CN114213645B - Bimetallic catalyst for synthesizing pure ethylene oxide polyether and preparation method thereof - Google Patents
Bimetallic catalyst for synthesizing pure ethylene oxide polyether and preparation method thereof Download PDFInfo
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- 229920000570 polyether Polymers 0.000 title claims abstract description 107
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 38
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 37
- 239000011592 zinc chloride Substances 0.000 claims abstract description 36
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 36
- 239000013589 supplement Substances 0.000 claims abstract description 31
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 72
- 238000009210 therapy by ultrasound Methods 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 36
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 18
- 239000011591 potassium Substances 0.000 claims description 18
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- XYBUIQUQPGBKAR-UHFFFAOYSA-N tripotassium;chromium(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Cr+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XYBUIQUQPGBKAR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000004606 Fillers/Extenders Substances 0.000 claims description 15
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 13
- -1 polytetrahydrofuran-oxypropylene Polymers 0.000 abstract description 11
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a bimetallic catalyst for synthesizing pure ethylene oxide polyether and a preparation method thereof, and particularly relates to the technical field of bimetallic catalysts, wherein the bimetallic catalyst comprises zinc chloride, polytetrahydrofuran-oxypropylene block polyether, sulfuric acid polyether ester, potassium hexacyanocobaltate, a supplement and cobalt chloride. The invention can effectively strengthen the catalytic stability and safety of the bimetallic catalyst and effectively improve the catalytic treatment effect of the bimetallic catalyst after repeated use; a bimetallic catalyst which takes cobalt ions as the center and is matched with the mutual synergy among zinc ions, copper ions and silver ions can be formed; meanwhile, the activated carbon in the replenisher is a support carrier of the bimetallic complex and the phosphotungstic acid, so that the phosphotungstic acid and the bimetallic complex can be effectively supported, and the phosphotungstic acid and the bimetallic complex are compounded, so that the bimetallic catalyst can still keep an excellent catalytic treatment effect when being repeatedly used; the high catalytic activity of the bimetallic catalyst and the stability of the catalyst can be further improved.
Description
Technical Field
The invention relates to the technical field of bimetallic catalysts, in particular to a bimetallic catalyst for synthesizing pure ethylene oxide polyether and a preparation method thereof.
Background
The double metal cyanide complex (DMC) catalyst belongs to the coordination ring-opening polymerization catalysis system of double-base metal coordination complex, the polyether polyol synthesized by the double metal catalyst has narrow molecular weight distribution, low unsaturation degree and higher product quality than the traditional alkali-catalyzed polyether. From the reaction process, the activity of the bimetallic catalytic polymerization reaction is high, the reaction time is shortened, the energy is saved, and the consumption is reduced; no post-treatment is needed, the product yield is improved, no waste residue is discharged, and the method is an energy-saving and environment-friendly green production process. One of the characteristics of DMC catalysts is the variability of their catalytic activity, i.e., catalysts prepared from the same starting materials also have a large difference in their catalytic activity; the second feature is the need for polyether oligomers as starters, which are generally believed to deactivate DMC by small molecule alcohols such as propylene glycol, glycerol, etc.; the third feature is that DMC can not prepare pure ethylene oxide polyether; there are also some bimetallic catalysts available to catalyze the preparation of pure ethylene oxide polyethers.
The existing bimetallic catalyst has poor stability in preparing pure ethylene oxide polyether by catalysis, and the bimetallic catalyst has poor catalytic effect after repeated use.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art, embodiments of the present invention provide a bimetallic catalyst for pure ethylene oxide polyether synthesis and a method for preparing the same.
A bimetallic catalyst for synthesizing pure ethylene oxide polyether comprises the following components in percentage by weight: 13.60 to 14.20 percent of zinc chloride, 11.80 to 12.40 percent of polytetrahydrofuran-propoxylene block polyether, 11.60 to 12.60 percent of sulfuric acid polyether ester, 7.50 to 7.90 percent of potassium hexacyanocobaltate, 35.50 to 36.30 percent of extender, and the balance of cobalt chloride.
Further, the supplement: 20.50 to 21.10 percent of copper nitrate, 21.60 to 22.60 percent of silver nitrate, 11.20 to 12.20 percent of phosphotungstic acid, 19.40 to 20.40 percent of activated carbon, and the balance of potassium hexacyano chromate.
