CN1281569C - Preparation of azelaic acid by catalytic oxidizing system - Google Patents
Preparation of azelaic acid by catalytic oxidizing system Download PDFInfo
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- CN1281569C CN1281569C CN 200510052293 CN200510052293A CN1281569C CN 1281569 C CN1281569 C CN 1281569C CN 200510052293 CN200510052293 CN 200510052293 CN 200510052293 A CN200510052293 A CN 200510052293A CN 1281569 C CN1281569 C CN 1281569C
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Abstract
The present invention relates to a preparation method of azelaic acid by a catalytic oxidation system. Oleic acid, tungstic acid and solvent are uniformly stirred and mixed, the temperature of the mixture rises, a hydrogen peroxide solution is dripped in the mixture, and the temperature rises, the solvent is recovered in a rotary evaporation mode, 9, 10-dioxystearic acid can be obtained through recrystallization by ethyl acetate, a catalytic oxidation system solution is added in an oil phase of the 9, 10-dioxystearic acid, and the product of azelaic acid can be extracted in reaction liquid through extracting, filtering and baking. The highest yield of the product of the azelaic acid can reach 75% when calculated by the oleic acid, and can reach 95% when calculated by the 9, 10-dioxystearic acid. The present invention has the advantages of clean process, environment protection, no environment pollution, no need of noble metal catalyst, no need of long time oxygen supply and ozone supply, no need of high pressure in reaction, simple implementation condition and convenient scaled production.
Description
Technical field
The present invention relates to the method that a kind of catalytic oxidation system prepares nonane diacid
Background technology
Nonane diacid (Azelaic acid) be lepargylic acid again, is that a kind of white is to little yellow monoclinic prisms, needle-like crystal or powder.Molecular formula C
9H
16O
4, molecular weight 188.22, proportion 1.0291 (4 ℃), 1.225 (25 ℃), 106.5 ℃ of fusing points, 286.5 ℃ of boiling points (13.33kPa), specific refractory power 1.4303 (111 ℃), the carbochain of moderate-length is added two carboxyls, gives nonane diacid wide purposes, is important organic synthesis intermediate.
Nonane diacid can be used to products such as synthetic dioctyl azelate (DOZ) softening agent, synthetic perfume, lubricating oil and polymeric amide.Dioctyl azelate, nonane diacid didecyl ester, the two tridecane esters of nonane diacid all are good lubricants.Nonane diacid also is used for the production of nylon 69 and nylon 9.Nonane diacid makes amino-nonanoic acid through amination, hydrogenation, and the amino-nonanoic acid direct condensation can be produced nylon 9.Nonane diacid can improve the snappiness of unsaturated polyester, can be used as the properties-correcting agent of terephthalic acid-polyglycol ester.In addition, other of nonane diacid used and also comprised dielectric liquid, emulsion splitter, mothproofing agent, urethane methyl ester foam, hydraulic efficiency oil, high molten coating, tackiness agent and water soluble resin etc.
The discovered in recent years nonane diacid has superior electrical property, is used for manufacturing (fine chemistry industry, 1994,11 (1): 56-58) of electrical condenser.Nonane diacid also is used to dermopathic control.The too much disease of acne, rosacea, chloasma and cutaneous pigmentation (Chinese Hospitals pharmaceutical journal, 2002,22 (4): 242-243) have been used for the treatment of clinically
At present, the production method of nonane diacid mainly is the oxidation style of unsaturated fatty acidss such as oleic acid, and used oxygenant has potassium permanganate, nitric acid, chromic acid, hydrogen peroxide, hypochlorite, ozone etc.
