CN114700108A - Method for removing carbon deposition in inactivated propylene epoxy titanium silicalite molecular sieve catalyst - Google Patents
Method for removing carbon deposition in inactivated propylene epoxy titanium silicalite molecular sieve catalyst Download PDFInfo
- Publication number
- CN114700108A CN114700108A CN202210359060.7A CN202210359060A CN114700108A CN 114700108 A CN114700108 A CN 114700108A CN 202210359060 A CN202210359060 A CN 202210359060A CN 114700108 A CN114700108 A CN 114700108A
- Authority
- CN
- China
- Prior art keywords
- propylene
- deactivated
- molecular sieve
- carbon deposition
- titanium silicalite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 70
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 67
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 62
- 239000010936 titanium Substances 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 230000008021 deposition Effects 0.000 title claims abstract description 31
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 31
- 239000004593 Epoxy Substances 0.000 title claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 20
- 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
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 230000001939 inductive effect Effects 0.000 claims abstract description 3
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 3
- -1 deactivated propylene titanium oxide silicon Chemical class 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 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
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 101710154778 Thymidylate synthase 1 Proteins 0.000 description 19
- 238000001157 Fourier transform infrared spectrum Methods 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 11
- BFFQFGGITJXTFP-UHFFFAOYSA-N 3-methyldioxetane Chemical compound CC1COO1 BFFQFGGITJXTFP-UHFFFAOYSA-N 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 239000000203 mixture Substances 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
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater 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
- 230000001590 oxidative effect Effects 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
- NCDCHVDCHMNCCB-UHFFFAOYSA-N prop-1-ene;titanium Chemical class [Ti].CC=C NCDCHVDCHMNCCB-UHFFFAOYSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 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
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
Images
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
- 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
Landscapes
- 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 a deactivated propylene epoxidation titanium silicalite molecular sieve catalyst, which comprises the following steps: soaking the deactivated propylene epoxy titanium silicon molecular sieve catalyst containing carbon deposition into a low-concentration hydrogen peroxide aqueous solution, dripping 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 hydrogen peroxide to generate active hydroxyl free radicals, and removing the deactivated propylene epoxy titanium silicon molecular sieve carbon deposition through oxidative degradation to restore the activity of the catalyst. The method of the invention uses low hydrogen peroxide concentration and low treatment temperature, and solves the serious problems of waste gas pollution, potential safety hazard, high energy consumption and the like in the existing carbon deposition removing process by adopting a roasting technology and a high-concentration hydrogen peroxide oxidation technology.
Description
Technical Field
The invention relates to a method for removing carbon deposition in a deactivated propylene epoxidation titanium silicalite molecular sieve catalyst, in particular to a method for removing carbon deposition in a deactivated TS-1 titanium silicalite molecular sieve catalyst in a propylene epoxidation reaction.
Background
The TS-1 type titanium-silicon molecular sieve is a transition metal heteroatom molecular sieve with MFI structure containing framework titanium atoms, and has the unique shape-selective action, excellent stability and hydrophobicity of the MFI structure high-silicon molecular sieve and the titanium active site pair H2O2Has unique adsorption and activation performance, thereby having very high catalytic oxidation activity in the reaction of various organic compounds, high product selectivity, mild reaction conditions, no pollution emission in the whole catalytic oxidation process and good application prospect when being used as a catalyst. Under the existence of hydrogen peroxide, the TS-1 type titanium silicalite molecular sieve is used for catalyzing propylene to be epoxidized to synthesize propylene oxide, catalyzing phenol to be hydroxylated to prepare o- (p) -benzenediol, catalyzing cyclohexanone to be ammoximated to prepare cyclohexanone oxime and the like, and the industrial application is realized.
