CN102417452A - Preparation method of citrate - Google Patents
Preparation method of citrate Download PDFInfo
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- CN102417452A CN102417452A CN2011104222604A CN201110422260A CN102417452A CN 102417452 A CN102417452 A CN 102417452A CN 2011104222604 A CN2011104222604 A CN 2011104222604A CN 201110422260 A CN201110422260 A CN 201110422260A CN 102417452 A CN102417452 A CN 102417452A
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- hydrocerol
- citrate
- citric acid
- alcohol
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Abstract
The invention provides a preparation method of citrate. The method comprises the following step of: undergoing a contact reaction on citric acid and monohydric alcohol in the presence of a catalyst to obtain citrate, wherein the citric acid is citric acid containing one or more of Fe<3+>, Al<3+> and Cu<2+> prepared with at least one of the following methods: in a method I, a clear citric acid zymotic fluid is separated and purified with a calcium salt method to obtain the citric acid containing one or more of Fe<3+>, Al<3+> and Cu<2+>; and in a method II, a clear citric acid zymotic fluid is separated and purified with a chromatography to obtain the citric acid containing one or more of Fe<3+>, Al<3+> and Cu<2+>. By adopting the method disclosed by the invention for preparing the citric acid, the procedure can be simplified, the dosage of a catalyst can be reduced, and the yield and purity of the citrate are increased.
Description
Technical field
The present invention relates to a kind of preparation method of citrate.
Background technology
That citrate has is nontoxic, biological degradability good, volatility is little and advantage such as resistance to bacteria excellence, is a kind of environmental friendliness type material.In recent years, to the research Showed Very Brisk of citrate, successfully develop the multiple kind that is applicable to different field at present both at home and abroad.The Application Areas of citrate is boundless, not only can be used as nonpoisonous and tasteless environmental protection softening agent, also can be used as tensio-active agent and metal chelator etc.
Citrate is as a kind of softening agent of excellent performance because have that consistency is good, plasticizing efficiency is high, advantage such as nontoxic, not volatile and weathering resistance is strong and extensively being paid close attention to.What become first-selection at present can substitute the Green Product of phthalate as softening agent.
Citrate has worldwide obtained widespread use as a kind of important tensio-active agent.The citrate tensio-active agent has good emulsifying, moistening, solubilising and dispersing property, is a kind of nontoxic, pollution-free, non-stimulated and biological degradability is good " green chemical industry product ".
Usually, citrate is in the presence of catalyzer (the for example vitriol oil), and Hydrocerol A and monohydroxy-alcohol esterification are made.But when said catalyzer was the vitriol oil, shortcomings such as side reaction took place in the color of the product that catalyst consumption yield big, citrate is lower and existence is comparatively serious to equipment corrosion, obtain more deeply, easily.In addition; The said Hydrocerol A that is used for esterification generally be through with citric acid fermentation broth through press filtration, neutralization, acidolysis, decolouring, IX, concentrate, operations such as crystallization and oven dry purify and obtain; Perhaps through press filtration, membrane filtration, chromatogram, IX, concentrate, comparatively purified Hydrocerol A that operations such as crystallization and oven dry are purified and obtained, operation is more loaded down with trivial details, cost is higher.
Summary of the invention
The objective of the invention is in order to overcome when adopting existing method to prepare citrate; Have that complex procedures, catalyst levels are big, the yield of citrate is lower and esterification generates the more defective of impurity, and the preparation method who provides a kind of and can simplify working process, reduce the yield of catalyst levels, citrate higher, produces the less citrate of impurity.
The invention provides a kind of preparation method of citrate, this method is included under the existence of catalyzer, with Hydrocerol A and monohydroxy-alcohol contact reacts, obtains citrate, and wherein, said Hydrocerol A is to contain Fe by what at least a in the following method prepared
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As:
Method I separates the Fe that contains that purifies and obtain with the citric acid fermentation broth clear liquid with calcium salt method
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As;
Method II separates the Fe that contains that purifies and obtain with the citric acid fermentation broth clear liquid with chromatography
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As.
