CN103044239A - Production method of sodium citrate - Google Patents
Production method of sodium citrate Download PDFInfo
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- CN103044239A CN103044239A CN2012105500207A CN201210550020A CN103044239A CN 103044239 A CN103044239 A CN 103044239A CN 2012105500207 A CN2012105500207 A CN 2012105500207A CN 201210550020 A CN201210550020 A CN 201210550020A CN 103044239 A CN103044239 A CN 103044239A
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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
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 purify by chemistry (calcium salt method and hydrogen calcium method) or physical purification (chromatography and extraction process) acquisition citric acid purification liquid, with the acquisition sodium citrate solution, obtain the Trisodium Citrate product through condensing crystal again in citric acid purification liquid and the ion film caustic soda.
At present, the domestic technique that has by suction-joint method and the purification of single stage method realization Trisodium Citrate.Wherein One-step production Trisodium Citrate technique is to realize the purification of Trisodium Citrate with the citrate of lime that produces in the citric acid purification process and soda ash (yellow soda ash) replacement(metathesis)reaction.There is following shortcoming in this technique: 1, raw material defective: cause the underproof leading indicator iron ion of Trisodium Citrate product, chlorion and readily carbonizable substances.Soda ash is the chlor-alkali industry goods, contains a large amount of chlorions and iron ion, and this technique can be brought the chlorion in all yellow soda ash and iron ion in the Trisodium Citrate purification liquid into, causes the mother liquor of Trisodium Citrate to return the throwing amount large, and soda ash (yellow soda ash) unit consumption is high.2, the citrate of lime that makes take neutralization reaction of this technique is raw material and excessive yellow soda ash reaction, therefore, needs in the citric acid behind a large amount of purifying after replacement(metathesis)reaction finishes and excessive yellow soda ash.
Also there is at present report to substitute citrate of lime and yellow soda ash or sodium bicarbonate or sodium hydroxide by calcium hydrogen citrate and carries out replacement(metathesis)reaction, the technique of generation Trisodium Citrate.But in this technique, calcium hydrogen citrate easily causes existing in the final sodium citrate solution a large amount of calcium ions (Calcium hydrogen carbonate or calcium hydroxide) as a kind of acid salt, causes the product calcium ion to exceed standard.
In addition, the purity requirement to calcium carbonate or calcium hydroxide in the method for existing production calcium hydrogen citrate is very high, thereby causes cost high.When using limestone powder as raw material, because the calcium carbonate content 90-99% of limestone powder, therefore the solution mesosilicic acid salt ratio that accounts for the calcium hydrogen citrate crystal reaches 0.5-2.5%, account for the 0.5-4 ‰ of solution, therefore the impurity of not removing in the limestone powder can be larger on the quality product impact, impurity is very large on the impact of citric acid byproduct calcium sulfate simultaneously, so that calcium sulfate can't deep processing.Although the Wingdale mineral reserve of China are abundant, the mineral reserve that purity is higher are less.Therefore the technique that develops low-grade limestone powder and do not affect 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, the present invention mainly be with after limestone powder and citric acid fermentation broth reaction, filtration, the crystallization again through at least one times and crystallisation process directly make continuously the calcium hydrogen citrate crystal, and make the mixing solutions of itself and yellow soda ash and sodium hydroxide carry out neutralization reaction and replacement(metathesis)reaction prepares Trisodium Citrate and calcium carbonate.
Its concrete steps are:
(1) calcium agent, stirring reaction will be added in the citric acid fermentation filtrate;
(2) step (1) gained slurries and limestone powder slurries are added in the reactor simultaneously, rapid stirring filters;
(3) clear liquid after will filtering mixes with the slurries of the calcium hydrogen citrate of backflow and carries out the one-level crystallization;
(4) the magma hydrorrhea after the one-level crystallization is flow to the secondary crystallization tank, and to wherein slowly stream add the limestone powder slurries, carry out in the secondary and crystallization;
(5) the magma hydrorrhea behind the secondary crystallization is flow to three grades of crystallizers, and to wherein slowly stream add the limestone powder slurries, carry out in three grades and crystallization;
(6) will in and the magma liquid after the crystallization flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to the one-level crystallisation process, lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) with sodium carbonate solution in the step (2) with join affination after ion film caustic soda liquid mixes after calcium hydrogen citrate magma bucket in react, filter, calcium carbonate replacement limestone powder is back to whole production process, filtrate making with extra care to get Trisodium Citrate.
