CN102304045B - Integrated process for synthesizing acetyl tributyl citrate by using activated carbon immobilized sulfuric acid catalyst - Google Patents
Integrated process for synthesizing acetyl tributyl citrate by using activated carbon immobilized sulfuric acid catalyst Download PDFInfo
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- CN102304045B CN102304045B CN201110191984.2A CN201110191984A CN102304045B CN 102304045 B CN102304045 B CN 102304045B CN 201110191984 A CN201110191984 A CN 201110191984A CN 102304045 B CN102304045 B CN 102304045B
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- tributyl citrate
- sulfuric acid
- acetyl tributyl
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- tbc
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 230000036571 hydration Effects 0.000 claims abstract description 10
- 238000006703 hydration reaction Methods 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 7
- 239000002023 wood Substances 0.000 claims abstract description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000005917 acylation reaction Methods 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000003100 immobilizing effect Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000011973 solid acid Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 phthalic acid ester Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
An integrated process for synthesizing acetyl tributyl citrate by using an activated carbon immobilized sulfuric acid catalyst comprises the following steps: preparation of catalyst: soaking the wood activated carbon in a sulfuric acid solution which is 5-20 times of the wood activated carbon, stirring and immobilizing at normal temperature, filtering and drying to obtain an activated carbon immobilized sulfuric acid catalyst; preparing TBC: reacting (hydration) citric acid, n-butyl alcohol and a catalyst at 130-160 ℃ for 3.0-6.0 h, and dealcoholizing; preparing ATBC: adding acetic anhydride into the TBC, reacting for 0.5-1.5 h at 70-90 ℃, cooling and filtering the reaction liquid, adding water to recover acetic acid, and performing post-treatment to obtain the ATBC finished product. The method has the advantages of less catalyst consumption, easy separation and recovery, and decoloring function, directly performs acylation reaction without separation after the dealcoholization of the TBC, saves the links of TBC refining, decoloring and the like, obviously reduces three wastes, reduces the cost, improves the product yield, and is suitable for industrial application.
Description
Technical field
The present invention relates to the synthetic method of a kind of softening agent tributyl acetylcitrate (ATBC), particularly relate to the integration synthesis process of the immobilized sulfuric acid catalyst synthesizing acetyl tributyl citrate of a kind of gac, belong to chemosynthesis and technology field.
Background technology
Traditional plasticizer phthalic acid ester class may be brought out carcinogenic, and the restriction of abroad having made laws is used.Tributyl acetylcitrate (ATBC) is as " green " environment-friendly plasticizer, having obtained U.S. food and Drug Administration (FDA) approval uses, there is nontoxic, tasteless, anti-mildew, the advantage such as plasticizing effect is good, cold-resistant, fast light, water-fast, volatility is little, be widely used in the fields such as food product pack, medical article, toy for children, become the first-selected product that substitutes phthalic ester plasticizer.
ATBC domestic market vacancy is huge at present, the synthetic traditional method of ATBC is to take the homogeneous system that vitriol oil etc. is catalyzer, although homogeneous system excellent catalytic effect, but also have obvious shortcoming: by product is many, equipment corrosion is serious, catalyzer is difficult for and raw material and product separation, need a large amount of alkali lye to neutralize and wash, aftertreatment is complicated, and " three wastes " discharge is large, contaminate environment.ATBC preparation technology of the prior art, is first that to take (hydration) citric acid and propyl carbinol be raw material, under catalyst action, through esterification, neutralization, washing, de-alcohol and water, decolouring, makes tributyl citrate (TBC) finished product; And then make ATBC finished product through acetylize, depickling, neutralization, washing, dehydration, decolouring.This complex technical process, production cycle length, product loss are large, facility investment is large, " three wastes " quantity discharged is large, contaminate environment.
Therefore,, for overcoming the shortcoming of homogeneous system and complex process, research solid acid catalyst and succinct technique are significant to exploitation tributyl acetylcitrate.
