CN103041852A - Extrusion molding method of TS-1 titanium silicalite molecular sieve catalyst - Google Patents
Extrusion molding method of TS-1 titanium silicalite molecular sieve catalyst Download PDFInfo
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Abstract
The invention provides an extrusion molding method of a TS-1 titanium silicalite molecular sieve catalyst. The extrusion molding method is characterized by kneading raw TS-1 raw powder, silica sol, an extrusion assistant and an active carbon fiber to form a wet plastomer, and then drying and roasting to obtain the extruded TS-1 catalyst. Since the active carbon fiber is added in the extrusion molding process, the roasted formed catalyst has a diffusion path through the whole granule; on the one hand, the heat transmission efficiency in a catalytic oxidization process is increased and the catalyst granules are prevented from being sintered because of adverse heat radiation; on the other hand, the mass transfer efficiency in the catalytic oxidization process can be promoted, secondary side reaction and catalyst inactivation caused by product retention are avoided, and the service life of the catalyst is prolonged.
Description
Technical field
The invention belongs to the 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.The TS-1 molecular sieve has huge application potential in the selective oxidation field.Following patent and open source literature have been introduced the application of TS-1:
Such 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.Because the TS-1 molecular sieve is used for the specific (special) requirements of selective oxidation, so the processing and forming of TS-1 molecular sieve is different from Si-Al molecular sieve, need the special forming technique of exploitation.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 for preparing titanium silicalite shaped body.Its technical characterictic is, at 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, and is 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%.HTS is made into glue with silicon source, titanium source, template, alkali and distilled water by certain mol proportion, and mixing, hydrothermal crystallizing make.Inorganic oxide is selected from TiO
2, SiO
2, ZrO
2, Al
2O
3, Na
2O, K
2O, CaO, PbO or the compound among 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 that is comprised of silicon source, titanium source, template, alkali and distilled water, makes HTS growth in situ on inorganic oxide.The gained composite Ti-Si catalyst is spherical or irregular particle, can directly use in fixed bed, moving bed or catalytic distillation reaction unit.
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 the MFI structure molecular screen is combined with the alkaline silica gel of pH8-10, and take ammoniacal liquor or tetraethyl ammonium hydroxide as gelatinizing agent, the sesbania powder is auxiliary agent extrusion or compression molding, drying, 500-650 ℃ lower roasting 4-24 hour.Make the requirement that the catalyst crushing strength can satisfy fixed-bed process, and this catalyst regeneration is functional, can satisfy 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 the formed in situ legal system standby, powdered graphite is introduced the HTS Hydrothermal Synthesis system that is 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, HTS and nano aluminium oxide, aluminium colloidal sol, perforating agent and the auxiliary agent agent of MFI structure mixed, and the method preparation by extruded moulding has the high catalyst of mechanical strength.
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 with HTS (such as TS-1, TS-2 etc.) with compound the forming of the diatomite with specific chemical property that specific process was processed, to carry out chemical modification with transition metal oxide again after the moulding.Said preparation method after diatomite is carried out acid solution, aqueous slkali processing, carry out high-temperature heat treatment to it and make it have specific chemical property; Use again transition metal oxide (such as lanthanum, nickel etc.) to carry out chemical modification in type titanium-silicon molecular sieve/tripolite composite catalyst.
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, adopt that the standby titanium hydroxide of super solubilising micelle legal system-the silicon hydroxide gel 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 form behind the moisture and still have bar-shaped basic structure, obtain the frame structure carrier of unordered accumulation.This carrier pore volume is large, and the aperture is large, and porosity is high, and outer surface orifice is larger, the duct penetrability is good, especially concerning large molecule, can not look like the aperture of ink bottle type, because the aperture obstruction makes 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, polymerization single polymerization monomer and perforating agent that HTS powder, preparation resin are used fully mix, in the presence of initator, carry out again polymerisation, with the blocks of solid catalyst breakage that obtains, then be added in the halogenated hydrocarbons after the swelling, adopt solvent extraction, obtain the catalyst of moulding.Described perforating agent is gasoline, C
5～C
13N-alkane, C
4~ C
12In the fatty alcohol one or more, described initator are benzoyl peroxide/or azo two isobutanols.The catalyst of gained has solved Ti-Si catalyst powder and the problem that reactant liquor is difficult to separate, and 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, in the presence of initator, carry out again polymerisation, with the blocks of solid catalyst breakage that obtains, then be added in the halogenated hydrocarbons after the 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
