CN103008003A - Performed forming method of high-strength TS-1 titanium silicalite molecular sieve catalyst - Google Patents
Performed forming method of high-strength TS-1 titanium silicalite molecular sieve catalyst Download PDFInfo
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Abstract
The invention provides a performed forming method of a high-strength TS-1 titanium silicalite molecular sieve catalyst. The method is characterized by comprising the steps: kneading TS-1 molecular sieve powder, silica carriers, adhesive, activated carbon fiber, and boric acid to an even plastomer according to proportion, and conducting performed forming, drying and roasting to obtain the perform-formed TS-1 catalyst. The activated carbon fiber introduced in the forming forms a dispersion channel penetrating through the whole granules after being roasted, thereby improving the heat transfer and mass transfer efficiency, avoiding secondary adverse reaction and catalyst deactivation due to retention of the product, and preventing the catalyst granules from being roasted due to bad heat dissipation. In the meantime, through the roasted boric acid introduced in the forming process, the mechanical strength of the formed catalyst can be improved, impact produced in transportation, loading and using processes and wear caused by flowing of fluid can be effectively prevented, and the service life of the catalyst can be favorably prolonged.
Description
Technical field
The invention belongs to the petrochemical catalyst technical field, relate to a kind of forming method of high strength titanium silicalite 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 has adopted 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 contain 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 that easy-formation, the degree of order are 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.
Simultaneously, existing TS-1 forming method has reduced the mechanical strength of preformed catalyst after introducing above-mentioned pore creating material, occurs wearing and tearing or broken in the easier process using.
Summary of the invention
The invention provides a kind of compression molding method of high strength TS-1 titanium-silicon molecular sieve catalyst.The method is to introduce an amount of boric acid of active carbon fibre peacekeeping of suitable length in the process of compression molding, the NACF roasting removes the diffusion admittance that rear formation connects whole tablet, and boric acid forms the mechanical strength of the oxide enhancing preformed catalyst of boron through roasting.
Technical scheme of the present invention is as follows:
The first step, described TS-1 HTS powder, NACF, silica supports and intensity auxiliary agent are fully stirred in mixer, be kneaded into uniform mixed material, then in mixed material, spray into adhesive, be kneaded into the moulding plastic body for compressing tablet.
Wherein said silica supports is the silica supports that aluminium content is lower than 1000 ppm, and silica supports can be one or more the mixture in white carbon, solid silicone or the precipitation silicon ball.The mass percent that silica supports accounts for for the moulding plastic body of compressing tablet is 5-30%, preferred 10-25%.
Said NACF can be artificial NACF or natural fiber, artificial NACF adopts viscose glue base, phenolic aldehyde base, polyacrylonitrile-radical, asphalt based active carbon fiber, and one or several the mixture in the NACF that makes take polyvinylidene chloride, polyimide fiber, styroflex, vinal, lignin fibre and some natural fibers as raw material.The mass percent that NACF accounts for for the moulding plastic body of compressing tablet is 0.5-20%, preferred 1-10%.The NACF length range is 0.5-10 mm, preferred 1-5mm.
Said intensity auxiliary agent is boric acid, and the mass percent that the addition of boric acid accounts for for the moulding plastic body of compressing tablet is 0.1-10%, preferred 0.1-2.0%.
Said adhesive is comprised of Ludox and shaping assistant.Said Ludox is the Ludox that aluminium content is lower than 1000 ppm, its SiO
2Content is 20-40%, preferred 30-40%.Said shaping assistant is selected from one or several the mixture in atoleine, glycerine or the citric acid, and its mass percent that accounts for adhesive is 0.5-20%, preferred 1-10%.The mass percent that adhesive accounts for for the plastic body of compressing tablet moulding is 1-15%, preferred 3-8%.
Second step is pressed into tablet with the moulding plastic body for compressing tablet for preparing in tablet press machine.Tablet thickness is 0.2-15mm, preferred 2-10mm; Diameter is 5-40mm, preferred 10-30mm.
In the 3rd step, the resulting tablet of second step at air drying 0-48 hour that is no more than 80 ℃, is preferably 0.5-6 hour.Then with dried tablet in 80-200 ℃ air dry 1-24 hour again, preferably 100-150 ℃ air drying 2-5 hour.
The 4th step, the tablet of drying is being contained the nitrogen atmosphere Program intensification roasting of oxygen, process making sheet catalyst.
The said oxygen content that contains oxygen nitrogen is 0.2-21%; Said temperature-programmed calcination temperature is 200-800 ℃, preferred 350-600 ℃; Said heating rate is 10-100 ℃/hour, preferred 20-50 ℃/hour.
