CN102260165A - Method for co-production of citric acid and calcium sulfate dihydrate - Google Patents
Method for co-production of citric acid and calcium sulfate dihydrate Download PDFInfo
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- CN102260165A CN102260165A CN2011101448793A CN201110144879A CN102260165A CN 102260165 A CN102260165 A CN 102260165A CN 2011101448793 A CN2011101448793 A CN 2011101448793A CN 201110144879 A CN201110144879 A CN 201110144879A CN 102260165 A CN102260165 A CN 102260165A
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- temperature
- citric acid
- calcium
- terra alba
- sulphate hemihydrate
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- 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 392
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title abstract 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 106
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000243 solution Substances 0.000 claims abstract description 70
- 239000007788 liquid Substances 0.000 claims abstract description 68
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims abstract description 64
- 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 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 29
- 239000007790 solid phase Substances 0.000 claims abstract description 29
- 230000007704 transition Effects 0.000 claims abstract description 17
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims abstract description 14
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 150
- 238000005406 washing Methods 0.000 claims description 53
- 239000011259 mixed solution Substances 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 16
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 16
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 239000004571 lime Substances 0.000 claims description 16
- PFKGDYCESFRMAP-UHFFFAOYSA-L dicalcium citrate Chemical compound [Ca+2].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O PFKGDYCESFRMAP-UHFFFAOYSA-L 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 7
- 210000000689 upper leg Anatomy 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 3
- 238000003379 elimination reaction Methods 0.000 claims description 3
- OWFJMGQSOHDIPP-UHFFFAOYSA-L monocalcium citrate Chemical compound [Ca+2].OC(=O)CC(O)(C(O)=O)CC([O-])=O.OC(=O)CC(O)(C(O)=O)CC([O-])=O OWFJMGQSOHDIPP-UHFFFAOYSA-L 0.000 claims description 2
- 238000012163 sequencing technique Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 50
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000001354 calcium citrate Substances 0.000 abstract 2
- 235000013337 tricalcium citrate Nutrition 0.000 abstract 2
- 239000013078 crystal Substances 0.000 description 29
- 235000011132 calcium sulphate Nutrition 0.000 description 19
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 17
- 229910001424 calcium ion Inorganic materials 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 239000002002 slurry Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LNIZKKFWMDARJV-UHFFFAOYSA-H tricalcium;2-hydroxypropane-1,2,3-tricarboxylate;tetrahydrate Chemical compound O.O.O.O.[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 LNIZKKFWMDARJV-UHFFFAOYSA-H 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- -1 this Chemical compound 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for the co-production of citric acid and calcium sulfate dihydrate. The method comprises the following steps: (1) carrying out contact reaction on calcium citrate and sulfuric acid aqueous solution to obtain a mixed liquid of citric acid and calcium sulfate hemihydrate, wherein the temperature of the contact reaction between the calcium citrate and the sulfuric acid aqueous solution is higher than the transition temperature at which calcium sulfate hemihydrate is converted into calcium sulfate dihydrate; (2) cooling the mixed liquid of citric acid and calcium sulfate hemihydrate to a temperature lower than the transition temperature at which calcium sulfate hemihydrate is converted into calcium sulfate dihydrate, so that calcium sulfate hemihydrate is converted into calcium sulfate dihydrate, thus obtaining a mixed liquid of citric acid and calcium sulfate dihydrate; and (3) carrying out solid-liquid separation on the mixed liquid of citric acid and calcium sulfate dihydrate to obtain citric acid solution and solid-phase calcium sulfate dihydrate. Through the method disclosed by the invention, the content of free water is low in the produced calcium sulfate dihydrate while ensuring low citric acid residues, and the produced citric acid has high concentration (up to 0.6 g/ml or above). The method disclosed by the invention can be widely used in industrial production.
Description
Technical field
The present invention relates to the method for a kind of coproduction citric acid and terra alba.
Background technology
Calcium sulfate is of many uses, but residual in the calcium sulfate that calcium citrate salts and sulfuric acid reaction make citric acid and contain more free-water is arranged, and has restricted the application of product calcium sulfate, can not bring into play its due value.
Calcium citrate salts and sulfuric acid solution are produced citric acid and calcium sulfate, and traditional method and thinking have two kinds, and a kind of is to obtain citric acid and calcium sulphate hemihydrate, and another is to obtain citric acid and terra alba.The crystal formation of calcium sulfate has three kinds, be respectively anhydrous calciumsulphate, calcium sulphate hemihydrate, terra alba, what reaction obtained is the calcium sulfate of which kind of crystal formation, depend on factors such as temperature of reaction, reaction times, reactant concn, according to the needs of producing, under the situation that reaction times and reactant concn are determined, temperature is a controlling factor.When control calcium citrate salts and vitriolic temperature of reaction were lower than the transition temperature of terra alba/calcium sulphate hemihydrate, the product that obtains was citric acid and terra alba; Otherwise when temperature of reaction was higher than the transition temperature of terra alba/calcium sulphate hemihydrate, the product that obtains was citric acid and calcium sulphate hemihydrate.
