CN103041853B - A kind of fiber catalyst forming method of TS-1 titanium silicon molecular sieve catalyst - Google Patents
A kind of fiber catalyst forming method of TS-1 titanium silicon molecular sieve catalyst Download PDFInfo
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- CN103041853B CN103041853B CN201210514414.7A CN201210514414A CN103041853B CN 103041853 B CN103041853 B CN 103041853B CN 201210514414 A CN201210514414 A CN 201210514414A CN 103041853 B CN103041853 B CN 103041853B
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Abstract
The invention provides a fiber catalyst forming method of a TS-1 titanium silicalite molecular sieve catalyst. The catalyst is formed by a fiber forming method by using a mixed viscous solution of carbon-containing refractory polymer material and TS-1 molecular sieve. By introducing the carbon-containing fibrous polymer, through holes are formed in the molded catalyst after the molded catalyst is calcined, so that high specific surface area is obtained, the contact probability among reactants is increased, and the occurrence of catalytic oxidation reaction is promoted.
Description
Technical field
The invention belongs to petrochemical catalyst technical field, relate to a kind of forming method of titanium-silicon molecular sieve catalyst.
Background technology
HTS (titanium silicalite-1) is the novel hetero-atom molecular-sieve of a kind of MFI of having type structure of early eighties exploitation in last century, is called for short TS-1.TS-1 molecular sieve has huge application potential in selective oxidation field.Following patent and open source literature have been introduced the application of TS-1:
As CN1376151A (2000-08-08), CN1314348A (2001-03-30), CN1387948A (2002-02-05), CN1534030A (2003-03-28), CN1651405A (2004-11-04), CN1769277A (2005-11-14), CN1810772A (2006-01-24), CN101172970A (2007-10-12), catalysis journal, 25 (2004) 49-54; Journal of Molecular Catalysis, 19 (2005) 7-11; Petroleum journal (PETROLEUM PROCESSING), 22 (2006) 72-77; Applied catalysis A:General, 246 (2003) 69-77; Journal of molecular catalysis A:chemical, 210 (2004) 171-178; Journal of molecular catalysis A:chemical, 229 (2005) 71-75; Chemical engineering journal, 116 (2006) 179-186; Journal of catalysis, 253 (2008) 148-158 etc.
The processing and forming of TS-1 molecular sieve is the important step of its application.Due to the specific (special) requirements of TS-1 molecular sieve for selective oxidation, so the processing and forming of TS-1 molecular sieve is different from Si-Al molecular sieve, need to develop special forming technique.Following patent and open source literature have been introduced the preparation method of TS-1 preformed catalyst:
Patent CN 1419475 (01807020.5 applying date of application number 2001-03-21) has disclosed a kind of method of preparing titanium silicalite shaped body.Its technical characterictic is, first forms the plastic composition of a kind of titan silicate, binding agent and a kind of paste making agent, forms a kind of formed body of life, dry through different condition, and calcining, forms required formed body.
Patent CN 1346705 (01140509.0 applying date of application number 2001-09-13) has disclosed a kind of preparation method of composite catalyst.Its technical characterictic is that catalyst is comprised of the MFI structure titanium silicon molecular sieve of 2.0～95.0wt% and the inorganic oxide of 5.0～98.0wt%.Silicon source, titanium source, template, alkali and distilled water for HTS, be made into glue by certain mol proportion, mixes, hydrothermal crystallizing makes.Inorganic oxide is selected from TiO
2, SiO
2, ZrO
2, Al
2o
3, Na
2o, K
2o, CaO, PbO or the compound in them or mixture.The composite catalyst of the spherical or irregular particle of making by extrusion or spray mo(u)lding method.
Patent CN 1398674 (02126775.8 applying date of application number 2002-07-25) has disclosed a kind of composite Ti-Si catalyst and in-situ forming preparation process thereof.Its technical characterictic is to be comprised of the MFI structure titanium silicon molecular sieve (TS-1) of 1.0-80.0% (weight) and the inorganic oxide of 20.0-99.0% (weight).Composite Ti-Si catalyst is the preparation method who adopts formed in situ, is about to inorganic oxide and introduces in the HTS Hydrothermal Synthesis system being comprised of silicon source, titanium source, template, alkali and distilled water, makes HTS growth in situ on inorganic oxide.Gained composite Ti-Si catalyst is spherical or irregular particle, can directly in fixed bed, moving bed or catalytic distillation reaction unit, use.
