CN102503812A - Method for increasing citric acid yield in extracting process of citric acid with calcium-salt method - Google Patents
Method for increasing citric acid yield in extracting process of citric acid with calcium-salt method Download PDFInfo
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- CN102503812A CN102503812A CN2011103427645A CN201110342764A CN102503812A CN 102503812 A CN102503812 A CN 102503812A CN 2011103427645 A CN2011103427645 A CN 2011103427645A CN 201110342764 A CN201110342764 A CN 201110342764A CN 102503812 A CN102503812 A CN 102503812A
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- calcium
- citric acid
- calcium ions
- ions compound
- hydrocerol
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Abstract
The invention discloses a method for increasing citric acid yield in the extracting process of citric acid with a calcium-salt method. The method comprises the following steps of: contacting a citric acid fermentation clear liquid with a first calcium ion-containing compound and a second calcium ion-containing compound; performing solid-liquid separation on a contact product; and performing acidolysis on a solid phase obtained by solid-liquid separation to obtain a citric acid solution and calcium sulfate solid residues. In an improved calcium-salt method provided by the invention for extracting citric acid, the average content of the citric acid in a liquid left after a neutralization reaction counted by citric acid monohydrate is lowered to be lower than 0.15 percent, the yield of the citric acid is increased to over 98.5 percent, and the using amount of sulfuric acid in an acidolysis working section is not increased. Moreover, the second calcium ion-containing compound can be provided by extracting calcium sulfate solid waste residues generated in the citric acid acidolysis working section with the calcium-salt method, so that a part of the calcium sulfate waste residues can be consumed, a certain pressure is lowered for environmental protection, and the yield of the citric acid is increased on the premise of maintaining cost invariable.
Description
Technical field
The present invention relates to a kind of method that improves the Hydrocerol A yield, particularly in not increasing acidolysis workshop section, improve the method that calcium salt method extracts Hydrocerol A yield in the Hydrocerol A technology under the prerequisite of sulfuric acid consumption.
Background technology
Hydrocerol A is a kind of organic acid that is widely used in industries such as beverage, food and medicine.China is citric acid production big country, and the YO of Hydrocerol A is about 400,000 tons (2002), but also is constantly stablizing increase to satisfy the demand of domestic industry and outlet.At present; The process for extracting of domestic Hydrocerol A is mainly calcium salt method; Promptly use certain density lime carbonate or calcium hydroxide slurry and citric acid fermentation clear liquid generation neutralization reaction, generate citrate of lime, through adopting the mode of arranging the liquid after the neutralization reaction; Remove wherein impurity, citrate of lime obtains Hydrocerol A through the acidolysis step again.
When adopting calcium salt method to extract Hydrocerol A; In order to guarantee lower sulfuric acid consumption; The weight ratio of calcium ion gets 1 usually in citric acid fermentation clear liquid (in Citric acid monohydrate Food grade) and used lime carbonate or the calcium hydroxide: about 0.29-0.5; After the neutralization reaction in the liquid average content of Hydrocerol A be about 0.25% (in Citric acid monohydrate Food grade), the yield of Hydrocerol A is about 98%.Increase the consumption of lime carbonate or calcium hydroxide; Can make after the neutralization reaction that the average content of Hydrocerol A is reduced to below 0.15% (in the Citric acid monohydrate Food grade) in the liquid; The yield of Hydrocerol A is brought up to more than 98.5%; But so not only increased the cost of lime carbonate or calcium hydroxide, and along with the increase of lime carbonate or calcium hydroxide consumption, the vitriolic consumption is also wanted corresponding increase in the follow-up acidolysis workshop section; Therefore, also need explore a kind of method that under the prerequisite that does not increase extraction cost, improves the Hydrocerol A yield.
In addition, produce a large amount of calcium sulfate in the acidolysis process, calcium sulfate is as solid waste, and contaminate environment also can improve the cost that waste residue is handled in the citric acid production process.
Summary of the invention
The objective of the invention is in order to overcome the defective of existing calcium salt method, provide a kind of and in not increasing acidolysis workshop section, improve the method that calcium salt method extracts Hydrocerol A yield in the Hydrocerol A technology under the prerequisite of sulfuric acid consumption.