The active sites of the TS-1 type titanium silicalite molecular sieves are isolated titanium atoms on the framework, most of the active sites are located in a microporous structure (the aperture is only about 0.55 nm), and when the TS-1 type titanium silicalite molecular sieves are used as catalysts to operate for a certain time in the epoxidation reaction of propylene peroxide, the TS-1 type titanium silicalite molecular sieves are difficult to contact with the titanium atom active sites to generate the catalytic reaction because byproducts are easy to gather in the microporous pore channels of the TS-1 type titanium silicalite molecular sieves and cover the titanium atom active sites, so that the capability of the TS-1 type titanium silicalite molecular sieves for catalyzing the epoxidation reaction of propylene peroxide is obviously reduced, and the molecular sieves are inactivated.
The existing regeneration technology of the TS-1 type titanium silicalite molecular sieve inactivated in the epoxidation reaction of propylene generally adopts methods such as roasting, oxide oxidation, solvent washing and the like. EPO100119 adopts a titanium silicalite molecular sieve to catalyze propylene to epoxidize to prepare propylene oxide, and adopts two molecular sieve regeneration methods of high-temperature roasting at 550 ℃ and methanol or solvent washing used in the reaction process respectively. USP 6878836B 2 discloses a method for high temperature washing regeneration with methanol, which uses a washing temperature above 100 ℃ to wash the deactivator with methanol.
In addition, CN101602011A discloses a regeneration method of deactivated Ti-MWW by treating with acid and alkali solution. However, the method has the disadvantages of complicated operation process, repeated filtration and washing, high energy consumption and poor economical efficiency, and generates a large amount of industrial wastewater containing acid, ammonia nitrogen and the like.
Disclosure of Invention
The invention aims to provide a method for removing carbon deposition in a deactivated propylene epoxidized titanium silicalite molecular sieve catalyst, which is environment-friendly, safe and more efficient on the basis of the prior art. The method comprises the steps of soaking the deactivated titanium-silicon molecular sieve catalyst containing carbon deposition in a hydrogen peroxide solution under the irradiation of ultraviolet light, heating for a certain time, and oxidizing, degrading and removing the carbon deposition under the combined action of the ultraviolet light and the hydrogen peroxide.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for removing carbon deposition in a deactivated propylene epoxidized titanium silicalite molecular sieve catalyst specifically comprises the following steps: soaking the deactivated propylene epoxy titanium silicon molecular sieve catalyst containing carbon deposition into aqueous hydrogen peroxide solution, slowly stirring, dripping 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 hydrogen peroxide to generate active hydroxyl free radicals, and removing the carbon deposition of the deactivated propylene epoxy titanium silicon molecular sieve through oxidative degradation to restore the activity of the catalyst.
Further, carbon deposition in the deactivated propylene epoxidation titanium silicalite molecular sieve catalyst is TS-1 type titanium silicalite molecular sieve catalyst used for catalyzing organic matters remained on the surface of the molecular sieve or/and in the pore channel after propylene epoxidation.
Further, the concentration of the aqueous hydrogen peroxide solution is 1 to 5%, preferably 2 to 3%, in terms of the mass fraction of hydrogen oxide.
Further, the amount of the aqueous hydrogen peroxide solution is 10-20 times, preferably 14-16 times, the mass of the deactivated propylene epoxidized titanium silicalite molecular sieve catalyst.
Further, the wavelength of the ultraviolet light is 360-405 nm, and preferably 360-365 nm.
Further, the ultraviolet light irradiation is 50 to 500 milliwatts per square meter, preferably 150 to 300 milliwatts per square meter.
Further, the lower temperature is 10-50 ℃, and preferably 20-35 ℃.
Further, the method is used for removing carbon deposition at a lower temperature for 20-60 min, preferably 30-45 min.
Furthermore, 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 in mass fraction.
Further, the acetone solution of the phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is used in an amount of 2 to 5 percent, preferably 3 to 4 percent, based on the mass of the aqueous hydrogen peroxide solution.
