CN1413768A - Method for modifying titanium silicon zeolite by aqueous solution containing ammonia - Google Patents
Method for modifying titanium silicon zeolite by aqueous solution containing ammonia Download PDFInfo
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- CN1413768A CN1413768A CN 02144875 CN02144875A CN1413768A CN 1413768 A CN1413768 A CN 1413768A CN 02144875 CN02144875 CN 02144875 CN 02144875 A CN02144875 A CN 02144875A CN 1413768 A CN1413768 A CN 1413768A
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- zeolite
- hydrogen peroxide
- aqueous solution
- modification
- ammonia
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 86
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000010457 zeolite Substances 0.000 title claims abstract description 86
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 27
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 230000004048 modification Effects 0.000 claims description 58
- 238000012986 modification Methods 0.000 claims description 58
- 229910004339 Ti-Si Inorganic materials 0.000 claims description 54
- 229910010978 Ti—Si Inorganic materials 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- -1 wherein Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 229910008484 TiSi Inorganic materials 0.000 abstract 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 144
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 76
- 238000006243 chemical reaction Methods 0.000 description 45
- 239000001294 propane Substances 0.000 description 39
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 20
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 102000002322 Egg Proteins Human genes 0.000 description 6
- 108010000912 Egg Proteins Proteins 0.000 description 6
- 210000003278 egg shell Anatomy 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
A process for modifying the TiSi zeolite used as catalyst features that the said TiSi zeolite is modified by making the ammonia contained aqueous solution in liquid or gas phase contact with it or the oxide copmosition containing TiSi zeolite at 80-600 deg.C for 0.5-1200 hr. When the modified catalyst is used to prepare epoxy propane by epoxidizing propene, the output rate can be greatly increased.
Description
Technical field
The invention belongs to the petrochemical catalyst technical field.Relate to the complex oxide of the aqueous solution that contains ammonia modifying titanium-silicon zeolite or titaniferous silicon zeolite under the condition of heating.It is the selective oxidation reaction of the various hydro carbons of oxygen source that the catalyst that is modified is used for rare hydrogen peroxide, the epoxidation reaction of particularly rare hydrogen peroxide and propylene.
Background technology
With TS-1 (Titanium silicalite-1) is that the Ti-Si zeolite of representative can make alkene initial ring oxidation reaction generate epoxides in conjunction with the hydrogen peroxide in rare hydrogen peroxide, make phenyl ring generation hydroxylating generate phenol or benzenediol, make cyclohexanone generation ammoxidation reaction generate cyclohexanone oxime, make alcohols generation selective oxidation reaction generate aldehydes or ketones.Above-mentioned catalytic reaction is carried out the reaction condition gentleness usually under room temperature or the liquid-solid phase condition a little more than room temperature.Because it is pollution-free that titanium silicalite catalyst itself does not have corrosion, can regenerate and use repeatedly, what hydrogen peroxide reaction back was remaining is water, so Ti-Si zeolite is broken away from the existing intrinsic problem of environmental pollution of industrial technology opportunity is provided for developing the production new technique of oxygen-bearing organic matter.
Since nineteen eighty-three U.S. Pat P4,410,501 disclose since Ti-Si zeolite TS-1 (having the MFI topological structure identical with sial ZSM-5) synthetic, and existing multiple Ti-Si zeolite is come out one after another.The synthetic method of Ti-β (having and sial β zeolite facies topological structure together) is disclosed as U.S. Pat P5412122.Reddy G., et al reported TS-2 (having the MEL topological structure identical) with sial ZSM-11 synthetic method (Appl.Catal., 1990,58:L1), belgian patent Belgian Pat No1001038 discloses the synthetic method of TS-3.Ti-Si zeolite is actually titanium atom replaces the framework aluminum generation of Si-Al zeolite with four-coordination form (Ti (the IV)) isomorphous new material.As the then corresponding generation of aluminium TS-12 (MTW topological structure), Ti-M and the Ti-ZSM-48 on titanium atom isomorphous replacement ZSM-12, ZSM-48 and modenite (M) skeleton.
