CN104513155A - Organic acid metal salt producing method - Google Patents
Organic acid metal salt producing method Download PDFInfo
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- CN104513155A CN104513155A CN201310461204.0A CN201310461204A CN104513155A CN 104513155 A CN104513155 A CN 104513155A CN 201310461204 A CN201310461204 A CN 201310461204A CN 104513155 A CN104513155 A CN 104513155A
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Abstract
The invention provides an organic acid metal salt producing method which comprises following steps: contacting an aqueous solution containing an organic acid with one or more compounds selected from the group including a crude carbonate, a crude hydroxide and a crude oxide of a metal M to obtain a crude organic acid metal salt crystal; performing acidolysis to the crude organic acid metal salt crystal with hydrochloric acid to obtain a solution with filtration; and contacting a filtrate with one or more from the group including a carbonate of an alkali metal, a hydroxide of the alkali metal and a oxide of the alkali metal, ammonium carbonate and ammonium bicarbonate to obtain the organic acid metal salt of the metal M. The organic acid is an organic carboxylic acid and/or an organic phosphoric acid, wherein the organic carboxylic acid is 1-7 in carbon atom number and is 1-4 in carboxyl group number. The metal M is at least one selected from the group including magnesium, calcium, aluminum, lead, zinc, copper, titanium, cerium and manganese. By means of the method, the high-purity organic acid metal salt which is 99.9-99.99% in purity can be obtained.
Description
Technical field
The present invention relates to a kind of production method of metal salts of organic acids.
Background technology
In prior art, metal salts of organic acids must use the carbonate of the organic acid of higher degree and highly purified metal, oxyhydroxide or oxide compound to be obtained by reacting, and therefore production cost is too high.
A kind of method producing magnesium citrate is disclosed in CN101591234A.The method comprises and is obtained by reacting highly purified magnesium citrate with high purity magnesiumcarbonate, magnesium oxide or magnesium hydroxide and edible citric acid.The edible citric acid used in the method needs to purify in advance, a kind of need from organic acid fermentation liquid to high purity organic acid method of purification to carry out to filter, neutralize, sulfuric acid solution, decolouring, from steps such as friendship, condensing crystals, need to consume multiple auxiliary materials in the process of purifying, another kind of high purity Extraction Methods of Organic Acids membrane filtration chromatogram rule needs to carry out membrane filtration, in purification process, need special equipment for purifying from steps such as friendship, chromatogram, condensing crystals, and needs the supplementary materials such as consumption acids, alkali, resin; The preparation process of the high-purity carbonate of metal, oxide compound or oxyhydroxide relates to complicated purification process; Therefore this metal salts of organic acids preparation method power consumption and consume supplementary material more while, can produce multiple pollutant, prior art production high purity metal salts of organic acids cost drops into high, complex procedures and pollutant emission is many as can be seen here.
Therefore, need to develop a kind of acidolysis of saving in preparation high purity organic acid process, from handing over, condensing crystal supervisor and save the production method of the carbonate of metal, oxide compound or oxyhydroxide purification step, and while reaching effect same as the prior art, the input of the costs such as remarkable reduction equipment, water consumption, energy consumption, auxiliary material, artificial, safety and environmental protection, obtains the production method meeting the high purity metal salts of organic acids of country and company standard.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect existed in prior art, providing a kind of without the need to extracting high purity organic acid in advance and without the need in advance to the production method of the high purity metal salts of organic acids that the carbonate of metal, oxide compound or hydroxide source are refined.
To achieve these goals, the invention provides a kind of production method of metal salts of organic acids, wherein, the method comprises containing the organic acid aqueous solution and the thick carbonate being selected from M metal, thick oxyhydroxide contacts with one or more in thick oxide compound and obtains thick metal salts of organic acids crystal, with hydrochloric acid, described thick metal salts of organic acids crystal acidolysis is obtained solution, and filter, by the filtered solution of acquisition and alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt contacts the metal salts of organic acids obtaining M metal with one or more in bicarbonate of ammonia,
Wherein, described organic acid is organic carboxyl acid and/or organic phosphoric acid; Described organic carboxyl acid is carbonatoms is 1-7, carboxyl number is the organic carboxyl acid of 1-4;
Wherein, described M metal is selected from least one in magnesium, calcium, aluminium, lead, zinc, copper, titanium, cerium and manganese.
Can be found out by the result of the embodiment of the present invention, utilize the production method of metal salts of organic acids provided by the invention without the need to extracting high purity organic acid in advance, the thick carbonate to M metal is not needed yet, thick oxyhydroxide and thick oxide raw material are refined, can directly utilize containing impurity containing the organic acid aqueous solution, as through the organic acid fermentation clear liquid containing thalline and part residual sugar of simple filtration and/or the organic acid crystallization mother liquor thick carbonate with the M metal containing impurity, at least one reaction in thick oxyhydroxide and thick oxide compound obtains thick metal salts of organic acids crystal settling, only need afterwards to carry out disposable filtering removal of impurities, and by the filtered solution of acquisition and alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, one or more in volatile salt and bicarbonate of ammonia carry out contact reacts, the purity of the metal salts of organic acids obtained just can reach the thick carbonate adopting refining organic acid and refining M metal, the purity of the metal salts of organic acids that the method that thick oxyhydroxide and thick oxide compound produce metal salts of organic acids obtains.Adopt production method provided by the invention, the high purity metal salts of organic acids that purity is 99.9-99.99% can be obtained.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the production process route schema of high purity metal salts of organic acids of the present invention.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the present invention, the production method of described metal salts of organic acids comprises: by containing the organic acid aqueous solution be selected from the thick carbonate of M metal, thick oxyhydroxide and one or more in thick oxide compound and contact and obtain thick metal salts of organic acids crystal, with hydrochloric acid, described thick metal salts of organic acids crystal acidolysis is obtained solution, and filter, the filtered solution and the alkali-metal carbonate that obtain, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt and one or more in bicarbonate of ammonia are contacted the metal salts of organic acids obtaining M metal;
Wherein, described organic acid is organic carboxyl acid and/or organic phosphoric acid; Described organic carboxyl acid is carbonatoms is 1-7, carboxyl number is the organic carboxyl acid of 1-4;
Wherein, described M metal is selected from least one in magnesium, calcium, aluminium, lead, zinc, copper, titanium, cerium and manganese.
