CN114275752A - Preparation method of high-purity copper pyrophosphate - Google Patents
Preparation method of high-purity copper pyrophosphate Download PDFInfo
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- CN114275752A CN114275752A CN202210072904.XA CN202210072904A CN114275752A CN 114275752 A CN114275752 A CN 114275752A CN 202210072904 A CN202210072904 A CN 202210072904A CN 114275752 A CN114275752 A CN 114275752A
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- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 52
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 239000002244 precipitate Substances 0.000 claims abstract description 23
- CSCNMBQITNFHLH-UHFFFAOYSA-L copper;hydrogen phosphate Chemical compound [Cu+2].OP([O-])([O-])=O CSCNMBQITNFHLH-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- MELBZJNMLHHZBH-UHFFFAOYSA-L copper;dihydrogen phosphate Chemical compound [Cu+2].OP(O)([O-])=O.OP(O)([O-])=O MELBZJNMLHHZBH-UHFFFAOYSA-L 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- 230000003247 decreasing effect Effects 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 21
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000000843 powder Substances 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 11
- 238000007747 plating Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 5
- 235000011180 diphosphates Nutrition 0.000 description 5
- 229940048084 pyrophosphate Drugs 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- VRUVRQYVUDCDMT-UHFFFAOYSA-N [Sn].[Ni].[Cu] Chemical compound [Sn].[Ni].[Cu] VRUVRQYVUDCDMT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of high-purity copper pyrophosphate, which comprises the following steps: s1, sequentially adding copper acetate and pure water into a reaction container, heating the reaction container under a stirring state until the copper acetate is completely dissolved, cooling and filtering the reaction container, collecting filtrate A, adding hydrogen peroxide into the filtrate A, adding ammonia water to adjust the pH value to 3.5-4.2, standing the filtrate A until the precipitate is completely precipitated, filtering the filtrate, and collecting filtrate B; s2, adding the filtrate B into a phosphoric acid solution, fully and uniformly mixing, adding ammonia water to adjust the pH value to 1.3-1.8, and after complete reaction, filtering, washing precipitates and drying to obtain copper monohydrogen phosphate solid; and S3, calcining the copper monohydrogen phosphate solid to obtain the high-purity copper pyrophosphate. Copper pyrophosphate powder is used as a raw material, impurities are removed through dissolution, and then high-purity copper pyrophosphate is obtained through calcination, wherein the purity can reach 99.9%.
Description
Technical Field
The invention relates to the technical field of raw material additives of electrolytic copper plating, in particular to a preparation method of high-purity copper pyrophosphate.
Background
The pyrophosphate copper is mainly used for cyanide-free electroplating, is a main salt for supplying copper ions in a plating solution, is suitable for a copper bottom layer of a decorative protective layer and a local anti-carburizing coating of a part requiring carburization, is used for pyrophosphate copper plating, bronze plating, nickel-copper-tin alloy plating, tungsten alloy plating and the like, and is also used for an analytical reagent. Copper pyrophosphate is a main salt which supplies copper ions in a copper pyrophosphate electroplating solution, is complexed with sodium (or potassium) pyrophosphate in the plating solution to form sodium (or potassium) pyrophosphate, enables metal ions to exist stably in the form of complex ions, is an ideal raw material for copper plating, is one of effective substitutes for copper cyanide-containing plating, and has better dispersing ability and covering ability, higher use safety and higher cathodic current efficiency compared with acidic copper plating solutions and copper cyanide plating solutions.
The preparation of copper pyrophosphate in the current market adopts a more traditional double decomposition method, namely soluble copper salt reacts with soluble pyrophosphate to prepare copper pyrophosphate; the common raw materials are copper dichloride and sodium pyrophosphate, copper dichloride and sodium pyrophosphate are respectively prepared into solutions with certain concentration, the solutions are filtered and purified, a quantitative sodium pyrophosphate solution is dripped into the copper dichloride solution under the stirring condition, the pH value is controlled to be about 5-5.5, the copper dichloride solution and the sodium pyrophosphate solution react, and crude copper pyrophosphate is obtained by filtration, the relative density of the product is 0.402, the crystal diameter is about 70 mu m, and the water content is 43.6%. The preparation method has the disadvantages that the product has fine granularity and is easy to form mixed salt, so the dosage ratio of reactants must be strictly controlled, and simultaneously, the product has more impurity elements and lower purity. According to the method, copper acetate and phosphoric acid are used as raw materials, a preparation route of preparing a precursor by precipitation and calcining is adopted, the cleaner precursor is obtained after special impurity removal and purification is carried out, and then the copper pyrophosphate solid powder with higher purity and smaller particles is obtained by controlling accurate calcining conditions.