But from the angle analysis of commercial Application, Ti-Si zeolite remains at catalyst efficiency low as the selective oxidation catalyst, i.e. the low problem of the space-time yield of product.Main cause is, Ti-Si zeolite is generally used for (the too high then hydrogen peroxide of reaction temperature can decompose automatically) in the low temperature liquid and solid phase reaction environment, (≤diffusion velocity in 1nm) is unfavorable, and its unfavorable degree increases along with the increase (zeolite micropore growth) of Ti-Si zeolite grain size at zeolite micropore for reactant and product molecule for this reaction condition.
For this reason, open source literature (Schmidt J., et al, Chem.Commun., 2000,2157-2158) attempt to improve the diffusion of Ti-Si zeolite, thereby improve the catalytic efficiency of Ti-Si zeolite in the low temperature liquid phase reaction by the method for hydro-thermal synthesizing superfine zeolite or by the synthetic method that contains mesoporous zeolite of hydro-thermal.Contain the synthesis technique that mesoporous Ti-Si zeolite not only needs complexity but hydro-thermal synthesizing superfine Ti-Si zeolite and hydro-thermal are synthetic, and need expensive synthesis material, these all are unfavorable for the practical application of Ti-Si zeolite.
Summary of the invention
The present invention proposes with the aqueous solution that contains ammonia Ti-Si zeolite to be carried out modification according to the imagination of control reaming, purpose provides a kind ofly improves Ti-Si zeolite by post processing, especially big crystal grain Ti-Si zeolite micropore diffusion, and then improve the straightforward procedure of its catalytic efficiency.
Technical scheme of the present invention is: the Ti-Si catalyst after the roasting is contacted under heating state with the aqueous solution that contains ammonia with powder type or shaped granule form, by liquid-solid volume ratio, modification temperature (pressure), the time parameter control modification degree of selecting ammonia solution concentration, ammonia solution and catalyst.
The step that realizes technical solution of the present invention is as follows:
Step 1
At first with synthetic Ti-Si zeolite or the complex oxide drying, roasting that contain Ti-Si zeolite to remove organic matter in catalyst surface and the micropore (introduce with template agent form in the hydro-thermal building-up process or put procedure in organic matter in the absorption environment).
Said Ti-Si zeolite is meant the zeolite that contains four-coordination titanium Ti (IV) in the silicon skeleton among the present invention, as TS-1 (ZSM-5 type), and TS-2 (ZSM-11 type), Ti-β (β type), Ti-M (mercerising type), TS-12 (ZSM-12 type), Ti-ZSM-48 (ZSM-48 type).Can contain aluminium or other hetero atom in the said Ti-Si zeolite.The hydrothermal synthesis method of Ti-Si zeolite is seen patent USP4410501 and Chinese patent application 01140509.0.The gas-solid phase isomorphous of Ti-Si zeolite replaces preparation method and sees Chinese patent application 01143048.6.
Said Ti-Si zeolite/complex oxide is meant the compound of above said Ti-Si zeolite and titanium dioxide, silica, lanthana, cerium oxide among the present invention.The original position hydrothermal synthesis method of Ti-Si zeolite/complex oxide is seen Chinese patent application 99122122.2.In addition, Ti-Si zeolite is carrier by mechanical-moulded preparation with above-mentioned oxide catalyst granules also belongs to Ti-Si zeolite/complex oxide.Ti-Si zeolite/complex oxide shape of catalyst by mechanical-moulded preparation comprises bar cylindricality of extruding with the axial banded extruder of twin-screw and ' the eggshell shape ' for preparing with commercially available fluidisation spraying comminutor.Moulding for convenience should adopt the precursor-hydroxide gel of above-mentioned oxide to mix with Ti-Si zeolite.