Preferably, described M metal is at least one in magnesium, calcium, zinc, copper and titanium.More preferably, described M metal is calcium, magnesium or copper.
Described organic acid is have acid organic compound, organic acid of the present invention is can react with one or more in the thick carbonate of M metal, thick oxyhydroxide and thick oxide compound, generate organic carboxyl acid and/or the organic phosphoric acid of metal salts of organic acids, preferably, one or more in formic acid, acetic acid, citric acid, lactic acid, gluconic acid, equisetic acid, oxysuccinic acid, methylene-succinic acid and tartrate, described organic phosphoric acid is one or more in phytic acid, Triphosaden and adenosine diphosphate (ADP); More preferably, described organic acid is at least one in citric acid, lactic acid, tartrate and methylene-succinic acid, most preferably is citric acid and/or lactic acid.
The metal salts of organic acids adopting method of the present invention to produce can be the normal salt of metal, acid salt or subsalt; Wherein, described normal salt comprises such as citric acid, lactic acid, gluconic acid, equisetic acid, oxysuccinic acid, methylene-succinic acid, tartrate etc. and is neutralized completely by alkali or basic cpd containing the hydrogen ion in the carboxylic acid of carboxylic group or organic phosphoric acid or replace the salt of acquisition, and the hydrogen ion that described acid salt comprises in carboxylic acid containing carboxylic group of such as citric acid, lactic acid, gluconic acid, equisetic acid, oxysuccinic acid, methylene-succinic acid, tartrate etc. or organic phosphoric acid is partially neutralized or replaces the salt of acquisition; Described subsalt comprises hydroxide radical in the alkali such as such as alkaline cupric tartrate, monobasic lead acetate by acid completely and the product of gained, that is, in subsalt except metal ion and acid ion are thought also containing one or more hydroxyls or oxygen base.
According to the present invention, be describedly preferably 0.5-10mol/L containing organic acid content in the organic acid aqueous solution, turbidity is less than or equal to 20NTU.Such as, described can for being dissolved with the organic acid aqueous solution containing aqueous solutions of organic acids, concrete, can be the organic acid aqueous acid containing impurity purifying to be separated of chemosynthesis.Because method of the present invention is specially adapted to directly to utilize the aqueous solutions of organic acids containing impurity, as the thick carbonate containing organic acid fermentation clear liquid and/or organic acid crystallization mother liquor and the M metal containing impurity containing thalline and part residual sugar through simple filtration, at least one reaction in thick oxyhydroxide and thick oxide compound obtains thick metal salts of organic acids crystal settling, only need afterwards to carry out disposable filtering removal of impurities, and by the filtered solution of acquisition and alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, one or more in volatile salt and bicarbonate of ammonia carry out contact reacts and namely can obtain the higher metal salts of organic acids of purity, therefore, preferably, described is organic acid fermentation clear liquid and/or organic acid crystallization mother liquor containing the organic acid aqueous solution.
Described organic acid fermentation clear liquid is that known in those skilled in the art directly organic acid fermentation liquid process filtration obtains; The method of described filtration is also conventionally known to one of skill in the art, and in the described organic acid fermentation clear liquid obtained, organic acid content is 0.5-10mol/L, and turbidity is less than or equal to 20NTU, without the visible solid substance of naked eyes in clear liquid.Wherein, described organic acid fermentation clear liquid can adopt method known in those skilled in the art to prepare, and does not repeat them here.
Described organic acid crystallization mother liquor is to have the debris after also filtering containing organic acid solution crystallization, and crystallization herein can refer to that evaporative crystallization also can refer to recrystallization, and the turbidity of described organic acid crystallization mother liquor is less than or equal to 20NTU; When using organic acid crystallization mother liquor, the viscosity as fruit mother liquor is greater than 10Pas, when turbidity is greater than 20NTU, by the mode of thin up, the viscosity of crystalline mother solution can be adjusted to below 5Pas, flocculation or filter and turbidity is adjusted to be less than or equal to 20NTU.
Containing impurity in the thick carbonate of described M metal, in the thick oxyhydroxide of M metal and in the thick oxide compound of M metal, described impurity be generally total amount not higher than 5 % by weight be selected from silicon-dioxide, heavy metal compound (metallic compound as at least one in copper, lead, zinc, tin, nickel, cobalt, antimony, mercury, cadmium and bismuth), aluminum contained compound (as aluminium sesquioxide, aluminate etc.), containing rare-earth compound (as containing the compound such as cerium, yttrium with the association of natural whiting ore) and insoluble silicate (as feldspar (K
2al
2si
6o
16), asbestos (CaMg
3si
4o
12) etc.) and in one or more.
In order to make the thick carbonate of M metal, thick oxyhydroxide or thick oxide compound more abundant with the contact containing the organic acid aqueous solution, the particle diameter of the thick carbonate of described M metal, thick oxyhydroxide and thick oxide compound is preferably 10-400 micron, such as, the mode of conventional fragmentation or grinding can be adopted to reach the requirement of described preferable particle size.
In the production method of metal salts of organic acids of the present invention, containing the organic acid aqueous solution be selected from the thick carbonate of M metal, thick oxyhydroxide and one or more in thick oxide compound and contact the condition generating thick metal salts of organic acids crystal and comprise:
Temperature is 30-150 DEG C, and be preferably 30-90 DEG C, the pH value of terminal is 4.0-6.0, and be preferably 4.6-4.8, the thick metal salts of organic acids of acquisition is the thick organic acid metal normal salt crystal of M metal;
Temperature is 30-120 DEG C, is preferably 30-90 DEG C, and controlling endpoint pH is 2.5 to being less than 4.0, and be preferably 2.8-3.0, the thick metal salts of organic acids of acquisition is the thick organic acid metal acid salt crystal of M metal;
Temperature is 30-120 DEG C, and be preferably 30-90 DEG C, control endpoint pH is 7-9, and be preferably 7.5-8.5, the thick metal salts of organic acids of acquisition is the thick organic acid metal basic salt crystal of M metal.