CN201010583409.2 discloses a kind of method of synthesizing citric acid tri-n-butyl, in ester building-up process, with gel starch base carbon-based solid acid as catalyst, after reaction finishes, catalyzer is filtered out from reaction mixture, through processing such as washing, alkali cleaning, distillations, can obtain tributyl citrate.The method of preparing gel starch base carbon-based solid acid is, 10g starch is added in the water of 50ml, after 70 ℃ of heated and stirred 4h, obtain starch gel, starch gel is placed in to 85 ℃ of baking ovens to be dried, after finally adding 5g hydroxyethylsulfonic acid to be uniformly mixed, be placed in silica tube retort furnace, logical nitrogen replacement air wherein, in nitrogen atmosphere, be heated to carry out at 200 ℃ carburizing reagent 12h, obtain the solid of black, until solid cooled after room temperature, add 80 ℃ of above hot water to wash, and filter, until filtrate clarification does not have acidity, the baking oven that again solid is placed in to 120 ℃ is dried 1 day, obtain preparing gel starch base carbon-based solid acid.
CN201010535730.3 discloses a kind of Catalysts and its preparation method for the synthesis of tributyl citrate, it is carrier that described catalyzer be take strongly-acid mesoporous material prepared by hydrothermal synthesis method, on mesoporous material carrier with the mode chemical bonding acidic ion liquid of finishing, mesoporous material is mesoporous silicon, mesoporous zirconium or mesoporous titanium, and acidic ion liquid is the ionic liquid that contains phosphate radical or sulfate radical.Use this catalyzer citric acid transformation efficiency 90～99%.
CN200610024372.3 discloses a kind of method that tributyl citrate is prepared in heterogeneous catalysis, it is in ester building-up process, to take carbon back sulfonic acid as catalyzer, the preparation process of carbon back sulfonic acid, that the vitriol oil of 8～15ml is added in 10～15g C 9 fraction of cracking, 200～250 ℃ are carried out reacting by heating 3～5h, then add boiling water to reflux and stir 2～4h, suction filtration, 130～150 ℃ of oven dry, obtain carbon back sulfonic acid.
CN200810195075.4 and CN200510030100.X make the synthetic TBC of catalyzer with rare-earth salts and the composite solid acid of organic acid and mesopore molecular sieve respectively.
Disclosed technical scheme in above-mentioned patent documentation, its catalyzer building-up process is complicated, esterification by filtering, the aftertreatment such as water (alkali) is washed, distillation can obtain tributyl citrate.For obtaining ATBC, in prior art, be that technical process is long by the TBC crude product making further acidylate under the katalysis such as the vitriol oil, tosic acid, thionamic acid, complicated operation, product yield is low.
Summary of the invention
The object of the invention is to propose the integral process of synthesizing acetyl tributyl citrate under a kind of solid acid catalysis effect; the shortcomings such as the existing complex process of preparation method, the production cycle that has overcome existing tributyl acetylcitrate grown, product loss is large, " three wastes " are many, contaminate environment; method TBC of the present invention is without separated and washing; after dealcoholysis, directly carry out acylation reaction; simple, easily separated recovery prepared by catalyzer; reaction conditions is gentle, good product quality.
The technical solution adopted in the present invention is as follows:
An integral process for the immobilized sulfuric acid catalyst synthesizing acetyl tributyl citrate of gac, comprises the following steps:
1) preparation of catalyzer
Take a certain amount of wood activated charcoal and be soaked in sulphuric acid soln, the mass ratio of sulphuric acid soln and gac is 5 ~ 20:1, immobilized under stirring at normal temperature condition, catalyzer after filtration, dry to constant weight, obtain the immobilized sulfuric acid catalyst (C-H of gac
2sO
4);
2) tributyl citrate preparation
The catalyzer C-H that adds (hydration) citric acid, propyl carbinol and step 1) to make in reactor
2sO
4, at 130 ℃ ~ 160 ℃, react the synthetic TBC of 3.0h ~ 6.0h, dealcoholysis;
3) tributyl acetylcitrate preparation
To step 2) add acetic anhydride in TBC after dealcoholysis, at 70 ℃ ~ 90 ℃, react 0.5h ~ 1.5h, reaction solution cooled and filtered catalyzer, filtrate is hydrolyzed acetic anhydride after adding water, recovery of acetic acid, aftertreatment makes ATBC finished product.
