CN112705274A - Catalyst regeneration and formaldehyde recovery method - Google Patents
Catalyst regeneration and formaldehyde recovery method Download PDFInfo
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- CN112705274A CN112705274A CN201911019846.9A CN201911019846A CN112705274A CN 112705274 A CN112705274 A CN 112705274A CN 201911019846 A CN201911019846 A CN 201911019846A CN 112705274 A CN112705274 A CN 112705274A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 267
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000011069 regeneration method Methods 0.000 title claims abstract description 41
- 230000008929 regeneration Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000011084 recovery Methods 0.000 title claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 9
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 238000004939 coking Methods 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 description 12
- -1 leatherworking Substances 0.000 description 8
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001107 thermogravimetry coupled to mass spectrometry Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- B01J38/02—Heat treatment
-
- 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
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/55—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of oligo- or polymeric oxo-compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- 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
A catalyst regeneration and formaldehyde recovery method, wherein the catalyst is used in a reaction taking formaldehyde as a reaction raw material, the method comprises the steps of roasting the catalyst in an environment containing regeneration gas, and then contacting the roasted gas with an absorption liquid to enable the absorption liquid to absorb the formaldehyde to obtain a recovery liquid containing the formaldehyde. The method can solve the problems of catalyst coking inactivation and low formaldehyde utilization rate in the process of preparing methyl acrylate by condensing methyl acetate and formaldehyde in the prior art.
Description
Technical Field
The invention relates to a catalyst regeneration and formaldehyde recovery method.
Background
Methyl acrylate is an important fine chemical raw material with wide application, is mainly used as an organic synthesis intermediate and a high molecular monomer, and a polymer prepared by taking methyl acrylate as the monomer is widely used in the industries of coatings, textiles, leatherworking, adhesives and the like.
The acrylic acid and its ester are produced mainly by the propylene oxidation method, the acrylonitrile hydrolysis method, the vinyl ketone method, the propane oxidation method, the methyl formate method, and the like. However, the methods have the defects of serious pollution, high energy consumption, low product yield and the like. Therefore, the development of a green and efficient new production process has very important significance.
The yield of methyl acetate in China is greatly surplus, and the green synthesis of methyl acrylate can be realized by taking industrial byproduct methyl acetate as a raw material, adopting a safe, environment-friendly and nontoxic solid base catalyst and a clean synthesis process.
At present, the research on the synthesis of methyl acrylate by taking methyl acetate and formaldehyde as raw materials is not industrialized, the research is only in the research stage at present, but the cost advantage is very obvious as a new process route, and the process is researched and developed by large-scale transnational chemical companies by investing manpower and material resources.
The process engineering research institute of Chinese academy of sciences reports that methyl acetate and formaldehyde are used as raw materials, and Cs-P/Al is used2O3The yield of the catalyst, namely methyl acrylate, reaches 40%, but the catalyst is quickly deactivated within 100h, and the stability needs to be further improved. In addition, there have been some studies on Cs-La-Sb/SiO2The catalyst is used for preparing methyl acrylate by gas-phase condensation of methyl acetate and formaldehyde, the yield of the methyl acrylate is 8-10%, but the yield is reduced to 5-6% after the reaction is carried out for 100 hours.
Because formaldehyde is easily polymerized into polyformaldehyde to be attached to the surface of the catalyst under the alkaline condition, the pore blocking is inactivated, and the long-term use effect of the catalyst is poor. Therefore, in order to utilize the catalyst more efficiently, catalyst regeneration is required.
Disclosure of Invention
The invention provides a catalyst regeneration and formaldehyde recovery method in order to regenerate a catalyst and recycle formaldehyde, which can solve the problems of coking and inactivation of the catalyst and low formaldehyde utilization rate in the process of preparing methyl acrylate by condensing methyl acetate and formaldehyde in the prior art.
The inventor of the present application found that the substance attached to the surface of the catalyst is mainly polyoxymethylene, that is, formaldehyde which does not participate in the reaction self-polymerizes, by conducting a nitrogen atmosphere TG-MS test on the coke-deactivated catalyst. The mass spectrum characteristic m/z ratio of formaldehyde is 28, 29 and 30, a large amount of gas is discharged when the temperature is raised to more than 300 ℃ under nitrogen atmosphere by combining TG-MS, and mass spectrum analysis is carried out on the discharged gas to find that a large amount of formaldehyde is generated, so that the surface of the catalyst is mainly polyoxymethylene.