According to the present invention, thick carbonate containing the organic acid aqueous solution and M metal, thick oxyhydroxide and one or more in thick oxide compound contacts the method obtaining thick metal salts of organic acids crystal also preferably include: the thick carbonate containing the organic acid aqueous solution and M metal, slightly the contact reacts product of oxyhydroxide or oxide compound are filtered, if suction filtration is to remove partial impurities (as protein, carbohydrate, fermentation thalli, organic heteroacid, lipid and inorganic salt etc.), obtain the thick metal salts of organic acids crystal that free water content is 10-50 % by weight.
Under preferable case, the method to be also included in before the acidolysis of thick metal salts of organic acids crystal with hydrochloric acid, washes thick metal salts of organic acids crystal.Particularly when use containing the organic acid aqueous solution for organic acid fermentation clear liquid or crystalline mother solution time, preferably described thick metal salts of organic acids crystal is washed.Washing the standard that will reach is the content that HPLC or GCMS detects impurity in thick metal salts of organic acids crystal, and namely carbohydrate and protein impurities content is not higher than 1 % by weight.By accounting for look >=10min to the metal salts of organic acids affination water potassium permanganate oxidation of thick metal salts of organic acids crystal, moisture≤50 % by weight, readily carbonizable substance absorbance ratio≤5 judge, if reach above-mentioned standard, show its carbohydrate and protein impurities content substantially not higher than 1 % by weight.The method of washing can adopt the method for well known to a person skilled in the art to carry out, if washing temperature can be 20-100 DEG C.Solubility with temperature due to part organic acid salt (as calcium lactate) raises and increases, and in order to not affect the yield of the final product obtained, for difference washing object, can carry out suitable adjustment to the temperature of washing, preferred washing temperature is 75-85 DEG C.Volume ratio for the water washed and wet metal salts of organic acids is preferably 0.5-3:1.Preferably, after control after washing (such as by the mode such as suction filtration, drying) washing, the water content of wet organic acid salt is not higher than 50 % by weight, such as, can be 10-40 % by weight.Wet organic acid salt solid aqueous amount after washing is lower, contact the molten damage of organic acid salt in the mother liquor of the sodium chloride-containing that postprecipitation is discharged after hydrochloric acidolysis with alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt and at least one in bicarbonate of ammonia lower, be more conducive to the raising of yield.In addition, the wet organic acid salt solid that water content is low can the lower hydrochloric acidolysis of working concentration.
Method of the present invention also comprises carries out acidolysis acquisition solution with hydrochloric acid to thick metal salts of organic acids crystal, preferably, total mole number that the consumption of the hydrochloric acid of acidolysis thick metal salts of organic acids crystal makes molecular state conciliate the hydrogenchloride of amorph is 2.5-3:1 with the ratio of the mole number of organic acid in thick metal salts of organic acids crystal.
The hydrochloric acid used in the present invention can be concentrated hydrochloric acid or dilute hydrochloric acid, when using concentrated hydrochloric acid, suitable quantity of water dilution need be added to ensure carrying out smoothly of filtering and impurity removing step thereafter in reaction system, special restriction is not done to the add-on of the water for diluting, but preferably, the final concentration of hydrochloric acid is 5-37 % by weight.
Method of the present invention also comprises filters with the solution obtained after hydrochloric acidolysis, thus filter out the hydrochloric acid insoluble substance and other impurity that exist in solution, general, the content of hydrochloric acid insoluble substance in solution (albumen etc. that such as silicon-dioxide, the insoluble heavy metal compound of hydrochloric acid, insoluble silicate, flocculation sediment get off) can be effectively reduced by this step, final acquisition turbidity≤0.5NTU, the solution of readily carbonizable substance absorbance ratio≤3.The method of this area routine can be adopted to filter, such as Plate Filtration or micro-filtrate membrane filtration method, when adopting Plate Filtration method, can in advance in sheet frame precoated diatomite or perlite form flocculating aids filter cake, then make solution by sheet frame again, filter.
According to method of the present invention, by obtain filtered solution with alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt with in one or more steps contacted in bicarbonate of ammonia, the purity of described alkaline carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt and bicarbonate of ammonia is all not less than 95 quality %, the most preferably, described alkali-metal carbonate is sodium carbonate, described alkali-metal oxyhydroxide is sodium hydroxide, and described alkali-metal oxide compound is sodium oxide.
According to method of the present invention, the filtered solution of acquisition and alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt and one or more in bicarbonate of ammonia are contacted the condition generating metal salts of organic acids and generally includes temperature and endpoint pH, the selectable range of above-mentioned condition is wider.
Wherein, the filtered solution of acquisition is comprised with one or more conditions contacting the organic acid normal salt generating M metal in bicarbonate of ammonia with alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt: temperature is 60-100 DEG C, be preferably 75-85 DEG C, endpoint pH is 4.0-6.0, is preferably 4.6-4.8.
The filtered solution of acquisition is comprised with one or more conditions contacting the organic acid acid salt generating M metal in bicarbonate of ammonia with alkaline carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt: temperature is 60-100 DEG C, be preferably 75-85 DEG C, endpoint pH is 2.5 to being less than 4.0, is preferably 2.8-3.0.The generation of the organic acid acid salt of M metal also can by contacting the organic acid normal salt being separated the M metal obtained and alkaline carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt and one or more in bicarbonate of ammonia further, controlling the pH value of terminal is 2.5 to being less than 4.0, be preferably 2.8-3.0, generate the organic acid acid salt of M metal.
The filtered solution of acquisition is comprised with one or more conditions contacting the organic acid subsalt generating M metal in bicarbonate of ammonia with alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt: temperature is 30-120 DEG C, be preferably 30-90 DEG C, endpoint pH is 7-9, is preferably 7.5-8.5.