Liang Fangzhen uses phase-transfer catalyst (TBAB), and potassium permanganate is oxygenant, prepares nonane diacid from the Fructus Zanthoxyli oil soap stock.Yang Yang etc. compare and discuss (Jiangsu Petrochemical Engineering College journal, 2001,13 (1): 5-7) to the effect of several ammonium class phase-transfer catalysts.High farm member has inquired into reaction conditions (Hunan chemical industry, 2000,30 (3): 36-37) that utilize potassium permanganate to prepare nonane diacid.Sabarino Giampiero is with HWO
4Be catalyzer, with H
2O
2The oleic acid of oxidation purity 80%, the reaction intermediate blend is forced into about 70 normal atmosphere in the presence of cobaltous acetate, and reaction 4.5h obtains people such as nonane diacid and n-nonanoic acid .Pultinas EdmundP and utilizes 70% H under 66 ℃
2O
2Make acetate be converted into Peracetic Acid, again with CH
3COON (CH
3)
2Be solvent, at (CH
3COO)
2Co exists down, oxidation 9, and the 10-dihydroxystearic acid obtains reaction mixture, obtains nonane diacid and n-nonanoic acid through dioxygen oxidation again.It is the nitric acid oxidation process of raw material that National Oil Products Co. has developed with the Witconol 2301.Human oxyethyl group lauryl alcohols such as Zaidman B are mixed with the O/W emulsion to oleic acid, with RuCl
3Be catalyzer, use chlorine bleach liquor's oxidation, obtain nonane diacid and n-nonanoic acid (Speciality Petrochemicals, 1998, (6): 40-43) through separation.
Employing ozone oxidation legal systems such as Qian Weiqun are equipped with nonane diacid, and productive rate is about 45% (fine chemistry industry, 1994,11 (1): 56-58) under laboratory scale.
The king is big, and strange the grade with Oleum Gossypii semen soap stock lipid acid is raw material, adopts the ozone oxidation method to make nonane diacid (research and development of natural products, 1997,9 (2): 39-42).
English Patent GB 813,842 adopts the method for nitric acid oxidation to prepare nonane diacid.
The Emery Industries Inc (U.S. Pat 2,813,113) of the U.S. at first produces n-nonanoic acid and nonane diacid as oxygenant from oleic acid with ozone on industrial production.Their production method is roughly as follows: the mixture that at first makes oleic acid and n-nonanoic acid is by ozonizer, and adverse current contacts with oxygen (containing 2% ozone), generates oleic ozonide; In the presence of manganese salt, utilize oxygen to make bond rupture again, produce the mixture of azelaic semialdehyde and aldehyde C-9, and be oxidized to nonane diacid and n-nonanoic acid.Distill above oxidation mixture and obtain n-nonanoic acid, remaining resistates is used the water hot extraction, obtains product of nonane diacid with evaporation or crystalline method again.
(Catalysis Today. 79-80 (2003): 59-65) method of Cai Yonging is wolframic acid to be made the product that the catalyzer hydrogen peroxide oxidation produced pour autoclave into to people such as E.Santacesaria, and adding is dissolved with 300 ml distilled waters of 1.2 grams, four water cobaltous acetates, and be heated to 70 the degree, feed 15 atmospheric oxygen and 30 atmospheric nitrogen and impel 9, the oxicracking of 10-dihydroxystearic acid.
The method that people (Journal of molecular catalysis:chemical150 (1999) 105-111) such as M.chael A adopt: in 25 milliliters of there-necked flasks,, add oleic acid 2.0 mmoles at the bottom aerating oxygen.0.03 the mmole wolframic acid, 5 milliliters of trimethyl carbinols, 11 moles of hydrogen peroxide drip, and are heated to reflux 2 hours, and temperature is transferred to 75 degree again, add 8 milligrams of NHPI, 8 milligrams of acetylacetone cobalts, aerating oxygen (0.5 milliliter of per minute), stir separated in 3-5 hour product.
A kind of method that the patent WO of World Intellectual Property Organization 9410122 adopts is: with wolframic acid, molybdic acid or its basic metal or alkaline earth salt as catalyzer, the 50-70% hydrogen peroxide oxidation obtain 9,10-dihydroxyl intermediate product adds autoclave, the aqueous solution that adds cobaltous acetate, be pressurized to 70 normal atmosphere, reaction is 4.5 hours under the temperature of 66 degree, and the refrigerated separation purifying gets nonane diacid and n-nonanoic acid.
