CN103601615B - A kind of preparation method of 2,4-Sorbic Acid - Google Patents

A kind of preparation method of 2,4-Sorbic Acid Download PDF

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CN103601615B
CN103601615B CN201310586957.4A CN201310586957A CN103601615B CN 103601615 B CN103601615 B CN 103601615B CN 201310586957 A CN201310586957 A CN 201310586957A CN 103601615 B CN103601615 B CN 103601615B
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acid
sorbic acid
sorbic
preparation
depolymerization
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CN103601615A (en
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丁彩峰
朱小刚
刘芳
姚俊生
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Nantong Acetic Acid Chemical Co Ltd
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Nantong Acetic Acid Chemical Co Ltd
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
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Abstract

The invention provides a kind of preparation method of 2,4-Sorbic Acid, in turn include the following steps: take Glacial acetic acid as raw material, obtain ketene through 700-800 DEG C of Pintsch process; Gained ketene and the condensation of Beta-methyl propenal are obtained 2,4-Sorbic Acid polyester; By gained 2,4-Sorbic Acid polyester under the catalysis of composite solid acid catalyst, obtain 2,4-Sorbic Acid crude product through depolymerization, obtain product 2,4-Sorbic Acid through aftertreatment.The method makes 2,4-Sorbic Acid polyester be hydrolyzed completely, improves 2,4-Sorbic Acid polyester depolymerization yield, single depolymerization yield reaches 90%, and product yield is high, unreacted Beta-methyl propenal, solvent and ethanolic soln is capable of circulation applies mechanically, produce without brine waste, really achieve cleaner production.

Description

A kind of preparation method of 2,4-Sorbic Acid
Technical field
The invention belongs to chemical production field, be specifically related to a kind of preparation method of 2,4-Sorbic Acid.
Background technology
2,4-Sorbic Acid, outward appearance is generally white needles or Powdered crystal, is slightly soluble in water, can be dissolved in multiple organic solvent.Molecular weight: 112.13; Fusing point: 132-135 DEG C; Boiling point: 228 DEG C (decomposition); Density: 1.204(19 DEG C); Flash-point: 127 DEG C.This product a kind ofly has the unsaturated fatty acids gripping diene altogether, it can the activity of mould fungus inhibition, yeast and aerobic bacteria effectively, it suppresses the effect of harmful microorganism development and fecundity stronger than germicidal action, is the sanitas that United Nations's grain tissue is recommended to countries in the world.2,4-Sorbic Acid has been widely used in the anticorrosion and fresh-keeping of the industries such as various food, veterinary antibiotics, medicine, rubber, papermaking, animal-feed, makeup, paint, tobacco, beverage.
Prior art synthesis technique:
Exemplary production method in current industrial production is: acetic acid Pintsch process obtains ketene, the condensation under catalyst action of Beta-methyl propenal and ketene generates 2,4-Sorbic Acid polyester, polyester is hydrolyzed into crude product 2 under concentrated hydrochloric acid existent condition, 4-Sorbic Acid,, decolorization filtering tar removing molten through alkali again, obtains 2,4-Sorbic Acid finished product with acid out, filtration, washing, oven dry in hydrochloric acid.The shortcoming of this technique is, 2,4-Sorbic Acid polyester is under concentrated hydrochloric acid existent condition, and depolymerization is incomplete, and finished product 2,4-Sorbic Acid yield is low, and wastewater flow rate is large, and brine waste is difficult.
Summary of the invention
Be concentrated hydrochloric acid, the vitriol oil etc. for the depolymerization catalyst used main in existing technique, depolymerization yield only have 80%, wastewater flow rate is large, the unmanageable shortcoming of brine waste.The object of the invention is the preparation method providing a kind of 2,4-Sorbic Acid, and the method makes 2,4-Sorbic Acid polyester be hydrolyzed completely, and improve 2,4-Sorbic Acid polyester depolymerization yield, product yield is high, solvent recoverable, produces without brine waste.