Under preferable case, method of the present invention is also included in the filtered solution of acquisition and alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, before volatile salt contacts with one or more in bicarbonate of ammonia, filtered solution is decoloured, to remove the larger molecular organicses such as the pigment be present in filtered solution, the method of described decolouring can adopt various method known in those skilled in the art, under preferable case, the method of described decolouring is contacted with discoloring agent by filtered solution, more preferably, the method of described decolouring comprises: passed into by filtered solution and be equipped with in the decolorizing column of discoloring agent, filtered solution is contacted with discoloring agent, and the filtrate through decolouring is drawn.Described discoloring agent can adopt conventional discoloring agent, as powdered carbon or granulated active carbon, preferably adopts granulated active carbon.In addition, in order to make decolorizing effect better, preferred described decolouring is carried out at 40-80 DEG C, and further preferably bleaching temperature is 50-60 DEG C.
In the production method of metal salts of organic acids of the present invention, under preferable case, the method also comprises carries out deleading, washing, oven dry, to improve purity and the quality of product further to the metal salts of organic acids of the final M metal obtained.
Wherein, the method of deleading is conventionally known to one of skill in the art, such as, can for generate M metal in reaction metal salts of organic acids after in reaction system, add dilute acetic acid to reactant and eluriate, concrete operation method can be: add the dilute acetic acid solution of 20 % by weight in system after the completion of reaction in reactor, add the dilute acetic acid solution of 20-40ml by every 100Kg output, and carry out stirring 15-20 minute.After removing acid solution, residual acetic acid is removed in washing again.
Wherein, washing, the method for drying can adopt various method well known in the art, the condition of preferably washing comprises the deionized water using heat, solubility with temperature due to part organic acid salt (as calcium lactate) raises and increases, in order to not affect the yield of the final product obtained, for difference washing object, suitable adjustment can be carried out to the temperature of washing, preferred washing temperature is 75-85 DEG C, be washed till without acetic acid smell by organic acid metal salt-pepper noise, the temperature that the condition of oven dry comprises oven dry is 60-100 DEG C.
Below will be described the present invention by embodiment.
In following examples, turbidity parameter is by upper dried shrimps Qing Ke necessary instrument company, and WZS-200 type turbidometer measures; Acidity parameters is recorded by 0.1429mol/L aqueous sodium hydroxide solution titration method; The organic acid aqueous solution comprises: citric acid fermentation aqueous solution, and the concentration of this citric acid fermentation aqueous solution is in Citric acid monohydrate Food grade, and unit is g/L; Lactic acid aqueous solution, the concentration of this lactic acid aqueous solution is in lactic acid, and unit is g/L.
Metal salts of organic acids affination water potassium permanganate oxidation accounts for look and records by the following method: with the deionized water wash machine acid metal salt of 100ml, 75-95 DEG C, elutant is mixed, filters, the filtered solution obtained after being filtered by 25ml is placed in colorimetric cylinder, instill the potassium permanganate solution of 21 weight ‰, observe the time that potassium permanganate oxidation accounts for look (ie in solution presents blush).
Lead content in the purity of readily carbonizable substance absorbance ratio, organic acid metal product salt and organic acid metal product salt according to: the method specified in GB1987-2007 calculates;
The measuring method of hydrochloric acid insoluble substance is as follows: the 5g(that materialses is accurate to 0.001g), add 6mol hydrochloric acid 10ml and water 50ml, mixing post-heating 30min, with No. three sand core funnel vacuum filtrations, rinse three times with 200ml water, throw out is dry 2h at 105 DEG C.The hydrochloric acid insoluble substance of national regulations and residue should be no more than 10mg(that is 0.2%);
Heavy metal content according to: the method that specifies in GB/T5009.74-2003 calculates;
Arsenic content according to: the method that specifies in GB/T7686-2008 calculates;
Content of fluoride according to: the method that specifies in GB7484-87 calculates.
Citric acid fermentation broth adopts following method to prepare:
0.872 kg corn SFSP series beater disintegrating machine is pulverized, obtains 0.871 kilogram of crushed products that average particulate diameter is 2 millimeters (adopting the AccuSizer TM780 optics droplet measurement instrument of PPS company of the U.S. to measure); Crushed products is mixed with amylase and carries out steam ejection liquefaction, the control temperature that once liquefies is 83 ± 1 DEG C, once liquefaction is held time as 2-5 minute, and secondary liquefaction control temperature is 93 ± 1 DEG C, and secondary liquefaction was held time as 90-150 minute, and (pH value of described enzymolysis maintains 5.7-6.2; With the dry weight basis of every gram of crushed products, the consumption of α-amylase (purchased from Novozymes Company) is 40 enzyme activity units, wherein, enzyme activity unit is defined as: pH value be 6.0, under temperature is the condition of 70 DEG C, the enzyme amount of 1 milligram of Starch Conversion needed for reducing sugar is an enzyme activity unit by 1 minute), obtain enzymolysis product.
By Partial digestion product by carrying out press filtration with fluid pressure type plate-and-frame filter press, isolate clear liquid and filter residue, wherein, the solid content of filter residue is 50 % by weight.
By joining in the fermentor tank of 300L after the clear liquid of 172.8 kilograms, 43.2 kilograms of enzymolysis product sterilizings, obtain fermention medium.
It is 10 % by weight that Partial digestion product obtained above is diluted with water to total reducing sugar, obtain seed culture medium, seed culture medium is dropped into seeding tank, be heated to 121 DEG C of sterilizations, maintain fast cooling to 36 DEG C after 30 minutes, access aspergillus niger strain, in often liter of seed culture medium, the inoculum size of aspergillus niger is 2 × 10
8individual spore.36 DEG C, initial ph value is 5.5,0.6 volume: carry out spawn culture under the aeration condition of (volume minute); By sampling sediments microscope inspection, acid test and pH measure the growth of aspergillus niger is observed, when pH < 2.0, acidity > 1g/100mL, bacterium ball size is even, mycelia is sturdy stretch out time, stop cultivate.
