CN106045850B - A kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate - Google Patents

A kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate Download PDF

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CN106045850B
CN106045850B CN201610376027.XA CN201610376027A CN106045850B CN 106045850 B CN106045850 B CN 106045850B CN 201610376027 A CN201610376027 A CN 201610376027A CN 106045850 B CN106045850 B CN 106045850B
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citrate
catalyst
catalyzing
synthesizing
composite mixed
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CN106045850A (en
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周喜
李泽贤
张超
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Shaoyang University
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Shaoyang University
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium

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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)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to a kind of methods that composite mixed phosphotungstate catalyzes and synthesizes citrate, and using composite mixed phosphotungstate as catalyst, esterification synthesizing citric acid ester occurs by citric acid and fatty alcohol.The skeleton symbol for the composite mixed phosphotungstate that the present invention uses are as follows: (NH4)xAl(3‑x‑y)/3HyPW12O40, wherein x=0.4 ~ 1.1, y=0.4 ~ 1.1.Method advantage provided by the invention is that catalyst is low in cost, easily prepared, and high catalytic efficiency, and the separation of catalyst and product is simple, and catalyst repeat performance is excellent.

Description

A kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate
Technical field
The present invention relates to a kind of method of synthesizing citric acid ester, in particular to a kind of composite mixed phosphotungstate catalyzes and synthesizes The method of citrate.
Background technique
Citrate is a kind of widely used nontoxic plasticizer, it has nontoxic, and volatility is small, and plasticizing efficiency is high and phase The advantages that capacitive is good.As traditional one of green substitute of phthalic ester plasticizer, U.S.'s food and drug prison It superintends and directs management board and has been approved by and citric acid ester plasticizer is applied to packaging material for food, medical apparatus and personal hygiene article etc. Aspect.In recent years, citric acid ester type has become environment-friendlyplasticizer plasticizer both at home and abroad first.
In the traditional processing technology of citrate, mainly use the concentrated sulfuric acid for catalyst.The concentrated sulfuric acid it is cheap, and Catalytic activity is higher.However, the by-product of reaction is more, bigger difficulty is caused to the separating-purifying of product.In addition, sulfuric acid pair Equipment seriously corroded, and a large amount of acid-bearing wastewaters are generated, cause serious environmental pollution.In order to overcome disadvantages described above, grind both at home and abroad The person of studying carefully develops a series of solid acid catalysts for synthesizing citric acid ester, such as molecular sieve, solid super-strong acid, inorganic salts, sun Ion exchange resin and heteropoly acid etc..Wherein, heteropoly acid has the characteristics that green non-poisonous, activity and selectivity is high, is widely applied In the reaction of synthesizing citric acid ester.However, heteropoly acid is there is also being soluble in, polar reaction medium, specific surface area be low and thermostabilization The problems such as property is poor.Solution to the problems described above is that heteropoly acid is immobilized or is transformed into the catalysis of insoluble heteropoly acid salt Agent.Compared with carried heteropoly acid, heteropoly acid salt is strong with acidity, surface acidity center density is high and easily prepared etc. excellent Gesture, be it is a kind of obtain the heavy duty detergent solid acid catalyst of extensive concern, as aluminium phosphotungstic acid (old equality, Industrial Catalysis, 2007, 15,46-49), 1- (3- sulfonic group) propyl -3- methylimidazole phosphotungstate (Yu Shengjian etc., Industrial Catalysis, 2012,20, 52-55) etc. heteropolyacid salt catalysts have been applied in the reaction system of synthesizing citric acid ester.However, above-mentioned heteropoly acid salt There is the defects of activity is not high, preparation process is complicated, dosage is larger or repeat performance is poor in catalyst.
105061204 A of CN uses molecular formula for (NH4)xAgyH3-x-yPW12O40(x=0.3~0.8, y=0.3~0.8) Ammonium, the composite mixed phosphotungstate of silver catalyze and synthesize citrate, the activity of catalyst is higher than traditional single type ion doping Phosphotungstic acid, the high income of product, catalyst is easily separated, and repeat performance is preferable.However, making since the price of silver is higher Its application is restricted.Therefore, exploitation is suitable for the cheap, efficient, stable and easily prepared of industrialized production citrate Solid acid catalyst is those skilled in the art's technical problem in the urgent need to address.
Summary of the invention
The purpose of the present invention is to provide a kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate, this method The advantages such as low with production cost, efficient and environmentally friendly.
