. "Chemistry and technology of film-forming substances), Chemistry, 1989, S. 415 - 416/. The obstacles to achieve the desired technical result is that this process consists of the following main stages:
1) epoxidation of vegetable oils in the form of a toluene solution;
2) rinse epoxidizing vegetable oil water;
3) drying oils and distillation of toluene.As a result, this method requires high cost of reagents: hydrogen peroxide, formic acid or acetic acid, toluene, and obtained a large amount of wastewater is difficult in hardware design, long time.The task of the invention is to develop effective ecologie forming wastewater.The technical result obtained using the present invention is to simplify technology. The technical result is achieved by the fact that the oxidation of vegetable oils or waste carried out in air with UV light for 6 hours while cooling them to 6-10oC.A thin film of vegetable oil reacts with oxygen of air at the lighting of fluorescent lamp
< / BR>Were used, such oil as well as sunflower and mustard, as well as waste mustard and sunflower oils having the same composition as that according to GOST 8807-74, but with increased acidity, component of 14.0 mg NaOH/g, and edible mustard oil must have an acidity of not more than 3 mg NaOH/gProcessing of vegetable oils or waste carried out in a laboratory setup. The reactor of large diameter was cooled with a mixture of ice with salt and lit from above fluorescent lamp (60, 4000-7000 angstroms). After lighting a thin layer of vegetable oil with UV light in the air are formed in the active particles of oxygen and ozone, which interact with molecules of triglycerides nanalysis or their waste.This double bonds in triglycerides of unsaturated carboxylic acids interact with the active particles of oxygen or ozone to form epoxypropyl, also there is an increase in acid number due to the formation of free carboxylic groups.Due to the absence of any moving parts, dosing devices and mixers this method of obtaining epoxydecane vegetable oils has increased reliability, along with good technological and economic indicators makes it very promising. In addition, the production is waste. The effectiveness of the proposed method stems from the fact that when illuminated with UV light to form the active particles of oxygen and ozone, which together constitute a valid factor in the initiation of radical reactions oxidation of vegetable oils (triglycerides of unsaturated carboxylic acids), resulting in epoxydecane vegetable oils of high purity (containing no moisture or residual solvent).Given the applicant's analysis of the prior art, including the search for patent materials and scientific and technological sources informalities not found similar, characterized by signs, identical to all the essential features of the claimed invention. The definition from the list of identified unique prototype, as the closest solutions to the totality of symptoms, revealed a set of essential towards perceived by the applicant to the technical result of the distinctive features in the claimed object set forth in the claims. Therefore, the claimed invention meets the requirement of "Novelty" by applicable law.To verify compliance of the claimed invention to the requirement of "Inventive step", the applicant conducted an additional search of the known solutions in order to identify characteristics that match the distinctive features of the prototype of the characteristics of the claimed invention, the results of which showed that the claimed invention to a person skilled not obvious from the prior art.Therefore, the claimed invention meets the requirement of "Inventive step".The method of epoxidation of vegetable oils is as follows. In the reactor of large diameter glass is placed a thin layer of vegetable oil over the surface is formed, and the temperature of the vegetable oil in it does not exceed 10oC, depending on the requirements of the experience of changing the thickness of the oil layer and the dwell time of the oil under UV light. And depending on trebovani experience vegetable oil or waste is treated within the required time, that is required to reduce the iodine value, as well as to the required number of epoxy groups.After conducting relevant experiments performed research on the composition epoxydecane vegetable oils or waste. Determined by the standard method GOST 5475-69 iodine number and the number of epoxy groups of THE 6-10-722-86.Here is an example of a specific implementation of the method:
Example 1.As the object use mustard oil, having the following composition according to GOST 8807-74 (wt.% in terms of fatty acids)
Saturated fatty acids 4-7%