The preferred Activated carbon for refining of suger of described wood activated charcoal.
Described sulphuric acid soln mass concentration preferably 20% ~ 50%.
In step 1), the immobilized time of sulfuric acid is 20h ~ 60h.
In step 1), catalyzer bake out temperature is 100～150 ℃.
Immobilized sulfuric acid catalyst (the C-H of gac that step 1) makes
2sO
4), according to weightening finish method or titration measuring, in catalyzer, the mass ratio of sulfuric acid is 55% ~ 75%.
Described (hydration) citric acid and the mol ratio of propyl carbinol are 1:3 ~ 7, preferably 1:4 ~ 5.
Step 2), in, the consumption of described catalyzer is 0.2% ~ 1.0% of (hydration) citric acid quality.
In step 3), described acetic anhydride is 1 ~ 2:1, preferably 1.1 ~ 1.5:1 with the mol ratio of (hydration) citric acid.
In step 3), described aftertreatment comprises neutralization, washing and processed.
The present invention has following useful technique effect:
1. the present invention adopts solid acid catalysis synthesizing acetyl tributyl citrate, and catalyzer is easily separated, equipment corrosion is few, and acid catalyst, without carrying out alkali neutralization, is avoided acid catalyst to enter waste water and brought environmental pollution.
2. the immobilized sulfuric acid catalyst of gac of the present invention integrates the decolouring of the efficient and gac of acid, not only catalysis but also decolour of catalyzer, and product, without doing decolouring processing, saves independent decolouring step.
3. catalyst levels few (0.2% ~ 1.0%), preparation technology is simple, with low cost, thereby has significantly reduced product cost.
4. integral process of the present invention has saved refining TBC link in traditional technology, after TBC dealcoholysis, without separation, directly carries out acylation reaction, reduces " three wastes ", reduces costs, and improves product yield.
5. the inventive method esterification yield high (>=98.5%), good product quality, tributyl acetylcitrate purity >=99.3%, color and luster≤15#.
In sum, the inventive method is easy and simple to handle, " three wastes " less, cost is low, quality product is high, according to the inventive method synthesizing acetyl tributyl citrate, not only economy but also environmental protection, be applicable to industrialization.
Below in conjunction with specific embodiment, describe the present invention.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
Embodiment
Embodiment 1
The integral method of the immobilized sulfuric acid catalyst synthesizing acetyl tributyl citrate of gac, comprises the following steps:
1) catalyzer (C-H
2sO
4) preparation
Take in the sulphuric acid soln that 1kg Activated carbon for refining of suger is soaked in 5kg ~ 20kg 20% ~ 50%, the immobilized 20h ~ 60h of stirring at normal temperature, catalyzer after filtration, 120 ℃ dry to constant weight, obtain the immobilized sulfuric acid catalyst (C-H of gac
2sO
4), the mass ratio that is calculated sulfuric acid in catalyzer by weightening finish method is 55% ~ 75%.
2) tributyl citrate preparation
To being furnished with in the reaction flask of agitator, thermometer, water trap and prolong, add monohydrate potassium 21.0kg(0.1kmol), propyl carbinol 29.7kg(0.4kmol) and above-mentioned catalyzer C-H
2sO
40.105kg(monohydrate potassium quality 0.5%), stirring reaction 3.0h ~ 6.0h at 130 ℃ ~ 160 ℃, synthetic TBC, surveys acid number by GB 1668-81, esterification yield>=98.5%, product must TBC crude product after dealcoholysis.
3) tributyl acetylcitrate preparation
In the TBC crude product (35.7kg) making to step 1), add acetic anhydride 12.1kg(0.12kmol), at 70 ℃ ~ 80 ℃, react 0.5h ~ 1.5h, synthetic ATBC, then filtering catalyst, filtrate adds water (amount that adds water equal or be slightly larger than the needed amount of unreacted acetic anhydride complete hydrolysis), recovery of acetic acid after acetic anhydride hydrolysis, neutralizes once, washes twice, dehydration with 5% sodium carbonate alkali lye, obtains ATBC finished product.Color and luster≤15#(platinum-cobalt), product purity >=99.3%, acid number≤0.020mgKOH/g, moisture≤0.020%.