Joined in fermentor tank by aspergillus niger strain through cultivating and start fermentation, in often liter of fermention medium, inoculum size is 2.2 × 10
7individual spore, it is 36 DEG C that fermentation condition comprises temperature, and initial ph value is 4.5, and air flow is 0.8 volume: (volume minute), fermentation also reaches below 0.3g/100mL and stops fermentation to fermented liquid, then the fermented liquid obtained is carried out filtration and obtains citric acid fermentation aqueous solution.
Embodiment 1
The present embodiment is for illustration of the production method of metal salts of organic acids of the present invention.
By the citric acid fermentation aqueous solution of 1000ml, (acidity is 130g/L, turbidity is 20NTU) and 100 grams of calcium carbonate granule (pure calcium carbonate 95 % by weight, hydrochloric acid insoluble substance content 3 % by weight, heavy metal content 0.5 % by weight, lead content 0.3 % by weight, arsenic content 0.2 % by weight, content of fluoride 0.1 % by weight, diameter: 10-400 micron) contact at 80 DEG C and carry out neutralization reaction, the pH controlling reaction end is 4.7.Suction filtration is carried out to gained neutralized reaction product and obtains the thick calcium citrate crystals that free water content is 50 % by weight, it is the thick calcium citrate crystals of hot wash of 80 DEG C of wet citrate of lime volume 2 times by total amount, making washing sugar with calcium cirtrate water potassium permanganate oxidation account for look is 3min, obtaining moisture content is 40 % by weight, the thick calcium citrate crystals that readily carbonizable substance absorbance ratio is less than 5.Add in thick calcium citrate crystals 250 milliliters, mass percent concentration be 30% hydrochloric acidolysis citrate of lime to wet crystal, make the H of the HCl of the HCl(molecular form in hydrochloric acid and form of dissociating
+, Cl
-) be 2.8:1 with the mol ratio of citrate in calcium salt.With scribbling diatomaceous sheet frame in advance by the hydrochloric acid insoluble substance in Plate Filtration method removal solution and other impurity; at 60 DEG C, solution is passed in the decolorizing column that granulated active carbon GH-11 is housed again and carry out (the pillar diameter 35mm that decolours; length 1000mm; gac loading level 550g; the flow velocity controlling filtrate makes be 40min the duration of contact of filtrate and activated carbon); acquisition turbidity is 0.5NTU, and readily carbonizable substance absorbance ratio is 3, without the colourless filtered solution of macroscopic solid substance.The sodium carbonate that 110 grams of purity are 99 % by weight is added in filtered solution, control temperature of reaction 80 DEG C, terminal pH:4.7, after reaction terminates, add the dilute acetic acid solution of 20 % by weight in reactor, add the dilute acetic acid solution of 30ml by every 100Kg output, carry out stirring 15-20 minute, then use the hot deionized water of 80 DEG C washing calcium citrate crystals to be precipitated to without acetic acid smell, and dry at 75 DEG C, obtain citrate of lime product.Measure the purity of the citrate of lime product obtained, result is as shown in table 1.
Embodiment 2
The present embodiment is for illustration of the production method of metal salts of organic acids of the present invention.
By the citric acid fermentation aqueous solution of 1000ml, (acidity is 130g/L, turbidity is 20NTU) and 100 grams of calcium carbonate granule (pure calcium carbonate 95.5 % by weight, hydrochloric acid insoluble substance content 3 % by weight, heavy metal content 0.5 % by weight, lead content 0.3 % by weight, arsenic content 0.1 % by weight, content of fluoride 0.1 % by weight, diameter: 10-400 micron) contact at 75 DEG C and carry out neutralization reaction, the pH controlling reaction end is 4.6.Suction filtration is carried out to gained neutralized reaction product and obtains the thick calcium citrate crystals that free water content is 50 % by weight, it is the thick calcium citrate crystals of hot wash of 75 DEG C of wet citrate of lime volume 0.5 times by total amount, making washing sugar with calcium cirtrate water potassium permanganate oxidation account for look is 3min, obtaining moisture content is 40 % by weight, the thick calcium citrate crystals that readily carbonizable substance absorbance ratio is less than 5.Add in thick calcium citrate crystals 1500 milliliters, mass percent concentration be 5% hydrochloric acidolysis citrate of lime to wet crystal, make the H of the HCl of the HCl(molecular form in hydrochloric acid and form of dissociating
+, Cl
-) be 2.5:1 with the mol ratio of citrate in metal-salt.With scribbling diatomaceous sheet frame in advance by the hydrochloric acid insoluble substance in Plate Filtration method removal solution and other impurity; at 60 DEG C, solution is passed in the decolorizing column that granulated active carbon GH-11 is housed again and carry out (the pillar diameter 35mm that decolours; length 1000mm; gac loading level 550g; the flow velocity controlling filtrate makes be 40min the duration of contact of filtrate and activated carbon); acquisition turbidity is 0.5NTU, and readily carbonizable substance absorbance ratio is 3, without the colourless filtered solution of macroscopic solid substance.The sodium hydroxide that 73 grams of purity are 99 % by weight is added in filtered solution, control temperature of reaction 75 DEG C, terminal pH:4.6, after reaction terminates, add the dilute acetic acid solution of 20 % by weight in reactor, add the dilute acetic acid solution of 30ml by every 100Kg output, carry out stirring 15-20 minute, then use the hot deionized water of 75 DEG C washing calcium citrate crystals to be precipitated to without acetic acid smell, and dry at 75 DEG C, obtain citrate of lime product.Measure the purity of the citrate of lime product obtained, result is as shown in table 1.
Embodiment 3
The present embodiment is for illustration of the production method of metal salts of organic acids of the present invention.