Compared with the prior art, the invention has the beneficial effects that:
the method disclosed by the invention has the advantages that the concentration of the hydrogen peroxide 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 process of removing carbon deposition by adopting a roasting technology and a high-concentration hydrogen peroxide oxidation technology in the prior art are solved.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of a deactivated TS-1 type titanium silicalite molecular sieve catalyst after epoxidation of propene in comparative example 1;
FIG. 2 is a Fourier transform infrared spectrum of an unused TS-1 type titanium silicalite molecular sieve catalyst in comparative example 2;
FIG. 3 is a Fourier transform infrared spectrum of the regenerated TS-1 type titanium silicalite molecular sieve catalyst obtained in comparative example 3;
FIG. 4 is a Fourier transform infrared spectrum of the regenerated TS-1 type titanium silicalite molecular sieve catalyst obtained in example 1;
FIG. 5 is a Fourier transform infrared spectrum of the regenerated TS-1 type titanium silicalite molecular sieve catalyst obtained in example 2;
FIG. 6 is a Fourier transform infrared spectrum of the regenerated TS-1 type titanium silicalite molecular sieve catalyst obtained in example 3;
FIG. 7 is a Fourier transform infrared spectrum of the regenerated TS-1 type titanium silicalite molecular sieve catalyst obtained in example 4;
FIG. 8 is a Fourier transform infrared spectrum of the regenerated TS-1 type titanium silicalite molecular sieve catalyst obtained in example 5;
FIG. 9 is a Fourier transform infrared spectrum of the regenerated TS-1 type titanium silicalite molecular sieve catalyst obtained in example 6.
Detailed Description
The technical solutions and effects of the present invention will be further described with reference to the drawings and specific embodiments, but the scope of the present invention is not limited thereto.
In the following control examples and examples, the reagents used were all commercially available chemical pure reagents.
Comparative example 1
The deactivated TS-1 type titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of propylene peroxide is simply dried for 6 hours in a vacuum drying oven at 105 ℃, and a Fourier transform infrared spectrogram of the catalyst is shown in figure 1.
Comparative example 2
The Fourier transform infrared spectrogram of the unused TS-1 type titanium silicalite molecular sieve catalyst is shown in figure 2 of the attached drawing.
Comparative example 3
The deactivated TS-1 type titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of propylene peroxide is simply dried for 6 hours at 105 ℃ in a vacuum drying oven and is roasted for 5 hours at 500 ℃ in air atmosphere, and the Fourier transform infrared spectrogram of the catalyst is shown in an attached figure 3.
Example 1
The deactivated TS-1 type titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of propylene peroxide is simply dried for 6 hours in a vacuum drying oven at 105 ℃. Soaking 10 g of dried inactivated TS-1 type titanium silicalite molecular sieve raw powder into 150 g of 3% aqueous hydrogen peroxide, heating to 35 ℃, dropwise adding 6 g of acetone solution containing 6% of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide under stirring under the irradiation of ultraviolet light with the radiation intensity of 300 milliwatts per square meter and the wavelength of 360-365 nm, continuously treating for 45min, filtering, drying, and performing Fourier transform infrared spectrum test on a sample to obtain a graph shown in an attached figure 4.
Example 2
The deactivated TS-1 type titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of propylene peroxide is simply dried for 6 hours in a vacuum drying oven at 105 ℃. 10 g of dried inactivated TS-1 type titanium silicalite molecular sieve raw powder is soaked into 200 g of 5% aqueous hydrogen peroxide, the mixture is heated to 50 ℃,4 g of acetone solution containing 8% of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is added dropwise under stirring under the irradiation of ultraviolet light with the radiation intensity of 500 milliwatts per square meter and the wavelength of 405nm, the continuous treatment time is 20min, the mixture is dried after filtration, a sample is taken for Fourier transform infrared spectrum test, and the obtained test pattern is shown in attached figure 5.
