CN114054102B - Recovery and activation method of failure catalyst in DMMn synthesis process - Google Patents
Recovery and activation method of failure catalyst in DMMn synthesis process Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000004913 activation Effects 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 238000011084 recovery Methods 0.000 title claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 17
- 239000011973 solid acid Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 9
- 239000008213 purified water Substances 0.000 claims abstract description 9
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract 2
- 238000001914 filtration Methods 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052680 mordenite Inorganic materials 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 16
- 238000001994 activation Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000002283 diesel fuel Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005699 methyleneoxy group Chemical group [H]C([H])([*:1])O[*:2] 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the technical field of energy chemical catalysis, and provides a recovery and activation method of a failure catalyst in a DMMn synthesis process, which comprises the following steps: adding the spent catalyst into quantitative water, adding a certain amount of octyl phenol polyoxyethylene ether (OP-10) and a certain amount of polyvinyl alcohol (17-99, 17-88), adding sulfuric acid to adjust the PH value to 1, gradually heating to 50-60 ℃ to keep the PH value below 1, slowly stirring and activating for a certain time, cooling and filtering out the catalyst, adding purified water to wash to neutrality, and obtaining the solid acid catalyst with recovered activity.
Description
Technical Field
The invention belongs to the technical field of energy chemical catalysis, and particularly discloses a recovery and activation method of a failure catalyst in a DMMn synthesis process.
Background
Polymethoxy dimethyl ether, english name: polyoxymethylene dimethyl ethers, PODE or DMMn for short, is a low molecular weight acetal polymer with dimethoxy methane as a matrix and methyleneoxy as a main chain, and has the general formula shown as follows: CH3O (CH 2O) nCH3. Wherein, the polymethoxy dimethyl ether with the polymerization degree of 3-8 is abbreviated as DMM3-8, which is used for cleaning the blending components of diesel oil, the physical properties of the blending components are similar to those of the diesel oil, and the blending components are used in the diesel oil without modifying the oil supply system of the vehicle engine. The cetane number of the diesel oil is up to 76, the oxygen content is 47% -50%, the diesel oil is free of sulfur and aromatic hydrocarbon, 10% -20% of the diesel oil is blended in the diesel oil, the cold filter plugging point of the diesel oil can be obviously reduced, the combustion quality of the diesel oil in an engine can be improved, and the thermal efficiency is improved. Simultaneously, DMM3, DMM4 and DMM5 are also solvents with extremely strong dissolving capacity, and are applied to paint, coating, printing ink, adhesive, cleaning agent, electrolyte solvent and the like.
Polymethoxy dimethyl ether is generally prepared by reacting methanol or methylal with formaldehyde solution, gaseous formaldehyde, hemiacetal, trioxymethylene or paraformaldehyde in the presence of an acidic catalyst, and the reaction basic equation is as follows:
the solid acid catalyst is only applied to the synthesis and production of polymethoxy dimethyl ether in a plurality of acid catalysts, has various advantages, has no corrosion to equipment (fixed bed catalysis and fluidized bed catalysis can be arranged), generates no waste water, is environment-friendly, can be applied to various forms (powdery, annular, rod-shaped, spherical and granular, fibrous and the like), can be repeatedly used and easily regenerated after being deactivated, and has great industrial application prospect; however, the existing solid acid catalysts have some disadvantages: the catalytic capability of the fresh catalyst is higher, after a period of time, the catalyst is easy to deactivate and the acid strength is reduced due to aggregation of macromolecular polymers in a reaction system and the blocking effect of colloidal particles floating in materials on the surface and pore channels of the catalyst, if the reaction is continued, the reaction is incomplete, the impurities are more, the single-pass conversion rate is reduced, and the energy consumption is increased.
In order to fully exert the catalytic action of the solid acid catalyst on the polymethoxy dimethyl ether industrialization road, the method has great significance for effectively regenerating the deactivated catalyst.