By the citric acid fermentation aqueous solution of 1000ml, (acidity is 130g/L, turbidity is 20NTU) and 100 grams of calcium carbonate granule (pure calcium carbonate 96 % by weight, hydrochloric acid insoluble substance content 3 % by weight, heavy metal content 0.5 % by weight, lead content 0.3 % by weight, arsenic content 0.1 % by weight, content of fluoride 0.2 % by weight, diameter: 10-400 micron) contact at 85 DEG C and carry out neutralization reaction, the pH controlling reaction end is 4.8.Suction filtration is carried out to gained neutralized reaction product and obtains the thick calcium citrate crystals that free water content is 50 % by weight, it is the thick calcium citrate crystals of hot wash of 85 DEG C of wet citrate of lime volume 3 times by total amount, making washing sugar with calcium cirtrate water potassium permanganate oxidation account for look is 3min, obtaining moisture content is 40 % by weight, the thick calcium citrate crystals that readily carbonizable substance absorbance ratio is less than 5.Add in thick calcium citrate crystals 200 milliliters, mass percent concentration be 37% hydrochloric acidolysis citrate of lime to wet crystal, make the H of the HCl of the HCl(molecular form in hydrochloric acid and form of dissociating
+, Cl
-) be 3.1:1 with the mol ratio of citrate in metal-salt.With scribbling diatomaceous sheet frame in advance by the hydrochloric acid insoluble substance in Plate Filtration method removal solution and other impurity; at 60 DEG C, solution is passed in the decolorizing column that granulated active carbon GH-11 is housed again and carry out (the pillar diameter 35mm that decolours; length 1000mm; gac loading level 550g; the flow velocity controlling filtrate makes be 40min the duration of contact of filtrate and activated carbon); acquisition turbidity is 0.5NTU, and readily carbonizable substance absorbance ratio is 3, without the colourless filtered solution of macroscopic solid substance.The sodium carbonate that 93 grams of purity are 99 % by weight is added in filtered solution, control temperature of reaction 85 DEG C, terminal pH:4.8, after reaction terminates, add the dilute acetic acid solution of 20 % by weight in reactor, add the dilute acetic acid solution of 30ml by every 100Kg output, carry out stirring 15-20 minute, then use the hot deionized water of 85 DEG C washing calcium citrate crystals to be precipitated to without acetic acid smell, and dry at 85 DEG C, obtain citrate of lime product.Measure the purity of the citrate of lime product obtained, result is as shown in table 1.
Embodiment 4
The present embodiment is for illustration of the production method of metal salts of organic acids of the present invention.
By the citric acid fermentation aqueous solution of 1000ml, (acidity is 13g/100ml, turbidity is 20NTU) and 100 grams of calcium carbonate granule (pure calcium carbonate 95 % by weight, hydrochloric acid insoluble substance content 3.5 % by weight, heavy metal content 0.6 % by weight, lead content 0.4 % by weight, arsenic content 0.1 % by weight, content of fluoride 0.2 % by weight, diameter: 10-400 micron) contact at 80 DEG C and carry out neutralization reaction, the pH controlling reaction end is 2.9.Suction filtration is carried out to gained neutralized reaction product and obtains the thick calcium hydrogen citrate crystal that free water content is 50 % by weight, it is the thick calcium hydrogen citrate crystal of the hot wash of 80 DEG C of wet calcium hydrogen citrate volume 2 times by total amount, making calcium hydrogen citrate affination water potassium permanganate oxidation account for look is 3min, obtaining moisture content is 40 % by weight, the thick calcium hydrogen citrate crystal that readily carbonizable substance absorbance ratio is less than 5.Add in thick calcium hydrogen citrate crystal 270 milliliters, mass percent concentration be 19% hydrochloric acidolysis calcium hydrogen citrate to wet crystal, make the H of the HCl of the HCl(molecular form in hydrochloric acid and form of dissociating
+, Cl
-) be 2.8:1 with the mol ratio of citrate in metal-salt.With scribbling diatomaceous sheet frame in advance by the hydrochloric acid insoluble substance in Plate Filtration method filtration removal solution and other impurity; at 50 DEG C, solution is passed in the decolorizing column that granulated active carbon GH-11 is housed again and carry out (the pillar diameter 35mm that decolours; length 1000mm; gac loading level 550g; the flow velocity controlling filtrate makes be 40min the duration of contact of filtrate and activated carbon); acquisition turbidity is 0.5NTU, and readily carbonizable substance absorbance ratio is 3, without the colourless filtered solution of macroscopic solid substance.The sodium carbonate that 62 grams of purity are 99 % by weight is added in filtered solution, control temperature of reaction 80 DEG C, terminal pH:2.9, after reaction terminates, add the dilute acetic acid solution of 20 % by weight in reactor, add the dilute acetic acid solution of 30ml by every 100Kg output, carry out stirring 15-20 minute, then use the hot deionized water washing calcium hydrogen citrate crystal settling of 80 DEG C extremely without acetic acid smell, and dry at 80 DEG C, obtain hydrogen citrate calcium product.Measure the purity of the hydrogen citrate calcium product obtained, result is as shown in table 1.
Embodiment 5
Citrate of lime is prepared according to the method for embodiment 1, unlike, desolventing technology is not carried out to solution with after the thick citrate of lime of hydrochloric acidolysis.Measure the purity of the hydrogen citrate calcium product obtained, result is as shown in table 1.
Comparative example 1
This comparative example is for illustration of the preparation method of the calcium citrate salts of prior art.
During citric acid fermentation aqueous solution is carried out and acidolysis, decolour from friendship, obtain through refining citric acid solution (acidity is 40g/100ml, and turbidity is 0.8NTU).By following weight ratio: calcium carbonate: 30 % by weight hydrochloric acid (folding hydrogenchloride): water=1:2.5:8 makes calcium chloride solution after fully reacting, and carries out filtering and clarify acquisition calcium chloride solution.Obtained calcium chloride solution (calcium chloride content accounts for 40 % by weight) is reacted by following weight ratio and bicarbonate of ammonia, calcium chloride: bicarbonate of ammonia=1:1.55, obtained calcium carbonate, by calcium carbonate through dehydration, washing, dry, after cooling with the above-mentioned citric acid solution (edible citric acid) that obtains after refining and water according to following weight ratio, calcium carbonate: the amount of the Citric acid monohydrate Food grade in the citric acid solution obtained after refining: water=1:1.3:8 is configured to solution at 80 DEG C, react under the condition of pH value >=7, after reaction terminates, add the dilute acetic acid solution of 20 % by weight in reactor, the dilute acetic acid solution of 30ml is added by every 100Kg output, carry out stirring 15-20 minute, then the hot deionized water of 80 DEG C washing calcium citrate crystals is used to be precipitated to without acetic acid smell, and dry at 80 DEG C, obtain citrate of lime product.Measure the purity of the citrate of lime product obtained, result is as shown in table 1.
