CN110548539A - Modification method of titanium silicalite molecular sieve catalyst for HPPO - Google Patents
Modification method of titanium silicalite molecular sieve catalyst for HPPO Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 59
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 53
- 239000010936 titanium Substances 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002715 modification method Methods 0.000 title abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 159000000008 strontium salts Chemical class 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 150000003608 titanium Chemical class 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 7
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 5
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- ZAWGLAXBGYSUHN-UHFFFAOYSA-M sodium;2-[bis(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CC([O-])=O ZAWGLAXBGYSUHN-UHFFFAOYSA-M 0.000 claims description 4
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 4
- TZXKOCQBRNJULO-UHFFFAOYSA-N Ferriprox Chemical compound CC1=C(O)C(=O)C=CN1C TZXKOCQBRNJULO-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229940080258 tetrasodium iminodisuccinate Drugs 0.000 claims description 3
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 claims description 3
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 229960003540 oxyquinoline Drugs 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 9
- 238000006735 epoxidation reaction Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000011282 treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
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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)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention provides a modification method of a titanium silicalite molecular sieve catalyst for HPPO, which comprises the following steps: soaking the titanium-silicon molecular sieve in a strontium salt aqueous solution for a period of time, filtering, washing, drying and roasting; and (3) treating with a complexing agent solution, and washing with water to obtain the modified titanium silicalite molecular sieve. The method can effectively reduce the content of non-skeleton titanium, adjust the acid distribution and reduce the alkali dosage in the epoxidation reaction.
Description
Technical Field
The invention belongs to the technical field of inorganic chemistry, and relates to a modification method of a titanium silicalite molecular sieve for HPPO (HPPO), in particular to a method for modifying the titanium silicalite molecular sieve by a metal strontium salt and a complexing agent.
Background
in 1983, Taramasso et al introduce a transition metal titanium atom with valence-change characteristics into a molecular sieve framework to prepare a titanium-containing heteroatom molecular sieve with an MFI structure, which has good catalytic oxidation activity and selectivity and is widely applied to olefin epoxidation, arene hydroxylation, cyclohexanone ammoximation and other reactions. In 7 months of 2008, 10 ten thousand tons per year of propylene oxide by hydrogen peroxide (HPPO) production was put into operation by SKC corporation of korea, and the device uses a titanium silicalite molecular sieve as a catalyst and hydrogen peroxide as an oxidant to directly oxidize propylene into propylene oxide, so that industrialization of an olefin epoxidation process using hydrogen peroxide as an oxidant was first realized.
In the preparation process of the titanium silicalite, the inevitable generation of non-skeleton titanium due to preferential hydrolysis of titanate results in increased hydrogen peroxide decomposition, reduced hydrogen peroxide utilization rate, coexistence of oxygen generated by decomposition and flammable and explosive propylene in the system, and increased risk of production devices, trace metal impurities (such as Al 3+ and Fe 3+) often contained in the raw materials for preparing the titanium silicalite generate strong acid centers and cause formation of byproducts, therefore, modification treatment is necessary to improve the catalytic activity of the titanium silicalite, and numerous patents disclose methods for post-treating modified titanium silicalite and improving the catalytic oxidation performance thereof, such as:
patent CN201611256492.6 introduces silicon tetrachloride gas into a dried titanium-silicon molecular sieve, and after washing, filtering, drying, roasting and other treatments, the acid distribution of the molecular sieve is modulated, the conversion rate of hydrogen peroxide and the selectivity of propylene oxide are improved, but waste acid generated in the process needs neutralization treatment, and the requirement is provided for the corrosion resistance of equipment.
Patent CN201410811161.9 adopts the mixed solution of strong acid and hydrofluoric acid to carry out modification treatment on the titanium-silicon molecular sieve, removes non-skeleton titanium, and makes the titanium-silicon molecular sieve have better catalytic activity and longer service life, but fluoride ions have strong electron-donating effect, the electropositivity of Ti active center is weakened by five-coordination SiO 4/2 F - group in a hydrogen bond mode, and further release and promotion of catalytic performance are hindered, and in addition, the use of the mixed solution of strong acid and hydrofluoric acid puts forward severe requirements on equipment materials.
Patent CN200810115866.1 discloses adding a titanium silicalite molecular sieve, a protective agent and a noble metal source into an organic amine aqueous solution, mixing uniformly, adding a titanium hydrolysis solution, mixing uniformly, transferring into a reaction kettle for hydrothermal treatment, and recovering the titanium silicalite molecular sieve, which improves the oxidation activity, selectivity and stability of the titanium silicalite molecular sieve, but the process has low noble metal utilization rate, difficult recovery and high cost.