In the production process, at first calcium agent stirring reaction will be added in the citric acid fermentation filtrate.The calcium agent that the present invention adopts is the citrate of lime slurries that calcium carbonate or hydrogen citrate mother liquor of calcium reclaim, the preferred latter, this is because after citrate of lime is added in the citric acid fermentation filtrate, being converted into calcium hydrogen citrate is dissolved in the whole reaction system, also easily induce late phase reaction to carry out to the direction that generates calcium hydrogen citrate, and the oxalic acid in remaining calcium ion meeting and the citric acid fermentation filtrate fully reacts the formation calcium oxalate precipitation.In order to guarantee that citrate of lime is converted into the calcium hydrogen citrate dissolving fully, simultaneously so that caoxalate fully precipitate, the temperature of reaction that the present invention adopts is 50-85 ℃, reaction times is 0.5-4h, the mol ratio of citrate is 1:0.1-0.25 in citric acid in the citric acid fermentation filtrate and the citrate of lime slurries, if ratio is excessive, then can cause having part citric acid calcium to dissolve, remain in the whole reaction system, induce final product to carry out or in filter progress, be removed to the citrate of lime direction, affect ultimate yield; Ratio is too small, the hydrogen citrate hypocalcia that then generates.After stirring reaction was finished, the main component in the slurries was citric acid, calcium hydrogen citrate, caoxalate.
The slurries of step (1) gained and limestone powder slurries are added in the reactor mix, in order to guarantee to react between citric acid in the slurries and the calcium carbonate in the limestone powder slurries, and reaction is to carry out towards the direction that generates calcium hydrogen citrate, need to guarantee that by the flow of regulating slurries and limestone powder slurries the mol ratio of citric acid molecule and calcium ion is 1:0.65-0.85 in the whole reaction system.If be lower than this ratio, this process economy is poor, and the calcium hydrogen citrate that generates simultaneously very little; If be higher than 0.85 ratio, the citrate of lime precipitation just easily appears, generate the citrate of lime precipitation thereby cause whole reaction to turn to.The slurries of step (1) gained and limestone powder slurries adopt the mode that adds simultaneously, avoid the phenomenon that appearance calcium is excessive or the pH value is excessively low of local long period, cause occurring the citrate of lime precipitation.
When adding simultaneously step (1) gained slurries and limestone powder slurries in the reactor, the citrate of lime that has a large amount of calcium hydrogen citrates and trace generates, and this moment therefore easily occurs the precipitation of calcium hydrogen citrate and citrate of lime.But, because citric acid is tribasic carboxylic acid, surge time is long, the contriver finds, this mixed system was not easy to occur precipitation in 60 minutes, the total time of therefore stirring in the step (2) and filtering can not surpass 60 minutes, and the calcium hydrogen citrate supersaturated solution that so not only can guarantee acquisition in the short period of time does not produce crystal but also avoids overlong time and generate the citrate of lime crystal.
When step (1) gained slurries and limestone powder slurries add in the reactor simultaneously, can produce a large amount of carbonic acid gas, adopt ion film caustic soda liquid with carbon dioxide absorption this moment, the Formed acid sodium solution.Can cause final sodium citrate solution concentration too low because the massfraction of ion film caustic soda liquid is crossed to hang down, 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 make itself and divided calcium carbonate from the time wash water consumption increase.The contriver found through experiments when the massfraction of ion film caustic soda liquid is 5-32%, best results.
Calcium carbonate mass content in the limestone powder that adopts in the step (2)〉90%, particle is less than 100 orders; Solid masses content is 50%-60% in the limestone powder slurries.Filtrate after the filtration mainly contains calcium hydrogen citrate, dihydrogen citrate calcium and citric acid, and turbidity is in 5NTU, and filter residue is once to filter the impurity such as mycelium that do not filter fully in insoluble impurities, caoxalate and the fermented liquid in the limestone powder.