Embodiment 6
The present embodiment is for illustration of the production method of metal salts of organic acids of the present invention.
By the lactic acid aqueous solution of 1000ml (by lactic acid fermentation liquid is obtained except thalline and cryogenic vacuum concentrate after filtration, acidity is 720g/L, turbidity is 20NTU) (magnesiumcarbonate is from magnesite with 350 grams of hydrotalcite particles, purity 95 % by weight, hydrochloric acid insoluble substance content 3 % by weight, heavy metal content 0.5 % by weight, lead content 0.3 % by weight, arsenic content 0.2 % by weight, content of fluoride 0.1 % by weight, diameter: 10-400 micron) contact under 70 DEG C of conditions and carry out neutralization reaction, the pH value controlling reaction end is 5.5.Suction filtration is carried out to gained neutralized reaction product and obtains the crude lactic acid magnesium crystal that free water content is 40 % by weight, it is the pure water crude lactic acid magnesium crystal of 45 DEG C of wet magnesium lactate volume 2 times by total amount, magnesium lactate affination water potassium permanganate oxidation is made to account for look for being greater than 10min, obtaining moisture content is 40 % by weight, the crude lactic acid magnesium crystal that readily carbonizable substance absorbance ratio is less than 3.Add in crude lactic acid magnesium crystal 800 milliliters, mass percent concentration be 30% hydrochloric acidolysis magnesium lactate to wet crystal, make the H of the HCl of the HCl(molecular form in hydrochloric acid and form of dissociating
+, Cl
-) be 0.85:1 with the mol ratio of lactate in magnesium salts.With scribbling diatomaceous sheet frame in advance by the hydrochloric acid insoluble substance in Plate Filtration method removal solution and other impurity; at 60 DEG C, solution is passed in the decolorizing column that granulated active carbon GH-11 is housed again and carry out (the pillar diameter 35mm that decolours; length 1000mm; gac loading level 550g; the flow velocity controlling filtrate makes be 40min the duration of contact of filtrate and activated carbon); acquisition turbidity is 0.5NTU, readily carbonizable substance absorbance ratio for being less than or equal to 3, without the colourless filtered solution of macroscopic solid substance.The sodium carbonate that 370 grams of purity are 99 % by weight is added in filtered solution, control temperature of reaction 60 DEG C, terminal pH:6, after reaction terminates, add the dilute acetic acid solution of 20 % by weight in reactor, add the dilute acetic acid solution of 30ml by every 100Kg output, carry out stirring 15-20 minute, then use the hot deionized water of 40 DEG C washing lactic acid magnesium crystal to be precipitated to without acetic acid smell, and dry at 75 DEG C, obtain magnesium lactate product.Measure the purity of the magnesium lactate product obtained, as shown in table 1.
Table 1
Note: the value of embodiments of the invention hydrochloric acid insoluble substance can lower than 2mg, and namely content can lower than 0.04%.
As can be seen from the result of embodiment 1-6, utilize the production method of metal salts of organic acids provided by the invention, the highly purified calcium citrate salts and the magnesium lactate product that meet food and requirements for pharmaceuticals can be obtained, and, can be found out by the result of embodiment 1-5 and comparative example 1, method provided by the present invention eliminates the acidolysis in citric acid fermentation broth extraction, from friendship, the purification step of condensing crystal supervisor and calcium carbonate, while reaching effect same as the prior art, significantly reduce equipment, water consumes, energy consumption, auxiliary material, manually, the cost such as safety and environmental protection.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive 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.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different 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.
Claims (10)
1. the production method of a metal salts of organic acids, it is characterized in that, the method comprise by containing the organic acid aqueous solution be selected from the thick carbonate of M metal, thick oxyhydroxide and one or more in thick oxide compound and contact and obtain thick metal salts of organic acids crystal, with hydrochloric acid, described thick metal salts of organic acids crystal acidolysis is obtained solution, and filter, the filtered solution and the alkali-metal carbonate that obtain, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt and one or more in bicarbonate of ammonia are contacted the metal salts of organic acids obtaining M metal;
Wherein, described organic acid is organic carboxyl acid and/or organic phosphoric acid; Described organic carboxyl acid is carbonatoms is 1-7, carboxyl number is the organic carboxyl acid of 1-4;
Wherein, described M metal is selected from least one in magnesium, calcium, aluminium, lead, zinc, copper, titanium, cerium and manganese.
2. method according to claim 1, wherein, described organic carboxyl acid is one or more in formic acid, acetic acid, citric acid, lactic acid, gluconic acid, equisetic acid, oxysuccinic acid, methylene-succinic acid and tartrate, and described organic phosphoric acid is one or more in phytic acid, Triphosaden and adenosine diphosphate (ADP);
Described M metal is selected from least one in magnesium, calcium, zinc, copper and titanium;
The metal salts of organic acids of described M metal is the organic acid normal salt of M metal, acid salt or subsalt.
3. method according to claim 1 and 2, wherein, described organic acid is at least one in citric acid, lactic acid, tartrate and methylene-succinic acid, is more preferably citric acid and/or lactic acid, and described M metal is calcium, magnesium or copper.
