CN1995005A - Distannous citrate preparation method - Google Patents
Distannous citrate preparation method Download PDFInfo
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- CN1995005A CN1995005A CN 200610124388 CN200610124388A CN1995005A CN 1995005 A CN1995005 A CN 1995005A CN 200610124388 CN200610124388 CN 200610124388 CN 200610124388 A CN200610124388 A CN 200610124388A CN 1995005 A CN1995005 A CN 1995005A
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- China
- Prior art keywords
- citrate
- stannous
- disodium
- stannous citrate
- citric acid
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- 238000002360 preparation method Methods 0.000 title claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 title abstract 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 17
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000001509 sodium citrate Substances 0.000 claims abstract description 10
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 8
- USYAMXSCYLGBPT-UHFFFAOYSA-L 3-carboxy-3-hydroxypentanedioate;tin(2+) Chemical compound [Sn+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O USYAMXSCYLGBPT-UHFFFAOYSA-L 0.000 claims description 75
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 21
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 17
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 239000001119 stannous chloride Substances 0.000 claims description 17
- 235000011150 stannous chloride Nutrition 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229940058023 trisodium citrate anhydrous Drugs 0.000 claims 1
- KEKGADJNWGDDIO-UHFFFAOYSA-H disodium;2-hydroxypropane-1,2,3-tricarboxylate;tin(4+) Chemical compound [Na+].[Na+].[Sn+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KEKGADJNWGDDIO-UHFFFAOYSA-H 0.000 abstract 3
- 239000013049 sediment Substances 0.000 abstract 2
- CQMNNMLVXSWLCH-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;tin(4+) Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O CQMNNMLVXSWLCH-UHFFFAOYSA-B 0.000 abstract 1
- 239000002526 disodium citrate Substances 0.000 abstract 1
- 235000019262 disodium citrate Nutrition 0.000 abstract 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 abstract 1
- FUSNMLFNXJSCDI-UHFFFAOYSA-N tolnaftate Chemical group C=1C=C2C=CC=CC2=CC=1OC(=S)N(C)C1=CC=CC(C)=C1 FUSNMLFNXJSCDI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 11
- 235000013373 food additive Nutrition 0.000 description 8
- 239000002778 food additive Substances 0.000 description 8
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 6
- 235000019263 trisodium citrate Nutrition 0.000 description 6
- 239000012265 solid product Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000834 fixative Substances 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 244000136475 Aleurites moluccana Species 0.000 description 1
- 235000006667 Aleurites moluccana Nutrition 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 235000021537 Beetroot Nutrition 0.000 description 1
- 235000018244 Castanea mollissima Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- 244000194101 Ginkgo biloba Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000758791 Juglandaceae Species 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 244000141359 Malus pumila Species 0.000 description 1
- 244000183278 Nephelium litchi Species 0.000 description 1
- 235000015742 Nephelium litchi Nutrition 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013574 canned fruits Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 disodium stannous citrate compound Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 244000013123 dwarf bean Species 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000021331 green beans Nutrition 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021018 plums Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a making method of tin disodium citrate, which comprises the following steps: making ditin citrate sediment in the water dielectric; reacting ditin citrate and citrate in the alcohol to form tin citrate; reacting with sodium hydroxide to form the sediment of tin disodium citrate; filtering; drying to obtain loose white powder of tin disodium citrate or the composition of tritin citrate and trisodium citrate; dissolving the composition to obtain the disodium citrate.
Description
Technical Field
The invention relates to a preparation method of a food additive, in particular to a preparation method of disodium stannous citrate.