Embodiment 2
The integral method of the immobilized sulfuric acid catalyst synthesizing acetyl tributyl citrate of gac, comprises the following steps:
1) catalyzer (C-H
2sO
4) preparation
Take in the sulphuric acid soln that 1kg Activated carbon for refining of suger is soaked in 5kg ~ 20kg 20% ~ 50%, the immobilized 20h ~ 60h of stirring at normal temperature, catalyzer after filtration, 120 ℃ dry to constant weight, obtain the immobilized sulfuric acid catalyst (C-H of gac
2sO
4), the mass ratio that is calculated sulfuric acid in catalyzer by weightening finish method is 55% ~ 75%.
2) tributyl citrate preparation
To being furnished with in the reaction flask of agitator, thermometer, water trap and prolong, add monohydrate potassium 21.0kg(0.1kmol), propyl carbinol 37.1kg(0.5kmol) and above-mentioned catalyzer C-H
2sO
40.042kg(monohydrate potassium quality 0.2%), stirring reaction 3.0h ~ 6.0h at 130 ℃ ~ 160 ℃, synthetic TBC, surveys acid number by GB 1668-81, esterification yield>=98.5%, product must TBC crude product after dealcoholysis.
3) tributyl acetylcitrate preparation
In the TBC crude product (35.5kg) making to step 1), add acetic anhydride 15.3kg(0.15kmol), at 70 ℃ ~ 80 ℃, react 0.5h ~ 1.5h, synthetic ATBC, then filtering catalyst, filtrate adds water (amount that adds water equal or be slightly larger than the needed amount of unreacted acetic anhydride complete hydrolysis), recovery of acetic acid after acetic anhydride hydrolysis, neutralizes once, washes twice, dehydration with 5% sodium carbonate alkali lye, obtains ATBC finished product.Color and luster≤15#(platinum-cobalt), product purity >=99.3%, acid number≤0.020mgKOH/g, moisture≤0.020%.
Embodiment 3
The integral method of the immobilized sulfuric acid catalyst synthesizing acetyl tributyl citrate of gac, comprises the following steps:
1) catalyzer (C-H
2sO
4) preparation
Take in the sulphuric acid soln that 1kg Activated carbon for refining of suger is soaked in 5kg ~ 20kg 20% ~ 50%, the immobilized 20h ~ 60h of stirring at normal temperature, catalyzer after filtration, 120 ℃ dry to constant weight, obtain the immobilized sulfuric acid catalyst (C-H of gac
2sO
4), the mass ratio that is calculated sulfuric acid in catalyzer by weightening finish method is 55% ~ 75%.
2) tributyl citrate preparation
To being furnished with in the reaction flask of agitator, thermometer, water trap and prolong, add citric acid 19.2kg(0.1kmol), propyl carbinol 29.7kg(0.4kmol) and above-mentioned catalyzer C-H
2sO
40.192kg(citric acid quality 1.0%), stirring reaction 3.0h ~ 6.0h at 130 ℃ ~ 160 ℃, synthetic TBC, surveys acid number by GB 1668-81, esterification yield>=98.5%, product must TBC crude product after dealcoholysis.
3) tributyl acetylcitrate preparation
In the TBC crude product (35.8kg) making to step 1), add acetic anhydride 12.1kg(0.12kmol), at 70 ℃ ~ 80 ℃, react 0.5h ~ 1.5h, synthetic ATBC, then filtering catalyst, filtrate adds water (amount that adds water equal or be slightly larger than the needed amount of unreacted acetic anhydride complete hydrolysis), recovery of acetic acid after hydrolysis acetic anhydride, neutralizes once, washes twice, dehydration with 5% sodium carbonate alkali lye, obtains ATBC finished product.Color and luster≤15#(platinum-cobalt), product purity >=99.3%, acid number≤0.020mgKOH/g, moisture≤0.020%.
