CN103044239B - Production method of sodium citrate - Google Patents

Production method of sodium citrate Download PDF

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CN103044239B
CN103044239B CN201210550020.7A CN201210550020A CN103044239B CN 103044239 B CN103044239 B CN 103044239B CN 201210550020 A CN201210550020 A CN 201210550020A CN 103044239 B CN103044239 B CN 103044239B
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citrate
calcium
calcium hydrogen
slurries
crystallization
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CN103044239A (en
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李昌涛
安丰民
孔玉
刘剑雄
任守会
周昊
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RIZHAO RIJIN BOYUAN BIOCHEMISTRY CO Ltd
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RIZHAO RIJIN BOYUAN BIOCHEMISTRY CO Ltd
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Abstract

The invention relates to a production method of sodium citrate. The method comprises the main steps that limestone powder and citric acid fermentation liquor are reacted, filtered and crystallized, and then are conducted to at least one time of neutralization and crystallization, so that calcium hydrogen citrate crystal is continuously and directly obtained; and the calcium hydrogen citrate crystal is reacted with the mixed solution of sodium hydroxide and sodium carbonate, so that sodium citrate and calcium carbonate are obtained. The method increases the content of carbonate in a whole system, reduces the hydrolysis rate of the carbonate, avoids the affect to finished products by calcium bicarbonate, and prevents the calcium ion in the finished products from exceeding standard. Part of sodium in the sodium citrate is provided by ionic membrane caustic soda, and compared with the traditional one-step method for producing sodium citrate, the production method has the advantages that the purity of solution is high, contents of calcium ion, iron ion and chloride ion are low, and return rate of sodium citrate mother liquor is greatly reduced.

Description

A kind of production method of Trisodium Citrate
Technical field
The present invention relates to a kind of production method of Trisodium Citrate.
Background technology
Trisodium Citrate is the maximum derived product of citric acid, and it is mainly used in the fields such as bulk drug, high-end food-drink, healthcare products, high-end cosmetics of everyday use, detergent industry and cleaning industry.Its preparation method generally comprises: starchy material obtains fermentation clear liquid after fermentation is filtered, then citric acid purification liquid is obtained by chemistry (calcium salt method and hydrogen calcium method) purification or physical purification (chromatography and extraction process), in citric acid purification liquid and ion film caustic soda and obtains sodium citrate solution, then through condensing crystal acquisition Trisodium Citrate product.
At present, domestic have the technique being realized Trisodium Citrate purification by suction-joint method and single stage method.Wherein One-step production Trisodium Citrate technique is the purification realizing Trisodium Citrate with the citrate of lime produced in citric acid purification process and soda ash (sodium carbonate) replacement(metathesis)reaction.There is following shortcoming in this technique: 1, raw material defect: cause the underproof leading indicator iron ion of Trisodium Citrate product, chlorion and readily carbonizable substances.Soda ash is chlor-alkali industry goods, and containing a large amount of chlorions and iron ion, the chlorion in all sodium carbonate and iron ion can be brought in Trisodium Citrate purification liquid by this technique, and cause the mother liquor of Trisodium Citrate to return throwing amount large, soda ash (sodium carbonate) unit consumption is high.2, the citrate of lime that obtains with neutralization reaction of this technique reacts for raw material and excessive sodium carbonate, and therefore, replacement(metathesis)reaction terminates sodium carbonate in the citric acid after a large amount of purifying of rear needs He excessive.
Also there is at present report to substitute citrate of lime and sodium carbonate or sodium bicarbonate or sodium hydroxide by calcium hydrogen citrate and carry out replacement(metathesis)reaction, the technique of generation Trisodium Citrate.But in this technique, calcium hydrogen citrate easily causes there is a large amount of calcium ion (Calcium hydrogen carbonate or calcium hydroxide) in final sodium citrate solution as a kind of acid salt, causes product calcium ion to exceed standard.
