CN102285882B - Method for synthesizing acetyl tributyl citrate (ATBC) by adopting composite ionic liquid catalyst - Google Patents
Method for synthesizing acetyl tributyl citrate (ATBC) by adopting composite ionic liquid catalyst Download PDFInfo
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- 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 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000002608 ionic liquid Substances 0.000 title abstract description 3
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 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 63
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005886 esterification reaction Methods 0.000 claims abstract description 47
- 230000032050 esterification Effects 0.000 claims abstract description 45
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 239000002918 waste heat Substances 0.000 claims abstract description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 51
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- 238000003786 synthesis reaction Methods 0.000 claims description 23
- 238000005917 acylation reaction Methods 0.000 claims description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000021736 acetylation Effects 0.000 abstract 2
- 238000006640 acetylation reaction Methods 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 24
- -1 compound ion Chemical class 0.000 description 20
- 238000001514 detection method Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 230000009466 transformation Effects 0.000 description 9
- 239000004902 Softening Agent Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004042 decolorization Methods 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000004134 energy conservation Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013316 zoning Methods 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- PESZCXUNMKAYME-UHFFFAOYSA-N Citroflex A-4 Chemical class CCCCOC(=O)CC(O)(C(=O)OCCCC)C(C(C)=O)C(=O)OCCCC PESZCXUNMKAYME-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for synthesizing acetyl tributyl citrate (ATBC) by adopting a composite ionic liquid catalyst. The method is characterized by comprising the following steps: firstly carrying out esterification on citric acid and n-butyl alcohol which serve as raw materials in the presence of the catalyst, after esterification is qualified, directly utilizing the waste heat to reduce pressure and eliminate alcohol in a reaction kettle to obtain a crude product of tributyl citrate containing the catalyst, then carrying out acetylation and finally carrying out deacidification, standing, cooling, catalyst separation, neutralization, washing and reduced pressure distillation, thus obtaining the colorless transparent liquid ATBC without decoloration and pressure filtration. The method has the following advantages: the same amount of the same catalyst is used in esterification and acetylation, thus realizing reuse of the catalyst; the conversion rate is high, the by-products are few and the yield is more than 98%; aftertreatment is simple and convenient, excessive alkaline water for neutralization and washing is not needed, the washing clear water can be reused and no pollutants are discharged; and the reaction temperature is low, the production period is short, the equipment investment is low, the energy consumption is low, and the cost is low.
Description
Technical field
The present invention relates to efficient energy-saving, the new cleanproduction process of a kind of compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate (hereinafter to be referred as ATBC).
Technical background
At present, in whole softening agent extended familys, the softening agent kind of consumption maximum is adjacent benzene class softening agent, account for about 70% of whole market consumption, it is reported domesticly to account for about 90% especially, but existingly discover that in a large number some plasticising has its potential carinogenicity in this a series of softening agent, really can bring out animal teratogenesis, mutagenesis and even death, abroad strict its use of control.China has also worked out relevant laws and rules, will progressively eliminate phthalate and use at aspects such as packaging material for food, medical apparatus, toy for children and personal hygiene articles.Therefore, the Application Areas of conventional plasticizers will be restricted, and recommend use the novel green softening agent, and ATBC (ATBC) is one of softening agent kind of using always the most, also be one of universally acknowledged the safest softening agent.
ATBC (ATBC) has advantages such as tasteless, that intermiscibility good, oil-proofness good, plasticizing efficiency is high, volatility is little as a kind of non-toxic plasticizer, and its photostabilization, winter hardiness and have excellent water-resistance also have mould resistance.After its plasticising, the plastics cold flexibility is good, thermally-stabilised when molten envelope, nondiscoloration.ATBC (ATBC), because its hydroxyl seals by ethanoyl, so its volatility and water sensitivity are further improved.On the plasticising performance, ATBC (ATBC) is the most similar with dimixo-octyl phthalate (DOP), fully alternative traditional phthalic ester plasticizer.Abroad, citrate has been realized suitability for industrialized production as the PVC softening agent, obtained good application, and China starts late, and develops unsatisfactoryly, has only a spot of suitability for industrialized production and application.This mainly is that the catalysis synthesizing technology level is not high, causes that byproduct of reaction is many, yield is low, production cost is high, causes product price to be lacked competitiveness.In addition, because factor such as the marketing dynamics is limited causes share of market not, domestic environment-friendly plasticizer new variety also do not form market scale in addition.