According to the invention, a catalyst regeneration and formaldehyde recovery method is provided, wherein the catalyst is used in the reaction taking formaldehyde as a reaction raw material,
the method comprises the steps of roasting the catalyst in an environment containing regeneration gas, and then contacting the roasted gas with absorption liquid to enable the absorption liquid to absorb formaldehyde so as to obtain recovery liquid containing formaldehyde.
According to a preferred embodiment of the invention, the regeneration gas comprises one or more of nitrogen, water vapour, argon and helium, preferably nitrogen and/or helium.
According to a preferred embodiment of the present invention, the flow rate of the regeneration gas is 100-.
According to the preferred embodiment of the present invention, the temperature of the baking is 250-450 ℃, for example, 250 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃ and any value therebetween, preferably 300-360 ℃.
According to a preferred embodiment of the invention, the pressure of the calcination is between 0 and 1.0MPa, and may be, for example, 0, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1.0MPa and any value therebetween, preferably between 0 and 0.4 MPa.
According to a preferred embodiment of the present invention, the catalyst is calcined in an atmosphere containing a regeneration gas, and the calcination is preferably stopped when the formaldehyde content in the calcined gas is less than 0.005 mol%.
According to a preferred embodiment of the present invention, the catalyst is a solid base catalyst, preferably, the catalyst is a Cs-supported solid base catalyst. In the reaction taking formaldehyde as a raw material, the formaldehyde is easily polymerized into polyformaldehyde to be attached to the surface of the catalyst under an alkaline condition, so that the pore blocking and the inactivation are caused.
According to a preferred embodiment of the present invention, the method for regenerating the catalyst comprises: in the presence of regeneration gas, the temperature of the coking deactivated catalyst bed layer is raised, so that the coking substances on the surface of the catalyst are decomposed into formaldehyde, and the decomposed substance formaldehyde leaves the reactor along with the inert gas.
The inventor of the present application found that the substance attached to the surface of the catalyst is mainly polyoxymethylene, that is, formaldehyde which does not participate in the reaction self-polymerizes, by conducting a nitrogen atmosphere TG-MS test on the coke-deactivated catalyst. The mass spectrum characteristic m/z ratio of formaldehyde is 28, 29 and 30, a large amount of gas is discharged when the temperature is raised to more than 300 ℃ under nitrogen atmosphere by combining TG-MS, and mass spectrum analysis is carried out on the discharged gas to find that a large amount of formaldehyde is generated, so that the surface of the catalyst is mainly polyoxymethylene.
According to a preferred embodiment of the present invention, the absorption liquid comprises one or more of water, methanol and ethanol.
According to a preferred embodiment of the present invention, the absorption liquid is an aqueous solution of methanol, preferably, the mass concentration of methanol is 0.1-10%.
According to a preferred embodiment of the present invention, when the content of formaldehyde after the calcined gas is absorbed by the absorption liquid is higher than 0.0005 mol%, the absorption liquid is replaced.
According to the preferred embodiment of the invention, the catalyst is used in the reaction of methyl acetate and methyl acrylate prepared from formaldehyde.
According to a preferred embodiment of the invention, the catalyst is subjected to a regeneration treatment when the conversion of the feedstock drops below 70% of the initial conversion.
According to a preferred embodiment of the present invention, the method further comprises separating formaldehyde from the absorption liquid containing formaldehyde and using it as a reaction raw material.
The invention also provides a formaldehyde recovery system, which is used for recovering the formaldehyde attached to the surface of the catalyst after polymerization and reusing the formaldehyde in polymerization reaction, thereby improving the utilization rate of the formaldehyde.
According to a preferred embodiment of the invention, the formaldehyde recovery system comprises a gas inlet and a gas outlet connected to the absorber.
According to a preferred embodiment of the present invention, a sparger is provided in the absorber to allow more sufficient contact between the gas and the absorption liquid.
According to a preferred embodiment of the invention, the gas inlet is arranged at a lower end of the absorber and the gas outlet is arranged at an upper end of the absorber.
According to the preferred embodiment of the invention, the roasted gas is introduced into the absorber containing the absorption liquid from the gas inlet, the roasted gas is absorbed by the absorption liquid and then discharged from the gas outlet, the gas enters the evacuation line in two paths and is analyzed by gas chromatography, and when the content of formaldehyde in the gas absorbed by the absorption liquid is detected to exceed 0.005 mol%, the absorption liquid is replaced.
The method provided by the invention can effectively regenerate the solid base catalyst, and ensures the long-term stable operation of the catalyst. Meanwhile, unreacted formaldehyde can be recycled, and the utilization rate of raw materials is improved.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Example 1
1. Catalyst regeneration
10 g of catalyst to be regenerated is loaded into a regeneration reactor (the inner diameter is 16mm and the length is 1500mm), after three times of replacement by nitrogen, the reactor is heated to 300 ℃, nitrogen is introduced, the flow is 400mL/min, the pressure is 0.08MPa, the outlet formaldehyde concentration is measured every hour and kept for 12 hours, and finally the outlet formaldehyde concentration is measured to be 0.003 percent (mol), and the regeneration is finished.