Patent CN 1600428 (03126438.7 applying date of application number 2003-09-28) has disclosed a kind of preparation method of molecular sieve catalyst of the MFI of containing structure.The method is that MFI structure molecular screen is combined with the alkaline silica gel of pH8-10, take ammoniacal liquor or tetraethyl ammonium hydroxide as gelatinizing agent, and sesbania powder is auxiliary agent extrusion or compression molding, dry, roasting 4-24 hour at 500-650 ℃.Make the requirement that catalyst crushing strength can meet fixed-bed process, and this catalyst regeneration is functional, can meet the requirement of industrial application.
Patent CN 1554483 (200310120868.7 applying date of application number 2003-12-27) has disclosed a kind of composite Ti-Si catalyst and preparation method thereof.Its technical characterictic is, adopt formed in situ legal system standby, powdered graphite is introduced to the HTS Hydrothermal Synthesis system being formed by silicon source, titanium source, template, alkali and distilled water, make HTS growth in situ on powdered graphite, then composite is separated with mother liquor, drying, roasting are made.
Patent CN 101371989 (200710120615.8 applying date of application number 2007-08-22) has disclosed a kind of titanium-silicon molecular sieve catalyst and its preparation method and application.Its technical characterictic is, the HTS of MFI structure is mixed with nano aluminium oxide, aluminium colloidal sol, perforating agent and auxiliary agent agent, and the method preparation by extruded moulding has the catalyst that mechanical strength is high.
Patent CN 101264453 (200810034431.4 applying date of application number 2008-03-10) has disclosed a kind of titanium-silicon molecular sieve/tripolite composite catalyst and preparation method.Its technical characterictic is, by HTS (as TS-1, TS-2 etc.) and compound the forming of the diatomite with specific chemical property of processing with specific process, after moulding, carries out chemical modification again with transition metal oxide.Said preparation method carries out, after acid solution, aqueous slkali processing, carrying out high-temperature heat treatment to it and making it have specific chemical property to diatomite; To in type titanium-silicon molecular sieve/tripolite composite catalyst, use again transition metal oxide (as lanthanum, nickel etc.) to carry out chemical modification.
Patent CN 101890376A (200910206227.0 applying date of application number 2009-10-18) has disclosed a kind of preparation method of titanium-silicon composite oxide carrier.Its technical characterictic is, adopting the standby titanium hydroxide-silicon hydroxide gel of super solubilising micelle legal system is raw material, owing to containing surfactant and hydrocarbon component in this gel, after moulding and roasting, make the titanium hydroxide of polymerization and silicon hydroxide deviate from the nano-titanium oxide and the silicon oxide particle that after moisture, form and still there is bar-shaped basic structure, obtain the frame structure carrier of unordered accumulation.This carrier pore volume is large, and aperture is large, and porosity is high, and outer surface orifice is larger, duct penetrability is good, especially, concerning large molecule, can not look like the aperture of ink bottle type, because of aperture, stop up and make catalysqt deactivation, be conducive to increase the deposition of impurity, the service cycle of extending catalyst.
Patent CN 102049304A (200910188161.7 applying date of application number 2009-10-27) has disclosed a kind of HTS and resin compounded Catalysts and its preparation method.Its technical characterictic is, by HTS powder, prepare polymerization single polymerization monomer and the perforating agent that resin uses and fully mix, under initator exists, carry out again polymerisation, by the blocks of solid catalyst breakage obtaining, then be added in halogenated hydrocarbons after swelling, adopt solvent extraction, obtain the catalyst of moulding.Described perforating agent is gasoline, C
5～C
13n-alkane, C
4~ C
12one or more in fatty alcohol, described initator is benzoyl peroxide/or azo two isobutanols.The catalyst of gained has solved Ti-Si catalyst powder and has been difficult to separated problem with reactant liquor, has improved reaction efficiency.
Patent CN 102049305A (200910188162.1 applying date of application number 2009-10-27) has disclosed a kind of preparation method of titanium-silicon molecular sieve catalyst.Its technical characterictic is, HTS powder, polymerization single polymerization monomer styrene, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed, under initator exists, carry out again polymerisation, by the blocks of solid catalyst breakage obtaining, then be added in halogenated hydrocarbons after swelling, adopt solvent extraction, obtain the titanium-silicon molecular sieve catalyst of moulding.Described perforating agent is gasoline, C
5～C
13n-alkane, C
4~ C
12one or more in fatty alcohol, described initator is benzoyl peroxide/or azo two isobutanols.The catalyst of gained has solved Ti-Si catalyst powder and has been difficult to separated problem with reactant liquor, has improved reaction efficiency.
Patent CN 102259023A (201010184391.9 applying date of application number 2010-05-27) has disclosed a kind of forming method of titanium-silicon molecular sieve catalyst.Its technical characterictic is, HTS powder, aluminium hydrate powder, aluminium colloidal sol, pore-foaming agent, extrusion aid and the water with MFI topological structure are mixed to knead and obtain a kind of plastic plastic body, with banded extruder, extrude plastic thing, obtain wet strip formed body, dry and roasting obtains stripe shape catalyst.Described aluminium oxide is from aluminium hydrate powder and aluminium colloidal sol, and side pressure breaking strength is 70～150N/cm.Said pore-foaming agent is APES, and extrusion aid is one or several in sesbania powder, starch and citric acid.
Patent CN 101935064A (201010275332.2 applying date of application number 2010-09-07) has disclosed the synthetic method of the order mesoporous titanium silicalite material of a kind of easy-formation.Its technical characterictic is, adopting new synthesizing mesoporous monox is silicon source, after utilizing under the condition that water or ethanol are solvent, graft technology is incorporated into organic or inorganic titanium source in the system of mesopore silicon oxide, through ultrasonic, dry, volatilization, surfactant is removed in recycling roasting, makes easy-formation, the degree of order is high, specific area is large, aperture is large, pore volume is large, Ti content is high, silicon titanium is than adjustable mesoporous titanium-silicon material.
Patent CN 102441429A (201010511564.3 applying date of application number 2010-10-11) has disclosed a kind of forming method of HTS.Its technical characterictic is that by the mixture of HTS, amorphous silica and alkaline earth oxide and water, moulding obtains formed body, and described formed body is dry, roasting.
Patent CN 102451763A (201010522141.1 applying date of application number 2010-10-15) has disclosed a kind of titanium-silicon molecular sieve compound catalyst and preparation method thereof.Its technical characterictic is, HTS, acidic molecular sieve, polymerization single polymerization monomer polyene-based compound and perforating agent are fully mixed, under initator exists, carry out again polymerisation, by the blocks of solid catalyst breakage obtaining, then be added in halogenated hydrocarbons after swelling, adopt solvent extraction activation, obtain the titanium-silicon molecular sieve compound catalyst of moulding.Described perforating agent is gasoline, C
5～C
13n-alkane, C
4~ C
12one or more in fatty alcohol, described initator is benzoyl peroxide/or azo two isobutanols.The catalyst of gained of the present invention can be realized the process that alkene epoxidation, hydration single step reaction are prepared corresponding diol compound, can also solve Ti-Si catalyst powder and be difficult to separated problem with reactant liquor simultaneously, improves reaction efficiency.
Patent CN 102091651A (201010597078.8 applying date of application number 2010-12-10) has disclosed a kind of method of TS-1 extruded moulding.Its technical characterictic is TS-1 powder and sesbania powder, Ludox, atoleine to be mixed to kneading, extruded moulding, drying and roasting, the salting liquid of excessive dipping nickel or cobalt, drying and roasting, the salting liquid of excessive dipping molybdenum or tungsten, drying and roasting.
Patent CN 102614911A (application number 201210042471.X applying date 2012-02-23) has disclosed a kind of one-step moulding method of HTS.Its technical characterictic is, by after the HTS crystallization of Hydrothermal Synthesis, save separation, washing, do not carry out roasting, but directly add stroma ground substance, adhesive, peptizing agent, polyethylene glycol or sesbania powder, it is expanding agent, through the laggard row spray shaping of pulling an oar, microballoon after moulding carries out roasting again and removes template, and then obtains oarse-grained moulding HTS particle.
As everyone knows, the catalytic oxidation process that TS-1 participates in belongs to strong exothermal reaction process.At present, the heat problem of removing of reactor has mainly been considered in technological design, but cannot solve the dissipation of heat of catalyst inside.In the catalyst granules of moulding, introduce abundant through duct and be conducive to mass-and heat-transfer.Existing TS-1 forming method has adopted gasoline, C
5～C
13n-alkane, C
4~ C
12the pore creating materials such as fatty alcohol, polyethylene glycol, graphitic carbon and sesbania powder.Yet, above-mentioned pore creating material or small-sizedly can not cause through duct, otherwise belonging to granular pattern material can only cause cavity can not cause access opening.