The production technique of tradition synthesis of acetyl tri-n-butyl citrate (ATBC) is to be raw material with citric acid and propyl carbinol; under catalyzer (vitriol oil or other) effect through esterification; neutralization; washing; the decompression dealcoholysis; operations such as decolorization filtering make tri-n-butyl citrate (TBC); be raw material with tri-n-butyl citrate (TBC) and acetic anhydride again; through acetylize; depickling; neutralization; washing; dry; operations such as decolorization filtering make lemon ATBC (ATBC) finished product; this technical process as shown in Figure 1; make catalyzer with the vitriol oil; though its cost is low; catalytic activity is higher, but complex technical process; equipment corrosion is serious; reaction time is long; facility investment is big; reaction preference is poor; quality product is low; the cost height; product colour is dark; by product makes the post-processing operation complexity more; wastewater flow rate is big; a series of shortcomings such as environmental pollution is serious.
In recent years, Application and Development toluenesulphonic acids, inorganic salt, thionamic acid, heteropolyacid and solid super-strong acid etc. replace the scientific research report increasing day by day of sulfuric acid catalyst synthesis of acetyl tri-n-butyl citrate (ATBC), but Shang Weijian successfully is used for industrial report.
For ATBC (ATBC) production technique, the problem of traditional technology is complex manufacturing, reaction time is long, product colour is dark, facility investment is big, seriously corroded, problems such as generation waste water is many, aftertreatment is complicated, contaminate environment, production cost height.
Therefore, for reach esterification, the acylation reaction temperature is low, the time is short, transformation efficiency is high, yield is high, non-pollutant discharge, the easy purpose of aftertreatment, save operations such as decolorization filtering, realize the repeated use of catalyzer, in recent years, research and development are used the scientific research report increasing day by day of replacement sulfuric acid catalysts such as toluenesulphonic acids, inorganic salt, thionamic acid, heteropolyacid, solid super-strong acid and ionic liquid and (are for example thanked " Speciality Petrochemicals " 1998 such as Wen Lei, 4:7-9; Deng Xuzhong etc. " fine chemistry industry " 2001,18 (2): 83-85; Mao Lixin etc. " Hunan Technology College's journal " 2005,18 (2): 36-38; CN101402571A such as Liu Bing; Yan Leng et al.Angew.Chem.Int.Ed.2009,48:168-171; Teng Junjiang etc. " Industrial Catalysis " 2010,18:67-70; Cai Zhuanhong, Zhengzhou University's master thesis " technological design of 500 tons of non-toxic plasticizer tributyl acetylcitrates of annual output " 2005; Wang Tao etc., 200810042466.2; Yang Jianguo etc., 200610024372.3, but Shang Weijian successfully is used for industrial report.The raising of aspects such as reaction conversion ratio, selectivity, catalytic activity, the product colour that obtains by these methods shoals, the minimizing of wastewater flow rate, catalyst recirculation use, environment protection can not be said so enough.
Summary of the invention
The purpose of this invention is to provide a kind of compound ion liquid catalyst and substitute tradition with efficient energy-saving, the cleaner production novel method of sulfuric acid catalyst synthesis of acetyl tri-n-butyl citrate (ATBC), obtain colourless transparent liquid ATBC (ATBC) product.