Contain Fe in the Hydrocerol A of the present invention
3+, Cu
2+And Al
3+In one or more ions, these three kinds of ions can catalysis Hydrocerol A and monohydroxy-alcohol generation esterification, will contain Fe
3+, Cu
2+And Al
3+In one or more ionic Hydrocerol As and monohydroxy-alcohol carry out contact reacts; Not only can reduce the yield of catalyst consumption, raising citrate; Can also save in the Hydrocerol A purification process from handing over removing the operation of impurity cationic wherein, thereby can effectively utilize the Fe in the said Hydrocerol A dexterously
3+, Cu
2+And Al
3+To improve esterification yield, can also reduce the cost of water consumption, energy consumption and environmental protection treatment and the cost that Hydrocerol A is purified Deng impurity cationic.In addition, a preferred embodiment of the invention, in order to obtain more purified citrate, this method also comprise with said Hydrocerol A neutralize with the product that obtains after monohydroxy-alcohol contacts, washing, dealcoholysis, decolouring; Wherein, the neutral purpose is in order to remove liquid an acidic catalyst and since according to method of the present invention can save catalyst consumption, correspondingly, also can reduce with the consumption of agents useful for same in said, and then reduce production costs.
Other features and advantages of the present invention will partly specify in embodiment subsequently.
Embodiment
Following specific embodiments of the invention is elaborated.Should be understood that embodiment described herein only is used for explanation and explains the present invention, is not limited to the present invention.
According to the present invention, the preparation method of said citrate is included under the existence of catalyzer, with Hydrocerol A and monohydroxy-alcohol contact reacts, obtains citrate, and wherein, said Hydrocerol A is to contain Fe by what at least a in the following method prepared
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As:
Method I separates the Fe that contains that purifies and obtain with the citric acid fermentation broth clear liquid with calcium salt method
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As;
Method II separates the Fe that contains that purifies and obtain with the citric acid fermentation broth clear liquid with chromatography
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As.
As a rule, itself can contain a certain amount of Fe in the citric acid fermentation clear liquid
3+, Al
3+And Cu
2+Deng impurity cationic; In order to obtain more purified Hydrocerol A; Prior art adopts calcium salt method or chromatography from the citric acid fermentation clear liquid, to extract in the process of Hydrocerol A usually; Need be after with the sulfuric acid solution citrate of lime, or after extracting Hydrocerol A, adopt Zeo-karb to remove the Fe in the Hydrocerol A again with chromatographic separation
3+, Al
3+And Cu
2+Deng impurity cationic.Yet contriver of the present invention is surprised to find that, Fe
3+, Al
3+And Cu
2+The reaction of catalysis Hydrocerol A and monohydroxy-alcohol generates citrate effectively, therefore, not only can effectively utilize the Fe in the citric acid fermentation clear liquid
3+, Al
3+And Cu
2+, reduce catalyst consumption, improve esterification yield, also simplify the preparation section of Hydrocerol A, thereby realized the object of the invention.
Therefore, said Hydrocerol A can be for not passing through a certain amount of Fe that contains that ion-exchange step prepares
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As, by at least a the preparing in the following method:
Method I separates the Fe that contains that purifies and obtain with the citric acid fermentation broth clear liquid with calcium salt method
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As;
Method II separates the Fe that contains that purifies and obtain with the citric acid fermentation broth clear liquid with chromatography
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As.
According to the present invention, said Hydrocerol A can be to add with crystalline form, also can be to add with the solution form.
For example, obtain containing Fe when adopting calcium salt method to separate purification
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As the time, said Hydrocerol A can be for containing Fe
3+, Al
3+And Cu
2+In one or more ionic citric acid fermentation clear liquids contact with lime carbonate and/or calcium hydroxide obtain citrate of lime, the citric acid solution that again citrate of lime is obtained after acidolysis.Said Hydrocerol A contacts the condition that obtains citrate of lime with lime carbonate and/or calcium hydroxide be conventionally known to one of skill in the art; For example; The pH value that the condition of said contact generally includes the contact terminal point can be 5.4-8; The temperature of contact can be 70-85 ℃, and the time of contact can be 0.5-1.5 hour; Under the preferable case, the pH value of said contact terminal point is 5.8-7, and the temperature of contact is 75-85 ℃, and the time of contact is 0.5-1 hour.PH value guaranteeing the contact terminal point is 5.4-8, is preferably under the condition of 5.8-7, can make the Fe in the citric acid fermentation clear liquid
3+, Al
3+And Cu
2+Ion is precipitated with citrate of lime, even contain Fe in the Hydrocerol A that obtains after the acidolysis
3+, Al
3+And Cu
2+In one or more ions.With the citrate of lime acidolysis obtain methods of citric acid comprise with hydrogen citrate calcium with acid contact; The condition of acidolysis comprises that the pH value is 1.5-1.8, and the temperature of acidolysis is 70-95 ℃, and the time of acidolysis is 40-60 minute.The used acid of said acidolysis is generally sulfuric acid or aqueous sulfuric acid.