Disclosure of Invention
In order to solve the problems in the background technology, the invention provides a preparation method of high-purity copper pyrophosphate, which adopts copper acetate powder as a raw material, and obtains the high-purity copper pyrophosphate through dissolution, impurity removal and calcination, wherein the purity can reach 99.9 percent, and the preparation method has simple and controllable process and can meet the use requirements of different types.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of high-purity copper pyrophosphate, which comprises the following steps:
s1, sequentially adding copper acetate and pure water into a reaction container, heating the reaction container under a stirring state until the copper acetate is completely dissolved, cooling and filtering the reaction container, collecting filtrate A, adding hydrogen peroxide into the filtrate A, adding ammonia water to adjust the pH value to 3.5-4.2, fully stirring the mixture to react, standing the mixture until the precipitate is completely precipitated, filtering the mixture, and collecting filtrate B;
s2, adding the filtrate B obtained in the step S1 into a phosphoric acid solution, fully stirring and uniformly mixing, adding ammonia water to adjust the pH value to 1.3-1.8, fully stirring, standing until the precipitation reaction is complete, filtering, washing the precipitate, and drying to obtain a copper monohydrogen phosphate solid;
s3, calcining the copper monohydrogen phosphate solid obtained in the step S2 to obtain the high-purity copper pyrophosphate.
Adopt above-mentioned technical scheme:
the preparation principle of the high-purity copper pyrophosphate is as follows:
in step S1, firstly, pure water is added to completely dissolve the copper acetate, then ammonia water is used to adjust the pH value of the system, and hydrogen peroxide is added to precipitate the metal ion impurities (Fe, Co, Cr, Mn, Ni, Pb, etc.) in the system except for Cu in the form of hydroxide, thereby achieving the purpose of removing the impurity metal ions and obtaining the high-purity copper acetate solution with extremely low impurity content.
In step S2, after the high-purity copper acetate solution and the phosphoric acid solution are mixed, the reaction is performed in a direction favorable for forming a copper monohydrogen phosphate precipitate by adjusting the pH value of the reaction system again within a certain range by using the characteristic that copper monohydrogen phosphate is insoluble, and the high-purity copper monohydrogen phosphate is obtained by filtering, washing and drying the precipitate.
In step S3, the obtained copper monohydrogen phosphate is calcined at high temperature to obtain high-purity copper pyrophosphate.
Specifically, in the step S1, the copper acetate is industrial-grade copper acetate, the concentration of the hydrogen peroxide is 25-35%, and the mass ratio of the copper acetate to the hydrogen peroxide is (190-210): 1.
the industrial-grade copper acetate powder is used as a copper source, the raw materials are easy to obtain and low in price, and pure water is added and stirred under a heating condition to ensure that the copper acetate is completely dissolved.
By accurately regulating and controlling the dosage and the proportion of hydrogen peroxide and copper acetate and then regulating and controlling the pH value of a system, metal ion impurities (Fe, Co, Cr, Mn, Ni, Pb and the like) except Cu are precipitated in the form of hydroxide, so that the aim of removing the metal impurities is fulfilled, and the high-purity copper acetate solution with extremely low impurity content is obtained.
Specifically, in step S2, the phosphoric acid solution is obtained by diluting electronic grade phosphoric acid with a mass fraction of 85%, and the concentration of the diluted phosphoric acid solution is 0.1mol/L to 0.4 mol/L.
Specifically, the mass ratio of the copper acetate to the electronic grade phosphoric acid is 1 (1-1.2).
