CN115805103A - Regeneration method of deactivated titanium-silicon molecular sieve - Google Patents
Regeneration method of deactivated titanium-silicon molecular sieve Download PDFInfo
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- 238000011069 regeneration method Methods 0.000 title claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 title abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title abstract description 7
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical class [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000605 extraction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003607 modifier Substances 0.000 claims abstract description 24
- 230000008929 regeneration Effects 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 238000000194 supercritical-fluid extraction Methods 0.000 claims abstract description 11
- 230000001172 regenerating effect Effects 0.000 claims abstract description 5
- HQALDKFFRYFTKP-UHFFFAOYSA-N 2-[4-[4-(2-benzyl-1-benzothiophen-3-yl)phenyl]-2-bromo-6-(3-methoxyphenyl)phenoxy]acetic acid Chemical compound COC1=CC=CC(C=2C(=C(Br)C=C(C=2)C=2C=CC(=CC=2)C=2C3=CC=CC=C3SC=2CC=2C=CC=CC=2)OCC(O)=O)=C1 HQALDKFFRYFTKP-UHFFFAOYSA-N 0.000 claims abstract description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- BLKPORNCZKTARK-UHFFFAOYSA-N O[S+]1C2=CC=CC=C2C=C1 Chemical compound O[S+]1C2=CC=CC=C2C=C1 BLKPORNCZKTARK-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- DOFIAZGYBIBEGI-UHFFFAOYSA-N 3-sulfanylphenol Chemical compound OC1=CC=CC(S)=C1 DOFIAZGYBIBEGI-UHFFFAOYSA-N 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001347 alkyl bromides Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 15
- 238000005805 hydroxylation reaction Methods 0.000 abstract description 11
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 239000012530 fluid Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241001122767 Theaceae Species 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 1
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 description 1
- 241001657422 Camellia petelotii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007262 aromatic hydroxylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006146 oximation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Classifications
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a method for regenerating an inactivated titanium-silicon molecular sieve (TS-1) catalyst, which aims at the characteristic that the catalyst is easy to adsorb tar and is inactivated in the phenol hydroxylation reaction process, and realizes effective extraction of the tar by utilizing the better solubility of supercritical carbon dioxide and adding a small amount of extraction modifier, thereby achieving the aim of regenerating the catalyst. In addition, the invention provides a novel synthesis method of the extraction modifier, so that the benzothiophene derivative is synthesized and applied to supercritical extraction. The whole regeneration process is carried out in the reactor, continuous reaction is realized, the operation is simple, the complex catalyst dismounting and mounting process is avoided, and the performance of the regenerated catalyst can reach the level of a fresh catalyst.
Description
Technical Field
The invention relates to a regeneration method of an inactivated titanium silicalite molecular sieve, in particular to a titanium silicalite molecular sieve which is suitable for a phenol hydroxylation reaction.
Background
Titanium silicalite molecular sieve (TS-1) is a catalyst with high-efficiency type-selective oxidation, is a typical MFI structure and is firstly synthesized by Taramasso et al in 1983. Under the action of TS-1, the hydrogen peroxide can selectively oxidize reactants to generate target products, has the characteristics of mild reaction conditions, high yield and the like, and is widely applied to the fields of propylene epoxidation, aromatic hydroxylation, amine oximation and the like.
Pyrocatechol and hydroquinone are important chemical products, wherein the hydroquinone is a high-efficiency polymerization inhibitor, and the pyrocatechol is a main raw material for preparing spices such as vanillin and the like. Phenol and hydrogen peroxide are subjected to hydroxylation reaction under the catalytic action of TS-1, so that the method is a green and efficient production process for preparing the benzenediol, and is gradually applied industrially in recent years. A large amount of tar can be generated in the phenol hydroxylation reaction process, most of the tar is macromolecular phenolic substances, and the tar can be adsorbed on the surface of the TS-1 catalyst to block inner and outer pore channels of the catalyst, so that the catalyst is quickly inactivated and needs to be regenerated.