Example 3
The deactivated TS-1 type titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of propylene peroxide is simply dried for 6 hours in a vacuum drying oven at 105 ℃. Soaking 10 g of dried inactivated TS-1 type titanium silicalite molecular sieve raw powder into 200 g of 5% aqueous hydrogen peroxide, heating to 50 ℃, dropwise adding 8 g of acetone solution containing 4% of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide under stirring under the irradiation of ultraviolet light with the radiation intensity of 50 milliwatts per square meter and the wavelength of 360-365 nm, continuously treating for 20min, filtering, drying, and performing Fourier transform infrared spectrum test on a sample to obtain a graph shown in figure 6.
Example 4
The deactivated TS-1 type titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of propylene peroxide is simply dried for 6 hours in a vacuum drying oven at 105 ℃. 10 g of dried inactivated TS-1 type titanium silicalite molecular sieve raw powder is soaked into 200 g of 1% hydrogen peroxide water solution, the solution is heated to 40 ℃,6 g of acetone solution containing 6% of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is added dropwise 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 continuous treatment time is 60min, drying is carried out after filtration, a sample is subjected to Fourier transform infrared spectrum test, and the obtained spectrum is shown in the attached figure 7.
Example 5
The deactivated TS-1 type titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of propylene peroxide is simply dried for 6 hours in a vacuum drying oven at 105 ℃. Soaking 10 g of dried inactivated TS-1 type titanium silicalite molecular sieve raw powder into 200 g of 1% aqueous hydrogen peroxide, cooling to 10 ℃, dropwise adding 8 g of acetone solution containing 6% of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide 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, continuously treating for 60min, drying after filtering, and performing Fourier transform infrared spectrum test on a sample to obtain a graph shown in an attached figure 8.
Example 6
The deactivated TS-1 type titanium silicalite molecular sieve catalyst after catalyzing the epoxidation reaction of propylene peroxide is simply dried for 6 hours in a vacuum drying oven at 105 ℃. Soaking 10 g of dried inactivated TS-1 type titanium silicalite molecular sieve raw powder into 200 g of 4% aqueous hydrogen peroxide, heating to 40 ℃, dropwise adding 8 g of acetone solution containing 6% of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide 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, continuously treating for 20min, drying after filtering, and performing Fourier transform infrared spectrum test on a sample to obtain a graph shown in a figure 9.
Example 7
This example illustrates the effect of the ultrafine titanium silicalite molecular sieves obtained by the method of the present invention and the method of the comparative example on the catalytic reaction of propylene epoxidation. The titanium silicalite molecular sieves separated and recovered in the above examples and comparative examples were placed in a high-pressure reaction kettle with polytetrafluoroethylene lining according to the weight ratio of titanium silicalite molecular sieve, methanol, hydrogen peroxide and water of 1:96:4.5:12, stirred magnetically, heated to 45 ℃, and then stirred while propylene was introduced to the reaction kettle under the pressure of 0.6Mpa, and the reaction results are shown in table 1.
TABLE 1 results of epoxidation reaction of propylene catalyzed by titanium silicalite molecular sieve separated and recovered in examples and comparative examples
In table 1, the hydrogen peroxide conversion rate (amount of the hydrogen peroxide solution-amount of the remaining hydrogen peroxide solution)/amount of the hydrogen peroxide solution added × 100%;
the yield of propylene oxide is equal to the amount of the substance generating propylene oxide/the amount of the substance added with hydrogen peroxide multiplied by 100 percent;
the selectivity for propylene oxide is defined as the 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 from a deactivated propylene titanium silicalite catalyst according to the present invention has a catalytic performance similar to that of the unused TS-1 type titanium silicalite catalyst described in comparative example 2 after the deactivated molecular sieve catalyst is regenerated, and compared with the method for regenerating a molecular sieve catalyst described in comparative example 3, the regenerated molecular sieve catalyst obtained in the present invention has a catalytic performance similar to or better than that of the deactivated molecular sieve catalyst, 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 appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for removing carbon deposition in a deactivated propylene titanium oxide silicon molecular sieve catalyst is characterized by comprising the following steps: soaking the deactivated propylene epoxy titanium silicon molecular sieve catalyst containing carbon deposition into aqueous hydrogen peroxide solution, slowly stirring, dripping 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 hydrogen peroxide to generate active hydroxyl free radicals, and removing the carbon deposition of the deactivated propylene epoxy titanium silicon molecular sieve through oxidative degradation to restore the activity of the catalyst.