The sign of Ti-Si zeolite makes with the following method in the above-mentioned material: crystal structure characterizes (CuK α) with X-ray polycrystal powder diffractive technology routinely; Skeleton four-coordination titanium (Ti (IV)) absorbs middle infrared 960cm with infrared spectrum (pressing potassium bromide troche technology)
-1The absworption peak at place is in conjunction with characterizing with ultraviolet-visible spectrum picked-up 210nm place's absworption peak (is reference with magnesia); Element is formed employing x-ray fluorescence spectrometry method and is analyzed (no standard specimen analysis); Grain size adopts scanning electron microscope analysis.
The drying of Ti-Si zeolite and Ti-Si zeolite/complex oxide adopts normal pressure and air atmosphere, and baking temperature is 100 ℃～120 ℃, 3～12 hours duration.Normal pressure and air atmosphere are also adopted in roasting, for hydro-thermal synthetic Ti-Si zeolite that contains the agent of organic amine template and the former powder of Ti-Si zeolite/complex oxide, adopt following temperature-programmed calcination mode: promptly rise to 3O0 ℃ with the heating rate of 1 ℃/min, 300 ℃ of following constant temperature 1 hour from room temperature; Be warming up to 400 ℃ with same heating rate again, 400 ℃ of following constant temperature 1 hour; Be warming up to 500 ℃ with same heating rate again, 500 ℃ of following constant temperature 1 hour; Be warming up to 550 ℃ with same heating rate again, spend the night at 550 ℃ of following constant temperature.For removed template method but deposit in the process might adsorb organic compound Ti-Si zeolite and Ti-Si zeolite/complex oxide, directly rise to 550 ℃ and constant temperature from room temperature with the heating rate of 1 ℃/min and got final product in 3 hours.
Step 2
Ti-Si zeolite contacts under the condition of heating with the aqueous solution that contains ammonia with Ti-Si zeolite/complex oxide and carries out modification.
The aqueous solution molar concentration of ammonia is selected 0.01～16M (NH
3).If want catalyst is done slight modification, then should select the ammonia spirit of low concentration for use.Otherwise,, then should select the ammonia spirit of higher concentration for use if want catalyst is done degree of depth modification.
The liquid-solid volume ratio of the aqueous solution of ammonia and catalyst solid selects 1.0～1000.Choose bigger liquid-solid volume ratio and help improving the modification degree, help reducing the modification degree otherwise choose less liquid-solid volume ratio.
Modification temperature is selected 80 ℃～600 ℃.Select higher modification temperature to help improving the modification degree, on the contrary, select lower modification temperature to help reducing the modification degree.
Modification time is selected 0.5 hour～1200 hours.The long then modification degree height of modification time, on the contrary, the short then modification degree of modification time is low.
Be lower than under 200 ℃ the modification temperature, the stainless steel still that uses airtight nothing to stir carries out modification.The stainless steel still is particularly suitable for the modification of Powdered Ti-Si zeolite and Ti-Si zeolite/complex oxide.When modification temperature was not higher than 100 ℃, modification was carried out in the normal pressure liquid phase; When modification temperature was higher than 100 ℃, modification was carried out (self-generated pressure) in the pressurization liquid phase.
Be higher than under 200 ℃ the modification temperature, using the atmospheric fixed bed reactor of stainless steel to carry out modification.Fixed bed reactors are particularly suitable for the modification of preformed catalyst (bar cylindricality and ' eggshell shape ').The aqueous solution of the ammonia that modification is used is squeezed into continuously with feed pump.The flow of feed pump calculates according to the aqueous solution of selected modification time and ammonia and the liquid-solid volume ratio of catalyst solid.
Step 3
The filtration of modifying titanium-silicon zeolite and Ti-Si zeolite/complex oxide, washing, drying and roasting.
If Ti-Si zeolite and Ti-Si zeolite/complex oxide adopt powdered form in modification, then will be after the modification at first through filtering.Require during washing at room temperature to wash pH value 7.0 with deionized water.Dry normal pressure and the air atmosphere of adopting, baking temperature is 100 ℃～120 ℃, 3～12 hours duration.Normal pressure and air atmosphere are also adopted in roasting, directly rise to 550 ℃ from room temperature with the heating rate of 1 ℃/min, and constant temperature is 3 hours then.So far finish the modification of catalyst.