Disclosure of Invention
1. The invention aims to: the invention aims to provide a recovery and activation method of a spent catalyst in a DMMn synthesis process, which can clean macromolecular polymers and colloid particles attached to and hidden in the surface and the inside of catalyst particles under the condition of not damaging the basic structure of the catalyst, so that the activity of the catalyst is recovered as before. The whole process is operated in a suspension state, and the method has the advantages of easily available raw materials, no toxic or side effect, small wastewater pollution, safety and environmental protection and suitability for industrial production.
2. The technical scheme is as follows: according to the recovery and activation method of the spent catalyst in the DMMn synthesis process, the spent catalyst is added into quantitative water, a certain amount of octyl phenol polyoxyethylene ether (OP-10) is added as an excellent surfactant and a dispersing agent to promote the close combination and cleaning action of all components in an activation system, a certain amount of polyvinyl alcohol (17-99, 17-88) is added to play a thickening role, so that catalyst particles are not damaged by collision under stirring, sulfuric acid is added to adjust the PH value to 1, the temperature is gradually increased to an activation temperature and kept below the PH value, the decomposition and dissolution effects on polyformaldehyde and colloid substances in the catalyst are achieved through the strong acidity of sulfuric acid, after the catalyst is slowly stirred and activated for a certain time, the catalyst is cooled and filtered, purified water is added to wash the catalyst to neutrality, and the solid acid catalyst with recovered activity is obtained.
3. The technical effects are as follows: according to the recovery and activation method of the failure catalyst in the DMMn synthesis process, under the condition that the basic structure of the catalyst is not damaged, macromolecular polymers and colloid particles adhered to and hidden in the surface and the interior of catalyst particles are cleaned, so that the activity of the catalyst is recovered as before. The whole process runs in a suspension state, and has no damage to catalyst particles, and the method has the advantages of easily available raw materials, convenient industrialization realization, low wastewater pollution, safety and environmental protection, and is suitable for industrial production. Solves the basic problem of recovery and activation of the dead solid acid catalyst in the current polymethoxy dimethyl ether synthesis process.
The specific aspects are as follows:
(1) The invention adopts water as a medium for recycling the deactivated catalyst, and has the advantages of safety, environmental protection, good effect, low cost and the like;
(2) According to the invention, octyl phenol polyoxyethylene ether (OP-10) is used as a surfactant and a dispersing agent, so that the close combination and the rapid cleaning action of all components in an activation reaction system are promoted;
(3) According to the invention, polyvinyl alcohol (17-99, 17-88) is used as a thickening agent, so that catalyst particles can not collide and be damaged under long-term stirring;
(4) The invention adopts sulfuric acid as a catalytic activating reagent, plays a role in decomposing and dissolving polyformaldehyde and colloid matters in the catalyst, and does not change the property of the catalyst or dissolve the catalyst, so that the activating work cannot be performed.
4. The specific embodiments of the present invention are as follows:
example 1: 100 g of spent catalyst (sulfonate resin, after drying, the content of detected acid is 12.2%) is added into 300ml of water, then 3 g of octyl phenol polyoxyethylene ether (OP-10) and 3 g of polyvinyl alcohol (17-99, 17-88) are added, stirring and dissolving are carried out, then sulfuric acid (50%) is added to adjust the PH value to be below 1, the temperature is gradually increased to 60 ℃, the PH value is kept below 1, after slow stirring and activation is carried out for 24 hours, the catalyst is cooled and filtered, 100ml of purified water is added for washing 5-10 times each time to neutrality, and the solid acid catalyst with recovered activity (after drying, the content of detected acid is 21.2%) is obtained.