In 20～85 ℃ of scopes of temperature, the solubleness of terra alba in aqueous citric acid solution is less than calcium sulphate hemihydrate, solubleness in aqueous citric acid solution is little, can reduce calcium ion, sulfate ion content in the aqueous citric acid solution, reduction reduces regeneration frequency to the pollution of follow-up ion-exchange process resin.But directly obtain citric acid and terra alba with citrate of lime and sulfuric acid reaction, the calcium sulphate crystal particle that obtains is little, inhomogeneous, and terra alba is a needle-like crystal, filter and the washing difficulty, need a large amount of water washing solid phases, in order to reduce the residual quantity of citric acid in calcium sulfate, like this, the calcium sulfate free water content height that obtains after the solid-liquid separation, citric acid solution concentration is low, has influenced the application of calcium sulfate and has improved the concentrated expense of citric acid solution.
React being higher than under the transition temperature of terra alba/calcium sulphate hemihydrate with citrate of lime and sulfuric acid, obtain the mixture of citric acid solution and calcium sulphate hemihydrate.The calcium sulphate hemihydrate crystal is a tabular crystal, is easy to filter and washing, and the calcium sulphate hemihydrate free water content that obtains is low.But its shortcoming also is significantly, owing to need react under higher temperature, the readily carbonizable substance of carrying secretly in the citrate of lime can be by vitriol oil carbonization, and the citric acid solution colourity that reaction obtains increases; The solubleness of calcium sulphate hemihydrate in aqueous citric acid solution is higher than the solubleness of terra alba in aqueous citric acid solution, and calcium ion after the solid-liquid separation in the aqueous citric acid solution and sulfate ion content height can pollute resin, increases regeneration frequency; To equipment and environment requirement, during solid-liquid separation, there is the higher potential safety hazard that causes of Yin Wendu in the reacting liquid temperature height when having improved follow-up solid-liquid separation simultaneously, and relevant safe precaution measure need be arranged.
The reactant calcium citrate salts is a solid, product calcium sulfate also is solid, when reaction when that sulfuric acid adds is too fast, slow with excessivelying, stop over or stir when inhomogeneous, the phenomenon of calcium sulfate embedding calcium citrate salts all can appear, (the tie pot) phenomenon that can occur when serious that material lumps in the retort.The embedding of calcium citrate salts causes the citric acid yield losses when causing the calcium sulfate purity drop, make follow-up solid-liquid separation difficulty, this phenomenon be above-mentioned two kinds of production technique can't avoid fully.
Summary of the invention
To the objective of the invention is the defective that exists in above-mentioned two kinds of production technique in order overcoming, a kind of new coproduction citric acid and the method for terra alba to be provided.
The present inventor is unexpected under study for action to be found, by the crystal conversion of calcium sulphate hemihydrate to terra alba, can improve the yield of citric acid, and under the low situation of the residual quantity of the citric acid in the terra alba that guarantees to obtain, can obtain the low terra alba of high concentration of citric solution and free water content.
The invention provides the method for a kind of coproduction citric acid and terra alba, said method comprising the steps of:
(1) make calcium citrate salts and aqueous sulfuric acid contact reacts, the catalytic temperature of described calcium citrate salts and aqueous sulfuric acid is higher than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba, obtains the mixed solution of citric acid and calcium sulphate hemihydrate;
(2) temperature of the mixed solution of citric acid and calcium sulphate hemihydrate is reduced to is lower than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba, make calcium sulphate hemihydrate change terra alba into, obtain the mixed solution of citric acid and terra alba;
(3) mixed solution with citric acid and terra alba carries out solid-liquid separation, obtains citric acid solution and solid phase terra alba.
Preferably, calcium citrate salts and catalytic time of aqueous sulfuric acid are 30-120min in the described step (2), and making the time that calcium sulphate hemihydrate changes terra alba in the described step (3) is 60-240min.
The present inventor finds that also multistage progressively cooling can make calcium sulphate hemihydrate change terra alba more completely into, and the calcium sulfate dihydrate particles that is transformed into is bigger and more even, easier solid-liquid separation and washing in high grinding.Preferably, make the method that calcium sulphate hemihydrate changes terra alba into comprise that elder generation is reduced to t with the temperature of the mixed solution of citric acid and calcium sulphate hemihydrate
1Temperature is again from t
1Temperature is reduced to t
2Temperature, described t
1Temperature and t
2Temperature is lower than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba respectively, and described t
2Temperature is lower than described t
1Temperature.
More preferably, catalytic temperature of described calcium citrate salts and aqueous sulfuric acid and described t
1The temperature head of temperature and described t
1Temperature and described t
2The temperature head of temperature is respectively 5-15 ℃ separately.Be reduced to described t from described calcium citrate salts and the catalytic temperature of aqueous sulfuric acid
1The average cooling rate of temperature and from described t
1Temperature is reduced to described t
2The average cooling rate of temperature is preferably respectively more than 0.1 ℃/minute separately.
At described t
1The time of the transformation under the temperature is preferably 30-120min, at described t
2The time of the transformation under the temperature is preferably 30-120min.