The slurries that add the calcium hydrogen citrate that refluxes on calcium hydrogen citrate emptying tank upper strata in the clear liquid after the filtration of step (2) gained are carried out the one-level crystallization, and the clear liquid after the filtration is 1:0.1-0.5 with the calcium hydrogen citrate slurry volume ratio of backflow.If it is very few that the calcium hydrogen citrate slurries that reflux add, can only introduce fewer calcium hydrogen citrate crystal seed, be unfavorable for the release of later stage calcium hydrogen citrate degree of supersaturation; If the calcium hydrogen citrate slurries that reflux add too much, then easily cause liquor capacity excessive, solid content is excessively low in the increase of required equipment volume and the whole solution system.Because the clear liquid after the filtration of step (2) gained is the supersaturated solution of calcium hydrogen citrate, in case mix with the slurries that contain calcium hydrogen citrate, degree of supersaturation is discharged under the inducing of crystal seed, 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, needing the pH value of the whole system of control is 2.8-3.2, and Tc is 60-90 ℃, and crystallization time is 0.5-6h.The adjusting of pH value can realize by refining dilture acid and citric acid mother liquor behind the interpolation citric acid.Too high pH value might cause generating the citrate of lime precipitation or cause the too many calcium hydrogen citrate crystal of excessive, the easy appearance of saturation ratio, so that crystal grain is too little in the last magma; Cross low pH value, need a large amount of citric acids, may cause the hydrogen citrate calcium deposit on the low side.Main component is citric acid, calcium hydrogen citrate, dihydrogen citrate calcium in the magma liquid after the one-level crystallization.
Magma hydrorrhea after the one-level crystallization is flow to the secondary crystallization tank, and to wherein slowly stream add the limestone powder slurries, carry out in the secondary and crystallization; Limestone powder slurries and citric acid or dihydrogen citrate calcium react and are converted into calcium hydrogen citrate in this process, from and formed the supersaturated solution that contains calcium hydrogen citrate, under the inducing of calcium hydrogen citrate crystal seed, degree of supersaturation further is released again, realizes the further growth of calcium hydrogen citrate.For the waste that is beneficial to the calcium hydrogen citrate crystal structure and avoids the energy, Tc is 60-90 ℃ in this step.In like manner, for guarantee in the whole system to produce fair amount, crystal formation Calcium hydrogen carbonate crystal preferably, system pH is 3.0-3.5, crystallization time is 1-6h.Owing to will there not be the chance of repurity from the limestone slurry of this introducing, the impurity that this place introduces easily takes in the product, and the calcium carbonate mass content is 97-99% in the limestone powder that therefore herein adopts, and particle is less than 100 orders; Solid masses content is 50%-60% in the limestone powder slurries.In the secondary and crystallization after magma liquid in main component be citric acid, calcium hydrogen citrate, dihydrogen citrate calcium.
With in the secondary and the magma hydrorrhea after the crystallization flow in three grades and crystallizer, and to wherein slowly stream add the limestone powder slurries, carry out in three grades and crystallization; In like manner, limestone powder slurries and citric acid or dihydrogen citrate calcium react and are converted into calcium hydrogen citrate in this process, from and formed the supersaturated solution that contains calcium hydrogen citrate, under the inducing of calcium hydrogen citrate crystal seed, degree of supersaturation further is released again, realizes the further growth of calcium hydrogen citrate.For the waste that is beneficial to the calcium hydrogen citrate crystal structure and avoids the energy, Tc is 60-90 ℃ in this step, and the pH value is 3.5-4.5, and crystallization time is 1-6h.Owing to will there not be the chance of repurity from the limestone slurry of this introducing, the impurity that this place introduces easily takes in the product, and the calcium carbonate mass content is 97-99% in the limestone powder that therefore herein adopts, and particle is less than 100 orders; Solid masses content is 50%-60% in the limestone powder slurries.
In concrete operating process, if through behind foregoing three grades of crystallisation processs, still contain the compositions such as citric acid, dihydrogen citrate calcium in the magma liquid, still can repeat again in the third stage and crystallisation process, until the calcium hydrogen citrate crystallization is complete in the whole system.
With the magma liquid inflow slurry tank in final and after the crystallization, upper strata calcium hydrogen citrate backflow of particles is to the one-level crystallisation process, and lower floor's calcium hydrogen citrate crystal enters the affination operation, and what affination operation of the present invention adopted is this area known technology commonly used.
