CN118183820A - Cu/SiO2Comprehensive utilization method of waste catalyst - Google Patents
Cu/SiO2Comprehensive utilization method of waste catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002699 waste material Substances 0.000 title claims description 13
- 239000010949 copper Substances 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012065 filter cake Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
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- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000005751 Copper oxide Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- URJDFYQNAFUJJQ-UHFFFAOYSA-N tetrakis-decyl silicate Chemical compound CCCCCCCCCCO[Si](OCCCCCCCCCC)(OCCCCCCCCCC)OCCCCCCCCCC URJDFYQNAFUJJQ-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
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- 239000000843 powder Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
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- 238000004458 analytical method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- DARFZFVWKREYJJ-UHFFFAOYSA-L magnesium dichloride dihydrate Chemical compound O.O.[Mg+2].[Cl-].[Cl-] DARFZFVWKREYJJ-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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- 239000002893 slag Substances 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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Abstract
The invention relates to a comprehensive utilization method of a Cu/SiO 2 spent catalyst. The method comprises the following steps: and (3) heating and refluxing the copper-containing spent catalyst, alcohol, catalyst and cocatalyst in a carbon dioxide atmosphere for reaction. After the reaction is completed, the solvent is distilled off under reduced pressure, a proper amount of organic solvent is added into the residue, the mixture is stirred at room temperature and filtered, and the filtrate is distilled off under reduced pressure at 60 ℃ to remove the organic solvent, so that the organosilicon monomer is obtained. Washing the filter cake with water, adding into acid liquor, stirring, filtering, adding precipitator into the filtrate, stirring, filtering, washing and drying to obtain copper-containing solid.
Description
Technical Field
The invention relates to the field of comprehensive utilization of waste catalysts, in particular to recycling of copper oxide.
Background
Dimethyl oxalate hydrogenation is a core and key step in the technical route of coal-to-ethylene glycol. Copper-based catalysts are commonly used in hydrogenation reactions, and Cu/SiO 2 is considered as one of the most effective catalysts for preparing ethylene glycol by hydrogenating dimethyl oxalate, and the catalyst has short service life and large waste catalyst production due to the reduction of catalytic activity caused by poor thermal stability. The massive accumulation of the waste copper-based catalyst can cause pollution to the environment, toxic and harmful components in the waste copper-based catalyst can enter water and soil along with the flushing of rainwater, harm the water and the soil, vegetation, organisms and the like, and endanger the health of human bodies through a food chain. The most common methods for treating waste copper-based catalysts at present are (1) dry: heating and melting the catalyst, the reducing agent and the fluxing agent in a heating furnace, and extracting metal components in the form of metal or alloy through reduction and melting, wherein the fluxing agent and the carrier are discharged in the form of slag; (2) wet method: and (3) dissolving the industrial waste catalyst by using acid, alkali solution or other solvents, removing impurities from the filtrate, purifying, separating, and drying to obtain a final product. The conventional processes have the defects that the process is complex and a large amount of carrier parts are difficult to recycle.
The invention makes full use of the silicon dioxide carrier of the waste catalyst to directly synthesize the organic silicon monomer, can recycle the copper oxide, and is a comprehensive utilization method of the Cu/SiO 2 waste catalyst with simple operation, low cost and environmental friendliness.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to invent a method for comprehensively utilizing a copper-containing dead catalyst. Namely, the waste catalyst is utilized to directly synthesize the organic silicon monomer and recycle the copper-containing waste catalyst.
The specific embodiment of the invention is as follows: and (3) heating and refluxing the copper-containing spent catalyst, the n-decyl alcohol, the catalyst and the cocatalyst in a carbon dioxide atmosphere for reaction. After the reaction is completed, the solvent is distilled off under reduced pressure, a proper amount of organic solvent is added into the residue, the mixture is stirred at room temperature and filtered, and the filtrate is distilled off under reduced pressure at 60-80 ℃ to obtain the tetradecyloxy silane. Washing the filter cake with water, adding into acid liquor, stirring, filtering, adding precipitator into the filtrate, regulating the pH value of the solution, stirring, filtering, washing and drying to obtain copper oxide.
By adopting the scheme, the mass fractions of silicon, copper, aluminum and oxygen in the copper-containing spent catalyst are 25% -35%, 20% -30%, 0.01% -0.5% and 40% -45%, respectively.
With the scheme, the catalyst is anhydrous magnesium chloride, and the cocatalyst is anhydrous calcium chloride.
With the scheme, the molar ratio of the copper-containing dead catalyst to anhydrous calcium chloride and anhydrous magnesium chloride is as follows: 1:2 to 5:0.5 to 1.5.