In patent CN200910226733.6, a solution of inorganic ammonium salt, ammonia water, and organic ammonia is mixed with a titanium silicalite molecular sieve, hydrothermal crystallization is performed at 190 ℃ for 24-120h, and the modified titanium silicalite molecular sieve is obtained through the steps of filtering, washing, drying, roasting, etc., so as to reduce the content of non-framework titanium, make the pore passage more unobstructed, make the crystal grains more complete, and improve the catalytic oxidation performance. The modification method is used for long-time treatment at the temperature of 130-.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides an efficient titanium silicalite molecular sieve modification method, which can effectively reduce the content of non-framework titanium, adjust acid distribution and reduce the alkali consumption in epoxidation reaction, and can take the formed titanium silicalite molecular sieve as a modification object, so that the modified titanium silicalite molecular sieve has higher catalytic activity and longer service life in propylene epoxidation reaction.
The invention provides a modification method of a titanium silicalite molecular sieve catalyst for HPPO, which comprises the following steps:
(1) preparing strontium salt and water into a strontium salt aqueous solution according to a certain proportion, soaking a titanium silicalite molecular sieve in the strontium salt aqueous solution for a period of time, filtering, washing and drying, and roasting the obtained solid at a certain temperature;
(2) And filling the roasted titanium silicalite molecular sieve into a fixed bed device, allowing a complexing agent solution to pass through the fixed bed device at a certain space velocity at a certain temperature, and washing with water to be neutral to obtain the modified titanium silicalite molecular sieve.
The strontium salt in the step (1) is preferably at least one selected from strontium nitrate, strontium hydroxide and strontium acetate, and the strontium salt: water: the weight ratio of the titanium-silicon molecular sieve is 0.01-0.5: 1-3: 1;
the titanium silicalite molecular sieve in the step (1) is at least one of a spherical titanium silicalite molecular sieve, a strip-shaped titanium silicalite molecular sieve and a sheet-shaped titanium silicalite molecular sieve;
The dipping temperature in the step (1) is 20-80 ℃, and the time is 12-72 h; the roasting temperature is 500-600 ℃;
the complexing agent solution in the step (2) is at least one of triethanolamine, ethylenediamine, gluconic acid, 1, 2-dimethyl-3-hydroxy-4-pyridone, sodium oxalate, tetrasodium iminodisuccinate, sodium aminotriacetate, 8-hydroxyquinoline and the like, and the concentration of the complexing agent solution is 0.1-3%;
In the step (2), the weight hourly space velocity of the complexing agent solution passing through the fixed bed device is 0.1-1h -1, the temperature is 40-90 ℃, and the time is 12-96 h.
Compared with the prior art, the invention has the following advantages:
(1) Through the compound modification of strontium salt and complexing agent, non-framework titanium species are effectively reduced, the decomposition of hydrogen peroxide is reduced, and the process safety is enhanced;
(2) The metal salt and the complexing agent change the microstructure of the molecular sieve, effectively reduce/shield strong acid centers on the surface of the titanium silicalite molecular sieve, change the acid distribution of the titanium silicalite molecular sieve, reduce the ammonia dosage in the propylene epoxidation reaction to zero, and reduce the ammonia nitrogen content in the wastewater from the source.
Detailed Description
The following detailed description of specific embodiments of the present invention is provided, but the present invention is not limited to the following description.
The titanium silicalite molecular sieves used in the examples were prepared as follows: the titanium silicalite molecular sieve raw powder was prepared according to the methods described in the classical literature "Thangaraj A, Eapen M J, Sivasanker S, et al. Studies on the synthesis of titanium silicalite, TS-1[ J ]. Zeolite, 1992,12(8): 943-: taking ethyl orthosilicate as a silicon source, tetrabutyl titanate as a titanium source and tetrapropylammonium hydroxide as a template agent, crystallizing at the temperature of 150-200 ℃ for 12-48h, and filtering, washing, drying and roasting to obtain the titanium-silicon molecular sieve raw powder. After 20g of titanium-silicon molecular sieve raw powder and 1 g of sesbania powder are uniformly mixed, 14 ml of 30 wt% silica sol is added for further uniform mixing, extrusion, rolling and slicing are used for forming, a formed sample is dried at 100 ℃ for 12 hours and then is roasted at 550 ℃ for 6 hours, and the titanium-silicon molecular sieve is marked as a 'control titanium-silicon molecular sieve'.
Example 1
mixing 0.3g of strontium hydroxide and 30g of water to prepare a 1 wt% strontium hydroxide aqueous solution, soaking 30g of a control titanium silicalite molecular sieve (sheet) in the solution for 72 hours at 20 ℃, filtering, washing and drying, and roasting the obtained solid for 6 hours at 500 ℃.
and filling the calcined catalyst into a fixed bed device, pumping 0.1 wt% of 1, 2-dimethyl-3-hydroxy-4-pyridone aqueous solution for 72h at the temperature of 60 ℃ at the weight hourly space velocity of 0.1h -1, and washing the aqueous solution with water to be neutral to obtain the modified titanium silicalite molecular sieve (sheet) -1.
Example 2
Mixing 5g of strontium acetate and 30g of water to prepare a 14 wt% strontium acetate aqueous solution, soaking 30g of a control titanium silicalite molecular sieve (strip) in the solution at 80 ℃ for 12 hours, filtering, washing and drying, and roasting the obtained solid at 600 ℃ for 6 hours.
