JPH0272887A - Separation and purification of citric acid - Google Patents
Separation and purification of citric acidInfo
- Publication number
- JPH0272887A JPH0272887A JP5316788A JP5316788A JPH0272887A JP H0272887 A JPH0272887 A JP H0272887A JP 5316788 A JP5316788 A JP 5316788A JP 5316788 A JP5316788 A JP 5316788A JP H0272887 A JPH0272887 A JP H0272887A
- Authority
- JP
- Japan
- Prior art keywords
- citric acid
- alkali metal
- aqueous solution
- acid
- liquid
- 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.)
- Pending
Links
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 238000000926 separation method Methods 0.000 title description 4
- 238000000746 purification Methods 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- -1 alkali metal salt Chemical class 0.000 claims abstract description 13
- 238000000855 fermentation Methods 0.000 claims abstract description 13
- 230000004151 fermentation Effects 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 9
- 230000001580 bacterial effect Effects 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 abstract description 5
- 239000001509 sodium citrate Substances 0.000 abstract description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 abstract description 5
- 230000001877 deodorizing effect Effects 0.000 abstract description 2
- 230000000813 microbial effect Effects 0.000 abstract 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 20
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 description 19
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000005253 yeast cell Anatomy 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
40発明の目的
産W冴剪七r顆
本発明は、クエン酸、特に発酵法により製造したクエン
酸からイソクエン酸を分離する方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION 40 Objects of the Invention The present invention relates to a method for separating isocitric acid from citric acid, particularly citric acid produced by a fermentation method.
の” しよ゛と る
従来醗酵法により培養して得た培養液からクエン酸を採
取するには、培養液にpl(3〜5になるように水酸化
カルシウム及び塩化カルシウムを添加し、副生ずるイソ
クエン酸を分離除去して、クエン酸カルシウム及び酵母
菌体を含む固型分を得、次いでこれを水に溶解した後、
硫酸を添加して、pHを1.2〜1.8となし、生成す
る硫酸カルシウムおよび酵母菌体を含む固型分を分離除
去して得られるクエン酸水溶液をイオン交換樹脂、活性
炭処理を行った後濃縮、晶析してクエン酸を回収する方
法である(特公昭47−20395号公報)。To collect citric acid from a culture solution obtained by culturing using the conventional fermentation method, add calcium hydroxide and calcium chloride to the culture solution to make the amount of pl (3 to 5), and The resulting isocitric acid is separated and removed to obtain a solid containing calcium citrate and yeast cells, which is then dissolved in water.
Sulfuric acid is added to adjust the pH to 1.2 to 1.8, and the resulting citric acid aqueous solution is treated with an ion exchange resin and activated carbon. After that, citric acid is recovered by concentration and crystallization (Japanese Patent Publication No. 47-20395).
又、特公昭48−6446号公報記載の方法はクエン酸
およびイソクエン酸を含む溶液からクエン酸を晶出させ
る場合に硫酸を共存させて濃縮し、クエン酸結晶を析出
、分取させる方法である。In addition, the method described in Japanese Patent Publication No. 48-6446 is a method in which when citric acid is crystallized from a solution containing citric acid and isocitric acid, the solution is concentrated in the presence of sulfuric acid, and citric acid crystals are precipitated and separated. .
特開昭47−2359号公報記載の方法は醗酵液のpH
を特定の範囲に調整することによって醗酵液よりクエン
酸ナトリウムおよびイソクエン酸すトリウムを直接回収
する方法である。The method described in JP-A No. 47-2359 is based on the pH of the fermentation liquid.
This is a method for directly recovering sodium citrate and isothorium isocitrate from the fermentation liquid by adjusting the amount within a specific range.
従来のクエン酸およびイソクエン酸の分離法はクエン酸
水溶液をイオン交換樹脂、活性炭処理をおこなったりし
て操作が繁雑であった。また、クエン酸とイソクエン酸
との分離収率も十分ではなかった。Conventional methods for separating citric acid and isocitric acid require complicated operations, such as treating an aqueous citric acid solution with an ion exchange resin and activated carbon. Moreover, the separation yield of citric acid and isocitric acid was also not sufficient.