The invention has the beneficial effects as follows, the NACF by in forming process, introducing suitable length and an amount of boric acid so that the preformed catalyst after the roasting have connect whole particle than major path, have simultaneously stronger mechanical strength.Can improve mass transfer in the catalytic oxidation process, heat transfer efficiency on the one hand, avoid preventing that because product is detained secondary side reaction and the catalysqt deactivation that causes catalyst granules from causing sintering because the dissipation of heat is unfavorable; On the other hand, can effectively resist the wearing and tearing that the impact that produces and Fluid Flow in A cause in transportation, filling and use procedure, be conducive to the service life of extending catalyst.
The specific embodiment
Following embodiment will the present invention is further illustrated, 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.Preformed catalyst intensity is tested at ZQJ-II Intelligent testing machine for particle.
The comparative example 1
Synthesize micron TS-1 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.
Micron TS-1 molecular sieve powder and white carbon carrier are fully stirred in mixer, then in mixed material, spray into adhesive, be kneaded into the plastic body for the compressing tablet moulding.Wherein to account for the mass percent for compressing tablet moulding plastic body be 15% to the white carbon carrier; The mass percent that adhesive accounts for for compressing tablet moulding plastic body is 5%.The mass percent that described shaping assistant glycerine accounts for adhesive is 4%, the SiO of described Ludox
2The quality percentage composition is 35%.In tablet press machine, press above-mentioned plastic body to such an extent that thickness is that 5mm, diameter are the tablet of 20mm.With the tablet that obtains 40 ℃ lower dry 3 hours, 120 ℃ lower dry 3 hours, be under 10% the nitrogen atmosphere in oxygen content, ℃ carry out roasting with 30 ℃/hour heating rates to 550, obtain the sheet catalyst product A.
The 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 and white carbon carrier are fully stirred in mixer, then in mixed material, spray into adhesive, be kneaded into the plastic body for the compressing tablet moulding.Wherein to account for the mass percent for compressing tablet moulding plastic body be 15% to the white carbon carrier; The mass percent that adhesive accounts for for compressing tablet moulding plastic body is 5%.The mass percent that described shaping assistant glycerine accounts for adhesive is 4%, the SiO of described Ludox
2The quality percentage composition is 35%.In tablet press machine, press above-mentioned plastic body to such an extent that thickness is that 5mm, diameter are the tablet of 20mm.With the tablet that obtains 40 ℃ lower dry 3 hours, 120 ℃ lower dry 3 hours, be under 10% the nitrogen atmosphere in oxygen content, ℃ carry out roasting with 30 ℃/hour heating rates to 550, obtain the sheet catalyst product B.
The comparative example 3
Be that the polyacrylonitrile radical active carbon fiber of 3mm fully stirs in mixer with micron TS-1 molecular sieve powder, white carbon carrier and length, then in mixed material, spray into silica sol binder, be kneaded into the plastic body for the compressing tablet moulding.Wherein to account for the mass percent for the plastic body of compressing tablet moulding be 15% to the white carbon carrier; The mass percent that polyacrylonitrile radical active carbon fiber accounts for for the plastic body of compressing tablet moulding is 5%; The mass percent that adhesive accounts for for the plastic body of compressing tablet moulding is 5%.The mass percent that described shaping assistant glycerine accounts for adhesive is 4%, the SiO of described Ludox
2The quality percentage composition is 35%.Said mixture is kneaded into even plastic body, and it is that 5mm, diameter are the tablet of 20mm that compression molding obtains thickness.The tablet that obtains is lower dry 3 hours at 40 ℃, lower dry 3 hours at 120 ℃, be under 10% the nitrogen atmosphere in oxygen content, ℃ carry out roasting with 30 ℃/hour heating rates to 550, obtain ratio that its macropore volume of sheet catalyst products C accounts for total pore volume and compare with product A and increased by 13.5%.
Embodiment 1
Be that the polyacrylonitrile radical active carbon fiber of 3mm and boric acid fully stir in mixer with micron TS-1 molecular sieve powder, white carbon carrier, length, then in mixed material, spray into silica sol binder, be kneaded into the plastic body for the compressing tablet moulding.Wherein to account for the mass percent for the plastic body of compressing tablet moulding be 15% to the white carbon carrier; The mass percent that polyacrylonitrile radical active carbon fiber accounts for for the plastic body of compressing tablet moulding is 5%; The mass percent that adhesive accounts for for the plastic body of compressing tablet moulding is 5%; The mass percent that boric acid accounts for for the plastic body of compressing tablet moulding is 1.0%.The mass percent that described shaping assistant glycerine accounts for adhesive is 4%, the SiO of described Ludox
2The quality percentage composition is 35%.Said mixture is kneaded into even plastic body, and it is that 5mm, diameter are the tablet of 20mm that compression molding obtains thickness.The tablet that obtains is lower dry 3 hours at 40 ℃, lower dry 3 hours at 120 ℃, be under 10% the nitrogen atmosphere in oxygen content, ℃ carry out roasting with 30 ℃/hour heating rates to 550, obtain sheet catalyst product D, the ratio that its macropore volume accounts for total pore volume is compared with product A and has been increased by 13.3%.Its intensity is compared with products C has increased by 40.2%.
