CN105669443A - Method of preparing tributyl citrate with nano-scale intercalated hydrotalcite catalyst - Google Patents
Method of preparing tributyl citrate with nano-scale intercalated hydrotalcite catalyst Download PDFInfo
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- CN105669443A CN105669443A CN201511012936.7A CN201511012936A CN105669443A CN 105669443 A CN105669443 A CN 105669443A CN 201511012936 A CN201511012936 A CN 201511012936A CN 105669443 A CN105669443 A CN 105669443A
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- tributyl citrate
- intercalated houghite
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- 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
Abstract
The invention discloses a method of preparing tributyl citrate with a nano-scale intercalated hydrotalcite catalyst. The method includes the steps of: A) material addition: adding the nano-scale intercalated hydrotalcite catalyst, citric acid, and excessive butyl alcohol into a container with uniform stirring; B) esterification reaction: heating the container in oil bath, and performing reflux condensation for separating water generated in the reaction, wherein the esterification reaction time is 6-10 h; C) purification, when the esterification reaction is finished, filtering the nano-scale intercalated hydrotalcite catalyst away, and neutralizing, water-washing, dealcoholizing and decoloring, and purifying reaction products to obtain the tributyl citrate. Through the method, the conversion rate on the citric acid is increased and the purity of the product is improved with the nano-scale intercalated hydrotalcite catalyst for producing the tributyl citrate. The whole catalytic reaction is easy to operate, the reaction temperature is easy to control, and the catalyst can be reused after filtration.
Description
Technical field
The present invention relates to chemical catalysis method, be specifically related to a kind of method utilizing hydrotalcite catalyst to prepare tributyl citrate.
Background technology
Tri-n-butyl citrate, chemical name 3-hydroxyl-3-carboxyl 1,3-propanedicarboxylic acid tributyl, is a kind of ester type compound, and water white transparency high boiling liquid is slightly soluble in water, dissolves each other with most organic solvents. Industrial general reaction with n-butyl alcohol by citric acid forms, and can be directly used for plasticizer, it is possible to be further processed into the plasticizer tributyl 2-acetylcitrate of function admirable. Tributyl citrate (TBC) nontoxic odorless, plasticizing efficiency is high, it is widely used in the fields such as packaging material for food, medical apparatus, toy for children and personal hygiene article, becomes " green " substitute products of phthalic ester plasticizer, have wide market prospect.
In commercial production, citric acid generates tributyl citrate with n-butyl alcohol at catalyst and effect under water preparation exists of holding under the arm, obtains product through operations such as dealcoholysis, neutralization, washing, stripping, decolouring, filter pressings. Conventional catalyst is inorganic or organic acid, and holding water preparation under the arm is n-butyl alcohol itself.
The catalyst adopted in conventional synthesis TBC method mostly is concentrated sulphuric acid, and the method exists that esterifying efficiency is low, equipment corrosion serious, easily produces side reaction and produce the shortcomings such as substantial amounts of acid waste water, contaminated environment. In recent years, the catalyst finding replacement concentrated sulphuric acid has become the focus in commercial production research.
" new method of Catalytic Synthesis of Tri-n-butyl Citrate " (Zheng Yu, Wang Jiye, Tan Mingchuan, Zheng Shiqing, " organic chemical industry and catalysis ", in April, 2004) literary composition have studied the reaction with butyl titanate for catalyst synthesizing citric acid tributyl.
The domestic article also having some research solid acid catalyst synthesizing citric acid tributyls at present, if Period In Maoming institute chemistry and Life Science College Qiao Yan brightness etc. are at solid super-strong acid S2O8 2-/SnO2-SiO2Catalysis under, with citric acid and the n-butyl alcohol tributyl citrate that has been Material synthesis. Changjiang University's chemistry with Environmental Engineering School in soldier river etc. with complex solid superacid SO4 2-/ZrO2-TiO2Synthesize tributyl citrate for catalyst, investigate the impact on reaction of catalyst amount, rate of charge and reaction end temperature.
But in above-mentioned numerous researchs all rare have utilize polyacid to be inserted into hydrotalcite catalyst to carry out the research of catalytic citric acid tributyl.