Sodium carbonate solution with after ion film caustic soda liquid mixes, is joined in the calcium hydrogen citrate magma bucket behind the affination and reacts.In this step, the hydrogen ion in the calcium hydrogen citrate at first carries out neutralization reaction with ion film caustic soda, and then the carbonate in calcium ion and the sodium carbonate solution reacts the generation precipitation of calcium carbonate, and citrate and sodium ion reaction generate Trisodium Citrate.In this step, to the sodium carbonate solution massfraction without too much requirement.Sodium carbonate solution can be made by the yellow soda ash that market is bought, and also can make by the carbon dioxide that produces in the ion film caustic soda liquid absorption step (2).When selecting the yellow soda ash of market purchase, although wherein contain a large amount of chlorions and iron ion, but because a part of sodium ion in the final Trisodium Citrate product comes from ion film caustic soda liquid, greatly reduce so the consumption of yellow soda ash remains for traditional technology, iron in the finished product, chlorine ion concentration are relatively low.In order more effectively to avoid the introducing of iron in the finished product, chlorion, the sodium carbonate solution that the present invention preferably makes by the carbon dioxide that produces in the ion film caustic soda liquid absorption step (2).The contriver finds through long-felt, with molar ratio computing, work as calcium hydrogen citrate: yellow soda ash: sodium hydroxide=1:1.05-1.2:0.6-1.03, optimum proportion is calcium hydrogen citrate: yellow soda ash: during sodium hydroxide=1:1.08-1.12:1.0-1.01, can guarantee that carbonate concentration is higher in this system, the hydroxide radical relative concentration is lower, and reaction at utmost generates the higher Trisodium Citrate of purity, the pH value was 10-13 when reaction was finished, and had avoided the later stage to adopt too much citric acid to carry out the pH value and had regulated.
Comparatively fast to finish in order guaranteeing to react, also to avoid energy dissipation, temperature of reaction is 60-85 ℃, and is consistent with calcium hydrogen citrate magma initial temperature.Reaction times is too short, causes reaction not exclusively, can have more calcium ion in the system, and completely calcium hydrogen citrate of unreacted is also arranged simultaneously; The long generation that then easily causes calcium hydroxide of reaction times is partially soluble in the reaction system, and calcium ion content is too high, and the calcium hydroxide granularity strengthens with the Trisodium Citrate separating difficulty near colloid, and therefore, the reaction times, 1-6h was advisable.In like manner, can cause final sodium citrate solution concentration too low because the massfraction of ion film caustic soda liquid is crossed to hang down, 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 make itself and divided calcium carbonate from the time wash water consumption increase.The contriver found through experiments when the massfraction of ion film caustic soda liquid is 5-32%, best results.
The dope filtration that above-mentioned reaction is complete, filter residue are calcium carbonate, and filtrate is sodium citrate solution.Owing to only containing a small amount of pigment and readily carbonizable substances in the calcium carbonate, therefore calcium carbonate purity 〉=99% in the solid substance can replace it limestone powder to be back in the whole production process.At 7.0-8.5, filter by decolouring, essence through refining citric acid solution adjust pH for filtrate, concentrated, crystalline Trisodium Citrate product.
In sum, the present invention has following beneficial effect:
1, at first shortens citric acid to the reaction times of dihydrogen citrate calcium and calcium hydrogen citrate, then provide the supersaturated solution of calcium hydrogen citrate to realize the continuation crystallization of calcium hydrogen citrate by multistage neutralization reaction, prolong the crystallization time of calcium hydrogen citrate, realized the sufficient crystallising of calcium hydrogen citrate, the resulting calcium hydrogen citrate crystal grain of the present invention is large and evenly, purity is higher than traditional citrate of lime far away;
2, the present invention has reduced silicate impurity that limestone powder purity defective brings etc. to the impact of quality product and byproduct calcium sulfate quality, removes simultaneously most oxalic acid, has realized that the low-grade limestone powder prepares the method for higher-grade calcium hydrogen citrate;
3, the sodium carbonate solution of the present invention's employing is that the carbonic acid gas that ion film caustic soda liquid absorption reaction is emitted makes, avoided chlorion and iron ion are brought in the Trisodium Citrate purification liquid, cause the mother liquor of Trisodium Citrate to return the throwing amount large, the high problem of soda ash (yellow soda ash) unit consumption;
4, generate purity calcium carbonate in the production process of the present invention, be back in the whole production process environmental protection, economy with the limestone powder that replaces low-purity;
5, the present invention will add yellow soda ash and ion film caustic soda liquid in the calcium hydrogen citrate slurries, make it that neutralization and replacement(metathesis)reaction occur, improve carbonate concentration in the whole system, reduce hydroxide radical concentration, avoided this acid salt of calcium hydrogen citrate on the impact of the finished product, avoided that calcium ion exceeds standard in the finished product;
6, the present invention adopts ion film caustic soda liquid, has reduced the chlorion in the alkali, has guaranteed the quality of the finished product.
