CN114700108B - Method for removing carbon deposition in deactivated propylene titanium oxide silicon molecular sieve catalyst - Google Patents
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- CN114700108B CN114700108B CN202210359060.7A CN202210359060A CN114700108B CN 114700108 B CN114700108 B CN 114700108B CN 202210359060 A CN202210359060 A CN 202210359060A CN 114700108 B CN114700108 B CN 114700108B
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008021 deposition Effects 0.000 title claims abstract description 20
- -1 deactivated propylene titanium oxide silicon Chemical class 0.000 title claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 68
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 21
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 4
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 230000001939 inductive effect Effects 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 38
- 229910052719 titanium Inorganic materials 0.000 claims description 37
- 239000010936 titanium Substances 0.000 claims description 35
- 238000006735 epoxidation reaction Methods 0.000 claims description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- NCDCHVDCHMNCCB-UHFFFAOYSA-N prop-1-ene;titanium Chemical class [Ti].CC=C NCDCHVDCHMNCCB-UHFFFAOYSA-N 0.000 claims description 4
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 2
- 101710154778 Thymidylate synthase 1 Proteins 0.000 description 23
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- OUGQFBYPDNWTGC-UHFFFAOYSA-N hydrogen peroxide 2-methyloxirane Chemical compound OO.CC1CO1 OUGQFBYPDNWTGC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- 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
- B01J38/70—Wet oxidation of material submerged in liquid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for removing carbon deposition in an inactivated propylene titanium oxide silicon molecular sieve catalyst, which specifically comprises the following steps: soaking the inactivated propylene titanium oxide silicon molecular sieve catalyst containing carbon deposition into a low-concentration hydrogen peroxide aqueous solution, dropwise adding an acetone solution of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide at a lower temperature of not more than 50 ℃ under the irradiation of ultraviolet light of 360-405 nm, dissociating the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide under the action of the ultraviolet light to generate free radicals, inducing the hydrogen peroxide to generate active hydroxyl free radicals, and oxidizing and degrading to remove the activated propylene titanium oxide silicon molecular sieve carbon deposition, so that the catalyst is recovered to activity. The method provided by the invention has the advantages that the hydrogen peroxide concentration is low, the treatment temperature is low, and the serious problems of waste gas pollution, potential safety hazard, high energy consumption and the like in the existing carbon deposit removal process by adopting the roasting technology and the high-concentration hydrogen peroxide oxidation technology are solved.
Description
Technical Field
The invention relates to a method for removing carbon deposition in an inactivated propylene titanium silicalite molecular sieve catalyst, in particular to a method for removing carbon deposition in an inactivated TS-1 titanium silicalite molecular sieve catalyst in propylene epoxidation reaction.
Background
The TS-1 type titanium-silicon molecular sieve is an MFI structure transition metal heteroatom molecular sieve containing framework titanium atoms, and has unique shape-selecting function, excellent stability and hydrophobicity of the MFI structure high-silicon molecular sieve, and the titanium active site is opposite to H 2 O 2 Has unique adsorption and activation properties, thus can be used in a plurality ofThe organic compound has high catalytic oxidation activity in the reaction, high product selectivity, mild reaction conditions, no pollution emission in the whole catalytic oxidation process, and good application prospect as a catalyst. In the presence of hydrogen peroxide, TS-1 titanium-silicon molecular sieve has been used for catalyzing propylene epoxidation to synthesize epoxypropane, catalyzing phenol hydroxylation to prepare o (p) benzene diphenol, and catalyzing cyclohexanone ammoximation to prepare cyclohexanone oxime.
When the TS-1 type titanium-silicon molecular sieve is used as a catalyst to run for a certain time in the epoxidation reaction of hydrogen peroxide propylene oxide, by-products are easily gathered in the micropore channels of the TS-1 type titanium-silicon molecular sieve to cover the titanium atom active sites, so that reactant molecules are difficult to contact with the titanium atom active sites to perform the catalytic reaction, and the capability of the TS-1 type titanium-silicon molecular sieve to catalyze the epoxidation reaction of hydrogen peroxide propylene oxide is obviously reduced, thereby inactivating the molecular sieve.
In the existing regeneration technology of the TS-1 titanium silicalite molecular sieve deactivated in the epoxidation reaction of propylene, methods such as roasting, oxide oxidation, solvent washing and the like are generally adopted. EPO100119 adopts titanium-silicon molecular sieve to catalyze propylene to epoxidize to prepare propylene oxide, which adopts a method of washing two molecular sieves to regenerate respectively by roasting at 550 ℃ and using methanol or solvent used in the reaction process. USP 6878836B 2 discloses a method for regeneration by high temperature methanol washing, which uses a washing temperature of 100 ℃ or higher to wash the deactivator with methanol.