From the industrial application perspective and catalyst cost considerations, it is of great significance to find an efficient and economical catalyst regeneration process. Chinese patent CN102941117A adopts solvent such as cumene to clean deactivated catalyst bed layer, and completes regeneration of titanium-silicon molecular sieve catalyst; US patent US6878836B2 discloses a method for washing deactivated catalyst with a high temperature solvent, which achieves catalyst regeneration with methanol solvent at 100 ℃. The two solvent regeneration methods are both used for dissolving the blocked macromolecular phenolic substances in the catalyst by using an organic solvent so as to achieve the purpose of regenerating the catalyst, but the method is only suitable for the regeneration of the catalyst in the propylene epoxidation field, has the characteristics of large tar generation amount, complex structure and large molecular weight in the phenol hydroxylation field, and is difficult to realize the regeneration of the catalyst by only washing with the solvent.
Supercritical fluid is a fluid with properties between gas and liquid when a substance is in a state above the critical temperature and critical pressure. It has both good diffusion capacity similar to gas and good dissolving capacity similar to liquid, and is used for extracting some insoluble organic matters. CN107913530A utilizes supercritical carbon dioxide to extract tea polyphenol from camellia chrysantha leaves, the tea polyphenol is a general name of polyphenol substances in the tea leaves, and can be well dissolved in supercritical fluid, and patent CN20041083885 discloses a method for regenerating a catalyst by supercritical fluid: the deactivated catalyst is placed in an extraction kettle, supercritical carbon dioxide is used as an extracting agent to extract the deactivated catalyst, unsaturated olefin adsorbed on the catalyst is dissolved, and the regeneration of the catalyst can also be realized. However, the carbon dioxide fluid only extracts substances with small molecular weight and low polarity, and the extraction effect is relatively common for large conjugated phenols and polar substances.
In view of the above, the present invention uses supercritical fluid to extract the phenol tar in the deactivated catalyst, so as to realize the regeneration of the catalyst.
Disclosure of Invention
Aiming at the characteristics of large tar generation amount and large molecular weight in the phenol hydroxylation reaction process, the invention provides a novel catalyst regeneration method, which utilizes the supercritical fluid and simultaneously adds a small amount of extraction modifier to better dissolve tar adsorbed on the catalyst, thereby showing active sites on the catalyst and participating in the reaction again to achieve the purpose of catalyst regeneration.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
(1) Washing the deactivated catalyst with solvent, stoving and crushing;
(2) Adding the crushed catalyst into a supercritical extraction kettle, continuously introducing carbon dioxide and an extraction modifier, raising the temperature to a specified temperature and pressure, and performing supercritical extraction;
(3) Opening an outlet valve, taking out tar along with the supercritical fluid, controlling the gas outlet rate to maintain the pressure and the temperature in the kettle unchanged, and completing the regeneration of the catalyst after extracting for a period of time.
In the method of the present invention, the solvent for washing in step (1) is selected from toluene, tetrahydrofuran, acetone, DMF, DMAC, MIBK, water, preferably toluene and/or acetone. The mass ratio of the washing solvent to the deactivated catalyst is 10-50:1;
in the process of the present invention, in the step (1), the deactivated catalyst is pulverized into fine particles having a size of 50 to 100 mesh.
In the method, in the step (2), the extraction temperature is 35-55 ℃, and preferably 40-50 ℃; the pressure is 25-40MPa, preferably 30-35MPa.
In the method, the extraction modifier is continuously injected into the supercritical extraction kettle, and the mass flow rate is 0.5-5g/h, preferably 1-3g/h.
In the method, after the supercritical extraction is stable, the gas inlet rate is equal to the gas outlet rate, and the gas outlet rate is 1-10L/min, preferably 2-6L/min.
In the method of the invention, in the step (3), the supercritical extraction time is 2-30h, preferably 5-15h.
In the method, the extraction modifier is a benzothiophene extraction modifier, and the synthetic route is as follows:
3-mercaptophenol reacts with acetylene to obtain 1-hydroxybenzothiophene, and then reacts with long-chain bromohydrocarbon to generate benzothiophene derivatives, wherein R represents an alkyl chain with 6-10 carbon atoms, and the introduction of R can greatly improve the solubility of the modifier.
In the step of synthesizing the extraction modifier, the reaction temperature of the 3-mercaptophenol and the acetylene is 40-100 ℃, and the preferable reaction temperature is 50-70 ℃; the reaction pressure is 0.1-2MPa, preferably 0.5-1.5MPa; the reaction time is 10-70min, preferably 30-50min.
In the step of synthesizing the extraction modifier, the mass ratio of the 1-hydroxybenzothiophene to the bromoalkane is 1: (2-8), preferably 1: (3-5).
The brominated alkane is represented by Br-R, wherein R represents an alkyl chain with the carbon number of 6-10, and can be bromohexane, bromoheptane, bromooctane, bromononane and bromodecane.