2. Formaldehyde recovery
Introducing nitrogen containing formaldehyde into an absorber (with the inner diameter of 200mm and the length of 400mm, and containing 5 layers of distributors and 8 floating heads in each layer) at 150 ℃, wherein the absorption liquid is 5% methanol aqueous solution, measuring the concentration of the outlet formaldehyde per hour, keeping for 12 hours, and finally measuring the concentration of the outlet formaldehyde to be 0.002% (mol), and completing absorption.
Example 2
1. Catalyst regeneration
10 g of catalyst to be regenerated is loaded into a regeneration reactor (the inner diameter is 16mm and the length is 1500mm), after the catalyst is replaced by steam for three times, the temperature of the reactor is raised to 300 ℃, the steam is introduced, the flow rate is 400mL/min, the pressure is 0.08MPa, the concentration of the outlet formaldehyde is measured every hour and kept for 8 hours, and finally the concentration of the outlet formaldehyde is measured to be 0.002% (mol), and the regeneration is finished.
2. Formaldehyde recovery
Introducing water vapor containing formaldehyde into an absorber (with the inner diameter of 200mm and the length of 400mm, and containing 5 layers of distributors and 8 floating heads in each layer) under the condition of 150 ℃ heat tracing, wherein the absorption liquid is 5% methanol-containing aqueous solution, measuring the concentration of the formaldehyde at an outlet per hour, keeping the concentration for 8 hours, and finally measuring the concentration of the formaldehyde at the outlet to be 0.002% (mol), thus completing the absorption.
Example 3
1. Catalyst regeneration
10 g of catalyst to be regenerated is loaded into a regeneration reactor (the inner diameter is 16mm and the length is 1500mm), after the catalyst is replaced by water vapor for three times, the reactor is heated to 400 ℃, nitrogen is introduced, the flow is 400mL/min, the pressure is 0.08MPa, the concentration of the outlet formaldehyde is measured every hour and kept for 8 hours, and finally the concentration of the outlet formaldehyde is measured to be 0.002% (mol), and the regeneration is finished.
2. Formaldehyde recovery
Introducing water vapor containing formaldehyde into an absorber (with the inner diameter of 200mm and the length of 400mm, and containing 5 layers of distributors and 8 floating heads in each layer) under the condition of 150 ℃ heat tracing, wherein the absorption liquid is 5% methanol-containing aqueous solution, measuring the concentration of the formaldehyde at an outlet per hour, keeping the concentration for 8 hours, and finally measuring the concentration of the formaldehyde at the outlet to be 0.002% (mol), thus completing the absorption.
Example 4
1. Catalyst regeneration
10 g of catalyst to be regenerated is loaded into a regeneration reactor (the inner diameter is 16mm and the length is 1500mm), after three times of replacement by nitrogen, the reactor is heated to 300 ℃, nitrogen is introduced, the flow is 400mL/min, the pressure is 0.5MPa, the outlet formaldehyde concentration is measured per hour and kept for 16 hours, and finally the outlet formaldehyde concentration is measured to be 0.003 percent (mol), and the regeneration is finished.
2. Formaldehyde recovery
Introducing nitrogen containing formaldehyde into an absorber (with an inner diameter of 200mm and a length of 400mm, and containing 5 layers of distributors and 8 floating heads in each layer) at 150 ℃ under the condition of heat tracing, wherein the absorption liquid is 5% methanol-containing aqueous solution, measuring the concentration of the outlet formaldehyde per hour, keeping for 16 hours, and finally measuring the concentration of the outlet formaldehyde to be 0.001% (mol), and completing absorption.
Example 5
1. Catalyst regeneration
10 g of catalyst to be regenerated is loaded into a regeneration reactor (the inner diameter is 16mm and the length is 1500mm), after three times of replacement by nitrogen, the reactor is heated to 300 ℃, nitrogen is introduced, the flow is 1000mL/min, the pressure is 0.08MPa, the outlet formaldehyde concentration is measured every hour and kept for 12 hours, and finally the outlet formaldehyde concentration is measured to be 0.003 percent (mol), and the regeneration is finished.