The method that composite mixed phosphotungstate provided by the invention catalyzes and synthesizes citrate, with composite mixed phosphotungstate For catalyst, esterification synthesizing citric acid ester, the structure of the composite mixed phosphotungstate are occurred by citric acid and fatty alcohol Skeleton symbol are as follows: (NH4)xAl(3-x-y)/3 HyPW12O40, wherein x=0.4 ~ 1.1, y=0.4 ~ 1.1.
Further, the fatty alcohol is C4~C16Linear chain or branched chain fatty alcohol, more preferably n-butanol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-octyl alcohol, Decanol or laruyl alcohol.
Further, the composite mixed phosphotungstate catalyst preparation process comprising steps of
(1) ammonium salt, aluminium salt and phosphotungstic acid are mixed in solution；
(2) the isolated composite mixed phosphotungstate after reacting.
Further, the step (1) specifically:
Aluminium salt is added in the aqueous solution of phosphotungstic acid；
Ammonium salt is added in aforementioned mixed solution.
Further, the ammonium salt is ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride or ammonium nitrate.
Further, the aluminium salt is aluminum nitrate, aluminum sulfate or aluminium chloride.
Further, the temperature of the esterification is 120 ~ 170 DEG C.
Further, the ratio between amount of substance of citric acid and fatty alcohol is 1:2 ~ 5.
Further, the mass ratio of catalyst and citric acid is 0.5 ~ 3:100.
Further, the reaction time is 2 ~ 5 hours.
The technical scheme provided by the invention has the following advantages: it is without precious metal in (1) catalytic component, it is at low cost It is honest and clean, it is easily prepared, and high catalytic efficiency；(2) separation of catalyst and product is simple, and catalyst can realize reuse；(3) lemon The high income of lemon acid esters.
Specific embodiment
Specific embodiments of the present invention will be described in further detail below.For those of skill in the art For member, from detailed description of the invention, above and other objects, features and advantages of the invention be will be evident.
Embodiment 1:
The preparation of catalyst: it is molten that 0.375 mmol ammonium carbonate, 0.5 mmol aluminum nitrate and 1 mmol phosphotungstic acid difference are weighed Solution is in 20 ml deionized waters；After dissolution, under conditions of room temperature and lasting stirring, aluminum nitrate solution is slowly added dropwise to phosphorus In tungstic acid, reacts 0.5 hour, then sal volatile is slowly added dropwise, increasingly generate white precipitate；After dripping, it is further continued for It is stirred to react 0.5 hour, still aging 1 hour, dry after precipitating is separated by filtration, it is (NH that molecular formula, which can be obtained,4)0.75Al0.5H0.75PW12O40Composite mixed phosphotungstate.
Embodiment 2:
The preparation of catalyst: the additional amount of ammonium carbonate is only changed to 0.2 mmol with embodiment 1 by preparation process, can be obtained Molecular formula is (NH4)0.4Al0.5H1.1PW12O40Composite mixed phosphotungstate.
Embodiment 3:
The preparation of catalyst: the additional amount of ammonium carbonate is only changed to 0.55 mmol with embodiment 1 by preparation process, can be obtained Molecular formula is (NH4)1.1Al0.5H0.4PW12O40Composite mixed phosphotungstate.
Embodiment 4:
The preparation of catalyst: ammonium salt is only changed to 0.6 mmol ammonium hydrogen carbonate with embodiment 1 by preparation process, aluminum nitrate Additional amount is changed to 0.6 mmol, and it is (NH that molecular formula, which can be obtained,4)0.6Al0.6H0.6PW12O40Composite mixed phosphotungstate.
Embodiment 5:
The preparation of catalyst: ammonium salt is only changed to 0.6 mmol ammonium chloride, molecule can be obtained by preparation process with embodiment 4 Formula is (NH4)0.6Al0.6H0.6PW12O40Composite mixed phosphotungstate.
Embodiment 6:
The preparation of catalyst: aluminium salt is only changed to 0.6 mmol aluminium chloride, molecule can be obtained by preparation process with embodiment 4 Formula is (NH4)0.6Al0.6H0.6PW12O40Composite mixed phosphotungstate.
Embodiment 7:
Be added in the reactor for being equipped with thermometer, water segregator and condenser pipe 19.21 g citric acids (0.1 mol), (the NH prepared in 29.6 g n-butanols (0.4 mol) and 0.29 g embodiment 14)0.75Al0.5H0.75PW12O40Catalyst is opened Stirring, is warming up to 150 DEG C, starts timing when starting to occur backflow phenomenon in condenser pipe, reacts 3 h.Reaction system is cooled to It after room temperature, is separated by filtration, filtrate uses gas chromatographic detection, and product yield is shown in Table 1.
Embodiment 8:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 2 (NH4)0.4Al0.5H1.1PW12O40, product yield is shown in Table 1.
Embodiment 9:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 3 (NH4)1.1Al0.5H0.4PW12O40, product yield is shown in Table 1.
Embodiment 10:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 4 (NH4)0.6Al0.6H0.6PW12O40, product yield is shown in Table 1.
Embodiment 11:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 5 (NH4)0.6Al0.6H0.6PW12O40, product yield is shown in Table 1.
Embodiment 12:
Using reaction condition and detection method same as Example 7, only catalyst is changed to prepare in embodiment 6 (NH4)0.6Al0.6H0.6PW12O40, product yield is shown in Table 1.