Embodiment
Embodiment 1
A kind of production method of Trisodium Citrate, its concrete steps are:
(1) will add the citrate of lime slurries in the citric acid fermentation filtrate, 60 ℃ of stirring reaction 1.5h, wherein, the mol ratio of citrate is 1:0.25 in the citric acid in the citric acid fermentation filtrate and the citrate of lime slurries;
(2) add simultaneously step (1) gained slurries and limestone powder slurries in the reactor, guarantee that the mol ratio of citric acid molecule and calcium ion is 1:0.65 in the whole system, finishing rapid stirring in 15 minutes filters, and be the carbonic acid gas that 25% ion film caustic soda liquid absorption reaction is emitted with massfraction, make sodium carbonate solution; Wherein, the calcium carbonate mass content is 91% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 50% in the limestone powder slurries;
(3) slurries that add the calcium hydrogen citrate that refluxes in the clear liquid after will filtering carry out the one-level crystallization; Clear liquid after wherein filtering is 1:0.1 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 80 ℃, and the pH value is 3.0, and crystallization time is 2h;
(4) the magma hydrorrhea after the one-level crystallization is flow to the secondary crystallization tank, and to wherein slowly stream add the limestone powder slurries, carry out in the secondary and crystallization; Wherein Tc is 78 ℃, and the pH value is 3.0, and crystallization time is 2h; The calcium carbonate mass content is 98% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 50% in the limestone powder slurries;
(5) the magma hydrorrhea behind the secondary crystallization is flow to three grades of crystallizers, and to wherein slowly stream add the limestone powder slurries, carry out in three grades and crystallization; Tc is 75 ℃, and the pH value is 3.5, and crystallization time is 2h; The calcium carbonate mass content is 98% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 50% in the limestone powder slurries;
(6) will in and the magma liquid after the crystallization flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to the one-level crystallisation process, lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) with sodium carbonate solution in the step (2) and massfraction be in the calcium hydrogen citrate magma bucket that joins after 18% ion film caustic soda liquid mixes behind the affination 60 ℃ reacted 4 hours, wherein, with molar ratio computing, calcium hydrogen citrate: yellow soda ash: 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 is made with extra care to get Trisodium Citrate.
Embodiment 2
A kind of production method of Trisodium Citrate, its concrete steps are:
(1) will add the citrate of lime slurries in the citric acid fermentation filtrate, 70 ℃ of stirring reaction 2h, wherein, the mol ratio of citrate is 1:0.1 in the citric acid in the citric acid fermentation filtrate and the citrate of lime slurries;
(2) step (1) gained slurries and limestone powder slurries are added in the reactor simultaneously, guarantee that the mol ratio of citric acid molecule and calcium ion is 1:0.70 in the whole system, finish rapid stirring in 30 minutes and filter; Wherein, the calcium carbonate mass content is 92% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 52% in the limestone powder slurries;
(3) slurries that add the calcium hydrogen citrate that refluxes in the clear liquid after will filtering carry out the one-level crystallization; Clear liquid after wherein filtering is 1:0.1 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 75 ℃, and the pH value is 3.1, and crystallization time is 3h;
(4) the magma hydrorrhea after the one-level crystallization is flow to the secondary crystallization tank, and to wherein slowly stream add the limestone powder slurries, carry out in the secondary and crystallization; Wherein Tc is 60 ℃, and the pH value is 3.2, and crystallization time is 6h; The calcium carbonate mass content is 97% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 52% in the limestone powder slurries;
(5) the magma hydrorrhea behind the secondary crystallization is flow to three grades of crystallizers, and to wherein slowly stream add the limestone powder slurries, carry out in three grades and crystallization; Tc is 85 ℃, and the pH value is 3.8, and crystallization time is 3h; The calcium carbonate mass content is 97% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 52% in the limestone powder slurries;
(6) will in and the magma liquid after the crystallization flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to the one-level crystallisation process, lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) yellow soda ash of buying being configured to massfraction is 30% solution, and be 85 ℃ of reactions 1 hour in the calcium hydrogen citrate magma bucket that joins after 12% ion film caustic soda liquid mixes behind the affination with massfraction, wherein, with molar ratio computing, calcium hydrogen citrate: yellow soda ash: 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 is made with extra care to get Trisodium Citrate.
Embodiment 3
A kind of production method of Trisodium Citrate, its concrete steps are:
(1) will add the citrate of lime slurries in the citric acid fermentation filtrate, 80 ℃ of stirring reaction 3h, wherein, the mol ratio of citrate is 1:0.17 in the citric acid in the citric acid fermentation filtrate and the citrate of lime slurries;
(2) add simultaneously step (1) gained slurries and limestone powder slurries in the reactor, guarantee that the mol ratio of citric acid molecule and calcium ion is 1:0.75 in the whole system, finishing rapid stirring in 45 minutes filters, and be the carbonic acid gas that 18% ion film caustic soda liquid absorption reaction is emitted with massfraction, make sodium carbonate solution; Wherein, the calcium carbonate mass content is 95% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 55% in the limestone powder slurries;
(3) slurries that add the calcium hydrogen citrate that refluxes in the clear liquid after will filtering carry out the one-level crystallization; Clear liquid after wherein filtering is 1:0.2 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 80 ℃, and the pH value is 2.8, and crystallization time is 1h;
(4) the magma hydrorrhea after the one-level crystallization is flow to the secondary crystallization tank, and to wherein slowly stream add the limestone powder slurries, carry out in the secondary and crystallization; Wherein Tc is 80 ℃, and the pH value is 3.4, and crystallization time is 3h; The calcium carbonate mass content is 99% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 55% in the limestone powder slurries;
(5) the magma hydrorrhea behind the secondary crystallization is flow to three grades of crystallizers, and to wherein slowly stream add the limestone powder slurries, carry out in three grades and crystallization; Tc is 80 ℃, and the pH value is 4.0, and crystallization time is 4h; The calcium carbonate mass content is 99% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 55% in the limestone powder slurries;
(6) will in and the magma liquid after the crystallization flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to the one-level crystallisation process, lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) with sodium carbonate solution in the step (2) and massfraction be in the calcium hydrogen citrate magma bucket that joins after 5% ion film caustic soda liquid mixes behind the affination 65 ℃ reacted 2 hours, wherein, with molar ratio computing, calcium hydrogen citrate: yellow soda ash: 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 is made with extra care to get Trisodium Citrate.
Embodiment 4
A kind of production method of Trisodium Citrate, its concrete steps are:
(1) will add the citrate of lime slurries in the citric acid fermentation filtrate, 85 ℃ of stirring reaction 0.5h, wherein, the mol ratio of citrate is 1:0.15 in the citric acid in the citric acid fermentation filtrate and the citrate of lime slurries;
(2) add simultaneously step (1) gained slurries and limestone powder slurries in the reactor, guarantee that the mol ratio of citric acid molecule and calcium ion is 1:0.80 in the whole system, finishing rapid stirring in 20 minutes filters, and be the carbonic acid gas that 5% ion film caustic soda liquid absorption reaction is emitted with massfraction, make sodium carbonate solution; Wherein, the calcium carbonate mass content is 94% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 58% in the limestone powder slurries;
(3) slurries that add the calcium hydrogen citrate that refluxes in the clear liquid after will filtering carry out the one-level crystallization; Clear liquid after wherein filtering is 1:0.4 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 60 ℃, and the pH value is 3.0, and crystallization time is 6h;
(4) the magma hydrorrhea after the one-level crystallization is flow to the secondary crystallization tank, and to wherein slowly stream add the limestone powder slurries, carry out in the secondary and crystallization; Wherein Tc is 90 ℃, and the pH value is 3.3, and crystallization time is 1h; The calcium carbonate mass content is 98% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 58% in the limestone powder slurries;
(5) the magma hydrorrhea behind the secondary crystallization is flow to three grades of crystallizers, and to wherein slowly stream add the limestone powder slurries, carry out in three grades and crystallization; Tc is 60 ℃, and the pH value is 4.2, and crystallization time is 6h; The calcium carbonate mass content is 98% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 58% in the limestone powder slurries;
(6) will in and the magma liquid after the crystallization flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to the one-level crystallisation process, lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) with sodium carbonate solution in the step (2) and massfraction be in the calcium hydrogen citrate magma bucket that joins after 32% ion film caustic soda liquid mixes behind the affination 70 ℃ reacted 3 hours, wherein, with molar ratio computing, calcium hydrogen citrate: yellow soda ash: 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 is made with extra care to get Trisodium Citrate.