With the scheme, the reaction temperature is 200-230 ℃.
In the above scheme, the organic solvent is one or more of methyl tertiary butyl ether, isopropyl ether, dichloromethane, chloroform, methanol, ethanol and tetrahydrofuran.
With the above scheme, the acid liquid is one or more of hydrochloric acid solution, sulfuric acid solution and nitric acid solution.
With the above scheme, the precipitant is one or two of sodium hydroxide and potassium hydroxide.
By adopting the scheme, the pH value range is 9-11.
Under the action of high temperature and a catalyst, silicon dioxide in the copper-containing spent catalyst reacts with the n-decyl alcohol, and tetradecyl orthosilicate is obtained through dehydration. Copper in the copper-containing spent catalyst has stronger interaction with decanol and has an inhibition effect on the reaction of silicon dioxide and decanol. Calcium chloride can inhibit the formation of copper and decanol complexes, thereby playing a role in promoting catalysis. The magnesium chloride dihydrate is dehydrated to MgOHCl at 180 ℃, and the reaction temperature is 200-230 ℃. At this temperature, anhydrous magnesium chloride loses its ability to absorb water and cannot remove the water of reaction. Calcium chloride is very easy to absorb water to form calcium chloride hexahydrate, becomes dihydrate at 200 ℃, and becomes white porous anhydrous calcium chloride after being heated to 260 ℃. The reaction temperature of the invention is 200 ℃, and at the temperature, the anhydrous calcium chloride has stronger water absorption capacity, and can remove water generated by the reaction in time, thereby promoting the forward progress of the reaction.
The invention has the beneficial effects that:
1. The method adopted by the invention is simple, the silicon dioxide carrier can be used for synthesizing the tetradecyloxy silane, and the recovered copper oxide has high purity, so that the method is a comprehensive utilization method of the Cu/SiO 2 waste catalyst with simple operation and low cost.
2. The method has the advantages of mild reaction conditions, safe operation, less byproducts and environmental friendliness.
Drawings
FIG. 1 is an infrared spectrum of the silicone monomer compound prepared in example 1.
FIG. 2 is an X-ray diffraction pattern of a standard card of solid and copper oxide obtained in example 1.
FIG. 3 is an infrared spectrum of the liquid obtained in comparative example 1.
FIG. 4 is an infrared spectrum of the liquid obtained in comparative example 2.
FIG. 5 is a photograph of a sample of spent catalyst.
Detailed description of the preferred embodiments
For a better understanding of the present invention, reference will now be made to the following examples, which are intended to illustrate the present invention and are not intended to represent or limit the scope of the invention, but are intended to provide a thorough understanding of the technical aspects and advantages of the present invention, as defined by the appended claims, by way of example only.
The spent catalyst sample shown in fig. 5 was ground to powder and then subjected to N 2 adsorption-desorption and wavelength dispersive X-ray fluorescence (XRF) analysis. The data of the N 2 adsorption and desorption test of the finely ground copper-containing dead catalyst are shown as follows:
The mass fractions of silicon, copper, aluminum and oxygen in the copper-containing spent catalyst are 33.3 wt%, 22.9 wt%, 0.02 wt%, 43.7 wt% and other unavoidable impurities respectively.
Example 1
2.02 G spent catalyst (using the above ground spent catalyst powder) was added to a two-necked flask containing excess n-decanol, then 2.53: 2.53 g anhydrous magnesium chloride and 8.31: 8.31 g anhydrous calcium chloride were added, replaced with carbon dioxide gas, and then reacted under reflux at 215 ℃ for 10 hours, after which the solids were not dissolved and heating was stopped. After nitrogen substitution, n-decanol was distilled off under reduced pressure at 190℃and the residue was dissolved with methyl tert-butyl ether and filtered, and the filtrate was distilled off under reduced pressure at 60℃to give 12.99 g as an oily liquid product with a silicon utilization of 82.3%. Washing the filter cake with water, adding the filter cake into a reaction bottle filled with 50 mL hydrochloric acid solution, stirring for more than 3h, filtering, dripping NaOH aqueous solution into the filtrate, adjusting the pH value to 9.5, stirring for 1 h, filtering, washing the filter cake with water, drying, weighing to obtain 0.53 g solid, and recovering 92% of copper. The solid material was analyzed by XRD as CuO.