In the step of synthesizing the extraction modifier, the reaction solvent of the 1-hydroxybenzothiophene and the brominated alkane is water, acetone, ethanol, DMF and the like.
In the step of synthesizing the extraction modifier, the reaction conditions of the 1-hydroxybenzothiophene and the alkyl bromide are normal temperature and normal pressure, and the reaction time is 3-8h, preferably 4-6h.
The invention has the beneficial effects that:
according to the characteristics of tar, the invention introduces a novel benzothiophene extraction modifier, and introduces long-chain alkane on benzothiophene, so that the solubility in carbon dioxide can be improved, and the extraction effect on tar is improved to a great extent. The whole regeneration process can be carried out in the reactor, continuous reaction is realized, the operation is simple, the complex catalyst disassembly and assembly processes are avoided, and the performance of the regenerated catalyst can reach the level of a fresh catalyst.
Detailed Description
The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.
The phenol hydroxylation reaction conditions are as follows: reaction temperature is 60-70 ℃, pressure is slight positive pressure, phenol: the molar ratio of hydrogen peroxide is 4.
After the continuous reaction is operated for a period of time, the catalyst TS-1 (medium petrochemical, changling petrochemical, HTS) begins to be coked and deactivated, the utilization rate of hydrogen peroxide is reduced from about 90% in the initial stage to about 60%, and the deactivated catalyst needs to be regenerated.
The instrument used for characterization of the invention is liquid chromatography, and the elution solvent is acetonitrile and water.
Example 1:
120g of 3-mercaptophenol is added into a reaction kettle, the temperature is raised to 50 ℃, acetylene is introduced to 0.5MPa, and 1-hydroxybenzothiophene is obtained after reaction for 50min. And then 130g of 1-hydroxybenzothiophene and 300g of octyl bromide are dissolved in acetone, reacted for 4 hours at normal temperature, and purified to obtain a benzothiophene derivative which is used as an extraction modifier for the following extraction.
100g of the deactivated TS-1 catalyst is taken, washed by 1000g of toluene, dried and crushed into particles of 100 meshes, and then the particles are added into a high-pressure reaction kettle. Raising the temperature of the reaction kettle to 55 ℃, introducing carbon dioxide gas and benzothiophene derivatives, wherein the introducing speed of the benzothiophene derivatives is 5g/h, opening and stirring when the pressure is increased to 25MPa, slowly opening an exhaust valve, controlling the gas discharge speed to be 5L/min by using a flowmeter, maintaining the pressure and the temperature in the reaction kettle unchanged, taking out tar along with the supercritical fluid, closing a carbon dioxide gas inlet valve after extracting for 15h, closing a heating button, and completing the regeneration of the catalyst.
The regenerated catalyst was taken out for performance evaluation. Thermogravimetric analysis (TGA): before and after the catalyst regeneration, the thermal weight loss is reduced by 94.8% before 600 ℃, and tar is effectively removed. The regenerated catalyst is introduced into the raw materials for the phenol hydroxylation reaction, and the utilization rate of hydrogen peroxide reaches 88.3 percent.
Example 2:
120g of 3-mercapto phenol is added into a reaction kettle, the temperature is raised to 90 ℃, acetylene is introduced to 1MPa, and 1-hydroxybenzothiophene is obtained after 15min of reaction. And then 130g of 1-hydroxybenzothiophene and 900g of bromohexane are dissolved in ethanol, react for 6 hours at normal temperature, and are purified to obtain benzothiophene derivatives which are used as extraction modifiers in the following extraction.
100g of the inactivated TS-1 catalyst is taken, washed by 4000g of DMF, dried and crushed into particles of 50 meshes, and then the particles are added into a high-pressure reaction kettle. Raising the temperature of the reaction kettle to 35 ℃, introducing carbon dioxide gas and an extraction modifier, wherein the introduction speed of the modifier is 1g/h, opening the stirring when the pressure is increased to 38MPa, slowly opening an exhaust valve, controlling the gas discharge speed to be 2L/min by using a flowmeter, maintaining the pressure and the temperature in the reaction kettle unchanged, taking out tar along with the supercritical fluid, closing a carbon dioxide gas inlet valve after extracting for 5h, closing a heating button, and finishing the regeneration of the catalyst.