Danish Patent DE 2035558 is with 9, the 10-dihydroxystearic acid is a raw material, and vinylbenzene is solvent, cobaltous acetate (or manganous acetate, iron, lead, nickel) be catalyzer, with Peracetic Acid oxicracking 9, the 10-dihydroxystearic acid, product is handled with benzene, obtains nonane diacid with water crystallization, and the benzole soln underpressure distillation obtains n-nonanoic acid.
Danish Patent DE 2144015 is with 9, and the 10-dihydroxystearic acid is a raw material, and Glacial acetic acid is a solvent, cobaltous acetate is catalyzer and adds a certain amount of Peracetic Acid, is heated to 100 degree, first blowing air 3 hours, add Peracetic Acid again, and aerating oxygen 1 hour, obtain nonane diacid and n-nonanoic acid.
The WO of World Intellectual Property Organization 9312064 adopts 35% hydrogen peroxide oxidation, and wolframic acid is made catalyzer and added phase-transfer catalyst Arqual 2HT (or tricaprylmethylammonium),, 100-104 degree reaction 6 hours, reaction was finished, and separation and purification gets nonane diacid and n-nonanoic acid.
It is catalyzer that U.S. Pat 809451 adopts cobalt naphthenate, and oxidation oleic acid prepares nonane diacid.
The method that people such as S.E.Turnwald (Journal of materials science letters17 (1998) 1305-1307) adopt is under a kind of new catalyst P CWP effect, prepares nonane diacid with hydrogen peroxide oxidation oleic acid.
It is oxygenant that European patent EP 122804 adopts 40% hydrogen peroxide, at [(C
8H
17)
3NCH
3]
3PW
4O
22Under the catalysis, and add 1, the 2-ethylene dichloride 80 degrees centigrade of reactions 5 hours, gets the nonane diacid of productive rate 83% and 66% n-nonanoic acid as solvent.
Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences's (Chinese patent, application number: 02150179.3 publication number: CN 1415593A) adopt the mesopore molecular sieve W-MCM-41 that supports tungsten to make the Preparation of Catalyst nonane diacid, with oleic acid, mesopore molecular sieve W-MCM-41, the superoxol and the trimethyl carbinol mix, under the stirring and refluxing state logical oxygen reaction 1-3 days, from reaction solution, extract the product nonane diacid.
The selectivity of nitric acid oxidation method reaction is not high, and serious to equipment corrosion.With potassium permanganate is the thickened oil acid system of oxygenant, and yield is low, consumes a large amount of sulfuric acid and potassium permanganate again, cost height not only, and also seriously polluted.Although can improve the technology of potassium permanganate process with emulsion process, the consumption of potassium permanganate is still very big, and aftertreatment is very numerous and diverse, and is inadvisable economically., cost an arm and a leg as oxygenant with chromic acid, and make the oxidation products degradation easily, produce the low carbon chain diprotic acid, resulting product purity is not high.This shows in many prior arts, some method contaminate environment, the method steps that has is more numerous and diverse, and the method that has need support noble metal catalyst, and needs long-time logical oxygen, length consuming time, cost height.Some method needs high pressure, the implementation condition harshness, and the cost costliness is difficult to carry out large-scale production.
The present invention is providing a kind of catalytic oxidation system to prepare the method for nonane diacid according to problems of the prior art through after a large amount of tests.Compared with the prior art this method has tangible technical progress with different.
Summary of the invention
The present invention seeks to overcome the deficiencies in the prior art and provide a kind of catalytic oxidation system to prepare the method for nonane diacid.This method is oleic acid, wolframic acid, and solvent mixes, and heats up, and drips superoxol, heats up, and rotary evaporation reclaims solvent, adopts re-crystallizing in ethyl acetate can obtain 9, the 10-dihydroxystearic acid; With 9, add catalytic oxidation system solution in the oil phase of 10-dihydroxystearic acid, extract from reaction solution through extraction, filtration, oven dry and obtain the product nonane diacid.This method is compared with many prior arts, technology cleaning of the present invention, and environmental friendliness, free from environmental pollution, need not noble metal catalyst, do not need logical for a long time oxygen, ozone does not need high pressure in the reaction, and implementation condition is simple, is convenient to carry out large-scale production.