Technical solution of the present invention is as follows: a kind of preparation method of 2,4-Sorbic Acid, in turn includes the following steps: take Glacial acetic acid as raw material, obtain ketene through 700-800 DEG C of Pintsch process; Gained ketene and the condensation of Beta-methyl propenal are obtained 2,4-Sorbic Acid polyester;
It is characterized in that: by gained 2,4-Sorbic Acid polyester under the catalysis of composite solid acid catalyst, obtain 2,4-Sorbic Acid crude product through depolymerization, obtain product 2,4-Sorbic Acid through aftertreatment;
Described composite solid acid catalyst is composed as follows:
A-B mO n/C xO y
One wherein in A=Pt, Co, Ni, Mn, Cu;
One in B=Si, Ti, Mo, W, B;
One in C=Zr, Ti, Sn, Si, Mn;
m=1～2，
x=1～2，
The oxygen atomicity of n and y required for metallic element,
n=1～3，
y=1～3。
According to the preparation method of 2,4-Sorbic Acids provided by the invention, preferably, the mass ratio of described 2,4-Sorbic Acid polyester and composite solid acid catalyst is 200:1 ~ 3.
According to the preparation method of 2,4-Sorbic Acids provided by the invention, further preferably, the mass ratio of described 2,4-Sorbic Acid polyester and composite solid acid catalyst is 200:1.5 ~ 2.
According to the preparation method of 2,4-Sorbic Acids provided by the invention, preferably, the temperature of described depolymerization is 70 ~ 85 DEG C, and the depolymerization time is 2 ~ 4 hours.
According to the preparation method of 2,4-Sorbic Acids provided by the invention, further preferably, the temperature of described depolymerization is 75 ~ 80 DEG C.
According to provided by the invention 2, the preparation method of 4-Sorbic Acid, preferably, described aftertreatment is after depolymerization terminates, cooling, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery and solvent, remove tar with the centrifugal drip washing of ethanol, then obtain product 2,4-Sorbic Acid through refining, washing, oven dry.
According to the preparation method of 2,4-Sorbic Acids provided by the invention, preferably, described cooling temperature is 40 ~ 45 DEG C.
According to the preparation method of 2,4-Sorbic Acids provided by the invention, preferably, described solvent is selected from the one in benzene,toluene,xylene.
According to provided by the invention 2, the preparation method of 4-Sorbic Acid, preferably, described composite solid acid catalyst is made up of following steps: the Nitric Acid Oxidation compound or halides with water miscible C are made the aqueous solution by (1), add the precipitation of hydroxide that ammoniacal liquor obtains C again, filtration, washing, dry, porphyrize, then flood with B acid ammonium, finally oven dry, roasting, obtained B mo n/ C xo y; (2) be external phase with hexanaphthene, add tensio-active agent, cosurfactant and aqueous phase and form microemulsion system, wherein aqueous phase is A acid or the muriate of A and the mixture of ammoniacal liquor or hydrazine hydrate; (3) B is added to described microemulsion system mo n/ C xo y, add tetrahydrofuran (THF) breakdown of emulsion again under stirring, be separated, dry, solid roasting, the B of obtained load A mo n/ C xo ycomposite solid acid catalyst.
In the preparation of composite solid acid catalyst, described halides, is preferably chloro thing.
In the preparation of composite solid acid catalyst, described tensio-active agent, the one preferably in cetyl trimethylammonium bromide (CTAB), polyoxyethylene nonylphenol ether (TX-10), polyoxyethylene sorbitan monolaurate (Tween-40).
In the preparation of composite solid acid catalyst, the preferred n-hexyl alcohol of described cosurfactant.
According to the preparation method of 2,4-Sorbic Acids provided by the invention, preferably, described in the preparation of composite solid acid catalyst, A acid is chlorine A acid.