Background
Disodium stannous citrate also known as disodium stannous citrate, sodium stannous citrate, 8301 color fixative, formula C6H6O8SnNa2Molecular weight 370.79, structural formula:
the disodium stannous citrate is a white powdery solid, is very easy to dissolve in water, absorb moisture, deliquesce and oxidize. Melting point was 250 deg.C (decomposition), yellowing started at 260 deg.C, and brown at 283 deg.C. Oral administration of LD to mice502700mg/Kg, negative in mutagenicity and teratogenicity test, and belongs to a slightly toxic chemical. The product has strong reducibility, and can be used as antioxidant, antiseptic and color fixative in food additive. According to the revised hygienic standards for use of food additives (GB2760-1996) of 2003-05-28, the disodium stannous citrate is suitable for canned fruits and vegetables such as mushrooms, apples, lemons, Chinese chestnuts, gingkoes, green plums, lilies, oranges, walnuts, asparagus, green beans, lychees, carrots, beetroot, fruit juice and the like, so that the disodium stannous citrate is a widely applied food additive. The principle that disodium stannous citrate can play the roles of antioxidation, corrosion prevention and color protection and can maintain the color quality and flavor of food is based on the principle that the disodium stannous citrate can gradually consume residual oxygen, Sn, in cans2+Is oxidized to Sn4+. Because of its low toxicity, it can safely and effectively replace sulfur-containing color fixative, and its color-protecting effect is superior to that of sulfur-containing compound.
Disodium stannous citrate has been widely used abroad as a food additive. However, no preparation method of disodium stannous citrate is introduced in foreign patents or published data so far. The Chinese food additive industry network (www.faic.cn) simply introduced the preparation method of disodium stannous citrate in the column of stabilizing and coagulating agent, which is prepared by the reaction of stannous chloride, citric acid and sodium hydroxide. However, the preparation of disodium stannous citrate from stannous chloride as a raw material has two major disadvantages, namely, the content of sodium chloride is high; secondly, a large amount of solid substances which are difficult to dissolve in water are easily obtained, and the obtained product cannot meet the standard requirement.
A second edition of food additive handbook compiled by Lingtongting, mentioned in the specification, is prepared by first generating stannous citrate precipitate from citric acid, stannous chloride and sodium hydroxide, then reacting with sodium hydroxide and citric acid to obtain a stannous citrate disodium water solution, vacuum concentrating, filtering out insoluble substances, and vacuum drying. Although the method can solve the problem of high chloride ion in the product, because the disodium stannous citrate is difficult to crystallize, the concentration of the disodium stannous citrate solution must be completed and dried to take out the blocky solid, and the product can be crushed to obtain amorphous powder, so that the product is seriously adhered to the wall in the drying process, the product is difficult to take out, and the evaporation energy consumption of a large amount of water is very high. The method mentioned in the handbook of food additives usually has difficulty in meeting the requirements of the national enterprise standards due to the insoluble water which is subjected to the concentration process and the oxidation.
Disclosure of Invention
The invention aims to overcome the defects and provide a method for obtaining disodium stannous citrate crystal precipitate, thereby simplifying the production steps, reducing the energy consumption and improving the product quality.
In order to achieve the purpose, firstly, preparing a stannous citrate precipitate in an aqueous medium, putting the stannous citrate in an ethanol medium, wherein the solubility of the stannous citrate in ethanol is higher than that of the stannous citrate, the solubility of the stannous citrate in ethanol is higher than that of the disodium stannous citrate, reacting the stannous citrate and citric acid in the ethanol medium, gradually dissolving the stannous citrate to convert the stannous citrate into the stannous citrate, then, reacting the stannous citrate with a sodium hydroxide ethanol solution, converting the stannous citrate into the disodium stannous citrate, and filtering and drying the precipitate to obtain loose disodium stannous citrate white powdery solid. The method specifically comprises the following steps:
A. dissolving stannous chloride in water, adding a sodium hydroxide aqueous solution under stirring at 35-60 ℃ until the pH value of a reaction system is 8-10;
B. adding a citric acid aqueous solution into the reaction system according to the molar ratio of stannous chloride to citric acid of 1: 0.45-0.55, keeping the temperature at 40-55 ℃, stirring for 0.5-10 hours, cooling to room temperature, filtering, washing to remove sodium chloride, and preparing a stannous citrate precipitate;
C. adding ethanol into the stannous citrate according to the weight ratio of 1: 1.5-4, uniformly stirring, adding citric acid with the same amount of citric acid as that in the step B at 40-65 ℃, continuously stirring for 0.5-10 hours, and converting the stannous citrate into stannous citrate;
D. and C, adding an ethanol solution of sodium hydroxide into the system obtained in the step C, keeping the temperature at 50-70 ℃, stirring for 1-10 hours, cooling to room temperature, filtering, and drying the solid to obtain a disodium stannous citrate product.