The common calcium salts method is extracted in the Hydrocerol A technology; After the neutralization reaction in the liquid Hydrocerol A average content be 0.2-0.3% (in Citric acid monohydrate Food grade); It is about 2% that Hydrocerol A loses, and is to improve the yield that calcium salt method extracts Hydrocerol A in the Hydrocerol A technology, and contriver of the present invention has carried out big quantity research to the calcium salt method of prior art; Find owing in Hydrocerol A and workshop section, contain a certain amount of positively charged ion in the citric acid fermentation clear liquid (like K
+, Na
+, NH
4 +, Mg
2+, Fe
3+, Al
3+Deng), the very big salt of above-mentioned positively charged ion and Hydrocerol A formation solubility in the neutral process when separation of citric acid calcium, is drained with waste water, thereby has reduced the yield of Hydrocerol A.Therefore; Contriver of the present invention is on the basis of existing calcium salt method; In with operation (being that the citric acid fermentation clear liquid contacts the operation that generates calcium salt with the calcium ions compound) in use the second calcium ions compound, improved the yield of Hydrocerol A greatly and do not increased vitriolic consumption in the acidolysis workshop section again.
Raising calcium salt method provided by the invention extracts in the Hydrocerol A technology method of Hydrocerol A yield and comprises the citric acid fermentation clear liquid is contacted with the calcium ions compound; And the product after will contacting carries out solid-liquid separation; The solid phase that then solid-liquid separation is obtained is carried out acidolysis; Obtain citric acid solution and calcium sulphate solid residue, it is characterized in that, said calcium ions compound is the first calcium ions compound and the second calcium ions compound; The said first calcium ions compound is lime carbonate and/or calcium hydroxide; The said second calcium ions compound be solubleness in water greater than in the calcium ions compound of the solubleness of calcium hydroxide in water one or more, in calcium ion, the weight ratio of the said first calcium ions compound and the second calcium ions compound is 1: 0.01-0.06.
Pass through technique scheme; Under the preferable case; In Citric acid monohydrate Food grade, after the neutralization reaction in the liquid average content of Hydrocerol A be reduced to below 0.15%, the Hydrocerol A yield is brought up to more than 98.5%; But do not increase lime carbonate or calcium hydroxide and vitriolic consumption, therefore method of the present invention has improved the yield of Hydrocerol A under the prerequisite that does not increase calcium salt method extraction Hydrocerol A cost.In addition; The second calcium ions compound can extract the calcium sulphate solid waste residue that the acidolysis workshop section of Hydrocerol A technology produces by calcium salt method among the present invention provides; So both can consume part of sulfuric acid calcium waste residue; For environmental protection alleviates certain pressure, also under the constant prerequisite of carrying cost, improved the yield of Hydrocerol A simultaneously.
Other features and advantages of the present invention will partly specify in embodiment subsequently.
Embodiment
Following specific embodiments of the invention is elaborated.Should be understood that embodiment described herein only is used for explanation and explains the present invention, is not limited to the present invention.
Among the present invention; Improving calcium salt method extracts in the Hydrocerol A technology method of Hydrocerol A yield and comprises the citric acid fermentation clear liquid is contacted with the calcium ions compound; And the product after will contacting carries out solid-liquid separation; The solid phase that then solid-liquid separation is obtained is carried out acidolysis, obtains citric acid solution and calcium sulphate solid residue, it is characterized in that; Said calcium ions compound is the first calcium ions compound and the second calcium ions compound; The said first calcium ions compound is lime carbonate and/or calcium hydroxide, the said second calcium ions compound be solubleness in water greater than in the calcium ions compound of the solubleness of calcium hydroxide in water one or more, the said second calcium ions compound is gone up inorganic calcium salt commonly used for well known to a person skilled in the art industry.
According to the present invention, through in operation in be used in combination solubleness in water greater than the second calcium ions compound of the solubleness of calcium hydroxide in water, can make in the citric acid fermentation clear liquid with other positively charged ions (like K
+, Na
+, NH
4 +, Mg
2+, Fe
3+, Al
3+Deng) the bonded citrate ion combines with calcium ion in the second calcium ions compound, generate citrate of lime, thereby improve the Hydrocerol A yield.Well known to a person skilled in the art and be; The solubleness of compound in water is relevant with temperature; Among the present invention, if guarantee this second calcium ions compound in the temperature condition of operation under solubleness in water greater than calcium hydroxide solubleness in water under this temperature.