2. The method for removing carbon deposition in the deactivated propylene epoxy titanium silicalite catalyst according to claim 1, wherein the carbon deposition in the deactivated propylene epoxy titanium silicalite catalyst is organic matter remaining on the surface of the molecular sieve or/and in the pore channel after the TS-1 type titanium silicalite catalyst is used for catalyzing epoxidation of propylene.
3. The method for removing carbon deposition in the deactivated propylene-epoxidized titanium silicalite catalyst according to claim 1, wherein the concentration of the aqueous hydrogen peroxide solution is 1-5% by mass of hydrogen oxide.
4. The method for removing carbon deposition in the deactivated propylene-epoxidized titanium silicalite catalyst according to claim 1, wherein the amount of the aqueous hydrogen peroxide solution is 10-20 times of the mass of the deactivated propylene-epoxidized titanium silicalite catalyst.
5. The method for removing carbon deposition in the deactivated propylene epoxy titanium silicalite molecular sieve catalyst according to claim 1, wherein the wavelength of the ultraviolet light is 360-405 nm.
6. The method for removing carbon deposition in the deactivated propylene epoxy titanium silicalite molecular sieve catalyst according to claim 1, wherein the ultraviolet light irradiation is 50-500 milliwatts per square meter.
7. The method for removing carbon deposition in the deactivated propylene epoxidized titanium silicalite molecular sieve catalyst according to claim 1, wherein the lower temperature is 10-50 ℃.
8. The method for removing carbon deposition in the deactivated propylene epoxidized titanium silicalite molecular sieve catalyst according to claim 1, wherein the method is used for removing the carbon deposition for 20-60 min at a lower temperature.
9. The method for removing carbon deposit in the deactivated propylene-epoxidized titanium silicalite catalyst according to claim 1, wherein 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 by mass fraction.
10. The method for removing carbon deposition in the deactivated propylene-epoxidized titanium silicalite catalyst according to claim 1, wherein the acetone solution of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is used in an amount of 2-5% by mass of the aqueous hydrogen peroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210359060.7A CN114700108B (en) | 2022-04-07 | 2022-04-07 | Method for removing carbon deposition in deactivated propylene titanium oxide silicon molecular sieve catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210359060.7A CN114700108B (en) | 2022-04-07 | 2022-04-07 | Method for removing carbon deposition in deactivated propylene titanium oxide silicon molecular sieve catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114700108A true CN114700108A (en) | 2022-07-05 |
| CN114700108B CN114700108B (en) | 2023-12-01 |
Family
ID=82173794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210359060.7A Active CN114700108B (en) | 2022-04-07 | 2022-04-07 | Method for removing carbon deposition in deactivated propylene titanium oxide silicon molecular sieve catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114700108B (en) |
Citations (7)
| 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 |
| US20090074611A1 (en) * | 2005-09-15 | 2009-03-19 | Battelle Memorial Institute | Photolytic generation of hydrogen peroxide |
| CN103182323A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Regeneration method of deactivated titanium-silicon molecular sieve catalyst |
| CN105413745A (en) * | 2015-12-28 | 2016-03-23 | 郑州大学 | Method for removing carbon deposit from deactivated titanium silicalite molecular sieve catalyst |
| CN105732710A (en) * | 2016-03-16 | 2016-07-06 | 三峡大学 | Preparation method and application of photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine |
| CN108409893A (en) * | 2018-03-07 | 2018-08-17 | 华南理工大学 | A kind of surface-modified nano ZnO photoinitiators and preparation method thereof |
| 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 |
-
2022
- 2022-04-07 CN CN202210359060.7A patent/CN114700108B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090074611A1 (en) * | 2005-09-15 | 2009-03-19 | Battelle Memorial Institute | Photolytic generation of hydrogen peroxide |
| CN101346364A (en) * | 2005-12-20 | 2009-01-14 | 利安德化学技术有限公司 | Process for oxidizing organic compounds |
| CN103182323A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Regeneration method of deactivated titanium-silicon molecular sieve catalyst |
| CN105413745A (en) * | 2015-12-28 | 2016-03-23 | 郑州大学 | Method for removing carbon deposit from deactivated titanium silicalite molecular sieve catalyst |
| CN105732710A (en) * | 2016-03-16 | 2016-07-06 | 三峡大学 | Preparation method and application of photo-initiator diphenyl tetra(2,4,6-trimethylbenzoyl)oxyphosphine |
| CN108409893A (en) * | 2018-03-07 | 2018-08-17 | 华南理工大学 | A kind of surface-modified nano ZnO photoinitiators and preparation method thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 张锡辉: "《高等环境化学与微生物学原理及应用》", 化学工业出版社, pages: 168 - 169 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114700108B (en) | 2023-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101480623B (en) | Method for regenerating titanium-silicon molecular sieve catalyst | |
| Wu et al. | In-depth understanding of acid catalysis of solvolysis of propene oxide over titanosilicates and titanosilicate/H2O2 systems | |
| US5621122A (en) | Epoxidation process | |
| US5684170A (en) | Epoxidation process | |
| JP2020519774A (en) | Catalyst material for catalytically activating persulfate and target decomposition of typical pollutants in papermaking wastewater, its synthesis method and application | |
| EP1907115B1 (en) | Method of regeneration of titanium-containing molecular sieve catalyst | |
| Hutter et al. | Titania-Silica Mixed Oxides: III. Epoxidation of α-Isophorone with Hydroperoxides | |
| Yu et al. | Insights into the efficiency of hydrogen peroxide utilization over titanosilicate/H2O2 systems | |
| CN112675907B (en) | In-situ combined regeneration method of deactivated titanium-silicon molecular sieve catalyst | |
| US10968110B2 (en) | Method for preparing titanium silicon molecular sieve | |
| CN108654678A (en) | One type Fenton oxidation catalyst and its application | |
| CN106824264B (en) | A kind of Titanium Sieve Molecular Sieve and its method of modifying and application | |
| US8679999B2 (en) | Process for regeneration of titano silicate catalyst | |
| CN105413745A (en) | Method for removing carbon deposit from deactivated titanium silicalite molecular sieve catalyst | |
| CN102309982A (en) | Steam regeneration method of deactivated titanium-silicon molecular sieve | |
| WO2019232715A1 (en) | Selective oxidation of alcohols | |
| CN114700108B (en) | Method for removing carbon deposition in deactivated propylene titanium oxide silicon molecular sieve catalyst | |
| CN101439299B (en) | Catalyst regeneration process | |
| CN111978538A (en) | Sulfur-doped covalent triazine framework polymer, preparation method thereof and application thereof in preparation of phenol | |
| JP4847666B2 (en) | Method for regenerating working solution in hydrogen peroxide production process | |
| RU2251451C2 (en) | Method of a catalyst carrier material production of and a method of production of the catalyst | |
| CN109433259B (en) | Method for in-situ modification of propylene epoxidation catalyst | |
| CN112920142A (en) | Preparation method of styrene oxide | |
| CN105970248A (en) | Electrochemical synthesis method of titanium tetraisopropanolate | |
| Adam et al. | The Mechanism of the Double Bond Cleavage in the Titanium Zeolite‐catalyzed Oxidation of α‐Methylstyrene by Hydrogen Peroxide: the β‐Hydroperoxy Alcohol as Intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |