CN1033324C - New Technology for preparing sodium citrate - Google Patents
New Technology for preparing sodium citrate Download PDFInfo
- Publication number
- CN1033324C CN1033324C CN 92107081 CN92107081A CN1033324C CN 1033324 C CN1033324 C CN 1033324C CN 92107081 CN92107081 CN 92107081 CN 92107081 A CN92107081 A CN 92107081A CN 1033324 C CN1033324 C CN 1033324C
- Authority
- CN
- China
- Prior art keywords
- citrate
- citric acid
- solution
- sodium citrate
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention belongs to novel technology for citrate sodium production, which uses pressed acid and mother liquid as raw materials for changing the condition of directly using the finished citric acid, wherein the pressed acid is obtained by pressing waste mycelium dregs generated in the producing fermentation process of a citric acid plant, and the circulation of the mother liquid is 3 to 4 times in the producing process. The novel technology uses the main steps of neutralization, decomposition, purification, concentration, crystallization, etc., for producing the qualified product which reaches or exceeds the national standard and the standard of the China pharmacopoeia. The technology has the advantages of advanced production, low cost, good product quality and strong market competitive capability. Meanwhile, the technology cancels solvent extraction, promotes safe production, reduces pollution and is favorable for environment protection.
Description
The present invention relates to a kind of new process of production that is widely used in the Trisodium Citrate of industry such as medicine, food, photograph, plating and washing.
The traditional method of producing Trisodium Citrate is by Trisodium Citrate and sodium hydroxide or yellow soda ash neutralization, through concentrate, crystallization and making, its Production Flow Chart synoptic diagram is in accompanying drawing 2.
Carry out neutralization reaction with finished lemon acid and sodium hydroxide or yellow soda ash in the aqueous solution and generate Trisodium Citrate, the adding activated carbon is to adsorb coloured goods and materials and impurity in above-mentioned mixing solutions.Be equipped with filter the suction filtration bucket on, above-mentioned mixed solution is carried out suction filtration, with the elimination activated carbon, thereby obtain purified sodium citrate solution, purified sodium citrate solution heating is concentrated, make Trisodium Citrate become crystal to discharge, by tripod pendulum type batch centrifugal with above-mentioned solution separating, mother liquor returns to enrichment process, and crystal carries out drying, promptly obtains finished lemon acid sodium.
The method of taking solvent to get in addition, promptly citric acid and alkali and after, directly get, then Crystallization Separation, drying and obtain Trisodium Citrate with ethanol.
Traditional method has its tangible weakness.
(1) adopt finished lemon acid on raw material, price is higher, is unfavorable for reducing production costs.
(2) adopt processes production Trisodium Citrates such as neutralization, zwitterion exchange, solvent extraction on technology, complex process is operated loaded down with trivial detailsly, and with an organic solvent, brings the hidden danger in the production, needs fire prevention, blasting protection facilities.
(3) draw in the material balance analysis, the traditional method acid recovering rate is low, and yield only reaches 70%, therefore, is necessary traditional method is improved.
The present invention's---New Technology for preparing sodium citrate---adopts Citric Acid Plant to produce that the waste mycelium dreg that is produced in the fermenting process squeezes the squeezing acid of acquisition and the mother liquor of circulation 3-4 time in the citric acid production process, from squeeze acid and waste liquor, obtain a large amount of citric acids, to change direct situation with finished lemon acid.
The citric acid production process flow diagram is seen accompanying drawing 3.
Citric acid production technology is as follows:
Bacterial classification promptly arrives seeding tank fermentation enlarged culturing behind primary fermentation, continue to send ferment tank after the seed tank culture.After fully fermenting, obtain the higher fermentation materials of citric acid yield, fermentation materials is filtered, the solid filter residue is sent into storage storehouse standby (including 6% citric acid).Filtrate adds alkali and carries out neutralization reaction, and further acidolysis.By anion and cation exchange resin, remove impurity, obtain purified citric acid solution.This solution concentration, Crystallization Separation, during its mother liquor (including 30% citric acid) returns and operation, citric acid crystal drying, sieve the back and the citric acid finished product, packing is dispatched from the factory.
The present invention's---New Technology for preparing sodium citrate---adopts replacement(metathesis)reaction, select for use certain scavenging agent removing impurity in process of production, thereby technology is reasonable, and is simple to operate, removed solvent extraction process, production safety.