In addition, CN101602011a discloses a regeneration method of deactivated titanium silicalite molecular sieve Ti-MWW treated with acid and alkali solutions. However, the method is complicated in operation process, needs repeated filtration and washing, generates a large amount of industrial wastewater containing acid, ammonia nitrogen and the like, and has higher energy consumption and poorer economical efficiency.
Disclosure of Invention
The invention aims to provide an environment-friendly, safe and more efficient method for removing carbon deposition in an inactivated propylene titanium oxide silicon molecular sieve catalyst based on the prior art. The invention is characterized in that the deactivated titanium-silicon molecular sieve catalyst containing carbon deposit is soaked into hydrogen peroxide solution under the irradiation of ultraviolet light and heated for a certain time, and the carbon deposit is oxidized, degraded and removed under the combined action of the ultraviolet light and the hydrogen peroxide.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for removing carbon deposition in an inactivated propylene titanium oxide silicon molecular sieve catalyst comprises the following steps: soaking the inactivated propylene titanium silicon oxide molecular sieve catalyst containing carbon deposition into hydrogen peroxide water solution, slowly stirring, dropwise adding an acetone solution of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide at a lower temperature under the irradiation of ultraviolet light, dissociating the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide under the action of the ultraviolet light to generate free radicals, inducing the hydrogen peroxide to generate active hydroxyl free radicals, and oxidizing and degrading to remove the carbon deposition of the inactivated propylene titanium silicon oxide molecular sieve, so that the catalyst is recovered.
Further, carbon deposition in the deactivated propylene epoxidation titanium silicalite molecular sieve catalyst is TS-1 titanium silicalite molecular sieve catalyst which is used for catalyzing propylene epoxidation, and organic matters remained on the surface of the molecular sieve or/and in the pore canal.
Further, the concentration of the aqueous hydrogen peroxide solution is 1 to 5%, preferably 2 to 3% by mass of hydrogen oxide.
Further, the amount of the aqueous hydrogen peroxide solution is 10 to 20 times, preferably 14 to 16 times, the mass of the deactivated propylene titanium silicon oxide molecular sieve catalyst.
Further, the ultraviolet light has a wavelength of 360 to 405nm, preferably 360 to 365nm.
Further, the ultraviolet irradiance is 50 to 500 milliwatts per square meter, preferably 150 to 300 milliwatts per square meter.
Further, the lower temperature is 10 to 50 ℃, preferably 20 to 35 ℃.
Further, the method has a carbon deposit removal time of 20 to 60 minutes, preferably 30 to 45 minutes, at a relatively low temperature.
Further, the concentration of the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide in the acetone solution of the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide is 4 to 8 percent, preferably 5 to 7 percent, by mass fraction.
Further, the acetone solution of the phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide is used in an amount of 2 to 5 percent, preferably 3 to 4 percent, of the mass of the aqueous hydrogen peroxide solution.
Compared with the prior art, the invention has the beneficial effects that:
the method solves the serious problems of waste gas pollution, potential safety hazard, high energy consumption and the like in the existing carbon deposit removal process by adopting a roasting technology and a high-concentration hydrogen peroxide oxidation technology.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of a deactivated TS-1 type titanium silicalite catalyst after propylene epoxidation reaction in comparative example 1;
FIG. 2 is a Fourier transform infrared spectrum of the unused TS-1 type titanium silicalite catalyst of comparative example 2;
FIG. 3 is a Fourier transform infrared spectrum of the regenerated TS-1 type titanium silicalite catalyst obtained in comparative example 3;
FIG. 4 is a Fourier transform infrared spectrum of a regenerated TS-1 type titanium silicalite catalyst obtained in example 1;
FIG. 5 is a Fourier transform infrared spectrum of a regenerated TS-1 type titanium silicalite catalyst obtained in example 2;
FIG. 6 is a Fourier transform infrared spectrum of a regenerated TS-1 type titanium silicalite catalyst obtained in example 3;
FIG. 7 is a Fourier transform infrared spectrum of a regenerated TS-1 type titanium silicalite catalyst obtained in example 4;
FIG. 8 is a Fourier transform infrared spectrum of a regenerated TS-1 type titanium silicalite catalyst obtained in example 5;
FIG. 9 is a Fourier transform infrared spectrum of a regenerated TS-1 type titanium silicalite catalyst obtained in example 6.