The regenerated catalyst was taken out for performance evaluation. Thermogravimetric (TGA) analysis: before and after the catalyst is regenerated, the thermal weight loss is reduced by 98.9 percent before 600 ℃, and tar is effectively removed. The regenerated catalyst is introduced into the raw materials for the phenol hydroxylation reaction, and the utilization rate of hydrogen peroxide reaches 90.3 percent.
Example 3:
120g of 3-mercapto phenol is added into a reaction kettle, the temperature is raised to 70 ℃, acetylene is introduced to 1.7MPa, and 1-hydroxybenzothiophene is obtained after 15min of reaction. And then dissolving 130g of 1-hydroxybenzothiophene and 650g of bromodecane in DMF, reacting for 8h at normal temperature, purifying to obtain benzothiophene derivatives, and applying the benzothiophene derivatives as an extraction modifier in the following extraction.
100g of the deactivated TS-1 catalyst is washed by 2000g of MIBK, dried and crushed into particles of 50 meshes, and then the particles are added into a high-pressure reaction kettle. Raising the temperature of the reaction kettle to 35 ℃, introducing carbon dioxide gas and an extraction modifier, wherein the introduction speed of the modifier is 1g/h, opening the stirring when the pressure is increased to 32MPa, slowly opening an exhaust valve, controlling the gas discharge speed to be 3L/min by using a flowmeter, maintaining the pressure and the temperature in the reaction kettle unchanged, taking out tar along with the supercritical fluid, closing a carbon dioxide gas inlet valve after extracting for 8 hours, closing a heating button, and finishing the regeneration of the catalyst.
The regenerated catalyst was taken out for performance evaluation. Thermogravimetric (TGA) analysis: before and after the catalyst is regenerated, the thermal weight loss is reduced by 93.6 percent before 600 ℃, and tar is effectively removed. The regenerated catalyst is introduced into the raw materials for the phenol hydroxylation reaction, and the utilization rate of hydrogen peroxide reaches 88.5 percent.
Comparative example 1
100g of the deactivated TS-1 catalyst is washed by 3000g of acetone, dried and crushed into particles of 30 meshes, and then the particles are added into a high-pressure reaction kettle. Raising the temperature of the reaction kettle to 45 ℃, introducing carbon dioxide gas, adding no extraction modifier, opening the stirrer when the pressure is increased to 30MPa, slowly opening an exhaust valve, controlling the gas exhaust speed to be 5L/min by using a flowmeter, maintaining the pressure and the temperature in the reaction kettle unchanged, bringing out tar along with the supercritical fluid, extracting for 10 hours, closing a carbon dioxide gas inlet valve, closing a heating button, and finishing the regeneration of the catalyst.
The regenerated catalyst was taken out for performance evaluation. Thermogravimetric analysis (TGA): before and after the catalyst regeneration, the thermal weight loss is reduced by 77.5 percent before 600 ℃, and tar is removed. The regenerated catalyst is introduced into the raw materials for the phenol hydroxylation reaction, and the utilization rate of hydrogen peroxide reaches 78.2 percent.
Claims (10)
1. A benzothiophene derivative having the structure:
2. A process for preparing benzothiophene derivatives as defined in claim 1, which comprises:
3-mercapto phenol reacts with acetylene to obtain 1-hydroxy benzothiophene, and then reacts with alkyl bromide to generate benzothiophene derivatives.
3. The method according to claim 2, wherein the reaction temperature of the 3-mercaptophenol and acetylene is 40-100 ℃, the reaction pressure is 0.1-2MPa, and the reaction time is 10-70min.
4. The method according to claim 2 or 3, wherein the mass ratio of the 1-hydroxybenzothiophene to the brominated alkane is 1: (2-8) the reaction time is 3-8h.
5. A method for regenerating a deactivated titanium silicalite catalyst, comprising:
(1) Washing the deactivated catalyst with solvent, stoving and crushing;
(2) Adding the crushed catalyst into a supercritical extraction kettle, continuously introducing carbon dioxide and an extraction modifier, raising the temperature to a certain temperature and pressure, and performing supercritical extraction; wherein the extraction modifier is the benzothiophene derivative of any one of claims 1 to 4;
(3) Controlling the gas outlet speed to maintain the pressure and the temperature in the kettle unchanged, and completing the regeneration of the catalyst after extracting for a period of time.
6. The process according to claim 5, wherein the solvent in step (1) is selected from the group consisting of toluene, tetrahydrofuran, acetone, DMF, DMAC, MIBK, water,
preferably, the mass ratio of the solvent to the deactivated catalyst is 10-50:1.