For example, obtain containing Fe when adopting chromatography to separate purification
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As the time, said Hydrocerol A can be for containing Fe
3+, Al
3+And Cu
2+In one or more ionic citric acid fermentation clear liquids remove the citric acid solution that obtains behind residual sugar, albumen, pigment and the mineral acid with liquid-phase chromatographic column.Said chromatography is separated purification and is obtained containing Fe
3+, Al
3+And Cu
2+In one or more ionic methods of citric acid be conventionally known to one of skill in the art, for example, with the citric acid fermentation clear liquid chromatographic column of flowing through.Anionite-exchange resin in the said chromatographic column can be various anionite-exchange resin known in the field; For example; Can be in macroporous type anionite-exchange resin and/or the gel-type anionite-exchange resin one or more, be preferably macroporous type anionite-exchange resin; One or more in macroreticular weakly base vinylbenzene anionite-exchange resin and/or the macroreticular weakly base acrylic acid type anion exchange resin more preferably; Further be preferably in D301T macroreticular weakly base vinylbenzene anionite-exchange resin, D301R macroreticular weakly base vinylbenzene anionite-exchange resin, D382 macroreticular weakly base vinylbenzene anionite-exchange resin, D311 macroreticular weakly base acrylic anionic exchange resin, D318 macroreticular weakly base acrylic acid type anion exchange resin and the D815 macroporous acrylic property anionite-exchange resin one or more; Further be preferably D318 macroreticular weakly base acrylic acid type anion exchange resin.The temperature that the condition of said chromatographic separation generally includes chromatographic separation can be 30-80 ℃; The weight of every milliliter of handled citric acid fermentation broth of anionite-exchange resin can be 0.1-0.6g/mL, and the residence time of said eluent in chromatography column is at least 5min; Preferably; The condition of said chromatographic separation comprises that the temperature of chromatographic separation is 40-70 ℃; The weight of every milliliter of handled citric acid fermentation broth of anionite-exchange resin is 0.15-0.45g/mL, and the residence time of said eluent in chromatography column is 10-30min.
In addition, said Hydrocerol A can also for the above-mentioned citric acid solution that obtains with calcium salt method and/or chromatography through concentrating the Hydrocerol A liquid concentrator that obtains, perhaps can also be for the Hydrocerol A crystal that obtains after the crystallization of above-mentioned Hydrocerol A liquid concentrator.As long as contain Fe in the Hydrocerol A that adopts above-mentioned calcium salt method and/or chromatography to obtain
3+, Al
3+And Cu
2+In one or more ions get final product, under the preferable case, be benchmark with the weight of Hydrocerol A, said Fe
3+, Al
3+And Cu
2+Total content be 0.5-1 weight %.In order to satisfy Fe
3+, Al
3+And Cu
2+In one or more ionic content requirement, also can be in the Hydrocerol A that obtains suitably extraly add a certain amount of Fe
3+, Al
3+And Cu
2+In one or more ions.
According to the present invention, said citric acid fermentation broth can be the citric acid fermentation broth that adopts various fermentation condition known in the field to obtain.Particularly, can be the fermented liquid that adopts fermenting raw materials such as potato dry powder, Tapioca Starch, Semen Maydis powder, potato powder, starch and glucose mother liquid to obtain.Said heating, filtration, neutralization, acidolysis, decolouring, spissated method are conventionally known to one of skill in the art, repeat no more at this.