Controlling the excessive amount of the added electronic grade phosphoric acid to ensure that the high-purity copper acetate solution and the phosphoric acid fully react to generate the copper monohydrogen phosphate.
Specifically, in the step S3, the copper monohydrogen phosphate solid is crushed and then sent into a calcination furnace, the calcination temperature is 450-650 ℃, the calcination time is 2.5-4h, and then the temperature is naturally reduced to room temperature.
The calcination temperature and the calcination time are set, so that the final product is guaranteed to be the target product copper pyrophosphate.
Compared with the prior art, the invention has the following beneficial effects:
the method abandons the traditional preparation method, adopts a production method which looks like the conventional practice and has high efficiency and strong practicability, regulates and controls the pH value of the system and adds hydrogen peroxide, has simple operation, and causes other metal ion impurities (Fe, Co, Cr, Mn, Ni, Pb, etc.) except Cu to be precipitated in the form of hydroxide, thereby realizing the purpose of precipitating, filtering and removing the impurity metal ions and obtaining the high-purity copper acetate solution with extremely low impurity content; putting the copper dihydrogen phosphate into a phosphoric acid solution for mixing reaction, performing precipitation reaction by adjusting the pH value of a reaction system to be in a certain range again by utilizing the characteristic that the copper dihydrogen phosphate is insoluble, performing the reaction in a direction favorable for forming the copper dihydrogen phosphate to obtain copper dihydrogen phosphate precipitate, filtering, washing, drying and crushing the precipitate, then performing high-temperature calcination, and crushing to obtain copper pyrophosphate powder;
compared with the traditional production method of copper pyrophosphate, the method has the advantages of simple and easily controlled whole process flow, strong process operability, good repeatability, easily obtained raw materials, low price, high sexual purity of the obtained product which can reach more than 99.9 percent and suitability for large-scale production.
Drawings
The invention is described in further detail below with reference to specific embodiments and with reference to the following drawings.
FIG. 1 is an X-ray powder diffraction (XRD) pattern of a copper pyrophosphate sample prepared in example 1.
Detailed Description
The following are specific examples of the present invention, which are merely illustrative of the method for producing high-purity copper pyrophosphate of the present invention and are not intended to limit the scope of the present invention.
Example 1
A preparation method of high-purity copper pyrophosphate comprises the following steps:
s1, sequentially adding 80g of industrial-grade copper acetate and 1000mL of pure water into a reaction kettle (the kettle body is made of a titanium alloy material, and the inner lining of the kettle body is made of polytetrafluoroethylene), heating the mixture under a stirring state until the copper acetate is completely dissolved, cooling the mixture, removing insoluble impurities by suction filtration by using a suction filter, collecting filtrate A, adding 0.4g of hydrogen peroxide with the concentration of 30% into the filtrate A, adding ammonia water with the concentration of 5% to adjust the pH value of the system to 3.5, fully stirring the mixture for reaction, standing the mixture until the precipitate is completely precipitated, filtering the mixture to remove the precipitate, and collecting filtrate B;
s2, adding the filtrate B obtained in the step S1 into 1000mL of a 0.4mol/L phosphoric acid solution (the phosphoric acid solution is obtained by diluting electronic-grade phosphoric acid with the mass fraction of 85%), fully mixing and stirring uniformly, adding ammonia water with the concentration of 5% to adjust the pH value to 1.3, fully stirring, standing to obtain dark blue precipitate copper monohydrogen phosphate, and after the precipitation reaction is completed, filtering, washing the precipitate and drying to obtain 56.5g of copper monohydrogen phosphate solid;
s3, crushing the copper monohydrogen phosphate solid obtained in the step S2, feeding the crushed copper monohydrogen phosphate solid into a calcining furnace, heating to 450 ℃, preserving heat for 4 hours, naturally cooling to normal temperature, and crushing to obtain 52.75g of dark blue powdery material, namely the copper pyrophosphate.
