CN117069079B - Preparation process and application of potassium dihydrogen phosphite - Google Patents
Preparation process and application of potassium dihydrogen phosphite Download PDFInfo
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- CN117069079B CN117069079B CN202310979233.XA CN202310979233A CN117069079B CN 117069079 B CN117069079 B CN 117069079B CN 202310979233 A CN202310979233 A CN 202310979233A CN 117069079 B CN117069079 B CN 117069079B
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- ethanol
- potassium dihydrogen
- phosphorous acid
- dihydrogen phosphite
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- BZHCGFBZBPVRFE-UHFFFAOYSA-N monopotassium phosphite Chemical compound [K+].OP(O)[O-] BZHCGFBZBPVRFE-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 126
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 80
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 40
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 229910052734 helium Inorganic materials 0.000 claims abstract description 11
- 239000001307 helium Substances 0.000 claims abstract description 11
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 41
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 19
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 19
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 7
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- IVJBMYHEEHJJHU-UHFFFAOYSA-N C(C)O.P(O)(O)O Chemical compound C(C)O.P(O)(O)O IVJBMYHEEHJJHU-UHFFFAOYSA-N 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009775 high-speed stirring Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RDXARWSSOJYNLI-UHFFFAOYSA-N [P].[K] Chemical compound [P].[K] RDXARWSSOJYNLI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010829 isocratic elution Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/163—Phosphorous acid; Salts thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/26—Phosphorus; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Zoology (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
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Abstract
The application relates to the technical field of potassium dihydrogen phosphite chemical industry, in particular to a preparation process and application of potassium dihydrogen phosphite. The preparation method comprises the following preparation steps: s1, mixing phosphorous acid and ethanol under the atmosphere of nitrogen or helium, refluxing and heating to 75-80 ℃, adding potassium carbonate for mixing, stirring, reacting for 2-3h at a stirring speed of 1000-1500min, filtering, and leaching with ethanol to obtain a crude product; s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating, cooling to 20-25 ℃, adding ethanol, crystallizing, centrifuging, eluting with ethanol, and drying to obtain the potassium dihydrogen phosphite solid. By adopting the preparation method, the phosphorous acid and the ethanol are mixed to form the phosphorous acid-ethanol solution, so that the phosphorous acid-ethanol solution is easier to react with the potassium carbonate, and the high-speed stirring state is required to be kept all the time in the reaction process, so that the potassium carbonate can fully react, the reaction time of the phosphorous acid and the potassium carbonate is shortened to 2-3 hours, and the phosphorous acid-ethanol solution can be completed, and compared with the prior art, the method saves 6-12 hours.
Description
Technical Field
The application relates to the technical field of potassium dihydrogen phosphite chemical industry, in particular to a preparation process and application of potassium dihydrogen phosphite.
Background
The potassium dihydrogen phosphite is produced in the agricultural field, is often applied to the aspects of high-efficiency phosphorus-potassium fertilizer, plant photosynthesis increasing, plant immunity improving and the like, and has the effects of non-toxicity, sterilization and disease resistance. At present, few reports are reported in China on the preparation of potassium dihydrogen phosphite. The application number is CN01134148.3, the patent name is potassium dihydrogen phosphite and the preparation process of the potassium dihydrogen phosphite is disclosed in the production method, and the process is as follows: reacting phosphorous acid with potassium carbonate in the presence of nitrogen, helium or liquid nitrogen as a stabilizer to obtain a potassium dihydrogen phosphate solution, wherein the reaction formula is as follows: the molar ratio of the potassium carbonate to the phosphorous acid in the reaction is 1:1.5-2.5, the temperature in the reaction process is 70-100 ℃, and the reaction time is 8-15 hours; concentrating the potassium dihydrogen phosphite solution obtained by the reaction at 85-130 ℃, dynamically crystallizing, centrifuging, and collecting precipitate to obtain potassium dihydrogen phosphite solid.
The method has the advantages of simple production method, easy operation and available raw materials, but the time required for the method is longer, only 8-15 hours are required for the reaction stage, and the time cost is high, so the method needs improvement.
Disclosure of Invention
In order to shorten the production period of potassium dihydrogen phosphite, save the time cost and improve the purity of the potassium dihydrogen phosphite at the same time, the application provides a preparation process and application of the potassium dihydrogen phosphite.
In a first aspect, the present application provides a preparation process and application of potassium dihydrogen phosphite, which adopts the following technical scheme: a preparation process of potassium dihydrogen phosphite comprises the following preparation steps:
s1, mixing phosphorous acid and ethanol under the atmosphere of nitrogen or helium, refluxing and heating to 75-80 ℃, adding potassium carbonate for mixing, stirring, reacting for 2-3h at a stirring speed of 1000-1500min, filtering, and leaching with ethanol to obtain a crude product;
s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating, cooling to 20-25 ℃, adding ethanol, crystallizing, centrifuging, eluting with ethanol, and drying to obtain the potassium dihydrogen phosphite solid.
By adopting the technical scheme, the production period for producing the potassium dihydrogen phosphate is shortened, and the purity and the productivity of the potassium dihydrogen phosphate are improved.
The method comprises the steps of mixing phosphorous acid and ethanol to form a phosphorous acid-ethanol solution, and enabling the phosphorous acid-ethanol solution to react with potassium carbonate more easily, wherein the reaction process needs to keep a high-speed stirring state all the time, so that the potassium carbonate can fully react, the reaction time of the phosphorous acid and the potassium carbonate can be shortened to 2-3 hours, and compared with the prior art, the method is saved by 6-12 hours. In addition, the amount of phosphorous acid in the application exceeds the amount of potassium carbonate, firstly, the potassium carbonate is completely reacted, secondly, the phosphorous acid is dissolved in ethanol for subsequent impurity removal treatment, and the phosphorous acid which does not participate in the reaction is removed through ethanol, so that the purity of the potassium dihydrogen phosphate is further improved.
Through the step S2 of concentration and crystallization, the purity of the potassium dihydrogen phosphite is improved to be more than 98 percent. At this time, no crystals appear in the concentrating step, after ethanol is added, the crystals appear, the saturated solution can be formed by reducing the temperature after concentration, and when ethanol is added, part of water is compatible with ethanol, so that the saturated solution can be formed, and the purity of the crystals can be improved.
Conventionally, a hot saturated solution is cooled to cause supersaturation of the solution due to reduced solubility, so that the solute is separated out in a crystal form, and then mother liquor separation is performed to obtain crystals. And the supersaturated solution is formed by adding ethanol and placing, so that other impurities are dissolved in redundant water and ethanol, and the problems of high impurity content and low purity of crystals caused by supersaturation are well solved.
Preferably, the molar ratio of the potassium carbonate to the phosphorous acid is (0.7-0.9): 2.
by adopting the technical scheme, the potassium carbonate can be fully reacted, the productivity of potassium dihydrogen phosphate is improved, and the difficulty in subsequent removal of the potassium carbonate is reduced. Since potassium carbonate and potassium dihydrogen phosphite are both water-soluble substances, it is troublesome to remove potassium carbonate from phosphorous acid, and thus it is necessary to sufficiently react potassium carbonate in the reaction stage, and it is not necessary to remove impurities from potassium carbonate. By the range of the molar ratio of the potassium carbonate to the phosphorous acid, the yield of the monopotassium phosphate can be improved while the potassium carbonate is fully and completely reacted. The molar quantity of the phosphorous acid is more than twice of that of the potassium carbonate, so that the potassium carbonate can completely react without residue.
Preferably, in step S2, the crystallization process is as follows:
and (3) further cooling the ethanol-added concentrated solution to 10-15 ℃, placing the glass spheres attached with the potassium dihydrogen phosphate seed crystal into the ethanol-added concentrated solution, and stirring until no crystals appear, thereby completing the crystallization process.
By adopting the technical scheme, the potassium dihydrogen phosphite with high purity, regular crystal shape and uniform size is obtained. By lowering the temperature of the concentrate while introducing the glass spheres with potassium dihydrogen phosphite seeds, potassium dihydrogen phosphite can be precipitated and crystals with good structure are formed during the precipitation.
Preferably, the stirring speed after adding the glass beads is 300-500r/min.
By adopting the technical scheme, the potassium dihydrogen phosphite crystals with uniform and moderate size are obtained, so that the crystallization process is stable, and crystals with uniform shapes and structures are formed. The stirring speed after the glass beads are added is less than 300r/min, so that the crystallization speed is easy to be slow, the sizes of crystals are different, and the output of crystals is less; if the stirring speed after adding the glass beads is more than 500r/min, the crystals are easily broken to form fine crystals, so that the yield of potassium dihydrogen phosphite is reduced.
Preferably, the average particle size of the seed crystal is 800-1500um, and the seed crystal is used in an amount of 1-3% of the weight of the phosphorous acid.
By adopting the technical scheme, the formed potassium dihydrogen phosphite crystals have small size and structure difference, large average granularity, good crystal form and high purity. The generation of fine crystals is reduced by controlling the particle size distribution of the seed crystal, which is beneficial to improving the yield of potassium dihydrogen phosphite. If the particle size distribution of the seed crystal is not accurately controlled, there is a possibility that the agglomeration of crystals is serious, and the yield is reduced.
Preferably, the diameter of the glass sphere is 3-8m.
By adopting the technical scheme, the potassium dihydrogen phosphite is properly extruded, so that the potassium dihydrogen phosphite is preferable, the concentration treatment temperature is 100-110 ℃, and the concentration is carried out until the volume of the solution is 1/4-1/3 of the original volume.
Preferably, the volume of ethanol added in step S2 is 2-3 times that of the concentrated liquid.
By adopting the technical scheme, the yield of the potassium dihydrogen phosphite is improved, and the unsaturated potassium dihydrogen phosphite solution is obtained through concentration, and the point is slightly worse than the saturated potassium dihydrogen phosphite, so that the subsequent ethanol addition is facilitated to separate out potassium dihydrogen phosphite crystals. The impurity in potassium dihydrogen phosphite is further removed by accurately controlling the amount of the concentrated solution and the amount of the added ethanol, and simultaneously, the supersaturation degree of the overliquid is prevented, the larger the supersaturation degree is, the more crystal nuclei are generated, the smaller the crystal grain size is, and the yield of the potassium dihydrogen phosphite can be reduced.
Preferably, the centrifugation is carried out in step S2 at a rate of 2000-2500min and at a temperature of 60-70 ℃.
By adopting the technical scheme, the separation of potassium dihydrogen phosphite and the solution is facilitated by controlling the speed and the temperature of centrifugation, and the drying is facilitated.
In a second aspect, the present application provides an application of potassium dihydrogen phosphite, which adopts the following technical scheme:
the application of potassium dihydrogen phosphite is that the potassium dihydrogen phosphite is used for pesticide, pesticide bactericide or water treatment agent of organic phosphorus, and the potassium dihydrogen phosphite is prepared by the preparation process of the potassium dihydrogen phosphite in the first aspect.
By adopting the technical scheme, the potassium dihydrogen phosphite produced in the application can be used as an intermediate of pesticides and bactericides and waste materials on pesticides, can provide phosphorus and potassium required by plant growth, can kill fungi of plants, and has the advantages of haze and no residue; meanwhile, the potassium dihydrogen phosphite prepared by the method can be directly applied to a self-circulating water system, has the functions of sterilizing and complexing calcium ions and magnesium ions, can be used for replacing an organic phosphine water treatment agent, reduces environmental pollution, and is short in production period, free of pollution in the whole process, environment-friendly and energy-saving.
In summary, the present application has the following beneficial effects:
1. mixing phosphorous acid and ethanol under the protection of nitrogen or helium, heating to 75 ℃ under reflux, adding potassium carbonate, mixing, stirring, reacting for 2 hours, and filtering to obtain a crude product; adding the crude product into the water from which the oxygen has been removed, stirring uniformly, concentrating, adding ethanol, crystallizing, centrifuging and drying to obtain potassium dihydrogen phosphite solid. The method shortens the time and the reaction efficiency of generating the potassium dihydrogen phosphite by using the mode of mixing and reacting the phosphorous acid with the overflowed water firstly, and simultaneously improves the purity of the potassium dihydrogen phosphite by using the operations of mixing and concentrating the crude product with the water with oxygen removed, adding ethanol and the like.
Detailed Description
Examples
Example 1
A preparation process of potassium dihydrogen phosphite comprises the following preparation steps:
s1, mixing phosphorous acid and ethanol under the atmosphere of nitrogen, refluxing and heating to 75 ℃, adding potassium carbonate for mixing, stirring, reacting for 2 hours at the stirring speed of 1000min, filtering, and leaching with ethanol to obtain a crude product;
s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating to a temperature of 100 ℃, concentrating to a solution volume of 1/4 of the original solution volume, cooling to 20 ℃, adding ethanol, the volume of which is twice that of the concentrated solution, crystallizing, directly evaporating the water solution and the ethanol, centrifuging for 2000min at a temperature of 60 ℃, leaching with ethanol, and drying to obtain the potassium dihydrogen phosphate solid.
Wherein, the molar ratio of the phosphorous acid to the potassium carbonate is 2:1.
example 2
A preparation process of potassium dihydrogen phosphite comprises the following preparation steps:
s1, mixing phosphorous acid and ethanol in helium atmosphere, refluxing and heating to 80 ℃, adding potassium carbonate for mixing, stirring, reacting for 3 hours at a stirring speed of 1500min, filtering, and leaching with ethanol to obtain a crude product;
s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating, wherein the concentration treatment temperature is 110 ℃, concentrating until the volume of the solution is 1/3 of the original volume, cooling to 25 ℃, adding ethanol, wherein the volume of the ethanol is three times that of the concentrated solution, crystallizing, directly evaporating the water solution and the ethanol, centrifuging, wherein the centrifuging speed is 2500min, the temperature is 70 ℃, leaching with ethanol, and drying to obtain the potassium dihydrogen phosphate solid.
Wherein, the molar ratio of the phosphorous acid to the potassium carbonate is 2:1.
example 3
A preparation process of potassium dihydrogen phosphite comprises the following preparation steps:
s1, mixing phosphorous acid and ethanol in helium atmosphere, heating to 75 ℃, adding potassium carbonate for mixing, stirring, reacting for 3 hours at a stirring speed of 1500min, filtering, and leaching with ethanol to obtain a crude product;
s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating, wherein the concentration treatment temperature is 110 ℃, concentrating until the volume of the solution is 1/3 of the original volume, cooling to 25 ℃, adding ethanol, wherein the volume of the ethanol is three times that of the concentrated solution, crystallizing, directly evaporating the water solution and the ethanol, centrifuging, wherein the centrifuging speed is 2500min, the temperature is 70 ℃, leaching with ethanol, and drying to obtain the potassium dihydrogen phosphate solid.
Wherein, the molar ratio of the phosphorous acid to the potassium carbonate is 2:0.7.
example 4
A preparation process of potassium dihydrogen phosphite comprises the following preparation steps:
s1, mixing phosphorous acid and ethanol in helium atmosphere, heating to 100 ℃, adding potassium carbonate for mixing, stirring, reacting for 3 hours at a stirring speed of 1500min, filtering, and leaching with ethanol to obtain a crude product;
s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating, wherein the concentration treatment temperature is 110 ℃, concentrating until the volume of the solution is 1/3 of the original volume, cooling to 25 ℃, adding ethanol, wherein the volume of the ethanol is three times that of the concentrated solution, crystallizing, directly evaporating the water solution and the ethanol, centrifuging, wherein the centrifuging speed is 2500min, the temperature is 70 ℃, leaching with ethanol, and drying to obtain the potassium dihydrogen phosphate solid.
Wherein, the molar ratio of the phosphorous acid to the potassium carbonate is 2:0.9.
example 5
A preparation process of potassium dihydrogen phosphite comprises the following preparation steps:
s1, mixing phosphorous acid and ethanol in helium atmosphere, heating to 100 ℃, adding potassium carbonate for mixing, stirring, reacting for 3 hours at a stirring speed of 1500min, filtering, and leaching with ethanol to obtain a crude product;
s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating, wherein the concentration treatment temperature is 110 ℃, concentrating until the volume of the solution is 1/3 of that of the original solution, cooling to 25 ℃, adding ethanol, wherein the volume of the ethanol is three times that of the concentrated solution, crystallizing, centrifuging for 2500min at the temperature of 70 ℃, leaching with ethanol, and drying to obtain the potassium dihydrogen phosphate solid.
Wherein, the molar ratio of the phosphorous acid to the potassium carbonate is 2:0.7.
in step S2, the crystallization process is as follows:
and (3) further cooling the ethanol-added concentrated solution to 10 ℃, placing the glass spheres attached with the potassium dihydrogen phosphite crystal seeds into a supersaturated solution, wherein the diameter of the glass spheres is 3mm, the stirring speed after adding the glass beads is 300r/min, the average grain size of the crystal seeds is 800um, the consumption of the crystal seeds is 1% of the weight of the phosphorous acid, and stirring until no crystal appears, thereby completing the crystallization process.
Example 6
A preparation process of potassium dihydrogen phosphite comprises the following preparation steps:
s1, mixing phosphorous acid and ethanol in helium atmosphere, heating to 100 ℃, adding potassium carbonate for mixing, stirring, reacting for 3 hours at a stirring speed of 1500min, filtering, and leaching with ethanol to obtain a crude product;
s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating, wherein the concentration treatment temperature is 110 ℃, concentrating until the volume of the solution is 1/3 of that of the original solution, cooling to 25 ℃, adding ethanol, wherein the volume of the ethanol is three times that of the concentrated solution, crystallizing, centrifuging for 2500min at the temperature of 70 ℃, leaching with ethanol, and drying to obtain the potassium dihydrogen phosphate solid.
Wherein, the molar ratio of the phosphorous acid to the potassium carbonate is 2:0.7.
in step S2, the crystallization process is as follows:
and (3) further cooling the ethanol-added concentrated solution to 15 ℃, placing the glass spheres attached with the potassium dihydrogen phosphite crystal seeds into a supersaturated solution, wherein the diameter of the glass spheres is 3mm, the stirring speed after adding the glass beads is 300r/min, the average grain size of the crystal seeds is 1500um, the consumption of the crystal seeds is 1% of the weight of the phosphorous acid, and stirring until no crystal appears, thereby completing the crystallization process.
Example 7
The preparation process of potassium dihydrogen phosphite is different from that of example 6 in that the diameter of the glass ball is 8mm, and the rest of experimental steps are the same as those of example 6.
Example 8
The preparation process of potassium dihydrogen phosphite in this example was different from example 6 in that the amount of seed crystal was 3% by weight of phosphorous acid, and the rest of the experimental procedures were the same as in example 6.
Example 9
The preparation process of potassium dihydrogen phosphite in this example was different from example 6 in that the average particle diameter of the seed crystal was 50um, and the rest of the experimental procedures were the same as in example 6.
Example 10
The preparation process of potassium dihydrogen phosphite in this example and example 6 were different in that the stirring speed after adding glass beads was 500r/min, and the rest of the experimental procedures were the same as in example 6.
Comparative example
Comparative example 1
The comparative example differs from example 1 in that the ethanol in step S1 was replaced with an equal amount of water, and the rest of the experimental steps were identical to those of example 1.
Comparative example 2
A preparation process of potassium dihydrogen phosphite is different from that of the embodiment 1 in that S1, in the atmosphere of helium, phosphorous acid is heated to 100 ℃, potassium carbonate is added for mixing, stirring is carried out for 1500min, reaction is carried out for 3h, eluting is carried out by ethanol, crude products are obtained, and the rest experimental steps are the same as those of the embodiment 1.
The amounts of the raw materials used in examples 1 to 10 and comparative examples 1 to 2 were identical.
Performance test
The purity test and yield calculation were performed by preparing monopotassium phosphite from examples 1 to 10 and comparative examples 1 to 2.
Detection method/test method
Purity of potassium dihydrogen phosphite: the purity of the potassium dihydrogen phosphate is measured by adopting an ion chromatography method, 1.0000g of potassium dihydrogen phosphate sample is taken, water is added for dissolution, then the solution is transferred into a 500ml volumetric flask, and the solution is diluted to scale marks for a long time and is uniformly mixed. Transferring 1ml into a 50ml volumetric flask, diluting with water to a graduated scale, filtering with a 0.22um filter membrane, sampling, and using a Dionex IC S-90A ion chromatograph, wherein the chromatographic column is a Dionex Ionpac AS22 anion separation column (4 mm x 250 mm), and the mixture ratio AG (4 mm x 50 mm) is used for protecting the column, and the column temperature is 30 ℃; the eluent is a mixed solution of sodium bicarbonate with the concentration of 1.4mmol/L and sodium carbonate with the concentration of 4.5 mmol/L; the elution mode is isocratic elution; the flow quantity of the mobile phase is 1.2ml/min; the detector is a conductivity detector; the sample loading was 10uL. Calculation of PO in samples according to Standard Curve 3 3- The content of the potassium dihydrogen phosphate is converted into the purity of the potassium dihydrogen phosphate.
Phosphorus stock solution (p (PO) 3 3- ) 2000 ug/ml): weighing 1.4306g of baked potassium dihydrogen phosphate with optimal grade. Placed in a 250ml beaker, 100ml of water was added and dissolved with stirring. 2ml of nitric acid is added, transferred to a 500ml volumetric flask, and mixed well with water to a constant volume.
Phosphorus standard solution (p (PO) 3 3- ) 200 ug/ml): 10ml of the phosphorus stock solution was removed and placed in a 100ml volumetric flask, and the volume was fixed with water and mixed well.
Preparation of a standard curve: sucking 1.00, 2.00, 3.00, 5.00, 10.00 and 25.00ml of phosphorus standard solution, respectively transferring into 6 volumetric flasks of 50ml, diluting with water to scale, and shaking thoroughly to obtain P (PO) 3 3- ) 4, 8, 12, 20, 40, 100ug/ml of the series of phosphorus standard solutions, respectively. Taking the standard solution, sequentially injecting ion chromatography, and drawing a standard curve.
Yield rate: yield (%) = (amount of m actual output/m theoretical output) ×100%, experimental data are shown in table 1:
TABLE 1 Experimental data for examples 1-10 and comparative examples 1-2
From examples 1 to 10 and comparative examples 1 to 2 in combination with Table 1, it is understood that the preparation of potassium dihydrogen phosphite by the preparation process of the present application has the advantages of short production period, high purity, high yield, and the like.
The comparison of example 1 and comparative examples 1-2, in which the purity and yield of potassium dihydrogen phosphite were lower than those of example 1, shows that the purity and yield of potassium dihydrogen phosphite can be remarkably improved by the preparation process of the present application while shortening the production cycle.
In example 1 and example 3 compared with example 3, in example 3 of potassium dihydrogen phosphite purity and yield are greater than example 1, demonstrating by optimizing the amount of phosphorus acid and potassium carbonate, is beneficial to improve potassium dihydrogen phosphite purity and productivity.
Example 3 and example 5 compared with example 3, example 3 in the potassium dihydrogen phosphite purity is greater than example 1, which shows through optimization of the crystallization step, can improve the potassium dihydrogen phosphite purity.
Examples 6-10 are compared to demonstrate that by adjusting parameters near the crystallization process, the purity of potassium dihydrogen phosphite is advantageously increased.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (1)
1. The preparation process of the monopotassium phosphite is characterized by comprising the following preparation steps:
s1, mixing phosphorous acid and ethanol under the atmosphere of nitrogen or helium, refluxing and heating to 75-80 ℃, adding potassium carbonate for mixing, stirring, reacting for 2-3 hours at the stirring speed of 1000-1500r/min, filtering, and leaching with ethanol to obtain a crude product;
s2, adding the crude product into the water from which the oxygen has been removed, uniformly stirring, concentrating, cooling to 20-25 ℃, adding ethanol, crystallizing, centrifuging, leaching with ethanol, and drying to obtain a potassium dihydrogen phosphite solid;
the molar ratio of the potassium carbonate to the phosphorous acid is (0.7-0.9): 2;
in step S2, the crystallization process is as follows:
cooling the ethanol-added concentrated solution to 10-15 ℃, placing the glass spheres attached with the potassium dihydrogen phosphate seed crystal into the ethanol-added concentrated solution, and stirring until no crystals appear, thereby completing the crystallization process;
the stirring speed after adding the glass beads is 300-500r/min;
the average particle size of the seed crystal is 800-1500 mu m, and the dosage of the seed crystal is 1-3% of the weight of the phosphorous acid;
the diameter of the glass ball is 3-8mm;
concentrating at 100-110deg.C to 1/4-1/3 of the original volume of the solution;
the volume of ethanol added in the step S2 is 2-3 times of that of the concentrated liquid.
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| CN110775952B (en) * | 2019-12-16 | 2023-01-31 | 瓮福达州化工有限责任公司 | Preparation process of food-grade potassium dihydrogen phosphate |
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| US2595199A (en) * | 1948-09-25 | 1952-04-29 | Monsanto Chemicals | Phosphorous acid salts and method of preparing same |
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