In theory, if the solubleness of this second calcium ions compound in water greater than the condition of the solubleness of calcium hydroxide in water can impel in the citric acid fermentation clear liquid with other positively charged ions (like K
+, Na
+, NH
4 +, Mg
2+, Fe
3+, Al
3+Deng) the bonded citrate ion combines with calcium ion in the second calcium ions compound; Generate citrate of lime; Thereby reach the object of the invention, but under the preferable case, carry out as early as possible and as far as possible fully in order to make above-mentioned combination; The solubleness of the said second calcium ions compound in water is than the big at least 0.03g/100g water of the solubleness of calcium hydroxide in water, further preferred big 0.03-150g/100g water.
Under the preferable case, the said second calcium ions compound is one or more in calcium sulfate, calcium chloride and the nitrocalcite.Consider that use can increase follow-up workshop section vitriolic consumption with the second calcium ions compound that sulfuric acid reacts, the therefore further preferred said second calcium ions compound be not with the calcium ions compound of the acid generation chemical reaction of acidolysis step; Consider and introduce the burden that new negatively charged ion can increase follow-up Hydrocerol A purification step; The said second calcium ions compound is calcium sulfate more preferably; Said calcium sulfate can be provided by the industrial residue that contains calcium sulfate, and for example calcium salt method extracts the calcium sulfate waste residue that produces in the hydrolysis procedure of Hydrocerol A technology.The calcium sulfate waste residue that produces in the hydrolysis procedure by calcium salt method extraction Hydrocerol A technology is as the source of the second calcium ions compound; Can avoid introducing new impurity negatively charged ion on the one hand; The calcium sulfate waste residue that produces in the hydrolysis procedure is utilized effectively; Solve the emission problem of outsourcing second calcium ions compound and calcium sulfate simultaneously, so the present invention is with respect to prior art, under the situation that has improved the Hydrocerol A yield; Can not increase cost on the one hand, also alleviate pressure on the other hand for the environmental protection treatment stage.
According to the present invention, the mode that the citric acid fermentation clear liquid is contacted with the calcium ions compound can be for contacting with the first calcium ions compound citric acid fermentation clear liquid or the citric acid fermentation clear liquid being contacted with the second calcium ions compound with the first calcium ions compound successively simultaneously with the second calcium ions compound.The said second calcium ions compound can add in the fermentation clear liquid after the first calcium ions compound is even; Also can, the Hydrocerol A generation neutralization reaction in the first calcium ions compound and the fermentation clear liquid add again after finishing; Consider with the first calcium ions compound uniform mixing after add and need not to add in addition feeding equipment; Do not produce equipment cost and operation is comparatively convenient, preferably with behind the first calcium ions compound uniform mixing add again.
According to the present invention; In calcium ion; The weight ratio of the said first calcium ions compound and the second calcium ions compound can be 1: 0.01-0.06; Be preferably 1: 0.02-0.05, when the weight ratio of the first calcium ions compound and the second calcium ions compound was in above-mentioned preferable range, the yield of Hydrocerol A can further improve.
According to the present invention; The first calcium ions compound that adds can make that the Hydrocerol A 98% or more (in Citric acid monohydrate Food grade) gets final product with calcium ion formation calcium precipitation in the citric acid fermentation clear liquid; Therefore; The consumption of lime carbonate or calcium hydroxide got final product when the consumption of the said first calcium ions compound equaled conventional calcium salts method extraction Hydrocerol A; In Citric acid monohydrate Food grade, in the said citric acid fermentation clear liquid in citrate ion and the said first calcium ions compound weight ratio of calcium ion be 1: 0.29-0.5.
According to the present invention; The condition that said citric acid fermentation clear liquid contacts with the calcium ions compound can be carried out under the broad condition; The Hydrocerol A more than 98.5% fully is converted into deposition in the citric acid fermentation clear liquid as long as can make; Said contact conditions comprises that temperature is 70-75 ℃, and the pH of reaction end is 4.5-5.5, and the time is 15-40 minute.