Example 2
A preparation method of high-purity copper pyrophosphate comprises the following steps:
s1, sequentially adding 40g of industrial-grade copper acetate and 500mL of pure water into a reaction kettle (the kettle body is made of titanium alloy materials, the inner lining of the kettle body is made of polytetrafluoroethylene), heating the mixture under a stirring state until the copper acetate is completely dissolved, cooling the mixture, removing insoluble impurities by suction filtration through a suction filter, collecting filtrate A, adding 0.21g of hydrogen peroxide with the concentration of 25% into the filtrate A, adding hydrogen peroxide with the concentration of 5% to adjust the pH value of the system to 3.8, fully stirring the mixture for reaction, standing the mixture until the mixture is completely precipitated, filtering the mixture to remove the precipitate, and collecting filtrate B;
s2, adding the filtrate B obtained in the step S1 into 1000mL of a 0.22mol/L phosphoric acid solution (the phosphoric acid solution is obtained by diluting electronic-grade phosphoric acid with the mass fraction of 85%), fully mixing and stirring uniformly, adding ammonia water with the concentration of 5% to adjust the pH value to 1.5, fully stirring, standing to obtain dark blue precipitate copper monohydrogen phosphate, and after the precipitation reaction is completed, filtering, washing the precipitate and drying to obtain 30.52g of copper monohydrogen phosphate solid;
s3, crushing the copper monohydrogen phosphate solid obtained in the step S2, feeding the crushed copper monohydrogen phosphate solid into a calcining furnace, heating to 600 ℃, preserving heat for 3 hours, naturally cooling to normal temperature, and crushing to obtain 28.42g of dark blue powdery material, namely copper pyrophosphate.
Example 3
A preparation method of high-purity copper pyrophosphate comprises the following steps:
s1, sequentially adding 20g of industrial-grade copper acetate and 500mL of pure water into a reaction kettle (the kettle body is made of titanium alloy materials, the inner lining of the kettle body is made of polytetrafluoroethylene), heating the mixture under a stirring state until the copper acetate is completely dissolved, cooling the mixture, removing insoluble impurities by suction filtration by using a suction filter, collecting the filtrate A, adding 0.095g of 35% hydrogen peroxide into the filtrate A, adding 5% ammonia water to adjust the pH value of the system to 4.2, fully stirring the mixture for reaction, standing the mixture until the precipitate is completely precipitated, filtering the mixture to remove the precipitate, and collecting filtrate B;
s2, adding the filtrate B obtained in the step S1 into 1200mL of a 0.1mol/L phosphoric acid solution (the phosphoric acid solution is obtained by diluting electronic-grade phosphoric acid with the mass fraction of 85%), fully mixing and stirring uniformly, adding ammonia water with the concentration of 5% to adjust the pH value to 1.8, fully stirring, standing to obtain dark blue precipitate copper monohydrogen phosphate, and after the precipitation reaction is completed, filtering, washing the precipitate and drying to obtain 14.36g of copper monohydrogen phosphate solid;
s3, crushing the copper dihydrogen phosphate solid obtained in the step S2, feeding the crushed copper dihydrogen phosphate solid into a calcining furnace, heating to 650 ℃, preserving heat for 2.5 hours, naturally cooling to normal temperature, and crushing to obtain 13.25g of dark blue powdery material, namely the copper pyrophosphate.
The sample pattern obtained by taking the copper pyrophosphate prepared in the example 1 and carrying out XRD test is shown in figure 1, and as can be seen from the test pattern in figure 1, the peak value of the copper pyrophosphate prepared in the example 1 is completely consistent with the standard pattern of the copper pyrophosphate, which indicates that the product prepared by the preparation method is the copper pyrophosphate and indicates the stability of the quality of the copper pyrophosphate crystal prepared by the preparation method.
The contents of impurities in the copper pyrophosphate products prepared in examples 1 to 3 were measured by microwave-digested graphite oven atomic absorption spectrophotometry, and the detection results are shown in table 1.
TABLE 1
As is apparent from the test results shown in Table 1, the copper pyrophosphate products obtained in examples 1 to 3 had a purity of 99.9% by mass, a metallic element impurity Fe content of less than 1.6ppm, a Co content of less than 0.17ppm, a Cr content of less than 1.0ppm, a Mn content of less than 0.7ppm, a Ni content of less than 0.8ppm, and a Pb content of less than 0.9 ppm. It can be seen that the purity of the copper pyrophosphate products obtained in examples 1 to 3 reached the use requirements.