Embodiment 2
Repeat embodiment 1, but the mass percent that polyacrylonitrile radical active carbon fiber is accounted for the plastic body that supplies the compressing tablet moulding changes 1%, 4%, 10% into, the ratio that the sheet catalyst product macropore volume that obtains accounts for total pore volume is compared with product A and has been increased by 8.0%, 10.2%, 14.3%, and its intensity is compared with products C has increased respectively 40.5%, 40.6%, 40.3%.
Embodiment 3
Repeat embodiment 1, but the polypropylene-base NACF is changed into, viscose glue base, phenolic aldehyde base, asphalt based active carbon fiber, and with polyvinylidene chloride, polyimide fiber, styroflex, vinal, lignin fibre, ratio and products C that the macropore volume of the sheet catalyst product that obtains accounts for total pore volume are suitable, and its intensity is suitable with catalyst prod D simultaneously.
Embodiment 4
Repeat embodiment 1, but the length that will add the polypropylene-base NACF changes respectively 1mm, 2mm, 4mm, 5mm into, the sheet catalyst product macropore volume that obtains accounts for ratio and the products C no significant difference of total pore volume, and its intensity is suitable with catalyst prod D simultaneously.
Embodiment 5
Repeat embodiment 1, but change the white carbon carrier into solid silicone carrier, precipitation silicon ball carrier, the ratio that the macropore volume of the sheet catalyst product that obtains accounts for total pore volume is compared with product A and has been increased respectively 13.2%, 13.8%, and its intensity is suitable with catalyst prod D simultaneously.
Embodiment 6
Repeat embodiment 1, but the mass percent that the white carbon carrier is accounted for for compressing tablet moulding plastic body changes 10%, 13%, 25% into, and the ratio that the sheet catalyst product macropore volume that obtains accounts for total pore volume is compared with product A and increased respectively 13.5%, 13.4%, 13.7%.Its intensity is suitable with catalyst prod D simultaneously.
Embodiment 7
Repeat embodiment 1, but the mass percent that adhesive is accounted for for compressing tablet moulding plastic body changes 3%, 4%, 8% into, the ratio that the sheet catalyst product macropore volume that obtains accounts for total pore volume is compared with product A and has been increased respectively 13.2%, 13.5%, 13.8%.Its intensity is suitable with catalyst prod D simultaneously.
Embodiment 8
Repeat embodiment 1, but the mass percent that boric acid is accounted for for compressing tablet moulding plastic body changes 0.1%, 0.8%, 1.5%, 2.0% into, the ratio that the sheet catalyst product macropore volume that obtains accounts for total pore volume is compared with product A and has been increased by 13.8%, 13.6%, 12.5%, 11.9%, and its intensity is compared with sample D has increased respectively 32.6%, 39.4%, 42.4%, 45.7%.
Embodiment 9
Repeat embodiment 1, but change the thickness of tablet into 2mm, 6mm, 10mm, the sheet catalyst product macropore volume that obtains accounts for the ratio of total pore volume and compares no significant difference with products C, and its intensity is suitable with catalyst prod D simultaneously.
Embodiment 10
Repeat embodiment 1, but change the diameter of tablet into 10mm, 15mm, 30mm, the sheet catalyst product macropore volume that obtains accounts for the ratio of total pore volume and compares no significant difference with products C, and its intensity is suitable with catalyst prod D simultaneously.
Embodiment 11
Repeat embodiment 1, but with 20 ℃/hour of the heating rates of roasting, 40 ℃/hour, 50 ℃/hour, the sheet catalyst product macropore volume that obtains accounts for the ratio of total pore volume and compares no significant difference with products C, its intensity is suitable with catalyst prod D simultaneously.
Embodiment 12
Repeat embodiment 1, but roasting Oxygen in Nitrogen content is become 0.2%, 1%, 3%, 7%, 13%, 21%, the sheet catalyst product macropore volume that obtains accounts for the ratio of total pore volume and compares no significant difference with products C, and its intensity is suitable with catalyst prod D simultaneously.