Pour into the reactor with a thin film thickness of 0.6 mm mustard oil in a quantity of 50 ml 46,00 g and illuminate the fluorescent lamp (4000-7000 angstroms), while cooling to a 6-10oC. Process air oxidation is performed 6 hours, get 46,98 g epoxidizing oil, which at room the content of epoxy groups of 6.8% and the iodine value, mg J2/1 g was 9.33.Example 2.The experiment is carried out according to the method of example 1 with the difference that the film thickness is 1.2 mm, receive and 47.0 g epoxidizing mustard oil with iodine number, mg J2/1 g of 18.4, content of epoxy groups of 5.83%.Example 3.The experiment is carried out according to the method of example 1 with the difference that the film thickness is 1.8 mm Get to 46.8 g epoxidizing mustard oil with iodine number, mg J2/1 g 25,3. The content of epoxy groups was 4.6%.Example 4.Unlike example 1 as the object of use of the non-conforming waste mustard oil. The qualitative composition of mustard oil and its waste are identical, the difference is that substandard oil has inflated acid number (>2 mg NaOH/g), and this determines its unsuitability for food purposes. Received and 47.0 g epoxidizing mustard oil with iodine number, mg J2/1 g of 8,9, content of epoxy groups of 7.2%.Example 5.The experiment is carried out according to the method of example 4 with the difference that the film thickness is 1.2 mm Obtain 47 g epoxidizing mustard oil with iodine number, mg J2/1 g - 17,6; the content of the epoxy GRI is 1.8 mm Get 48 g epoxidizing mustard oil with iodine number, mg J2/ 1 g 19,8, content of epoxy groups 5,0%.Example 7.Unlike example 1 as the object used sunflower oil having the following composition according to GOST 8807-74.(wt.% in terms of fatty acids)
The process of oxidation by oxygen in the air spend 6 hours when cooled to 6-8oC. Receive and 47.5 g epoxidizing sunflower oil, which at room temperature is a colorless homogeneous liquid which does not change during storage. According to the analysis of the content of epoxy groups is 5.0% and the iodine value of 20.7.Example 8.Unlike example 7, the film thickness of sunflower oil is 1.2 mm. Receive 48,0 g epoxidizing sunflower oil containing epoxy groups 4,33% and the iodine value mg J2/1 g 32,6.Example 9.Unlike example 7, the film thickness of sunflower oil is 1.8 mm Get to 48.5 g epoxidizing sunflower oil containing epoxy groups of 3.6% and the iodine value is, mg J2/1 g 40,5.The best conditions will be the temperature of 6-10oC, time epoxidation 6 hours. In the case of sunflower oil - temperature better support 5-7oC, because the presence of double bonds separated by a simple relationship increases the reactivity of apachegroup and interact oxide with a carboxylic acid.The process proceeded, and the oxidation reaction occurs at the interface, so the thinner the film, the better is the oxidation.Thus, the above data confirm that the implementation of the use of the claimed invention the following cumulative conditions:
1) the method embodying the claimed invention in its implementation is intended for use epoxydecane vegetable oils as a non-toxic plasticizer - stabilizers of different polymer compositions;
2) for the claimed invention in the form as it is described in the independent clause following claims, confirmed the possibility of its implementation using the above described in the application or known before the priority date methods and techniques;
3) the method embodying the claimed invention in its implementation, retina meets the requirements of "Industrial applicability" under the current law. The method of obtaining epoxydecane vegetable oils by oxidation, characterized in that the oxidation of oils or waste carried out in air with UV light for 6 h while cooling to 6 to 10oC.
FIELD: process engineering.
SUBSTANCE: invention relates to activation at epoxidation plants. Proposed method comprises: driving the reactor including high-selectivity silver-based catalyst to first temperature with the help of external thermal source despite the reactor design constraints and maintenance of gas flow to reactor in the range of 25-100% of designed flow rates, and introducing, at least, olefin and, then, oxygen to fed gas to cause reaction heat in said reactor for increasing first temperature to second temperature, and adjusting oxygen concentration at reactor outlet exceeding about 0.5%.
EFFECT: activation ensures reaching required reaction heat.
SUBSTANCE: invention relates to a method of producing epichlorohydrin which is used as a solvent for cellulose, resins and dyes, as fumigant and as a structural unit when producing plastic, epoxy resins and phenol resins. The method involves reaction of allyl chloride with an oxidant in the presence of a catalyst which contains a water-soluble manganese complex in an aqueous reaction medium with molar ratio of allyl chloride to the oxidant ranging from 1:0.1 to 1:1.2, followed by removal of the epichlorohydrin product. Normally the catalyst contains a mononuclear manganese complex of general formula (I): [LMnX3]Y (1) or a binuclear manganese complex of general formula (II): [LMn(|µ-X)3MnL]Y2 (II), where Mn is manganese; L or each L independently denotes a polydentate ligand; each X independently denotes coordination compounds and each µ-X independently denotes bridge coordination compounds selected from a group consisting of: RO-, Cl-, Br-, I-, F-, NCS-, N3 -, I3 -, NH3, NR3, RCOO-, RSO3 -, RSO4 -, OH-, O2-, O2 2-, HOO-, H2O, SH-, CN-, OCN-, and S4 2- combinations thereof, where R is a C1-C20 radical selected from a group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y denotes an oxidation-stable counter-ion.
EFFECT: method enables to carry out the process with high selectivity and number of rotations.