7. the process according to claim 5 or 6, wherein in the step (2), the extraction temperature is 35-55 ℃ and the pressure is 25-40MPa.
8. The process as claimed in any one of claims 5 to 7, wherein the mass flow rate of the extraction modifier into the supercritical extraction vessel is from 0.5 to 5g/h.
9. The process of any one of claims 5 to 8, wherein the inlet gas rate is equal to the outlet gas rate after the supercritical extraction has stabilized, and is in the range of 1 to 10L/min.
10. The process according to any one of claims 5 to 9, wherein the supercritical extraction time is from 2 to 30h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111075668.9A CN115805103B (en) | 2021-09-14 | 2021-09-14 | Regeneration method of deactivated titanium-silicon molecular sieve |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111075668.9A CN115805103B (en) | 2021-09-14 | 2021-09-14 | Regeneration method of deactivated titanium-silicon molecular sieve |
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| Publication Number | Publication Date |
|---|---|
| CN115805103A true CN115805103A (en) | 2023-03-17 |
| CN115805103B CN115805103B (en) | 2024-04-09 |
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Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992003427A1 (en) * | 1990-08-17 | 1992-03-05 | Yoshitomi Pharmaceutical Industries, Ltd. | Ketone compound and remedy for osteoporosis |
| WO2001047632A1 (en) * | 1999-12-28 | 2001-07-05 | Basf Aktiengesellschaft | Method for regenerating catalyzers |
| US6291685B1 (en) * | 1999-08-02 | 2001-09-18 | Hoffmann-La Roche Inc. | Methods for the preparation of 4-hydroxybenzothiophene |
| CN1762600A (en) * | 2004-10-22 | 2006-04-26 | 中国石油化工股份有限公司 | A kind of method of reproducing catalyst by supercritical fluid |
| CN1762601A (en) * | 2004-10-22 | 2006-04-26 | 中国石油化工股份有限公司 | A kind of process of reproducing catalyst by supercritical fluid |
| CN101255352A (en) * | 2008-04-21 | 2008-09-03 | 大连理工大学 | Method for removing sulfides in gasoline by oxidation-absorption under mild conditions |
| JP2008272646A (en) * | 2007-04-27 | 2008-11-13 | Shimane Univ | Hydrogenation catalyst re-activation method and manufacturing method of hydrogenation catalyst |
| CN101508691A (en) * | 2003-05-16 | 2009-08-19 | 特拉梅克斯实验室 | Sulphaminic acid benzothiophene ester derivative used as steroid sulfatase restrainer |
| JP2011057575A (en) * | 2009-09-07 | 2011-03-24 | Nippon Nohyaku Co Ltd | Manufacturing method of 4-hydroxybenzothiophene derivative |
| CN102019209A (en) * | 2009-09-11 | 2011-04-20 | 尤雷卡特股份公司 | Method for sulphidation of hydrocarbon processing catalysts |
| JP2011190306A (en) * | 2010-03-12 | 2011-09-29 | Jx Nippon Oil & Energy Corp | Method for producing kerosine-gas oil base material and alkylbenzenes |
| US20140066525A1 (en) * | 2012-02-29 | 2014-03-06 | Peter J. Tijm | Methods for improving higher alcohol yields from syngas by altering flow regimes within a reactor |
| CN105399736A (en) * | 2016-01-07 | 2016-03-16 | 安徽省逸欣铭医药科技有限公司 | Novel preparation method of brexpiprazole |
| CN106062965A (en) * | 2014-03-03 | 2016-10-26 | 富士胶片株式会社 | Organic thin film transistor and method for manufacturing same |
| US20170096407A1 (en) * | 2014-05-05 | 2017-04-06 | Novomer, Inc. | Catalyst recycle methods |
| 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 |
| CN108325567A (en) * | 2018-03-12 | 2018-07-27 | 河南工业大学 | A kind of regeneration method of supported ruthenium catalyst |
| CN110484346A (en) * | 2019-09-18 | 2019-11-22 | 中国人民解放军陆军勤务学院 | Based on supercritical CO2Regenerate the method for waste lubricating oil |