According to the preparation method of 2,4-Sorbic Acids provided by the invention, can be preferably, described composite solid acid catalyst is made up of following steps: B acid esters is dissolved in alcoholic solvent by (1), with the solvent impregnated silica-gel carrier of gained, drips deionized water, dry, obtained B mo n/ SiO 2; (2) be external phase with hexanaphthene, add tensio-active agent, cosurfactant and aqueous phase and form microemulsion system, wherein aqueous phase is the muriate of A and the mixture of ammoniacal liquor or hydrazine hydrate; (3) obtained B is added mo n/ SiO 2, add tetrahydrofuran (THF) breakdown of emulsion under stirring, be separated, dry, solid roasting, the B of obtained load A mo n/ SiO 2composite solid acid catalyst.
According to the preparation method of 2,4-Sorbic Acids provided by the invention, preferably, described in the preparation of composite solid acid catalyst, B acid esters is B acid four butyl esters.
In the preparation of composite solid acid catalyst, described tensio-active agent, the one preferably in cetyl trimethylammonium bromide (CTAB), polyoxyethylene nonylphenol ether (TX-10), polyoxyethylene sorbitan monolaurate (Tween-40).
In the preparation of composite solid acid catalyst, the preferred n-hexyl alcohol of described cosurfactant.
Of the present inventionly refine as by 2,4-Sorbic Acid crude product anhydrous alcohol solution, with gac 40-60 DEG C decolorizing and refining.
Solvent of the present invention is the fragrant same clan not with ketene and Beta-methyl acrolein reaction, as benzene,toluene,xylene etc.
The invention solves the depolymerization of 2,4-Sorbic Acid polyester incomplete, the gordian technique difficult problems such as depolymerization yield is low.How the present patent application just makes 2, the hydrolysis of 4-Sorbic Acid polyester completely, show that key is the selection of hydrolyst, for the shortcoming of current depolymerization catalyst, the application adopts composite solid acid as catalyzer, improves 2,4-Sorbic Acid polyester depolymerization yield, product yield is high, solvent recoverable, produces without brine waste.
According to provided by the invention 2, the preparation method of 4-Sorbic Acid, Glacial acetic acid is by Pintsch process ketene, with Beta-methyl propenal under catalysts conditions, condensation obtains 2, 4-Sorbic Acid polyester, get 1000 weight parts 2, 4-Sorbic Acid polyester and the acid of 5 ~ 15 parts by weight solids, 70 ~ 85 DEG C of insulation depolymerization after 2 ~ 4 hours, be cooled to 40 ~ 45 DEG C, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and solvent, tar is removed with the centrifugal drip washing of 800 ~ 1600 weight part 60 ~ 70% ethanol, again through refining, washing, oven dry obtains finished product 2, 4-Sorbic Acid.
2,4-Sorbic Acid polyester of the present invention are made up of following steps: Glacial acetic acid, at 700-800 DEG C, becomes ketene at acetic acid cracking stove Pintsch process.Beta-methyl propenal and zinc acetate, methylacrylic acid zinc, α-methylpyridine, zinc chloride, aluminum chloride catalyst is added in condensation kettle, the ketene gas that Pintsch process produces is passed into again in condensation kettle, there is condensation reaction at 40 ~ 70 DEG C and generate 2,4-Sorbic Acid polyester.
Advantageous Effects:
Provided by the invention 2, the preparation method of 4-Sorbic Acid, the method makes 2,4-Sorbic Acid polyester be hydrolyzed completely, improves 2,4-Sorbic Acid polyester depolymerization yield, single depolymerization yield reaches 90%, and product yield is high, unreacted Beta-methyl propenal, solvent and ethanolic soln is capable of circulation applies mechanically, produce without brine waste, really achieve cleaner production.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated, it will be appreciated by those skilled in the art that described embodiment is only for example, and do not form any restriction to the present invention.
In following examples, involved 2,4-Sorbic Acid polyester is prepared by the method preparing it conventional in prior art, makes: Glacial acetic acid, at 700-800 DEG C, becomes ketene at acetic acid cracking stove Pintsch process primarily of lower step.In condensation kettle, add Beta-methyl propenal and catalyst acetic acid zinc, then in condensation kettle, pass into the ketene gas of Pintsch process generation, at 40 ~ 70 DEG C, condensation reactions occur and generate 2,4-Sorbic Acid polyester.
Embodiment 1: composite solid acid catalyst Pt-WO of the present invention 3/ ZrO 2preparation method:
By 7.62gZrO (NO 3) 2make the aqueous solution, then add ammoniacal liquor and obtain Zr (OH) 4precipitation, then filters, washs, dry, porphyrize, with 104.75g ammonium tungstate dipping 6 ~ 8 hours, finally dries, roasting, obtained WO 3/ ZrO 2.
Take hexanaphthene as external phase, cetyl trimethylammonium bromide (CTAB) is tensio-active agent, and n-hexyl alcohol is cosurfactant, with the Platinic chloride (H of 5.13ml, 0.15mol/L 2ptCl 6) solution and 104.21g massfraction be 40% hydrazine hydrate (N 2h 4h 2o) for aqueous phase forms microemulsion system, obtained WO is added to this microemulsion system 3/ ZrO 2, add tetrahydrofuran (THF) breakdown of emulsion under stirring, be separated, dry, solid, in the roasting of 400-550 degree, obtains the WO of 100g supporting Pt 3/ ZrO 2solid super-strong acid.The massfraction of Pt is the massfraction of 0.15%, Zr is 3%.
Embodiment 2: composite solid acid catalyst Ni-WO of the present invention 3/ ZrO 2preparation method:
By 6.35gZrO (NO 3) 2make the aqueous solution, then add ammoniacal liquor and obtain Zr (OH) 4precipitation, then filters, washs, dry, porphyrize, then with 105.42g ammonium tungstate dipping 6 ~ 8 hours, finally dry, roasting, obtain WO 3/ ZrO 2.
Take hexanaphthene as external phase, cetyl trimethylammonium bromide (CTAB) is tensio-active agent, and n-hexyl alcohol is cosurfactant, with the NiCl of 3.38ml, 1mol/L 2solution and 109.68g massfraction are the hydrazine hydrate (N of 40% 2h 4h 2o) for aqueous phase forms microemulsion system, obtained WO is added to this microemulsion system 3/ ZrO 2, add tetrahydrofuran (THF) breakdown of emulsion under stirring, be separated, dry, solid, in the roasting of 400-550 degree, obtains the WO of 100g load Ni 3/ ZrO 2solid super-strong acid.The massfraction of Ni is the massfraction of 0.2%, Zr is 2.5%.
Embodiment 3: composite solid acid catalyst Ni-MoO of the present invention 3/ MnO 2preparation method:
By 6.87gMnCl 2make the aqueous solution, then add ammoniacal liquor and obtain Mn (OH) 4precipitation, then filters, washs, dry, porphyrize, then with 116.55g ammonium molybdate dipping 6 ~ 8 hours, finally dry, roasting, obtain MoO 3/ MnO 2.
Take hexanaphthene as external phase, polyoxyethylene nonylphenol ether (TX-10) is tensio-active agent, and propyl carbinol is cosurfactant, with the NiCl of 3.38ml, 1mol/L 2solution and ammoniacal liquor are that aqueous phase forms microemulsion system, add obtained MoO to this microemulsion system 3/ MnO 2, add tetrahydrofuran (THF) breakdown of emulsion under stirring, be separated, dry, solid, in the roasting of 400-550 degree, obtains the MoO of load Ni 3/ MnO 2solid super-strong acid.The massfraction of Ni is the massfraction of 0.2%, Mn is 3%.
Embodiment 4: composite solid acid catalyst Ni-B of the present invention 2o 3/ ZrO 2preparation method:
By 6.35gZrO (NO 3) 2the aqueous solution, then add ammoniacal liquor and obtain Zr (OH) 4precipitation, then filters, washs, dry, porphyrize, then with 157.72g ammonium borate dipping 6 ~ 8 hours, finally dry, roasting, obtain B 2o 3/ ZrO 2.