Summary of the invention
The invention provides a kind of fiber catalyst forming method of TS-1 titanium-silicon molecular sieve catalyst.The method is to introduce appropriate carbon fiber as the carrier of catalyst, by roasting after moulding, in the inside of catalyst, forms through hole, to obtain high-specific surface area, thereby increases the contact probability between reactant, promotes the generation of catalytic oxidation.
Technical scheme of the present invention is as follows:
The first step, the polymeric material of infusibility that can carbonization is placed on the spinning solution that is dissolved into viscous in solvent, then TS-1 molecular sieve powder is put into viscous solution, prepares uniform sizing material.
Said TS-1 molecular sieve powder can be according to existing patent and open source literature preparation.Such as preparing with reference to following patent and list of references: CN1167082A, CN1239016A, CN1169952A, CN1217232A, CN1275530A, CN1239015AZL, CN1245089A, CN1247771A, CN1294030A, CN1327947A, CN1418813A, CN1216801C, CN1401569A, CN1488438C, CN101190792A, CN101434400A, CN101327934B, CN101696019A, US5656252, WO2009077086, Journal of Molecular Catalysis, 01 (1996) 25-32; Oil refinery and chemical industry, 31 (2000) 33-37; Chemistry of fuel journal, 33 (2005) 112-116; Journal of Molecular Catalysis, 21 (2007) 458-462; SCI, 29 (2008) 1926-1929; Zeolites, 16 (1996) 184-195; Microporous and mesoporous materials, 22 (1998) 23-31; Microporous and mesoporous material, 66 (2003) 143-156; Catalysis today, 158 (2010) 510-514; Chemical engineering journal, 147 (2009) 316-322 etc.
Polymeric material can be used polypropylene fibre or regenerated celulose fibre, and the mass fraction that accounts for slurry is 10-95%, preferably 20-80%.
Second step, is sprayed into this viscous solution thread, then carbon fiber is carried out to carbonization treatment, finally carries out activation processing.The pre-oxidation 1-24 hour in the air of 200-300 ℃ of elder generation when carbonization and activation processing, preferably in the air of 230-270 ℃, activate in advance 3-8 hour, and then be heated to 850-1000 ℃ in the inert atmosphere such as nitrogen, helium, finally import steam, carbon dioxide, at 850-1000 ℃, carry out activation processing 1-24 hour, preferably 3-8 hour.
The invention has the beneficial effects as follows, adopt fibrous carrier to carry out moulding to catalyst, thereby obtain the fiber catalyst of high-specific surface area.
The specific embodiment
The present invention is further illustrated for following embodiment, but do not limit the present invention.The specific area of preformed catalyst is tested at the Tristar3020 type physical adsorption appearance of U.S. Mecromeritics company.
Comparative example 1
According to the disclosed synthetic micron of the method TS-1 of document Catalysis Today 74 (2002) 65 – 75, silicon titanium ratio is 33, and grain size is at 6 μ m * 1, μ m * 2 μ m.
Micron TS-1 molecular sieve powder is mixed in proportion with white carbon black powder, make white carbon account for 50% of shaped article, spray into adhesive, wherein the dioxide-containing silica of Ludox is 15%, prepares uniform sizing material.Adopt hydrocarbon-ammonia post method of forming preformed catalyst, at 40 ℃, after dry 3h, at 120 ℃, be dried 3 hours, under the nitrogen atmosphere that is 10% in oxygen content, with the heating rates to 550 of 30 ℃/h ℃, carry out roasting, obtain spheric catalyst products A, testing its specific area is 300m
2/ g.
Comparative example 2
According to document < < catalysis journal > > (2001,22(6): 513 ~ 514) disclosed method synthesis of nano TS-1, silicon titanium ratio is 41, grain size is 0.2 μ m.
Nano-scale TS-1 molecular sieve powder is mixed in proportion with white carbon black powder, make white carbon account for 50% of shaped article, wherein the dioxide-containing silica of Ludox is 15%, prepares uniform sizing material.Adopt hydrocarbon-ammonia post method of forming preformed catalyst, at 40 ℃, after dry 3h, at 120 ℃, be dried 3 hours, under the nitrogen atmosphere that is 10% in oxygen content, with the heating rates to 550 of 30 ℃/h ℃, carry out roasting, obtain spheric catalyst product B, testing its specific area is 360m
2/ g.
Embodiment 1.
The polymeric material of infusibility that can carbonization is placed on the spinning solution that is dissolved into viscous in solvent, again micron TS-1 molecular sieve powder is put into viscous solution, mix, make carrier account for 20% of shaped article, this viscous solution is sprayed into thread, then carbon fiber is carried out to carbonization treatment, finally carry out activation processing.Pre-oxidation 3 hours in the air of present 230 ℃ when carbonization and activation processing, and then be heated to 850 ℃ in the inert atmosphere such as nitrogen, helium, and then import steam, carbon dioxide, at 850 ℃, carry out activation processing 3 hours, obtain product B, its specific area increases by 10.3% than products A.
Embodiment 2
Repeat embodiment 1, but the content that carrier accounts for shaped article is adjusted to 40%, 60%, 80%, the specific area that obtains catalyst prod increases by 13.4%, 16.7%, 20.1% than product B.
Embodiment 3
Repeat embodiment 1, but Pre oxidation is adjusted to 250 ℃, 270 ℃, the specific area and the product B that obtain catalyst prod are suitable.
Embodiment 4
Repeat embodiment 1, but preoxidation time is adjusted to 4,5,8 hours, the specific area that obtains catalyst prod increases by 10.7%, 12.6%, 14.8% than product B.
Embodiment 5
Repeat embodiment 1, but soak time is adjusted to 4,5,8 hours, the specific area that obtains catalyst prod increases by 17.7%, 19.6%, 20.8% than product B.
Claims (4)
1. a fiber catalyst forming method for TS-1 titanium-silicon molecular sieve catalyst, is characterized in that comprising the steps:
The first step, the polymeric fiber material of infusibility that can carbonization is placed on the spinning solution that is dissolved into viscous in solvent, then TS-1 molecular sieve powder is put into viscous solution, prepares uniform sizing material; The mass fraction that charcoal polymeric fiber material carrier accounts for slurry is 10-95%;
Second step, is sprayed into this viscous solution thread, then carbon fiber is carried out to carbonization treatment, finally carries out activation processing; When carbonization and activation processing, the pre-oxidation 1-24 hour in the air of 200-300 ℃ of elder generation is then heated to 850-1000 ℃ in inert atmosphere, finally imports steam or carbon dioxide, carries out activation processing 1-24 hour at 850-1000 ℃.
2. fiber catalyst forming method according to claim 1, is characterized in that, described charcoal polymeric fiber material carrier is polypropylene fibre or regenerated celulose fibre, and the addition of carrier is 20-80%.
3. fiber catalyst forming method according to claim 1, is characterized in that, second step, and pre-activation condition is: by fiber-like catalyst pre-oxidation 3-8 hour in the air of 230-270 ℃, then in nitrogen or helium inert atmosphere, be heated to 850-1000 ℃.
4. fiber catalyst forming method according to claim 1, is characterized in that, second step, and activation condition is: import steam or carbon dioxide, carry out activation processing 3-8 hour at 850-1000 ℃.
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| CN113083360B (en) * | 2019-12-23 | 2023-07-25 | 中国石油化工股份有限公司 | Preparation method of titanium-silicon molecular sieve catalyst taking carbon nanofibers as carrier |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101199941A (en) * | 2007-08-03 | 2008-06-18 | 华东理工大学 | A kind of preparation method of composite catalyst of titanium silicon molecular sieve/nano carbon fiber |
| CN101767036A (en) * | 2009-12-25 | 2010-07-07 | 湘潭大学 | Titanium silicalite TS-1 catalyst preparation method |
| CN102614911A (en) * | 2012-02-23 | 2012-08-01 | 湘潭大学 | One-step molding method of titanium silicalite molecular sieve |
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| CN1132699C (en) * | 1999-12-24 | 2003-12-31 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| KR100604138B1 (en) * | 2004-07-05 | 2006-07-25 | 요업기술원 | Method for producing titanium silicalite zeolite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101199941A (en) * | 2007-08-03 | 2008-06-18 | 华东理工大学 | A kind of preparation method of composite catalyst of titanium silicon molecular sieve/nano carbon fiber |
| CN101767036A (en) * | 2009-12-25 | 2010-07-07 | 湘潭大学 | Titanium silicalite TS-1 catalyst preparation method |
| CN102614911A (en) * | 2012-02-23 | 2012-08-01 | 湘潭大学 | One-step molding method of titanium silicalite molecular sieve |
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