A kind of catalytic oxidation system of the present invention prepares the method for nonane diacid, follows these steps to carry out:
A, at first prepare 9, the 10-dihydroxystearic acid: with oleic acid, wolframic acid, the Virahol mass ratio mixed according to 1: 0.0075: 2, when being warmed up to 55-65 ℃, drip 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 60-70 ℃, react after 30-60 minute, rotary evaporation reclaims Virahol, adopts re-crystallizing in ethyl acetate to obtain 9,10---dihydroxystearic acid;
Synthesizing of b, nonane diacid: be equipped with 9, add catalytic oxidation system solution in the container of 10-dihydroxystearic acid, wherein contain Peracetic Acid, hydrogen peroxide, acetate, water and sulfuric acid in this solution, 100 ℃ of reactions of temperature 1-4 hour, reaction end back rotary evaporation removes and desolvates, and obtains product nonane diacid and by product n-nonanoic acid through extracting, filter, dry to extract from reaction solution.
Oleic acid, Peracetic Acid, hydrogen peroxide, acetate, water and vitriolic mass ratio are 1 in the catalytic oxidation system solution: 0.5-3: 0.5-3: 2-5: 2-5.5: 0.1-1.
The catalyzer that is adopted is the vitriol oil.
Characteristics of the present invention are to have adopted a kind of new catalytic oxidation system, and promptly Peracetic Acid+hydrogen peroxide+acetate+water+sulfuric acid system prepares nonane diacid.Oxygenant is hydrogen peroxide and Peracetic Acid in this system; Solvent acetic acid can recycle and reuse; The present invention compared with the prior art,
Have following characteristics:
(1), the productive rate of product of nonane diacid is higher, reaches as high as 75% (in oleic acid) by 9,10-dihydroxystearic acid meter can reach 95%;
(2), that the intermediate product after adopt purifying can obtain purity as reactant is very high, the good nonane diacid product of crystal formation;
(3), reaction process is simple, do not need high pressure in the reaction;
(4), solvent acetic acid can recycle and reuse;
(5) need not noble metal catalyst;
(6) do not need logical for a long time oxygen;
(7) be converted into water behind the hydroperoxidation, Peracetic Acid is converted into acetate.Therefore being that the method for oxygenant is compared with potassium permanganate, nitric acid, hypochlorite, is a kind of free from environmental pollution, the technology cleaning, and environmental friendliness is convenient to the method for large-scale production.
Embodiment
The present invention will be further described below by embodiment.
Embodiment 1
9, the preparation of 10-dihydroxystearic acid
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 55 ℃, drip 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 60 ℃, react after 30 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate, can obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid, Peracetic Acid, hydrogen peroxide, acetate, water and the vitriol oil in the 10-dihydroxystearic acid oil phase, its mass ratio is 1: 0.5: 0.5: 2: 2: 0.1,100 ℃ of reactions of temperature 1 hour, reaction finishes the back rotary evaporation except that desolvating, and adopts the water hot extraction 6 times, puts into the refrigerator cool overnight, produce crystallisate and filter the back, obtain nonane diacid 60 ℃ of oven dry; Put into the refrigerator after-filtration after the filtrate rotary evaporation concentrated, and with cold water washing 3 times, the nonane diacid of getting back after the oven dry, total recovery 50% (by oleic acid).
Embodiment 2
9, the preparation of 10-dihydroxystearic acid
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 65 ℃, drip 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 70 ℃, react after 60 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate, can obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid, Peracetic Acid, hydrogen peroxide, acetate, water and the vitriol oil in the 10-dihydroxystearic acid oil phase, its mass ratio is 1: 3: 3: 5: 5.5: 1 100 ℃ of reactions of temperature 4 hours, reaction finishes the back rotary evaporation except that desolvating, adopt the water hot extraction 6 times, put into the refrigerator cool overnight, produce crystallisate and filter the back, obtain nonane diacid 60 ℃ of oven dry; Put into the refrigerator after-filtration after the filtrate rotary evaporation concentrated, and with cold water washing 3 times, the nonane diacid of getting back after the oven dry, total recovery 76% (by oleic acid).