12In the fatty alcohol one or more, described initator are benzoyl peroxide/or azo two isobutanols.The catalyst of gained has solved Ti-Si catalyst powder and the problem that reactant liquor is difficult to separate, and 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, to have the HTS powder, aluminium hydrate powder, aluminium colloidal sol, pore-foaming agent, extrusion aid of MFI topological structure and water mixes to knead and obtains a kind of plastic plastic body, extrude plastic thing with banded extruder, the strip formed body that obtains wetting, dry and roasting obtains the stripe shape catalyst.Described aluminium oxide is from aluminium hydrate powder and aluminium colloidal sol, and the 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 the 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 the silicon source, graft technology is incorporated into organic or inorganic titanium source in the system of mesopore silicon oxide after utilizing under water or ethanol are the condition of solvent, through ultrasonic, dry, volatilization, surfactant is removed in the recycling roasting, makes easy-formation, the degree of order is high, specific area is large, the aperture is large, pore volume is large, Ti content is high, the 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 with 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, in the presence of initator, carry out again polymerisation, with the blocks of solid catalyst breakage that obtains, then be added in the halogenated hydrocarbons after the swelling, adopt the 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
12In the fatty alcohol one or more, described initator are benzoyl peroxide/or azo two isobutanols.The catalyst of gained of the present invention can realize that alkene epoxidation, hydration single step reaction prepare the process of corresponding diol compound, can also solve Ti-Si catalyst powder and the problem that reactant liquor is difficult to separate 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 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, after the HTS crystallization with Hydrothermal Synthesis, save separation, washing, do not carry out roasting, be expanding agent but directly add stroma ground substance, adhesive, peptizing agent, polyethylene glycol or sesbania powder, through the laggard row spray shaping of pulling an oar, microballoon after the moulding carries out roasting again and removes template, and then obtains oarse-grained moulding HTS particle.
As everyone knows, the catalytic oxidation process of TS-1 participation belongs to strong exothermal reaction process.At present, the heat problem of removing of reactor has mainly been considered in technological design, but can't 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 the granular pattern material can only cause cavity can not cause access opening.
Summary of the invention
The invention provides a kind of extruded moulding method of TS-1 titanium-silicon molecular sieve catalyst, the method is to introduce the NACF of suitable length in the process of extruded moulding, and the NACF roasting removes the diffusion admittance that rear formation connects whole particle.
Technical scheme of the present invention is as follows:
The first step fully stirs TS-1 HTS powder, active carbon fibre peacekeeping Ludox in mixer, is kneaded into wet even plastic body.
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; The 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.
NACF can be artificial NACF or natural fiber, the mixture of one or several in artificial NACF employing viscose glue base, phenolic aldehyde base, polyacrylonitrile-radical, asphalt based active carbon fiber, polyvinylidene chloride, polyimide fiber, styroflex, vinal, the lignin fibre.
Ludox is that aluminium content is less than the alkaline silica sol of 1000 ppm, wherein SiO
2The content mass percent is at 20-40 %, and preferred mass percentage is at 25-35 %.
The mass percent of NACF wet plastic body after accounting for and mediating is 1-20%, preferred 2-15%.The NACF length range is 0.5-10 mm, preferred 1-5mm; Ludox is (with SiO
2Meter) accounting for the mass percent of mediating the rear plastic body that wets is 2-30%, preferred 5-25%; The mass percent of said extrusion aid wet plastic body after accounting for and mediating is 0.2-15%, preferred 1-10%.
The present invention can add extrusion aid, and extrusion aid is selected from one or several in atoleine, starch, glycerine and the polybasic carboxylic acid.
Second step, with the even plastic body extrusion molding in banded extruder for preparing, bar footpath scope is 0.5-10 mm, preferred 1-6 mm; The preformed catalyst of the shapes such as the optional solid cylindrical of stripe shape, cloverleaf pattern and star is extruded the preferred 1-600mm of length, is convenient to drying and roasting.
In the 3rd step, with extruding the air drying 1-48 h of wet feed in room temperature to 80 ℃, be preferably 3-24 h; Then.With the air drying 1-24h of material at 100-200 ℃, preferably at 100-150 ℃ air drying 1-12h.
In the 4th step, the molding materials of drying is made preformed catalyst through calcination process.Roasting condition is: 200-800 ℃ of lower roasting 1-48 h, and preferably at 350-700 ℃ of lower roasting 3-10 h.Calcination atmosphere is the nitrogen atmosphere Program intensification roasting that contains oxygen, processes to make the extruded moulding catalyst.The said oxygen content that contains oxygen nitrogen is 0.2-21%; Heating rate is 10-100 ℃/hour, preferred 20-50 ℃/hour.
The invention has the beneficial effects as follows, by in forming process, introducing the NACF of suitable length, so that the preformed catalyst after the roasting have connect whole particle than major path, can improve heat transfer efficiency in the catalytic oxidation process on the one hand, avoid catalyst granules to cause sintering because the dissipation of heat is unfavorable; Can promote on the other hand the mass-transfer efficiency in the catalytic oxidation process, avoid product to be detained secondary side reaction and the catalysqt deactivation that causes, be conducive to the service life of extending catalyst.