Take hexanaphthene as external phase, polyoxyethylene nonylphenol ether (TX-10) is tensio-active agent, and propyl carbinol is cosurfactant, with the NiCl of 3.38ml, 1mol/L 2solution and 51.28g ammoniacal liquor are that aqueous phase forms microemulsion system, add obtained B to this microemulsion system 2o 3/ ZrO 2, add tetrahydrofuran (THF) breakdown of emulsion under stirring, be separated, dry, solid, in the roasting of 400-550 degree, obtains the B of 100g load Ni 2o 3/ ZrO 2solid super-strong acid.The massfraction of Ni is the massfraction of 0.2%, Zr is 2.5%.
Embodiment 5: composite solid acid catalyst Pt-MoO of the present invention 3/ ZrO 2preparation method:
By 6.35gZrO (NO 3) 2the aqueous solution, then add ammoniacal liquor and obtain Zr (OH) 4precipitation, then filters, washs, dry, porphyrize, then with 119.46g ammonium molybdate dipping 6 ~ 8 hours, finally dry, roasting, obtain MoO 3/ ZrO 2.
Take hexanaphthene as external phase, cetyl trimethylammonium bromide (CTAB) is tensio-active agent, and n-hexyl alcohol is cosurfactant, with the Platinic chloride (H of 3.42ml, 0.15mol/L 2ptCl 6) hydrazine hydrate (N of solution and 113.41 massfractions 40% 2h 4h 2o) for aqueous phase forms microemulsion system, obtained MoO is added to this microemulsion system 3/ ZrO 2, add tetrahydrofuran (THF) breakdown of emulsion under stirring, be separated, dry, solid, in the roasting of 400-550 degree, obtains the MoO of 100g supporting Pt 3/ ZrO 2solid super-strong acid.The massfraction of Pt is the massfraction of 0.1%, Zr is 2.5%.
Embodiment 6: composite solid acid catalyst Co-TiO of the present invention 2/ SiO 2preparation method:
28.33g tetrabutyl titanate is dissolved in dehydrated alcohol, the 151.96g silica-gel carrier that pretreatment is good, drips deionized water, dry, obtained TiO 2/ SiO 2.
Take hexanaphthene as external phase, polyoxyethylene sorbitan monolaurate (Tween-40) is tensio-active agent, and propyl carbinol is cosurfactant, with the CoCl of 1.67ml, 1mol/L 2solution and 110.79g massfraction are the hydrazine hydrate (N of 40% 2h 4h 2o) for aqueous phase forms microemulsion system, obtained TiO is added to this microemulsion system 2/ SiO 2, add tetrahydrofuran (THF) breakdown of emulsion under stirring, be separated, dry, solid, in the roasting of 400-550 degree, obtains the TiO of 100g load C o 2/ SiO 2solid super-strong acid.The massfraction of Co is the massfraction of 0.1%, Ti is 4%.
The preparation method of embodiment 7:2,4-Sorbic Acid
Get 1000g2, composite solid acid catalyst Co-TiO prepared by 4-Sorbic Acid polyester and 5g embodiment 6 2/ SiO 2be dissolved in toluene solution, after 2.5 hours, be cooled to 40 DEG C 70 DEG C of insulation depolymerization, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and toluene, with 900g, tar is removed in the centrifugal drip washing of 60 ~ 70% ethanol, 2 are obtained again through refining, washing, oven dry, 4-Sorbic Acid finished product 908g, content is greater than 99.5%, and 2,4-Sorbic Acid polyester depolymerization yield is 90.8%, unreacted Beta-methyl propenal, toluene and ethanolic soln recovery.