4. according to the method in claim 1-3 described in any one, wherein, comprise with one or more conditions contacted in thick oxide compound with thick carbonate, the slightly oxyhydroxide being selected from M metal containing the organic acid aqueous solution:
Temperature is 30-150 DEG C, and the pH value of terminal is 4.0-6.0, and the thick metal salts of organic acids of acquisition is the thick organic acid metal normal salt crystal of M metal;
Temperature is 30-120 DEG C, and controlling endpoint pH is 2.5 to being less than 4.0, and the thick metal salts of organic acids of acquisition is the thick organic acid metal acid salt crystal of M metal;
Temperature is 30-120 DEG C, and control endpoint pH is 7-9, and the thick metal salts of organic acids of acquisition is the thick organic acid metal basic salt crystal of M metal.
5. method according to claim 1, wherein, the total mole number that the consumption of hydrochloric acid makes molecular state conciliate the hydrogenchloride of amorph is 2.5-3:1 with the ratio of the mole number of organic acid in thick metal salts of organic acids crystal, and the concentration of hydrochloric acid is 5-37 % by weight.
6. the filtered solution of acquisition and alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt and one or more in bicarbonate of ammonia are contacted the condition generating metal salts of organic acids and comprise by method according to claim 1:
Temperature is 20-160 DEG C, and the pH value of terminal is 4.0-6.0, and the metal salts of organic acids of the M metal of acquisition is the organic acid metal normal salt crystal of M metal;
Temperature is 30-120 DEG C, and controlling endpoint pH is 2.5 to being less than 4.0, and the metal salts of organic acids of acquisition is the organic acid metal acid salt crystal of M metal,
Temperature is 30-120 DEG C, and control endpoint pH is 7-9, and the metal salts of organic acids of acquisition is the organic acid metal basic salt crystal of M metal.
7. method according to claim 1 or 5, wherein, the method to be also included in before the acidolysis of thick metal salts of organic acids crystal with hydrochloric acid, washes thick metal salts of organic acids crystal, the temperature of washing is 20-100 DEG C, and the volume ratio for the water washed and thick metal salts of organic acids is 0.5-3:1.
8. the method according to claim 1 or 6, wherein, the method be also included in by the filtered solution of acquisition be selected from before alkali-metal carbonate, alkali-metal oxyhydroxide, alkali-metal oxide compound, volatile salt and one or more in bicarbonate of ammonia contact, filtered solution is decoloured, the method of described decolouring is contacted with discoloring agent by filtered solution, the temperature of contact is 40-80 DEG C, and described discoloring agent is gac.
9. method according to claim 1 and 2, wherein, described is 0.5-10mol/L containing organic acid content in the organic acid aqueous solution, and turbidity is less than or equal to 20NTU; Preferably, described is organic acid fermentation clear liquid and/or organic acid crystallization mother liquor containing the organic acid aqueous solution;
Described organic acid fermentation clear liquid is obtained after filtration by organic acid fermentation liquid;
Described organic acid crystallization mother liquor be will containing organic acid solution crystallization and filter after debris.
10. method according to claim 1, wherein, containing impurity in the thick carbonate of described M metal, in the thick oxyhydroxide of M metal and in the thick oxide compound of M metal, described impurity be total amount not higher than 5 % by weight be selected from silicon-dioxide, heavy metal compound, aluminum contained compound, containing one or more in rare-earth compound and insoluble silicate;
The particle diameter of the thick carbonate of described M metal, thick oxyhydroxide and thick oxide compound is 10-400 micron.
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Cited By (9)
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| CN104876816A (en) * | 2015-04-29 | 2015-09-02 | 广州驱动力饲料有限公司 | Synthetic method of ferrous lactate |
| CN105941866A (en) * | 2016-05-24 | 2016-09-21 | 安徽五粮泰生物工程股份有限公司 | Preparation method of zinc citrate for feeding |
| CN105941867A (en) * | 2016-05-24 | 2016-09-21 | 安徽五粮泰生物工程股份有限公司 | Preparation method of ferric citrate for feeding |
| CN105961848A (en) * | 2016-05-24 | 2016-09-28 | 安徽五粮泰生物工程股份有限公司 | Preparation method of feed calcium citrate |
| CN106212896A (en) * | 2016-08-03 | 2016-12-14 | 安徽五粮泰生物工程股份有限公司 | A kind of preparation method of feeding ferrous lactate |
| CN106234773A (en) * | 2016-08-03 | 2016-12-21 | 安徽五粮泰生物工程股份有限公司 | A kind of preparation method of feeding zinc lactate |
| CN106260600A (en) * | 2016-08-03 | 2017-01-04 | 安徽五粮泰生物工程股份有限公司 | A kind of preparation method of feeding calcium lactate |
| CN106478405A (en) * | 2015-11-25 | 2017-03-08 | 衡阳屹顺化工有限公司 | A kind of preparation method of acylate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104876816A (en) * | 2015-04-29 | 2015-09-02 | 广州驱动力饲料有限公司 | Synthetic method of ferrous lactate |
| CN106478405A (en) * | 2015-11-25 | 2017-03-08 | 衡阳屹顺化工有限公司 | A kind of preparation method of acylate |
| CN105941866A (en) * | 2016-05-24 | 2016-09-21 | 安徽五粮泰生物工程股份有限公司 | Preparation method of zinc citrate for feeding |
| CN105941867A (en) * | 2016-05-24 | 2016-09-21 | 安徽五粮泰生物工程股份有限公司 | Preparation method of ferric citrate for feeding |
| CN105961848A (en) * | 2016-05-24 | 2016-09-28 | 安徽五粮泰生物工程股份有限公司 | Preparation method of feed calcium citrate |
| CN106212896A (en) * | 2016-08-03 | 2016-12-14 | 安徽五粮泰生物工程股份有限公司 | A kind of preparation method of feeding ferrous lactate |
| CN106234773A (en) * | 2016-08-03 | 2016-12-21 | 安徽五粮泰生物工程股份有限公司 | A kind of preparation method of feeding zinc lactate |
| CN106260600A (en) * | 2016-08-03 | 2017-01-04 | 安徽五粮泰生物工程股份有限公司 | A kind of preparation method of feeding calcium lactate |
| CN111187914A (en) * | 2020-02-25 | 2020-05-22 | 广州市尚信净化工程有限公司 | Method for recovering lithium from lithium battery positive electrode material |
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