Hydrotalcite intercalation material (LDHs) is the novel nano inorganic functional material that a class has layer structure, and it is similar to that shepardite, and composition formula can be expressed as: [M2+ 1-xM3+ x(OH)2]x+(An-) x/n mH2O, wherein M2+And M3+The respectively metal cation of bivalence and trivalent in laminate, as: Mg2+、Ni2+、Co2+、Zn2+、Cu2+And Al3+、Cr3+、Fe3+Deng; An-It is interlayer anion, as: CO3 2-、NO3 -、Cl-、OH-、SO4 2-、PO4 3-、C6H4(COO)2 2-, heteropolyanion etc.; X is M3+/ (M2++M3+) molar ratio, its value is typically between 0.1~0.5; M is the number of intermediary water molecule. Metal cation on LDHs laminate, due to the impact by the minimum effect of lattice energy and lattice orientation effect thereof, is uniformly distributed in a certain way on laminate so that in the construction unit that on laminate, each is small, and its chemical composition and structure is constant. Simultaneously, being positioned at the divalent metal on laminate can in certain proportion scope by the close trivalent metal cation isomorphous substitution of ionic radius, the Modulatory character of this chemical composition and the microscopic uniformity of structure so that it is become composite structure and form the good precursor material of uniform metal composite oxide.
Polyacid compound is the poly-metal deoxide that a class contains the metals such as V, Mo, W. Being same polyanionic by what oxyacid radical ion condensation of the same race was formed, isopolyacid is in its acid. Being heteropolyanion by what different types of oxygen-containing acid group anionic condensation was formed, heteropoly acid is in its acid. The atom being currently known nearly 70 kinds of elements can as the hetero atom in heteropoly acid, including whole First Series transition elements, second and third series transition elements most, adds B, Al, Ga, Si, Ge, Sn, P, As, Sb, Bi, Se, Te, I etc. And every kind of hetero atom often can different valence state be present in heteropolyanion, so kind is quite various.
Polyacid intercalation hydrotalcite catalyst is as active high with selectivity, the advantage such as corrosivity is little and reaction condition is gentle of catalyst, but its reaction condition is bad to be groped, in present specification namely novelty utilize polyacid intercalation hydrotalcite catalyst to carry out catalytic reaction to prepare tributyl citrate.
Summary of the invention
The present invention is based on the analysis of the production method of tributyl citrate of the prior art, and the research of polyacid intercalation hydrotalcite catalyst performance, creationary proposition utilizes polyacid intercalation hydrotalcite catalyst to carry out the production of catalytic citric acid tributyl, and grope concrete working condition, the preparation method obtaining maturation. This preparation method can effectively carry out the production to tributyl citrate, final products finished product colourity is in 5#-10#(Pt-Co colorimetry), citric acid conversion ratio >=99%, compared with the production method of the tributyl citrate of prior art, has significant technological progress.
For realizing said method, technical scheme disclosed by the invention is as follows:
A kind of method of nanoscale intercalated houghite catalyst preparing tributyl citrate, comprises the steps:
Step a, reinforced: addition nanoscale intercalated houghite catalyst, citric acid, excessive butanol toward container in, stir;
Step b, esterification: oil bath is heated, the water that condensing reflux separating reaction generates; The time of esterification is 6h-10h;
Step c, purification: after reaction to be esterified terminates, filter nanoscale intercalated houghite catalyst, is then passed through neutralization, washing, dealcoholysis decolouring, purification step obtain finished lemon/lime acid tributyl.
Preferably, time reinforced in step a, the mol ratio of citric acid and butanol is 1:(4-6).
Preferably, described citric acid is 1:(0.03 ~ 0.05 with the mass ratio of nanoscale intercalated houghite catalyst).
Preferably, in step b, oil bath is heated, and maintains reaction temperature between 130-140 DEG C.
Preferably, in step c, esterification terminates rear system and is cooled in 75-80 DEG C of backward container and adds 5-10%Na2CO3Solution is neutralized reaction, controls system pH=8 ~ 9; Neutralization reaction performs twice at.
Preferably, described nanoscale hydrotalcite catalyst is introducing the 3rd metal component M in brucite laminate, improves carrier acid-resisting, and it consists of MMgAl-LDHs type intercalation catalyst. In the present invention, the 3rd described metal component M is Zn.
Preferably, described nanoscale intercalated houghite catalyst is the one of the magnesium aluminum-hydrotalcite of polyacid intercalation, zinc-aluminum hydrotalcite.
Preferably, the chemical formula of the anion of described polyacid is [XM11CoO39]n-, wherein X=P or Si; M=W or Mo; N is valence number, n=5-6.