The infrared spectrum of the oily liquid product is shown in figure 1. 1448 The methylene bending vibration peak is at cm -1, the methylene asymmetric stretching vibration peak is at 2975 cm -1, the methylene symmetric stretching vibration peak is at 2927 cm -1, the stretching vibration peaks of Si-O-C are at 1087 cm -1 and 877 cm -1, and the C-O bending vibration peak is at 1036 cm -1. 3255 The O-H stretching vibration peak is the hydroxyl peak of residual alcohol at cm -1. The product proved to be mainly tetradecyl orthosilicate. The XRD pattern of the solid is shown in figure 2, which is consistent with the standard card for copper oxide XRD, demonstrating that the solid is copper oxide.
Example 2
2.01 G spent catalyst (using the above ground spent catalyst powder) was added to a two-necked flask containing excess n-decanol, then 1.76 g anhydrous magnesium chloride and 10.02 g anhydrous calcium chloride were added, and after displacement with carbon dioxide gas, the reflux reaction was carried out at 232 ℃ for 10h, and the heating was stopped after the solids did not dissolve. The n-decanol was distilled off under reduced pressure at 200℃after nitrogen substitution, the residue was dissolved in isopropyl ether and filtered, and the filtrate was distilled off under reduced pressure at 60℃to give 13.30 g as an oily liquid product, the silicon utilization was 84.7%. Washing the filter cake with water, adding the filter cake into a reaction bottle filled with 50 mL hydrochloric acid solution, stirring for 3 to h, filtering, dripping NaOH aqueous solution into the filtrate, adjusting the pH value to 9.8, stirring for 1 to h, filtering, washing the filter cake with water, drying, weighing to obtain 0.52 g copper oxide, and the recovery rate of copper is 91.5%.
Example 3
3.21 G spent catalyst (using the above ground spent catalyst powder) was added to a two-necked flask containing excess n-decanol, 2.30 g anhydrous magnesium chloride and 18.31 g anhydrous calcium chloride were added, and after displacement with carbon dioxide gas, the reaction was refluxed at 232 ℃ for 10 h, and the heating was stopped after the solids did not dissolve. After nitrogen substitution, the residue was distilled to dryness under reduced pressure at 200℃and filtered after dissolution in methylene chloride, and the solvent was removed by distillation of the filtrate under reduced pressure at 60℃to give 20.60 g as an oily liquid product, the silicon utilization was 82.1%. Washing the filter cake with water, adding the filter cake into a reaction bottle filled with 50mL hydrochloric acid solution, stirring for more than 3 h, filtering, dripping KOH aqueous solution into the filtrate, adjusting the pH value to 10.1, stirring for 1 h, filtering, washing the filter cake with water, drying, weighing to obtain 0.80 g copper oxide, and obtaining the recovery rate of copper with 88%.
Example 4
2.02 G spent catalyst (using the above ground spent catalyst powder) was added to a two-necked flask containing excess n-decanol, followed by addition of 2.34 g magnesium chloride and 12.07 g anhydrous calcium chloride, displacement with carbon dioxide gas, reflux reaction at 215℃for 10 h, and distillation under reduced pressure at 190℃to remove n-decanol. To the residue was added an appropriate amount of dichloromethane, stirred at room temperature for 1. 1h, and then filtered, and the filtrate was distilled off under reduced pressure at 60℃to give 12.91 g as an oily liquid product, the recovery rate of silicon being 81.8%. Washing the filter cake with water, adding the filter cake into a reaction bottle filled with 50 mL hydrochloric acid solution, stirring for 3 to h, filtering, dripping KOH aqueous solution into the filtrate, adjusting the pH value to 10.9, stirring for 1 to h, filtering, washing the filter cake with water, drying, weighing to obtain 0.52 g copper oxide, wherein the recovery rate of copper is 90%.
Example 5
2.34 G spent catalyst (using the above ground spent catalyst powder) was added to a two-necked flask containing excess n-decanol, 3.61 g magnesium chloride and 5.63 g anhydrous calcium chloride were added, and after displacement with carbon dioxide gas, the reaction was refluxed at 215℃for 10 hours, and distilled off under reduced pressure at 190 ℃. To the residue was added an appropriate amount of methyl tert-butyl ether, stirred at room temperature for 1h and then filtered, and the filtrate was distilled off under reduced pressure at 60℃to give 14.86. 14.86 g as an oily liquid product, with a silicon recovery of 81.3%. Washing the filter cake with water, adding the filter cake into a reaction bottle filled with 50 mL hydrochloric acid solution, stirring for more than 3h, filtering, dripping NaOH aqueous solution into the filtrate, adjusting the pH value to 10.6, stirring for 1h, filtering, washing the filter cake with water, drying, weighing to obtain 0.61 g copper oxide, and the recovery rate of copper is 91%.