Embodiment 13:
Be added in the reactor for being equipped with thermometer, water segregator and condenser pipe 19.21 g citric acids (0.1 mol), (the NH prepared in 26.05 g n-octyl alcohols (0.2 mol), 5 mL water entrainer hexamethylenes and 0.29 g embodiment 14)0.75Al0.5H0.75PW12O40Catalyst opens stirring, is warming up to 160 DEG C, starts when starting to occur backflow phenomenon in condenser pipe 3 h are reacted in timing.It after reaction system is cooled to room temperature, is separated by filtration, filtrate uses gas chromatographic detection, and product yield is shown in Table 1。
Embodiment 14:
Using reaction condition identical with embodiment 13 and detection method, it is different pungent that raw material n-octyl alcohol is only changed to 26.05 g Alcohol (0.2 mol), product yield is shown in Table 1.
Embodiment 15:
Be added in the reactor for being equipped with thermometer, water segregator and condenser pipe 19.21 g citric acids (0.1 mol), (the NH prepared in 37.26 g lauryl alcohols (0.2 mol), 5 mL water entrainer hexamethylenes and 0.29 g embodiment 14)0.75Al0.5H0.75PW12O40Catalyst opens stirring, is warming up to 165 DEG C, starts when starting to occur backflow phenomenon in condenser pipe 4 h are reacted in timing.It after reaction system is cooled to room temperature, is separated by filtration, filtrate uses liquid chromatographic detection, and product yield is shown in Table 1。
Embodiment 16:
Be added in the reactor for being equipped with thermometer, water segregator and condenser pipe 19.21 g citric acids (0.1 mol), (the NH prepared in 48.5 g hexadecanols (0.2 mol), 5 mL water entrainer hexamethylenes and 0.29 g embodiment 14)0.75Al0.5H0.75PW12O40Catalyst opens stirring, is warming up to 170 DEG C, starts when starting to occur backflow phenomenon in condenser pipe 5 h are reacted in timing.It after reaction system is cooled to room temperature, is separated by filtration, filtrate uses liquid chromatographic detection, and product yield is shown in Table 1。
Embodiment 17:
Using reaction condition and detection method same as in Example 10, the dosage of n-butanol is only changed to 14.8 g(0.2 Mol), product yield is shown in Table 1.
Embodiment 18:
Using reaction condition and detection method same as in Example 10, the dosage of n-butanol is only changed to 22.2 g(0.3 Mol), product yield is shown in Table 1.
Embodiment 19:
Using reaction condition and detection method same as in Example 10, the dosage of n-butanol is only changed to 37 g(0.5 Mol), product yield is shown in Table 1.
Embodiment 20:
Using reaction condition identical with embodiment 11 and detection method, the dosage of catalyst is only changed to 0.1 g, product Yield is shown in Table 1.
Embodiment 21:
Using reaction condition identical with embodiment 11 and detection method, the dosage of catalyst is only changed to 0.38 g, is produced Object yield is shown in Table 1.
Embodiment 22:
Using reaction condition identical with embodiment 12 and detection method, reaction temperature is only changed to 130 DEG C, product yield It is shown in Table 1.
Embodiment 23:
Using reaction condition and detection method same as Example 7, will only be changed in the reaction time 5 hours, product yield It is shown in Table 1.
Embodiment 24:
Circulation by catalyst used in embodiment 7, without any processing after being separated by filtration, for next batch Reaction, the reaction condition and detection method of circular response are same as Example 7, and after being recycled 15 times, product yield is shown in Table 1.
Comparative example 1:
Using reaction condition and detection method same as in Example 10, catalyst is only changed to (NH4)2.4H0.6PW12O40, Product yield is shown in Table 1.
Comparative example 2:
Using reaction condition and detection method same as in Example 10, catalyst is only changed to Al0.8H0.6PW12O40, produce Object yield is shown in Table 1.
Table 1: the product yield of embodiment and comparative example.
According to the result of table 1, composite mixed phosphotungstate of the present invention has the reaction of lactate synthesis citrate There is very excellent catalytic performance, catalytic activity is better than traditional single type ion doping phosphotungstate, and catalyst is through 15 times Do not occur the phenomenon that activity is decreased obviously after reuse.In addition, catalyst is low in cost, and easily prepared.Therefore, this hair The bright technical solution being related to is suitable for industrial applications.It will be apparent to those skilled in the art that ammonium salt uses ammonium carbonate, bicarbonate Ammonium, ammonium chloride or ammonium nitrate, aluminium salt use aluminum nitrate, aluminum sulfate or aluminium chloride, are able to achieve technical effect of the invention.This hair Bright applicable fatty alcohol includes the linear chain or branched chain fatty alcohol of C4 ~ C16.
It should be appreciated that although the present invention has carried out clear explanation by above embodiments, without departing substantially from the present invention Spirit and its essence in the case where, person of ordinary skill in the field make in accordance with the present invention it is various it is corresponding variation and Amendment, but these corresponding variations and modifications all should belong to scope of protection of the claims of the invention.