According to the present invention, said acidolysis can be carried out well known to a person skilled in the art under the condition, and under the preferable case, said acidolysis condition comprises that pH is 1.45-1.55, and temperature is 75-85 ℃, and the time is 30-50 minute.
According to the present invention, the kind of the acid that said acidolysis is used can be for well known to a person skilled in the art various acid, and generally, working concentration is the above vitriol oil of 98 weight % more preferably more than the 90 weight %.
According to the present invention, the citric acid solution that acidolysis obtains is that Hydrocerol A slightly extracts product, can pass through IX well known to those skilled in the art again, concentrates, crystallization and drying and other steps be further purified.
According to the present invention, in Citric acid monohydrate Food grade, the content of Hydrocerol A is 100-130g/L in the said citric acid fermentation clear liquid.Said citric acid fermentation clear liquid can use the method for well known to a person skilled in the art to make, and for example generally obtains through back enzymolysis that W-Gum is sized mixing, fermentation back press filtration.Because with the improvement of operation, and the preparation method of citric acid fermentation clear liquid had been well known to those skilled in the art during the present invention related generally to and extracts in the Hydrocerol A technology to calcium salt method, therefore, the present invention repeats no more to the preparation process of citric acid fermentation clear liquid.
Below will describe the present invention through embodiment.In following examples, the concentration of Citric acid monohydrate Food grade is recorded by efficient liquid-phase chromatography method; After the concentration of the content of the middle Hydrocerol A of citric acid fermentation clear liquid, lime carbonate or calcium hydroxide slurry and the solid-liquid separation in the liquid content of Hydrocerol A etc. all according to quality (kg)/volume (m
3) * 100% calculates; In Citric acid monohydrate Food grade, content * 100% of Hydrocerol A in the yield of Hydrocerol A=(in the citric acid fermentation clear liquid after the content-neutralization reaction of Hydrocerol A in the liquid content of Hydrocerol A)/citric acid fermentation clear liquid.
Embodiment 1
The citric acid fermentation clear liquid that content is about 11% (in Citric acid monohydrate Food grade) and concentration are that 55% calcium carbonate serosity adds in the neutralization tank and mix (add-on of lime carbonate is 80kg in every cubic metre of citric acid fermentation clear liquid); Stir; The temperature of regulating in the neutralization tank is 75 ℃, and the pH that reacts slurries in 20 minutes post neutralization jars is about 5, reaches reaction end; In neutralization tank, add the calcium sulfate waste residue (acid hydrolysate for preparing the hydrolysis procedure of Hydrocerol A for calcium salt method again; Moisture is about 40 weight %), add-on is to add calcium sulfate waste residue 5kg in every cubic metre of citric acid fermentation clear liquid, stirs; Carry out natural subsidence behind the 10min, the content that records Hydrocerol A in the liquid after the solid-liquid separation is 0.14% (in Citric acid monohydrate Food grade).
Again solid is got into hydrolysis procedure, being 75 ℃ in temperature is that the vitriol oil (vitriol oil is 1: 1.94 with the solid weight ratio) of 98 weight % contacts 30 minutes with concentration down, and filtration obtains calcium sulphate solid and citric acid solution then.Through calculating the yield of confirming Hydrocerol A is 98.73%.
Comparative Examples 1
Method according to embodiment 1 adopts calcium salt method from the citric acid fermentation clear liquid, to extract Hydrocerol A; Different is; Do not comprise the step that in neutralization tank, adds the calcium sulfate waste residue; Promptly reach and directly carry out behind the reaction end settlement separately, the content that records Hydrocerol A in the liquid after the solid-liquid separation is 0.21% (in Citric acid monohydrate Food grade), is 98.1% through calculating the yield of confirming Hydrocerol A.
Embodiment 2
The citric acid fermentation clear liquid that content is about 11% (in Citric acid monohydrate Food grade) and concentration are that 55% calcium hydroxide slurry adds in the neutralization tank and mix (add-on of calcium hydroxide is 62kg in every cubic metre of citric acid fermentation clear liquid); Stir, the temperature of regulating in the neutralization tank is 75 ℃, and the pH that reacts slurries in 20 minutes post neutralization jars is about 5; Reach reaction end; In neutralization tank, add calcium chloride again, add-on is to add calcium chloride 5.5kg in every cubic metre of citric acid fermentation clear liquid, stirs; Carry out natural subsidence behind the 10min, the content that records Hydrocerol A in the liquid after the solid-liquid separation is 0.142% (in Citric acid monohydrate Food grade).