Embodiment 13
Repeat embodiment 1, compare no significant difference but change the temperature-programmed calcination temperature into ratio that 350 ℃, 400 ℃, 500 ℃, the 600 ℃ sheet catalyst product macropore volume that obtain account for total pore volume with products C, its intensity is suitable with catalyst prod D simultaneously.
Embodiment 14
Repeat embodiment 1, but change micron TS-1 molecular sieve powder into nano-scale TS-1 molecular sieve powder, the ratio that the sheet catalyst product F that obtains, its macropore volume account for total pore volume is compared with product B and has been increased by 14.1%, and intensity is compared with product B has increased by 38.8%.
Claims (10)
1. the compression molding method of a high strength TS-1 titanium-silicon molecular sieve catalyst is characterized in that comprising the steps:
The first step, described TS-1 HTS powder, NACF, silica supports and intensity auxiliary agent are fully stirred in mixer, be kneaded into uniform mixed material, then in mixed material, spray into adhesive, be kneaded into the plastic body for the compressing tablet moulding;
Silica supports be aluminium content less than the silica supports of 1000ppm, its mass percent that accounts for for compressing tablet moulding plastic body is 5-30%;
The mass percent that NACF accounts for for the plastic body of compressing tablet moulding is 0.5-20%.The NACF length range is 0.5-10 mm;
The intensity auxiliary agent is boric acid, and the mass percent that its addition accounts for for the plastic body of compressing tablet moulding is 0.1-10%;
Adhesive is comprised of Ludox and shaping assistant.Ludox is the Ludox that aluminium content is lower than 1000 ppm, wherein SiO
2The quality percentage composition be 20-40%; The mass percent that shaping assistant accounts for adhesive is 0.5-20%; The mass percent that adhesive accounts for for the plastic body of compressing tablet moulding is 1-15%;
Second step is pressed into tablet with the plastic body for the compressing tablet moulding for preparing in tablet press machine.Tablet thickness is 0.2-15mm; Diameter is 5-40mm;
In the 3rd step, the tablet that second step is obtained is being no more than 80 ℃ air drying 0-48 hour, dried tablet in 80-200 ℃ air dry 1-24 hour again;
In the 4th step, the 3rd tablet that goes on foot the drying that obtains containing the nitrogen atmosphere Program intensification roasting of oxygen, is made the sheet catalyst product;
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. compression molding method according to claim 1, it is characterized in that, described NACF is artificial NACF or natural fiber, and artificial NACF is one or more 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; The mass percent that NACF accounts for for compressing tablet moulding plastic body is 1-10%, and the NACF length range is 1-5mm.
3. compression molding method according to claim 1 is characterized in that, the mass fraction that the addition of described boric acid accounts for for compressing tablet moulding plastic body is 0.1-2.0%.
4. according to claim 1,2 or 3 described compression molding methods, it is characterized in that the plastic body mass percent that the addition of described silica supports accounts for for the compressing tablet moulding is 10-25%.
5. according to claim 1,2 or 3 described compression molding methods, it is characterized in that described silica supports is one or several the mixture in white carbon, solid silicone, the precipitation silicon ball.
6. according to claim 1,2 or 3 described compression molding methods, it is characterized in that the percentage composition of silica is 30-40% in the described Ludox; The mass percent that shaping assistant accounts for adhesive is 1-10%; The mass percent that adhesive accounts for for the plastic body of compressing tablet moulding is 3-8%.
7. according to claim 1,2 or 3 described compression molding methods, it is characterized in that described shaping assistant is one or several the mixture in atoleine, glycerine and the citric acid.
8. according to claim 1,2 or 3 described compression molding methods, it is characterized in that described tablet thickness 2-10mm; Diameter 10-30mm.
9. according to claim 1,2 or 3 described compression molding methods, it is characterized in that the 3rd step had been no more than 80 ℃ air drying 0.5-6 hour with tablet, dried tablet in 100-150 ℃ air dry 2-5 hour again.
10. according to claim 1,2 or 3 described compression molding methods, it is characterized in that, the 4th the step, sintering temperature is 350-600 ℃, roasting time is 6-24 hour, heating rate is 20-50 ℃/hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107879897A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | The method of one-step synthesis method vicinal diamines class compound |
| CN107879897B (en) * | 2016-09-29 | 2022-11-22 | 中国石油化工股份有限公司 | One-step method for synthesizing o-diol compound |
| CN110924175A (en) * | 2019-12-13 | 2020-03-27 | 广州立白企业集团有限公司 | Fabric care tablet |
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