The object of the present invention is achieved like this: a kind of method that adopts the compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate; be that raw material drops into reactor with citric acid and propyl carbinol; under the effect of compound ion liquid catalyst, carry out esterification; after esterification is qualified; directly in this reactor, utilize waste heat decompression dealcoholysis; obtain containing the tri-n-butyl citrate crude product of catalyzer; carry out acetylization reaction then, carry out depickling at last, leave standstill, separating catalyst, neutralization, washing, underpressure distillation can obtain the colourless transparent liquid ATBC.
When carrying out esterification, the mol ratio of citric acid and propyl carbinol is 1: 3～6, and the catalytic amount that this process is added is 0.1～1.5% of citric acid quality, 50～110 ℃ of temperature of reaction, 2～3 hours reaction times; During acetylization reaction, containing the tri-n-butyl citrate crude product of catalyzer and the mol ratio of acetic anhydride is 1: 1.1～1.6,30～56 ℃ of temperature of reaction, 1～2 hour reaction times.
When carrying out esterification, the mol ratio of citric acid and propyl carbinol is 1: 4～6, preferred 1: 4～5.
When carrying out esterification, 60～100 ℃ of temperature of reaction, preferred 65～90 ℃.
Containing the tri-n-butyl citrate crude product of catalyzer and the mol ratio of acetic anhydride is 1: 1.2～1.6, preferred 1; 3～1.5.
During acetylization reaction, 35～55 ℃ of temperature of reaction, preferred 45～50 ℃.
Use equivalent catalyzer of the same race in described esterification, the acylation reaction, what adopt during acylation reaction is the catalyzer that adds in the esterification reaction process.
At least comprise a kind of in the compound ion liquid catalyst
Acidic ion liquid and at least a inorganic salt.
In the described compound ion liquid catalyst
Acidic ion liquid is a kind of in the following structural compounds:
Inorganic salt in the compound ion liquid catalyst are a kind of in the following compounds: NaHSO
4, NaH
2PO
4, KHSO
4, KH
2PO
4, ZnCl
2, CaCl
2, MgCl
2Or AlCl
3
In the compound ion liquid catalyst
The mole proportioning of acidic ion liquid and inorganic salt is 1: 0.5～1.
Beneficial effect of the present invention will be become clearer by following detailed description.
When carrying out esterification of the present invention, the composite catalyst that adds is by 0.1～1.5% of the citric acid quality, and more preferably 0.3～1.2%, most preferably 0.5～1.0%.When the amount of composite catalyst less than 0.1% the time, its shortcoming is that speed of reaction is too slow, transformation efficiency is low too.And the amount of working as composite catalyst is too big, and is especially greater than 1.5% o'clock, then uneconomical.
When carrying out esterification of the present invention, the material quantity that joins the reaction between above-mentioned citric acid and propyl carbinol is such, and namely based on 1 mole citric acid, the molar weight of propyl carbinol preferably is not less than 3 moles, and is preferred 3～6, more preferably 4～6, most preferably 4～5.When the add-on of propyl carbinol during less than 3 moles, the shortcoming of existence is, transformation efficiency reduces, and by product increases.And to get add-on too many when propyl carbinol, during especially greater than 5 moles, then uneconomical.
When carrying out esterification of the present invention, temperature of reaction is preferably 50～110 ℃ usually, and more preferably 60～100 ℃, most preferably 65～90 ℃.When temperature was lower than 50 ℃, its shortcoming was that speed of reaction is too slow, and transformation efficiency is low too, to such an extent as to can not reach the level of practical application.On the other hand, when temperature of reaction surpassed 110 ℃, its shortcoming was to form a large amount of by products.
When carrying out esterification of the present invention, 2～3 hours reaction times.
When carrying out acylation reaction of the present invention; the material quantity that joins the reaction between above-mentioned tri-n-butyl citrate and acetic anhydride is such; namely based on 1 mole tri-n-butyl citrate; the molar weight of acetic anhydride preferably is not less than 1.1 moles; preferred 1.1～1.6; more preferably 1.2～1.6, most preferably 1.3～1.5.When the add-on of acetic anhydride during less than 1.1 moles, the shortcoming of existence is, transformation efficiency reduces, and by product increases.And the add-on of working as acetic anhydride is too many, and is during especially greater than 1.6 moles, then uneconomical.