Although in the present invention, as long as said Hydrocerol A contains Fe
3+, Al
3+And Cu
2+In one or more ions get final product, still, in order to play the more efficiently katalysis that cooperates, be benchmark with the weight of Hydrocerol A with said catalyzer, said Fe
3+, Al
3+And Cu
2+Total content be 0.5-1 weight %.Need to prove that as stated, said Hydrocerol A can be for crystalline form or solution form, when said Hydrocerol A existed with crystalline form, the weight that " weight with Hydrocerol A is benchmark " refers to Citric Acid, usp, Anhydrous Powder was benchmark; When said Hydrocerol A existed with the solution form, the weight that " weight with Hydrocerol A is benchmark " refers to Citric acid monohydrate Food grade was benchmark.In addition, if contain Fe simultaneously in the said Hydrocerol A
3+, Al
3+And Cu
2+The time, " Fe then
3+, Al
3+And Cu
2+Total content " refer to Fe
3+, Al
3+And Cu
2+Total content; If contain Fe in the said Hydrocerol A
3+, Al
3+And Cu
2+In any two kinds the time, " Fe then
3+, Al
3+And Cu
2+Total content " refer to Fe
3+, Al
3+And Cu
2+In any two kinds total content; If only contain Fe in the said Hydrocerol A
3+, Al
3+Or Cu
2+In a kind of the time, said " Fe
3+, Al
3+And Cu
2+Total content " refer to Fe
3+Or Al
3+Or Cu
2+In content.
According to the present invention, said catalyst consumption can change in a big way, if can with Fe
3+, Al
3+And Cu
2+In one or more ions cooperate catalysis Hydrocerol As and monohydroxy-alcohol to react to obtain citrate and get final product.But, consider from combined factors such as catalytic efficiency (and product purity, under the preferable case, be benchmark with the weight of Hydrocerol A, said catalyst consumption is 0.1-0.5 weight %.Since in the present invention, Fe
3+, Cu
2+And Al
3+In at least a ionic exist and can play catalytic effect preferably, therefore, catalyst consumption can suitably reduce.
According to the present invention, said Fe
3+, Al
3+And Cu
2+Total content and the weight ratio of catalyzer can in relative broad range, select and adjust.Those skilled in the art should be understood that easily, Fe
3+, Al
3+And Cu
2+Can play collaborative katalysis with said catalyzer, therefore, as said Fe
3+, Al
3+And Cu
2+Total content when big, said catalyst consumption can be lower; As said Fe
3+, Al
3+And Cu
2+Content hour, said catalyst consumption should be higher; Under the preferable case, said Fe
3+, Al
3+And Cu
2+Total content and the weight ratio of catalyzer be 1-10: 1,1-5 more preferably: 1.
According to the present invention, said catalytic condition can be for well known to a person skilled in the art the various conditions that can make Hydrocerol A and monohydroxy-alcohol generation esterification.Generally, said catalytic condition comprises that catalytic temperature can be 120-145 ℃, and catalytic pressure can be 0.08-0.12MPa, and the catalytic time can be 240-300min; Under the preferable case, said catalytic temperature is 130-140 ℃, and catalytic pressure is 0.09-0.11MPa, and the catalytic time is 260-280min.
According to the present invention, said catalyzer can for existing various can the catalysis Hydrocerol A and monohydroxy-alcohol carry out the catalyzer of esterification.For example, said catalyzer can be selected from one or more in sulfuric acid, phenmethyl sulfonic acid, iron(ic)chloride and the Tai-Ace S 150, and all can be commercially available.
The present invention has no particular limits the mol ratio of monohydroxy-alcohol and Hydrocerol A, and for example, the mol ratio of said monohydroxy-alcohol and Hydrocerol A can be 4-6: 1, be preferably 4.5-5.5: 1.Need to prove that when said Hydrocerol A existed with crystalline form, " mol ratio of said monohydroxy-alcohol and Hydrocerol A " referred to the mol ratio of monohydroxy-alcohol and Citric Acid, usp, Anhydrous Powder; When said Hydrocerol A existed with the solution form, " mol ratio of said monohydroxy-alcohol and Hydrocerol A " referred to the mol ratio of monohydroxy-alcohol and Citric acid monohydrate Food grade.
According to the present invention, the kind of said monohydroxy-alcohol should reasonably be selected according to the kind of synthetic target citrate, can for existing various can with the monohydroxy-alcohol of Hydrocerol A generation esterification.For example, when needs synthesizing citric acid methyl esters, said monohydroxy-alcohol should be methyl alcohol; When needs synthesizing citric acid tri-n-butyl, said monohydroxy-alcohol should be propyl carbinol.Under the preferable case, said monohydroxy-alcohol can be selected from one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and the isopropylcarbinol.