Embodiment 5
A kind of production method of Trisodium Citrate, its concrete steps are:
(1) will add the citrate of lime slurries in the citric acid fermentation filtrate, 50 ℃ of stirring reaction 4h, wherein, the mol ratio of citrate is 1:021 in the citric acid in the citric acid fermentation filtrate and the citrate of lime slurries;
(2) add simultaneously step (1) gained slurries and limestone powder slurries in the reactor, guarantee that the mol ratio of citric acid molecule and calcium ion is 1:0.85 in the whole system, finishing rapid stirring in 60 minutes filters, and be the carbonic acid gas that 32% ion film caustic soda liquid absorption reaction is emitted with massfraction, make sodium carbonate solution; Wherein, the calcium carbonate mass content is 93% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 60% in the limestone powder slurries;
(3) slurries that add the calcium hydrogen citrate that refluxes in the clear liquid after will filtering carry out the one-level crystallization; Clear liquid after wherein filtering is 1:0.5 with the slurry volume ratio of the calcium hydrogen citrate of backflow; Tc is 90 ℃, and the pH value is 3.2, and crystallization time is 0.5h;
(4) the magma hydrorrhea after the one-level crystallization is flow to the secondary crystallization tank, and to wherein slowly stream add the limestone powder slurries, carry out in the secondary and crystallization; Wherein Tc is 88 ℃, and the pH value is 3.5, and crystallization time is 6h; The calcium carbonate mass content is 97% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 60% in the limestone powder slurries;
(5) the magma hydrorrhea behind the secondary crystallization is flow to three grades of crystallizers, and to wherein slowly stream add the limestone powder slurries, carry out in three grades and crystallization; Tc is 90 ℃, and the pH value is 4.5, and crystallization time is 1h; The calcium carbonate mass content is 97% in the limestone powder, and particle order number is less than 100 orders; Solid masses content is 60% in the limestone powder slurries;
(6) will in and the magma liquid after the crystallization flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to the one-level crystallisation process, lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) with sodium carbonate solution in the step (2) and massfraction be in the calcium hydrogen citrate magma bucket that joins after 25% ion film caustic soda liquid mixes behind the affination 75 ℃ reacted 6 hours, wherein, with molar ratio computing, calcium hydrogen citrate: yellow soda ash: 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 is made with extra care to get Trisodium Citrate.
Claims (10)
1. the production method of a Trisodium Citrate, it is characterized in that: with after limestone powder and citric acid fermentation broth reaction, filtration, the crystallization again through at least one times and crystallisation process directly make continuously the calcium hydrogen citrate crystal, and make the mixing solutions of itself and ion film caustic soda liquid and yellow soda ash carry out neutralization reaction and replacement(metathesis)reaction prepares Trisodium Citrate and calcium carbonate.
2. the production method of Trisodium Citrate according to claim 1, it is characterized in that: its concrete steps are:
(1) calcium agent, stirring reaction will be added in the citric acid fermentation filtrate;
(2) step (1) gained slurries and limestone powder slurries are added in the reactor simultaneously, rapid stirring filters;
(3) clear liquid after will filtering mixes with the slurries of the calcium hydrogen citrate of backflow and carries out the one-level crystallization;
(4) the magma hydrorrhea after the one-level crystallization is flow to the secondary crystallization tank, and to wherein slowly stream add the limestone powder slurries, carry out in the secondary and crystallization;
(5) the magma hydrorrhea behind the secondary crystallization is flow to three grades of crystallizers, and to wherein slowly stream add the limestone powder slurries, carry out in three grades and crystallization;
(6) will in and the magma liquid after the crystallization flow into slurry tank, upper strata calcium hydrogen citrate backflow of particles is to the one-level crystallisation process, lower floor's calcium hydrogen citrate crystal enters affination workshop section;
(7) with sodium carbonate solution with join affination after ion film caustic soda liquid mixes after calcium hydrogen citrate magma bucket in react, filter, calcium carbonate replaces limestone powder to be back to whole production process, the refining Trisodium Citrate that to get of filtrate.
