Composite Ti-Si catalyst and its in-situ forming prepn process

The compound titanium silicon catalyst and in-situ forming method

technical field

The invention relates to a composite titanium silicon catalyst and preparation method thereof.

background technology

US be USP 4,410,501 being is disclosed the MFI structure titanium silicon molecular sieve and preparation method thereof, comprising with four propyl ammonium hydroxide (i.e. TPAOH) is the template agent and alkali source, taking four alkyl group silicate or the silicon sols and silicon source, and hydrolisis titanium chemical composite of the titanium supply, a mixing according to multiple Moore them, a mixture of the substrate, the 130℃-200℃, A Fixed crystallizes for 6-30 days.

MFI structure titanium silicon molecular sieve, a group of making the oxidant of the hydrogen solution storing of the catalyzed oxidation system; the upper catalyzed performance, comprising a apply in alkene epoxidation, anone ammonia oxidation and aromatic hydroxylation, an oxidation hydrocarbon, alcohol type oxidation and a reactor, comprising a reaction preparing selective is high, the reaction which is temperate, simple technique alarm, the environmental friendly and a handle.

The US be 4,833,260 USP introduced with the recycling solution storing and oxidant, titanium silicon molecular sieve for olefin epoxidation process of catalyst. The reaction temperature is 0-150℃, the pressure of 1-100atm, the preferably solvent is a methanol, tert butyl alcohol and acetone. Taking the hydrogen solution storing and oxidant, ethenes, propenes, chloropropene, 2 and butylenes, 1 and octylenes and a alkene epoxidations, an of the result. The titanium silicon molecular sieve capable used for powdered or simple sheet, can be used for industrial continuous device.

Through a titanium silicon molecular sieve of water communis hot synthetic obtains of the grain size between 0.1-5 μ in the dust, a hard to with the reaction medium, can satisfy the production device comprises a catalyst intensity, life shape, and other surface of the airbag, therefore, the forming process of titanium silicon molecular sieve is wherein industrialization for basic the step.

From the industrial and viewpoint, the EP 0200260 grinding investigated the titanium silicon molecular sieve catalyst for forming goes. A with a SiO2 of the TS-1 crystal peripheral, then the atomizing moulding, is made of the lower particles 20 μ m high intensity micro-spheres. A on from epoxidation reaction of the dedusting reactor, the H2O2 variable rate of 97%, wherein the epoxypropane (PO) reaches preparing selective 92%. Continuous reactor of fixed bed reactor, 40 hours primarily stable, drives the hours 400, wherein the H2O2 variable rate stabilizes to 60%, PO preparing selective is 93% mm. The catalyst and preparation process for TPAOH massively, the cost is high, wherein activeness can with the industrial claim.

USP 5,756,778 is disclosed MFI or on the MEL structure silicon aluminium molecular sieve in-situ crystalline silicon titanium molecular sieve the composite catalyst for assembly. The silicon aluminium molecular sieve and introduce the powerful acid centre of the composite catalyst, a turn the epoxypropane of propylene epoxidation reaction production is further provided with a side reaction with a solvent.

USP 5,736,479 is disclosed composite catalyst for titanium silicon molecular sieve in-situ crystalline production of metal oxide composed of metal oxide and. The metal oxide refers to TiO2, SiO2, ZrO2, Al2O3 or two mixture. The catalyst for titanium silicon molecular sieve occupies the composite catalyst (1-90% heavy). Method for preparing the catalyst is: Lower template agent TPAOH exists, titanium the deposition device of supply and silicon source on the metal oxide, perhaps installed can the deposition for metal oxide with the titanium chemical composite fully, and lower substrate 150-200℃, spontaneity pressure reaction 48-240 hours. Metal oxide capable of ≤32 for μ in the dust, titanium silicon molecular sieve the composite catalyst of in-situ comprising a kettle for powdered, needs to further being shape, which is used for industrial reactor.

- Section now with a seen to synthesize inorganic oxide introduction titanium silicon molecular sieve Is Fixed on the system, made from the titanium silicon molecular sieve in-situ on the inorganic oxide to grow, making the compound titanium silicon catalyst, is used for fixing body, a moving bed or the report of catalyzed type oil reaction device directly.

An objective of the present invention claims a on the utility technology's base is of a structure MFI titanium silicon molecular sieve and inorganic oxide, the composite catalyst for from epoxidation reaction, and claims a composite catalyst and preparation method thereof.

The invention

The invention composite titanium silicon catalyst and 1.0-80.0% (heavy) MFI structure titanium silicon molecular sieve and 20.0-99.0% (heavy) and inorganic oxide is a spherical or irregular particle.

The moulding of titanium silicon molecular sieve be the silicon source, titanium supply, a template agent, alkaline and distilled water.

The silicon source elects from the silica gel; the silicon sol, the white carbon black or the universal type are (R1O) 4Si organic silicate, wherein the formula R1 is any carbon atoms alkyl sets.