In addition, very high to the purity requirement of calcium carbonate or calcium hydroxide in the method for existing production calcium hydrogen citrate, thus cause cost high.When using limestone powder for raw material, due to the calcium carbonate content 90-99% of limestone powder, therefore the ratio that solution mesosilicic acid salt accounts for calcium hydrogen citrate crystal reaches 0.5-2.5%, account for the 0.5-4 ‰ of solution, therefore the impurity do not removed in limestone powder can be larger on quality product impact, simultaneously impurity is very large on the impact of citric acid byproduct calcium sulfate, makes calcium sulfate cannot deep processing.Although the Wingdale of China is rich in mineral resources, the mineral reserve that purity is higher are less.Therefore low-grade limestone powder is developed and the technique not affecting the production citric acid of quality product just has important practical significance.
Summary of the invention
For the problems referred to above, the present invention proposes a kind of production method of Trisodium Citrate, limestone powder and citric acid fermentation broth mainly react by the present invention, filter, after crystallization again at least one times and crystallisation process direct obtained calcium hydrogen citrate crystal continuously, and make the mixing solutions of itself and sodium carbonate and sodium hydroxide carry out neutralization reaction and replacement(metathesis)reaction prepares Trisodium Citrate and calcium carbonate.
Its concrete steps are:
(1) calcium agent is added by citric acid fermentation filtrate, stirring reaction;
(2) step (1) gained slurries and limestone powder slurries are added in reactor, rapid stirring filters simultaneously;
(3) clear liquid after filtering is mixed with the slurries of the calcium hydrogen citrate of backflow carry out first degree crystalline;
(4) by the magma overflow after first degree crystalline to secondary crystallization tank, and wherein slowly stream add limestone powder slurries, carry out in secondary and crystallization;
(5) by magma overflow to the three grade crystallizer after secondary crystallization, and slow stream adds limestone powder slurries wherein, carries out in three grades and crystallization;
(6) by and crystallization after magma flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to first degree crystalline process, and lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) join in the calcium hydrogen citrate magma bucket after affination after being mixed with ion film caustic soda liquid by sodium carbonate solution in step (2) and react, filter, calcium carbonate replaces limestone powder to be back to whole production process, and filtrate refines to obtain Trisodium Citrate.
In production process, first will add calcium agent stirring reaction in citric acid fermentation filtrate.The calcium agent that the present invention adopts is the citrate of lime slurries of calcium carbonate or calcium hydrogen citrate disposing mother liquor, preferred the latter, this is because when citrate of lime is added into after in citric acid fermentation filtrate, being converted into calcium hydrogen citrate is dissolved in whole reaction system, also late phase reaction is easily induced to carry out to the direction generating calcium hydrogen citrate, and remaining calcium ion can and citric acid fermentation filtrate in oxalic acid fully react, formation calcium oxalate precipitation.In order to ensure that citrate of lime is converted into calcium hydrogen citrate completely and dissolves, make caoxalate fully precipitate simultaneously, the temperature of reaction that the present invention adopts is 50-85 DEG C, reaction times is 0.5-4h, in citric acid in citric acid fermentation filtrate and citrate of lime slurries, the mol ratio of citrate is 1:0.1-0.25, if ratio is excessive, then can cause having part citric acid calcium to dissolve, remain in whole reaction system, induction final product carries out to citrate of lime direction or is removed in filter progress, affects ultimate yield; Ratio is too small, then the hydrogen citrate hypocalcia generated.After stirring reaction completes, the main component in slurries is citric acid, calcium hydrogen citrate, caoxalate.
The slurries of step (1) gained and limestone powder slurries are added in reactor and mixes, in order to ensure can to react between the citric acid in slurries and the calcium carbonate in limestone powder slurries, and reaction carries out towards the direction generating calcium hydrogen citrate, need by regulating the flow of slurries and limestone powder slurries to ensure that the mol ratio of citric acid molecule and calcium ion in whole reaction system is 1:0.65-0.85.If lower than this ratio, this process economy is poor, and the calcium hydrogen citrate simultaneously generated very little; If higher than the ratio of 0.85, just easily occur that citrate of lime precipitates, thus cause whole reaction to turn to generation citrate of lime precipitation.The slurries of step (1) gained and limestone powder slurries adopt the mode simultaneously added, and avoid the phenomenon that appearance calcium is excessive or pH value is too low of local long period, cause occurring that citrate of lime precipitates.