The specific embodiment
The present invention is further illustrated for following embodiment, but do not limit the present invention.The pore size distribution parameter of preformed catalyst is tested at Pore Master 33/60 type mercury injection apparatus.
The comparative example 1
Synthesize micron TS-1 molecular sieve powder according to document Catalysis Today 74 (2002) 65 – 75 disclosed methods, silicon titanium ratio is 33, and grain size is at 6 μ m * 2 μ m * 1 μ m.
Be that 3% citric acid fully mixes with micron TS-1 powder and the mass percent of TS-1 molecular screen primary powder butt, will account for afterwards preformed catalyst (butt) mass fraction and be 20% silicon sol solution (SiO
2Content is 30%) fully stir to mediate and obtain the plasticity formed body; Adopt and mediate banded extruder, be extruded into the solid cylinder of wet strip by the orifice plate of Φ 1.5mm, in 40 ℃ baking oven, dry by the fire 10h, further be warmed up to 120 ℃ of dry 5h after, with the heating rate to 550 of 2 ℃/min ℃, obtain cylindrical bars formation type catalyst sample A at 550 ℃ of lower roasting 12h.
The comparative example 2
According to document " catalysis journal " (2001,22 (6): 513 ~ 514) disclosed method synthesis of nano TS-1 molecular sieve powder, silicon titanium ratio is 41, its grain size is at 0.2 μ m.
Repeat comparative example 1, but change micron TS-1 molecular sieve powder into nano-scale TS-1 molecular sieve powder, obtain preformed catalyst sample B.
Embodiment 1
With micron TS-1 powder and the mass percent that accounts for plastic body wet after the mediating fibre length that is respectively 3% citric acid and 5% be that the polyacrylonitrile radical active carbon fiber of 3mm fully mixes, will account for afterwards preformed catalyst (butt) mass fraction and be 35% silicon sol solution (SiO
2Content is 30%) fully stir to mediate and obtain the plasticity formed body; Mediate banded extruder with all steel, be extruded into the solid cylinder of wet strip by the orifice plate of Φ 1.5mm, after in 40 ℃ baking oven, drying by the fire 10h, with the heating rate to 550 of 2 ℃/min ℃, obtain cylindrical bars formation type catalyst sample C at 550 ℃ of lower roasting 12h, its macropore volume accounts for total pore volume and compares sample A and increased by 12.6%.
Embodiment 2
Repeat embodiment 1, but change micron TS-1 molecular sieve powder into nano-scale TS-1 molecular sieve powder, obtain preformed catalyst sample D, its macropore volume accounts for total pore volume and compares sample B and increased by 12.5%.
Embodiment 3
Repeat embodiment 1, but the addition of polyacrylonitrile radical active carbon fiber is become 10% and 15%, obtain successively sample E and F, its macropore volume accounts for total pore volume and compares sample A and increased respectively 18.1%, 24.3%.
Embodiment 4
Repeat embodiment 1, but the length of polyacrylonitrile radical active carbon fiber is become 1mm, 5mm, addition remains unchanged, and obtains successively sample G and H, and its macropore volume accounts for total pore volume and compares sample A and increased respectively 11.3% and 12.0%.
Embodiment 5
Repeat embodiment 1, but change the polypropylene-base NACF into viscose glue base, phenolic aldehyde base, asphalt based active carbon fiber, and with polyvinylidene chloride, polyimide fiber, styroflex, vinal, lignin fibre and natural fiber, addition and fibre length remain unchanged, consistent with embodiment 1, obtain successively the preformed catalyst sample, the ratio that the macropore volume of gained sample accounts for total pore volume is all suitable with the C sample.
Embodiment 6
Repeat embodiment 1, but change Ludox wherein into SiO
2Content is respectively 25% and 35%, and proportion is constant, obtains successively the preformed catalyst sample, and the ratio that the macropore volume of gained sample accounts for total pore volume is all suitable with the C sample.
Embodiment 7
Repeat embodiment 1, but change extrusion aid wherein into glycerine and atoleine, addition is constant, obtains successively the preformed catalyst sample, and the ratio that the macropore volume of gained sample accounts for total pore volume is all suitable with the C sample.
Embodiment 8
Repeat embodiment 1, but the addition of citric acid is changed to respectively 5%, 7% and 9%, obtain successively the preformed catalyst sample, the ratio that the macropore volume of gained sample accounts for total pore volume is suitable with sample C.
Embodiment 9
Repeat embodiment 1, but the temperature of drying is become 50 ℃, 65 ℃ and 80 ℃, and the temperature that will further heat up under each baking temperature becomes respectively 100 ℃ and 150 ℃, and drying time is constant, obtain successively the preformed catalyst sample, the mechanical strength of gained sample is all suitable with the C sample.
Embodiment 10
Repeat embodiment 1, but the temperature of roasting is become 450 ℃, 500 ℃ and 600 ℃, under each sintering temperature, the ascending order heating rate become respectively 20 ℃/hour, 30 ℃/hour and 40 ℃/hour, obtain successively the preformed catalyst product, ratio and mechanical strength that the macropore volume of products obtained therefrom accounts for total pore volume are suitable with product D.
Claims (9)
1. the extruded moulding method of a TS-1 titanium-silicon molecular sieve catalyst is characterized in that comprising the steps:
The first step fully stirs TS-1 HTS powder, NACF, Ludox and extrusion aid in mixer, is kneaded into wet even plastic body;
The mass percent of NACF wet plastic body after accounting for and mediating is 1-20%, and the NACF length range is 0.5-10 mm;
Ludox is that aluminium content is less than the alkaline silica sol of 1000 ppm, wherein SiO
2Mass percent content at 20-40%; With SiO
2The mass percent of meter, Ludox wet plastic body after accounting for and mediating is 5-25%;
Second step, with the even plastic body extrusion molding in banded extruder for preparing, bar footpath scope is 0.5-10 mm;
The 3rd step had been no more than 80 ℃ air drying 1-48 hour with extruding wet formed body, dried material in 100-200 ℃ air dry 1-24 hour again;
The 4th step was containing oxygen nitrogen atmosphere Program intensification roasting with the molding materials of drying, processed making the extruded moulding catalyst;
The oxygen content that contains oxygen nitrogen is 0.2-21%; Temperature programming speed is 10-100 ℃/hour, and sintering temperature is 200-800 ℃.
2. extruded moulding method according to claim 1, it is characterized in that, described NACF is artificial NACF or natural fiber, and artificial NACF is one or several the mixture in viscose glue base, phenolic aldehyde base, polyacrylonitrile-radical, asphalt based active carbon fiber, polyvinylidene chloride, polyimide fiber, styroflex, vinal, the lignin fibre.
3. extruded moulding method according to claim 1 and 2 is characterized in that, the mass percent of NACF wet plastic body after accounting for and mediating is 2-15%, and the NACF length range is 1-5mm.
4. extruded moulding method according to claim 1 and 2 is characterized in that, the mass percent of the extrusion aid of adding wet plastic body after accounting for and mediating is 0.2-15%.
5. extruded moulding method according to claim 1 and 2 is characterized in that, described extrusion aid is one or several in atoleine, starch, glycerine and the polybasic carboxylic acid.
6. extruded moulding method according to claim 1 and 2 is characterized in that, with SiO
2The mass percent of meter, Ludox wet plastic body after accounting for and mediating is 5-25%.
7. extruded moulding method according to claim 1 and 2 is characterized in that, with the even plastic body extrusion molding in banded extruder for preparing, bar footpath scope is 1-6 mm.
8. extruded moulding method according to claim 1 and 2 is characterized in that, the 3rd step, be no more than 80 ℃ air drying 3-24 hour with extruding wet formed body, and dried material is 100-150 ℃ air drying 1-12 hour.
9. extruded moulding method according to claim 1 and 2 is characterized in that, the 4th the step, roasting condition is: 350-700 ℃ lower roasting 3-10 hour, heating rate is 20-50 ℃/hour.
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| CN112007689A (en) * | 2019-05-31 | 2020-12-01 | 大连理工大学 | Catalyst and preparation method and application thereof |
| CN112520753A (en) * | 2020-10-19 | 2021-03-19 | 郑州大学 | Method for improving mechanical strength of titanium silicalite TS-1 |
| CN113083359A (en) * | 2019-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Hydrotalcite modified titanium silicalite molecular sieve catalyst, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105363489A (en) * | 2015-12-02 | 2016-03-02 | 中国天辰工程有限公司 | Extrusion molding method for Ti-Si molecular sieve catalyst with high molecular sieve content |
| CN109748292A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve bar shaped agent and its extruded moulding methods and applications |
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| CN112007689A (en) * | 2019-05-31 | 2020-12-01 | 大连理工大学 | Catalyst and preparation method and application thereof |
| CN112007689B (en) * | 2019-05-31 | 2021-10-19 | 大连理工大学 | Catalyst and preparation method and application thereof |
| CN113083359A (en) * | 2019-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Hydrotalcite modified titanium silicalite molecular sieve catalyst, preparation method and application |
| CN113083359B (en) * | 2019-12-23 | 2023-07-25 | 中国石油化工股份有限公司 | Hydrotalcite modified titanium-silicon molecular sieve catalyst, preparation method and application |
| CN112520753A (en) * | 2020-10-19 | 2021-03-19 | 郑州大学 | Method for improving mechanical strength of titanium silicalite TS-1 |
| CN112520753B (en) * | 2020-10-19 | 2022-09-23 | 郑州大学 | Method for improving mechanical strength of titanium silicalite TS-1 |
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