CN1398674A - Composite Ti-Si catalyst and its in-situ forming prepn process - Google Patents
Composite Ti-Si catalyst and its in-situ forming prepn process Download PDFInfo
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Abstract
A composite Ti-Si catalyst consists of MFI structure Ti-Si molecular sieve 1.0-80.0 wt% and inorganic oxide 20.0-99.0 wt%. It is prepared by the in-situ forming process, that is, inorganic oxide is introduced into Ti-Si molecular sieve hydrothermal synthesis system comprising Si source, Ti source, template agent, alkali and distilled water so that Ti-Si molecular sieve grows in the in-situ formation of inorganic oxide. The obtained composite Ti-Si catalyst is spherical or irregular particle, and may be used directly in fixed bed, mobile bed or catalytic rectifying reactor for the catalytic oxidation between propylene and hydrogen peroxide to product epoxy propane.
Description
Technical field the present invention relates to a kind of composite Ti-Si catalyst and preparation method thereof.
Background technology U.S. Pat P 4,410,501 had once disclosed HTS of MFI structure and preparation method thereof, it is to be template agent and alkali source with TPAOH (abbreviation TPAOH), is the silicon source with tetraalkyl esters of silicon acis or Ludox, and hydrolyzable titanium compound is the titanium source, they are mixed by certain molar ratio, mixture in autoclave, under 130 ℃-200 ℃, hydrothermal crystallizing 6-30 days.
The HTS of MFI structure, in a series of catalytic oxidation systems with hydrogen peroxide as oxidant, has superior catalytic performance, it can be applicable in the reactions such as alkene epoxidation, ammoxidation of cyclohexanone, aromatic hydrocarbons hydroxylating, saturated hydrocarbons oxidation, oxidation of alcohols, has the reaction selectivity height, the reaction condition gentleness, characteristics such as technology is simple and safe, and is environmentally friendly.
It is oxidant that another piece U.S. Pat P 4,833,260 has introduced with the hydrogen peroxide, and HTS is the olefin epoxidation process of catalyst.Reaction temperature is 0-150 ℃, and pressure is 1-100atm, and preferred solvent is methyl alcohol, the tert-butyl alcohol, acetone.With rare hydrogen peroxide is oxidant, and alkene epoxidations such as ethene, propylene, chloropropene, 2-butylene, 1-octene have all obtained result preferably.But wherein used HTS is powdery or simple compressing tablet, can not be used for industrial continuous device.
Usually the synthetic HTS that obtains of hydro-thermal is the fine powder of grain size between 0.1-5 μ m, be difficult to separate with reaction medium, can not satisfy the requirement of commercial plant to aspects such as catalyst strength, life-span, shapes, therefore, the forming process of HTS is an indispensable step of its industrial applications.
Consider that from the commercial Application angle EP 0200260 has studied the moulding problem of titanium-silicon molecular sieve catalyst.At TS-1 crystal periphery oligomerisation SiO
2, spray shaping has been made the high strength microballoon about average grain 20 μ m then.In batch reactor, carry out propylene ring oxidation reaction, H
2O
2Conversion ratio reach 97%, expoxy propane (PO) selectivity reaches 92%.Successive reaction in fixed bed reactors, stable after 40 hours, through running in 400 hours, H
2O
2Conversion ratio is stabilized in 60%, and the PO selectivity is 93%.A large amount of TPAOH that use in this catalyst preparation process, cost is higher, and its activity can not satisfy industrial requirements.
USP 5,756, and 778 have disclosed the composite catalyst that the in-situ crystallization HTS is formed on MFI or MEL structure Si-Al molecular sieve.But Si-Al molecular sieve can be introduced strong acid center in composite catalyst, promote expoxy propane that propylene ring oxidation reaction generates further with solvent generation side reaction.
USP 5,736, and 479 have disclosed the composite catalyst of being made up of the HTS of metal oxide and in-situ crystallization generation on metal oxide.Metal oxide is meant TiO
2, SiO
2, ZrO
2, Al
2O
3Or their mixture.HTS accounts for the 1-90% (weight) of composite catalyst in the catalyst.This Preparation of catalysts method is: in the presence of template agent TPAOH, the mixture in titanium source and silicon source is deposited on the metal oxide, or fully flood the metal oxide of deposition of silica with titanium compound, 150-200 ℃, self-generated pressure reaction 48-240 hour down in autoclave again.But used metal oxide is the fine powder of≤32 μ m, and the composite catalyst of HTS in-situ crystallization generation thereon still is a powdery, needs further moulding, just can be used for industrial reactor.