When step (1) gained slurries and limestone powder slurries being added in reactor, the citrate of lime having a large amount of calcium hydrogen citrates and trace generates, and therefore now easily occurs the precipitation of calcium hydrogen citrate and citrate of lime simultaneously.But, because citric acid is tribasic carboxylic acid, surge time is long, contriver finds, this mixed system was not easy to occur precipitation in 60 minutes, therefore to stir in step (2) and the total time of filtering more than 60 minutes, so not only can not can ensure that the short period of time calcium hydrogen citrate supersaturated solution of interior acquisition did not produce crystal but also avoids overlong time and generate calcium citrate crystals.
When step (1) gained slurries and limestone powder slurries add in reactor simultaneously, a large amount of carbonic acid gas can be produced, now adopt ion film caustic soda liquid by carbon dioxide absorption, Formed acid sodium solution.The too low meeting of massfraction due to ion film caustic soda liquid causes final sodium citrate solution concentration too low, and the concentrated energy consumption of the finished product is very high; Massfraction is too high not only can be increased raw materials cost but also cause final sodium citrate solution concentration too high, thus when making it be separated with calcium carbonate, wash water consumption increases.Contriver found through experiments when the massfraction of ion film caustic soda liquid is 5-32%, best results.
Calcium carbonate mass content >90% in the limestone powder adopted in step (2), particle is less than 100 orders; In limestone powder slurries, solid masses content is 50%-60%.Filtrate after filtration is mainly containing calcium hydrogen citrate, dihydrogen citrate calcium and citric acid, and turbidity is in 5NTU, and filter residue once filters the impurity such as the mycelium do not filtered completely in insoluble impurities, caoxalate and the fermented liquid in limestone powder.
The slurries of the calcium hydrogen citrate adding the backflow of calcium hydrogen citrate emptying tank upper strata in the clear liquid after the filtration of step (2) gained are carried out first degree crystalline, and the clear liquid after filtration is 1:0.1-0.5 with the calcium hydrogen citrate slurry volume ratio of backflow.If the calcium hydrogen citrate slurries of backflow add very few, fewer calcium hydrogen citrate crystal seed can only be introduced, be unfavorable for the release of later stage calcium hydrogen citrate degree of supersaturation; If backflow calcium hydrogen citrate slurries add too much, then easily cause liquor capacity excessive, required equipment volume increase and also whole solution system in solid content too low.Because the clear liquid after the filtration of step (2) gained is the supersaturated solution of calcium hydrogen citrate, once mix with the slurries containing calcium hydrogen citrate, under the induction of crystal seed, degree of supersaturation is discharged, and realizes the growth of calcium hydrogen citrate.Generate in order to ensure the direction of product to calcium hydrogen citrate, and be beneficial to the crystallization of calcium hydrogen citrate crystal, need the pH value controlling whole system to be 2.8-3.2, Tc is 60-90 DEG C, and crystallization time is 0.5-6h.The adjustment of pH value can be realized by dilture acid refining after interpolation citric acid and citric acid mother liquor.Too high pH value likely causes generating citrate of lime precipitation or causing the too many calcium hydrogen citrate crystal of excessive, the easy appearance of saturation ratio, makes crystal grain in last magma too little; Too low pH value, needs a large amount of citric acids, and hydrogen citrate calcium deposit may be caused on the low side.In magma after first degree crystalline, main component is citric acid, calcium hydrogen citrate, dihydrogen citrate calcium.
By the magma overflow after first degree crystalline to secondary crystallization tank, and slow stream adds limestone powder slurries wherein, carries out in secondary and crystallization; In this process, limestone powder slurries and citric acid or dihydrogen citrate calcium react and are converted into calcium hydrogen citrate, from and the supersaturated solution that defines containing calcium hydrogen citrate, under the induction of calcium hydrogen citrate crystal seed, degree of supersaturation is released again further, realizes the further growth of calcium hydrogen citrate.In order to be beneficial to calcium hydrogen citrate crystal structure and avoid the waste of the energy, in this step, Tc is 60-90 DEG C.In like manner, in order to ensure to produce in whole system fair amount, the good Calcium hydrogen carbonate crystal of crystal formation, system pH is 3.0-3.5, and crystallization time is 1-6h.Because the limestone slurry introduced from this will not have the chance of repurity, the impurity that this place introduces easily takes in product, and in the limestone powder therefore herein adopted, calcium carbonate mass content is 97-99%, and particle is less than 100 orders; In limestone powder slurries, solid masses content is 50%-60%.In magma in secondary and after crystallization, main component is citric acid, calcium hydrogen citrate, dihydrogen citrate calcium.