The present invention's---New Technology for preparing sodium citrate---can make the product Trisodium Citrate reach and surpass national standard.
The present invention's---New Technology for preparing sodium citrate---is to be raw material with round-robin waste liquor in the citric acid production factory and the waste mycelium dreg that dumps squeezing acid, make by master operations such as neutralization, decomposition, purification, condensing crystals, its reaction mechanism is in citric acid and the alkali and produces the citrate of lime precipitation; Citrate of lime enters in the solution generation Trisodium Citrate with the soda ash reaction again; The scavenging agent that adds significant quantity in sodium citrate solution makes gets rid of the impurity that brings in the solution, and Trisodium Citrate is purified; At last, purified sodium citrate solution under reduced pressure condensing crystal and making meet or exceed national standard and the " qualified product of Chinese pharmacopoeia standard.
The present invention's---New Technology for preparing sodium citrate---technology is advanced rationally to turn waste into wealth, and has reduced production cost effectively, and quality product is better than the product that traditional technology is produced, and whole production has favorable economic benefit, social benefit and environmental benefit.
Advantage of the present invention can be summarized as follows:
(1) production method advanced person obviously is better than traditional technology, and production cost is low, and good product quality has the stronger market competitiveness.
(2) in technological process, twice scavenging process adds the scavenging agent of significant quantity, removes impurity effectively, thereby guarantees that quality product reaches requirement.
(3) in technological process, adopt the concentrating under reduced pressure crystallization, be different from the normal pressure crystallization of traditional method, or use the alcoholic solvent extractive crystallization, compare with the normal pressure crystallization, primary crystallization rate height, cost is low; Compare with extractive crystallization, Production Flow Chart is simple, no inflammable substance.
(4) this production method reclaims citric acid from waste residue, greatly reduces the acid content of waste residue, has improved the rate of recovery of citric acid, thereby does not discharge deleterious waste residue and waste water in process of production, has reduced environmental pollution, helps environment protection.
The present invention's---New Technology for preparing sodium citrate---process flow diagram in after, further elaborate this new process of production content here.
(1) gets acid.The waste mycelium dreg of citric acid production factory in enlarging fermenting process generally all abandoned, contaminate environment, and the present invention at first is the fermented product filter residue (being waste mycelium dreg) after filtering that utilizes in the Citric Acid Plant fermentor tank, with its squeezing, contained 6% citric acid is leached, enter in the filtrate, because amount of water does not wait, contained citric acid content is 1%～6% not wait in this filtrate, next is with pipeline the mother liquor of the circulation behind condensing crystal 3-4 time from the citric acid production process to be received the Trisodium Citrate production process, mix with pressing filtrate, this mixed solution includes citric acid 5%～12%, and contains a large amount of impurity.
(2) neutralization.In mixed solution, add Paris white, stir, make lime carbonate and citric acid reactions, generate the citrate of lime white precipitate.
Its processing condition: temperature of reaction: 60～80 ℃
Reaction times: 1 hour
Reaction formula:
Citrate of lime
(3) affination places the caldron that fills filter cloth with citrate of lime, precipitates 3-4 time with hot water injection's citrate of lime, can be with sugar flush away contained in the citrate of lime.
(4) decompose.To replace classical neutralisation with double decomposition through adding soda ash solution in the citrate of lime behind the affination.Make citrate of lime be converted into Trisodium Citrate and enter among the solution, its process conditions is:
Temperature: 60～80 ℃
PH value of solution value: 6.5～7.5
Reaction times: 2～3 hours
(5) suction filtration filters sodium citrate solution, and precipitation of calcium carbonate is stayed on the filter cloth in the suction filter that the nylon filter cloth is housed, can be dried repeatedly to use.
(6) purify.The scavenging agent sodium sulphite of adding 1-2% significant quantity stirs in through the filtrate that obtains behind the suction filtration, removes to react fully to have impurity substances contained in the filtrate.
(7) suction filtration.Suction filtration is to carry out suction filtration through the mixed solution that purifies, to obtain purified solution for the second time.
(8) decolouring.In the solution of above-mentioned suction filtration, add activated carbon, to slough the impurity color of bringing in the solution.
(9) suction filtration.Suction filtration is that the mixed solution that will add activated carbon carries out suction filtration for the third time, obtains purified solution with the elimination activated carbon.