Do not see so far to have inorganic oxide is introduced HTS hydro-thermal synthetic system, make HTS growth in situ on inorganic oxide, make composite Ti-Si catalyst, be directly used in the report of fixed bed, moving bed or catalytic distillation reaction unit.
The objective of the invention is to provide on the basis of existing technology a kind of and form, be used for the composite catalyst of propylene ring oxidation reaction, and the preparation method of this composite catalyst is provided by MFI structure titanium silicon molecular sieve and inorganic oxide.
Summary of the invention composite Ti-Si catalyst of the present invention is formed spherical or irregular particle by the MFI structure titanium silicon molecular sieve of 1.0-80.0% (weight) and the inorganic oxide of 20.0-99.0% (weight).
The formation of HTS needs silicon source, titanium source, template agent, alkali and distilled water.
It is (R that the silicon source is selected from silica gel, Ludox, white carbon black or general formula
1O)
4The organosilicon acid esters of Si, R in the formula
1Alkyl for 1-4 carbon atom.
The titanium source is organic titanate or inorganic titanium salt.The general formula of organic titanate is (R
2O)
4Ti, R in the formula
2Alkyl for 1-4 carbon atom; Inorganic titanium salt is selected from TiCl
4, TiCl
3, TiOCl
2, TiOSO
4
The template agent is selected from tetraalkyl ammonium bromide (TRABr) or its corresponding quaternary ammonium base (TRAOH), and wherein alkyl R is selected from ethyl, propyl group, butyl.
Alkali is ammoniacal liquor or organic amine, and organic amine is that general formula is R
m 3[NH
(3-m)]
nFat amine compound, R wherein
3Alkyl for 1-6 carbon atom; M=1-3, n=1 or 2, fat amine compound are selected from a kind of in ethamine, n-propylamine, n-butylamine, ethylenediamine, hexamethylene diamine, diethylamine, triethylamine, tripropyl amine (TPA) or the tri-n-butylamine.
Inorganic oxide is selected from TiO
2, SiO
2, ZrO
2, Al
2O
3, Na
2O, CaO, K
2O, PbO or compound in them or mixture.Inorganic oxide is spherical or the irregular particle shape, and particle grain size is 0.1-20mm.
The in-situ forming preparation process of composite Ti-Si catalyst, be that inorganic oxide is incorporated into the silicon source: the titanium source: template agent: alkali: distilled water=1: 0 001-0.2: 0.03-0.5: 0.1-5: in the HTS hydro-thermal synthetic system that the 10-200 mol ratio is formed, before the normal crystallization, can be at 0-100 ℃ of following low temperature maturation 1-5 days, make the MFI structure titanium silicon molecular sieve separate out nucleus and growth in situ in inorganic oxide surface, the normal crystallization temperature is 120-200 ℃, crystallization time is 1-10 days, then composite is separated with mother liquor, drying, roasting is made.The composite catalyst that makes is again through 1-5 formed in situ, to increase the load capacity of MFI structure titanium silicon molecular sieve.
Composite Ti-Si catalyst profile provided by the invention is spherical or irregular particle, can directly use in fixed bed, moving bed or catalytic distillation propylene ring oxidation reaction device.
Composite Ti-Si catalyst of the present invention can be under common process conditions, be used for reactions such as alkene epoxidation, styrene oxidation, ammoxidation of cyclohexanone, aromatic hydrocarbons hydroxylating, saturated hydrocarbons oxidation, oxidation of alcohols, be particularly useful for the hydrogen peroxide is in the propylene ring oxidation reaction of oxidant, reaction temperature is 0-100 ℃, pressure 1-50atm, methyl alcohol is solvent, propylene/H
2O
2=1-10: 1.
Composite Ti-Si catalyst catalytic epoxidation of propone reaction in fixed-bed reactor of adopting the formed in situ method to make, the running reaction result saw Table 1 in 47 hours:
The table 1 composite catalyst catalytic epoxidation of propone reaction result time (hour) H
2O
2Conversion ratio (%) expoxy propane selectivity propylene glycol monomethyl ether selectivity
(%) (%) 8 91.4 82.9 15.2 23 95.9 88.3 11.1 26 94.4 82.5 16.5 29 94.8 80.8 18.1 32 93.8 84.1 14.8 35 94.8 86.1 13.6 47 92.7 89.2 10.8 mean values 94.0 84.8 14.3
The reaction condition of table 1 data: 55 ℃ of temperature, pressure 3.0Mpa, C
3H
6/ H
2O
2Mol ratio 4.17, solvent methanol, H
2O
20.85mol/l,
Propylene weight air speed 0.10h
-1
By table 1 as seen, in 47 hours, H
2O
2Conversion ratio remains on more than 90%, and expoxy propane selectivity mean value reaches 84.8% (accessory substance is propylene glycol monomethyl ether and the propane diols that expoxy propane further forms with solvent reaction).Show that composite catalyst provided by the invention is being in the propylene ring oxidation reaction of oxidant with the hydrogen peroxide, has higher activity and epoxidation selectivity.
Effect of the present invention: adopt the formed in situ legal system to be equipped with composite Ti-Si catalyst, the HTS hydro-thermal is synthetic, HTS moulding is integrated in a step to be carried out, and the gained catalyst can directly use in fixed bed, moving bed or catalytic distillation reaction unit.
The specific embodiment
Embodiment 1
Get the 1.2ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 20ml deionized water of 23.2g 30% (weight) mixed with 3.2g 4-propyl bromide (TPABr), stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 7ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the silicon ball of 6.0308g particle diameter 3mm,,,, obtain the 5.7020g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.Because the silicon ball is partly dissolved in the HTS hydro-thermal synthetic system of high-temperature alkaline, the silicon ball of composite Ti-Si catalyst quality before than moulding lacks 5.45% (weight).
Embodiment 2
Get the 1.2ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 20ml deionized water of 23.2g 30% (weight) mixed with 3.2g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 7ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the silicon ball of 5.9039g particle diameter 1mm,,,, obtain the 4.7701g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.Because the silicon ball is partly dissolved in the HTS hydro-thermal synthetic system of high-temperature alkaline, the silicon ball of composite Ti-Si catalyst quality before than moulding lacks 19.2% (weight).
Embodiment 3
Get the 1.2ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 20ml deionized water of 23.2g 30% (weight) mixed with 3.2g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 7ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the alumina silicate bead of 6.3182g particle diameter 0.9mm,,,, obtain the 6.5820g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 4.2% (weight).
Embodiment 4
Get the 12ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 20ml deionized water of 23.2g 30% (weight) mixed with 3.2g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 7ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the alumina silicate bead of 6.1228g particle diameter 1.8mm,,,, obtain the 6.3838g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 4.3% (weight).
Embodiment 5
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the alumina silicate bead of 6.0020g particle diameter 0.9mm,,,, obtain the 6.1586g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 2.6% (weight).
Embodiment 6
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the alumina silicate bead of 5.9934g particle diameter 0.9mm, 25 ℃ of ageings 2 days, then at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying,, obtain the 6.1676g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 2.9% (weight).
Embodiment 7
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the composite Ti-Si catalyst that 6.1586g embodiment 5 makes, at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying, in 540 ℃ of roastings 5 hours, obtain the 6.2848g composite Ti-Si catalyst.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 4.7% (weight).
Embodiment 8
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the composite Ti-Si catalyst that 6.2848g embodiment 7 makes, at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying, in 540 ℃ of roastings 5 hours, obtain the 6.3890g composite Ti-Si catalyst.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 6.4% (weight).
Embodiment 9
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the composite Ti-Si catalyst that 6.3890g embodiment 8 makes, at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying, in 540 ℃ of roastings 5 hours, obtain the 6.4834g composite Ti-Si catalyst.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 8.0% (weight).
Embodiment 10
Get the 3.8ml butyl titanate, under 0-5 ℃, slowly splash in the 180ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 210ml deionized water of 72.4g 30% (weight) mixed with 10.0g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 21.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, and adding the 9.0020g granularity is the 0.9-1.25mm ceramic bead, 25 ℃ of ageings 2 days, then at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying, in 540 ℃ of roastings 5 hours.Resultant composite is carried out formed in situ once more, obtain the 9.4742g composite Ti-Si catalyst at last.The ceramic bead of composite Ti-Si catalyst quality before than moulding increases by 5.2% (weight).
Embodiment 11
The present embodiment explanation is by the catalytic performance of composite Ti-Si catalyst in propylene ring oxidation reaction of the embodiment of the invention 10 preparations.
8.0g is packed in the pressurization static bed reactor of stainless steel by the composite Ti-Si catalyst of the embodiment of the invention 10 preparation, and maintenances system pressure is 3.0Mpa, and reaction temperature is 55 ℃, unlatching H
2O
2Methanol solution and the inlet valve of propylene, react.H
2O
2Concentration is 0.85mol/l in methanol solution.C
3H
6/ H
2O
2(mol ratio)=4.17.The propylene weight air speed is 0.10h
-1Timing sample analysis from the material receiving tube in cryostat.Iodimetric analysis H
2O
2Concentration.With day island proper Tianjin GC-8A of company type gas chromatograph analytical reactions product.React 47 hours the results are shown in Table 1.
Claims (7)
1, a kind of composite Ti-Si catalyst of being made by silicon source, titanium source, template agent, alkali, distilled water and inorganic oxide reaction is characterized in that this catalyst forms spherical or irregular particle by the MFI structure titanium silicon molecular sieve of 1.0-80.0% (weight) and the inorganic oxide of 20.0-99.0% (weight).
2,, it is characterized in that inorganic oxide is selected from TiO according to the described composite Ti-Si catalyst of claim 1
2, SiO
2, ZrO
2, Al
2O
3, Na
2O, CaO, K
2O, PbO or compound in them or mixture, inorganic oxide are spherical or the irregular particle shape, and particle diameter is 0.1-20mm.
3, a kind of preparation method with the described composite Ti-Si catalyst of claim 1, it is characterized in that this in-situ forming preparation process is that inorganic oxide is incorporated into the silicon source: titanium source: template agent: alkali: the mol ratio of distilled water is 1: in the MFI structure titanium silicon molecular sieve hydro-thermal synthetic system that 0.001-0.2: 0.03-0.5: 0.1-5: 10-200 forms, before the normal crystallization, can be at 0-100 ℃ of following low temperature maturation 1-5 days, make the MFI structure titanium silicon molecular sieve separate out nucleus and growth in situ in inorganic oxide surface, again at 120-200 ℃ of normal crystallization 1-10 days, then composite is separated with mother liquor, drying, roasting is made; The composite catalyst that makes is again through 1-5 formed in situ.
4,, it is characterized in that it is (R that the used silicon source of this method is selected from silica gel, Ludox, white carbon black or general formula according to the preparation method of the described composite Ti-Si catalyst of claim 3
1O)
4The organosilicon acid esters of Si, R in the formula
1Alkyl for 1-4 carbon atom.
5,, it is characterized in that the used titanium source of this method is selected from TiCl according to the preparation method of the described composite Ti-Si catalyst of claim 3
4, TiCl
3, TiOCl
2, TiOSO
4Or general formula is (R
2O)
4The organic titanate of Ti, wherein R
2Alkyl for 1-4 carbon atom.
6, according to the preparation method of the described composite Ti-Si catalyst of claim 3, it is characterized in that the used template agent of this method is selected from tetraalkyl ammonium bromide TRABr or its corresponding quaternary ammonium base TRAOH, wherein alkyl R is selected from ethyl, propyl group, butyl.
7, according to the preparation method of the described composite Ti-Si catalyst of claim 3, it is characterized in that the used alkali of this method is ammoniacal liquor or organic amine, the general formula of organic amine is R
m 3[NH
(3-m)]
nFat amine compound, R wherein
3Be the alkyl of 1-6 carbon atom, m=1-3, n=1 or 2 one of can be selected from ethamine, n-propylamine, n-butylamine, ethylenediamine, hexamethylene diamine, diethylamine, triethylamine, tripropyl amine (TPA) or the tri-n-butylamine.
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| CN1330416C (en) * | 2004-01-10 | 2007-08-08 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
| WO2008019586A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | An insitu synthesis method of a microsphere catalyst used for converting oxygen compound to olefine |
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| CN103706346B (en) * | 2013-12-27 | 2015-09-16 | 江苏晶晶新材料有限公司 | A kind of method improving activity of anthraquinone degradation product regeneration catalyst |
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| CN1140348C (en) | 2004-03-03 |
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