By in the magma overflow to three grade in secondary and after crystallization and crystallizer, and wherein slowly stream add limestone powder slurries, carry out in three grades and crystallization; In like manner, in this process, limestone powder slurries and citric acid or dihydrogen citrate calcium react and are converted into calcium hydrogen citrate, from and the supersaturated solution that defines containing calcium hydrogen citrate, under the induction of calcium hydrogen citrate crystal seed, degree of supersaturation is released again further, realizes the further growth of calcium hydrogen citrate.In order to be beneficial to calcium hydrogen citrate crystal structure and avoid the waste of the energy, in this step, Tc is 60-90 DEG C, and pH value is 3.5-4.5, and crystallization time is 1-6h.Because the limestone slurry introduced from this will not have the chance of repurity, the impurity that this place introduces easily takes in product, and in the limestone powder therefore herein adopted, calcium carbonate mass content is 97-99%, and particle is less than 100 orders; In limestone powder slurries, solid masses content is 50%-60%.
In concrete operating process, if after foregoing three grades of crystallisation processs, still containing the composition such as citric acid, dihydrogen citrate calcium in magma, still can repeat in the third stage again and crystallisation process, until calcium hydrogen citrate crystallization is complete in whole system.
Magma in final and after crystallization is flowed into slurry tank, and upper strata calcium hydrogen citrate backflow of particles is to first degree crystalline process, and lower floor's calcium hydrogen citrate crystal enters affination operation, the known technology commonly used for this area that affination operation of the present invention adopts.
After sodium carbonate solution is mixed with ion film caustic soda liquid, join in the calcium hydrogen citrate magma bucket after affination and react.In this step, first the hydrogen ion in calcium hydrogen citrate carries out neutralization reaction with ion film caustic soda, and the carbonate then in calcium ion and sodium carbonate solution carries out reaction and generates precipitation of calcium carbonate, and citrate and sodium ion react and generate Trisodium Citrate.In this step, to sodium carbonate solution massfraction without too much requirement.The sodium carbonate that sodium carbonate solution can be bought by market obtains, and also can be obtained by the carbon dioxide produced in ion film caustic soda liquid absorption step (2).During the sodium carbonate bought when selecting market, although wherein containing a large amount of chlorions and iron ion, but because a part of sodium ion in final Trisodium Citrate product comes from ion film caustic soda liquid, greatly reduce so the consumption of sodium carbonate remains for traditional technology, iron in the finished product, chlorine ion concentration are relatively low.In order to more effectively avoid the introducing of iron in the finished product, chlorion, the sodium carbonate solution that the present invention obtains preferably by the carbon dioxide produced in ion film caustic soda liquid absorption step (2).Contriver finds through long-felt, with molar ratio computing, work as calcium hydrogen citrate: sodium carbonate: sodium hydroxide=1:1.05-1.2:0.6-1.03, optimum proportion is calcium hydrogen citrate: sodium carbonate: during sodium hydroxide=1:1.08-1.12:1.0-1.01, can ensure that in this system, carbonate concentration is higher, hydroxide radical relative concentration is lower, and reaction at utmost generates the higher Trisodium Citrate of purity, when having reacted, pH value is 10-13, avoids the later stage to adopt too much citric acid to carry out pH value adjustment.
In order to ensure that reaction comparatively fast completes, also avoid energy dissipation, temperature of reaction is 60-85 DEG C, consistent with calcium hydrogen citrate magma initial temperature.Reaction times is too short, causes reaction not exclusively, can there is more calcium ion in system, also have unreacted calcium hydrogen citrate completely simultaneously; Reaction times is long, easily causes the generation of calcium hydroxide, and be partially soluble in reaction system, calcium ion content is too high, and calcium hydroxide granularity, close to colloid, strengthens with Trisodium Citrate separating difficulty, and therefore, the reaction times, 1-6h was advisable.In like manner, the too low meeting of the massfraction due to ion film caustic soda liquid causes final sodium citrate solution concentration too low, and the concentrated energy consumption of the finished product is very high; Massfraction is too high not only can be increased raw materials cost but also cause final sodium citrate solution concentration too high, thus when making it be separated with calcium carbonate, wash water consumption increases.Contriver found through experiments when the massfraction of ion film caustic soda liquid is 5-32%, best results.
Filtered by slurries complete for above-mentioned reaction, filter residue is calcium carbonate, and filtrate is sodium citrate solution.Owing to only containing a small amount of pigment and readily carbonizable substances in calcium carbonate, pure calcium carbonate >=99% in solid substance, therefore can be replaced limestone powder to be back in whole production process.Filtrate is through refining citric acid solution adjust pH at 7.0-8.5, and decolouring, essence are filtered, concentrated, crystalline Trisodium Citrate product.
In sum, the present invention has following beneficial effect:
1, the reaction times of citric acid to dihydrogen citrate calcium and calcium hydrogen citrate is first shortened, then by continuation crystallization that multistage neutralization reaction provides the supersaturated solution of calcium hydrogen citrate to realize calcium hydrogen citrate, extend the crystallization time of calcium hydrogen citrate, achieve the sufficient crystallising of calcium hydrogen citrate, the calcium hydrogen citrate crystal grain that the present invention obtains is large and evenly, purity is far away higher than traditional citrate of lime;
2, present invention reduces the impact on quality product and byproduct calcium sulfate quality such as silicate impurity that limestone powder purity defect brings, remove most oxalic acid simultaneously, achieve the method that low-grade limestone powder prepares higher-grade calcium hydrogen citrate;
3, the sodium carbonate solution that the present invention adopts is that the carbonic acid gas that ion film caustic soda liquid absorption reaction is released obtains, avoid and chlorion and iron ion are brought in Trisodium Citrate purification liquid, the mother liquor of Trisodium Citrate is caused to return throwing amount large, the problem that soda ash (sodium carbonate) unit consumption is high;
4, purity calcium carbonate is generated in production process of the present invention, to replace the limestone powder of low-purity to be back in whole production process, environmental protection, economy;
5, the present invention will add sodium carbonate and ion film caustic soda liquid in calcium hydrogen citrate slurries, make it that neutralization and replacement(metathesis)reaction occur, improve carbonate concentration in whole system, reduce hydroxide radical concentration, avoid this acid salt of calcium hydrogen citrate to the impact of the finished product, avoid calcium ion in the finished product and exceed standard;
6, the present invention adopts ion film caustic soda liquid, reduces the chlorion in alkali, ensure that the quality of the finished product.
Embodiment
Embodiment 1
A production method for Trisodium Citrate, its concrete steps are:
(1) add citrate of lime slurries by citric acid fermentation filtrate, 60 DEG C of stirring reaction 1.5h, wherein, in the citric acid in citric acid fermentation filtrate and citrate of lime slurries, the mol ratio of citrate is 1:0.25;
(2) step (1) gained slurries and limestone powder slurries are added in reactor simultaneously, ensure that the mol ratio of citric acid molecule and calcium ion in whole system is 1:0.65, complete rapid stirring in 15 minutes to filter, and be the carbonic acid gas that 25% ion film caustic soda liquid absorption reaction is released with massfraction, obtained sodium carbonate solution; Wherein, in limestone powder, calcium carbonate mass content is 91%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 50%;
(3) slurries adding the calcium hydrogen citrate of backflow in the clear liquid after filtration are carried out first degree crystalline; Clear liquid after wherein filtering is 1:0.1 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 80 DEG C, and pH value is 3.0, and crystallization time is 2h;
(4) by the magma overflow after first degree crystalline to secondary crystallization tank, and wherein slowly stream add limestone powder slurries, carry out in secondary and crystallization; Wherein Tc is 78 DEG C, and pH value is 3.0, and crystallization time is 2h; In limestone powder, calcium carbonate mass content is 98%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 50%;
(5) by magma overflow to the three grade crystallizer after secondary crystallization, and slow stream adds limestone powder slurries wherein, carries out in three grades and crystallization; Tc is 75 DEG C, and pH value is 3.5, and crystallization time is 2h; In limestone powder, calcium carbonate mass content is 98%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 50%;
(6) by and crystallization after magma flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to first degree crystalline process, and lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) be to join in the calcium hydrogen citrate magma bucket after affination 60 DEG C after 18% ion film caustic soda liquid mixes to react 4 hours by sodium carbonate solution in step (2) and massfraction, wherein, with molar ratio computing, calcium hydrogen citrate: sodium carbonate: sodium hydroxide=1:1.2:1.03, reaction end pH value is 11, filter, calcium carbonate replaces limestone powder to be back to whole production process, and filtrate refines to obtain Trisodium Citrate.