Again solid is got into hydrolysis procedure, being 75 ℃ in temperature is that the sulfuric acid (sulfuric acid is 1: 1.94 with the solid weight ratio) of 98 weight % contacts 30 minutes with concentration down, and filtration obtains calcium sulphate solid and citric acid solution then.Through calculating the yield of confirming Hydrocerol A is 98.71%.
Embodiment 3
Be to add the calcium sulfate waste residue (acid hydrolysate for preparing the hydrolysis procedure of Hydrocerol A for calcium salt method in 55% the calcium carbonate serosity toward concentration; Moisture is about 40 weight %) the uniform mixing slurries of preparation lime carbonate and calcium sulfate; Add calcium sulfate waste residue 25kg in every cubic metre 55% calcium carbonate serosity; Mixed serum and content are about 11% citric acid fermentation clear liquid (in Citric acid monohydrate Food grade) add in the neutralization tank and mix (add-on of lime carbonate is 80kg in every cubic metre of citric acid fermentation clear liquid), stir, the temperature of regulating in the neutralization tank is 75 ℃; The pH that reacts slurries in 15 minutes post neutralization jars is about 5; Reach reaction end, natural subsidence, the content that records Hydrocerol A in the liquid after the solid-liquid separation is 0.135% (in Citric acid monohydrate Food grade).
Again solid is got into hydrolysis procedure, being 75 ℃ in temperature is that the sulfuric acid (sulfuric acid is 1: 1.94 with the solid weight ratio) of 98 weight % contacts 30 minutes with concentration down, and filtration obtains calcium sulphate solid and citric acid solution then.Through calculating the yield of confirming Hydrocerol A is 98.77%.
Embodiment 4
Be to add the uniform mixing slurries that nitrocalcite prepares lime carbonate and nitrocalcite in 55% the calcium carbonate serosity toward concentration; Add nitrocalcite 9.1kg in every cubic metre 55% calcium carbonate serosity; Mixed serum and content are about 11% citric acid fermentation clear liquid (in Citric acid monohydrate Food grade) add in the neutralization tank and mix (add-on of lime carbonate is 80kg in every cubic metre of citric acid fermentation clear liquid), stir, the temperature of regulating in the neutralization tank is 75 ℃; The pH that reacts slurries in 15 minutes post neutralization jars is about 5; Reach reaction end, natural subsidence, the content that records Hydrocerol A in the liquid after the solid-liquid separation is 0.15% (in Citric acid monohydrate Food grade).
Again solid is got into hydrolysis procedure, being 75 ℃ in temperature is that the sulfuric acid (sulfuric acid is 1: 1.94 with the solid weight ratio) of 98 weight % contacts 30 minutes with concentration down, and filtration obtains calcium sulphate solid and citric acid solution then.Through calculating the yield of confirming Hydrocerol A is 98.64%.
Can find out from above embodiment; The yield of Hydrocerol A is all greater than the yield of Hydrocerol A in the Comparative Examples 1 among the embodiment 1-4; In improved more than 0.5% with yield, be 400,000 tons with the Hydrocerol A YO and calculate that the output of Hydrocerol A can increase about 2000 tons under not extra increase condition of cost.Use the preferred second calcium ions compound of the present invention; Can make all after the neutralization reaction that the content of Hydrocerol A is reduced to (in Citric acid monohydrate Food grade) below 0.15% in the liquid; And don't can increase vitriolic consumption in the acidolysis workshop section, if use calcium sulfate waste residue that acidolysis workshop section produces as the source of the second calcium ions compound then can be implemented in more than the yield to 98.5% that improves Hydrocerol A under the prerequisite that does not increase extraction cost.
More than combine embodiment to 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.