The method of coproduction citric acid of the present invention and terra alba, because end product is terra alba and citric acid, therefore calcium ion content is low in the citric acid solution of producing, citric acid purity height; Because what carry out solid-liquid separation is citric acid and terra alba, reacting liquid temperature is lower, to equipment and environment requirement, has reduced the potential safety hazard that Yin Gaowen causes simultaneously when having reduced solid-liquid separation; The inventive method has improved the yield of citric acid, and theoretical derivation may be because calcium sulphate hemihydrate changes to terra alba, and be released in calcium sulfate crystal conversion process by the calcium citrate salts of calcium sulfate embedding early stage, thereby be able to and sulfuric acid reaction; The transformation of crystal formation has prolonged calcium citrate salts and catalytic time of sulfuric acid, helps calcium citrate salts and vitriolic thoroughly reacts; The terra alba crystalline growth that changes into of crystal formation provides time enough and nucleus, make the terra alba crystal grain of producing big and even, solid-liquid separation and washing easily, therefore the residual quantity of citric acid is lower than under the situation of 0.15 weight % in guaranteeing the terra alba of producing, the content of the free-water in the terra alba of producing is low, and the citric acid concentration height of producing, the preferred repeatedly cooling of the inventive method can make the content of the free-water in the terra alba of producing lower, the concentration of the citric acid of producing is higher, and the concentration of the citric acid that the employing preferred embodiment of the present invention is produced can be up to more than the 0.5g/ml.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
The invention provides the method for a kind of coproduction citric acid and terra alba, said method comprising the steps of:
(1) make calcium citrate salts and aqueous sulfuric acid contact reacts, the catalytic temperature of described calcium citrate salts and aqueous sulfuric acid is higher than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba, obtains the mixed solution of citric acid and calcium sulphate hemihydrate;
(2) temperature of the mixed solution of citric acid and calcium sulphate hemihydrate is reduced to is lower than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba, make calcium sulphate hemihydrate change terra alba into, obtain the mixed solution of citric acid and terra alba;
(3) mixed solution with citric acid and terra alba carries out solid-liquid separation, obtains citric acid solution and solid phase terra alba.
Although contact reacts can realize purpose of the present invention under the temperature of transition temperature that calcium sulphate hemihydrate is transformed into terra alba being higher than to make calcium citrate salts and aqueous sulfuric acid, at the needs on the industrial applications, the present inventor's high spot reviews in the presence of high density citric acid (citric acid concentration of reaction solution through obtaining after the solid-liquid separation washing can reach more than the 0.4g/ml), the transition temperature of terra alba/calcium sulphate hemihydrate, test shows that transition temperature is about 91 ℃.But under the preferable case, the catalytic time of calcium citrate salts and aqueous sulfuric acid is 30-120min, more preferably 40-60min.By the reaction times is controlled in the above-mentioned scope, can obtain the unexpected technique effect in following two aspects: on the one hand shortened calcium citrate salts and the aqueous sulfuric acid catalytic time under comparatively high temps greatly, thereby the carbonization of the readily carbonizable substance of carrying secretly in the minimizing citrate of lime significantly reduces the colourity of reacting the citric acid solution that obtains; Can make most calcium citrate salts and aqueous sulfuric acid change calcium sulphate hemihydrate and citric acid on the other hand, calcium sulphate hemihydrate has prolonged the growth time and the abundance of having guaranteed the nucleus amount of terra alba to the transformation of terra alba subsequently, thereby guaranteed that the calcium sulfate dihydrate particles in the product is bigger and more even, be easier to solid-liquid separation and washing, thereby produce the citric acid solution and the lower terra alba of free water content of greater concn.
For calcium citrate salts and aqueous sulfuric acid fully being reacted control the excessive degree of vitriolic simultaneously reaction is carried out easily, the add-on of calcium citrate salts and aqueous sulfuric acid makes the specific conductivity of the mixed solution of the citric acid that obtains and calcium sulphate hemihydrate be preferably 6-15mS/cm, and whether the specific conductivity of mixed solution that can be by detecting citric acid and calcium sulphate hemihydrate adjusts the add-on of calcium citrate salts and aqueous sulfuric acid in preferable range.
Complete for crystal conversion, make the time that calcium sulphate hemihydrate changes terra alba into be preferably 60-240min.In order to make the further fully reaction of calcium citrate salts and aqueous sulfuric acid, the specific conductivity of the citric acid that obtains in the step (2) and the mixed solution of terra alba is preferably 2-6mS/cm, and visual response situation suitably adds calcium citrate salts or aqueous sulfuric acid is finely tuned.
Can adjust the add-on of calcium citrate salts and aqueous sulfuric acid according to the specific conductivity of reaction solution, the reaction solution that also need take a morsel before solid-liquid separation obtains the citric acid clear liquid with filter paper filtering, determines reaction end by two-tube dipl-clearance method.Described two-tube dipl-clearance method is: (1) gets 4ml filtered liquid and 20ml concentration is after the ethanol of 95 weight % mixes, and shakes up to filter to be analytic liquid.(2) get two test tubes of first, second, respectively get the 3m1 analytic liquid and add two in vitro, the first pipe is put into the H that concentration is 20 weight % again
2SO
4It is 20 weight %CaCl that solution 1ml, second pipe add concentration again
2Whether aqueous solution 1ml places 1min at 95 ℃ of water-baths and takes out, observe two-tube two clear.(3) if first pipe muddiness, can be in reactor little sulfuric acid that adds to two clear, as second pipe muddiness, can be in reactor little adding citric acid calcium salt to two clear, repeatable operation so repeatedly, when detecting in test tube first and the second liquid two clear till.