Embodiment 2
A production method for Trisodium Citrate, its concrete steps are:
(1) add citrate of lime slurries by citric acid fermentation filtrate, 70 DEG C of stirring reaction 2h, wherein, in the citric acid in citric acid fermentation filtrate and citrate of lime slurries, the mol ratio of citrate is 1:0.1;
(2) step (1) gained slurries and limestone powder slurries are added in reactor simultaneously, ensure that the mol ratio of citric acid molecule and calcium ion in whole system is 1:0.70, complete rapid stirring in 30 minutes and filter; Wherein, in limestone powder, calcium carbonate mass content is 92%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 52%;
(3) slurries adding the calcium hydrogen citrate of backflow in the clear liquid after filtration are carried out first degree crystalline; Clear liquid after wherein filtering is 1:0.1 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 75 DEG C, and pH value is 3.1, and crystallization time is 3h;
(4) by the magma overflow after first degree crystalline to secondary crystallization tank, and wherein slowly stream add limestone powder slurries, carry out in secondary and crystallization; Wherein Tc is 60 DEG C, and pH value is 3.2, and crystallization time is 6h; In limestone powder, calcium carbonate mass content is 97%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 52%;
(5) by magma overflow to the three grade crystallizer after secondary crystallization, and slow stream adds limestone powder slurries wherein, carries out in three grades and crystallization; Tc is 85 DEG C, and pH value is 3.8, and crystallization time is 3h; In limestone powder, calcium carbonate mass content is 97%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 52%;
(6) by and crystallization after magma flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to first degree crystalline process, and lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) sodium carbonate of purchase is configured to the solution that massfraction is 30%, and be to join in the calcium hydrogen citrate magma bucket after affination 85 DEG C after 12% ion film caustic soda liquid mixes to react 1 hour with massfraction, wherein, with molar ratio computing, calcium hydrogen citrate: sodium carbonate: sodium hydroxide=1:1.1:0.7, reaction end pH value is 10, filters, calcium carbonate replaces limestone powder to be back to whole production process, and filtrate refines to obtain Trisodium Citrate.
Embodiment 3
A production method for Trisodium Citrate, its concrete steps are:
(1) add citrate of lime slurries by citric acid fermentation filtrate, 80 DEG C of stirring reaction 3h, wherein, in the citric acid in citric acid fermentation filtrate and citrate of lime slurries, the mol ratio of citrate is 1:0.17;
(2) step (1) gained slurries and limestone powder slurries are added in reactor simultaneously, ensure that the mol ratio of citric acid molecule and calcium ion in whole system is 1:0.75, complete rapid stirring in 45 minutes to filter, and be the carbonic acid gas that 18% ion film caustic soda liquid absorption reaction is released with massfraction, obtained sodium carbonate solution; Wherein, in limestone powder, calcium carbonate mass content is 95%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 55%;
(3) slurries adding the calcium hydrogen citrate of backflow in the clear liquid after filtration are carried out first degree crystalline; Clear liquid after wherein filtering is 1:0.2 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 80 DEG C, and pH value is 2.8, and crystallization time is 1h;
(4) by the magma overflow after first degree crystalline to secondary crystallization tank, and wherein slowly stream add limestone powder slurries, carry out in secondary and crystallization; Wherein Tc is 80 DEG C, and pH value is 3.4, and crystallization time is 3h; In limestone powder, calcium carbonate mass content is 99%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 55%;
(5) by magma overflow to the three grade crystallizer after secondary crystallization, and slow stream adds limestone powder slurries wherein, carries out in three grades and crystallization; Tc is 80 DEG C, and pH value is 4.0, and crystallization time is 4h; In limestone powder, calcium carbonate mass content is 99%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 55%;
(6) by and crystallization after magma flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to first degree crystalline process, and lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) be to join in the calcium hydrogen citrate magma bucket after affination 65 DEG C after 5% ion film caustic soda liquid mixes to react 2 hours by sodium carbonate solution in step (2) and massfraction, wherein, with molar ratio computing, calcium hydrogen citrate: sodium carbonate: sodium hydroxide=1:1.05:0.6, reaction end pH value is 12, filter, calcium carbonate replaces limestone powder to be back to whole production process, and filtrate refines to obtain Trisodium Citrate.