Detailed Description
The technical solution and effects of the present invention will be further described with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited thereto.
In the following comparative examples and examples, the reagents used were all commercially available chemically pure reagents.
Comparative example 1
The inactivated TS-1 titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of the propylene oxide with hydrogen peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven, and the Fourier transform infrared spectrum is shown in figure 1 of the accompanying drawings.
Comparative example 2
The Fourier transform infrared spectrum of the unused TS-1 type titanium silicalite molecular sieve catalyst is shown in figure 2 of the accompanying drawings.
Comparative example 3
The inactivated TS-1 titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of the propylene oxide with hydrogen peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven and baked for 5 hours at 500 ℃ in an air atmosphere, and the Fourier transform infrared spectrum is shown in figure 3 of the accompanying drawings.
Example 1
The TS-1 titanium silicalite molecular sieve catalyst deactivated after the epoxidation reaction of the propylene oxide by catalytic hydrogen peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven. 10 g of dried inactivated TS-1 titanium silicalite molecular sieve raw powder is soaked in 150 g of 3% hydrogen peroxide aqueous solution, heated to 35 ℃, and under the irradiation of ultraviolet light with the radiation intensity of 300 milliwatts per square meter and the wavelength of 360-365 nm, 6 g of acetone solution containing 6% of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide is dropwise added under stirring for 45min, and the mixture is filtered and dried, and a sample is taken for Fourier transform infrared spectrum test, wherein the obtained spectrum is shown in figure 4.
Example 2
The TS-1 titanium silicalite molecular sieve catalyst deactivated after the epoxidation reaction of the propylene oxide by catalytic hydrogen peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven. 10 g of dried inactivated TS-1 titanium silicalite molecular sieve raw powder is soaked in 200 g of 5% hydrogen peroxide aqueous solution, heated to 50 ℃, and 4 g of acetone solution containing 8% of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide is dropwise added under stirring under the irradiation of ultraviolet light with the radiation intensity of 500 milliwatts per square meter and the wavelength of 405nm, the treatment lasts for 20min, the filtration and the drying are carried out, a sample is taken for carrying out a Fourier transform infrared spectrum test, and a spectrum obtained by the test is shown in figure 5 of the accompanying drawings.
Example 3
The TS-1 titanium silicalite molecular sieve catalyst deactivated after the epoxidation reaction of the propylene oxide by catalytic hydrogen peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven. 10 g of dried inactivated TS-1 titanium silicalite molecular sieve raw powder is soaked in 200 g of 5% hydrogen peroxide aqueous solution, heated to 50 ℃, and under the irradiation of ultraviolet light with the radiation intensity of 50 milliwatts per square meter and the wavelength of 360-365 nm, 8 g of acetone solution containing 4% of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide is dropwise added under stirring for 20min, and the solution is filtered and dried, and a sample is taken for Fourier transform infrared spectrum test, wherein the obtained spectrum is shown in figure 6.
Example 4
The TS-1 titanium silicalite molecular sieve catalyst deactivated after the epoxidation reaction of the propylene oxide by catalytic hydrogen peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven. 10 g of dried inactivated TS-1 titanium silicalite molecular sieve raw powder is soaked in 200 g of 1% hydrogen peroxide aqueous solution, heated to 40 ℃, and under the irradiation of ultraviolet light with the radiation intensity of 500 milliwatts per square meter and the wavelength of 360-365 nm, 6 g of acetone solution containing 6% of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide is dropwise added under stirring for 60min, and the solution is filtered and dried, and a sample is taken for Fourier transform infrared spectrum test, wherein the obtained spectrum is shown in figure 7.
Example 5
The TS-1 titanium silicalite molecular sieve catalyst deactivated after the epoxidation reaction of the propylene oxide by catalytic hydrogen peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven. 10 g of dried inactivated TS-1 titanium silicalite molecular sieve raw powder is soaked in 200 g of 1% hydrogen peroxide aqueous solution, cooled to 10 ℃, and 8 g of acetone solution containing 6% of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide is dropwise added under stirring under the irradiation of ultraviolet light with the radiation intensity of 500 milliwatts per square meter and the wavelength of 360-365 nm, the treatment lasts for 60min, the filtration and the drying are carried out, a sample is taken for carrying out Fourier transform infrared spectrum test, and a graph obtained by the test is shown in figure 8 of the accompanying drawings.