The chemical reaction that takes place in step a is:
in order to prevent oxidation of stannous and accelerate the dissolving process, the stannous chloride is preferably dissolved in hot water at 60-100 ℃, and a small amount of metallic tin powder is added into the hot water. When the sodium hydroxide solution is added for reaction, the pH value of the system is preferably 8.5-9.5, more preferably 8.5-9, and the temperature of the system is preferably 40-55 ℃.
The stannous hydroxide generated in the step A is flocculent solid and is fully dispersed in the reaction system to form a suspension emulsion, so that the stannous hydroxide can directly react with the citric acid in the step B to generate stannous citrate precipitate. Stannous citrate is also a water insoluble solid, but is easily filtered, and the sodium chloride produced can be conveniently removed by filtration and washing. The chemical reaction in the step B is as follows:
in the step C, the reaction temperature for adding the citric acid is preferably 45-55 ℃. The water content of the ethanol is preferably less than 15%, preferably less than 5%. The chemical reaction in step C is as follows:
the chemical reaction in the step D is as follows:
because the stannous citrate is insoluble in water but has higher solubility in ethanol, and the stannous citrate disodium has higher solubility in water and lower solubility in ethanol, solid precipitation can be directly formed in ethanol reaction liquid, so that the subsequent filtration and drying process is very simple, the obtained stannous citrate disodium product is loose white powdery solid, and the product appearance is relatively beautiful.
Another method of preparation of the present invention is to prepare a composition equivalent to disodium stannous citrate, which composition is converted to disodium stannous citrate upon dissolution in water. The method comprises the following steps:
A. dissolving stannous chloride in water, adding a sodium hydroxide aqueous solution under stirring at 40-55 ℃ until the pH value of a reaction system is 8-10;
B.adding citric acid aqueous solution into the system according to the molar ratio of stannous chloride to citric acid of 3: 0.9-1.1, continuously stirring for 0.5-3 hours, cooling to room temperature, filtering, washing, drying the solid in vacuum at 20-60 ℃, and crushing;
C. and C, mixing the solid obtained in the step B with trisodium citrate powder, mixing, stirring and grinding for 5-30 minutes according to the weight ratio of 1.1-1.2: 1 to obtain the equivalent composition of the disodium stannous citrate, wherein water is added into the composition to convert the composition into the disodium stannous citrate when the composition is used.
The trisodium citrate is preferably anhydrous trisodium citrate, and can be prepared from trisodium citrate dihydrate by drying and dehydrating.
The mixing and grinding time of the above solid with trisodium citrate is preferably 10 to 15 minutes.
The solid is stannous citrate by analysis, and the chemical reaction in the preparation of the solid is as follows:
although stannous citrate is insoluble in water, it is readily converted to disodium stannous citrate in the presence of trisodium citrate and dissolves in water. After stannous citrate and trisodium citrate are compounded and dissolved in water, the physical and chemical indexes of the compound are completely the same as those of a disodium stannous citrate water solution through inspection, so that the compound can replace disodium stannous citrate to be used in an aqueous system, and the preparation method is simpler. In an aqueous system, tri-stannous citrate is converted with tri-sodium citrate as follows:
the product prepared by the method has high purity, does not contain sodium chloride, has low content of water-insoluble substances, avoids difficult production operation and preparation of large vacuum concentration equipment, greatly reduces energy consumption, and has better appearance, fluidity and water-insoluble substances than the concentration method.
Detailed Description
Example 1:
160 g of sodium hydroxide was dissolved in 500mL of pure water with stirring, and filtered for use. 450 g of stannous chloride is weighed and dissolved in 250 g of hot water with the temperature of 80 ℃, 0.5 g of metallic tin powder is added, the reaction is carried out for half an hour under the condition of heat preservation and stirring, and the hot filtration is carried out. Adding the clear sodium hydroxide solution into the stannous chloride filtrate under stirring at 50 ℃ until the pH value of the system is 9, and obtaining the stannous hydroxide suspended substance. Adding a solution of 210 g of citric acid dissolved in 150 g of pure water at 50 ℃, continuing stirring for reaction for 1 hour after the addition, cooling to room temperature, centrifugally filtering, washing to remove sodium chloride, and centrifugally draining water to the greatest extent to obtain a stannous citrate intermediate. Adding wet stannous citrate into 1000mL of 95% ethanol, stirring uniformly, adding 210 g of citric acid at 50 ℃, continuing to stir for reaction for 1 hour, adding 160 g of sodium hydroxide solution into1500mL of 95% ethanol, and continuing to stir for 2 hours at 60 ℃ after the addition is finished. Then cooled to room temperature, centrifugally filtered and dried to obtain 710 g of a solid product. The solid product is completely the same as the disodium stannous citrate through element analysis and chemical property inspection, so that the solid product can be determined to be the disodium stannous citrate. The analysis result of the physical and chemical indexes of the product is as follows:
appearance: a loose white powdery solid;
tin content (wt%): 30.8
Arsenic (As, wt%): 0.00005;
heavy metals (in terms of Pb, wt%): 0.0002;
water insoluble matter (wt%): 0.001;
chlorine (as Cl)-Calculated by weight percent: 0.005.
Example 2:
240 g of sodium hydroxide was dissolved in 750mL of pure water with stirring, and filtered for use. 677 g stannous chloride is weighed and dissolved in 380 g hot water with the temperature of 80 ℃, 0.8 g metallic tin powder is added, the reaction is carried out for half an hour under the condition of heat preservation and stirring, and the hot filtration is carried out. Adding the clear sodium hydroxide solution into the stannous chloride filtrate under stirring at 50 ℃ until the pH value of the system is 9, and obtaining the stannous hydroxide suspended substance. Adding 210 g of citric acid solution dissolved in 150 g of pure water at 50 ℃, continuing stirring for reaction for 1 hour after the addition, cooling to room temperature, centrifugally filtering, washing to remove sodium chloride, centrifugally drying water as much as possible, filtering out part of unconverted tin hydroxide in the filtering due to extremely small particle size of stannous hydroxide suspended matter, drying the obtained solid in vacuum at 55 ℃ to obtain 570-580 g of white solid product, and crushing for later use. And (3) crushing the anhydrous trisodium citrate, and mixing and grinding the mixture for 10-15 minutes according to the weight ratio of the stannous citrate to the anhydrous trisodium citrate of 1.1-1.2: 1 to obtain the disodium stannous citrate compound product. After the product is dissolved in water, the chemical property and the using effect of the product are completely the same as those of a stannous citrate disodium water solution through inspection, and the analysis result of the physical and chemical indexes of the product is as follows:
appearance: a loose white powdery solid;
tin content (wt%): 30.2 of the total weight of the mixture;
arsenic (As, wt%): 0.00006;
heavy metals (in terms of Pb, wt%): 0.00016;
water insoluble matter (wt%): 0.0012;
chlorine (as C1)-Calculated by weight percent: 0.004.
Claims (10)
1. A preparation method of disodium stannous citrate comprises the following steps:
A. dissolving stannous chloride in water, adding a sodium hydroxide aqueous solution under stirring at 35-60 ℃ until the pH value of a reaction system is 8-10;
B. adding a citric acid aqueous solution into the reaction system according to the molar ratio of stannous chloride to citric acid of 1: 0.45-0.55, keeping the temperature at 40-55 ℃, stirring for 0.5-10 hours, cooling to room temperature, filtering, washing to remove sodium chloride, and preparing a stannous citrate precipitate;
C. adding ethanol into the stannous citrate according to the weight ratio of 1: 1.5-4, uniformly stirring, adding citric acid with the same amount of citric acid as that in the step B at 40-65 ℃, continuously stirring for 0.5-10 hours, and converting the stannous citrate into stannous citrate;
D. and C, adding an ethanol solution of sodium hydroxide into the system obtained in the step C, keeping the temperature at 50-70 ℃, stirring for 1-10 hours, cooling to room temperature, filtering, and drying the solid to obtain a disodium stannous citrate product.
2. The method for preparing disodium stannous citrate according to claim 1, wherein the step A comprises dissolving stannous chloride in hot water of 60-100 ℃ in the presence of metallic tin powder.
3. The method for preparing disodium stannous citrate according to claim 1, wherein in the step A, an aqueous sodium hydroxide solution is added until the pH value of the reaction system is 8.5-9.5;
4. the method for preparing disodium stannous citrate according to claim 1, wherein the reaction temperature of adding citric acid in the step C is 45-55 ℃.
5. The method of preparing disodium stannous citrate according to claim 1, wherein the water content of ethanol in step C is less than 15%.
6. The method of claim 5, wherein the ethanol has a water content of less than 5%.
7. The method for preparing disodium stannous citrate according to claim 1, wherein the reaction temperature in the step D is 55-60 ℃.
8. A preparation method of disodium stannous citrate is characterized by comprising the following steps:
A. dissolving stannous chloride in water, adding a sodium hydroxide aqueous solution under stirring at 40-55 ℃ until the pH value of a reaction system is 8-10;
B. adding citric acid aqueous solution into the system according to the molar ratio of stannous chloride to citric acid of 3: 0.9-1.0, continuously stirring for 0.5-3 hours, cooling to room temperature, filtering, washing, drying the solid in vacuum at 20-60 ℃, and crushing;
C. and C, mixing the solid obtained in the step B with trisodium citrate powder, mixing, stirring and grinding for 5-30 minutes according to the weight ratio of 1.1-1.2: 1 to obtain the equivalent composition of the disodium stannous citrate, wherein the composition is converted into the disodium stannous citrate by adding water when in use.
9. The method for preparing disodium stannous citrate according to claim 8, wherein the trisodium citrate is trisodium citrate anhydrous, and is prepared by drying and dehydrating trisodium citrate dihydrate.
10. The method for preparing disodium stannous citrate according to claim 7, wherein the mixing and grinding time of the solid in the step C and the trisodium citrate is 10-15 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101243881A CN100556885C (en) | 2006-12-25 | 2006-12-25 | The preparation method of distannous citrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101243881A CN100556885C (en) | 2006-12-25 | 2006-12-25 | The preparation method of distannous citrate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823954A (en) * | 2010-06-03 | 2010-09-08 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate |
| CN101844979A (en) * | 2010-06-03 | 2010-09-29 | 西陇化工股份有限公司 | Preparation method of disodium stannous citrate crystal |
| CN101862013A (en) * | 2010-06-03 | 2010-10-20 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate equivalent composition |
| CN102557921A (en) * | 2011-12-28 | 2012-07-11 | 合肥科尚医药科技有限公司 | Preparation method of potassium sodium hydrogen citrate complex salt hydrate |
| CN106083913A (en) * | 2016-06-14 | 2016-11-09 | 江苏飞拓界面工程科技有限公司 | A kind of organo-tin compound and synthetic method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3213120A (en) * | 1963-02-11 | 1965-10-19 | Pfizer & Co C | Tin salts of citric acid and method of preparation |
| US3214347A (en) * | 1963-11-18 | 1965-10-26 | Pan American Petroleum Corp | Azeotropic distillation process |
| CN1099565A (en) * | 1993-08-31 | 1995-03-08 | 河南省洛阳肉类联合加工厂 | Oxidation preventive for preventing meat food oxidation |
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2006
- 2006-12-25 CN CNB2006101243881A patent/CN100556885C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823954A (en) * | 2010-06-03 | 2010-09-08 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate |
| CN101844979A (en) * | 2010-06-03 | 2010-09-29 | 西陇化工股份有限公司 | Preparation method of disodium stannous citrate crystal |
| CN101862013A (en) * | 2010-06-03 | 2010-10-20 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate equivalent composition |
| CN101823954B (en) * | 2010-06-03 | 2012-11-21 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate |
| CN101844979B (en) * | 2010-06-03 | 2012-11-21 | 西陇化工股份有限公司 | Preparation method of disodium stannous citrate crystal |
| CN102557921A (en) * | 2011-12-28 | 2012-07-11 | 合肥科尚医药科技有限公司 | Preparation method of potassium sodium hydrogen citrate complex salt hydrate |
| CN106083913A (en) * | 2016-06-14 | 2016-11-09 | 江苏飞拓界面工程科技有限公司 | A kind of organo-tin compound and synthetic method thereof |
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| CN100556885C (en) | 2009-11-04 |
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Address after: 515064 Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 Patentee after: XILONG SCIENTIFIC CO., LTD. Address before: 515000 Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 Patentee before: Xilong Chemical Co., Ltd. |