According to the method for the invention, can adopt periodical operation, also can adopt operate continuously, feed way also can be for well known to a person skilled in the art any suitable mode, and the present invention does not all have particular requirement to this, repeat no more at this.
According to the present invention, in order to obtain more purified Hydrocerol A, preferably, this method also comprise with the citrate that obtains neutralize, washing, dealcoholysis and decolouring.Said neutralization is in order to remove unreacted Hydrocerol A, can be selected from yellow soda ash, sodium hydrogencarbonate, salt of wormwood, saleratus, volatile salt and the bicarbonate of ammonia one or more usually with agents useful for same in said.The Citrate trianion that neutralization reaction generates is water miscible, is easy to separate with the citrate of oil phase.The purpose of said washing is in order to be further purified citrate, the water-soluble impurity in the citrate to be removed.Said dealcoholysis mainly is for the purifying citrate and reclaims unreacted monohydroxy-alcohol, and the method for said dealcoholysis is conventionally known to one of skill in the art, for example, can use distillation, and is different with the boiling point of citrate and with these two kinds of separating substances according to monohydroxy-alcohol.Said decolouring is better for the color and luster that makes the citrate that obtains, and as a rule, thereby can the citrate after the dealcoholysis be contacted the purpose that reaches decolouring with gac.
Below will describe the present invention through embodiment.
PH tester in embodiment and the Comparative Examples is available from the happy Hua Xin in Shenzhen Electronics Co., Ltd., and model is S20; The purity of said citrate adopts the U.S. to produce SP-3700 type gas chromatograph and measures; Weight * 100% of the citrate that the weight/theory of the yield of citrate=actual citrate that obtains is deserved.
Citric acid fermentation clear liquid used in following examples can make through following method:
0.872 kg corn is pulverized with SFSP series beater disintegrating machine, and obtaining average particulate diameter is 0.871 kilogram of crushed products of 2 millimeters (adopting the Accu Sizer TM 780 optics particle diameter detectors of U.S. PPS company to measure); Product after pulverizing with respect to every gram adds the glycase (Novozymes Company, AMS) of 20 enzyme activity units, gets into injector, is enzymolysis 100 minutes under 5.5 the condition at 85 ℃, pH, obtains enzymolysis product A1.
The preparation fermention medium: enzymolysis product A1 through carrying out press filtration with the fluid pressure type plate-and-frame filter press, is isolated enzymatic liquefaction clear liquid and enzymolysis residue, and wherein, the water cut of enzymolysis residue is 50 weight %.With joining in the fermentor tank of 300L after 170 kilograms above-mentioned enzymatic liquefaction clear liquids, 2.0 kilograms the water sterilization of enzymolysis residue and 13 kilograms; Obtain fermention medium B1, wherein, carbon source content is 16 weight %; Nitrogenous source content is 0.095 weight %; Phosphorus source content is 0.06 weight %, inorganic salt content 0.4 weight %, and water-content is 83.4%.
With the above-mentioned part fermention medium that obtains, 1/10 of thin up to weight obtains nutrient solution.Nutrient solution is dropped into seeding tank, be heated to 121 ℃ of sterilizations, keep after 30 minutes fast cooling to 36 ℃, (inoculum size is for black mold T01, Tianjin industrial microorganism institute: every gram enzymatic liquefaction liquid 3 * 10 to insert aspergillus niger strain
5Individual colony-forming unit), at 36 ℃, 0.4 volume: carry out spawn culture under the aeration condition of volume minute; Measure through sampling sediments microscope inspection, acid test and pH the growth of black mold observed, when pH 2.0, acidity 1%, bacterium ball size evenly, mycelia is sturdy when stretching out, stop to cultivate.
The aspergillus niger strain that above-mentioned cultivation is obtained joins and begins fermentation in the fermentor tank that contains above-mentioned fermention medium, and inoculum size is: every gram fermention medium 3.3 * 10
4Individual colony-forming unit; Fermentation condition comprises that temperature is 35 ℃, and the pH value is 3, and the pressure of the air of feeding is 1.8-2.1MPa; The air air flow is 0.3 volume: volume minute feeds in fermentor tank in the closed ethanol fermentation process when beginning to ferment and obtains the CO that pressure is 2.1-2.3MPa
2Gas (CO
2CO in the gas
2Concentration be 96 volume %), said CO
2The air flow of gas is 0.0018 volume: volume minute, and behind fermentation 24h, with said CO
2The air flow of gas is increased to 0.06 volume: volume minute, until fermentation ends just stops to feed, when proceeding to the 69th hour, fermentation carries out solid-liquid separation, and obtain the citric acid fermentation clear liquid.
