CN101371989B - Titanium silicon molecular sieve catalyst as well as preparation method and use thereof - Google Patents
Titanium silicon molecular sieve catalyst as well as preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a titanium silicate molecular sieve catalyst and the preparation method and the application thereof. The catalyst comprises 25-65 percent of titanium silicate molecular sieve and 20-65 percent of nanometer alumina. The mechanical strength is 20-30N/cm<2>. Prepared by an extruded moulding method, the catalyst has the characteristics of high mechanical strength, high catalytic activity and selectivity, and the like, and is especially applied to catalyzing 3-chloropropene oxidation reaction to prepare epichlorohydrin.
Description
Technical field
The present invention relates to a kind of titanium-silicon molecular sieve catalyst and its production and application.
Background technology
HTS is the general name that titanium atom partly replaces a class zeolite of lattice framework silicon atom, as is similar to the titanium-containing zeolite TS-1 with MFI structure of ZSM-5 aluminosilicate zeolite and is similar to the titanium-containing zeolite TS-2 with MEL structure of ZSM-11 aluminosilicate zeolite and other titanium-containing zeolites that structure is similar to modenite, ZSM-12, ZSM-48 etc.HTS has unique catalytic performance to various organic oxidizing reactions, as selectivity height, reaction condition gentleness, deep oxidation and non-pollutant discharge etc. do not take place.Because TS-1 has special three-dimensional open-framework, make its performance in synthetic HTS the most excellent.
Epoxychloropropane is important Organic Chemicals, and its purposes is very extensive, as is used for synthetic glycerine, epoxy resin, chlorohydrin rubber, nitroglycerine, fiberglass, electric insulation goods etc.The propylene high-temperature chloridising is the classical way of industrial production epoxychloropropane, succeeds in developing and be applied to suitability for industrialized production first in 1948 by U.S. Shell company.The characteristics of propylene high-temperature chloridising are that production process is flexible, technical maturity, stable operation.Shortcoming is that the equipment corrosion that causes of raw material chlorine is serious, the material of purified propylene and reactor is required high, and energy consumption is big, chlorine consumption height, and accessory substance is many, and product yield is low.Production process produces contains calcium chloride and the organic chloride sewage quantity is big, the disposal cost height, and coke cleaning period is short.Another kind of method of producing epoxychloropropane is the allyl alcohol method, compares with the propylene high-temperature chloridising, and the material consumption of this technology, energy consumption, accessory substance and waste water all have decline in various degree, but its technological process is longer, and equipment corrosion and wastewater flow rate problem are still very serious.
In order to solve corrosion and the environmental issue in the epoxychloropropane production process, it is the method for Preparation of Catalyst epoxychloropropane with TS-1 that bibliographical information has been arranged, as USP4, and 833,260.Though TS-1 has excellent catalytic performance, but its average grain diameter has only 0.1～10 μ m usually, in solvent, can form suspension, make catalyst very difficult with separating of product, if adopt stirred tank or slurry attitude bed in the actual production, because the synthetic cost of TS-1 is higher, need to reclaim as far as possible, loop back reactor then.
Stirred tank and slurry attitude bed back-mixing are serious, and fixed bed reactors can overcome this shortcoming.In order to satisfy the requirement of fixed bed, TS-1 must be made suitable, the good preformed catalyst of mechanical strength of shape, and keep catalytic activity and the selectivity of TS-1 as far as possible catalyst particle size and intensity.
EP0200260 has reported a kind of Ti-Si catalyst of high mechanical properties, after it is dispersed in Ludox with HTS, through spray shaping, has made the high strength microballoon about average grain 20 μ m.The method needs to use a large amount of TPAOHs (TPAOH) in forming process, and cost is higher, and its activity can not well satisfy industrial requirements.
USP5,736,479 disclose the method for in-situ crystallization generation HTS on metal oxide.Its 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, in autoclave, reacted 48～240 hours under 150～200 ℃, self-generated pressure again.USP5756778 also discloses the method for in-situ preparing composite Ti-Si catalyst.When these class methods were used for alkene epoxidation, the conversion ratio of hydrogen peroxide was lower, and the epoxidation selectivity is also on the low side.