For the specific conductivity that obtains required reaction solution and in order to reach two-tube two clear and calcium citrate salts or sulfuric acid that trace adds can be ignored to the influence of the concentration of end product citric acid.
For make calcium sulphate hemihydrate to terra alba change more fully and obtain the bigger and uniform terra alba of crystal grain, under the preferable case, adopt multistage progressively cooling, a plurality of thermograde proceed step by step coolings are promptly adopted in described multistage progressively cooling, for example can adopt 2-5 thermograde proceed step by step cooling, more preferably, the temperature with the mixed solution of citric acid and calcium sulphate hemihydrate is reduced to t
1Temperature is again from t
1Temperature is reduced to t
2Temperature, described t
1Temperature and t
2Temperature is lower than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba respectively, and described t
2Temperature is lower than described t
1Temperature.The specific conductivity of control reaction solution is for reactant fully being reacted control the excessive degree of vitriolic simultaneously reaction to be carried out easily in above-mentioned scope, multistage when progressively lowering the temperature when adopting, the specific conductivity of preferred reaction liquid progressively reduces, when for example adopting for 2 steps lowered the temperature, and preferred t
2The specific conductivity of the citric acid that obtains under the temperature and the mixed solution of calcium sulphate hemihydrate is less than t
1The specific conductivity of the citric acid that obtains under the temperature and the mixed solution of calcium sulphate hemihydrate.
For the calcium sulfate dihydrate particles that makes generation is bigger more even, be easier to solid-liquid separation and washing, catalytic temperature of calcium citrate salts and aqueous sulfuric acid and t
1The temperature head of temperature and t
1Temperature and t
2The temperature head of temperature is respectively 5-15 ℃ separately, and more preferably 5-10 ℃, catalytic temperature of calcium citrate salts and aqueous sulfuric acid and t
1The temperature head of temperature and t
1Temperature and t
2The temperature head of temperature can be identical, also can be different.Be reduced to t from calcium citrate salts and the catalytic temperature of aqueous sulfuric acid
1The average cooling rate of temperature and from t
1Temperature is reduced to t
2The average cooling rate of temperature does not have particular requirement, consider the production efficiency in the actual production, average cooling rate is preferably more than 0.1 ℃/minute separately respectively, the inventive method is when carrying out with intermittent mode, consider production cost, average cooling rate is distinguished more preferably 0.5-0.7 ℃/minute separately, is reduced to t from calcium citrate salts and the catalytic temperature of aqueous sulfuric acid
1The average cooling rate of temperature and from t
1Temperature is reduced to t
2The average cooling rate of temperature can be identical, also can be different.
More preferably, at t
1The time of the transformation under the temperature is 30-120min, is preferably 40-60min, at t
2The time of the transformation under the temperature is 30-120min, is preferably 40-60min.
Described calcium citrate salts of the inventive method and aqueous sulfuric acid contact reacts are meant that calcium citrate salts and sulfuric acid are contact reactss under the state that water exists, for example can for first water or rare citric acid solution size mixing calcium citrate salts then with the sulfuric acid contact reacts, also can be with calcium citrate salts and the direct contact reacts of sulfuric acid, reaction is easier to be carried out in order to make, be preferably first water or rare citric acid solution size mixing calcium citrate salts then with the sulfuric acid contact reacts.For the concentration that makes the citric acid of producing is higher, the content of water makes that the concentration of citric acid of the citric acid solution that obtains behind citric acid and the calcium sulphate hemihydrate mixed solution elimination calcium sulphate hemihydrate is the 2.5-3.6 mol in the inventive method optimization citric acid calcium salt and the aqueous sulfuric acid.Reaction is easier to be carried out in order to make, and used vitriolic concentration is preferably 80-98 weight %, the more preferably vitriol oil of 98 weight %.When adopting the vitriol oil of 98 weight %, in order to make that the concentration of citric acid of the citric acid solution that obtains behind citric acid and the calcium sulphate hemihydrate mixed solution elimination calcium sulphate hemihydrate is the 2.5-3.6 mol, the content of water is 45-55 weight % in the calcium citrate salts slurries that obtain after sizing mixing.The inventive method does not have particular requirement to used calcium citrate salts, this area calcium citrate salts commonly used all can be realized purpose of the present invention, but consider that from the aspect of wide material sources, saving cost calcium citrate salts is preferably one or more in citrate of lime, hydrogen citrate calcium and the dihydrogen citrate calcium.
Step (3) solid-liquid separation can adopt this area various devices commonly used, for example can be preferably rubber belt type vacuum filter for plate-and-frame filter press, rubber belt type vacuum filter, mobile disk vacuum filter etc.
In addition, the inventive method comprises that also the solid phase terra alba that step (3) is obtained washs with washing water, washs that the residual quantity of citric acid is lower than 0.15 weight % to the solid phase terra alba.The unexpected temperature of washing water of finding of the present inventor is preferably 50-85 ℃, more preferably 60-80 ℃, in this preferable range, can significantly reduce the washing water consumption, improve the concentration of the citric acid of producing, and can further improve the yield of terra alba, reduce calcium sulfate foreign matter content in the citric acid of producing.
In order further to reduce the washing water consumption and to make washes clean thorough, described washing preferably adopts multistage cover to wash technology, described multistage cover is washed technology and is about to the solid phase terra alba and contacts with the multiply washing water that are arranged in order, according to the sequencing that contacts with the solid phase terra alba, back one washing water after the contact are returned as adjacent preceding one washing water, first strand of washing water after the contact can merge with the citric acid solution after the solid-liquid separation, also can be used for sizing mixing of calcium citrate salts, in order further to improve the yield of citric acid, first strand of washing water after the contact be preferably with solid-liquid separation after citric acid solution merge, described merging also can comprise first strand of washing water after the contact, take and be used for sizing mixing of calcium citrate salts on a small quantity, the citric acid solution after all the other and the solid-liquid separation merges.Because of the amount of the first strand of washing water after the used contact of sizing mixing seldom, so under the preferable case that first strand of washing water after the contact and the citric acid solution after the solid-liquid separation merge, whether take first strand of washing water after a small amount of contact and be used for sizing mixing of calcium citrate salts and can ignore for the influence of the concentration of end product citric acid solution.Described multiply washing water for example can be 2-5 thigh washing water, are preferably 3-4 thigh washing water.Adopt multistage cover to wash technology, adopt the water in the 60-80 ℃ of preferable range to wash, wash that the residual quantity of citric acid is lower than 0.15 weight % to the solid phase terra alba, with respect to the solid phase terra alba of 100 weight parts, the consumption of washing water is the 25-30 weight part.
The inventive method can be carried out with intermittent mode, also can carry out in a continuous manner.Continuous mode can adopt the method for carrying out in a plurality of retort, control the temperature difference of the reaction solution in each retort respectively, to satisfy following needs: make calcium citrate salts and aqueous sulfuric acid generate calcium sulphate hemihydrate and citric acid earlier, multistage then progressively cooling makes calcium sulphate hemihydrate be transformed into terra alba.Pass through pipe connection between each retort, the cross-sectional area of pipeline is far smaller than the cross-sectional area of retort, thereby make when system stable operation, the volume of liquid that enters unit time such as p.s. retort by pipeline is reduced to consistent with the temperature of reacting pot liquid rapidly by the temperature that pipeline enters the liquid of retort much smaller than the volume of reaction pot liquid thus.When adopting above-mentioned continuous mode to carry out, average cooling rate is the time of the temperature head of two adjacent retort divided by the pipe-line transportation between two adjacent retort.When carrying out with above-mentioned continuous mode, in order to realize fast cooling, make cooling rate be far longer than 0.1 ℃/minute, generally make the pipeline that connects adjacent two retort short as far as possible.Because the differential responses jar is used to realize different reactions, therefore, also each retort is called every order reaction jar.When carrying out in a continuous manner, reaction times in each order reaction jar is controlled with the input speed that enters retort by the liquid level of retort, operation for convenience and control, and the liquid level that is preferably every order reaction jar is identical, the input speed of every order reaction jar is identical, when the liquid level of retort is 3-5m
3The time, input speed is preferably 3-7m
3/ h.When carrying out in a continuous manner, regulate two-tube two clear for convenience, preferably after multistage progressively cooling, with material input fine setting jar, described fine setting jar is about to the reaction solution fine setting to two-tube two clear jars, and the fine setting jar only plays and adds sulfuric acid or calcium citrate salts therein with the extremely two-tube pair clear effects of reaction solution fine setting, and do not participate in temperature-fall period, temperature to the fine setting jar is not done concrete setting, and the temperature that experimental results show that the fine setting jar can not considered whole reaction system not influence basically.Fine setting in the fine setting jar to two-tube material after two clear is carried out foregoing solid-liquid separation and washing.
More than describe preferred implementation of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment under reconcilable situation, can make up by any suitable manner, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Embodiment
Following embodiment will the present invention is further illustrated, but therefore do not limit the present invention.
In the following embodiments:
The thick product of used calcium citrate salts is that citric acid and the calcium carbonate reaction that fermentation method is produced obtains in embodiment and the Comparative Examples, and the purity of the thick product of calcium citrate salts that obtains is meant the content of calcium citrate salts and the ratio of the thick product gross dry weight of calcium citrate salts.
Used other reagent are commercially available chemically pure reagent in embodiment and the Comparative Examples.
The mensuration of citric acid concentration is drawn by the aqueous sodium hydroxide solution direct titration among the present invention;
The instrument that the mensuration of free-water and crystal water is used is a HB43-S halogen moisture content tester, and temperature is set at 55 ℃ when measuring free-water, and temperature is set at 140 ℃ when measuring crystal water, draws moisture content by weight loss.
The temperature of the reaction solution in the first step retort in embodiment and the Comparative Examples, second stage retort, the third stage retort is different, and all is equipped with whipping appts in every order reaction jar.
Embodiment 1
The thick product of citrate of lime (purity 94.1 weight %, moisture 36.9 weight %) water is sized mixing, and the content of water is 50 weight % in the citrate of lime slurries that obtain, and the vitriol oil of citrate of lime slurries and 98 weight % is with 4m
3The input speed of/h together adds in the first step retort continuously, and reacting liquid temperature is 93 ℃ in the control first step retort, and control reaction solution specific conductivity is 12 ± 3mS/cm, when the retort liquid level reaches 4m
3The time, the material in second stage retort input first step retort, the material input speed is 4m
3/ h, keeping first step retort liquid level simultaneously is 4m
3
Reacting liquid temperature is 85 ℃ in the retort of the control second stage, and specific conductivity is 4 ± 2mS/cm, and the retort liquid level reaches 4m when the second stage
3The time, the material in the retort of the third stage retort input second stage, the material input speed is 4m
3/ h, average cooling rate is 54 ℃/minute, keeping second stage retort liquid level simultaneously is 4m
3
Reacting liquid temperature is 80 ℃ in the control third stage retort, and specific conductivity is 3 ± 1mS/cm, and average cooling rate is 34 ℃/minute, when third stage retort liquid level reaches 4m
3The time, the material in fine setting jar input third stage retort, keeping third stage retort liquid level simultaneously is 4m
3
It is extremely two-tube clearly two with the reaction solution fine setting to add sulfuric acid or citrate of lime slurries in the fine setting jar, after the fine setting, with rubber belt type vacuum filter the material in the fine setting jar is carried out solid-liquid separation, the solid phase terra alba that separates after the back is adopted washing water that multistage cover washes 3 strands 80 ℃ of process using and separated contacts, wash that the residual quantity of citric acid is lower than 0.15 weight % to the solid phase terra alba, the consumption of the washing water of the solid phase terra alba of per 100 weight parts is 25 weight parts, first strand of washing water and the citric acid solution after the solid-liquid separation after the contact merge, after the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content the results are shown in Table 1.
Embodiment 2
The thick product of hydrogen citrate calcium of 1000 weight parts (purity 98.2 weight %, moisture 42.2 weight %) size mixing with rare citric acid solution (concentration 6.7 weight %), the content of water is 55 weight % in the hydrogen citrate calcium slurries that obtain, the vitriol oil of hydrogen citrate calcium slurries and 98 weight % together adds in the retort, the retort temperature is 96 ℃, control reaction solution specific conductivity is 8 ± 2mS/cm, and the reaction times is 50 minutes.
Under stirring condition, temperature was reduced to 81 ℃ and insulated and stirred 50 minutes with 0.5 ℃/minute average cooling rate, finely tuned with sulfuric acid or hydrogen citrate calcium slurries with retort, and control reaction solution specific conductivity is 5 ± 1mS/cm.
Under stirring condition, temperature was reduced to 75 ℃ and insulated and stirred 50 minutes with 0.5 ℃/minute average cooling rate, finely tuned with sulfuric acid or hydrogen citrate calcium slurries with retort, and control reaction solution specific conductivity is 3 ± 1mS/cm.
With rubber belt type vacuum filter the material in the retort is carried out solid-liquid separation, the solid phase terra alba that separates after the back is adopted washing water that multistage cover washes 4 strands 70 ℃ of process using and separated contacts, wash that the residual quantity of citric acid is lower than 0.15 weight % to the solid phase terra alba, the consumption of the washing water of the solid phase terra alba of per 100 weight parts is 28 weight parts, first strand of washing water and the citric acid solution after the solid-liquid separation after the contact merge, after the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content the results are shown in Table 1.
Embodiment 3
The thick product of hydrogen citrate calcium (purity 98.4 weight %, moisture 38.6 weight %) water is sized mixing, and the content of water is 45 weight % in the hydrogen citrate calcium slurries that obtain, and the vitriol oil of hydrogen citrate calcium slurries and 98 weight % is with 5m
3The input speed of/h together adds in the first step retort continuously, and reacting liquid temperature is 94 ℃ in the control first step retort, and control reaction solution specific conductivity is 7 ± 1mS/cm, when the retort liquid level reaches 4m
3The time, the material in second stage retort input first step retort, the material input speed is 5m
3/ h, average cooling rate is 76 ℃/minute, keeping first step retort liquid level simultaneously is 4m
3
Reacting liquid temperature is 84 ℃ in the retort of the control second stage, and specific conductivity is 5 ± 1mS/cm, and the retort liquid level reaches 4m when the second stage
3The time, the material in the retort of the third stage retort input second stage, the material input speed is 5m
3/ h, average cooling rate is 38 ℃/minute, keeping second stage retort liquid level simultaneously is 4m
3
Reacting liquid temperature is 79 ℃ in the control third stage retort, and specific conductivity is 3 ± 1mS/cm, when third stage retort liquid level reaches 4m
3The time, the material in fine setting jar input third stage retort, keeping third stage retort liquid level simultaneously is 4m
3
It is extremely two-tube clearly two with the reaction solution fine setting to add sulfuric acid or citrate of lime slurries in the fine setting jar, after the fine setting, with rubber belt type vacuum filter the material in the fine setting jar is carried out solid-liquid separation, the solid phase terra alba that separates after the back is adopted washing water that multistage cover washes 3 strands 60 ℃ of process using and separated contacts, wash that the residual quantity of citric acid is lower than 0.15 weight % to the solid phase terra alba, the consumption of the washing water of the solid phase terra alba of per 100 weight parts is 30 weight parts, first strand of washing water and the citric acid solution after the solid-liquid separation after the contact merge, after the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content the results are shown in Table 1.
Embodiment 4
Identical with the method for embodiment 1, different is, second stage retort temperature is 75 ℃, third stage retort temperature is 55 ℃, the consumption of washing water is 30 weight parts, after the whole system steady running, and the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content, the results are shown in Table 1.
Embodiment 5
Identical with the method for embodiment 2, different is, the reaction times under 96 ℃ of temperature is 20 minutes.After the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content the results are shown in Table 1.
Embodiment 6
Identical with the method for embodiment 2, different is, the reaction times under 81 ℃ of temperature is 20 minutes; Reaction times under 75 ℃ of temperature is 20 minutes, and after the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content the results are shown in Table 1.
Embodiment 7
Identical with the method for embodiment 1, different is, it is 80 ℃ that retort has only the temperature of two and second stage retort, the consumption of washing water is 35 weight parts, after the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content the results are shown in Table 1.
Embodiment 8
Identical with the method for embodiment 1, different is, adopt 50 ℃ washing water that the solid phase terra alba is washed, wash that the residual quantity of citric acid is lower than 0.15 weight % to the solid phase terra alba, the consumption of the washing water of the solid phase terra alba of per 100 weight parts is 40 weight parts, after the whole system steady running, and the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content, the results are shown in Table 1.
Embodiment 9
Identical with the method for embodiment 1, different is, terra alba after the washing solid-liquid separation does not adopt multistage cover to wash technology, but directly wash with clear water, the result washs that the residual quantity of citric acid is lower than 0.15 weight % to the solid phase terra alba, and the consumption of the washing water of the solid phase terra alba of per 100 weight parts is 50 weight parts.After the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content the results are shown in Table 1.
Embodiment 10
Identical with the method for embodiment 1, different is, adopt sulfuric acid and the citrate of lime slurry reaction of 80 weight %, after the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content, the results are shown in Table 1.
Embodiment 11
Identical with the method for embodiment 1, different is that the content of water is 80 weight % in the citrate of lime slurries that obtain after sizing mixing.After the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content the results are shown in Table 1.
Comparative Examples 1
Identical with the method for embodiment 11, different is, there are not second stage retort and third stage retort, the vitriol oil of citrate of lime slurries and 98 weight % is reaction 150 minutes in 93 ℃ the first step retort at reacting liquid temperature only, directly enter the fine setting jar after the reaction and finely tune, after the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content, the results are shown in Table 1.
Comparative Examples 2
Identical with the method for embodiment 11, different is, there are not first step retort and third stage retort, the vitriol oil of citrate of lime slurries and 98 weight % is reaction 150 minutes in 85 ℃ the second stage retort at reacting liquid temperature only, directly enter the fine setting jar after the reaction and finely tune, after the whole system steady running, the concentration of the citric acid solution that records, calcium ion content and yield, and the free water content of the terra alba that obtains, crystal water content, the results are shown in Table 1.
Table 1
Crystal water content from table 1 adopts calcium sulfate that the inventive method produces based on terra alba as can be seen.Embodiment 1-11 and Comparative Examples 1 and Comparative Examples 2 are compared respectively as can be seen, and the inventive method is than the concentration height, the yield height that generate calcium sulphate hemihydrate separately or generate terra alba separately the citric acid that is obtained, and the free water content of product calcium sulfate is low; Embodiment 1 and embodiment 4 are compared as can be seen, and the excessive temperature differentials of cooling is unfavorable for the coproduction of citric acid and terra alba; Embodiment 2 and embodiment 5 and embodiment 6 are compared as can be seen the too short coproduction that also is unfavorable for citric acid and terra alba of reaction times respectively; Embodiment 1 and embodiment 7 are compared as can be seen, carry out a step temperature-fall period not as carrying out the effective of two step temperature-fall periods; Embodiment 1 and embodiment 8 and 9 are compared respectively as can be seen, the temperature of bath water is low or do not adopt multistage cover to wash technology, all can cause the concentration of the citric acid solution that obtains low, theoretical derivation may be that washing water temperature is low or do not adopt multistage cover to wash technology, wash the residual quantity of the citric acid that requires, water consumption causes more; Embodiment 1 and embodiment 10 are compared as can be seen, and the concentration of the citric acid solution that the gas washing in SA production of high density goes out is higher; Embodiment 1 and embodiment 11 are compared as can be seen, and the content height of water in the citrate of lime slurries that obtain after sizing mixing can reduce the concentration of the citric acid solution that obtains.
The content of the free-water in the terra alba that the inventive method is produced is low, the concentration of the citric acid solution of producing and yield height, the content of calcium ion is low in the citric acid solution, and the concentration of the citric acid solution that the employing preferred embodiment of the present invention is produced can be up to more than the 0.6g/ml.The inventive method can be widely used in industrial production.
Claims (14)
1. the method for coproduction citric acid and terra alba said method comprising the steps of:
(1) make calcium citrate salts and aqueous sulfuric acid contact reacts, the catalytic temperature of described calcium citrate salts and aqueous sulfuric acid is higher than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba, obtains the mixed solution of citric acid and calcium sulphate hemihydrate;
(2) temperature of the mixed solution of citric acid and calcium sulphate hemihydrate is reduced to is lower than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba, make calcium sulphate hemihydrate change terra alba into, obtain the mixed solution of citric acid and terra alba;
(3) mixed solution with citric acid and terra alba carries out solid-liquid separation, obtains citric acid solution and solid phase terra alba.
2. method according to claim 1, wherein, described calcium citrate salts of step (1) and catalytic time of aqueous sulfuric acid are 30-120min, the described time that makes calcium sulphate hemihydrate change terra alba into of step (2) is 60-240min.
3. method according to claim 1 wherein, describedly makes method that calcium sulphate hemihydrate changes terra alba into comprise that earlier the temperature with the mixed solution of citric acid and calcium sulphate hemihydrate is reduced to t
1Temperature is again from t
1Temperature is reduced to t
2Temperature, described t
1Temperature and described t
2Temperature is lower than the transition temperature that calcium sulphate hemihydrate is transformed into terra alba respectively, and described t
2Temperature is lower than described t
1Temperature.
4. method according to claim 3, wherein, catalytic temperature of described calcium citrate salts and aqueous sulfuric acid and described t
1The temperature head of temperature and described t
1Temperature and described t
2The temperature head of temperature is respectively 5-15 ℃ separately, is reduced to described t from described calcium citrate salts and the catalytic temperature of aqueous sulfuric acid
1The average cooling rate of temperature and from described t
1Temperature is reduced to described t
2The average cooling rate of temperature is respectively more than 0.1 ℃/minute separately.
5. method according to claim 3, wherein, at described t
1The time of the transformation under the temperature is 30-120min, at described t
2The time that changes under the temperature is 30-120min.
6. according to any described method among the claim 1-5, wherein, the add-on of described calcium citrate salts and aqueous sulfuric acid makes that the specific conductivity of mixed solution of citric acid that step (1) obtains and calcium sulphate hemihydrate is 6-15mS/cm.
7. according to any described method among the claim 1-5, wherein, this method also is included in and adds calcium citrate salts or aqueous sulfuric acid in the step (2), and making the specific conductivity of the mixed solution of the citric acid that obtains and terra alba is 2-6mS/cm.
8. according to any described method among the claim 1-5, wherein, the content of water makes that the citric acid concentration of the citric acid solution that obtains behind citric acid and the calcium sulphate hemihydrate mixed solution elimination calcium sulphate hemihydrate is the 2.5-3.6 mol in described calcium citrate salts and the aqueous sulfuric acid.
9. according to any described method among the claim 1-5, wherein, described calcium citrate salts is one or more in citrate of lime, hydrogen citrate calcium and the dihydrogen citrate calcium.
10. according to any described method among the claim 1-5, wherein, described vitriolic concentration is 80-98 weight %
11. according to any described method among the claim 1-5, wherein, this method comprises that also the solid phase terra alba that step (3) is obtained washs with washing water, washs that the residual quantity of citric acid is lower than 0.15 weight % to the solid phase terra alba.
12. method according to claim 11, wherein, the temperature of described washing water is 50-85 ℃.
13. method according to claim 11, wherein, the mode of described washing comprises the solid phase terra alba is contacted with the multiply washing water that are arranged in order, according to the sequencing that contacts with the solid phase terra alba, back one washing water after the contact are returned as adjacent preceding one washing water.
14. method according to claim 13, wherein, described multiply washing water are 2-5 thigh washing water, are preferably 3-4 thigh washing water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102692357A (en) * | 2012-06-06 | 2012-09-26 | 中粮生物化学（安徽）股份有限公司 | Quantitative analysis method for calcium sulphate crystal |
| CN105568388A (en) * | 2015-12-28 | 2016-05-11 | 日照金禾博源生化有限公司 | Method for preparing gypsum whiskers from calcium hydrogen citrate |
| CN112479866A (en) * | 2020-12-07 | 2021-03-12 | 福建康鸿生物科技有限公司 | Method for co-producing citric acid complex calcium, malic acid complex calcium and fruit acid chelated calcium products |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5527860A (en) * | 1978-08-16 | 1980-02-28 | Sumitomo Metal Mining Co Ltd | Production of 2-type anhydrous gypsum |
| CN1547554A (en) * | 2001-08-24 | 2004-11-17 | Method for the preparation of lactic acid and calcium sulphate dihydrate |
-
2011
- 2011-05-30 CN CN201110144879.3A patent/CN102260165B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5527860A (en) * | 1978-08-16 | 1980-02-28 | Sumitomo Metal Mining Co Ltd | Production of 2-type anhydrous gypsum |
| CN1547554A (en) * | 2001-08-24 | 2004-11-17 | Method for the preparation of lactic acid and calcium sulphate dihydrate |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102692357A (en) * | 2012-06-06 | 2012-09-26 | 中粮生物化学（安徽）股份有限公司 | Quantitative analysis method for calcium sulphate crystal |
| CN102692357B (en) * | 2012-06-06 | 2013-11-20 | 中粮生物化学（安徽）股份有限公司 | Quantitative analysis method for calcium sulphate crystal |
| CN105568388A (en) * | 2015-12-28 | 2016-05-11 | 日照金禾博源生化有限公司 | Method for preparing gypsum whiskers from calcium hydrogen citrate |
| CN112479866A (en) * | 2020-12-07 | 2021-03-12 | 福建康鸿生物科技有限公司 | Method for co-producing citric acid complex calcium, malic acid complex calcium and fruit acid chelated calcium products |
| CN112479866B (en) * | 2020-12-07 | 2023-08-11 | 福建康鸿生物科技有限公司 | A method for co-producing citrate complexed calcium, malic acid complexed calcium and fruit acid chelated calcium products |
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