The present invention adopts propylene ring oxidation reaction to estimate the actual effect of above-mentioned modification.Propylene ring oxidation reaction adopts two kinds of reactive modes:
First, batch still evaluation method: get modified powder shape catalyst 0.4g, methanol solvate 32ml, 30% hydrogen peroxide raw material 2.0ml, add successively in the water leg formula stainless steel still device (volume 250ml), after putting into magnetic stick reactor is sealed, with keeping this propylene pressure behind the air in 0.4MPa propylene (polymer grade) metathesis reactor.Under magnetic agitation (300rpm) to keep temperature of reactor with thermostatic water-circulator bath recirculated water be 60 ℃, the reaction of clocking.Behind the reaction 1.5h, close water bath with thermostatic control and magnetic stirring apparatus, cool off reactor with frozen water then.At last, open reactor, supernatant analytical reactions result is got in sampling and centrifugation.
The second, the fixed bed evaluation method:
The catalyst granules of getting the 8g modification is loaded in the middle of the stainless steel tube fixed bed reactors that internal diameter is φ 7, the sial porcelain ball that the two ends loaded particles degree of bed is suitable.Reactor is heated to 55 ℃ with circulator bath, boosts to 3.0Mpa with nitrogen.With methyl alcohol is solvent, and 30% hydrogen peroxide and polymerization-grade propylene are raw material, according to methyl alcohol/hydrogen peroxide mol ratio 23 preparation mixed liquors, is 4 and propylene weight air speed WHSV according to propylene/hydrogen peroxide mol ratio
Propylene=0.23～0.7h
-1uTo reactor feed.Reactor adopts charging top discharge reactive mode down, gets product liquid and analyzes.
No matter intermittent reaction or continuous fixed bed reaction all comprise two aspects to the analysis of product liquid: adopt hydrogen peroxide concentration remaining in the conventional iodometric determination product liquid to calculate the hydrogen peroxide conversion ratio on the one hand; Use gas-chromatography (fid detector, chromatographic column are the PEG20M capillary column, 30 meters of length) analyzing organic substance to form ring Ethylene Oxide selectivity on the other hand.In addition, calculate the effective rate of utilization and the yield of propylene oxide of hydrogen peroxide respectively according to measurement result.Wherein each index is defined as follows:
Hydrogen peroxide conversion ratio, residual hydrogen dioxide molal quantity in hydrogen peroxide molal quantity-product in the %=[(charging) hydrogen peroxide molal quantity in the ÷ charging] * 100.
Hydrogen peroxide effective rate of utilization, %=[(propylene oxide in products molal quantity+propane diols molal quantity+propylene glycol monomethyl ether molal quantity) ÷ (in the charging in hydrogen peroxide molal quantity-product residual hydrogen dioxide molal quantity)] * 100.
The expoxy propane selectivity, %=[propylene oxide in products molal quantity ÷ (propylene oxide in products molal quantity+propane diols molal quantity+propylene glycol monomethyl ether molal quantity)] * 100.
Expoxy propane space-time yield (in hydrogen peroxide)=hydrogen peroxide conversion ratio, % * hydrogen peroxide effective rate of utilization, % * expoxy propane selectivity, % * hydrogen peroxide charging mM air speed, mmol.h
-1.g
-1
Effect of the present invention and benefit be, adopts the aqueous solution modifying titanium-silicon zeolite or the Ti-Si zeolite/complex oxide under the condition of heating that contain ammonia, and method is simple, and expense is low.When big crystal grain Ti-Si zeolite or Ti-Si zeolite/complex oxide were used for propylene ring oxidation reaction through modification, its reactivity (hydrogen peroxide conversion ratio), hydrogen peroxide effective rate of utilization and expoxy propane space-time yield were all than significantly improving before the modification.Carbon three above epoxidation Reaction of Alkenes, ammoxidation of cyclohexanone reaction, epoxidation of styrene reaction, benzene or phenol hydroxylation reaction and oxidation of alcohols that the modified catalyst that obtains with the present invention can also be used to have rare hydrogen peroxide to participate in react.