Embodiment 3
9, the preparation of 10-dihydroxystearic acid
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 60 ℃, drip 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 65 ℃, react after 45 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate, can obtain 9, the 10-dihydroxystearic acid;
(2) nonane diacid is synthetic
With 9 of preparation, add catalytic oxidation system solution oleic acid, Peracetic Acid, hydrogen peroxide, acetate, water and the vitriol oil in the 10-dihydroxystearic acid oil phase, its mass ratio is 1: 2.5: 0.5: 4: 2.8: 0.2,100 ℃ of reactions of temperature 3 hours, reaction finishes the back rotary evaporation except that desolvating, and adopts the water hot extraction 6 times, puts into the refrigerator cool overnight, produce crystallisate and filter the back, obtain nonane diacid 60 ℃ of oven dry; Put into the refrigerator after-filtration after the filtrate rotary evaporation concentrated, and with cold water washing 3 times,, the nonane diacid of getting back after the oven dry, total recovery 70% (by oleic acid).
Embodiment 4
9, the preparation of 10-dihydroxystearic acid
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 62 ℃, drip 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 68 ℃, react after 50 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate, can obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid in the 10-dihydroxystearic acid oil phase, Peracetic Acid, hydrogen peroxide, acetate, the water and the vitriol oil, its mass ratio is 1: 3: 0.8: 4.5: 1.3: 0.5,100 ℃ of reactions of temperature 2 hours, reaction finishes the back rotary evaporation except that desolvating, adopt the water hot extraction 6 times, put into the refrigerator cool overnight, produce crystallisate and filter the back 60 ℃ of oven dry, obtain nonane diacid, put into the refrigerator after-filtration after the filtrate rotary evaporation is concentrated, and wash 3 times with cold water, can obtain nonane diacid again after the oven dry, total recovery 75% (by oleic acid).
Embodiment 5
9, the preparation of 10-dihydroxystearic acid
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 62 ℃, drip 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 62 ℃, react after 40 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate, can obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid, Peracetic Acid, hydrogen peroxide, acetate, water and the vitriol oil in the 10-dihydroxystearic acid oil phase, its mass ratio is 1: 1.5: 2: 3: 3.4: 0.1,100 ℃ of reactions of temperature 3 hours, reaction finishes the back rotary evaporation except that desolvating, adopt the water hot extraction 6 times, put into the refrigerator cool overnight, produce crystallisate and filter the back 60 ℃ of oven dry, obtain nonane diacid, the filtrate rotary evaporation is concentrated, put into the refrigerator after-filtration, and with cold water washing 3 times, the nonane diacid total recovery 50% of getting back after the oven dry (by oleic acid).
Embodiment 6
9, the preparation of 10-dihydroxystearic acid and purification
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 55 ℃, drips 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 60 ℃, and reacting after 30 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate to obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid, Peracetic Acid, hydrogen peroxide, acetate, water and the vitriol oil in the 10-dihydroxystearic acid oil phase, its mass ratio is 1: 2.42: 0.55: 3.93: 2.6: 0.5,100 ℃ of reactions of temperature 1 hour, reaction finished the back rotary evaporation except that desolvating, and adopts the water hot extraction 6 times, put into the refrigerator cool overnight, and carry out a recrystallization and handle, produce crystallisate and filter the back 60 ℃ of oven dry, get nonane diacid; The filtrate rotary evaporation is concentrated to, puts into the refrigerator after-filtration, and wash 3 times with cold water, the nonane diacid of getting back after the oven dry, total recovery 90% (by 9,10-dihydroxystearic acid meter) is by oleic acid 72%.
