CN1056191C - Trisodium citrate preparing process using anion exchange resin - Google Patents
Trisodium citrate preparing process using anion exchange resin Download PDFInfo
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- CN1056191C CN1056191C CN95119599A CN95119599A CN1056191C CN 1056191 C CN1056191 C CN 1056191C CN 95119599 A CN95119599 A CN 95119599A CN 95119599 A CN95119599 A CN 95119599A CN 1056191 C CN1056191 C CN 1056191C
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- exchange resin
- citric acid
- citrate
- trisodium citrate
- removal
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Abstract
The present invention relates to a method for preparing trisodium citrate by using anion exchange resin, which comprises the steps of using a fermenting plate frame for the micro-hole filtration of filtrated liquid for removing impurities, removing the impurities by the decolorization of activated carbon, removing impure metal ions by using cation exchange resin, removing impure anions by using anion exchange resin, using MI: 8310<#> anion exchange resin for adsorption and exchanging citric acid groups, using a citrate sodium buffering solution for removing easy carbon compounds, and using sodium hydroxide for analyzing the citric acid groups, and the steps of condensation and crystallization. When the method of the present invention is used, the conversion rate of using the citric acid for generating the citrate sodium can be 90%, and the product quality reaches the BP-88 standard of the British pharmacopoeia.
Description
The present invention relates to technical field of biochemical industry, relate in particular to a kind of method of producing trisodium citrate with anionite-exchange resin.
Trisodium citrate claims 2-hydroxy propane 1,2 again, and the 3-carboxylic acid sodium is a kind of organic acid salt that is widely used in food, medicine and chemical field.
The method of traditional production sodium citrate salt has two kinds [J.pharmacol, Exp.Ther.94,65 (1948)], and first neutralisation is promptly used the reaction of pure product citric acid and sodium hydroxide, generates Trisodium Citrate; It two is double decompositions, even citrate of lime and yellow soda ash reaction generate Trisodium Citrate and lime carbonate, removes lime carbonate through separation, can obtain Trisodium Citrate.Neutralisation is because of using pure citric acid, so production cost is higher.Double decomposition so product yield is low, has only the citric acid of 60-70% to be converted into Trisodium Citrate because of product separates the difficulty of bringing usually.
In order to overcome the aforesaid method shortcoming, the present invention adopts homemade MI:8310
#Weak base anion-exchange resin is as key step, and is auxiliary with other means, realized directly producing from the citric acid fermentation mash purpose of Trisodium Citrate, and conversion rate of products is 85%-90%.
Processing technology routine of the present invention is as follows:
Citric acid fermentation mash filtration sterilization body → microporous filter essence filters out impurities →
Decolorizing with activated carbon →
Zeo-karb removal of impurities positively charged ion →
Anionite-exchange resin removal of impurities negatively charged ion →
MI:8310
#Anionite-exchange resin absorption, exchange citrate →
Sodium hydroxide desorb Radix Citri Limoniae →
Concentrated, crystallization that Trisodium Citrate enters.
To be described further operational path of the present invention below.
In the fermentation mash, produce trisodium citrate and be divided into eight step operations.
The first step operation is filter to remove impurity such as mycelium in the mash, the non-solubility solid substance that is not utilized by microorganism and precipitating proteins.This step uses flame filter press or band filter to finish usually, is that present calcium salt precipitation method is produced the general means of citric acid.
Smart filter of second step operation is in order to remove small quantities of particles and the throw out that sheet frame filter or belt filter filtration procedure are missed, to carry out smoothly to guarantee subsequent handling.
Three-procedure adopts K-15 activated carbon dress post with impurity such as pigment in the removal filtrate and part metals ions.The present invention can accomplish: decolorizing with activated carbon volume ratio (material liquid volume/active carbon column volume that is decoloured) is no less than 12: 1; Average removal rate to the barium in the solution, iron, manganese, aluminium, calcium, zine ion is not less than 45%; The decolouring feed liquid can stably be controlled at 1.5-2.0vvh by the active carbon column flow velocity
-1In the scope.
The 4th step operation is with the assorted metal ion in (H) type strong-acid cation-exchange resin 732 (marques) removal filtrate.The present invention can accomplish: at 1.7vvh
-1Stablize under the flow velocity, the feed liquid effluent liquid iron concentration by 15 column volumes is below 10ppm.
The 5th step operation is removed assorted negatively charged ion in the solution with (OH) type weak basic anion exchange resin D315 (marque).The present invention can accomplish: with 1.8vvh
-1When stablizing flow velocity by this exchange column, the feed liquid effluent liquid chlorine ion concentration of 12 volumes of flowing through is below 2ppm.
The 6th step operation is with (OH) type MI:8310
#Weak basic anion exchange resin (marque) absorption, exchange citrate.The present invention can accomplish: this resin reaches 6.35 moles of/kilogram resins (dry weight) at room temperature (20 ℃) absorption down, exchange citric acid capacity; 2) even if the citric acid feed liquid of 1% (W/V) concentration, absorption, exchange capacity still can reach 5.28 moles of/kilogram resins (dry weight).