The specific embodiment
Below in conjunction with technical scheme, be described in detail most preferred embodiment of the present invention.
Embodiment 1: the contrast experiment
Described by Chinese patent application 01140509.0, hydro-thermal synthesis of titanium silicon zeolite ts-1-1.The grain size of gained TS-1 zeolite is 1 * 2 * 6 μ m, and the Si/Ti mol ratio is about 53, and the Si/Al mol ratio is 1343.The roasting of learning from else's experience removes powder TS-1 zeolite catalyst that organic mould pulls agent and estimates the catalytic performance of its epoxidation of propylene by the batch still evaluation method, and the result is as follows:
Hydrogen peroxide conversion ratio (%) 96.14
Expoxy propane selectivity (%) 92.46
Hydrogen peroxide effective rate of utilization (%) 89.21
Embodiment 2
Repeat embodiment 1, but the TS-1 zeolite catalyst carries out modification with the method for the invention before the reaction: 8 grams are put into 200ml stainless steel still through the powder TS-1 zeolite catalyst of roasting, add 100ml16M ammonia spirit (liquid-solid volume ratio is 12.5), in 170 ℃ of following closed processes (liquid phase mode, self-generated pressure).Parallel processing 3 duplicate samples were followed successively by 6 hours the sample time of 3 stills, and 79 hours, 360 hours.Sample takes out the back in 100 ℃ of oven dry, then 540 ℃ of following roastings 3 hours.It is as follows to estimate its propylene ring oxidation reaction performance with batch still:
Modification was handled 6 hours:
Hydrogen peroxide conversion ratio (%) 98.31
Expoxy propane selectivity (%) 85.71
Hydrogen peroxide effective rate of utilization (%) 99.11
Modification was handled 79 hours:
Hydrogen peroxide conversion ratio (%) 98.72
Expoxy propane selectivity (%) 69.66
Hydrogen peroxide effective rate of utilization (%) 99.04
Modification was handled 360 hours:
Hydrogen peroxide conversion ratio (%) 98.55
Expoxy propane selectivity (%) 69.79
Hydrogen peroxide effective rate of utilization (%) 99.50
Embodiment 3
Repeat embodiment 2, but (liquid phase mode, normal pressure) carried out in the modification of powder TS-1 zeolite catalyst under 80 ℃, the processing time was respectively 100 hours, 500 hours and 1200 hours.The reaction result of modified catalyst is as follows:
After the hydrothermal treatment consists 100 hours:
Hydrogen peroxide conversion ratio (%) 97.83
Expoxy propane selectivity (%) 91.06
Hydrogen peroxide effective rate of utilization (%) 96.74
After the hydrothermal treatment consists 500 hours:
Hydrogen peroxide conversion ratio (%) 98.92
Expoxy propane selectivity (%) 90.31
Hydrogen peroxide effective rate of utilization (%) 97.55
After the hydrothermal treatment consists 1200 hours:
Hydrogen peroxide conversion ratio (%) 99.17
Expoxy propane selectivity (%) 87.00
Hydrogen peroxide effective rate of utilization (%) 98.00
Embodiment 4: the contrast experiment
Repeat embodiment 1, but the catalyst that reacts used is the Ti-Si zeolite/complex oxide of the original position hydrothermal synthesis method preparation introduced according to patent 99122122.2 (Chinese patent application number), comprises TS-1/TiO
2(grain size is 2 * 6 * 6 μ m to compound, and the Si/Ti mol ratio is about 1.0, wherein TS-1 and TiO
2Content account for 40%wt and 60%wt respectively.), TS-1/La
2O
3(grain size is 3～5 μ m to compound, and the Si/Ti mol ratio is 50, and lanthana content accounts for 57%wt.), TS-1/CeO
2(grain size is 4～6 μ m to compound, and the Si/Ti mol ratio is 50, and cerium oxide content accounts for 57%wt.)。Reaction result is as follows:
TS/TiO
2Parent
Hydrogen peroxide conversion ratio (%) 92.74
Expoxy propane selectivity (%) 42.02
Hydrogen peroxide effective rate of utilization (%) 76.01
TS-1/La
2O
3Parent
Hydrogen peroxide conversion ratio (%) 58.12
Expoxy propane selectivity (%) 72.28
Hydrogen peroxide effective rate of utilization (%) 35.18
TS-1/CeO
2Parent
Hydrogen peroxide conversion ratio (%) 54.83
Expoxy propane selectivity (%) 35.85
Hydrogen peroxide effective rate of utilization (%) 75.25
Embodiment 5
Repeat embodiment 4, but Ti-Si zeolite/complex oxide is being used for carrying out modification with method provided by the invention before the reaction: 8 grams are put into 200ml stainless steel still through the Ti-Si zeolite/complex oxide catalyst of roasting, add 160ml 4M ammonia spirit (liquid-solid volume ratio is 20), in 170 ℃ of following closed processes 3 hours.The modification result is as follows:
TS/TiO behind the hydrothermal modification
2
Hydrogen peroxide conversion ratio (%) 98.29
Expoxy propane selectivity (%) 45.23
Hydrogen peroxide effective rate of utilization (%) 83.88
TS-1/La behind the hydrothermal modification
2O
3
Hydrogen peroxide conversion ratio (%) 97.88
Expoxy propane selectivity (%) 79.62
Hydrogen peroxide effective rate of utilization (%) 42.15
TS-1/CeO behind the hydrothermal modification
2
Hydrogen peroxide conversion ratio (%) 91.55
Expoxy propane selectivity (%) 57.11
Hydrogen peroxide effective rate of utilization (%) 77.08
Embodiment 6: the contrast experiment
Repeat embodiment 1, but the TS-1 zeolite catalyst that reacts used is prepared to ' eggshell shape ' catalyst through spray mo(u)lding.Having adopted a kind of diameter in the spray mo(u)lding is that the sial porcelain ball of φ 1 is made supporting body, and the employing Ludox is bonding agent (presoma of silica), wherein SiO in TS-1 zeolite and the bonding agent
2Part by weight be 60: 40.In ' eggshell shape ' catalyst, the thickness of eggshell part (coating of titaniferous silicon zeolite) is 0.5-1mm, and the TS-1 zeolite accounts for 30% in whole particle weight.In addition, continuous fixed bed reaction mode is adopted in the propylene ring oxidation reaction evaluation.At propylene feed weight space velocity WHSV
Propylene=0.50h
-1The time, the average response result who reacted 10 hours is:
Hydrogen peroxide conversion ratio (%) 88.07
Expoxy propane selectivity (%) 96.88
Hydrogen peroxide effective rate of utilization (%) 76.21
Expoxy propane space-time yield 1.94mmol.g
-1.h
-1
Embodiment 7
Repeat embodiment 6, but ' eggshell shape ' catalyst that reacts used is used the method for the invention modification in advance: (gas phase mode) carried out in modification in the atmospheric fixed bed reactor of stainless steel, loaded catalyst 8 grams (bulk density is about 1.0), the concentration of aqueous solution of ammonia is 0.5M (NH
3).During modification, the aqueous solution of ammonia is squeezed into continuously with feed pump, the flow of feed pump be made as 6 ml solns/hour.Parallelly do 5 modifications, modification temperature and time are taken as 170 ℃ * 1000 hours successively, 200 ℃ * 200 hours, 300 ℃ * 100 hours, 400 ℃ * 20 hours and 550 ℃ * 10 hours, then calculate the aqueous solution of ammonia and the liquid-solid volume ratio of catalyst solid and be respectively 750,150,75,15,7.5, the gained catalyst is at WHSV
Propylene=0.50h
-1Condition under as follows with 10 hours result of propylene ring oxidation reaction:
Modified condition is 170 ℃ * 1000 hours
Hydrogen peroxide conversion ratio (%) 94.93
Expoxy propane selectivity (%) 95.36
Hydrogen peroxide effective rate of utilization (%) 93.12
Expoxy propane space-time yield 2.51mmol.g
-1.h
-1
Modified condition is 200 ℃ * 200 hours
Hydrogen peroxide conversion ratio (%) 97.83
Expoxy propane selectivity (%) 96.47
Hydrogen peroxide effective rate of utilization (%) 94.81
Expoxy propane space-time yield 2.66mmol.g
-1.h
-1
Modified condition is 300 ℃ * 100 hours
Hydrogen peroxide conversion ratio (%) 98.90
Expoxy propane selectivity (%) 98.01
Hydrogen peroxide effective rate of utilization (%) 98.34
Expoxy propane space-time yield 2.84mmol.g
-1.h
-1
Modified condition is 400 ℃ * 50 hours
Hydrogen peroxide conversion ratio (%) 99.07
Expoxy propane selectivity (%) 99.45
Hydrogen peroxide effective rate of utilization (%) 98.78
Expoxy propane space-time yield 2.90mmol.g
-1.h
-1
Modified condition is 550 ℃ * 25 hours
Hydrogen peroxide conversion ratio (%) 99.83
Expoxy propane selectivity (%) 95.45
Hydrogen peroxide effective rate of utilization (%) 97.26
Expoxy propane space-time yield 2.76mmol.g
-1.h
-1
Embodiment 8: the contrast experiment
Repeat embodiment 6, but react used TS-1 zeolite process extruded moulding, Ludox (30%wt SiO
2) be bonding, the TS-1 zeolite accounts for 80% in whole particle weight, and the catalyst granules diameter is φ 1.At propylene feed weight space velocity WHSV
Propylene=0.50 h
-1The time, the average response result who reacted 10 hours is:
Hydrogen peroxide conversion ratio (%) 95.32
Expoxy propane selectivity (%) 88.00
Hydrogen peroxide effective rate of utilization (%) 92.87
Expoxy propane space-time yield 2.32mmol.g
-1.h
-1
Embodiment 9
Repeat embodiment 8, but the method modification that the TS-1 zeolite extruded catalyst that reacts used proposes with the present invention in advance: modification is carried out in the atmospheric fixed bed reactor of stainless steel, loaded catalyst 8 grams (bulk density is about 0.6), the aqueous solution of ammonia is squeezed into continuously with feed pump, the flow of feed pump be made as 6 ml solns/hour, modification temperature and time are decided to be 400 ℃ * 20 hours.Parallelly do 3 modifications, the concentration of aqueous solution of ammonia is taken as 0.05M respectively, 0.2M and 0.5M (NH
3).Calculating the aqueous solution of ammonia and the liquid-solid volume ratio of catalyst solid is 9.The gained catalyst is at WHSV
Propylene=0.50 h
-1Condition under as follows with 10 hours result of propylene ring oxidation reaction:
When the concentration of aqueous solution of ammonia is 0.05M
Hydrogen peroxide conversion ratio (%) 96.64
Expoxy propane selectivity (%) 91.55
Hydrogen peroxide effective rate of utilization (%) 97.90
Expoxy propane space-time yield 2.58mmol.g
-1.h
-1
When the concentration of aqueous solution of ammonia is 0.2M
Hydrogen peroxide conversion ratio (%) 98.12
Expoxy propane selectivity (%) 93.76
Hydrogen peroxide effective rate of utilization (%) 98.77
Expoxy propane space-time yield 2.70mmol.g
-1.h
-1
When the concentration of aqueous solution of ammonia is 0.5M
Hydrogen peroxide conversion ratio (%) 99.40
Expoxy propane selectivity (%) 93.45
Hydrogen peroxide effective rate of utilization (%) 99.20
Expoxy propane space-time yield 2.74mmol.g
-1.h
-1
Claims (4)
1, a kind of usefulness contains the method for the aqueous solution modifying titanium-silicon zeolite of ammonia, it is characterized in that, the aqueous solution that contains ammonia under the condition of heating contacts with liquid phase mode or gas phase mode and Ti-Si zeolite or the complex oxide catalyst that contains Ti-Si zeolite, wherein, Ti-Si zeolite refers to contain in the silicon skeleton zeolite of four-coordination titanium Ti (IV), and oxide refers to titanium oxide, silica, lanthana, cerium oxide etc.