Example 2: 100 g of spent catalyst (sulfonate resin, after drying, the content of detected acid is 12.2%) is added into 300ml of water, then 3 g of octyl phenol polyoxyethylene ether (OP-10) and 3 g of polyvinyl alcohol (17-99, 17-88) are added, stirring and dissolving are carried out, then sulfuric acid (50%) is added to adjust the PH value to be below 1, the temperature is gradually increased to 60 ℃, the PH value is kept below 1, after the slow stirring and activation is carried out for 48 hours, the catalyst is cooled and filtered, 100ml of purified water is added for washing 5-10 times each time to be neutral, and the solid acid catalyst with recovered activity (after drying, the content of detected acid is 23.3%) is obtained.
Example 3: 100 g of spent catalyst (sulfonate resin, after drying, the content of detected acid is 12.2%) is added into 300ml of water, then 3 g of octyl phenol polyoxyethylene ether (OP-10) and 3 g of polyvinyl alcohol (17-99, 17-88) are added, stirring and dissolving are carried out, then sulfuric acid (50%) is added to adjust the PH value to be below 1, the temperature is gradually increased to 60 ℃, the PH value is kept below 1, after the slow stirring and activation is carried out for 96 hours, the catalyst is cooled and filtered, 100ml of purified water is added for washing 5-10 times each time to be neutral, and the solid acid catalyst with recovered activity (after drying, the content of detected acid is 24.8%) is obtained.
Example 4: (comparative example) 100 g of spent catalyst (sulfonate, after drying, acid content was detected 12.2%) was added to 300ml of water, then 3 g of octylphenol polyoxyethylene ether (OP-10) was added, stirred and dissolved, then sulfuric acid (50%) was added to adjust the pH to less than 1, gradually heated to 60 ℃ and kept at pH below 1, and after slow stirring and activation for 48 hours, the catalyst was cooled and filtered, washed 5-10 times to neutrality each time with 100ml of purified water, and a solid acid catalyst with recovered activity (after drying, acid content was detected 23.8%, and more powder had broken down from the catalyst) was obtained.
Example 5: (comparative example) 100 g of spent catalyst (sulfonate, acid content 12.2% after drying) was added to 300ml of water, 3 g of polyvinyl alcohol (17-99, 17-88) was added, stirred and dissolved, sulfuric acid (50%) was added to adjust the pH to below 1, gradually heated to 60 ℃ and kept at pH below 1, stirred and activated slowly for 48 hours, and then cooled and filtered off, and washed 5-10 times to neutrality with 100ml of purified water each time to obtain a solid acid catalyst with recovered activity (acid content 17.6% after drying).
Example 6: (comparative example) 100 g of spent catalyst (sulfonate, after drying, acid content was detected 12.2%) was added to 300ml of water, 3 g of octylphenol polyoxyethylene ether (OP-10), and 3 g of polyvinyl alcohol (17-99, 17-88) were added, stirred and dissolved, gradually warmed to 60 ℃ and kept at pH below 1, and after slow stirring and activation for 48 hours, the catalyst was cooled and filtered, washed 5-10 times to neutrality with 100ml of purified water each time, to obtain a solid acid catalyst with recovered activity (acid content detected 18.5% after drying).
The invention solves the problems of incomplete reaction of the synthetic solution, more impurities, reduced single pass conversion, increased energy consumption, high catalyst unit consumption, delayed production of the disassembled catalyst and the like caused by the reduction of the catalytic activity of the catalyst after a period of use of the catalyst when the solid acid catalyst is used for catalytic synthesis in the process of producing the polymethoxy dimethyl ether by taking one or more of paraformaldehyde, trioxymethylene, formaldehyde aqueous solution, methanol, methylal, dimeric formaldehyde dimethyl ether and the like as raw materials at present. The invention cleans out macromolecular polymer and colloid particles adhered and hidden on the surface and inside of the catalyst particles under the condition of not damaging the basic structure of the catalyst by a special formula and an activation process, so that the activity of the catalyst is recovered as before. The whole process is operated in a suspension state, and the method has the advantages of easily available raw materials, no toxic or side effect, small wastewater pollution, safety and environmental protection and suitability for industrial production.