CN1114495C discloses a kind of method of making composite catalyst with the HTS and the inorganic oxide of MFI structure, and wherein inorganic oxide is SiO
2, Al
2O
3Or its compound.The forming method of composite catalyst is spray mo(u)lding and extruded moulding.In the extruded moulding, binding agent is selected from glycerine, polyvinylpyrrolidone, methylcellulose, CMC, polyvinyl alcohol or two or more the mixture in them.When this catalyst was used for the chlorallylene epoxidation, the conversion ratio and the effective rate of utilization of hydrogen peroxide were lower.
CN1830564A discloses a kind of chloro propylene epoxidation Preparation of catalysts method.It is with the cylindric porous ceramics Al of multichannel
2O
3, SiO
2Or cordierite is carrier, and carrier makes synthetic liquid with butyl titanate, ethyl orthosilicate, deionized water, TPAOH and isopropyl alcohol and mixes through after the calcination process, carries out the catalyst that crystallization obtains monolithic devices in crystallizing kettle.The catalyst of its preparation is used for the chloro propylene epoxidation reaction, and chloropropene conversion ratio and epoxychloropropane selectivity are respectively 79% and 57.8%.
Summary of the invention
Technical problem to be solved by this invention provides a kind of titanium-silicon molecular sieve catalyst and its production and application.In particular, technical problem to be solved by this invention provides a kind of catalytic activity and selectivity height, particle is big and mechanical strength is good titanium-silicon molecular sieve catalyst and preparation method thereof, and use it for batch still or fixed bed reactors, catalysis chloro propylene epoxidation prepared in reaction epoxychloropropane.
Titanium-silicon molecular sieve catalyst provided by the present invention comprises the HTS and 20%～65% nano aluminium oxide of 25%～65% MFI structure, and mechanical strength is 20～30N/cm
2
The invention provides above-mentioned Preparation of catalysts method, HTS and nano aluminium oxide, aluminium colloidal sol, pore-foaming agent and the extrusion aid of MFI structure are mixed, be extruded into strip with banded extruder, again through pelletizing, drying, roasting, finally obtain preformed catalyst, quality with HTS is a benchmark, and the prescription of extruded moulding comprises:
1 part of HTS;
0.4～2 part of nano aluminium oxide;
0.9～2.4 part of aluminium colloidal sol;
0.05～0.3 part of pore-foaming agent;
0.08～2 part of extrusion aid.
Wherein, the solid content of aluminium colloidal sol is 10%～40%, preferred 15%～25%.
Pore-foaming agent is an APES, and its alkyl carbon number is 2～16, is preferably 6～12; The degree of polymerization is 4～60, is preferably 10～30.
Extrusion aid is selected from one or more the mixture in sesbania powder, starch, polyethylene and the polyethylene glycol oxide.Wherein preferred starch, polyethylene glycol oxide or the mixture of the two.When the mixture that adopts starch and polyethylene glycol oxide was extrusion aid, starch was 2～20: 1 with the ratio of polyethylene glycol oxide quality, and the molecular weight of polyethylene glycol oxide is 50～8,000,000.
Also can comprise a spot of water in the prescription of extruded moulding, its addition is 0.04～0.12 part (mass fraction with HTS is 1).
Among the preparation method of the present invention, drying is to dry 0.5～5h down at 100～150 ℃, dries 1.5～3h down for preferred 110～125 ℃.
Among the preparation method of the present invention, roasting is 400～1000 ℃ of following roastings 2～16 hours, preferably 540～560 ℃ of following roastings 4～8 hours.
The invention provides the method for using above-mentioned Preparation of Catalyst epoxychloropropane.
When adopting batch reactor, be solvent with methyl alcohol, chlorallylene: hydrogen peroxide is 1～10: 1 (mol ratio), catalyst amount is 1～30%, preferred 3～15% of reaction feed liquid gross mass; Reaction temperature is 20～100 ℃, preferred 40～70 ℃; Pressure is 0.1～2MPa (absolute pressure), and the reaction time is 10～100 minutes, preferred 20～60 minutes.
When adopting fixed bed reactors, chlorallylene: hydrogen peroxide is 1～10: 1 (mol ratio), methyl alcohol: alkene is 1～20: 1 (mol ratio), the feed weight space-time speed 0.01～10h of hydrogen peroxide
-1Reaction temperature is 20～100 ℃, and pressure is 0.1～2MPa (absolute pressure).
Titanium-silicon molecular sieve catalyst particle diameter provided by the present invention is big, mechanical strength is high, and catalytic activity and stability have reached the effect of the former powder of HTS.It is applied to batch still and fixed bed reactors, and catalyst is easy to separate with liquid reacting product, has reduced production cost and operation easier.Shaping of catalyst technology provided by the present invention is simple, cost is low, easy suitability for industrialized production.Catalyst provided by the present invention is applicable to EPOXIDATION OF ALKENES CATALYZED BY, be specially adapted to catalysis chlorallylene epoxidation reaction and prepare epoxychloropropane, but its purposes is not limited thereto, and it also can be used for reactions such as catalysis of pimelinketone ammoxidation, aromatic hydrocarbons hydroxylating, saturated hydrocarbons oxidation and oxidation of alcohols.
The specific embodiment
In following examples and the Comparative Examples, HTS derives from the Hunan and builds feldspar oiling worker limited company, and particle size range is 0.2～300 μ m, can through or without calcination process; Starch source is in martial music chemical plant, Pengxian County, Sichuan Province, and is pure for analyzing; OPEO derives from Shanghai Synthetic Detergents Factory, and the trade mark is OP-10, OP-15 and OP-30; Polyethylene glycol oxide derives from Beijing compatriots health Science and Technology Ltd. of escaping, and the trade mark is PEO-400.The mechanical strength of catalyst adopts QCY-602 granule strength analyzer to measure among the present invention.
Embodiment 1
Aluminium colloidal sol, 8 gram starch, 2.0 gram polyethylene glycol oxides (PEO-400), 0.6 gram OPEO (OP-10), the 0.5 gram water of 12.0 gram HTSs, 5.6 gram nano aluminium oxides, 11.2 grams, 21.5% (quality) are mixed, kneading repeatedly, be extruded into the slice that diameter is 1.2mm with banded extruder, be cut into the particle that length is 1～3mm again, dry 2h down for 110～125 ℃, in 550 ℃ of roastings 6 hours, obtain strip catalyst, its mechanical strength is 22.3N/cm
2
The gained catalyst carries out the chloro propylene epoxidation reaction in batch still, reaction temperature is that 50 ℃, pressure are that the mol ratio of 0.1MPa (absolute pressure), chlorallylene and methyl alcohol is under 1: 5, chlorallylene and hydrogen peroxide mol ratio be 1.5: 1 and catalytic amount for reaction feed liquid gross mass 5% the condition, reaction time is 30 minutes, the hydrogen peroxide conversion ratio is 97.05%, the hydrogen peroxide effective rate of utilization is 96.19%, and the epoxychloropropane selectivity is 97.59%.
Embodiment 2
Aluminium colloidal sol, 8.6 gram starch, the 1.0 gram OPEOs (OP-15) of 12.0 gram HTSs, 5.0 gram nano aluminium oxides, 13.9 grams, 21.5% (quality) are mixed, kneading repeatedly, be extruded into the slice that diameter is 1.2mm with banded extruder, be cut into the particle that length is 1～3mm again, dry 2h down for 110～125 ℃, in 550 ℃ of roastings 6 hours, obtain strip catalyst, its mechanical strength is 22.8N/cm
2
The gained catalyst carries out the chloro propylene epoxidation reaction in batch still, reaction temperature is that 50 ℃, pressure are that the mol ratio of 0.1MPa (absolute pressure), chlorallylene and methyl alcohol is under 1: 5, chlorallylene and hydrogen peroxide mol ratio be 1.5: 1 and catalytic amount for reaction feed liquid gross mass 5% the condition, reaction time is 30 minutes, the hydrogen peroxide conversion ratio is 96.04%, the hydrogen peroxide effective rate of utilization is 96.94%, and the epoxychloropropane selectivity is 98.41%.