Claims (10)

1. a kind of method that composite mixed phosphotungstate catalyzes and synthesizes citrate, using composite mixed phosphotungstate as catalyst, Esterification synthesizing citric acid ester is occurred by citric acid and fatty alcohol, which is characterized in that the knot of the composite mixed phosphotungstate Structure skeleton symbol are as follows: (NH4)xAl(3-x-y)/3 HyPW12O40, wherein x=0.4 ~ 1.1, y=0.4 ~ 1.1.
2. the method according to claim 1 for catalyzing and synthesizing citrate, which is characterized in that the fatty alcohol is positive fourth Alcohol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-octyl alcohol, Decanol or laruyl alcohol.
3. the method according to claim 1 for catalyzing and synthesizing citrate, which is characterized in that the composite mixed phosphotungstic acid The preparation process of salt catalyst comprising steps of
(1) ammonium salt, aluminium salt and phosphotungstic acid are mixed in solution；
(2) the isolated composite mixed phosphotungstate after reacting.
4. the method according to claim 3 for catalyzing and synthesizing citrate, which is characterized in that the step (1) specifically:
Aluminium salt is added in the aqueous solution of phosphotungstic acid；
Ammonium salt is added in aforementioned mixed solution.
5. the method according to claim 3 for catalyzing and synthesizing citrate, which is characterized in that the ammonium salt be ammonium carbonate, Ammonium hydrogen carbonate, ammonium chloride or ammonium nitrate.
6. the method according to claim 3 for catalyzing and synthesizing citrate, which is characterized in that the aluminium salt be aluminum nitrate, Aluminum sulfate or aluminium chloride.
7. the method according to claim 1-6 for catalyzing and synthesizing citrate, which is characterized in that the esterification is anti- The temperature answered is 120 ~ 170 DEG C.
8. the method according to claim 1-6 for catalyzing and synthesizing citrate, which is characterized in that citric acid and rouge The ratio between amount of substance of fat alcohol is 1:2 ~ 5.
9. the method according to claim 1-6 for catalyzing and synthesizing citrate, which is characterized in that catalyst and lemon The mass ratio of lemon acid is 0.5 ~ 3:100.
10. the method according to claim 1-6 for catalyzing and synthesizing citrate, which is characterized in that the reaction time It is 2 ~ 5 hours.
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CN108187744B (en) * 2018-01-27 2020-08-04 邵阳学院 Method for catalytic synthesis of furfural ethylene glycol acetal from ammonium aluminum phosphotungstate complex salt

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JP2002167359A (en) * 2000-11-30 2002-06-11 Teijin Ltd Method for producing aromatic carbonate
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