Finally, the following is to be described: the foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but although the present invention has been described in detail with reference to the foregoing examples, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for recovering and activating a spent catalyst in a DMMn synthesis process comprises the following steps: adding the spent catalyst into quantitative water, adding a certain amount of octyl phenol polyoxyethylene ether-10 and a certain amount of polyvinyl alcohol with the product specification of 17-99 and 17-88, adding sulfuric acid to adjust the PH value to 1, gradually heating to an activation temperature and keeping the PH value below 1, stirring the activation temperature to 30-100 ℃, slowly stirring and activating for a certain time, cooling, filtering out the catalyst, adding purified water, washing to neutrality, and obtaining the solid acid catalyst with recovered activity.
2. A method for recovering and activating spent catalyst in DMMn synthesis procedures as claimed in claim 1, wherein said spent catalyst comprises: titanium silicalite, mordenite, large Kong Huangsuan resin, modified macroporous acidic sulfonic acid resin, silica gel particles having sulfuric acid adsorbed thereto, and mixtures thereof.
3. The method for recovering and activating a spent catalyst in a DMMn synthesis process according to claim 1, wherein the amount of water added is 1 to 20 times the volume of the spent catalyst.
4. The method for recovering and activating the spent catalyst in the DMMn synthesis process according to claim 1, wherein the adding amount of the octyl phenol polyoxyethylene ether is 1-10% of the weight of the spent catalyst.
5. The method for recovering and activating a spent catalyst in a DMMn synthesis process according to claim 1, wherein the polyvinyl alcohol is added in an amount of 0.5 to 20% by weight of the spent catalyst.
6. A method for recovering and activating a spent catalyst in a DMMn synthesis process as claimed in claim 1, wherein the stirring and activating time is 12-240 hours.
7. A process for the recovery and activation of spent catalyst in a DMMn synthesis process as claimed in claim 1, wherein the pH at activation is from-1 to 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2020107415491 | 2020-07-29 | ||
| CN202010741549 | 2020-07-29 |
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| CN114054102B true CN114054102B (en) | 2023-11-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008022900A1 (en) * | 2006-08-25 | 2008-02-28 | Basell Poliolefine Italia S.R.L. | Preparation of a catalytic paste for the olefin polymerization |
| CN106669864A (en) * | 2016-12-27 | 2017-05-17 | 环境保护部华南环境科学研究所 | Method for recycling and regenerating invalid denitration catalyst |
| CN106732656A (en) * | 2016-12-27 | 2017-05-31 | 浙江新和成股份有限公司 | A kind of biotin intermediate is hydrogenated with the process for reactivation of palladium carbon catalyst |
| CN106861775A (en) * | 2017-01-09 | 2017-06-20 | 中国科学院福建物质结构研究所 | A kind of activating and regenerating method of CO synthesizing dimethyl oxalates decaying catalyst |
| CN109529880A (en) * | 2018-12-19 | 2019-03-29 | 浙江常山科润新材料有限公司 | A kind of regeneration method of catalyst |
-
2020
- 2020-08-13 CN CN202010810945.5A patent/CN114054102B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008022900A1 (en) * | 2006-08-25 | 2008-02-28 | Basell Poliolefine Italia S.R.L. | Preparation of a catalytic paste for the olefin polymerization |
| CN106669864A (en) * | 2016-12-27 | 2017-05-17 | 环境保护部华南环境科学研究所 | Method for recycling and regenerating invalid denitration catalyst |
| CN106732656A (en) * | 2016-12-27 | 2017-05-31 | 浙江新和成股份有限公司 | A kind of biotin intermediate is hydrogenated with the process for reactivation of palladium carbon catalyst |
| CN106861775A (en) * | 2017-01-09 | 2017-06-20 | 中国科学院福建物质结构研究所 | A kind of activating and regenerating method of CO synthesizing dimethyl oxalates decaying catalyst |
| CN109529880A (en) * | 2018-12-19 | 2019-03-29 | 浙江常山科润新材料有限公司 | A kind of regeneration method of catalyst |
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