(10) smart filter.Suction filtration is removed the purified solution of activated carbon and carried out press filtration, further to remove the trace impurity that has in the filtrate by plate-and-frame filter press.
(11) concentrate.Pure filtrate after the essence filter delivered to adopt concentrating under reduced pressure in the still kettle, its operating procedure condition is: temperature: 35～45 ℃
Pressure (absolute pressure): 21KN/m
2
Stirring velocity: 15～20 rev/mins
(12) crystallization.After concentrating under reduced pressure acquired a certain degree in distillation, solution promptly began crystallization.
Separate (13).Emit from still kettle that the crystalline mixture carries out centrifuge dripping to the tripod pendulum type batch centrifugal that is lined with Nylon Bag, obtain solid citric acid sodium.
(14) drying.The solid citric acid sodium that will contain 1～2% moisture is sent into boiling drier dries, and reaches water content below 0.05% further to remove remaining moisture, to make.
Sieve (15).The exsiccant Trisodium Citrate that comes out from boiling drier is sent into vibratory screening apparatus sieve,, and macrobead is removed with the Trisodium Citrate crystal of acquisition crystallization unanimity.
(16) packing.Trisodium Citrate crystal after sieving can be packed, and the 25kg/ bag is through the purified Trisodium Citrate sale of can dispatching from the factory that reaches country of packing.
(17) crystalline mother solution purifies.The mother liquor of discharging during from (13) centrifugation contains 30% Trisodium Citrate, and small amount of impurities adds the scavenging agent activated carbon of 20-30% significant quantity and reductive agent hydrochloric acid to remove these impurity in this crystalline mother solution.
(18) suction filtration.Said mixture is carried out suction filtration,, obtain clean solution with elimination impurity.This solution with the neutralization of pump delivery to the second operation, is recycled.
The present invention's--New Technology for preparing sodium citrate--is through implementing, can be undertaken by following index, 0.95 the ton citric acid adds scavenging agent, the activated carbon of 0.8 ton in alkali and significant quantity, carry out according to technological process of the present invention, can obtain 1 ton of Trisodium Citrate, its economic target also is feasible, and quality product can be listed as follows with production contrast both at home and abroad:
| Standards project | ????BP80 | ????USP | ?GB?6782-86 | Chinese Pharmacopoeia (85 years) | Quality results of the present invention |
| Natrium citricum % acidity and basicity sulfate % heavy metal % arsenic % molysite % oxalates % calcium salt barium salt readily carbonizable substance chloride % tartrate moisture content % | 99.0～101.0 up to specification≤0.03≤0.001--≤0.04---≤0.005-11.0～13.0 | 99.0～100.5 up to specification-≤0.001-------up to specification 10.0～13.0 | 799.0 up to specification≤0.03≤0.0005≤0.0001≤0.001≤0.05 up to specification up to specification≤0.01-- | 799.0 up to specification≤0.05≤0.0005≤0.0001≤0.001 is up to specification-up to specification≤0.01 10.0-13.0 up to specification | 99.69 up to specification 0.005 does not detect 0.00005 0.0004 0.015 up to specification up to specification 0.004 up to specification 11.3 |
Claims (3)
1. New Technology for preparing sodium citrate, be that waste mycelium dreg squeezing acid and the round-robin waste liquor that dumps in producing with Citric Acid Plant is raw material to produce citric acid sodium, production technique has neutralization, affination, decomposition, purification, decolouring, concentrates, crystallization, separation, drying etc., it is characterized in that
(1) in and the time citric acid and milk of lime reaction generate citrate of lime and precipitate;
(2) reaction of citrate of lime and soda ash generates sodium citrate solution when decomposing;
(3) the scavenging agent sodium sulphite that adds the 1-2% significant quantity behind the decomposition process in suction filtration solution is got rid of the impurity that brings in the solution, and Trisodium Citrate is purified;
(4) purified sodium citrate solution condensing crystal under reduced pressure, the Trisodium Citrate crystal.
2. New Technology for preparing sodium citrate according to claim 1 is characterized in that: add the scavenging agent activated carbon and the reductive agent hydrochloric acid of 20-30% significant quantity in the mother liquor of Crystallization Separation gained, to remove impurity.