Further, the paint comprises the following components in percentage by weight: 13.60% of zinc chloride, 11.80% of polytetrahydrofuran-propoxy-ene block polyether, 11.60% of sulfuric acid polyether ester, 7.50% of potassium hexacyanocobaltate, 35.50% of extender and 20.00% of cobalt chloride; the supplement comprises: 20.50 percent of copper nitrate, 21.60 percent of silver nitrate, 11.20 percent of phosphotungstic acid, 19.40 percent of activated carbon and 27.30 percent of potassium hexacyano chromate.
Further, the paint comprises the following components in percentage by weight: 14.20% of zinc chloride, 12.40% of polytetrahydrofuran-propoxy-ene block polyether, 12.60% of sulfuric acid polyether ester, 7.90% of potassium hexacyanocobaltate, 36.30% of extender and 16.60% of cobalt chloride; the supplement comprises: 21.10 percent of copper nitrate, 22.60 percent of silver nitrate, 12.20 percent of phosphotungstic acid, 20.40 percent of activated carbon and 23.70 percent of potassium hexacyano chromate.
Further, the paint comprises the following components in percentage by weight: 13.90% of zinc chloride, 12.10% of polytetrahydrofuran propylene block polyether, 12.10% of sulfuric acid polyether ester, 7.70% of potassium hexacyanocobaltate, 35.90% of extender and 18.30% of cobalt chloride; the supplement is: 20.80 percent of copper nitrate, 22.10 percent of silver nitrate, 11.70 percent of phosphotungstic acid, 19.90 percent of activated carbon and 25.50 percent of potassium hexacyano chromate.
A preparation method of a bimetallic catalyst for synthesizing pure ethylene oxide polyether comprises the following specific preparation steps:
the method comprises the following steps: weighing zinc chloride, polytetrahydrofuran-propoxylene block polyether, sulfuric acid polyether ester, potassium hexacyanocobaltate, cobalt chloride and copper nitrate, silver nitrate, phosphotungstic acid, activated carbon and potassium hexacyanocobaltate in the supplement according to the weight part ratio;
step two: mixing and adding the zinc chloride and the cobalt chloride in the first step into deionized water, carrying out ultrasonic treatment for 2-4 minutes after complete dissolution, then adding the polytetrahydrofuran-oxypropylene block polyether, the polyether sulfate and the potassium hexacyanocobaltate in the first step into the solution together, and carrying out ultrasonic treatment for 2-4 minutes to obtain a mixture a;
step three: adding the copper nitrate and the silver nitrate in the first step into deionized water, carrying out ultrasonic treatment for 2-4 minutes after complete dissolution, then adding phosphotungstic acid, potassium hexacyano chromate and activated carbon into the solution, and carrying out ultrasonic treatment for 2-4 minutes to obtain a supplement;
step four: mixing the mixture a prepared in the step two and the supplement prepared in the step three, performing water bath ultrasonic treatment for 20-30 minutes, and performing centrifugal filtration to obtain a mixture b;
step five: and (4) carrying out flash evaporation drying treatment on the mixture b in the fourth step to obtain the pure ethylene oxide polyether synthesis bimetallic catalyst.
Further, in the second step, the ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water by weight is as follows: 1: 16-20, and the ultrasonic treatment frequency is as follows: 1.2-1.4 MHz, and the ultrasonic power is as follows: 300-400W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 16-20, and the ultrasonic treatment frequency is as follows: 1.2-1.4 MHz, and the ultrasonic power is as follows: 300-400W; in the fourth step, the ultrasonic treatment frequency is: 27-31 KHz, ultrasonic power is: 950-1050W, and the water bath temperature is 40-50 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: 270-290 ℃, the consumption of compressed air is as follows: 1.2-1.4 m 3 Min, pressure: 0.78-0.82 MPa.
Further, in step two, chlorineThe weight ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water is as follows: 1: 16, and the ultrasonic treatment frequency is as follows: 1.2MHz, ultrasonic power: 300W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 16, and the ultrasonic treatment frequency is as follows: 1.2MHz, ultrasonic power: 300W; in the fourth step, the ultrasonic treatment frequency is: 27KHz, ultrasonic power is: 950W, the water bath temperature is 40 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: at 270 ℃, the consumption of compressed air is: 1.2m 3 Min, pressure: 0.78MPa.