課業H」石九tA犬1夏礪1反
本発明は、クエン酸醗酵液をアルカリ金属塩またはアル
カリ金属水酸化物の水溶液にてpl+7.0〜8.0に
調整後菌体を分離し、得られた水溶液をクエン酸アルカ
リ金属塩濃度450 g/l以下に濃縮後、?濃縮液を
炭素数1ないし4のアルコール中に投入し、温度−50
“Cないし5℃に冷却して結晶化し、得られた結晶から
クエン酸を分離することを特徴とするクエン酸の分離精
製法に関するものである。Assignment H" Stone 9tA Dog 1 Summer 1 AntiThe present invention involves adjusting the citric acid fermentation solution to pl+7.0 to 8.0 with an aqueous solution of an alkali metal salt or alkali metal hydroxide, and then separating the bacterial cells. After concentrating the obtained aqueous solution to an alkali metal citrate concentration of 450 g/l or less, ? Pour the concentrated liquid into an alcohol having 1 to 4 carbon atoms, and bring the temperature to -50.
This invention relates to a method for separating and purifying citric acid, which is characterized by crystallizing it by cooling it to 5°C to 5°C and separating citric acid from the obtained crystals.
その目的とするところは、脱色、脱臭工程によることな
く、無色のクエン酸ナトリウムの結晶を。The aim is to produce colorless sodium citrate crystals without going through any bleaching or deodorizing processes.
得ると共にイソクエン酸を分離し、クエン酸の純度をあ
げることにある。The objective is to obtain citric acid and separate isocitric acid to increase the purity of citric acid.
さらに詳細には、本発明は、クエン酸醗酵後の醗酵液を
アルカリ金属塩またはアルカリ金属水酸化物(例えば水
酸化ナトリウムまたはカリウム)の水溶液にてp117
.0〜8.0、好ましくはpH7,5に調整後、菌体を
分離し、菌体分離後の水溶液をクエン酸アルカリ金属塩
濃度450 g//l以下、好ましくは300〜400
g/βに濃縮し、温度=50℃ないし5℃、好ましく
は一10℃ないし40℃のアルコール中に濃縮液をアル
コールと濃縮液との容量比2:1になるように加えて結
晶化し、得られた結晶は例えば遠心分離により濾過し、
真空乾燥した。More specifically, the present invention provides a method for treating the fermentation liquor after citric acid fermentation with an aqueous solution of an alkali metal salt or an alkali metal hydroxide (e.g. sodium or potassium hydroxide).
.. After adjusting the pH to 0 to 8.0, preferably 7.5, the bacterial cells are separated, and the aqueous solution after bacterial cell isolation is adjusted to an alkali metal citrate concentration of 450 g//l or less, preferably 300 to 400
g/β, and crystallize by adding the concentrate to alcohol at a temperature of 50°C to 5°C, preferably -10°C to 40°C at a volume ratio of alcohol to concentrate of 2:1, The obtained crystals are filtered, for example by centrifugation,
Vacuum dried.
本発明で使用するに適するアルカリ金属塩はアルカリ金
属の炭酸塩、アルカリ金属水酸化物は水酸化ナトリウム
または水酸化カリウムである。The alkali metal salts suitable for use in the present invention are alkali metal carbonates, and the alkali metal hydroxides are sodium hydroxide or potassium hydroxide.
また、本発明方法で使用するアルコールはC〜C4アル
コールであるが、好ましくはC3以下のアルコールであ
る。Further, the alcohol used in the method of the present invention is a C to C4 alcohol, preferably an alcohol of C3 or less.
また、菌体分離後の水溶液のクエン酸アルカリ金属塩濃
度が300 g / 1以下ではクエン酸とイソクエン
酸との分離はよいが、水溶液からのクエン酸の回収率は
低下し、また回収されるクエン酸に対するアルコールの
使用量が増加し、経済的でない。Furthermore, if the concentration of alkali metal citrate in the aqueous solution after bacterial cell isolation is 300 g/1 or less, separation of citric acid and isocitric acid is good, but the recovery rate of citric acid from the aqueous solution decreases, and the recovery rate of citric acid from the aqueous solution decreases. The amount of alcohol used relative to citric acid increases, making it uneconomical.
一方クエン酸アルカリ金属塩濃度が450 g/ρ以上
では、アルカリ金属塩の飽和濃度に近づくためクエン酸
とイソクエン酸との分離効率が低下する。On the other hand, if the concentration of alkali metal citrate is 450 g/ρ or more, the concentration of alkali metal salt approaches the saturation concentration, so that the separation efficiency between citric acid and isocitric acid decreases.