The preparation method of embodiment 8:2,4-Sorbic Acid
Get 1000g2, solid acid catalyst Ni-WO prepared by 4-Sorbic Acid polyester and 7g embodiment 2 3/ ZrO 2be dissolved in xylene solution, after 3 hours, be cooled to 42 DEG C 75 ± 1 DEG C of insulation depolymerization, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and dimethylbenzene, with 1100g, tar is removed in the centrifugal drip washing of 60 ~ 70% ethanol, 2 are obtained again through refining, washing, oven dry, 4-Sorbic Acid finished product 912g, content is greater than 99.5%, and 2,4-Sorbic Acid polyester depolymerization yield is 91.2%, unreacted Beta-methyl propenal, dimethylbenzene and ethanolic soln recovery.
The preparation method of embodiment 9:2,4-Sorbic Acid
Get 1000g2, solid acid catalyst Ni-MoO prepared by 4-Sorbic Acid polyester and 10g embodiment 3 3/ MnO 2be dissolved in toluene solution, after 3 hours, be cooled to 42 DEG C 75 ± 1 DEG C of insulation depolymerization, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and toluene, with 1100g, tar is removed in the centrifugal drip washing of 60 ~ 70% ethanol, 2 are obtained again through refining, washing, oven dry, 4-Sorbic Acid finished product 904g, content is greater than 99.5%, and 2,4-Sorbic Acid polyester depolymerization yield is 90.4%, unreacted Beta-methyl propenal, toluene and ethanolic soln recovery.
The preparation method of embodiment 10:2,4-Sorbic Acid
Get 1000g2, solid acid Ni-B prepared by 4-Sorbic Acid polyester and 15g embodiment 4 2o 3/ ZrO 2be dissolved in toluene solution, after 3 hours, be cooled to 45 DEG C 80 ± 1 DEG C of insulation depolymerization, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and toluene, with 1300g, tar is removed in the centrifugal drip washing of 60 ~ 70% ethanol, 2 are obtained again through refining, washing, oven dry, 4-Sorbic Acid finished product 910g, content is greater than 99.5%, and 2,4-Sorbic Acid polyester depolymerization yield is 91.0%, unreacted Beta-methyl propenal, toluene and ethanolic soln recovery.
The preparation method of embodiment 11:2,4-Sorbic Acid
Get 1000g2, solid acid Pt-MoO prepared by 4-Sorbic Acid polyester and 12g embodiment 5 3/ ZrO 2be dissolved in toluene solution, after 3 hours, be cooled to 45 DEG C 80 ± 1 DEG C of insulation depolymerization, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and toluene, with 1400g, tar is removed in the centrifugal drip washing of 60 ~ 70% ethanol, 2 are obtained again through refining, washing, oven dry, 4-Sorbic Acid finished product 907g, content is greater than 99.5%, and 2,4-Sorbic Acid polyester depolymerization yield is 90.7%, unreacted Beta-methyl propenal, toluene and ethanolic soln recovery.
The preparation method of embodiment 12:2,4-Sorbic Acid
Get 1000g2, solid acid Pt-WO prepared by 4-Sorbic Acid polyester and 12g embodiment 1 3/ ZrO 2be dissolved in toluene solution, after 3 hours, be cooled to 45 DEG C 85 DEG C of insulation depolymerization, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and toluene, with 1600g, tar is removed in the centrifugal drip washing of 60 ~ 70% ethanol, 2 are obtained again through refining, washing, oven dry, 4-Sorbic Acid finished product 905g, content is greater than 99.5%, and 2,4-Sorbic Acid polyester depolymerization yield is 90.5%, unreacted Beta-methyl propenal, toluene and ethanolic soln recovery.
Embodiment 13:
Get 1000g2, solid acid Ni-WO prepared by 4-Sorbic Acid polyester and 10g embodiment 2 3/ ZrO 2be dissolved in xylene solution, after 3 hours, be cooled to 42 DEG C 75 ± 1 DEG C of insulation depolymerization, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and dimethylbenzene, with 1100g, tar is removed in the centrifugal drip washing of 60 ~ 70% ethanol, 2 are obtained again through refining, washing, oven dry, 4-Sorbic Acid finished product 904g, content is greater than 99.5%, and 2,4-Sorbic Acid polyester depolymerization yield is 90.4%, unreacted Beta-methyl propenal, dimethylbenzene and ethanolic soln recovery.