2. Formaldehyde recovery
A formaldehyde-containing nitrogen gas was passed through an absorber (inner diameter 200mm, length 400mm, containing 5 layers of distributors, each layer containing 8 floating heads) at 150 ℃ with heat tracing, the absorption solution was a 5% methanol-containing aqueous solution, the outlet formaldehyde concentration was measured to be 0.01% (mol), an identical absorber was connected in series after that, the outlet formaldehyde concentration was measured to be 0.001% (mol), thereafter, the outlet formaldehyde concentration was measured every hour for 12 hours, and finally, the outlet formaldehyde concentration was measured to be 0.001% (mol), and the absorption was completed.
Example 6
1. Catalyst regeneration
10 g of catalyst to be regenerated is loaded into a regeneration reactor (the inner diameter is 16mm and the length is 1500mm), after three times of replacement by nitrogen, the reactor is heated to 300 ℃, nitrogen is introduced, the flow is 400mL/min, the pressure is 0.08MPa, the outlet formaldehyde concentration is measured every hour and kept for 12 hours, and finally the outlet formaldehyde concentration is measured to be 0.003 percent (mol), and the regeneration is finished.
2. Formaldehyde recovery
Introducing nitrogen containing formaldehyde into an absorber (with an inner diameter of 200mm and a length of 400mm, and containing 5 layers of distributors and 8 floating heads in each layer) at 150 ℃ under the condition of heat tracing, wherein the absorption liquid is 1% methanol-containing aqueous solution, measuring the concentration of the outlet formaldehyde per hour, keeping the concentration for 12 hours, and finally measuring the concentration of the outlet formaldehyde to be 0.001% (mol), and completing absorption.
Comparative example 1
10 g of the catalyst to be regenerated are loaded into a regeneration reactor (the inner diameter is 16mm and the length is 1500mm), after three times of replacement by nitrogen, the reactor is heated to 400 ℃, nitrogen (the flow rate is 400mL/min) and air (the flow rate is 20mL/min) are introduced, and the pressure is 0.08 MPa. When the bed temperature is close to 460 ℃, the air flow is reduced, when the bed has no hot spot and the bed temperature is lower than 460 ℃, the air flow is increased to 50mL/min, and the catalyst bed temperature can not exceed 460 ℃. When there was no temperature rise in the catalyst bed, the reactor was raised to 460 ℃ at 30 ℃/h and held for 4 hours. Analysis of reactor outlet gas composition, CO2The content is less than 0.3 percent (mol), the regeneration is completed, and the formaldehyde can not be recovered by the regeneration method.
Comparative example 2
The only difference from example 1 is that the absorption solution is a 1% sodium sulfite solution. Sodium sulfite reacts with formaldehyde to produce other substances, and the method cannot recover formaldehyde.
Comparative example 3
The only difference from example 1 is that the absorption solution is a 1% sodium hydroxide solution. Formaldehyde reacts with sodium hydroxide to produce methanol and sodium formate, which cannot be recovered.
Comparative example 4
The only difference from example 1 is that in the catalyst regeneration step, the reactor is warmed to 220 ℃ at which point the polyoxymethylene cannot depolymerize.
Comparative example 5
The only difference from example 1 is that in the catalyst regeneration step, the reactor was warmed to 500 c, at which temperature carbon deposits were generated after the catalyst was regenerated.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst regeneration and formaldehyde recovery method, wherein the catalyst is used in the reaction taking formaldehyde as reaction raw material,
the method comprises the steps of roasting the catalyst in an environment containing regeneration gas, and then contacting the roasted gas with absorption liquid to enable the absorption liquid to absorb formaldehyde so as to obtain recovery liquid containing formaldehyde.
2. The method of claim 1, wherein the regeneration gas comprises one or more of nitrogen, water vapor, argon and helium, preferably nitrogen and/or helium.
3. The method as claimed in claim 1 or 2, wherein the flow rate of the regeneration gas is 100-2000 mL/min.
4. The method of any of claims 1-3, wherein the firing conditions comprise: the temperature is 250 ℃ and 450 ℃, and/or the pressure is 0-1.0 MPa.
5. The process of any one of claims 1 to 4, wherein the catalyst is a solid base catalyst.
6. The method according to any one of claims 1 to 5, wherein the absorption liquid comprises one or more of water, methanol and ethanol.
7. The method according to any one of claims 1 to 6, wherein the absorption liquid is an aqueous solution of methanol.
8. The method according to claim 7, wherein the mass concentration of methanol is 0.1-10%.
9. The method according to any one of claims 1 to 8, wherein the catalyst is used in the reaction of methyl acetate and formaldehyde to methyl acrylate.
10. The process according to any one of claims 1 to 9, further comprising separating formaldehyde from the absorbing liquid containing formaldehyde and using it as a reaction raw material.
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