In order to remove easy carbon compound, the present invention has adopted the citric acid/sodium citrate damping fluid to wash the anion-exchange column of the 6th step operation, and this method can be removed easy carbon compound effectively, thereby the easy carbon compound in the solution is no longer exceeded standard.
Invention adopts the sodium hydroxide of 15%-20% to resolve citrate, makes the trisodium citrate mean concns of generation can reach 29.5%, thereby utilizes follow-up concentration section to save steam.
Adopt above-mentioned operation to produce trisodium citrate, citric acid is converted into the ratio of Trisodium Citrate at 85%-90%.Quality product can reach British Pharmacopoeia BP-88 specified standards.
Now enumerate following embodiment, and cooperate subordinate list, accompanying drawing, for further understanding technology contents of the present invention.
The present invention follows these steps to implement:
1) the decolouring removal of impurity
Clear liquid after the flame filter press that experiment is taken from the dried raw material citric acid production of potato factory with citric acid solution filters, this solution composition is as shown in table 1.For the removal of impurities of decolouring effectively, feed liquid enters before the decolorizing column, needs to remove particulate matter and the throw out of missing when flame filter press filters through microporous filter, and the clear liquid of acquisition can enter the carbon post decolouring removal of impurity.
Experiment is K-15 with the activated carbon model, active carbon column specification φ 500 * 3000mm, and actual work loading height is 2380mm, the carbon column material is a Reinforced Polypropylene.Feed liquid is at room temperature with 1.5-2.0vvh
-1Flow velocity treats that by the carbon post effluent liquid transmitance is lower than (420mm) at 75% o'clock, promptly stops decolouring.Handle through above-mentioned operation, the results are shown in Table 1 for the citric acid solution Impurity removal.
2) Zeo-karb removal of impurities positively charged ion.
Through the citric acid solution of decolorizing column decolouring, need remove assorted positively charged ion in the solution by Zeo-karb.H type Zeo-karb 732 (marque) has been selected in experiment for use, exchange column specification φ 800 * 4000mm, and actual work loading height 3500mm, exchange column are the carbon steel line with rubber.Feed liquid is at room temperature with 1.5-2.0vvh
-1Flow velocity is by the carbon post, when treating that Fe sees through exchange column (10ppm), promptly stops exchange, 12 times of volumes of the citric acid solution of commutative above-mentioned concentration.This moment, the solution metal ion content can satisfy the subsequent step technical requirements fully.
3) anionite-exchange resin removal of impurities negatively charged ion
Through the deimpurity feed liquid of Zeo-karb, again by (OH) type anionite-exchange resin D315 (marque).This resin can optionally be removed assorted negative ions such as chlorion, sulfate radical, and the citrate negative ion is hardly by this resins exchange, thereby reaches the purpose of removing assorted negative ion.A polypropylene exchange column is used in experiment, pillar specification φ 500 * 3000mm, and actual work loading height is 2000mm, operation flow velocity 1.5-2.0vvh
-1, when treating that the effluent liquid chlorine ion concentration is 2ppm, promptly stop exchange, 12 times of volumes of the citric acid solution of commutative above-mentioned concentration, the content of the negative ion of mixing in the solution this moment can satisfy the crystalline quality requirement fully.
4) MI:8310
#Anionite-exchange resin is produced Trisodium Citrate
Feed liquid through above-mentioned steps is handled can directly enter MI:8310 is housed
#(marque) be the exchange column of type anionite-exchange resin (OH), and this column material is the carbon steel line with rubber, and specification is φ 1000 * 2800mm, actual dress post 1900mm.
Upper prop feed liquid flow velocity 1.5-2.0vvh
-1Resin is at room temperature respectively with the citric acid feed liquid upper prop of 8.2 and 1% (W/V), treats that the effluent liquid pH value reduces to 6, stops charging.Record exchange capacity and be respectively 6.35 and 5.28 moles of/kilogram resins (dry weight) [seeing Table of the influence (20 ℃) of 2 different concns citric acid feed liquids] absorption, exchange capacity.Next the citric acid/sodium citrate damping fluid with the PH 3.5-5.0 of the deionized water of a column volume and a volume washs this post respectively, to remove easy carbon compound impurity.The above-mentioned steps carefully handled finishes, and with the sodium hydroxide solution wash-out citrate of 12-20%, when effluent liquid is measured pH value 7-8 after stirring, promptly carries feed liquid to arrive condensing crystal workshop section.
Sodium hydroxide with different concns is resolved citrate, and the sodium citrate concentration of generation is also different, and its rule is for raising with concentration sodium hydroxide.Consider that production concentration is low relatively and will cause that steam consumption increases when concentrating, the sodium hydroxide of 20% concentration is adopted in this experiment, its elution curve, i.e. and sodium hydroxide parsing citrate curve is as shown in Figure 1.Fig. 1 shows that the trisodium citrate mean concns of generation reaches 29.5%.Simultaneously, elution process is MI:8310
#The resin regeneration process, thereby simplified operation steps.