Embodiment 14:
Get 1000g2, solid acid Ni-MoO prepared by 4-Sorbic Acid polyester and 15g embodiment 3 3/ MnO 2be dissolved in toluene solution, after 3 hours, be cooled to 45 DEG C 75 ± 1 DEG C of insulation depolymerization, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery part and toluene, with 1300g, tar is removed in the centrifugal drip washing of 60 ~ 70% ethanol, 2 are obtained again through refining, washing, oven dry, 4-Sorbic Acid finished product 910g, content is greater than 99.5%, and 2,4-Sorbic Acid polyester depolymerization yield is 91.0%, unreacted Beta-methyl propenal, toluene and ethanolic soln recovery.
Comparative example 1:
With reference to technique used in current industrial production
Get the hydrochloric acid 5000g that 2,4-Sorbic Acid polyester 1000g adds 30%, be warmed up to 80 DEG C of insulation depolymerization reactions 3 hours, cold filtration obtains crude product Sorbic Acid.Crude product Sorbic Acid add water 5000ml with 30% aqueous sodium hydroxide solution to carry out alkali molten, adjust after pH value to 7.5 and add 100g activated carbon decolorizing except tar removing, filter, in filtrate hydrochloric acid and acid out, adjust pH value to 2.5, filter, washing, dry, obtain the finished product Sorbic Acid 832g of white, content is greater than 99.5%, is 83.2% to the depolymerization yield of Sorbic Acid polyester, produces 2936g brine waste.
Provided by the invention 2, the preparation method of 4-Sorbic Acid, the method makes 2,4-Sorbic Acid polyester be hydrolyzed completely, improves 2,4-Sorbic Acid polyester depolymerization yield, single depolymerization yield reaches 90%, and product yield is high, unreacted Beta-methyl propenal, solvent and ethanolic soln is capable of circulation applies mechanically, produce without brine waste, really achieve cleaner production.
Below the present invention is disclosed with preferred embodiment; all catalyst combination embodiments are not showed; so it is not intended to limiting the invention, and all employings are equal to replacement or the technical scheme that obtains of equivalent transformation mode, all drop within protection scope of the present invention.

Claims (8)

1. the preparation method of a Sorbic Acid, in turn includes the following steps: take Glacial acetic acid as raw material, obtains ketene through 700-800 DEG C of Pintsch process; Gained ketene and the condensation of Beta-methyl propenal are obtained 2,4-Sorbic Acid polyester;
It is characterized in that: by gained 2,4-Sorbic Acid polyester under the catalysis of composite solid acid catalyst, obtain 2,4-Sorbic Acid crude product through depolymerization, obtain product 2,4-Sorbic Acid through aftertreatment;
Described composite solid acid catalyst is composed as follows:
A-B mO n/C xO y
One wherein in A=Pt, Co, Ni;
One in B=Ti, Mo, W, B;
One in C=Zr, Sn, Si, Mn;
m＝1～2，
x＝1～2，
n＝1～3，
y＝1～3。
2. the preparation method of 2,4-Sorbic Acids according to claim 1, is characterized in that, the mass ratio of described 2,4-Sorbic Acid polyester and composite solid acid catalyst is 200: 1 ~ 3.
3. the preparation method of 2,4-Sorbic Acids according to claim 1, is characterized in that, the temperature of described depolymerization is 70 ~ 85 DEG C, and the depolymerization time is 2 ~ 4 hours.
4. according to claim 12, the preparation method of 4-Sorbic Acid, it is characterized in that, described aftertreatment is after depolymerization terminates, cooling, filtered and recycled solid acid catalyst, after the unreacted Beta-methyl propenal of filtrate Distillation recovery and solvent, remove tar with the centrifugal drip washing of ethanol, then obtain product 2,4-Sorbic Acid through refining, washing, oven dry.