2, a kind of usefulness according to claim 1 contains the method for the aqueous solution modifying titanium-silicon zeolite of ammonia, it is characterized in that NH in the used ammonia spirit
3Molar concentration be 0.01～16M; The liquid-solid volume ratio of the aqueous solution and Ti-Si catalyst is 1.0～1000.
3, a kind of usefulness according to claim 1 contains the method for the aqueous solution modifying titanium-silicon zeolite of ammonia, it is characterized in that, modification temperature is 80 ℃～600 ℃.
4, a kind of usefulness according to claim 1 contains the method for the aqueous solution modifying titanium-silicon zeolite of ammonia, it is characterized in that, modification time is 0.5 hour～1200 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428234B (en) * | 2007-11-07 | 2010-12-22 | 中国石油化工股份有限公司 | Process for producing titanium-silicon zeolite microcapsule |
| CN103785465A (en) * | 2013-12-26 | 2014-05-14 | 大连理工大学 | Modification method for titanium silicalite molecular sieves |
| CN107879355A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Modified with noble metals HTS and its preparation method and application and a kind of method of alkene direct oxidation |
| CN111085205A (en) * | 2018-10-23 | 2020-05-01 | 华东理工大学 | Carbon porous metal-based integral modified TS-1 catalyst, and preparation method and application thereof |
| CN111085264A (en) * | 2018-10-23 | 2020-05-01 | 华东理工大学 | Monolithic modified TS-1 catalyst based on carbon porous ceramic, and preparation method and application thereof |
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| WO2017089079A1 (en) * | 2015-11-26 | 2017-06-01 | Evonik Degussa Gmbh | Process for the epoxidation of propene |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428234B (en) * | 2007-11-07 | 2010-12-22 | 中国石油化工股份有限公司 | Process for producing titanium-silicon zeolite microcapsule |
| CN103785465A (en) * | 2013-12-26 | 2014-05-14 | 大连理工大学 | Modification method for titanium silicalite molecular sieves |
| CN107879355A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Modified with noble metals HTS and its preparation method and application and a kind of method of alkene direct oxidation |
| CN107879355B (en) * | 2016-09-30 | 2019-11-15 | 中国石油化工股份有限公司 | Modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of alkene direct oxidation |
| CN111085205A (en) * | 2018-10-23 | 2020-05-01 | 华东理工大学 | Carbon porous metal-based integral modified TS-1 catalyst, and preparation method and application thereof |
| CN111085264A (en) * | 2018-10-23 | 2020-05-01 | 华东理工大学 | Monolithic modified TS-1 catalyst based on carbon porous ceramic, and preparation method and application thereof |
| CN111085205B (en) * | 2018-10-23 | 2022-12-06 | 华东理工大学 | Carbon porous metal-based integral modified TS-1 catalyst, and preparation method and application thereof |
| CN111085264B (en) * | 2018-10-23 | 2022-12-06 | 华东理工大学 | Monolithic modified TS-1 catalyst based on carbon porous ceramic, and preparation method and application thereof |
| WO2020248696A1 (en) * | 2019-06-14 | 2020-12-17 | 大连理工大学 | Fluidized reaction method for synthesizing propylene oxide by gas phase epoxidation of propylene and hydrogen peroxide |
| US12054467B2 (en) | 2019-06-14 | 2024-08-06 | Dalian University Of Technology | Fluidized reaction method for synthesizing propylene oxide by gas phase epoxidation of propylene and hydrogen peroxide |
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