Further, in the second step, the ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water by weight is as follows: 1: 20, and the ultrasonic treatment frequency is as follows: 1.4MHz, ultrasonic power: 400W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 20, and the ultrasonic treatment frequency is as follows: 1.4MHz, ultrasonic power: 400W; in the fourth step, the ultrasonic treatment frequency is: 31KHz, ultrasonic power: 1050W, the water bath temperature is 50 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: 290 ℃, the compressed air consumption is: 1.4m 3 Min, pressure: 0.82MPa.
Further, in the second step, the ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water by weight is as follows: 1: 18, and the ultrasonic treatment frequency is as follows: 1.3MHz, the ultrasonic power is: 350W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 18, and the ultrasonic treatment frequency is as follows: 1.3MHz, the ultrasonic power is: 350W; in step four, the ultrasonic treatment frequency is: 29KHz, ultrasonic power: 1000W, and the water bath temperature is 45 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: the consumption of compressed air at 280 ℃ is as follows: 1.3m 3 Min, pressure: 0.80MPa.
The invention has the technical effects and advantages that:
1. the pure ethylene oxide polyether synthesis bimetallic catalyst prepared by the raw material formula can effectively enhance the catalytic stability and safety of the bimetallic catalyst and effectively improve the catalytic treatment effect of the bimetallic catalyst after repeated use; a bimetallic catalyst which takes cobalt ions as the center and is matched with the mutual cooperation among zinc ions, copper ions and silver ions can be formed; meanwhile, the activated carbon in the replenisher is a support carrier of the bimetallic complex and the phosphotungstic acid, so that the phosphotungstic acid and the bimetallic complex can be effectively supported, and the phosphotungstic acid and the bimetallic complex are compounded, so that the bimetallic catalyst can still keep an excellent catalytic treatment effect when being repeatedly used; the high catalytic activity of the bimetallic catalyst and the stability of the catalyst can be further improved, and the ring-opening treatment effect on the ethylene oxide can be effectively enhanced; phosphotungstic acid and a bimetallic complex are loaded on the surface of the activated carbon, and the strong interaction of phosphotungstic heteropolyanions, cations of the bimetallic complex and activated carbon microcrystals can further enhance the ring-opening treatment effect on ethylene oxide;
2. in the process of preparing the bimetallic catalyst for synthesizing pure ethylene oxide polyether, the cobalt and zinc bimetallic complex catalyst can be effectively prepared in the second step; in the third step, preparing a supplement which is activated carbon loaded with copper, silver metal complex and phosphotungstic acid; in the fourth step, the extender is compounded with a cobalt and zinc bimetallic complex catalyst to form an activated carbon catalyst simultaneously loaded with cobalt, zinc, copper and silver metal complexes and phosphotungstic acid; and in the fifth step, carrying out flash evaporation drying treatment on the mixture b to obtain the pure ethylene oxide polyether synthesis bimetallic catalyst.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a bimetallic catalyst for synthesizing pure ethylene oxide polyether, which comprises the following components in percentage by weight: 13.60% of zinc chloride, 11.80% of polytetrahydrofuran-propoxy-ene block polyether, 11.60% of sulfuric acid polyether ester, 7.50% of potassium hexacyanocobaltate, 35.50% of extender and 20.00% of cobalt chloride; the supplement comprises: 20.50% of copper nitrate, 21.60% of silver nitrate, 11.20% of phosphotungstic acid, 19.40% of activated carbon and 27.30% of potassium hexacyano chromate;
a preparation method of a bimetallic catalyst for synthesizing pure ethylene oxide polyether comprises the following specific preparation steps:
the method comprises the following steps: weighing zinc chloride, polytetrahydrofuran-propoxylene block polyether, sulfuric acid polyether ester, potassium hexacyanocobaltate, cobalt chloride and copper nitrate, silver nitrate, phosphotungstic acid, activated carbon and potassium hexacyanocobaltate in the supplement according to the weight part ratio;
step two: mixing and adding the zinc chloride and the cobalt chloride in the step one into deionized water, carrying out ultrasonic treatment for 2 minutes after complete dissolution, then adding the polytetrahydrofuran-oxypropylene block polyether, the sulfuric acid polyether ester and the potassium hexacyanocobaltate in the step one into the solution together, and carrying out ultrasonic treatment for 2 minutes to obtain a mixture a;
step three: adding the copper nitrate and the silver nitrate in the step one into deionized water, carrying out ultrasonic treatment for 2 minutes after complete dissolution, then adding phosphotungstic acid, potassium hexacyano chromate and activated carbon into the solution, and carrying out ultrasonic treatment for 2 minutes to obtain a supplement;
step four: mixing the mixture a prepared in the step two and the supplement prepared in the step three, performing water bath ultrasonic treatment for 20 minutes, and performing centrifugal filtration to obtain a mixture b;
step five: and (4) carrying out flash evaporation drying treatment on the mixture b in the fourth step to obtain the bimetallic catalyst for synthesizing pure ethylene oxide polyether.