And (3) filling the calcined catalyst into a fixed bed device, pumping a 3 wt% triethanolamine aqueous solution for 12h at 40 ℃ at a weight hourly space velocity of 0.5h -1, and then washing with water to be neutral to obtain the modified titanium silicalite molecular sieve (strip) -2.
Example 3
Mixing 15g of strontium nitrate and 90g of water to prepare 14 wt% of strontium nitrate aqueous solution, soaking 30g of contrast titanium silicalite molecular sieve (spherical) in the solution at 60 ℃ for 12h, filtering, washing and drying, and roasting the obtained solid at 550 ℃ for 6 h.
And filling the calcined catalyst into a fixed bed device, pumping 2 wt% of sodium aminotriacetate aqueous solution for 48 hours at 50 ℃ at a weight hourly space velocity of 0.5h -1, and washing with water to be neutral to obtain the modified titanium silicalite molecular sieve (spherical) -3.
Example 4
Mixing 0.5g of strontium hydroxide, 5.5g of strontium nitrate and 60g of water to prepare 9 wt% of mixed strontium salt aqueous solution, soaking 30g of contrast titanium silicalite molecular sieve (spherical) in the solution for 48 hours at 60 ℃, filtering, washing and drying, and roasting the obtained solid for 6 hours at 550 ℃.
And filling the calcined catalyst into a fixed bed device, pumping a mixed solution of 2 wt% of tetrasodium iminodisuccinate and 1 wt% of sodium aminotriacetate for 96h at the temperature of 90 ℃ at a weight hourly space velocity of 1h -1, and washing the mixed solution to be neutral by using water to obtain the modified titanium silicalite molecular sieve (spherical) -4.
Example 5
In order to evaluate the effect of the modified titanium-silicon molecular sieve catalyst in propylene liquid phase epoxidation, a fixed evaluation process comprises the steps of reacting at the pressure of 3MPa and at the temperature of 40 ℃, filling 10g of the catalyst, wherein the weight hourly space velocity of 50% hydrogen peroxide is 0.50h -1, the molar ratio of the hydrogen peroxide to propylene to methanol is 1: 3: 8, pre-mixing ammonia water into hydrogen peroxide solution, feeding the mixture with the hydrogen peroxide solution, and carrying out reaction result evaluation, wherein the main evaluation indexes of the reaction result comprise the hydrogen peroxide conversion rate X H2O2, the epoxypropane selectivity S PO and the hydrogen peroxide utilization rate U H2O2, wherein n 0 represents the molar number before reaction, n represents the molar number after reaction, PG represents 1, 2-propylene glycol, MME represents 1-methoxy-2 propanol and 2-methoxy-1 propanol, and the catalyst deactivation is judged according to the hydrogen peroxide conversion rate of less than 97%, and the one-way service life of the.
The invention is not limited to the embodiments of the invention described.
The structure and the implementation of the present invention are described herein by using specific examples, and the above description of the examples is only used to help understand the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (6)
1. a method for modifying a titanium silicalite molecular sieve catalyst for HPPO comprises the following steps:
(1) Preparing strontium salt and water into a strontium salt aqueous solution according to a certain proportion, soaking a titanium silicalite molecular sieve in the strontium salt aqueous solution for a period of time, filtering, washing and drying, and roasting the obtained solid at a certain temperature;
(2) And filling the roasted titanium silicalite molecular sieve into a fixed bed device, allowing a complexing agent solution to pass through the fixed bed device at a certain space velocity at a certain temperature, and washing with water to be neutral to obtain the modified titanium silicalite molecular sieve.
2. the method for modifying a titanium silicalite catalyst for HPPO according to claim 1, characterized in that said strontium salt in step (1) is selected from at least one of strontium nitrate, strontium hydroxide, strontium acetate, said strontium salt: water: the weight ratio of the titanium-silicon molecular sieve is 0.01-0.5: 1-3: 1.
3. The method for modifying a titanium silicalite molecular sieve catalyst for HPPO according to claim 1, wherein the titanium silicalite molecular sieve in step (1) is at least one of a spherical titanium silicalite molecular sieve, a bar-shaped titanium silicalite molecular sieve, and a sheet-shaped titanium silicalite molecular sieve.
4. the method for modifying a titanium silicalite catalyst for HPPO according to claim 1, characterized in that the impregnation in step (1) is carried out at a temperature of 20-80 ℃ for a time of 12-72 h; the roasting temperature is 500-600 ℃.
5. The method for modifying a titanium silicalite catalyst for HPPO according to claim 1, wherein the complexing agent solution in the step (2) is at least one of triethanolamine, ethylenediamine, gluconic acid, 1, 2-dimethyl-3-hydroxy-4-pyridone, sodium oxalate, tetrasodium iminodisuccinate, sodium aminotriacetate and 8-hydroxyquinoline, and the concentration of the complexing agent solution is 0.1-3%.
6. The method for modifying titanium silicalite catalyst for HPPO according to claim 1, wherein the weight hourly space velocity of the complexing agent solution passing through the fixed bed device in the step (2) is 0.1-1h -1, the temperature is 40-90 ℃, and the time is 12-96 h.
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Application publication date: 20191210 |