Embodiment 1
This embodiment is used to explain the preparation of citrate provided by the invention.
(1) contains Fe
3+, Al
3+And Cu
2+In the preparation of one or more ionic Hydrocerol As:
With above-mentioned 5L citric acid fermentation clear liquid (Citric acid monohydrate Food grade content: 16g/100mL); Added 1250g calcium carbonate serosity (lime carbonate concentration is 45 weight %) and be under 6 the condition reaction 4 hours at 75 ℃, pH; Standing demix, abandoning supernatant (promptly useless syrup) obtains the citrate of lime slurries.After the citrate of lime slurries were drained with vacuum, the vitriol oil that adds 560g carried out acidolysis reaction 10min, after reaction finishes, adopted the conveyor drive filtering separation, and product liquid is a Hydrocerol A acidolysis liquid, and solid product is a waste calcium sulfate.Hydrocerol A acidolysis liquid concentrates through after decolouring, crystallization, gets 0.66kg to the Hydrocerol A crystal; Wherein, contain Fe in the said Hydrocerol A crystal
3+, Al
3+And Cu
2+, and Fe
3+, Al
3+And Cu
2+Total content be 3.5g.
(2) preparation of citrate:
Under agitation, Hydrocerol A crystal, 4mol propyl carbinol and the 1.02g vitriol oil that 1mol is obtained by step (1) mix, and are heated to 120 ℃, and pressure-controlling is reacted 240min under 0.08MPa, obtain containing the solution of tributyl citrate.Using concentration is the pH regulator to 7.0 of the sodium carbonate solution of 3 weight % with the above-mentioned solution that contains tributyl citrate that obtains, and solid-liquid separation obtains oil-phase product.Oil-phase product with deionized water wash three times, and is distilled dealcoholysis with the ester that obtains in the vacuum distilling system, the product that obtains after the dealcoholysis is obtained tributyl citrate after with activated carbon decolorizing, purity is 98.9%, and yield is 98.7%.
Embodiment 2
This embodiment is used to explain the preparation of citrate provided by the invention.
(1) contains Fe
3+, Al
3+And Cu
2+In the preparation of one or more ionic Hydrocerol As:
With above-mentioned 5L citric acid fermentation clear liquid (Citric acid monohydrate Food grade content: 16g/100mL); Added 1250g calcium carbonate serosity (lime carbonate concentration is 45 weight %) and be under 8 the condition reaction 4 hours at 85 ℃, pH; Standing demix, abandoning supernatant (promptly useless syrup) obtains the citrate of lime slurries.After the citrate of lime slurries were drained with vacuum, the vitriol oil that adds 560g carried out acidolysis reaction 10min, after reaction finishes, adopted the conveyor drive filtering separation, and product liquid is a Hydrocerol A acidolysis liquid, and solid product is a waste calcium sulfate.Hydrocerol A acidolysis liquid concentrates after decolouring, and gets 0.66kg to the Hydrocerol A liquid concentrator; Wherein, contain Fe in the said Hydrocerol A liquid concentrator
3+, Al
3+And Cu
2+, and Fe
3+, Al
3+And Cu
2+Total content be 5.3g.
(2) preparation of citrate:
Under agitation, Hydrocerol A liquid concentrator, 6mol ethanol and 0.77g phenmethyl sulfonic acid that 1mol is obtained by step (1) mix, and are heated to 145 ℃, and pressure-controlling is reacted 300min under 0.1MPa, obtain containing the solution of tributyl citrate.Using concentration is the pH regulator to 7.0 of the sodium carbonate solution of 3 weight % with the above-mentioned solution that contains tributyl citrate that obtains, and solid-liquid separation obtains oil-phase product.Oil-phase product with deionized water wash three times, and is distilled dealcoholysis with the ester that obtains in the vacuum distilling system, the product that obtains after the dealcoholysis is obtained triethyl citrate after with activated carbon decolorizing, purity is 99 weight %, and yield is 98.9%.
Embodiment 3
This embodiment is used to explain the preparation of citrate provided by the invention.
(1) contains Fe
3+, Al
3+And Cu
2+In the preparation of one or more ionic Hydrocerol As:
With 5L citric acid fermentation clear liquid (Citric acid monohydrate Food grade content: 16g/100mL), add D318 macroreticular weakly base acrylic acid type anion exchange resin (Jiangsu Su Qing engineering of water treatment Group Co.,Ltd, the OH of 2300g
-Content is 15 mmoles/gram dried resin) soak to exchange and adsorb; Separate with vacuum filtration, Hydrocerol A is adsorbed on the resin, and impurity such as sugar, albumen are discharged with waste liquid; Dilute sulphuric acid with the 10 weight % of 2500mL carries out wash-out then; Promptly obtain the Hydrocerol A elutriant, the Hydrocerol A elutriant through concentrating, after the crystallization, 0.7kg to the Hydrocerol A crystal; Wherein, contain Fe in the said Hydrocerol A crystal
3+, Al
3+And Cu
2+, and Fe
3+, Al
3+And Cu
2+Total content be 7g.
(2) preparation of citrate:
Under agitation, Hydrocerol A crystal, 5mol n-propyl alcohol and the 0.39g vitriol oil that 1mol is obtained by step (1) mix, and are heated to 135 ℃, and pressure-controlling is reacted 270min under 0.12MPa, obtain containing the solution of tributyl citrate.Using concentration is the pH regulator to 7.0 of the sodium carbonate solution of 3 weight % with the above-mentioned solution that contains tributyl citrate that obtains, and solid-liquid separation obtains oil-phase product.Oil-phase product with deionized water wash three times, and is distilled dealcoholysis with the ester that obtains in the vacuum distilling system, the product that obtains after the dealcoholysis is obtained Hydrocerol A three propyl ester after with activated carbon decolorizing, purity is 98.9 weight %, and yield is 98.9%.
Embodiment 4
This embodiment is used to explain the preparation of citrate provided by the invention.
Method according to embodiment 1 prepares citrate, and different is, the consumption of said concentrated sulfuric acid catalyst is 2.94g, obtains tributyl citrate, and purity is 97.2 weight %, and yield is 93.5%.
Embodiment 5
This embodiment is used to explain the preparation of citrate provided by the invention.
Method according to embodiment 1 prepares citrate, and different is, the temperature of said reaction is 115 ℃, and the pressure of reaction is 0.07MPa, obtains tributyl citrate, and purity is 99.0 weight %, and yield is 90.1%.
Embodiment 6
This embodiment is used to explain the preparation of citrate provided by the invention.
Method according to embodiment 1 prepares citrate, and different is, this embodiment does not comprise the step of neutralization, washing, dealcoholysis and decolouring, obtains tributyl citrate, and purity is 90.2 weight %, and yield is 99.1%.
Comparative Examples 1
This Comparative Examples is used for explanation and adopts the synthetic citrate that obtains of existing method.
Method according to embodiment 1 prepares tributyl citrate, and different is that used raw material Hydrocerol A does not contain Fe
3+, Al
3+And Cu
2+, promptly in the preparation process of Hydrocerol A, also increased from the step of handing over, with Fe
3+, Al
3+And Cu
2+Remove, obtain tributyl citrate, purity is 98.3 weight %, and yield is 84.3%.
Can find out that from above result because embodiment 1-6 adopts method of the present invention to carry out the preparation of citrate, therefore, the yield of citrate and purity obviously are superior to Comparative Examples 1.Can find out that from the contrast of embodiment 1-3 and embodiment 4-6 adopt the preferred condition of the present invention, the yield of citrate and purity are all higher.In addition, adopt method of the present invention to prepare citrate and not only can omit the ion-exchange process in the lemon acid preparation process, and the Fe that contains in the Hydrocerol A raw material
3+, Al
3+And Cu
2+Can catalytic esterification, therefore, can also reduce catalyst levels, have prospects for commercial application.
Claims (8)
1. the preparation method of a citrate, this method is included under the existence of catalyzer, with Hydrocerol A and monohydroxy-alcohol contact reacts, obtains citrate, it is characterized in that, and said Hydrocerol A is to contain Fe by what at least a in the following method prepared
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As:
Method I separates the Fe that contains that purifies and obtain with the citric acid fermentation broth clear liquid with calcium salt method
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As;
Method II separates the Fe that contains that purifies and obtain with the citric acid fermentation broth clear liquid with chromatography
3+, Al
3+And Cu
2+In one or more ionic Hydrocerol As.
2. method according to claim 1 wherein, is a benchmark with the weight of Hydrocerol A, said Fe
3+, Al
3+And Cu
2+Total content be 0.5-1 weight %, said catalyst consumption is 0.1-0.5 weight %.
3. method according to claim 2, wherein, said Fe
3+, Al
3+And Cu
2+Total content and the weight ratio of catalyzer be 1-10: 1.
4. method according to claim 1, wherein, the mol ratio of said monohydroxy-alcohol and Hydrocerol A is 4-6: 1.
5. method according to claim 1, wherein, said catalytic condition comprises that catalytic temperature is 120-145 ℃; Catalytic pressure is 0.08-0.12MPa; The catalytic time is 240-300min.
6. according to claim 1,2 or 3 described methods, wherein, said catalyzer is selected from one or more in sulfuric acid, phenmethyl sulfonic acid, iron(ic)chloride and the Tai-Ace S 150.
7. according to claim 1 or 4 described methods, wherein, said monohydroxy-alcohol is selected from one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and the isopropylcarbinol.
8. method according to claim 1, wherein, this method also comprise with the citrate that obtains neutralize, washing, dealcoholysis and decolouring.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193641A (en) * | 2013-04-18 | 2013-07-10 | 湖南洞庭柠檬酸化学有限公司 | Process of producing citric acid ester through corn |
| CN105237395A (en) * | 2015-10-19 | 2016-01-13 | 北京石油化工学院 | Synthetic method of low-color-number triisooctyl citrate |
| CN105968003A (en) * | 2016-06-07 | 2016-09-28 | 济南大学 | Citrate fluorescent compound and application thereof to mercury ion detection |
| CN107573234A (en) * | 2017-07-28 | 2018-01-12 | 兰茂密 | A kind of industrial method for extracting citric acid |
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| CN1275975A (en) * | 1997-05-12 | 2000-12-06 | 莱利工业公司 | Processes for producing citrate esters |
| CN1557800A (en) * | 2004-02-06 | 2004-12-29 | 江南大学 | Process for preparing ethyl citrate suitable for industrialized production |
| CN101270045A (en) * | 2007-03-22 | 2008-09-24 | 北京化工大学 | Method for synthesizing triester citrate with hydrophobic solid acid as catalyst |
| CN101648864A (en) * | 2009-07-31 | 2010-02-17 | 安徽丰原生物化学股份有限公司 | Purification method of citric acid fermentation broth |
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Patent Citations (4)
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|---|---|---|---|---|
| CN1275975A (en) * | 1997-05-12 | 2000-12-06 | 莱利工业公司 | Processes for producing citrate esters |
| CN1557800A (en) * | 2004-02-06 | 2004-12-29 | 江南大学 | Process for preparing ethyl citrate suitable for industrialized production |
| CN101270045A (en) * | 2007-03-22 | 2008-09-24 | 北京化工大学 | Method for synthesizing triester citrate with hydrophobic solid acid as catalyst |
| CN101648864A (en) * | 2009-07-31 | 2010-02-17 | 安徽丰原生物化学股份有限公司 | Purification method of citric acid fermentation broth |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193641A (en) * | 2013-04-18 | 2013-07-10 | 湖南洞庭柠檬酸化学有限公司 | Process of producing citric acid ester through corn |
| CN105237395A (en) * | 2015-10-19 | 2016-01-13 | 北京石油化工学院 | Synthetic method of low-color-number triisooctyl citrate |
| CN105237395B (en) * | 2015-10-19 | 2017-10-24 | 北京石油化工学院 | A kind of synthetic method of the different monooctyl ester of low color citric acid three |
| CN105968003A (en) * | 2016-06-07 | 2016-09-28 | 济南大学 | Citrate fluorescent compound and application thereof to mercury ion detection |
| CN105968003B (en) * | 2016-06-07 | 2017-05-24 | 济南大学 | Citrate fluorescent compound and application thereof to mercury ion detection |
| CN107573234A (en) * | 2017-07-28 | 2018-01-12 | 兰茂密 | A kind of industrial method for extracting citric acid |
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| CN102417452B (en) | 2013-12-25 |
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