The gained catalyst carries out chloro propylene epoxidation reaction in fixed bed reactors, reaction temperature is that 50～65 ℃, pressure are that the mol ratio of 0.3～0.4MPa (absolute pressure), methyl alcohol and chlorallylene is that 5: 1, chlorallylene and hydrogen peroxide mol ratio are 2.5: 1, the feed weight space-time speed 0.13h of hydrogen peroxide
-1, reaction duration of runs is that 54h, hydrogen peroxide average conversion are 99.2%, hydrogen peroxide average effective utilization rate is 99.1%, the epoxychloropropane average selectivity is 96.9%.
Embodiment 3
Aluminium colloidal sol, 8 gram starch, 1.5 gram polyethylene glycol oxides (PEO-400), 1.0 gram OPEOs (OP-30), the 0.5 gram water of 12.0 gram HTSs, 5.6 gram nano aluminium oxides, 11.2 grams, 21.5% (quality) are mixed, kneading repeatedly, be extruded into the slice that diameter is 1.2mm with banded extruder, be cut into the particle that length is 1～3mm again, dry 2h down for 110～125 ℃, in 550 ℃ of roastings 6 hours, obtain strip catalyst, its mechanical strength is 23.4N/cm
2
The gained catalyst carries out the chloro propylene epoxidation reaction in batch still, reaction temperature is that 50 ℃, pressure are that the mol ratio of 0.1MPa (absolute pressure), chlorallylene and methyl alcohol is under 1: 5, chlorallylene and hydrogen peroxide mol ratio be 1.5: 1 and catalytic amount for reaction feed liquid gross mass 5% the condition, reaction time is 30 minutes, the hydrogen peroxide conversion ratio is 98.58%, the hydrogen peroxide effective rate of utilization is 97.06%, and the epoxychloropropane selectivity is 98.49%.
The gained catalyst carries out chloro propylene epoxidation reaction in fixed bed reactors, reaction temperature is that 50～65 ℃, pressure are that the mol ratio of 0.3～0.4Mpa (absolute pressure), methyl alcohol and chlorallylene is that 7.5: 1, chlorallylene and hydrogen peroxide mol ratio are 5: 1, the feed weight space-time speed 0.2h of hydrogen peroxide
-1, reaction duration of runs is that 30h, hydrogen peroxide average conversion are 98.72%, hydrogen peroxide average effective utilization rate is 98.91%, the epoxychloropropane average selectivity is 97.32%.
Embodiment 4
Aluminium colloidal sol, 8.5 gram starch, 1.0 gram polyethylene glycol oxides (PEO-400), 1.0 gram OPEOs (OP-15), the 0.5 gram water of 12.0 gram HTSs, 5.6 gram nano aluminium oxides, 11.2 grams, 21.5% (quality) are mixed, kneading repeatedly, be extruded into the slice that diameter is 1.2mm with banded extruder, be cut into the particle that length is 1～3mm again, dry 2h down for 110～125 ℃, in 550 ℃ of roastings 6 hours, obtain strip catalyst, its mechanical strength is 24.6N/cm
2
The gained catalyst carries out the chloro propylene epoxidation reaction in batch still, reaction temperature is that 50 ℃, pressure are that the mol ratio of 0.1MPa (absolute pressure), chlorallylene and methyl alcohol is under 1: 5, chlorallylene and hydrogen peroxide mol ratio be 1.5: 1 and catalytic amount for reaction feed liquid gross mass 5% the condition, reaction time is 30 minutes, the hydrogen peroxide conversion ratio is 97.55%, the hydrogen peroxide effective rate of utilization is 96.49%, and the epoxychloropropane selectivity is 97.79%.
Embodiment 5
Aluminium colloidal sol, 10.0 gram starch, 2 gram polyethylene glycol oxides (PEO-400), 1.0 gram OPEOs (OP-15), the 0.5 gram water of 12.0 gram HTSs, 5.0 gram nano aluminium oxides, 13.96 grams, 21.5% (quality) are mixed, kneading repeatedly, be extruded into the slice that diameter is 1.2mm with banded extruder, be cut into the particle that length is 1～3mm again, dry 2h down for 110～125 ℃, in 550 ℃ of roastings 6 hours, obtain strip catalyst, its mechanical strength is 23.2N/cm
2
The gained catalyst carries out propylene ring oxidation reaction in batch still, reaction temperature is 50 ℃, and pressure is 0.4MPa (absolute pressure), and the mol ratio of propylene and methyl alcohol is 1: 5, and the propylene air speed is 0.7h
-1, propylene and hydrogen peroxide mol ratio are 3: 1, and catalytic amount is 5% of reaction feed liquid gross mass, and the reaction time is 30 minutes, and the hydrogen peroxide conversion ratio is 97.21%, and the hydrogen peroxide effective rate of utilization is 96.85%, and the expoxy propane selectivity is 98.38%.
Embodiment 6
Aluminium colloidal sol, 10.0 gram starch, 1.5 gram polyethylene glycol oxides (PEO-400), 1.0 gram OPEOs (OP-15), 0.1 gram sesbania powder, the 0.5 gram water of 10.0 gram HTSs, 7.0 gram nano aluminium oxides, 13.96 grams, 21.5% (quality) are mixed, kneading repeatedly, be extruded into the slice that diameter is 1.2mm with banded extruder, be cut into the particle that length is 1～3mm again, dry 2h down for 110～125 ℃, then in 550 ℃ of roastings 6 hours, obtain strip catalyst, its mechanical strength is 23.8N/cm
2
The gained catalyst carries out the chloro propylene epoxidation reaction in batch still, reaction temperature is that 50 ℃, pressure are that the mol ratio of 0.1MPa (absolute pressure), chlorallylene and methyl alcohol is under 1: 5, chlorallylene and hydrogen peroxide mol ratio be 1.5: 1 and catalytic amount for reaction feed liquid gross mass 7.5% the condition, reaction time is 30 minutes, the hydrogen peroxide conversion ratio is 97.31%, the hydrogen peroxide effective rate of utilization is 97.05%, and the epoxychloropropane selectivity is 97.85%.
Embodiment 7
Aluminium colloidal sol, 12.5 gram starch, 3 gram polyethylene glycol oxides (PEO-400), 0.9 gram OPEO (OP-15), the 1 gram water of 9.0 gram HTSs, 16.5 gram nano aluminium oxides, 20.94 grams, 21.5% (quality) are mixed, kneading repeatedly, be extruded into the slice that diameter is 1.2mm with banded extruder, be cut into the particle that length is 1～3mm again, dry 2h down for 110～125 ℃, in 550 ℃ of roastings 6 hours, obtain strip catalyst, its mechanical strength is 20.8N/cm
2
The gained catalyst carries out the chloro propylene epoxidation reaction in batch still, reaction temperature is that 50 ℃, pressure are that the mol ratio of 0.1MPa (absolute pressure), chlorallylene and methyl alcohol is under 1: 5, chlorallylene and hydrogen peroxide mol ratio be 1.5: 1 and catalytic amount for reaction feed liquid gross mass 10% the condition, reaction time is 30 minutes, the hydrogen peroxide conversion ratio is 98.14%, the hydrogen peroxide effective rate of utilization is 97.16%, and the epoxychloropropane selectivity is 97.94%.
Comparative Examples 1
Press the HTS of the synthetic MFI structure of method of embodiment 1 among the CN1114495C, press the method extruded moulding of embodiment 14 then, the mechanical strength of gained catalyst is 9.1N/cm
2
The catalyst of making carries out the chloro propylene epoxidation reaction in batch still, reaction condition is with embodiment 1～4, and the hydrogen peroxide conversion ratio is 67.61%, and the hydrogen peroxide effective rate of utilization is 87.68%, and the epoxychloropropane selectivity is 96.15%.
Comparative Examples 2
The former powder of the used HTS of the present invention is carried out the chloro propylene epoxidation reaction in batch still, reaction temperature is 50 ℃, pressure is 0.1MPa (absolute pressure), the mol ratio of chlorallylene and methyl alcohol is 1: 5, and chlorallylene and hydrogen peroxide mol ratio are 1.5: 1, and catalyst amount is 3% of reaction feed liquid gross mass, reaction time is 30 minutes, the hydrogen peroxide conversion ratio is 99.48%, and the hydrogen peroxide effective rate of utilization is 97.50%, and the epoxychloropropane selectivity is 98.84%.
Claims (15)
1. the preparation method of a titanium-silicon molecular sieve catalyst, this catalyst comprises the HTS of 25%～65% MFI structure and 20%～65% nano aluminium oxide, the mechanical strength of catalyst is 20～30N/cm
2The HTS of MFI structure is mixed with nano aluminium oxide, aluminium colloidal sol, pore-foaming agent and extrusion aid, be extruded into strip with banded extruder, obtain preformed catalyst through pelletizing, drying, roasting again, wherein said pore-foaming agent is an APES; Quality with HTS is a benchmark, and the prescription of extruded moulding comprises:
1 part of HTS;
0.4～2 part of nano aluminium oxide;
0.9～2.4 part of aluminium colloidal sol;
0.05～0.3 part of pore-foaming agent;
0.08～2 part of extrusion aid.
2. according to the described preparation method of claim 1, the solid content that it is characterized in that aluminium colloidal sol is 10%～40%.
3. according to the described preparation method of claim 2, the solid content that it is characterized in that aluminium colloidal sol is 15%～25%.
4. according to the described preparation method of claim 1, it is characterized in that in the APES that the alkyl carbon number is 2～16.
5. according to the described preparation method of claim 4, it is characterized in that in the APES that the alkyl carbon number is 6～12.
6. according to the described preparation method of claim 1, the degree of polymerization that it is characterized in that APES is 4～60.
7. according to the described preparation method of claim 6, the degree of polymerization that it is characterized in that APES is 10～30.
8. according to the described preparation method of claim 1, it is characterized in that extrusion aid is one or more the mixture in sesbania powder, starch, polyethylene and the polyethylene glycol oxide.
9. according to the described preparation method of claim 8, it is characterized in that extrusion aid is the mixture of starch and polyethylene glycol oxide, the ratio of the two quality is 2～20: 1.
10. according to the described preparation method of claim 9, the molecular weight that it is characterized in that polyethylene glycol oxide is 50～8,000,000.
11., it is characterized in that also comprising 0.04～0.12 part water in the prescription of extruded moulding according to the described preparation method of claim 1.
12. catalyst according to the preparation of the method for claim 1.
13. the described Application of Catalyst of claim 12, being used for the chlorallylene is the feedstock production epoxychloropropane.
14. according to the described application of claim 13, it is characterized in that adopting batch reactor, solvent is a methyl alcohol, the mol ratio of chlorallylene and hydrogen peroxide is 1～10: 1, catalyst amount is 1～30% of reaction feed liquid gross mass, reaction temperature is 20～100 ℃, and pressure is 0.1～2MPa, and the reaction time is 10～100 minutes.
15. according to the described application of claim 13, it is characterized in that adopting fixed bed reactors, the mol ratio of chlorallylene and hydrogen peroxide is 1～10: 1, the mol ratio of methyl alcohol and chlorallylene is 1～20: 1, the feed weight space-time speed 0.01～10h of hydrogen peroxide
-1Reaction temperature is 20～100 ℃, and pressure is 0.1～2MPa.
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| CN102049305B (en) * | 2009-10-27 | 2012-09-12 | 中国石油化工股份有限公司 | Method for preparing titanium silicon molecular sieve catalyst |
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| CN106378185A (en) * | 2016-10-19 | 2017-02-08 | 中国天辰工程有限公司 | Extrusion moulding titanium silicalite molecular sieve catalyst and preparation method thereof |
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