By introducing the 3rd metal component M in brucite laminate in the present invention, improving carrier acid-resisting, it consists of MMgAl-LDHs type intercalation catalyst; And this MMgAl-LDHs type intercalation catalyst is nm-class catalyst, it is ensured that the accessibility of dispersion, reactant and substrate.
In the present invention, nanoscale intercalation catalyst is reusable edible after filtering, and activating component not easily runs off, long service life.
The present invention utilizes nanoscale intercalated houghite catalyst preparing tributyl citrate, after catalyst completes in the reaction, can reuse after filtration, compared with liquid catalyst, not only convenient recovery uses, and eliminate remove impurity operation, and avoid the possible side reaction brought in liquid catalyst.
The invention has the beneficial effects as follows: the employing nanoscale intercalated houghite of the invention does catalyst preparing tributyl citrate, not only increase citric acid conversion ratio >=99%, and the product purity prepared is higher, finished product colourity is 5#-10#(Pt-Co colorimetry); And whole catalytic reaction is easily operated, temperature is easily controllable, and catalyst may filter that rear Reusability, is greatly saved cost, improves production efficiency.
Detailed description of the invention
Below presently preferred embodiments of the present invention is described in detail, so that advantages and features of the invention can be easier to be readily appreciated by one skilled in the art, thus protection scope of the present invention being made apparent clear and definite defining.
Embodiment 1: a kind of method of nanoscale intercalated houghite catalyst preparing tributyl citrate, comprises the steps:
Step a, reinforced: addition nanoscale intercalated houghite catalyst, citric acid, excessive butanol toward container in, stir; Time reinforced, the mol ratio of citric acid and butanol is 1:(4-6); The mass ratio of citric acid and nanoscale intercalated houghite catalyst is 1:(0.03 ~ 0.05);
Step b, esterification: oil bath is heated, maintain reaction temperature between 130-140 DEG C; The water that condensing reflux separating reaction generates; The time of esterification is 6h-10h;
Step c, purification: after reaction to be esterified terminates, filter nanoscale intercalated houghite catalyst, is then passed through neutralization, washing, dealcoholysis decolouring, purification step obtain finished lemon/lime acid tributyl.
Nanoscale hydrotalcite catalyst described in the present embodiment is introducing the 3rd metal component M in brucite laminate, improves carrier acid-resisting, and it consists of MMgAl-LDHs type intercalation catalyst;Described nanoscale intercalated houghite catalyst is the one of the magnesium aluminum-hydrotalcite of polyacid intercalation, zinc-aluminum hydrotalcite.
Embodiment 2: the present embodiment and embodiment 1 are different in that, in the present embodiment, in step c, it is the Na of 5-10% that esterification terminates that rear system be cooled in 75-80 DEG C of backward container to add mass fraction2CO3Solution is neutralized reaction, controls system pH=8 ~ 9; Neutralization reaction performs twice at.
Embodiment 3: the present embodiment and embodiment 1 are different in that, in the present embodiment, the chemical formula of the anion of described polyacid is [XM11CoO39]n-, wherein X=P or Si; M=W or Mo; N is valence number, n=5-6.
Embodiment 4:A kind of method of nanoscale intercalated houghite catalyst preparing tributyl citrate, comprises the steps:
Step a, reinforced: addition nanoscale intercalated houghite catalyst, citric acid, excessive butanol toward container in, stir; Time reinforced, the mol ratio of citric acid and butanol is 1:4; The mass ratio of citric acid and nanoscale intercalated houghite catalyst is 1:0.03;
Step b, esterification: oil bath is heated, maintain reaction temperature between 135-140 DEG C; The water that condensing reflux separating reaction generates; The time of esterification is 6h;
Step c, purification: after reaction to be esterified terminates, filter nanoscale intercalated houghite catalyst, is then passed through neutralization, washing, dealcoholysis decolouring, purification step obtain finished lemon/lime acid tributyl;
Nanoscale hydrotalcite catalyst described in the present embodiment is introducing the 3rd metal component Zn in brucite laminate, improves carrier acid-resisting, and it consists of ZnMgAl-LDHs type intercalation catalyst; The chemical formula of the anion of the polyacid wherein adopted in polyacid intercalation in this nanoscale intercalated houghite catalyst is [PW11CoO39]5-。
Final products finished product colourity is in 8#-10#(Pt-Co colorimetry), citric acid conversion ratio >=99%, finished product acid number≤0.02%.