Example 6
The TS-1 titanium silicalite molecular sieve catalyst deactivated after the epoxidation reaction of the propylene oxide by catalytic hydrogen peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven. 10 g of dried inactivated TS-1 titanium silicalite molecular sieve raw powder is soaked in 200 g of 4% hydrogen peroxide aqueous solution, heated to 40 ℃, and under the irradiation of ultraviolet light with the radiation intensity of 500 milliwatts per square meter and the wavelength of 360-365 nm, 8 g of acetone solution containing 6% of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide is dropwise added under stirring for 20min, and the solution is filtered and dried, and a sample is taken for Fourier transform infrared spectrum test, wherein the obtained spectrum is shown in figure 9.
Example 7
This example illustrates the effect of the ultra-fine titanium silicalite molecular sieves obtained by the methods of the present invention and the comparative examples for the catalytic reaction of propylene epoxidation. The titanium silicon molecular sieves separated and recovered in the above examples and comparative examples were placed in a high-pressure reaction kettle with a polytetrafluoroethylene lining according to the weight ratio of titanium silicon molecular sieves to methanol to hydrogen peroxide to water=1:96:4.5:12, magnetically stirred, heated to 45 ℃, then propylene was introduced to a pressure of 0.6Mpa in a stirred state, and reacted for 1 hour, and the reaction results are shown in table 1.
TABLE 1 results of the epoxidation of propylene with the titanium silicalite molecular sieves separated and recovered in the examples and comparative examples
In table 1, hydrogen peroxide conversion= (amount of hydrogen peroxide added-amount of residual hydrogen peroxide) amount of hydrogen peroxide added x 100%;
propylene oxide yield = amount of propylene oxide forming substance/amount of hydrogen peroxide added x 100%;
selectivity of propylene oxide = amount of propylene oxide forming substance/(amount of propylene oxide forming substance + amount of by-product forming substance) ×100%.
As can be seen from Table 1, the method for removing carbon deposition in the deactivated propylene epoxidized titanium silicalite catalyst according to the present invention has similar catalytic performance to the unused TS-1 type titanium silicalite catalyst described in comparative example 2 after the deactivated molecular sieve catalyst is regenerated, and has similar or better catalytic performance than the regenerated molecular sieve catalyst described in comparative example 3, but the regeneration method of the present invention does not require high-temperature calcination of the deactivated molecular sieve catalyst, and the operation method is simpler and safer, thereby obtaining the beneficial effects of the present invention.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. A method for removing carbon deposition in an inactivated propylene titanium oxide silicon molecular sieve catalyst is characterized by comprising the following steps: soaking an inactivated propylene titanium silicon oxide molecular sieve catalyst containing carbon deposition into a hydrogen peroxide water solution, slowly stirring, dropwise adding an acetone solution of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide at a lower temperature under the irradiation of ultraviolet light, dissociating the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide under the action of the ultraviolet light to generate free radicals, inducing the hydrogen peroxide to generate active hydroxyl free radicals, and oxidizing and degrading to remove the carbon deposition of the inactivated propylene titanium silicon oxide molecular sieve to restore the activity of the catalyst;
the carbon deposition in the deactivated propylene epoxidation titanium silicalite molecular sieve catalyst is TS-1 titanium silicalite molecular sieve catalyst which is used for catalyzing propylene epoxidation, and organic matters remained on the surface of the molecular sieve or/and in the pore canal;
the concentration of the hydrogen peroxide aqueous solution is 2-3% by mass of hydrogen peroxide;
the ultraviolet light wavelength is 360-405 nm;
the irradiance of the ultraviolet light is 50-500 milliwatts per square meter;
the lower temperature is 10-50 ℃;
the concentration of the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide in the acetone solution of the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide is 4-8% in mass fraction;
the dosage of the acetone solution of the phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide is 2-5% of the mass of the hydrogen peroxide water solution.
2. The method for removing carbon deposition in the deactivated propylene titanium silicalite molecular sieve catalyst according to claim 1, wherein the amount of the aqueous hydrogen peroxide solution is 10-20 times the mass of the deactivated propylene titanium silicalite molecular sieve catalyst.
3. The method for removing carbon deposition in an inactivated propylene titanium silicalite molecular sieve catalyst according to claim 1, wherein the carbon deposition removal time is 20-60 min at a lower temperature.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101346364A (en) * | 2005-12-20 | 2009-01-14 | 利安德化学技术有限公司 | Process for oxidizing organic compounds |
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| CN105413745A (en) * | 2015-12-28 | 2016-03-23 | 郑州大学 | Method for removing carbon deposit from deactivated titanium silicalite molecular sieve catalyst |
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