In the second step, the weight ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water is as follows: 1: 16, and the ultrasonic treatment frequency is as follows: 1.2MHz, the ultrasonic power is: 300W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 16, and the ultrasonic treatment frequency is as follows: 1.2MHz, ultrasonic power: 300W; in step four, the ultrasonic treatment frequency is: 27KHz, ultrasonic power: 950W, the water bath temperature is 40 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: 270 ℃ compressed air consumptionThe amount is: 1.2m 3 Min, pressure: 0.78MPa.
Example 2:
different from the embodiment 1, the composite material comprises the following components in percentage by weight: 14.20% of zinc chloride, 12.40% of polytetrahydrofuran propylene block polyether, 12.60% of sulfuric acid polyether ester, 7.90% of potassium hexacyanocobaltate, 36.30% of extender and 16.60% of cobalt chloride; the supplement is: 21.10 percent of copper nitrate, 22.60 percent of silver nitrate, 12.20 percent of phosphotungstic acid, 20.40 percent of activated carbon and 23.70 percent of potassium hexacyano chromate.
Example 3:
different from the examples 1-2, the material comprises the following components in percentage by weight: 13.90% of zinc chloride, 12.10% of polytetrahydrofuran-propoxy-ene block polyether, 12.10% of sulfuric acid polyether ester, 7.70% of potassium hexacyanocobaltate, 35.90% of extender and 18.30% of cobalt chloride; the supplement is: 20.80 percent of copper nitrate, 22.10 percent of silver nitrate, 11.70 percent of phosphotungstic acid, 19.90 percent of activated carbon and 25.50 percent of potassium hexacyano chromate.
The bimetallic catalyst for synthesizing pure ethylene oxide polyether prepared in the above examples 1-3, the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the first control group, the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the second control group, the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the third control group, the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the fourth control group, the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the fifth control group and the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the sixth control group are taken respectively, the ratio of the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the first control group to the three phases of the examples has no cobalt chloride, the ratio of the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the second control group to the three phases of the examples has no copper nitrate, and the ratio of the bimetallic catalyst for synthesizing pure ethylene oxide polyether of the third control group to the three phases of the examples has no silver nitrate, the pure ethylene oxide polyether synthesis bimetallic catalyst of the control group IV has no phosphotungstic acid compared with the three phases of the examples, the pure ethylene oxide polyether synthesis bimetallic catalyst of the control group V has no active carbon compared with the three phases of the examples, the pure ethylene oxide polyether synthesis bimetallic catalyst of the control group VI has no supplement compared with the three phases of the examples, the pure ethylene oxide polyether synthesis bimetallic catalyst prepared in the three examples and the pure ethylene oxide polyether synthesis bimetallic catalyst of the six control groups are respectively tested in nine groups, 2.0mg of bimetallic cyanide catalyst is added into a 250mL high-pressure reaction kettle, vacuum pumping is carried out for 30 minutes, nitrogen is used for replacing three times, 3.5g of n-butyl alcohol and 13.5g of propylene oxide are added into the reaction kettle under nitrogen, the mixture is heated to 90 ℃ after being stirred for 10 minutes, when the pressure in the reaction kettle is obviously reduced, 120.0g of propylene oxide is slowly added, the adding speed is based on maintaining the pressure in the reaction kettle at about 0.60MPa, and after the alkylene oxide is added, the reaction is finished when the pressure in the reaction kettle is constant; filtering the reaction product to obtain pure ethylene oxide polyether, and recovering the catalyst; each 30 samples were grouped, and the test results are shown in table one:
table one:
as can be seen from Table I, when the pure ethylene oxide polyether is synthesized by using the bimetallic catalyst, the raw material ratio is as follows: comprises the following components in percentage by weight: 13.90% of zinc chloride, 12.10% of polytetrahydrofuran propylene block polyether, 12.10% of sulfuric acid polyether ester, 7.70% of potassium hexacyanocobaltate, 35.90% of extender and 18.30% of cobalt chloride; the supplement comprises: 20.80 percent of copper nitrate, 22.10 percent of silver nitrate, 11.70 percent of phosphotungstic acid, 19.90 percent of activated carbon and 25.50 percent of potassium hexacyano chromate, the catalytic stability and safety of the bimetallic catalyst can be effectively enhanced, and the catalytic treatment effect of the bimetallic catalyst after repeated use is effectively improved; therefore, example 3 is a preferred embodiment of the present invention, cobalt chloride provides cobalt ions for the bimetallic catalyst, zinc chloride provides zinc ions for the bimetallic catalyst, potassium hexacyanocobaltate forms cobalt and zinc metal complexes with the cobalt ions and the zinc ions, two ligands of polytetrahydrofuran propoxide block polyether and polyether sulfate are used to produce the cobalt and zinc bimetallic catalyst, copper nitrate in the replenisher provides supplementary copper ions for the bimetallic catalyst, silver nitrate in the replenisher provides supplementary silver ions for the bimetallic catalyst, copper and silver metal complexes are formed under the action of potassium hexacyanocobaltate and combined with the cobalt and zinc metal complexes to form the bimetallic catalyst centering on the cobalt ions and cooperating with the coordination among the zinc, copper and silver ions; meanwhile, the activated carbon in the replenisher is a support carrier of the bimetallic complex and the phosphotungstic acid, so that the phosphotungstic acid and the bimetallic complex can be effectively supported, meanwhile, the phosphotungstic acid and the bimetallic complex are compounded to form a bimetallic catalyst under the action of a ligand, so that the stability of the bimetallic catalyst can be effectively improved, and the bimetallic catalyst can still keep an excellent catalytic treatment effect when being repeatedly used; the cobalt and zinc metal complex can effectively ensure the high catalytic activity of the bimetallic catalyst; the cobalt ions and the copper ions are matched to form a cobalt-copper bimetallic complex, so that the high catalytic activity of the bimetallic catalyst and the stability of the catalyst can be further improved; the Cu and the silver form a Cu-Ag bimetallic catalyst, so that the ring opening treatment effect on the ethylene oxide can be effectively enhanced; phosphotungstic acid and a bimetallic complex are loaded on the surface of the activated carbon, and the strong interaction of the phosphotungstic heteropolyanion, the cation of the bimetallic complex and the activated carbon microcrystal can further enhance the ring-opening treatment effect on the ethylene oxide.
Example 4
In the above preferred technical solution, the present invention provides a bimetallic catalyst for synthesizing pure ethylene oxide polyether, comprising, by weight: 13.90% of zinc chloride, 12.10% of polytetrahydrofuran propylene block polyether, 12.10% of sulfuric acid polyether ester, 7.70% of potassium hexacyanocobaltate, 35.90% of extender and 18.30% of cobalt chloride; the supplement is: 20.80 percent of copper nitrate, 22.10 percent of silver nitrate, 11.70 percent of phosphotungstic acid, 19.90 percent of activated carbon and 25.50 percent of potassium hexacyano chromate.
A preparation method of a bimetallic catalyst for synthesizing pure ethylene oxide polyether comprises the following specific preparation steps:
the method comprises the following steps: weighing zinc chloride, polytetrahydrofuran-propoxylene block polyether, sulfuric acid polyether ester, potassium hexacyanocobaltate, cobalt chloride and copper nitrate, silver nitrate, phosphotungstic acid, activated carbon and potassium hexacyanocobaltate in the supplement according to the weight part ratio;
step two: mixing and adding the zinc chloride and the cobalt chloride in the first step into deionized water, carrying out ultrasonic treatment for 3 minutes after complete dissolution, then adding the polytetrahydrofuran-oxypropylene block polyether, the sulfuric acid polyether ester and the potassium hexacyanocobaltate in the first step into the solution together, and carrying out ultrasonic treatment for 3 minutes to obtain a mixture a;
step three: adding the copper nitrate and the silver nitrate in the step one into deionized water, carrying out ultrasonic treatment for 3 minutes after complete dissolution, then adding phosphotungstic acid, potassium hexacyano chromate and activated carbon into the solution, and carrying out ultrasonic treatment for 3 minutes to obtain a supplement;
step four: mixing the mixture a prepared in the step two and the supplement prepared in the step three, carrying out water bath ultrasonic treatment for 25 minutes, and carrying out centrifugal filtration to obtain a mixture b;
step five: and (4) carrying out flash evaporation drying treatment on the mixture b in the fourth step to obtain the pure ethylene oxide polyether synthesis bimetallic catalyst.
In the second step, the weight ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water is as follows: 1: 16, and the ultrasonic treatment frequency is as follows: 1.2MHz, the ultrasonic power is: 300W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 16, and the ultrasonic treatment frequency is as follows: 1.2MHz, ultrasonic power: 300W; in the fourth step, the ultrasonic treatment frequency is: 27KHz, ultrasonic power is: 950W, the water bath temperature is 40 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: 270 ℃, the compressed air consumption is: 1.2m 3 Min, pressure: 0.78MPa.
Example 5
Different from the embodiment 4, in the second step, the weight ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water is as follows: 1: 20, and the ultrasonic treatment frequency is as follows: 1.4MHz, ultrasonic power: 400W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 20, and the ultrasonic treatment frequency is as follows: 1.4MHz, ultrasonic power: 400W; in step fourIn (2), the ultrasonic treatment frequency is: 31KHz, ultrasonic power: 1050W, the water bath temperature is 50 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: 290 ℃, the compressed air consumption is: 1.4m 3 Min, pressure: 0.82MPa.
Example 6
Different from the examples 4 to 5, in the second step, the weight ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water is as follows: 1: 18, and the ultrasonic treatment frequency is as follows: 1.3MHz, the ultrasonic power is: 350W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 18, and the ultrasonic treatment frequency is as follows: 1.3MHz, the ultrasonic power is: 350W; in the fourth step, the ultrasonic treatment frequency is: 29KHz, ultrasonic power: 1000W, and the water bath temperature is 45 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: at 280 ℃, the consumption of compressed air is: 1.3m 3 Min, pressure: 0.80MPa.
Taking the bimetallic catalyst for synthesizing the pure ethylene oxide polyether prepared in the above examples 4-6 and the bimetallic catalyst for synthesizing the pure ethylene oxide polyether of the control group seven, the bimetallic catalyst for synthesizing the pure ethylene oxide polyether of the control group eight and the bimetallic catalyst for synthesizing the pure ethylene oxide polyether of the control group nine respectively, comparing the bimetallic catalyst for synthesizing the pure ethylene oxide polyether of the control group seven with the embodiment six, the operation in the step two is not subjected to ultrasonic treatment, comparing the bimetallic catalyst for synthesizing the pure ethylene oxide polyether of the control group eight with the embodiment six, the operation in the step three is not subjected to ultrasonic treatment, comparing the bimetallic catalyst for synthesizing the pure ethylene oxide polyether of the control group nine with the embodiment six, the operation in the step four is not subjected to ultrasonic treatment; respectively testing the pure ethylene oxide polyether synthesis bimetallic catalyst prepared in the three embodiments and three control groups of pure ethylene oxide polyether synthesis bimetallic catalysts, adding 2.0mg of the pure ethylene oxide polyether synthesis bimetallic catalyst into a 250mL high-pressure reaction kettle, vacuumizing for 30 minutes, replacing for three times with nitrogen, adding 3.5g of n-butanol and 13.5g of propylene oxide into the reaction kettle under the nitrogen, stirring for 10 minutes, heating to 90 ℃, slowly adding 120.0g of propylene oxide when the pressure in the reaction kettle is obviously reduced, keeping the pressure in the reaction kettle about 0.60MPa according to the adding speed, and finishing the reaction when the pressure in the reaction kettle is constant after the alkylene oxide is added; filtering the reaction product to obtain pure ethylene oxide polyether, and recovering the catalyst; each 30 samples were grouped, and the test results are shown in table two:
table two:
as can be seen from table two, in the process of preparing the bimetallic catalyst for synthesizing pure ethylene oxide polyether, when the preparation method in the sixth embodiment is the preferred scheme of the present invention, in the second step, zinc chloride and cobalt chloride are added into deionized water to be dissolved, after 1.3MHz ultrasonic treatment, cobalt ions and zinc ions in the solution are distributed more uniformly, and after adding polytetrahydrofuran propoxylene block polyether, polyether sulfate and potassium hexacyanocobaltate, further 1.3MHz ultrasonic treatment is performed, so that the cobalt and zinc bimetallic complex catalyst can be effectively prepared; in the third step, adding copper nitrate and silver nitrate into deionized water for dissolving, performing 1.3MHz ultrasonic treatment to uniformly distribute copper ions and silver ions into the solution, adding phosphotungstic acid, potassium hexacyano chromate and activated carbon into the solution, performing 1.3MHz ultrasonic treatment to prepare a supplement, wherein the supplement is activated carbon loaded with copper, a silver metal complex and phosphotungstic acid; in the fourth step, the extender and the mixture a are mixed, 29KHz ultrasonic treatment is carried out in 45 ℃ water bath, the extender is compounded with the cobalt and zinc bimetallic complex catalyst to form an activated carbon catalyst loaded with cobalt, zinc, copper and silver metal complexes and phosphotungstic acid at the same time, and the ultrasonic frequency in the fourth step and the ultrasonic frequency in the second step and the third step form dual-frequency ultrasonic waves, so that the ion combination effect in the catalyst can be effectively enhanced; and in the fifth step, the mixture b is subjected to flash evaporation drying treatment, so that the mixture b can be quickly dried to obtain the pure ethylene oxide polyether synthesis bimetallic catalyst.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A bimetal catalyst for synthesizing pure ethylene oxide polyether is characterized in that: the weight percentage of the components is as follows: 13.60 to 14.20 percent of zinc chloride, 11.80 to 12.40 percent of polytetrahydrofuran propylene block polyether, 11.60 to 12.60 percent of sulfuric acid polyether ester, 7.50 to 7.90 percent of potassium hexacyanocobaltate, 35.50 to 36.30 percent of extender and the balance of cobalt chloride; the supplement is: 20.50 to 21.10 percent of copper nitrate, 21.60 to 22.60 percent of silver nitrate, 11.20 to 12.20 percent of phosphotungstic acid, 19.40 to 20.40 percent of activated carbon, and the balance of potassium hexacyano chromate.
2. The bimetallic catalyst of claim 1, wherein: the weight percentage of the components is as follows: 13.60% of zinc chloride, 11.80% of polytetrahydrofuran propylene block polyether, 11.60% of sulfuric acid polyether ester, 7.50% of potassium hexacyanocobaltate, 35.50% of supplement and 20.00% of cobalt chloride; the supplement is: 20.50 percent of copper nitrate, 21.60 percent of silver nitrate, 11.20 percent of phosphotungstic acid, 19.40 percent of activated carbon and 27.30 percent of potassium hexacyano chromate.
3. The bimetallic catalyst for the synthesis of pure ethylene oxide polyethers according to claim 1, characterized in that: comprises the following components in percentage by weight: 14.20% of zinc chloride, 12.40% of polytetrahydrofuran propylene block polyether, 12.60% of sulfuric acid polyether ester, 7.90% of potassium hexacyanocobaltate, 36.30% of extender and 16.60% of cobalt chloride; the supplement comprises: 21.10 percent of copper nitrate, 22.60 percent of silver nitrate, 12.20 percent of phosphotungstic acid, 20.40 percent of activated carbon and 23.70 percent of potassium hexacyano chromate.
4. The bimetallic catalyst of claim 1, wherein: comprises the following components in percentage by weight: 13.90% of zinc chloride, 12.10% of polytetrahydrofuran propylene block polyether, 12.10% of sulfuric acid polyether ester, 7.70% of potassium hexacyanocobaltate, 35.90% of extender and 18.30% of cobalt chloride; the supplement is: 20.80 percent of copper nitrate, 22.10 percent of silver nitrate, 11.70 percent of phosphotungstic acid, 19.90 percent of activated carbon and 25.50 percent of potassium hexacyano chromate.
5. The method of any one of claims 1-4 for preparing a bimetallic catalyst for the synthesis of pure ethylene oxide polyethers, wherein: the preparation method comprises the following specific steps:
the method comprises the following steps: weighing zinc chloride, polytetrahydrofuran-propoxylene block polyether, sulfuric acid polyether ester, potassium hexacyanocobaltate, cobalt chloride and copper nitrate, silver nitrate, phosphotungstic acid, activated carbon and potassium hexacyanocobaltate in the supplement according to the weight part ratio;
step two: mixing and adding the zinc chloride and the cobalt chloride in the first step into deionized water, carrying out ultrasonic treatment for 2-4 minutes after complete dissolution, then adding the polytetrahydrofuran-propoxylene block polyether, the sulfuric acid polyether ester and the potassium hexacyanocobaltate in the first step into the solution together, and carrying out ultrasonic treatment for 2-4 minutes to obtain a mixture a;
step three: adding the copper nitrate and the silver nitrate in the step one into deionized water, carrying out ultrasonic treatment for 2-4 minutes after complete dissolution, then adding phosphotungstic acid, potassium hexacyano chromate and activated carbon into the solution, and carrying out ultrasonic treatment for 2-4 minutes to obtain a supplement;
step four: mixing the mixture a prepared in the step two and the supplement prepared in the step three, performing water bath ultrasonic treatment for 20-30 minutes, and performing centrifugal filtration to obtain a mixture b;
step five: and (4) carrying out flash evaporation drying treatment on the mixture b in the fourth step to obtain the bimetallic catalyst for synthesizing pure ethylene oxide polyether.
6. The method of claim 5, wherein the bimetallic catalyst is prepared by the following steps: in the second step, the weight ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water is as follows: 1: 16-20, and the ultrasonic treatment frequency is as follows: 1.2-1.4 MHz, and the ultrasonic power is as follows: 300-400W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 16-20, and the ultrasonic treatment frequency is as follows: 1.2-1.4 MHz, and the ultrasonic power is as follows: 300-400W; in the fourth step, the ultrasonic treatment frequency is: 27-31 KHz, ultrasonic power is: 950-1050W, and the water bath temperature is 40-50 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: 270-290 ℃, the consumption of compressed air is as follows: 1.2-1.4 m 3 Min, pressure: 0.78-0.82 MPa.
7. The method for preparing the bimetallic catalyst for synthesizing pure ethylene oxide polyether according to claim 6, characterized in that: in the second step, the ratio of the total weight of the zinc chloride and the cobalt chloride to the weight of the deionized water is as follows: 1: 16, and the ultrasonic treatment frequency is as follows: 1.2MHz, the ultrasonic power is: 300W; in step three, the total weight of the copper nitrate and the silver nitrate is equal toThe deionized water comprises the following components in parts by weight: 1: 16, and the ultrasonic treatment frequency is as follows: 1.2MHz, ultrasonic power: 300W; in step four, the ultrasonic treatment frequency is: 27KHz, ultrasonic power is: 950W, the water bath temperature is 40 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: at 270 ℃, the consumption of compressed air is: 1.2m 3 Min, pressure: 0.78MPa.
8. The method for preparing the bimetallic catalyst for synthesizing pure ethylene oxide polyether according to claim 6, characterized in that: in the second step, the ratio of the total weight of the zinc chloride and the cobalt chloride to the weight of the deionized water is as follows: 1: 20, and the ultrasonic treatment frequency is as follows: 1.4MHz, ultrasonic power: 400W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 20, and the ultrasonic treatment frequency is as follows: 1.4MHz, ultrasonic power: 400W; in the fourth step, the ultrasonic treatment frequency is: 31KHz, ultrasonic power: 1050W, the water bath temperature is 50 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: 290 ℃, the compressed air consumption is: 1.4m 3 Min, pressure: 0.82MPa.
9. The method of claim 6, wherein the bimetallic catalyst is prepared by the following steps: in the second step, the weight ratio of the total weight of the zinc chloride and the cobalt chloride to the deionized water is as follows: 1: 18, and the ultrasonic treatment frequency is as follows: 1.3MHz, the ultrasonic power is: 350W; in the third step, the weight ratio of the total weight of the copper nitrate and the silver nitrate to the deionized water is as follows: 1: 18, and the ultrasonic treatment frequency is as follows: 1.3MHz, the ultrasonic power is: 350W; in the fourth step, the ultrasonic treatment frequency is: 29KHz, ultrasonic power: 1000W, and the water bath temperature is 45 ℃; in the fifth step, the inlet air temperature of the flash evaporation treatment is as follows: the consumption of compressed air at 280 ℃ is as follows: 1.3m 3 Min, pressure: 0.80MPa.
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