冷却温度は一50℃ないし5℃の範囲であるが、クエン
酸アルカリ金属塩の濃度が高い程最適冷却温度は高温側
(5℃)に移り、−労咳濃度が低い程最適冷却温度が低
温側(−50℃)に移る。The cooling temperature ranges from -50°C to 5°C, but the higher the concentration of alkali metal citrate, the higher the optimal cooling temperature (5°C), and the lower the cough concentration, the lower the optimal cooling temperature. (-50°C).
本発明方法によるクエン酸とイソクエン酸との分離法を
示すと次のようである。The method for separating citric acid and isocitric acid according to the method of the present invention is as follows.
菌一体一分一離
濾過又は遠心分離
↓
掻−一一一一瞭
クエン酸ナトリウム塩
アルコール(1: エタノール) 5〜−50℃主
又猪益止 (好ましくは−10〜−40’C)
主−」L−丘 水酸化ナトリウム又は↓
免−一−−−慄
真空乾燥
↓
り」」1[L上
ニジしり1晶
ス」1舛
次に実施例を掲げて本発明を説明するが、これに限定さ
れるものではない。Filter or centrifuge the bacteria one minute at a time ↓ Remove the bacteria with sodium citrate salt alcohol (1: ethanol) 5 to -50°C (preferably -10 to -40'C)
The present invention will be described below with reference to Examples. It is not limited to this.
実施例1
クエン酸醗酵液(クエン酸52.7 g / e、イソ
クエン酸27.3g/j!、クエン酸比率65.9%、
pl+5.0) 11に水酸化ナトリウム水溶液を添
加し、p117.0〜8.0に調整後、濾紙(N113
1)にて吸引濾過し、菌体を分離した。Example 1 Citric acid fermentation liquid (citric acid 52.7 g/e, isocitric acid 27.3 g/j!, citric acid ratio 65.9%,
pl+5.0) Add sodium hydroxide aqueous solution to 11 and adjust the p117.0 to 8.0, then filter paper (N113
The bacterial cells were separated by suction filtration in step 1).
得られた濾液をロータリーエバポレーターにてクエン酸
濃度450g/6(クエン酸およびイソクエン酸の合計
量)に濃縮した。The obtained filtrate was concentrated using a rotary evaporator to a citric acid concentration of 450 g/6 (total amount of citric acid and isocitric acid).
濃縮後、濃縮液を5℃の冷却エタノール中に添加し、−
昼夜放置した。エタノールと濃縮液との割合は2 :
1 (vol比)であった。After concentration, the concentrate was added to chilled ethanol at 5°C, and -
I left it there day and night. The ratio of ethanol and concentrate is 2:
1 (vol ratio).
得られた結晶は、遠心分離(濾布1m200)後、真空
乾燥器にて30℃で一昼夜乾燥した。The obtained crystals were centrifuged (filter cloth 1 m200) and then dried in a vacuum dryer at 30° C. overnight.
得られた結晶は52.4g(クエン酸44.2 g、イ
ソクエン酸8.2g、クエン酸比率84.4%)であっ
た。The amount of crystals obtained was 52.4 g (citric acid 44.2 g, isocitric acid 8.2 g, citric acid ratio 84.4%).
クエン酸回収率83.9%、イソクエン酸除去率70.
0%であった。Citric acid recovery rate 83.9%, isocitric acid removal rate 70.
It was 0%.
実施例2〜3
クエン酸醗酵液のクエン酸濃度(クエン酸およびイソク
エン酸の合計it) 112.3 g/lおよび12
0g/fに変えて実施例1と同様にして処理した。試料
中のクエン酸とイソクエン酸との含量、クエン酸比率は
第1表に示した。Examples 2-3 Citric acid concentration of citric acid fermentation solution (total citric acid and isocitric acid it) 112.3 g/l and 12
The treatment was carried out in the same manner as in Example 1 except that the concentration was changed to 0 g/f. The contents of citric acid and isocitric acid in the sample and the citric acid ratio are shown in Table 1.
得られた結果後のクエン酸、イソクエン酸の含量、クエ
ン酸比率、イソクエン酸除去率、およびクエン酸回収率
はそれぞれ第1表に示した。The resulting citric acid, isocitric acid contents, citric acid ratio, isocitric acid removal rate, and citric acid recovery rate are shown in Table 1, respectively.
クエン酸比率は結晶化処理後いずれも向上した。The citric acid ratio improved in all cases after crystallization treatment.