When carrying out acylation reaction of the present invention, temperature of reaction is preferably 30～60 ℃ usually, and more preferably 35～55 ℃, most preferably 45～50 ℃.When temperature was lower than 30 ℃, its shortcoming was that speed of reaction is too slow, and transformation efficiency is low too, to such an extent as to can not reach the level of practical application.On the other hand, when temperature of reaction surpassed 60 ℃, its shortcoming was to form a large amount of by products.
When carrying out acylation reaction of the present invention, in 1～2 hour reaction times, do not need to add in addition again compound ion liquid catalyst during this acetylization reaction.
Technology of the present invention has been saved the process that citric acid and propyl carbinol esterification in the traditional technology generate the tri-n-butyl citrate product, the qualified back of esterification (through liquid chromatographic detection), the dealcoholysis of directly in this reactor, reducing pressure, be the acetylization reaction that raw material carries out next step with the resultant tri-n-butyl citrate (thick product) that contains catalyzer then, utilize the waste heat dealcoholysis so on the one hand, than after neutralization in the traditional technology, the washing again dealcoholysis reduced energy consumption, saved operations such as neutralization after the esterification, washing, decolouring press filtration simultaneously; Reduced the loss of intermediates tri-n-butyl citrate in the treating process on the other hand, all treating processes are carried out after all concentrating on acetylization reaction.At first reaction system is cooled off, left standstill, make catalyzer and product ester layer AUTOMATIC ZONING, direct separating catalyst, the catalyzer of recovery is reusable; Through getting product after neutralization, washing, the drying, dispense with decoloration filters again.This technology is succinct, and facility investment is few, does not need excessive buck neutralization, does not need a large amount of water washings, has shortened the production cycle greatly, has reduced production cost and energy consumption, has also reduced the discharging of the three wastes simultaneously, energy-saving and emission-reduction, environmental friendliness.
The present invention with make catalyzer synthesis of acetyl tri-n-butyl citrate (ATBC) technology with sulfuric acid following advantage relatively arranged:
1, compound ion liquid catalyst, it is except having than the stronger acidity of inorganic acid, also has the ability that to carry out homogeneous reaction with the liquid organic raw material, and can in esterification, acylation reaction, use equivalent catalyzer of the same race (not needing to add again catalyzer during acylation reaction), catalyzer and product ester layer AUTOMATIC ZONING, separate simple, reusable;
2, synthesis technique is succinct, the transformation efficiency height, and the esterification selectivity is greater than 99%; Yield reaches more than 98%, and by product is few, dispense with decoloration filtration etc.
3, the synthesis technique aftertreatment is easy, does not need excessive buck neutralization and washing, and the washing clear water is reusable, non-pollutant discharge, and water consumption reduces 60%;
4, the synthesis technique temperature of reaction is low, makes the catalyst process temperature than traditional sulfuric acid and reduces by 50～60%; With short production cycle, reduce the entire production process time about 60%; Facility investment is few; Energy consumption is little, energy-conservation reaching more than 50%, and cost reduces about 20～30%; This energy saving technology is efficient, environmental protection.
To sum up, the applicant has selected the synthetic lemon ATBC (ATBC) of compound ion liquid catalyst, this technology has been saved operations such as neutralization after the traditional technology esterification, washing, decolorization filtering, reduced the loss of intermediates tri-n-butyl citrate (TBC) in the treating process, concentrate on neutralize behind the acetylization reaction, washing, decolorization filtering etc., use equivalent catalyzer of the same race (not needing to add again catalyzer during acylation reaction) in esterification, the acylation reaction, the washing clear water is reusable, and water consumption reduces about 60%; The transformation efficiency height, by product is few, and the esterification selectivity is greater than 99%, and yield reaches more than 98%; Aftertreatment is easy, and catalyzer is reusable through simple separation, non-pollutant discharge; Temperature of reaction is low, makes the catalyst process temperature than traditional sulfuric acid and reduces by 50～60%; With short production cycle, the minimizing time about 60%; Facility investment is few; Energy consumption is little, energy-conservation reaching more than 50%, and it is about 20～30% that cost reduces, and then conditions such as required catalyst levels, temperature of reaction, reaction times in the synthesis technique optimized, and realized efficient, energy-conservation, suitability for industrialized production cleanly.