3. the production method of Trisodium Citrate according to claim 2, it is characterized in that: the calcium agent described in the step (1) is the citrate of lime slurries, the mol ratio of citrate is 1:0.1-0.25 in citric acid in the citric acid fermentation filtrate and the citrate of lime slurries, temperature of reaction is 50-85 ℃, and the reaction times is 0.5-4h.
4. the production method of Trisodium Citrate according to claim 2 is characterized in that: that stirs in the step (2) and filter is no more than 60 minutes total time, and the mol ratio of citric acid molecule and calcium ion is 1:0.65-0.85.
5. the production method of Trisodium Citrate according to claim 2 is characterized in that: the clear liquid after filtering in the step (3) and the slurry volume of the calcium hydrogen citrate of backflow are than being 1:0.1-0.5; Tc is 60-90 ℃, and the pH value is 2.8-3.2, and crystallization time is 0.5-6h.
6. the production method of Trisodium Citrate according to claim 2 is characterized in that: Tc is 60-90 ℃ in the step (4), and the pH value is 3.0-3.5, and crystallization time is 1-6h.
7. the production method of Trisodium Citrate according to claim 2 is characterized in that: Tc is 60-90 ℃ in the step (5), and the pH value is 3.5-4.5, and crystallization time is 1-6h.
8. the production method of Trisodium Citrate according to claim 2 is characterized in that: the described sodium carbonate solution of step (7) makes by the carbon dioxide that produces in the ion film caustic soda liquid absorption step (2).
9. the production method of Trisodium Citrate according to claim 2 is characterized in that: with molar ratio computing, and calcium hydrogen citrate in the step (7): yellow soda ash: sodium hydroxide=1:1.05-1.2:0.6-1.03.
10. the production method of Trisodium Citrate according to claim 2, it is characterized in that: the massfraction of step (7) intermediate ion film white liquor is 5-32%, temperature of reaction 60-85 ℃, reaction times 1-6 hour, reaction end pH value was 10-13.
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| CN103864604A (en) * | 2014-02-25 | 2014-06-18 | 日照金禾博源生化有限公司 | Purification treatment technology for iron removal from sodium citrate mother liquor |
| CN104478704A (en) * | 2014-12-22 | 2015-04-01 | 南通市飞宇精细化学品有限公司 | Preparation method of anhydrous trisodium citrate |
| CN105418411A (en) * | 2015-12-21 | 2016-03-23 | 日照金禾博源生化有限公司 | Preparation method for easily soluble calcium hydrogen citrate |
| CN114133325A (en) * | 2021-12-27 | 2022-03-04 | 南通醋酸化工股份有限公司 | Method for producing potassium sorbate by liquid-liquid neutralization reaction continuous cooling crystallization |
| CN114773182A (en) * | 2022-03-29 | 2022-07-22 | 南京化学试剂股份有限公司 | Synthetic method of medicinal sodium citrate |
| CN115212815A (en) * | 2022-08-13 | 2022-10-21 | 山东巨展新材料有限公司 | Preparation method of water-soluble citric acid colloid |
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| CN103864604A (en) * | 2014-02-25 | 2014-06-18 | 日照金禾博源生化有限公司 | Purification treatment technology for iron removal from sodium citrate mother liquor |
| CN103864604B (en) * | 2014-02-25 | 2015-10-14 | 日照金禾博源生化有限公司 | A kind of sodium citrate mother liquor deferrization purification process technique |
| CN104478704A (en) * | 2014-12-22 | 2015-04-01 | 南通市飞宇精细化学品有限公司 | Preparation method of anhydrous trisodium citrate |
| CN105418411A (en) * | 2015-12-21 | 2016-03-23 | 日照金禾博源生化有限公司 | Preparation method for easily soluble calcium hydrogen citrate |
| CN114133325A (en) * | 2021-12-27 | 2022-03-04 | 南通醋酸化工股份有限公司 | Method for producing potassium sorbate by liquid-liquid neutralization reaction continuous cooling crystallization |
| CN114773182A (en) * | 2022-03-29 | 2022-07-22 | 南京化学试剂股份有限公司 | Synthetic method of medicinal sodium citrate |
| CN114773182B (en) * | 2022-03-29 | 2023-02-03 | 南京化学试剂股份有限公司 | Synthetic method of medicinal-grade sodium citrate |
| CN115212815A (en) * | 2022-08-13 | 2022-10-21 | 山东巨展新材料有限公司 | Preparation method of water-soluble citric acid colloid |
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