Embodiment 7
9, the preparation of 10-dihydroxystearic acid and purification
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 65 ℃, drips 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 70 ℃, and reacting after 60 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate to obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid in the 10-dihydroxystearic acid oil phase, Peracetic Acid, hydrogen peroxide, acetate, the water and the vitriol oil, its mass ratio is 1: 2: 1: 3.5: 3: 0.5,100 ℃ of reactions of temperature 4 hours, reaction finished the back rotary evaporation except that desolvating, and adopts the water hot extraction 6 times, put into the refrigerator cool overnight, and carry out a recrystallization and handle, produce crystallisate and filter the back 60 ℃ of oven dry, get nonane diacid, the filtrate rotary evaporation is concentrated to, put into the refrigerator after-filtration, and wash 3 times with cold water, can obtain nonane diacid again after the oven dry, total recovery 80% (by 9,10-dihydroxystearic acid meter) is 64% by the oleic acid rate of collecting.
Embodiment 8
9, the preparation of 10-dihydroxystearic acid and purification
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 60 ℃, drips 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 65 ℃, and reacting after 45 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate to obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid in the 10-dihydroxystearic acid oil phase, Peracetic Acid, hydrogen peroxide, acetate, the water and the vitriol oil, its mass ratio is 1: 3: 0.5: 3.5: 2: 1,100 ℃ of reactions of temperature 3 hours, reaction finishes the back rotary evaporation except that desolvating, and adopts the water hot extraction 6 times, puts into the refrigerator cool overnight, and carry out a recrystallization and handle, produce crystallisate and filter the back, get nonane diacid, the filtrate rotary evaporation is concentrated 60 ℃ of oven dry, put into the refrigerator after-filtration, and, can obtain nonane diacid again after the oven dry with cold water washing 3 times, total recovery 93% is (by 9,10-dihydroxystearic acid meter), be 74.4% by the oleic acid rate of collecting.
Embodiment 9
9, the preparation of 10-dihydroxystearic acid and purification
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 55 ℃, drips 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 60 ℃, and reacting after 30 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate to obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid in the 10-dihydroxystearic acid oil phase, Peracetic Acid, hydrogen peroxide, acetate, the water and the vitriol oil, its mass ratio is 1: 1.5: 1: 3: 4: 0.5,100 ℃ of reactions of temperature 2 hours, reaction finishes the back rotary evaporation except that desolvating, and adopts the water hot extraction 6 times, puts into the refrigerator cool overnight, and carry out a recrystallization and handle, produce crystallisate and filter the back, get nonane diacid, the filtrate rotary evaporation is concentrated 60 ℃ of oven dry, put into the refrigerator after-filtration, and, can obtain nonane diacid again after the oven dry with cold water washing 3 times, total recovery 70% is (by 9,10-dihydroxystearic acid meter), be 56% by the oleic acid rate of collecting.
Embodiment 10
9, the preparation of 10-dihydroxystearic acid and purification
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 65 ℃, drips 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 70 ℃, and reacting after 60 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate to obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, add catalytic oxidation system solution oleic acid, Peracetic Acid, hydrogen peroxide, acetate, water and the vitriol oil in the 10-dihydroxystearic acid oil phase, its mass ratio is 1: 0.5: 2: 2: 5.5: 0.5,100 ℃ of reactions of temperature 3 hours, reaction finished the back rotary evaporation except that desolvating, and adopts the water hot extraction 6 times, put into the refrigerator cool overnight, and carry out a recrystallization and handle, produce crystallisate and filter the back 60 ℃ of oven dry, get nonane diacid; The filtrate rotary evaporation is concentrated to 100ml, puts into the refrigerator after-filtration, and with cold water washing 3 times, can obtain nonane diacid again after the oven dry, total recovery 40% (by 9,10-dihydroxystearic acid meter) is 32% by the oleic acid rate of collecting.