Description of drawings
Fig. 1 is the technological process of production figure of former ATBC (ATBC).
Fig. 2 is the technological process of production figure of ATBC of the present invention (ATBC).
Fig. 3 is synthetic tributyl acetylcitrate (content 97.85%) liquid chromatogram of traditional sulfuric acid catalysis.Moving phase: 90% acetonitrile, 10% water; Flow velocity: 1ml/mi.
Fig. 4 is the liquid chromatogram of the tributyl acetylcitrate (content 99.6%) that catalyzes and synthesizes of compound ion liquid provided by the invention.Moving phase: 90% acetonitrile, 10% water; Flow velocity: 1ml/mi.
Embodiment
Principle of the present invention is as follows: at first; in the presence of compound ion liquid catalyst, carry out the esterification between citric acid and propyl carbinol; the transformation efficiency of this esterification is usually less than 100%; therefore; when feeding intake that butanols is excessive; when reaction finishes after the liquid chromatographic detection esterification is qualified; under this temperature; the dealcoholysis of directly in this reactor, reducing pressure; change the tri-n-butyl citrate (thick product) that obtains containing catalyzer over to the acetylization reaction still; and the acetic anhydride that adds corresponding proportioning reacts (not needing to add catalyzer during acetylization reaction) again; the qualified back of acetylization reaction (through liquid chromatographic detection) is carried out depickling again; leave standstill; separating catalyst; neutralization; washing; underpressure distillation can obtain colourless transparent liquid product ATBC (ATBC).
Below the step (this step is a feature of the present invention) of the acylation reaction between tri-n-butyl citrate (TBC) and acetic anhydride is carried out in explanation in the presence of compound ion liquid catalyst.
Acetic anhydride and tri-n-butyl citrate (TBC) carry out acylation reaction and generate ATBC, and its chemical equation is:
Used catalyzer is the compound ion liquid catalyst of equivalent of the same race when esterification, acylation reaction.
At least comprise a kind of in the compound ion liquid catalyst
Acidic ion liquid and at least a inorganic salt.
In the described compound ion liquid catalyst
Acidic ion liquid is a kind of in the following structural compounds:
Inorganic salt in the compound ion liquid catalyst are a kind of in the following compounds: NaHSO
4, NaH
2PO
4, KHSO
4, KH
2PO
4, ZnCl
2, CaCl
2, MgCl
2Or AlCl
3
In the compound ion liquid catalyst
The mol ratio of acidic ion liquid and inorganic salt is 1: 0.5～1.
With specific embodiment technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto.
Shown in Fig. 2 flow process: by the production technique of synthesis of acetyl tri-n-butyl citrate of the present invention; in the 1000L reaction kettle of the esterification, add the 250kg citric acid successively; the 528kg propyl carbinol; the 2kg composite catalyst stirs; feed thermal oil in the reacting kettle jacketing reaction mass is heated to 85 ℃; react 2.5 hours to esterification qualified (through liquid chromatographic detection); under this temperature; the dealcoholysis of directly in this reactor, reducing pressure; change over to and stir (this acetylization reaction does not need to add catalyzer) in the acetylization reaction still again obtaining containing the tri-n-butyl citrate crude product of catalyzer and 139kg acetic anhydride; feed thermal oil in the acidylate still chuck reaction mass is heated to 40 ℃; react 1.5 hours to acidylate qualified (through liquid chromatographic detection), carry out depickling again; leave standstill; neutralization; washing; underpressure distillation can obtain colourless transparent liquid ATBC (ATBC) product 459kg.Through liquid chromatographic detection, productive rate reaches 99.6%.Product performance index sees Table 1 and table 2.