Embodiment 5:A kind of method of nanoscale intercalated houghite catalyst preparing tributyl citrate, comprises the steps:
Step a, reinforced: addition nanoscale intercalated houghite catalyst, citric acid, excessive butanol toward container in, stir; Time reinforced, the mol ratio of citric acid and butanol is 1:5; The mass ratio of citric acid and nanoscale intercalated houghite catalyst is 1:0.04;
Step b, esterification: oil bath is heated, maintain reaction temperature between 130-135 DEG C; The water that condensing reflux separating reaction generates; The time of esterification is 8h;
Step c, purification: after reaction to be esterified terminates, filter nanoscale intercalated houghite catalyst, is then passed through neutralization, washing, dealcoholysis decolouring, purification step obtain finished lemon/lime acid tributyl.
The chemical formula of the anion of the polyacid wherein adopted in polyacid intercalation in this nanoscale intercalated houghite catalyst is [SiMo11CoO39]6-;
Final products finished product colourity is in 5#-8#(Pt-Co colorimetry), citric acid conversion ratio >=99%, finished product acid number≤0.03%.
Embodiment 6:A kind of method of nanoscale intercalated houghite catalyst preparing tributyl citrate, comprises the steps:
Step a, reinforced: addition nanoscale intercalated houghite catalyst, citric acid, excessive butanol toward container in, stir; Time reinforced, the mol ratio of citric acid and butanol is 1:6; The mass ratio of citric acid and nanoscale intercalated houghite catalyst is 1:0.05;
Step b, esterification: oil bath is heated, maintain reaction temperature between 135-140 DEG C;The water that condensing reflux separating reaction generates; The time of esterification is 10h;
Step c, purification: after reaction to be esterified terminates, filter nanoscale intercalated houghite catalyst, is then passed through neutralization, washing, dealcoholysis decolouring, purification step obtain finished lemon/lime acid tributyl.
The chemical formula of the anion of the polyacid wherein adopted in polyacid intercalation in this nanoscale intercalated houghite catalyst is [SiW11CoO39]6-;
Final products finished product colourity is in 5#-10#(Pt-Co colorimetry), citric acid conversion ratio >=99%, finished product acid number≤0.02%.
Embodiment 7:A kind of method of nanoscale intercalated houghite catalyst preparing tributyl citrate, comprises the steps:
Step a, reinforced: addition nanoscale intercalated houghite catalyst, citric acid, excessive butanol toward container in, stir; Time reinforced, the mol ratio of citric acid and butanol is 1:6; The mass ratio of citric acid and nanoscale intercalated houghite catalyst is 1:0.04;
Step b, esterification: oil bath is heated, maintain reaction temperature between 135-140 DEG C; The water that condensing reflux separating reaction generates; The time of esterification is 9h;
Step c, purification: after reaction to be esterified terminates, filter nanoscale intercalated houghite catalyst, is then passed through neutralization, washing, dealcoholysis decolouring, purification step obtain finished lemon/lime acid tributyl.
The chemical formula of the anion of the polyacid wherein adopted in polyacid intercalation in this nanoscale intercalated houghite catalyst is [PMo11CoO39]6-;
Final products finished product colourity is in 5#-9#(Pt-Co colorimetry), citric acid conversion ratio >=99%, finished product acid number≤0.01%.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalent structure utilizing description of the present invention to make or equivalence flow process conversion; or directly or indirectly it is used in other relevant technical fields, all in like manner include in the scope of patent protection of the present invention.
Claims (8)
1. the method for a nanoscale intercalated houghite catalyst preparing tributyl citrate, it is characterised in that comprise the steps:
Step a, reinforced: addition nanoscale intercalated houghite catalyst, citric acid, excessive butanol toward container in, stir;
Step b, esterification: oil bath is heated, the water that condensing reflux separating reaction generates; The time of esterification is 6h-10h;
Step c, purification: after reaction to be esterified terminates, filter nanoscale intercalated houghite catalyst, is then passed through neutralization, washing, dealcoholysis, decolouring, purification step obtain finished lemon/lime acid tributyl.
2. the method for nanoscale intercalated houghite catalyst preparing tributyl citrate according to claim 1, it is characterised in that time reinforced in step a, the mol ratio of citric acid and butanol is 1:(4-6).
3. the method for nanoscale intercalated houghite catalyst preparing tributyl citrate according to claim 1, it is characterised in that the mass ratio of described citric acid and nanoscale intercalated houghite catalyst is 1:(0.03 ~ 0.05).