Embodiment 11
9, the preparation of 10-dihydroxystearic acid and purification
With oleic acid (percentage composition 73%), wolframic acid, Virahol mixes by mass ratio at 1: 0.0075: 2, when being warmed up to 60 ℃, drips 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 65 ℃, and reacting after 45 minutes, rotary evaporation reclaims Virahol, adopt re-crystallizing in ethyl acetate to obtain 9, the 10-dihydroxystearic acid;
Synthesizing of nonane diacid
With 9 of preparation, the mass ratio that adds catalytic oxidation system solution oleic acid, Peracetic Acid, hydrogen peroxide, acetate, water and the vitriol oil in the 10-dihydroxystearic acid oil phase is 1: 2.5: 0.5: 5: 1.5: 0.5,100 ℃ of reactions of temperature 2 hours, reaction finishes the back rotary evaporation except that desolvating, adopt the water hot extraction 6 times, put into the refrigerator cool overnight, and carry out a recrystallization and handle, produce crystallisate and filter the back, obtain nonane diacid 60 ℃ of oven dry; With the concentrated refrigerator after-filtration of putting into of filtrate rotary evaporation, and with cold water washing 3 times, can obtain nonane diacid again after the oven dry, total recovery 85% (by 9,10-dihydroxystearic acid meter) is 68% by the oleic acid rate of collecting.
Claims (3)
1, a kind of catalytic oxidation system prepares the method for nonane diacid, it is characterized in that following these steps to carrying out:
A, at first prepare 9, the 10-dihydroxystearic acid: with oleic acid, wolframic acid, the Virahol mass ratio mixed according to 1: 0.0075: 2, when being warmed up to 55-65 ℃, drip 50% superoxol of 0.3 times of oleic acid amount, in 20 minutes, be added dropwise to complete, and be warmed up to 60-70 ℃, react after 30-60 minute, rotary evaporation reclaims Virahol, adopts re-crystallizing in ethyl acetate to obtain 9,10---dihydroxystearic acid;
Synthesizing of b, nonane diacid: be equipped with 9, add catalytic oxidation system solution in the container of 10-dihydroxystearic acid, wherein contain Peracetic Acid, hydrogen peroxide, acetate, water and sulfuric acid in this solution, 100 ℃ of reactions of temperature 1-4 hour, reaction end back rotary evaporation removes and desolvates, and obtains product nonane diacid and by product n-nonanoic acid through extracting, filter, dry to extract from reaction solution.
2, a kind of catalytic oxidation system according to claim 1 prepares the method for nonane diacid, it is characterized in that oleic acid in the catalytic oxidation system solution, Peracetic Acid, hydrogen peroxide, acetate, water and vitriolic mass ratio are 1: 0.5-3: 0.5-3: 2-5: 2-5.5: 0.1-1.
3, a kind of catalytic oxidation system according to claim 1 prepares the method for nonane diacid, it is characterized in that the catalyzer that is adopted is the vitriol oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN101200735B (en) * | 2007-12-05 | 2011-04-13 | 中国科学院新疆理化技术研究所 | Method for preparing azelaic acid by enzyme catalysis of hydrogen dioxide oxygenated oleic acid |
| WO2018104208A1 (en) * | 2016-12-07 | 2018-06-14 | Solvay Sa | Method of cleaving oleic acid and/or derivatives thereof |
| CN111013646B (en) * | 2018-10-09 | 2023-01-13 | 中国石油化工股份有限公司 | Method for producing nonanal and nonanoic acid or methyl nonanal and nonanoic acid |
| CN109942407B (en) * | 2019-04-16 | 2022-04-01 | 中国日用化学研究院有限公司 | Method for synthesizing 9, 10-dihydroxyl octadecanoic acid |
| CN111925288B (en) * | 2020-08-21 | 2023-03-31 | 中国石油大学(华东) | Oil displacement agent for regulating and controlling interface infiltration and preparation method and application thereof |
| CN111943839A (en) * | 2020-08-26 | 2020-11-17 | 德州市晟昊生物科技有限公司 | Two-step oxidation method for preparing dibasic acid by oxidative cracking of unsaturated fatty acid |
| CN111892495A (en) * | 2020-08-26 | 2020-11-06 | 德州市晟昊生物科技有限公司 | Continuous oxidation method for preparing dibasic acid by oxidative cracking of unsaturated fatty acid |
| CN112812001A (en) * | 2020-12-29 | 2021-05-18 | 江南大学 | Preparation method of 9, 10-dihydroxystearic acid |
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