Embodiment 4
A production method for Trisodium Citrate, its concrete steps are:
(1) add citrate of lime slurries by citric acid fermentation filtrate, 85 DEG C of stirring reaction 0.5h, wherein, in the citric acid in citric acid fermentation filtrate and citrate of lime slurries, the mol ratio of citrate is 1:0.15;
(2) step (1) gained slurries and limestone powder slurries are added in reactor simultaneously, ensure that the mol ratio of citric acid molecule and calcium ion in whole system is 1:0.80, complete rapid stirring in 20 minutes to filter, and be the carbonic acid gas that 5% ion film caustic soda liquid absorption reaction is released with massfraction, obtained sodium carbonate solution; Wherein, in limestone powder, calcium carbonate mass content is 94%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 58%;
(3) slurries adding the calcium hydrogen citrate of backflow in the clear liquid after filtration are carried out first degree crystalline; Clear liquid after wherein filtering is 1:0.4 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 60 DEG C, and pH value is 3.0, and crystallization time is 6h;
(4) by the magma overflow after first degree crystalline to secondary crystallization tank, and wherein slowly stream add limestone powder slurries, carry out in secondary and crystallization; Wherein Tc is 90 DEG C, and pH value is 3.3, and crystallization time is 1h; In limestone powder, calcium carbonate mass content is 98%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 58%;
(5) by magma overflow to the three grade crystallizer after secondary crystallization, and slow stream adds limestone powder slurries wherein, carries out in three grades and crystallization; Tc is 60 DEG C, and pH value is 4.2, and crystallization time is 6h; In limestone powder, calcium carbonate mass content is 98%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 58%;
(6) by and crystallization after magma flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to first degree crystalline process, and lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) be to join in the calcium hydrogen citrate magma bucket after affination 70 DEG C after 32% ion film caustic soda liquid mixes to react 3 hours by sodium carbonate solution in step (2) and massfraction, wherein, with molar ratio computing, calcium hydrogen citrate: sodium carbonate: sodium hydroxide=1:1.15:0.8, reaction end pH value is 13, filter, calcium carbonate replaces limestone powder to be back to whole production process, and filtrate refines to obtain Trisodium Citrate.
Embodiment 5
A production method for Trisodium Citrate, its concrete steps are:
(1) add citrate of lime slurries by citric acid fermentation filtrate, 50 DEG C of stirring reaction 4h, wherein, in the citric acid in citric acid fermentation filtrate and citrate of lime slurries, the mol ratio of citrate is 1:021;
(2) step (1) gained slurries and limestone powder slurries are added in reactor simultaneously, ensure that the mol ratio of citric acid molecule and calcium ion in whole system is 1:0.85, complete rapid stirring in 60 minutes to filter, and be the carbonic acid gas that 32% ion film caustic soda liquid absorption reaction is released with massfraction, obtained sodium carbonate solution; Wherein, in limestone powder, calcium carbonate mass content is 93%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 60%;
(3) slurries adding the calcium hydrogen citrate of backflow in the clear liquid after filtration are carried out first degree crystalline; Clear liquid after wherein filtering is 1:0.5 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 90 DEG C, and pH value is 3.2, and crystallization time is 0.5h;
(4) by the magma overflow after first degree crystalline to secondary crystallization tank, and wherein slowly stream add limestone powder slurries, carry out in secondary and crystallization; Wherein Tc is 88 DEG C, and pH value is 3.5, and crystallization time is 6h; In limestone powder, calcium carbonate mass content is 97%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 60%;
(5) by magma overflow to the three grade crystallizer after secondary crystallization, and slow stream adds limestone powder slurries wherein, carries out in three grades and crystallization; Tc is 90 DEG C, and pH value is 4.5, and crystallization time is 1h; In limestone powder, calcium carbonate mass content is 97%, and particle order number is less than 100 orders; In limestone powder slurries, solid masses content is 60%;
(6) by and crystallization after magma flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to first degree crystalline process, and lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) be to join in the calcium hydrogen citrate magma bucket after affination 75 DEG C after 25% ion film caustic soda liquid mixes to react 6 hours by sodium carbonate solution in step (2) and massfraction, wherein, with molar ratio computing, calcium hydrogen citrate: sodium carbonate: sodium hydroxide=1:1.10:0.9, reaction end pH value is 10, filter, calcium carbonate replaces limestone powder to be back to whole production process, and filtrate refines to obtain Trisodium Citrate.