Claims (8)
1. an integral process for the immobilized sulfuric acid catalyst synthesizing acetyl tributyl citrate of gac, comprises the following steps:
1) preparation of catalyzer
Taking a certain amount of wood activated charcoal is soaked in sulphuric acid soln, described wood activated charcoal is Activated carbon for refining of suger, and the mass ratio of sulphuric acid soln and gac is 5 ~ 20:1, immobilized under stirring at normal temperature condition, catalyzer after filtration, dry to constant weight, obtain the immobilized sulfuric acid catalyst C-H of gac
2sO
4;
2) preparation of tributyl citrate
The catalyzer C-H that adds (hydration) citric acid, propyl carbinol and step 1) to make in reactor
2sO
4, at 130 ℃ ~ 160 ℃, react the synthetic TBC of 3.0h ~ 6.0h, dealcoholysis;
3) tributyl acetylcitrate preparation
To step 2) add acetic anhydride in TBC after dealcoholysis, at 70 ℃ ~ 90 ℃, react 0.5h ~ 1.5h, reaction solution cooled and filtered catalyzer, filtrate is hydrolyzed acetic anhydride after adding water, recovery of acetic acid, aftertreatment makes ATBC finished product.
2. the integral process of synthesizing acetyl tributyl citrate according to claim 1, is characterized in that: described sulphuric acid soln mass concentration is 20% ~ 50%.
3. the integral process of synthesizing acetyl tributyl citrate according to claim 1, is characterized in that: the immobilized time of described stirring is 20h ~ 60h.
4. the integral process of synthesizing acetyl tributyl citrate according to claim 1, is characterized in that: in the immobilized sulfuric acid catalyst of described gac, the mass ratio of sulfuric acid is 55% ~ 75%.
5. the integral process of synthesizing acetyl tributyl citrate according to claim 1, is characterized in that: described (hydration) citric acid and the mol ratio of propyl carbinol are 1:3 ~ 7.
6. the integral process of synthesizing acetyl tributyl citrate according to claim 1, is characterized in that: the consumption of described catalyzer is (hydration) citric acid quality 0.2% ~ 1.0%.
7. the integral process of synthesizing acetyl tributyl citrate according to claim 1, is characterized in that: in step 3), described acetic anhydride is 1 ~ 2:1 with the mol ratio of (hydration) citric acid.
8. the integral process of synthesizing acetyl tributyl citrate according to claim 1, is characterized in that: in step 3), described aftertreatment comprises neutralization, washing and processed.
Priority Applications (1)
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| CN102701975A (en) * | 2012-04-11 | 2012-10-03 | 江苏雷蒙化工科技有限公司 | Improvement of process for synthesizing acetyl tri-n-butyl citrate by activated carbon supported sulfuric acid |
| WO2013170430A1 (en) * | 2012-05-14 | 2013-11-21 | 南京工业大学 | Process for synthesizing acetyl citrate |
| CN103316696B (en) * | 2013-07-03 | 2015-02-25 | 宁波永顺精细化工有限公司 | Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method |
| CN104803847B (en) * | 2015-03-05 | 2016-11-23 | 江苏雷蒙化工科技有限公司 | A kind of technique of composite solid acid catalysis synthesizing acetyl tributyl citrate |
| CN104744245A (en) * | 2015-03-25 | 2015-07-01 | 南京航空航天大学 | Integrated process of synthesizing acetyl tributyl citrate by using activated carbon immobilized p-toluenesulfonic acid catalyst |
| CN105749967A (en) * | 2016-04-06 | 2016-07-13 | 南宁市化工研究设计院 | Method for preparing tributyl citrate in presence of bamboo-charcoal-based solid sulfonic acid catalyst |
| CN108892613B (en) * | 2018-07-11 | 2021-02-19 | 广东轻工职业技术学院 | Method for synthesizing tri-n-butyl citrate by using acid modified H-ZMS-5 type molecular sieve |
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| CN101402571A (en) * | 2008-11-06 | 2009-04-08 | 河南庆安化工高科技股份有限公司 | Process for producing acet-tributyl citrate |
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