4. the method for nanoscale intercalated houghite catalyst preparing tributyl citrate according to claim 1, it is characterised in that in step b, oil bath is heated, and maintains reaction temperature between 130-140 DEG C.
5. the method for nanoscale intercalated houghite catalyst preparing tributyl citrate according to claim 1, it is characterised in that in step c, esterification terminate rear system be cooled in 75-80 DEG C of backward container add mass fraction be the Na of 5-10%2CO3Solution is neutralized reaction, controls system pH=8 ~ 9;Neutralization reaction performs twice at.
6. the method for nanoscale intercalated houghite catalyst preparing tributyl citrate according to claim 1, it is characterized in that, described nanoscale hydrotalcite catalyst is introducing the 3rd metal component M in brucite laminate, improving carrier acid-resisting, it consists of MMgAl-LDHs type intercalation catalyst.
7. the method for nanoscale intercalated houghite catalyst preparing tributyl citrate according to claim 6, it is characterised in that described nanoscale intercalated houghite catalyst is the one of the magnesium aluminum-hydrotalcite of polyacid intercalation, zinc-aluminum hydrotalcite.
8. the method for nanoscale intercalated houghite catalyst preparing tributyl citrate according to claim 7, it is characterised in that the chemical formula of the anion of described polyacid is [XM11CoO39]n-, wherein X=P or Si; M=W or Mo; N is valence number, n=5-6.
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Publication number | Priority date | Publication date | Assignee | Title |
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CN106366009A (en) * | 2016-08-26 | 2017-02-01 | 安徽金邦医药化工有限公司 | Preparation method of chemical intermediate benzocaine |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1762969A (en) * | 2005-09-28 | 2006-04-26 | 华东师范大学 | Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst |
CN101092360A (en) * | 2007-07-03 | 2007-12-26 | 华东师范大学 | Method for catalyzing and synthesizing tri-butyl citrate from methylal naphthalene sulfonic acid |
CN101391957A (en) * | 2008-11-05 | 2009-03-25 | 江南大学 | Method for preparing tributyl citrate by using rare-earth salt binary complex type solid acid as catalyst |
CN102320970A (en) * | 2011-06-10 | 2012-01-18 | 四川大学 | With the modified cation-exchange resin is the method for Preparation of Catalyst tributyl citrate |
CN102584591A (en) * | 2011-12-23 | 2012-07-18 | 蚌埠丰原医药科技发展有限公司 | Method for preparing tributyl citrate through diatomite immobilized titanium sulfate used as catalyst |
CN103706403A (en) * | 2013-12-23 | 2014-04-09 | 北京化工大学 | Application of polyacid intercalated hydrotalcite catalyst in preparing glyceryl triacetate |
CN104447306A (en) * | 2014-10-23 | 2015-03-25 | 西安元创化工科技股份有限公司 | Method for synthesizing tributyl citrate |
CN104437637A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Epoxy resin loaded phosphotungstic acid catalyst as well as preparation method and application thereof |
-
2015
- 2015-12-31 CN CN201511012936.7A patent/CN105669443A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1762969A (en) * | 2005-09-28 | 2006-04-26 | 华东师范大学 | Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst |
CN101092360A (en) * | 2007-07-03 | 2007-12-26 | 华东师范大学 | Method for catalyzing and synthesizing tri-butyl citrate from methylal naphthalene sulfonic acid |
CN101391957A (en) * | 2008-11-05 | 2009-03-25 | 江南大学 | Method for preparing tributyl citrate by using rare-earth salt binary complex type solid acid as catalyst |
CN102320970A (en) * | 2011-06-10 | 2012-01-18 | 四川大学 | With the modified cation-exchange resin is the method for Preparation of Catalyst tributyl citrate |
CN102584591A (en) * | 2011-12-23 | 2012-07-18 | 蚌埠丰原医药科技发展有限公司 | Method for preparing tributyl citrate through diatomite immobilized titanium sulfate used as catalyst |
CN103706403A (en) * | 2013-12-23 | 2014-04-09 | 北京化工大学 | Application of polyacid intercalated hydrotalcite catalyst in preparing glyceryl triacetate |
CN104447306A (en) * | 2014-10-23 | 2015-03-25 | 西安元创化工科技股份有限公司 | Method for synthesizing tributyl citrate |
CN104437637A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Epoxy resin loaded phosphotungstic acid catalyst as well as preparation method and application thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106366009A (en) * | 2016-08-26 | 2017-02-01 | 安徽金邦医药化工有限公司 | Preparation method of chemical intermediate benzocaine |
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