Claims (9)

1. the production method of a Trisodium Citrate, it is characterized in that: limestone powder and citric acid fermentation broth are reacted, filter, after crystallization again at least one times and crystallisation process direct obtained calcium hydrogen citrate crystal continuously, and make the mixing solutions of itself and ion film caustic soda liquid and sodium carbonate carry out neutralization reaction and replacement(metathesis)reaction prepares Trisodium Citrate and calcium carbonate;
Its concrete steps are:
(1) calcium agent is added by citric acid fermentation filtrate, stirring reaction;
(2) step (1) gained slurries and limestone powder slurries are added in reactor, rapid stirring filters simultaneously;
(3) clear liquid after filtering is mixed with the slurries of the calcium hydrogen citrate of backflow carry out first degree crystalline;
(4) by the magma overflow after first degree crystalline to secondary crystallization tank, and wherein slowly stream add limestone powder slurries, carry out in secondary and crystallization;
(5) by magma overflow to the three grade crystallizer after secondary crystallization, and slow stream adds limestone powder slurries wherein, carries out in three grades and crystallization;
(6) by and crystallization after magma flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to first degree crystalline process, and lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) join after being mixed with ion film caustic soda liquid by sodium carbonate solution in the calcium hydrogen citrate magma bucket after affination and react, filter, calcium carbonate replaces limestone powder to be back to whole production process, and filtrate refines to obtain Trisodium Citrate.
2. the production method of Trisodium Citrate according to claim 1, it is characterized in that: the calcium agent described in step (1) is citrate of lime slurries, in citric acid in citric acid fermentation filtrate and citrate of lime slurries, the mol ratio of citrate is 1:0.1-0.25, temperature of reaction is 50-85 DEG C, and the reaction times is 0.5-4h.
3. the production method of Trisodium Citrate according to claim 1, is characterized in that: stir and be no more than 60 minutes the total time of filtering in step (2), the mol ratio of citric acid molecule and calcium ion is 1:0.65-0.85.
4. the production method of Trisodium Citrate according to claim 1, is characterized in that: the clear liquid after filtering in step (3) is 1:0.1-0.5 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 60-90 DEG C, and pH value is 2.8-3.2, and crystallization time is 0.5-6h.
5. the production method of Trisodium Citrate according to claim 2, is characterized in that: in step (4), Tc is 60-90 DEG C, and pH value is 3.0-3.5, and crystallization time is 1-6h.
6. the production method of Trisodium Citrate according to claim 1, is characterized in that: in step (5), Tc is 60-90 DEG C, and pH value is 3.5-4.5, and crystallization time is 1-6h.
7. the production method of Trisodium Citrate according to claim 1, is characterized in that: the sodium carbonate solution described in step (7) is obtained by the carbon dioxide produced in ion film caustic soda liquid absorption step (2).
8. the production method of Trisodium Citrate according to claim 1, is characterized in that: with molar ratio computing, calcium hydrogen citrate in step (7): sodium carbonate: sodium hydroxide=1:1.05-1.2:0.6-1.03.
9. the production method of Trisodium Citrate according to claim 1, is characterized in that: the massfraction of step (7) intermediate ion film white liquor is 5-32%, temperature of reaction 60-85 DEG C, reaction times 1-6 hour, and reaction end pH value is 10-13.
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