In the 1000L reaction kettle of the esterification, add the 250kg citric acid successively; the 355kg propyl carbinol; 2.5kg catalyzer stirs; feed thermal oil in the reacting kettle jacketing reaction mass is heated to 50 ℃; react 3 hours to esterification qualified (through liquid chromatographic detection); change the tri-n-butyl citrate (thick product) and the 145kg acetic anhydride that obtain containing catalyzer in acetylization reaction still stirring (this acetylization reaction does not need to add catalyzer again); feed thermal oil in the acidylate still chuck reaction mass is heated to 30 ℃; react 2 hours to acidylate qualified (through liquid chromatographic detection); other processing condition obtain colourless transparent liquid product ATBC (ATBC) 455kg with embodiment 1.Through liquid chromatographic detection, productive rate reaches 99.4%.Product performance index sees Table 1 and table 2.
In the 1000L reaction kettle of the esterification, add the 300kg citric acid successively; the 475kg propyl carbinol; 3.6kg catalyzer stirs; feed thermal oil in the reacting kettle jacketing reaction mass is heated to 90 ℃; react 2.5 hours to esterification qualified (through liquid chromatographic detection); change the tri-n-butyl citrate (thick product) and the 200kg acetic anhydride that obtain containing catalyzer in acetylization reaction still stirring (this acetylization reaction does not need to add catalyzer again); feed thermal oil in the acidylate still chuck reaction mass is heated to 50 ℃; react 1 hour to acidylate qualified (through liquid chromatographic detection); other processing condition obtain colourless transparent liquid product ATBC (ATBC) 553kg with embodiment 1.Through liquid chromatographic detection, productive rate reaches 99.8%.Product performance index sees Table 1 and table 2.
In the 1000L reaction kettle of the esterification, add the 300kg citric acid successively; the 530kg propyl carbinol; 0.9kg catalyzer stirs; feed thermal oil in the reacting kettle jacketing reaction mass is heated to 110 ℃; react 2 hours to esterification qualified (through liquid chromatographic detection); change the tri-n-butyl citrate (thick product) and the 175kg acetic anhydride that obtain containing catalyzer in acetylization reaction still stirring (this acetylization reaction does not need to add catalyzer again); feed thermal oil in the acidylate still chuck reaction mass is heated to 60 ℃; react 2 hours to acidylate qualified (through liquid chromatographic detection); other processing condition obtain colourless transparent liquid product ATBC (ATBC) 548kg with embodiment 1.Through liquid chromatographic detection, productive rate reaches 99.3%.Product performance index sees Table 1 and table 2.
In the 2000L reaction kettle of the esterification, add the 600kg citric acid successively; the 950kg propyl carbinol; 3.6kg catalyzer stirs; feed thermal oil in the reacting kettle jacketing reaction mass is heated to 70 ℃; react 3 hours to esterification qualified (through liquid chromatographic detection); change the tri-n-butyl citrate (thick product) and the 380kg acetic anhydride that obtain containing catalyzer in acetylization reaction still stirring (this acetylization reaction does not need to add catalyzer again); feed thermal oil in the acidylate still chuck reaction mass is heated to 45 ℃; react 1.5 hours to acidylate qualified (through liquid chromatographic detection); other processing condition obtain colourless transparent liquid product ATBC (ATBC) 1105kg with embodiment 1.Through liquid chromatographic detection, productive rate reaches 99.5%.Product performance index sees Table 1 and table 2.
Table 1 product performance index
Table 2 tributyl acetylcitrate (ATBC) performance index
| Project | Performance index | Method |
| Colourity (Pt-Co)≤ | 30 | GB605-88 |
| Density (25 ℃) g/cm 3 | 1.04～1.06 | GB3728-91 |
| Content (%)＞ | 99.2 | High pressure lipuid chromatography (HPLC) |
| Acid number (mgKOH/g)＜ | 0.1 | GB12589-90 |
| Moisture (%)＜ | 0.1 | GB12589-90 |
| Heavy metal is (with Pb 3+Meter)＜ | 0.0001 | GB10668-89 |
With processing condition and the detection method of embodiment 3, the situation that the catalyzer recirculation is used sees Table 3.