| CN112675907A (en) * | 2021-01-08 | 2021-04-20 | 中国科学院大连化学物理研究所 | In-situ combined regeneration method of deactivated titanium-silicon molecular sieve catalyst |
| CN113304773A (en) * | 2021-05-19 | 2021-08-27 | 万华化学集团股份有限公司 | In-situ regeneration method of deactivated titanium-silicon molecular sieve |
| CN114797967A (en) * | 2022-05-26 | 2022-07-29 | 岳阳长旺化工有限公司 | Regeneration method of deactivated catalyst, regenerated catalyst and application of regenerated catalyst |
-
2021
- 2021-09-14 CN CN202111075668.9A patent/CN115805103B/en active Active
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992003427A1 (en) * | 1990-08-17 | 1992-03-05 | Yoshitomi Pharmaceutical Industries, Ltd. | Ketone compound and remedy for osteoporosis |
| US6291685B1 (en) * | 1999-08-02 | 2001-09-18 | Hoffmann-La Roche Inc. | Methods for the preparation of 4-hydroxybenzothiophene |
| WO2001047632A1 (en) * | 1999-12-28 | 2001-07-05 | Basf Aktiengesellschaft | Method for regenerating catalyzers |
| CN101508691A (en) * | 2003-05-16 | 2009-08-19 | 特拉梅克斯实验室 | Sulphaminic acid benzothiophene ester derivative used as steroid sulfatase restrainer |
| CN1762600A (en) * | 2004-10-22 | 2006-04-26 | 中国石油化工股份有限公司 | A kind of method of reproducing catalyst by supercritical fluid |
| CN1762601A (en) * | 2004-10-22 | 2006-04-26 | 中国石油化工股份有限公司 | A kind of process of reproducing catalyst by supercritical fluid |
| JP2008272646A (en) * | 2007-04-27 | 2008-11-13 | Shimane Univ | Hydrogenation catalyst re-activation method and manufacturing method of hydrogenation catalyst |
| CN101255352A (en) * | 2008-04-21 | 2008-09-03 | 大连理工大学 | Method for removing sulfides in gasoline by oxidation-absorption under mild conditions |
| JP2011057575A (en) * | 2009-09-07 | 2011-03-24 | Nippon Nohyaku Co Ltd | Manufacturing method of 4-hydroxybenzothiophene derivative |
| CN102019209A (en) * | 2009-09-11 | 2011-04-20 | 尤雷卡特股份公司 | Method for sulphidation of hydrocarbon processing catalysts |
| JP2011190306A (en) * | 2010-03-12 | 2011-09-29 | Jx Nippon Oil & Energy Corp | Method for producing kerosine-gas oil base material and alkylbenzenes |
| US20140066525A1 (en) * | 2012-02-29 | 2014-03-06 | Peter J. Tijm | Methods for improving higher alcohol yields from syngas by altering flow regimes within a reactor |
| CN106062965A (en) * | 2014-03-03 | 2016-10-26 | 富士胶片株式会社 | Organic thin film transistor and method for manufacturing same |
| US20170096407A1 (en) * | 2014-05-05 | 2017-04-06 | Novomer, Inc. | Catalyst recycle methods |
| CN105399736A (en) * | 2016-01-07 | 2016-03-16 | 安徽省逸欣铭医药科技有限公司 | Novel preparation method of brexpiprazole |
| 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 |
| CN108325567A (en) * | 2018-03-12 | 2018-07-27 | 河南工业大学 | A kind of regeneration method of supported ruthenium catalyst |
| CN110484346A (en) * | 2019-09-18 | 2019-11-22 | 中国人民解放军陆军勤务学院 | Based on supercritical CO2Regenerate the method for waste lubricating oil |
| CN112675907A (en) * | 2021-01-08 | 2021-04-20 | 中国科学院大连化学物理研究所 | In-situ combined regeneration method of deactivated titanium-silicon molecular sieve catalyst |
| CN113304773A (en) * | 2021-05-19 | 2021-08-27 | 万华化学集团股份有限公司 | In-situ regeneration method of deactivated titanium-silicon molecular sieve |
| CN114797967A (en) * | 2022-05-26 | 2022-07-29 | 岳阳长旺化工有限公司 | Regeneration method of deactivated catalyst, regenerated catalyst and application of regenerated catalyst |
Non-Patent Citations (2)
| Title |
|---|
| ACS: "RN:2161772-71-8", ACS, pages 30 * |
| TONY Y ET AL.: "Recent Advances in the Synthesis and Applications of Benzo[b]thiophenes", 《SULFUR REPORTS》, vol. 22, pages 1 - 49 * |
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