15 cl, 4 ex, 3 tbl
SUBSTANCE: present invention relates to a method of producing propylene oxide. Described is a method of producing propylene oxide, which includes reacting propylene with hydrogen peroxide in the presence of a catalyst in an aqueous reaction medium which contains water with less than 10 vol% cosolvents, wherein the catalyst contains a water-soluble manganese complex which is a mononuclear complex of formula (I): [LMnX3]Y (I) or a binuclear complex of formula (II): [LMn(µ-X)3MnL]Y2 (II), where Mn denotes manganese; L or each of L independently denotes a polydentate ligand, each of X independently denotes a coordination fragment and each of µ-X independently denotes a bridge coordination fragment, and Y denotes a non-coordination counterion, wherein oxidation is carried out at pH in the range of 1.5 to 6.0 and molar ratio of propylene to hydrogen peroxide ranges from 1:1 to 10:1, where in the water-soluble manganese complex, each of X is independently selected from a group consisting of: RO-, Cl-, Br-, I-, F-, NCS-,
EFFECT: high efficiency and high selectivity of the method of producing propylene oxide.
20 cl, 4 ex
FIELD: updated methods of recuperation of heat in CO2 discharge systems in production of ethylene oxide.
SUBSTANCE: proposed method includes absorption of ethylene oxide from circulating gas flow by washing the gas in scrubber. Washed flow of circulating gas is brought in contact with hot absorbing carbonate solution for absorption of CO2 and flow of circulating gas after absorption of CO2 returning it to ethylene oxide production cycle; proposed method includes also bringing the said washed circulating gas flow in contact with heated liquid after removal of ethylene oxide at first contact stage, transferring the preheated circulating gas to stage of absorption by hot carbonate for removal of CO2, cooling the said circulating gas from stage of absorption by carbonate and removal of carbonate from it by bringing it in contact with said liquid from first contact stage at second contact stage after cooling this liquid, transferring the liquid from second contact stage to first contact stage and transferring the cooled circulating gas from second contact stage to reaction system for obtaining the ethylene oxide.
EFFECT: enhanced operational and economical efficiency of heat recuperation.
1 dwg, 1 ex
SUBSTANCE: invention relates to catalyst supports used for epoxidation. Described is an olefin epoxidation catalyst support, wherein said support has pore volume from pores with diameter smaller than 1 mcm of less than 0.20 ml/g and pore volume from pores with diameter greater than 5 mcm of less than 0.2 ml/l, wherein at least 40% of the pore volume consists of pores having diameter from 1 mcm to 5 mcm. Described is an olefin epoxidation catalyst support, having a support and a catalytically effective amount of silver on it, wherein said support has pore volume from pores with diameter smaller than 1 mcm of less than 0.20 ml/g and pore volume from pores with diameter greater than 5 mcm of less than 0.2 ml/l, wherein at least 40% of the pore volume consists of pores having diameter from 1 mcm to 5 mcm. Described is an olefin epoxidation catalyst which has a support and a catalytically effective amount of silver on it, wherein said support has total pore volume of 0.2-0.6 ml/g, surface area from about 0.3 m2/g to about 3 m2/g, at least 40% of the pore volume from pores with diameter ranging from 1 mcm to 5 mcm and average pore diameter from 1 mcm to 5 mcm, an in which pore volume from pores with diameter greater than 5 mcm is less than 0.20 ml/g, and pore volume from pores with diameter smaller than 1 mcm is less than 0.20 ml/g. Described is a method of oxidising ethylene to ethylene oxide, which involves vapour-phase oxidation of ethylene with molecular oxygen in a fixed bet, in a tubular reactor in the presence of the catalyst described above.
EFFECT: high activity, selectivity and stability of the epoxidation catalyst.
19 cl, 4 tbl, 3 ex
SUBSTANCE: present invention relates to a method of producing alkylene glycol, which can be used as a raw material in production of polyester fibres, polyethylene terephthalate plastic and resins, as well as in antifreeze liquids. The method involves the following steps: (a) reaction of alkene with oxygen in the presence of a catalyst in a reactor to obtain a gaseous composition which contains alkylene oxide, alkene, oxygen, carbon dioxide and water vapour, and removing contaminants from the gaseous composition; (b) feeding the gaseous composition from step (a) into an alkylene oxide absorber, having a column of vertically stacked plates or having a packed column, feeding the impoverished absorbent into the alkylene oxide absorber, bringing the gaseous composition into contact with the impoverished absorbent in the alkylene oxide absorber in the presence of one or more catalysts which facilitate carboxylation and hydrolysis, and removing the saturated absorbent from the alkylene oxide absorber, where the impoverished absorbent contains at least 20 wt % and less than 80 wt % water, wherein at least 50 wt % alkylene oxide coming into the alkylene oxide absorber is converted in the alkylene oxide absorber and where temperature in the alkylene oxide absorber ranges from 50 to 160°C; (c) optionally feeding a portion or all of the saturated absorbent from step (b) into one or more final treatment reactors and removing the product stream from the one or more final treatment reactors, where at least 90% of alkylene oxide and alkylene carbonate coming into one or more final treatment reactors are converted to alkylene glycol in one or more final treatment reactors; (d) optionally feeding the saturated absorbent from step (b) or the product stream from at least one or more final treatment reactors at step (c) into a flash vessel or into an apparatus for evaporating light fractions, and removing the light fractions; (e) feeding the saturated absorbent from step (b) or (d) or the product stream from step (c) or (d) into a dehydrator, removing water and obtaining a stream of dehydrated product; and (f) purifying the stream of dehydrated product from step (e) and obtaining a product stream of purified alkylene glycol.