The titanium source is a organic titanate or the inorganic titanium salt. Organic titanate's universal type are (R2O) 4Ti, wherein the formula R2 is any carbon atoms alkyl groups; the inorganic titanium salt elects from TiCl4, TiCl3, TiOCl2 and TiOSO4.

The template agent elects of four alkyl ammonium group bromide (TRABr) or a corresponding quaternary ammonium base (TRAOH), alkyl group R elects of ethyl set, propyl and butyl.

The base of the ammonia water or the organic amine, organic amine of universal type of the Rm3 (NH (3-m)) N oil amines chemical composite, R3 is any carbon atoms alkyl groups; m=1-3, n=1 or 2, amines oil chemical composite elects from a ethylamine, propylamine, the butylamine, ethylenediamine, hexamethylene-diamine, diethylamine, triethylamine, tripropyl amine or the tributyl amine.

The inorganic oxide elects from TiO2, SiO2, ZrO2, Al2O3, Na2O, Wherein K2O, and PbO perhaps of them the compound or a mixture. The inorganic oxide is spherical or irregular sand, the grain size of grains is 0.1-20mm.

In-situ forming method of compound titanium silicon catalyst, a machine oxide introduces the silicon source: titanium source: Moulding agent: alkali: Titanium silicon molecular sieve Is Fixed to the distilled water =1∶0 001-0.2∶0.03-0.5∶0.1-5∶10-200 Moore assembly for synthesizing of the system; the normal crystalline, capable of 0-100℃ low temperature aging any days, enable the MFI structure titanium silicon molecular sieve is provided with a machine oxide surface separation core and in-situ anion, the crystalline normal temperature is 120-200℃, comprising a time is 1-10 days, then and composite material and nut, the dry, the coating is. The composite catalyst for system made of through 1-5 home positions to take shape, and is increased the capacity of MFI structure titanium silicon molecular sieve.

The invention claims a composite titanium silicon catalyst for clamping the spherical or irregular nanoparticles, and catalyzed type oil from epoxidation reaction device for directly in the fixing body, a moving bed or a.

The invention composite titanium silicon catalyst of the lower usual technological strip, for olefin epoxidation, styrol oxidation, anone ammonia oxidation and aromatic hydroxylation, an oxidation hydrocarbon, alcohol type oxidation and a reactor, which can is used to take the recycling solution storing said and from epoxidation reaction of oxidant, the reaction temperature is 0-100℃, a 1-50atm, the methanol is a solvent, from /H2O2 =1-10∶1.

Using composite titanium silicon catalyst for in-situ forming law system made to catalyze from epoxidation reaction of the fixed holder reaction device, 47 hours rotating reaction sees model is 1: Table 1 composite catalyst from catalytic epoxidation reaction result time (hour) H2O2 variable rate (%) epoxypropane selective propylene glycol single dimethyl ether preparing selective (%) % (8) is 91.4 to 82.9 15.223 to 95.9 88.3 to 11.126 94.4 to 82.5 16.529 to 94.8 80.8 to 18.132 93.8 to 84.1 14.835 to 94.8 86.1 to 13.647 92.7 to 89.2 mean 10.8 and 94.0 to 84.8 table 14.3 and 1 reaction condition: Temperature 55℃, a 3.0Mpa, C3H6/H2O2 Moore 4.17, solvent methanol, H2O20.85mol/l, propylene by weight airspeed 0.10h-1.

And seen the Table 1, wherein hours 47, wherein the H2O2 variable rate placed more than 90%, wherein the epoxypropane selective mean value punch (84.8% by-product for epoxypropane further with propylene glycol single dimethyl ether and propylene of glycol solvent reaction of). Indicated of the invention claims a composite catalyst in each hydrogen solution storing and from epoxidation reaction of oxidant; the upper activeness and epoxidation preparing selective.

Effect of the invention: The in-situ forming method for preparing titanium composite silicon, catalyst for synthesizing, titanium silicon molecular sieve is integrated with the step titanium silicon molecular sieve Is Fixed, the obtained catalyst of which the catalyzed type oil reaction device for in the fixing body, a moving bed or a.

detailed description of illustrated embodiments

The implementation carrying claim 1 1.2ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 23.2g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 20ml deionized water and 3.2g four propyl ammonium bromide (TPABr) connected, and 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 7ml butylamine then, stirring 60min. Is arranged above preparing adjusting the kettle cover, into the 6.0308g particle size mm silicon ball; the 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 5.7020g composite titanium silicon catalyst. Because the silicon ball synthesizing the system part dissolving the high-temperature alkalinity titanium silicon molecular sieve Is Fixed; the compound titanium silicon catalyst weight of one of the silicon ball bracket (5.45%) heavy.

The implementation carrying claim 2 1.2ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 23.2g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 20ml deionized water and 3.2g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 7ml butylamine then, stirring 60min. Is arranged above preparing adjusting the kettle cover, into the 5.9039g particle size thick silicon ball; the 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 4.7701g composite titanium silicon catalyst. Because the silicon ball synthesizing the system part dissolving the high-temperature alkalinity titanium silicon molecular sieve Is Fixed; the compound titanium silicon catalyst weight of one of the silicon ball bracket (19.2%) heavy.

The implementation carrying 3 being 1.2ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 23.2g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 20ml deionized water and 3.2g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 7ml butylamine then, stirring 60min. Is arranged above preparing adjusting the kettle cover, into the 6.3182g particle size 0.9mm aluminium silicate particles, wherein 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 6.5820g composite titanium silicon catalyst. The compound titanium silicon catalyst weight of one of the aluminium silicate grains is increased (4.2%) heavy.

The implementation carrying 4 being 12ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 23.2g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 20ml deionized water and 3.2g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 7ml butylamine then, stirring 60min. Is arranged above preparing adjusting the kettle cover, into the 6.1228g particle size 1.8mm aluminium silicate particles, wherein 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 6.3838g composite titanium silicon catalyst. The compound titanium silicon catalyst weight of one of the aluminium silicate grains is increased (4.3%) heavy.

The implementation carrying 5 being 0.6ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 11.6g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 28ml deionized water and 1.6g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 3.5ml butylamine then, stirring 60min. Is arranged above preparing adjusting the kettle cover, into the 6.0020g particle size 0.9mm aluminium silicate particles, wherein 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 6.1586g composite titanium silicon catalyst. The compound titanium silicon catalyst weight of one of the aluminium silicate grains is increased (2.6%) heavy.

The implementation carrying 6 being 0.6ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 11.6g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 28ml deionized water and 1.6g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 3.5ml butylamine then, stirring 60min. Is arranged above preparing adjusting the kettle cover, into the 5.9934g particle size 0.9mm aluminium silicate particles, wherein 25℃ aging 2 days, then the 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 6.1676g composite titanium silicon catalyst. The compound titanium silicon catalyst weight of one of the aluminium silicate grains is increased (2.9%) heavy.

The implementation carrying 7 being 0.6ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 11.6g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 28ml deionized water and 1.6g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 3.5ml butylamine then, stirring 60min. Is arranged above preparing adjusting the substrate, the compound titanium silicon catalyst for cover of the 6.1586g implementation carrying 5 system result, wherein 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 6.2848g composite titanium silicon catalyst. The compound titanium silicon catalyst weight of one of the aluminium silicate grains is increased (4.7%) heavy.

The implementation carrying 8 being 0.6ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 11.6g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 28ml deionized water and 1.6g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 3.5ml butylamine then, stirring 60min. Is arranged above preparing adjusting the substrate, the compound titanium silicon catalyst for cover of the 6.2848g implementation carrying 7 system result, wherein 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 6.3890g composite titanium silicon catalyst. The compound titanium silicon catalyst weight of one of the aluminium silicate grains is increased (6.4%) heavy.

The implementation carrying 9 being 0.6ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 28ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 11.6g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 28ml deionized water and 1.6g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 3.5ml butylamine then, stirring 60min. Is arranged above preparing adjusting the substrate, the compound titanium silicon catalyst for cover of the 6.3890g implementation carrying 8 system result, wherein 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ tobacco hanging car for hours 5, obtains the 6.4834g composite titanium silicon catalyst. The compound titanium silicon catalyst weight of one of the aluminium silicate grains is increased (8.0%) heavy.

The implementation carrying 10 being 3.8ml titanic acid four T-shaped Paper, wherein 0-5℃, drips of the 180ml deionized water slowly; the pipe, stirring 30min, results in a liquid. The container, 72.4g (30%) of the silicon sol (Qingdao Layer And Chemical product), the 210ml deionized water and 10.0g TPABr mixed, stirring 30min, results in the A liquid. Feeding into a liquid the B solution, stirring 30min. Feeding into the 21.5ml butylamine then, stirring 60min. Is arranged above preparing adjusting the kettle cover, a 9.0020g the grain size of the 0.9-1.25mm ceramic particles, wherein 25℃ aging 2 days, then the 170℃ for crystallizes thermal forming for 4-9 days, the normal method and filter washing, dry, wherein 540℃ for tobacco hanging car 5 hours. And obtain the composite material is provided on in-situ forming being recycled, before obtains the 9.4742g composite titanium silicon catalyst. The compound titanium silicon catalyst weight of one of the ceramic particle is increased (5.2%) heavy.

Implementation carrying 11 implementation carrying explanations according to the invention implementation carrying 10 neck composite titanium silicon catalyst catalyzed performance of propylene epoxidation reaction.

Is a stainless steel materials according to the compound titanium silicon catalysts of the invention implementation carrying 10 8.0g neck of the compression fixing bed reactor, holding pressure system is 3.0Mpa, the reaction temperature is 55℃, and H2O2 methanol and solution from feeding valve, and on the reaction. H2O2 the concentration of the methanol liquid is 0.85mol/l. C3H6/H2O2 (Moore) =4.17. The propylene by weight airspeed is 0.10h-1. Timing of the sample of the frame charging barrel of cold - bath analyzes. the iodimetric analyzes the H2O2 density. With Japanese Shimatsu Connecting GC-8A gas chromatograph device analytical reaction product. A reaction 47 hours result sees 1 Table.