Claims (10)
1. one kind is improved the method that calcium salt method extracts Hydrocerol A yield in the Hydrocerol A technology; This method comprises the citric acid fermentation clear liquid is contacted with the calcium ions compound; And the product after will contacting carries out solid-liquid separation, and the solid phase that then solid-liquid separation is obtained is carried out acidolysis, obtains citric acid solution and calcium sulphate solid residue; It is characterized in that; Said calcium ions compound is the first calcium ions compound and the second calcium ions compound, and the said first calcium ions compound is lime carbonate and/or calcium hydroxide, and the said second calcium ions compound is that solubleness in water is greater than in the calcium ions compound of the solubleness of calcium hydroxide in water one or more; In calcium ion, the weight ratio of the said first calcium ions compound and the second calcium ions compound is 1: 0.01-0.06.
2. method according to claim 1, wherein, in calcium ion, the weight ratio of the first calcium ions compound and the second calcium ions compound is 1: 0.02-0.05.
3. method according to claim 1, wherein, in Citric acid monohydrate Food grade, in the said citric acid fermentation clear liquid in the citrate ion and the first calcium ions compound weight ratio of calcium ion be 1: 0.29-0.5.
4. method according to claim 1 and 2, wherein, the said second calcium ions compound is one or more in calcium sulfate, calcium chloride, the nitrocalcite.
5. according to claim 1,2 or 4 described methods, wherein, the said second calcium ions compound is provided by the calcium sulphate solid waste residue that calcium salt method extracts the acidolysis workshop section generation of Hydrocerol A technology.
6. method according to claim 1, wherein, the condition that said citric acid fermentation clear liquid contacts with the calcium ions compound comprises that temperature is 70-75 ℃, and the pH of reaction end is 4.5-5.5, and the time is 15-40 minute.
7. method according to claim 1, wherein, the condition of said acidolysis comprises that pH is 1.45-1.55, and temperature is 75-85 ℃, and the time is 30-50 minute.
8. according to claim 1 or 7 described methods, wherein, carrying out the used acid of acidolysis is the above vitriol oils of 98 weight %.
9. method according to claim 1; Wherein, the mode that the citric acid fermentation clear liquid is contacted with the calcium ions compound contacts with the first calcium ions compound citric acid fermentation clear liquid for the citric acid fermentation clear liquid is contacted with the second calcium ions compound perhaps with the first calcium ions compound simultaneously successively with the second calcium ions compound.
10. method according to claim 1, wherein, in Citric acid monohydrate Food grade, the content of Hydrocerol A is 100-130g/L in the said citric acid fermentation clear liquid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617333A (en) * | 2012-03-01 | 2012-08-01 | 中粮生物化学（安徽）股份有限公司 | Extraction method of citric acid |
| CN106957224A (en) * | 2016-01-12 | 2017-07-18 | 中粮生物化学（安徽）股份有限公司 | A kind of extracting method of citric acid |
| CN107573234A (en) * | 2017-07-28 | 2018-01-12 | 兰茂密 | A kind of industrial method for extracting citric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106788A (en) * | 1994-08-03 | 1995-08-16 | 王文忠 | Process for increasing extraction yield of citric acid with neutralizing promoter |
| CN101914580A (en) * | 2010-07-14 | 2010-12-15 | 莱芜泰禾生化有限公司 | Calcium salt method for producing citric acid by recycling waste residues calcium sulfate |
-
2011
- 2011-11-03 CN CN2011103427645A patent/CN102503812A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106788A (en) * | 1994-08-03 | 1995-08-16 | 王文忠 | Process for increasing extraction yield of citric acid with neutralizing promoter |
| CN101914580A (en) * | 2010-07-14 | 2010-12-15 | 莱芜泰禾生化有限公司 | Calcium salt method for producing citric acid by recycling waste residues calcium sulfate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617333A (en) * | 2012-03-01 | 2012-08-01 | 中粮生物化学（安徽）股份有限公司 | Extraction method of citric acid |
| CN106957224A (en) * | 2016-01-12 | 2017-07-18 | 中粮生物化学（安徽）股份有限公司 | A kind of extracting method of citric acid |
| CN107573234A (en) * | 2017-07-28 | 2018-01-12 | 兰茂密 | A kind of industrial method for extracting citric acid |
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Application publication date: 20120620 |