EFFECT: method enables to reduce the cost and complexity of the apparatus while ensuring high selectivity.
12 cl, 1 ex, 6 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to olefin epoxidation. method of epoxidising of olefin to olefin oxide comprises the following operations: bringing the load including, at least, oxygen and olefin, in reactor with catalyst including carrier with bimodal pore distribution in sizes, first types of pores with mean diameter of 0.01-5 mcm and second type of pores with mean diameter of pores of 5-50 mcm, catalytically active amount of silver or silver-bearing compound, promoting amount of rhenium or rhenium-bearing compound, and promoting amount of one or more alkaline metals or alkaline metal-bearing compound. Note here that said reactor has, at least, its outlet, while said olefin oxide resulted from aforesaid contact features concentration at reactor outlet of 2.2 vol. % of cesium, lithium and tungsten. It may comprise bringing the load including, at least, oxygen and olefin, in reactor with catalyst including carrier with total volume of pores of 0.41 cm3/g and bimodal pore distribution in sizes, first types of pores making 25% of total volume of pores with mean diameter of 0.7 mcm and second type of pores making 75% of total amount of pores with mean diameter of pores of 15.8 mcm, catalytically active amount of silver or silver-bearing compound, promoting amount of rhenium or rhenium-bearing compound, and promoting amount of one or more alkaline metals or alkaline metal-bearing compound. Note here that said reactor has, at least, its outlet, while said olefin oxide resulted from aforesaid contact features concentration at reactor outlet over about of 2.2 vol. % at 236°C.
EFFECT: higher selectivity and efficiency.
34 cl, 2 tbl, 1 dwg, 2 ex
SUBSTANCE: invention relates to a method of producing plasticiser for polymer materials from renewable material, such as esters of fatty acids. In accordance with invention, plasticiser is obtained by oxidation of alkyl esters of fatty acids of vegetable origin with oxygen-containing gas in presence of homogeneous catalysts - molybdic acid esters, and aliphatic dihydric alcohols. Process of oxidising is preferably carried out at 100-120 °C and atmospheric pressure.
EFFECT: simplified process.
2 cl, 2 tbl, 12 ex
FIELD: technological processes.
SUBSTANCE: present invention relates to a method of producing ethylene glycol, involving following steps: (i) supplying ethylene and oxygen and an organic chloride moderator to an ethylene oxide reactor wherein ethylene and oxygen react in presence of a catalyst to produce ethylene oxide, thereby producing a reactor product stream; (ii) supplying reactor product stream to an ethylene oxide absorber wherein ethylene oxide is recovered from reactor product stream by absorption in water in absorber section, thereby producing a rich absorbent stream; (iii) supplying rich absorbent stream to an ethylene oxide stripper wherein rich absorbent stream is steam stripped, thereby producing a concentrated ethylene oxide stream and a lean absorbent stream; (iv) recirculating lean absorbent stream through ethylene oxide absorber; (v) optionally supplying concentrated ethylene oxide stream to one or more carboxylation reactors wherein ethylene oxide reacts with carbon dioxide to form an ethylene carbonate stream; and (vi) supplying concentrated ethylene oxide stream and/or ethylene carbonate stream to one or more hydrolysis reactors wherein ethylene oxide and/or ethylene carbonate reacts with water in presence of a hydrolysis catalyst selected from one or more basic alkali metal salts to form an ethylene glycol stream. Method includes additional steps: (vii) removing a glycol bleed stream from ethylene oxide stripper and (viii) adding a base to ethylene oxide stripper such that pH in bottom section of stripper is maintained in range of from at least 9.5 to at most 12.0.
EFFECT: proposed method reduces amount of chloroethanol present in reaction, and reduces or completely prevents decomposition of hydrolysis catalyst.
10 cl, 2 dwg