5) product quality analysis
Through the trisodium citrate crystalline product that said extracted technology obtains, to analyze by the method for British Pharmacopoeia BP-88, analytical results is listed in table 3.The result shows that operational path of the present invention can reach this pharmacopeia specified standards fully.Table 1
* the table in data except that citric acid concentration in the percentage ratio, other are ppm.Table 2
Table 3 (continuous table)
* Pass Test refers to that the * * that conforms to quality requirements is not deeper than standard and refers to be not deeper than BP-88 pharmacopeia specified standards by the test of BP-88 official method.
| Sequence number | Analysis project | The | |
| 1 | Proterties | The white particle crystal | |
| 2 | Solubleness | Pass | |
| 3 | Telling test | Pass Test * | |
| 4 | Clarity and | Pass Test | * |
| 5 | Acidity and basicity | Pass Test * | |
| 6 | Heavy metal (in lead) | Less than | |
| 7 | Muriate (in chlorine) | Less than 50ppm | |
| 8 | Oxalate | Less than | |
| 9 | Easy carbon compound | Be not deeper than standard ** | |
| 10 | Vitriol | Pass | |
| 11 | Moisture content | 12.7％ | |
| 12 | Content | 99.6％ |
Claims (2)
1, a kind ofly produces the method for trisodium citrate, it is characterized in that, use homemade MI:8310 with anionite-exchange resin
#Weak base anion-exchange resin, its absorption, exchange citric acid capacity are 5.28-6.35 mole/kilogram resin (dry weight), produce by following technology:
1) with the removal of impurity of the smart filter plate frame of microporous filter filtrate;
2) with the removal of impurity of K-15 activity carbon column decoloring;
3) with 732 (H) type Zeo-karb removal of impurities metal ion;
4) with D315 (OH) type anionite-exchange resin removal of impurities negatively charged ion;
5) use MI:8310
#(OH) type anionite-exchange resin absorption, exchange citrate;
6) with the easy carbon compound of citric acid/sodium citrate buffer solution elution;
7) resolve with 12-20%NaOH, generate trisodium citrate concentration and reach 29%;
8) concentrated, crystallization.
2, the method for producing trisodium citrate as claimed in claim 1 is characterized in that, the material that is used for the easy carbon compound of wash-out is a PH3.5-5.0 citric acid/sodium citrate damping fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119599A CN1056191C (en) | 1995-12-04 | 1995-12-04 | Trisodium citrate preparing process using anion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119599A CN1056191C (en) | 1995-12-04 | 1995-12-04 | Trisodium citrate preparing process using anion exchange resin |
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| Publication Number | Publication Date |
|---|---|
| CN1153822A CN1153822A (en) | 1997-07-09 |
| CN1056191C true CN1056191C (en) | 2000-09-06 |
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| CN95119599A Expired - Fee Related CN1056191C (en) | 1995-12-04 | 1995-12-04 | Trisodium citrate preparing process using anion exchange resin |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407454B (en) * | 2007-10-13 | 2011-09-07 | 黄石兴华生化有限公司 | Process for preparing citrate salt from mother liquor for citric acid production |
| CN102617334B (en) * | 2012-03-02 | 2014-05-07 | 中粮生物化学（安徽）股份有限公司 | Refine method of sodium citrate mother solution |
| CN103058848B (en) * | 2012-11-01 | 2016-04-13 | 南京工业大学 | A kind of method intending homogeneous phase weak base anion-exchange resin separating organic acid |
| CN106349057B (en) * | 2016-08-29 | 2019-02-15 | 日照金禾博源生化有限公司 | A kind of sodium citrate mother liquor deferrization purification process technique |
| CN113880711A (en) * | 2021-11-01 | 2022-01-04 | 莱芜泰禾生化有限公司 | Purification preparation method of sodium citrate |
| CN114790467A (en) * | 2022-06-06 | 2022-07-26 | 杭州鸿满化工有限公司 | Citric acid fermentation process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851573A (en) * | 1986-12-18 | 1989-07-25 | Uop | Separation of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent |
| US4924027A (en) * | 1986-12-18 | 1990-05-08 | Uop | Separation of salts of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent |
| CN1090264A (en) * | 1992-10-07 | 1994-08-03 | 塞里斯塔控股有限公司 | The preparation method of alkali metal citrate |
-
1995
- 1995-12-04 CN CN95119599A patent/CN1056191C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851573A (en) * | 1986-12-18 | 1989-07-25 | Uop | Separation of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent |
| US4924027A (en) * | 1986-12-18 | 1990-05-08 | Uop | Separation of salts of citric acid from fermentation broth with a weakly basic anionic exchange resin adsorbent |
| CN1090264A (en) * | 1992-10-07 | 1994-08-03 | 塞里斯塔控股有限公司 | The preparation method of alkali metal citrate |
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| CN1153822A (en) | 1997-07-09 |
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