In conclusion, the pH value of the system is regulated and controlled, hydrogen peroxide is added, the operation is simple, and other metal ion impurities (Fe, Co, Cr, Mn, Ni, Pb and the like) except Cu are precipitated in the form of hydroxide, so that the aim of removing the impurity metal ions by precipitation and filtration is fulfilled, and the high-purity copper acetate solution with extremely low impurity content is obtained; putting the copper dihydrogen phosphate into a phosphoric acid solution for mixing reaction, performing precipitation reaction by adjusting the pH value of a reaction system to be in a certain range again by utilizing the characteristic that copper dihydrogen phosphate is insoluble, performing the reaction in a direction favorable for forming copper dihydrogen phosphate precipitate, filtering, washing, drying and crushing the prepared precipitate, then performing high-temperature calcination, and crushing to obtain copper pyrophosphate powder; compared with the traditional production method of copper pyrophosphate, the method has the advantages of simple and easily controlled whole process flow, strong process operability, good repeatability, easily obtained raw materials, low price, high sexual purity of the obtained product which can reach more than 99.9 percent and suitability for large-scale production.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (5)
1. A preparation method of high-purity copper pyrophosphate is characterized by comprising the following steps:
s1, sequentially adding copper acetate and pure water into a reaction container, heating the reaction container under a stirring state until the copper acetate is completely dissolved, cooling and filtering the reaction container to obtain a filtrate A, adding hydrogen peroxide into the filtrate A, adding ammonia water to adjust the pH value to 3.5-4.2, fully stirring the mixture to react, standing the mixture until the precipitate is completely precipitated, filtering the mixture to obtain a filtrate B;
s2, adding the filtrate B obtained in the step S1 into a phosphoric acid solution, fully stirring and uniformly mixing, adding ammonia water to adjust the pH value to 1.3-1.8, fully stirring, standing until the precipitation reaction is complete, filtering, washing the precipitate, and drying to obtain a copper monohydrogen phosphate solid;
s3, calcining the copper dihydrogen phosphate obtained in the step S2 to obtain the high-purity copper pyrophosphate.
2. The method for preparing high-purity copper pyrophosphate according to claim 1, wherein in step S1, the copper acetate is industrial-grade copper acetate, the concentration of hydrogen peroxide is 25-35%, and the mass ratio of copper acetate to hydrogen peroxide is (190-210): 1.
3. the method according to claim 1, wherein in step S2, the phosphoric acid solution is diluted with 85% by mass of electronic grade phosphoric acid to obtain a phosphoric acid solution having a concentration of 0.1mol/L to 0.4 mol/L.
4. The method for preparing high-purity copper pyrophosphate according to claim 3, wherein the mass ratio of the copper acetate to the electronic grade phosphoric acid is 1 (1-1.2).
5. The method as claimed in claim 1, wherein in step S3, the temperature for calcining the solid copper monohydrogen phosphate is 450-650 ℃, the time for calcining is 2.5-4h, and then the temperature is naturally decreased to room temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058162A (en) * | 2012-12-29 | 2013-04-24 | 广东光华科技股份有限公司 | Preparation method for electronic grade high-purity copper pyrophosphate |
| CN104741622A (en) * | 2015-04-15 | 2015-07-01 | 大冶有色金属有限责任公司 | Method for preparing high-purity copper powder |
| CN110040707A (en) * | 2019-05-13 | 2019-07-23 | 刘鹏 | A kind of preparation method of high-purity optical glass additive metaphosphoric acid copper |
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2022
- 2022-01-21 CN CN202210072904.XA patent/CN114275752A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058162A (en) * | 2012-12-29 | 2013-04-24 | 广东光华科技股份有限公司 | Preparation method for electronic grade high-purity copper pyrophosphate |
| CN104741622A (en) * | 2015-04-15 | 2015-07-01 | 大冶有色金属有限责任公司 | Method for preparing high-purity copper powder |
| CN110040707A (en) * | 2019-05-13 | 2019-07-23 | 刘鹏 | A kind of preparation method of high-purity optical glass additive metaphosphoric acid copper |
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