クエン酸の回収率は83.9%〜97.2%と画く、イ
ソクエン酸の含量が少い方がクエン酸の回収率は高くな
る傾向にあった。The recovery rate of citric acid ranged from 83.9% to 97.2%, and the recovery rate of citric acid tended to be higher as the content of isocitric acid was lower.
第 1 表
ハ、光房皇四果
+11 得られるクエン酸ナトリウム結晶は白色、無
臭のものである。Table 1 C, Kobo Koshika+11 The obtained sodium citrate crystals are white and odorless.
(2)本発明方法を用いると活性炭を使用する脱色、脱
臭工程が省略できる。(2) When the method of the present invention is used, the decolorization and deodorization steps using activated carbon can be omitted.
(3) イソクエン酸の除去が可能になる。(3) It becomes possible to remove isocitric acid.
Claims (1)
H7.0〜8.0に調整後、菌体を分離し、得られた水
溶液をクエン酸アルカリ金属塩濃度450g/l以下に
濃縮後、濃縮液を炭素数1ないし4のアルコール中に投
入し、温度−50℃ないし5℃に冷却して結晶化し、得
られた結晶からクエン酸を分離することを特徴とするク
エン酸の分離精製法。(2)クエン酸醗酵液をアルカリ
金属の水酸化物の水溶液にて費pH7.0〜8.0に調
整後、菌体を分離する請求項第1項記載のクエン酸の分
離精製法。(1) Pour the citric acid fermentation solution into an aqueous solution of an alkali metal salt.
After adjusting the pH to 7.0 to 8.0, the bacterial cells were separated, and the resulting aqueous solution was concentrated to an alkali metal citrate concentration of 450 g/l or less, and the concentrated solution was poured into alcohol having 1 to 4 carbon atoms. A method for separating and purifying citric acid, which comprises cooling to a temperature of -50°C to 5°C to crystallize, and separating citric acid from the obtained crystals. (2) The method for separating and purifying citric acid according to claim 1, wherein the citric acid fermentation liquid is adjusted to pH 7.0 to 8.0 with an aqueous solution of an alkali metal hydroxide, and then the bacterial cells are separated.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5316788A JPH0272887A (en) | 1988-03-07 | 1988-03-07 | Separation and purification of citric acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5316788A JPH0272887A (en) | 1988-03-07 | 1988-03-07 | Separation and purification of citric acid |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0272887A true JPH0272887A (en) | 1990-03-13 |
Family
ID=12935298
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5316788A Pending JPH0272887A (en) | 1988-03-07 | 1988-03-07 | Separation and purification of citric acid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0272887A (en) |
Cited By (6)
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CN102964242A (en) * | 2012-12-07 | 2013-03-13 | 中粮生物化学(安徽)股份有限公司 | Citric acid crystal and production method thereof |
CN104230695A (en) * | 2014-07-28 | 2014-12-24 | 中粮生物化学(安徽)股份有限公司 | Citric acid monohydrate crystals and production method thereof |
CN105797422A (en) * | 2016-04-20 | 2016-07-27 | 西安航天华威化工生物工程有限公司 | Citric acid continuous cooling crystallization system and method thereof |
CN106349057A (en) * | 2016-08-29 | 2017-01-25 | 日照金禾博源生化有限公司 | Treatment process for deferrization purification of sodium citrate mother liquor |
-
1988
- 1988-03-07 JP JP5316788A patent/JPH0272887A/en active Pending
Cited By (6)
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JP2002139182A (en) * | 2000-11-02 | 2002-05-17 | Sakura Gomme Kk | Hose for fire fighting |
JP2008232326A (en) * | 2007-03-22 | 2008-10-02 | Toyox Co Ltd | Pipe hose |
CN102964242A (en) * | 2012-12-07 | 2013-03-13 | 中粮生物化学(安徽)股份有限公司 | Citric acid crystal and production method thereof |
CN104230695A (en) * | 2014-07-28 | 2014-12-24 | 中粮生物化学(安徽)股份有限公司 | Citric acid monohydrate crystals and production method thereof |
CN105797422A (en) * | 2016-04-20 | 2016-07-27 | 西安航天华威化工生物工程有限公司 | Citric acid continuous cooling crystallization system and method thereof |
CN106349057A (en) * | 2016-08-29 | 2017-01-25 | 日照金禾博源生化有限公司 | Treatment process for deferrization purification of sodium citrate mother liquor |
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