3. New Technology for preparing sodium citrate according to claim 1 is characterized in that:
(1) neutral temperature of reaction: 60-80 ℃
Reaction times: 1 hour
(2) temperature of reaction of Fen Xieing: 60-80 ℃
PH value of solution value: 6.5-7.5
Reaction times: 2-3 hour
(3) concentrating under reduced pressure service temperature: 35-45 ℃
Pressure (absolute pressure): 2/KH/m
2
Stirring velocity: 15-20 rev/min
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92107081 CN1033324C (en) | 1992-08-08 | 1992-08-08 | New Technology for preparing sodium citrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92107081 CN1033324C (en) | 1992-08-08 | 1992-08-08 | New Technology for preparing sodium citrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1072169A CN1072169A (en) | 1993-05-19 |
| CN1033324C true CN1033324C (en) | 1996-11-20 |
Family
ID=4942645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92107081 Expired - Fee Related CN1033324C (en) | 1992-08-08 | 1992-08-08 | New Technology for preparing sodium citrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033324C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117314B (en) * | 2007-07-10 | 2011-05-18 | 安徽丰原生物化学股份有限公司 | Production method of sodium citrate |
| CN102557921A (en) * | 2011-12-28 | 2012-07-11 | 合肥科尚医药科技有限公司 | Preparation method of potassium sodium hydrogen citrate complex salt hydrate |
| CN102850210A (en) * | 2012-09-21 | 2013-01-02 | 中粮生物化学（安徽）股份有限公司 | Method for purifying sodium citrate mother liquor |
| CN104262139B (en) * | 2014-08-28 | 2016-05-04 | 华北制药集团先泰药业有限公司 | A kind of dilution crystallization is prepared the method for natrium citricum crystal |
| CN109438225A (en) * | 2018-11-21 | 2019-03-08 | 大自然生物集团有限公司 | A kind of preparation method of bulky grain anhydrous citric acid sodium |
| CN111909032B (en) * | 2020-08-07 | 2023-04-14 | 日照金禾博源生化有限公司 | Treatment method of unqualified sodium citrate mother liquor |
-
1992
- 1992-08-08 CN CN 92107081 patent/CN1033324C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1072169A (en) | 1993-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1170772C (en) | Process for removal of oxalate and/or sulphate from bayer liquors | |
| CN1152853C (en) | Process for preparing glycine | |
| CN101434970A (en) | Double decomposition precipitation transformation production method of potassium citrate | |
| CN1033324C (en) | New Technology for preparing sodium citrate | |
| CN101182079A (en) | Citric acid mother liquor treatment process | |
| CN112158865A (en) | Method for recycling lithium element in lithium precipitation mother liquor | |
| CN100343187C (en) | Treatment process for industrial wastewater of VB12 production and dedicated wastewater treatment machine therefor | |
| CN1456505A (en) | Method for preparing lithium compound from lithium metasilicate mixed salt | |
| CN1035000C (en) | Method of extracting citric acid from citric acid fermentation liquor | |
| CN1032940A (en) | The preparation method of crystalline xylose | |
| CN1164565C (en) | Process for preparing amino acids from natural albumen | |
| CN102344195A (en) | Cleaning and recycling method of waste liquid discharged from cinnamonvine acid hydrolysis process | |
| CN110922320B (en) | Method for extracting methyl isobutyl ketone and sodium p-toluenesulfonate | |
| CN1056190C (en) | Citric acid extracting process | |
| CN1054788A (en) | One step leaching grouts extract grease and tea saponin technology | |
| US6310239B1 (en) | Process for manufacturing terephthalic acid | |
| CN1056191C (en) | Trisodium citrate preparing process using anion exchange resin | |
| CN100469750C (en) | Method of extracting calcium gluconate from mother liquid after calcium gluconate crystallization | |
| CN1190365C (en) | Technique for producing magnesium hydroxide and mangesia by using ammonia complete cycle method | |
| CN108299538B (en) | Method for removing isoursodesoxycholic acid in duck bile | |
| CN85109246A (en) | The method for preparing crystalline L-glutamic acid and salt thereof | |
| CN1067049C (en) | Process for producing terephthalic acid | |
| CN1045603C (en) | Process for extracting caffeine from waste tea dust | |
| CN210419811U (en) | Amine alcohol compound reaction system | |
| CN1332144A (en) | Lactic acid separating and purifying process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |