CN100404495C - Tributyl citrate preparation method using ion liquid catalysis - Google Patents
Tributyl citrate preparation method using ion liquid catalysis Download PDFInfo
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- CN100404495C CN100404495C CNB2005100865464A CN200510086546A CN100404495C CN 100404495 C CN100404495 C CN 100404495C CN B2005100865464 A CNB2005100865464 A CN B2005100865464A CN 200510086546 A CN200510086546 A CN 200510086546A CN 100404495 C CN100404495 C CN 100404495C
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- Prior art keywords
- citric acid
- ionic liquid
- tributyl citrate
- reaction
- butanols
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- 239000007788 liquid Substances 0.000 title claims abstract description 9
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 title claims description 46
- 238000006555 catalytic reaction Methods 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 4
- 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 114
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000002608 ionic liquid Substances 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 12
- HXLMUUQFILSEMW-UHFFFAOYSA-N C(CC)S(=O)(=O)O.S(=O)(=O)(O)O.N1=CC=CC=C1 Chemical compound C(CC)S(=O)(=O)O.S(=O)(=O)(O)O.N1=CC=CC=C1 HXLMUUQFILSEMW-UHFFFAOYSA-N 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- RAGVGXLZTQDOKB-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;tributyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC RAGVGXLZTQDOKB-UHFFFAOYSA-N 0.000 abstract 3
- 238000004821 distillation Methods 0.000 abstract 2
- 238000005191 phase separation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 241000282326 Felis catus Species 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a citric acid tributyl citrate preparing method using ion liquid catalysis, which discloses a method using ion liquid as a catalyst and the reaction of citric acid and butanol for synthesizing citric acid tributyl citrate. The present invention has the technical key point that the ion liquid is used for catalyzing the raw materials of the citric acid tributyl citrate and the butanol for completing esterification reaction. After the reaction is completed, the ion liquid can be recovered by using phase separation, and the fine distillation of pressure reduction is used for recovering excess butanol. The used ion liquid does not pollute the environment, has no obvious corrosiveness, and can be easily recovered and repeatedly used. The excess raw material of butanol can be separated and recovered by the fine distillation of pressure reduction. The conversion rate of the citric acid is high. The product can be conveniently recovered, and the operation is simple. The present invention is suitable for industrial application.
Description
Technical field
The invention belongs to the chemical material preparing technical field, relate to a kind of new preparation process of tributyl citrate.Present method is applicable to that with citric acid and butanols be raw material, the occasion of synthesizing citric acid tri-n-butyl.
Background technology
The systematic naming method of tributyl citrate is a 2-hydroxyl-1,2,3-three positive butoxy carbonyl propane, and English name is Tri-butylCltric, is called for short TBC, molecular formula is C
18H
32O
7, chemical structural formula is:
This product normal temperature is colourless transparent liquid down, and refractive index is 1.4428 (20 ℃), and is water insoluble, is a kind of non-toxic plasticizer.Can be used for polyethylene, polyvinyl chloride, the plasticising of polypropylene and various celluosic resins, it is good to have intermiscibility, the plasticizing efficiency height, nontoxic, advantages such as volatility is little, and after its plasticising, plastics low temperature flex performance is good, when sealing by fusing to thermally-stabilised, nondiscoloration, its winter hardiness, photostabilization, have excellent water-resistance, also can be used for packaging material for food and health care goods, and in resin, do not grow mould, mould resistance is arranged, the defoamer that also can be used as protein-based solution, U.S.'s approved is in packaging material for food, use in field such as toy and daily necessities, substitutes poisonous plasticizer phthalic acid dibutylester and the dioctyl phthalate (DOP) that tradition is used gradually.
China is world citric acid production big country, and annual production reaches 360,000 tons, and consumption only has 110,000 tons, and major part is used for outlet.Therefore, synthesizing of development tributyl citrate for the deep processing field of widening citric acid, has important practical significance undoubtedly for plastics industry provides new plasticizer.
Tributyl citrate is a raw material with citric acid and propyl carbinol usually, and acid catalyzed esterification is synthetic.Over nearly 10 years, Chinese scholar has been carried out number of research projects to this reaction system.The catalyzer of being studied comprises solid super-strong acid, acid-salt, and heteropolyacid and carried active carbon or resin etc. have been obtained partly progress.But, the preparation process complexity of solid catalyst, and in reaction process, because esterification has water to generate, cause loss of active component, thereby cause catalyst deactivation; Catalyzer and product separation process also cause the loss of catalyzer.Above problem has reduced reaction yield, has limited the production of tributyl citrate.
Summary of the invention
The objective of the invention is catalyst preparation process complexity at the prior art existence, active ingredient easily runs off, and with the difficult isolating shortcoming of product, a kind of transformation efficiency height of raw material citric acid is provided, catalyzer and product are easily separated, the product purity height, and can avoid loss of active component, the ionic liquid-catalyzed method for preparing tributyl citrate that selection can be repeatedly used.
Technical scheme of the present invention is as follows:
A kind of ionic liquid-catalyzed method for preparing tributyl citrate is characterized in that this method carries out as follows:
1) adopting citric acid and butanols is raw material, ionic liquid is a catalyzer, the mol ratio of used material is a citric acid: butanols: ionic liquid=1: 3～15: 0.1～1.5, realize esterification in the flow point water reactor next time at normal pressure, 70～200 ℃ of temperature of reaction, the reaction times is 0.5～16 hour; In the disposable adding ionic liquid of described citric acid and butanols, or in 0.1～2 hour, add in the ionic liquid continuously; Described ion liquid structure is represented with following general formula:
[M
+][N](I)
Positively charged ion [M in the formula
+] for containing the organic cation of one or more sulfonic acid groups, [N in the formula
-] be the negatively charged ion of following structure: BF
4 -, PF
6 -, CF
3SO
3 -, CH
3(C
6H
4) SO
3 -, Cl
-, HSO
4 -, NO
3 -, H
2PO
4 -, C
nH
2n+1COO
-, N (C
2F
5SO
2)
2 -, C (CF
3SO
2 -)
3 -, C
nH
2n+1SO
3 -Or CF
3CO
2 -
2) form two-phase system after reaction finishes, add phase product in the water washing, the mol ratio that adds entry and raw material citric acid is a citric acid: water=1: 0.1～5;
3) reaction is finished and wash after the light phase product in upper strata shift out, in the rectification under vacuum device, carry out rectification under vacuum, 80～200 ℃ of tower still temperature, 20～100 ℃ of tower top temperatures, vacuum tightness 0.01～0.09MPa, 0.5～8 hour time; Isolate unreacted butanols, and reclaim and use.
In the general formula of the ionic liquid structure described in the present invention, organic cation [M
+] comprise pyridylium, its structure as shown in the formula:
Comprise quaternary ammonium cation, its structure as shown in the formula:
Comprise quaternary phosphonium cations, its structure as shown in the formula:
Comprise glyoxaline cation, its structure as shown in the formula:
Wherein, R1, R2, R3, R4, R5, R6 is identical or different, and has following implication respectively, separately or jointly:
-H
-halogen
-alkyl (C
1-C
12), can partly or completely be replaced by group F, SO3H, Cl or OH group.
The raw materials used preferred molar ratio of the present invention is a citric acid: butanols: ionic liquid=1: 3～8: 0.1～0.5.Esterification reaction temperature described in the step 1) is preferably 100～160 ℃, and the reaction times is preferably 1～8 hour.Step 2) add phase product in the water washing after reaction finishes in, the preferred molar ratio that adds entry and raw material citric acid is a citric acid: water=1: 2～5.The lower floor's ionic liquid phase that produces after the water washing, not treated, return in the step 1) and reuse.
Carry out rectification under vacuum in the step 3) of the present invention in the rectification under vacuum device, the preferred temperature of tower still is 110～200 ℃ during rectification under vacuum, 20～50 ℃ of the preferred temperature of cat head, and preferred vacuum tightness is 0.01～0.05MPa, preferred 0.5～2 hour time.
The chemical principle of institute of the present invention foundation is as follows:
According to the method for preparing tributyl citrate provided by the invention, its key problem in technology is to adopt ionic liquid-catalyzed raw material tributyl citrate and butanols, finishes esterification, after reaction finishes, it is recyclable ionic liquid that utilization is separated, and utilizes rectification under vacuum to reclaim excessive butanols.Its advantage is: 1. adopt ionic liquid as catalyzer, and easy to prepare, stable to water, avoid the loss of active ingredient, can use repeatedly; 2. catalyzer and reaction product phase-splitting can be reclaimed ionic liquid very easily, and the following phase ionic liquid after the use need not to carry out any processing, can reuse repeatedly; 3. the transformation efficiency height of raw material citric acid, selectivity is good, the product purity height.The purity 90～99% of product tributyl citrate, the transformation efficiency 90～98% of citric acid.Selectivity 90～99%.Present method is a kind of efficient, the economic and environment amenable ionic liquid-catalyzed method for preparing tributyl citrate.
Embodiment
Embodiment 1
In the branch water refluxing reactor of 200ml, add pyridine sulfate propane sulfonic acid ionic liquid 2.02g (0.01mol) successively, citric acid 38.42g (0.20mol), butanols 44.47g (0.60mol) was 70 ℃ of stirring reactions 6 hours.After reaction finishes, add water 6.00g, the light phase in upper strata is separated in the washing back, at vacuum tightness 0.06MPa, under 120 ℃ of the tower still temperature, 40 ℃ of tower top temperatures, rectification under vacuum 2 hours, the cat head separation obtains remaining butanols 3.55g, tower kettle product 66.32g, and the tributyl citrate productive rate that calculates with citric acid is 92.0%.
Embodiment 2
In the branch water refluxing reactor of 200ml, add pyridine sulfate propane sulfonic acid ionic liquid 5.05g (0.025mol) successively, citric acid 57.63g (0.30mol), butanols 81.53g (1.10mol) was 200 ℃ of stirring reactions 0.5 hour.After reaction finishes, add water 12.00g, the light phase in upper strata is separated in the washing back, at vacuum tightness 0.01MPa, under 80 ℃ of the tower still temperature, 45 ℃ of tower top temperatures, rectification under vacuum 0.5 hour, the cat head separation obtains remaining butanols 18.83g, tower kettle product 101.64g, and the tributyl citrate productive rate that calculates with citric acid is 94.0%.
Embodiment 3
In the branch water refluxing reactor of 200ml, add pyridine sulfate propane sulfonic acid ionic liquid 8.08g (0.04mol) successively, citric acid 76.84g (0.40mol), butanols 133.42g (1.80mol) was 140 ℃ of stirring reactions 16 hours.After reaction finishes, add water 18.00g, the light phase in upper strata is separated in the washing back, at vacuum tightness 0.09MPa, under 140 ℃ of the tower still temperature, 20 ℃ of tower top temperatures, rectification under vacuum 0.5 hour, the cat head separation obtains remaining butanols 51.59g, tower kettle product 132.64g, and the tributyl citrate productive rate that calculates with citric acid is 92.0%.
Embodiment 4
In the branch water refluxing reactor of 200ml, add pyridine sulfate propane sulfonic acid ionic liquid 10.10g (0.05mol) successively, citric acid 28.81g (0.15mol), butanols 66.71g (0.90mol) was 130 ℃ of stirring reactions 5 hours.After reaction finishes, add water 12.00g, the light phase in upper strata is separated in the washing back, at vacuum tightness 0.04MPa, under 160 ℃ of the tower still temperature, 65 ℃ of tower top temperatures, rectification under vacuum 8 hours, the cat head separation obtains remaining butanols 34.02g, tower kettle product 52.98g, and the tributyl citrate productive rate that calculates with citric acid is 98.0%.
Embodiment 5
In the branch water refluxing reactor of 200ml, utilize isolated aqueous sulfuric acid pyridine propane sulfonic acid ionic liquid among the embodiment 4, amount to 24.15g, add citric acid 57.63g (0.30mol), butanols 177.88g (2.4mol) was 140 ℃ of stirring reactions 6 hours.After reaction finishes, add water 10.00g, the light phase in upper strata is separated in the washing back, at vacuum tightness 0.06MPa, under 200 ℃ of the tower still temperature, 45 ℃ of tower top temperatures, rectification under vacuum 6 hours, the cat head separation obtains remaining butanols 116.52g, tower kettle product 99.48g, and the tributyl citrate productive rate that calculates with citric acid is 92.0%.
Embodiment 6
In the branch water refluxing reactor of 200ml, utilize isolated aqueous sulfuric acid pyridine propane sulfonic acid ionic liquid among the embodiment 5 once more, amount to 20.50g, citric acid 76.84g (0.40mol), butanols 148.24g (2.00mol) was 130 ℃ of stirring reactions 3 hours.After reaction finishes, add water 14.00g, the light phase in upper strata is separated in the washing back, at vacuum tightness 0.07MPa, under 115 ℃ of the tower still temperature, 100 ℃ of tower top temperatures, rectification under vacuum 4 hours, the cat head separation obtains remaining butanols 64.63g, tower kettle product 135.52g, and the tributyl citrate productive rate that calculates with citric acid is 94.0%.
Claims (5)
1. ionic liquid-catalyzed method for preparing tributyl citrate is characterized in that this method carries out as follows:
1) adopting citric acid and butanols is raw material, pyridine sulfate propane sulfonic acid ionic liquid is a catalyzer, the mol ratio of used material is a citric acid: butanols: ionic liquid=1: 3～15: 0.1～1.5, realize esterification in the flow point water reactor next time at normal pressure, 70～200 ℃ of temperature of reaction, the reaction times is 0.5～16 hour; In the disposable adding ionic liquid of described citric acid and butanols, or in 0.1～2 hour, add in the ionic liquid continuously; Described ion liquid structure is as follows:
2) form two-phase system after reaction finishes, add the light phase product in water washing upper strata, the mol ratio that adds entry and raw material citric acid is a citric acid: water=1: 0.1～5;
3) reaction is finished and wash after the light phase product in upper strata shift out, in the rectification under vacuum device, carry out rectification under vacuum, tower still temperature is 110～200 ℃ during rectification under vacuum, 20～50 ℃ of tower top temperatures, vacuum tightness 0.01～0.05MPa, 0.5～2 hour time; Isolate unreacted butanols, and reclaim and use.
2. according to the described ionic liquid-catalyzed method for preparing tributyl citrate of claim 1, it is characterized in that: raw materials used mol ratio is a citric acid: butanols: ionic liquid=1: 3～8: 0.1～0.5.
3. according to the described ionic liquid-catalyzed method for preparing tributyl citrate of claim 1, it is characterized in that: esterification reaction temperature described in the step 1) is 100～160 ℃, and the reaction times is 1～8 hour.
4. according to the described ionic liquid-catalyzed method for preparing tributyl citrate of claim 1, it is characterized in that: step 2) in reaction add the light phase product in water washing upper strata after finishing, the mol ratio that adds entry and raw material citric acid is a citric acid: water=1: 2～5.
5. according to claim 1 or 4 described methods, it is characterized in that: the lower floor's ionic liquid phase that produces after the water washing, not treated, return in the step 1) and reuse.
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| CN100404495C true CN100404495C (en) | 2008-07-23 |
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| CN101172253B (en) * | 2006-10-31 | 2010-05-12 | 中国石油化工股份有限公司 | Esterification catalysts and esterification process of organic acid |
| CN101024612B (en) * | 2007-03-16 | 2010-11-17 | 广东工业大学 | Method for catalyzing alcohol acid esterization by acidic ion liquid |
| CN101024613B (en) * | 2007-03-16 | 2010-11-17 | 广东工业大学 | Method for catalyzing alochol acid esterization by sulfonic-acid-radical functionized ion liquid |
| GB201109684D0 (en) | 2011-06-10 | 2011-07-27 | Ecosynth Bvba | Zwitterionic compounds useful as catalysts for esterification reactions and processes for their production |
| CN102336661A (en) * | 2011-07-21 | 2012-02-01 | 北京旭阳化工技术研究院有限公司 | Preparation method of methyl propionate |
| CN108558662B (en) * | 2018-05-16 | 2021-05-07 | 浙江工业大学 | Method for catalytically synthesizing isopropyl palmitate by multi-sulfonic functional ionic liquid |
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