Table 3
| Embodiment | Catalyzer reuse number of times | Productive rate (%) |
| 6 | 0 | 99.8 |
| 7 | 1 | 99.7 |
| 8 | 2 | 99.8 |
| 9 | 3 | 99.6 |
| 10 | 4 | 99.7 |
Claims (11)
1. method that adopts the compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate, it is characterized in that: be that raw material drops into reactor with citric acid and propyl carbinol, under the effect of compound ion liquid catalyst, carry out esterification, after esterification is qualified, directly in this reactor, utilize waste heat decompression dealcoholysis, obtain containing the tri-n-butyl citrate crude product of catalyzer, carry out acetylization reaction then, carry out depickling at last, leave standstill, separating catalyst, neutralization, washing, underpressure distillation can obtain the colourless transparent liquid ATBC, when carrying out esterification, the mol ratio of citric acid and propyl carbinol is 1:3～6, the catalytic amount that this process is added is 0.1～1.5% of citric acid quality, 50～110 ℃ of temperature of reaction, 2～3 hours reaction times; During acetylization reaction, containing the tri-n-butyl citrate crude product of catalyzer and the mol ratio of acetic anhydride is 1:1.1～1.6,30～56 ℃ of temperature of reaction, 1～2 hour reaction times; At least comprise a kind of in the described compound ion liquid catalyst
Acidic ion liquid and at least a inorganic salt; In the described compound ion liquid catalyst
Acidic ion liquid is a kind of in the following structural compounds:
Or
2. the method for employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate according to claim 1, it is characterized in that: when carrying out esterification, the mol ratio of citric acid and propyl carbinol is 1:4～6.
3. the method for employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate according to claim 1 and 2, it is characterized in that: when carrying out esterification, the mol ratio of citric acid and propyl carbinol is 1:4～5.
4. the method for employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate according to claim 1, it is characterized in that: when carrying out esterification, temperature of reaction is 60～100 ℃.
5. according to the method for claim 1 or 4 described employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate, it is characterized in that: when carrying out esterification, temperature of reaction is 65～90 ℃.
6. the method for employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate according to claim 1, it is characterized in that: containing the tri-n-butyl citrate crude product of catalyzer and the mol ratio of acetic anhydride is 1:1.2～1.6.
7. the method for employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate according to claim 1, it is characterized in that: during acetylization reaction, temperature of reaction is 35～55 ℃.
8. according to the method for claim 1 or 7 described employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate, it is characterized in that: during acetylization reaction, temperature of reaction is 45～50 ℃.
9. the method for employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate according to claim 1; it is characterized in that: use equivalent catalyzer of the same race in described esterification, the acylation reaction, what adopt during acylation reaction is the catalyzer that adds in the esterification reaction process.
10. the method for employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate according to claim 1 is characterized in that: the inorganic salt in the compound ion liquid catalyst are a kind of in the following compounds: NaHSO
4, NaH
2PO
4, KHSO
4, KH
2PO
4, ZnCl
2, CaCl
2, MgCl
2Or AlCl
3
11. the method for employing compound ion liquid catalyst synthesis of acetyl tri-n-butyl citrate according to claim 1 is characterized in that: in the compound ion liquid catalyst
The mol ratio of acidic ion liquid and inorganic salt is 1:0.5～1.
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| CN100579952C (en) * | 2007-09-17 | 2010-01-13 | 李祥庆 | Method for synthesizing acetyl tributyl citrate by using ion type catalyst |
| CN101348435A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Method for preparing tributyl citrate with ion liquid as catalyst |
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