5. the preparation method of 2,4-Sorbic Acids according to claim 4, is characterized in that, described cooling temperature is 40 ~ 45 DEG C.
6. the preparation method of 2,4-Sorbic Acids according to claim 4, is characterized in that, described solvent is selected from the one in benzene,toluene,xylene.
7. according to claim 12, the preparation method of 4-Sorbic Acid, it is characterized in that, described composite solid acid catalyst is made up of following steps: the Nitric Acid Oxidation compound or halides with water miscible C are made the aqueous solution by (1), add the precipitation of hydroxide that ammoniacal liquor obtains C again, filtration, washing, dry, porphyrize, then flood with B acid ammonium, finally oven dry, roasting, obtained B mo n/ C xo y; (2) be external phase with hexanaphthene, add tensio-active agent, cosurfactant and aqueous phase and form microemulsion system, wherein aqueous phase is A acid or the muriate of A and the mixture of ammoniacal liquor or hydrazine hydrate; (3) B is added to described microemulsion system mo n/ C xo y, add tetrahydrofuran (THF) breakdown of emulsion again under stirring, be separated, dry, solid roasting, the B of obtained load A mo n/ C xo ycomposite solid acid catalyst; Described A acid is chlorine A acid.
8. the preparation method of 2,4-Sorbic Acids according to claim 1, is characterized in that, described composite solid acid catalyst is made up of following steps: B acid esters is dissolved in alcoholic solvent by (1), with the solvent impregnated silica-gel carrier of gained, drips deionized water, dry, obtained B mo n/ SiO 2; (2) be external phase with hexanaphthene, add tensio-active agent, cosurfactant and aqueous phase and form microemulsion system, wherein aqueous phase is the muriate of A and the mixture of ammoniacal liquor or hydrazine hydrate; (3) obtained B is added mo n/ SiO 2, add tetrahydrofuran (THF) breakdown of emulsion under stirring, be separated, dry, solid roasting, the B of obtained load A mo n/ SiO 2composite solid acid catalyst; Described B acid esters is B acid four butyl esters; Described B acid four butyl esters are tetrabutyl titanate.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3461158A (en) * 1964-12-01 1969-08-12 Hoechst Ag Process for preparing sorbic acid and its salts
US3696147A (en) * 1969-06-20 1972-10-03 Wacker Chemie Gmbh Process for continuously producing pure sorbic acid
CN1850768A (en) * 2006-05-25 2006-10-25 宁波王龙集团有限公司 Process for preparing high purity crystalline sorbic acid
CN101402557A (en) * 2008-11-19 2009-04-08 南通百事特生物化学有限公司 Process for preparing sorbic acid potassium salt

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1068564A (en) * 1992-08-06 1993-02-03 张绍文 Produce the method for Sorbic Acid with crotonic aldehyde and acetaldehyde
JP2000095728A (en) * 1998-09-24 2000-04-04 Daicel Chem Ind Ltd Production of sorbic acid
CN101318891B (en) * 2008-05-08 2011-05-25 金能科技有限责任公司 Process for preparing sorbic acid
US8404890B2 (en) * 2010-11-10 2013-03-26 Wisconsin Alumni Research Foundation Production of 2,4-hexadienoic acid and 1,3-pentadiene from 6-methyl-5,6-dihydro-2-pyrone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3461158A (en) * 1964-12-01 1969-08-12 Hoechst Ag Process for preparing sorbic acid and its salts
US3696147A (en) * 1969-06-20 1972-10-03 Wacker Chemie Gmbh Process for continuously producing pure sorbic acid
CN1850768A (en) * 2006-05-25 2006-10-25 宁波王龙集团有限公司 Process for preparing high purity crystalline sorbic acid
CN101402557A (en) * 2008-11-19 2009-04-08 南通百事特生物化学有限公司 Process for preparing sorbic acid potassium salt

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