Comparative example 1
2.02 G spent catalyst (using the above ground spent catalyst powder) was added to a two-necked flask containing excess n-decanol, 2.34 g magnesium chloride was added, and after displacement with carbon dioxide gas, the reaction was refluxed at 215℃for 10 hours, and n-decanol was distilled off under reduced pressure at 190 ℃. To the residue was added an appropriate amount of methylene chloride, stirred at room temperature for 1h, and then filtered, and the filtrate was distilled off under reduced pressure at 60℃to obtain a small amount of liquid. The infrared analysis shows that the liquid is not the target product. In contrast to example 4, the target product could not be obtained by adding anhydrous magnesium chloride alone.
Comparative example 2
2.00 G spent catalyst (using the above ground spent catalyst powder) was added to a two-necked flask containing excess n-decanol, and 12.06 g anhydrous calcium chloride was replaced with carbon dioxide gas, and then reacted at 215℃under reflux for 10 hours, and distilled off under reduced pressure at 190 ℃. To the residue was added an appropriate amount of methylene chloride, stirred at room temperature for 1 h, and then filtered, and the filtrate was distilled off under reduced pressure at 60℃to obtain a small amount of liquid. The infrared analysis shows that the liquid is not the target product. In contrast to example 4, the target product could not be obtained by adding only anhydrous calcium chloride.
Comparative example 3
2.02 G spent catalyst (using the above ground spent catalyst powder) was added to a two-necked flask containing excess n-decanol, 12.69 g magnesium chloride was added, and after displacement with carbon dioxide gas, the reaction was refluxed at 215℃for 10 hours, and n-decanol was distilled off under reduced pressure at 190 ℃. To the residue was added an appropriate amount of methylene chloride, stirred at room temperature for 1h, and then filtered, and the filtrate was distilled off under reduced pressure at 60℃to obtain a small amount of liquid. The infrared analysis shows that the liquid is not the target product. In contrast to example 4, the substitution of anhydrous calcium chloride with equimolar amounts of anhydrous magnesium chloride did not result in the desired product.
Claims (9)
1. The comprehensive utilization method of the Cu/SiO 2 spent catalyst is characterized by comprising the following steps of: heating and refluxing the copper-containing spent catalyst, the n-decyl alcohol, the catalyst and the cocatalyst in the carbon dioxide atmosphere, distilling under reduced pressure to remove the solvent after the reaction is completed, adding a proper amount of organic solvent into the residue, stirring at room temperature, filtering, and heating and distilling the filtrate under reduced pressure to remove the organic solvent to obtain tetradecyloxy silane; washing the filter cake with water, adding into acid liquor, stirring, filtering, adding precipitator into the filtrate, regulating the pH value of the solution, stirring, filtering, washing and drying to obtain copper oxide.
2. The comprehensive utilization method of the Cu/SiO 2 waste catalyst according to claim 1, wherein the mass fractions of silicon, copper, aluminum and oxygen in the copper-containing waste catalyst are 25% -35%, 20% -30%, 0.01% -0.5% and 40% -45%, respectively.
3. The method for comprehensive utilization of Cu/SiO 2 spent catalyst according to claim 1, wherein the catalyst is anhydrous magnesium chloride and the cocatalyst is anhydrous calcium chloride.
4. The method for comprehensive utilization of Cu/SiO 2 spent catalyst according to claim 3, wherein the molar ratio of the copper-containing spent catalyst to anhydrous calcium chloride and anhydrous magnesium chloride is 1:2-5:0.5-1.5.
5. The method for comprehensive utilization of Cu/SiO 2 spent catalyst according to claim 1, wherein the reaction temperature is 200-230 ℃.
6. The method for comprehensively utilizing the Cu/SiO 2 spent catalyst according to claim 1, wherein the organic solvent is one or more of methyl tertiary butyl ether, isopropyl ether, methylene dichloride, chloroform, methanol, ethanol and tetrahydrofuran.
7. The method for comprehensively utilizing the Cu/SiO 2 spent catalyst according to claim 1, wherein the acid solution is one or more of hydrochloric acid solution, sulfuric acid solution and nitric acid solution.
8. The method for comprehensive utilization of Cu/SiO 2 spent catalyst according to claim 1, wherein the precipitant is one or both of sodium hydroxide and potassium hydroxide.
9. The method for comprehensive utilization of Cu/SiO 2 spent catalyst according to claim 1, wherein the pH value range is 9-11.
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| CN (1) | CN118183820A (en) |
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2024
- 2024-02-01 CN CN202410144491.0A patent/CN118183820A/en active Pending
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