CN102989504A - Rolling-ball forming method for high-strength TS-1 titanium silicalite molecular sieve catalyst - Google Patents
Rolling-ball forming method for high-strength TS-1 titanium silicalite molecular sieve catalyst Download PDFInfo
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Abstract
The invention provides a rolling-ball forming method for a high-strength TS-1 titanium silicalite molecular sieve catalyst, which is characterized by comprising the following steps of: adequately mixing a TS-1 molecular sieve powder, a silica carrier, an adhesive containing boric acid, and active carbon fibres in a ratio; forming by rolling balls, drying and roasting, thus obtaining the TS-1 catalyst formed by rolling balls. The roasted formed catalyst has a large channel penetrating through all grains, and has a strong mechanical strength simultaneously by introducing the active carbon fibres with a proper length and moderate boric acid during the rolling-ball forming process. On one hand, the mass-transferring efficiency and the heat-transferring efficiency during a catalytic oxidation process can be increased, thus being contributed to overcoming the secondary side reaction and the catalyst deactivation caused by product retention, and preventing the sintering of catalyst grains caused due to bad heat dissipation; on the other hand, the impact generated during transport, filling and use processes, and the wear caused by fluid flow can be effectively resisted, thus being contributed prolonging the service life of the catalyst.
Description
Technical field
The invention belongs to the petrochemical catalyst technical field, relate to a kind of roller 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, adhesive 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 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 more 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.
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 the pore creating materials such as gasoline, C5～C13 n-alkane, C4 ~ C12 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.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 roller forming 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 roller forming, the NACF roasting removes the diffusion admittance that rear formation connects whole particle, 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 fully stirs TS-1 molecular sieve powder, NACF, silica supports in mixer, is kneaded into uniform powder mixture.
Wherein said silica supports be aluminium content less than the silica supports of 1000ppm, silica supports can be one or more the mixture in white carbon, solid silicone, the precipitation silicon ball.The mass percent that silica supports accounts for powder mixture is 10-40%, preferred 20-30%.
Said 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 powder mixture is 1-30%, preferred 5-20%; The NACF length range is 0.5-10 mm, preferred 1-5mm.
Second step joins the intensity auxiliary agent in the mixed liquor of Ludox and shaping assistant under 60 ℃ in proportion, and fully stirring and dissolving makes adhesive.The uniform powder mixture for preparing is joined in the nodulizer, contact with the adhesive that atomizing type sprays into, obtain the roller forming thing.
Wherein said adhesive is comprised of Ludox, intensity auxiliary agent and shaping assistant, and the mass percent that the addition of adhesive accounts for powder mixture is 5-30%, preferred 8-20%.
Said Ludox be aluminium content less than the Ludox of 1000ppm, wherein the mass percent of silica is 5-40%, preferred 20-30%.
Said intensity auxiliary agent is boric acid, and the mass percent that the addition of boric acid accounts for adhesive is 1-30%, preferred 5-20%.
Said shaping assistant is selected from one or more the mixture in atoleine, glycerine, the citric acid.The mass fraction that shaping assistant accounts for adhesive is 0.5-20%, preferred 1-10%.
In the 3rd step, with in room temperature to 80 ℃ air drying 0-48 hour of roller forming thing, be preferably 0.5-6 hour.Then with at 80-200 ℃ air drying 1-24 hour of material, preferably 100-150 ℃ air drying 2-5 hour.
The 4th step, the roller forming material of drying is being contained the nitrogen atmosphere Program intensification roasting of oxygen, process making the roller forming 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 the roller 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 mechanical strength of preformed catalyst utilizes ZQJ-II Intelligent testing machine for particle to test, and the pore size distribution data of preformed catalyst are 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.
It is that 30% white carbon carrier fully stirs in kneader and mediates that micron TS-1 molecular sieve powder and addition are accounted for the powder mixture mass percent, obtains uniform powder mixture; Account for the mixing material of the citric acid of adhesive mass percent as 5% as adhesive take Ludox, the addition of quality percentage composition as 30%, be under 10% the condition at the mass percent that the adhesive addition accounts for powder mixture, the solid formed body that obtains wetting with the nodulizer spin.With this roller forming body under 25 ℃ temperature dry 6 hours, further be warmed up to 120 ℃ of dryings 5 hours.Then the heating rate by 50 ℃/hour obtains spherical preformed catalyst in 550 ℃ of lower roastings in Muffle furnace, obtains the preformed catalyst product A.
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 the preformed catalyst product B.
The comparative example 3
It is that 30% white carbon carrier and addition account for the powder mixture mass percent is 5%, length is 1mm polyacrylonitrile radical active carbon fiber and fully stir in kneader and mediate that micron TS-1 molecular sieve powder, addition are accounted for the powder mixture mass percent, obtains uniform powder mixture.Other Step By Conditions repeat comparative example 1, obtain the preformed catalyst products C, and the ratio that its macropore volume accounts for total pore volume is compared with product A and increased by 13.1%, and its mechanical strength is compared with product A and reduced by 8.3%.
Embodiment 1
Step according to scheme one, it is that 30% white carbon carrier and addition account for the powder mixture mass percent is 5%, length is 1mm polyacrylonitrile radical active carbon fiber and fully stir in kneader and mediate that micron TS-1 molecular sieve powder, addition are accounted for the powder mixture mass percent, obtains uniform powder mixture; Take Ludox, the addition of quality percentage composition as 30% account for the adhesive mass percent as 10% boric acid and the mixing material of 5% citric acid as adhesive, be that mass percent that 60 ℃, addition account for powder mixture is under 10% the condition in the adhesive temperature, the solid formed body that obtains wetting with the nodulizer spin.With this roller forming body under 25 ℃ temperature dry 6 hours, further be warmed up to 120 ℃ of dryings 5 hours.Then the heating rate by 50 ℃/hour obtains spherical preformed catalyst in 550 ℃ of lower roastings in Muffle furnace, obtain preformed catalyst product D, the ratio that its macropore volume accounts for total pore volume is compared with product A and has been increased by 12.3%, and its mechanical strength is compared with product A has increased by 43.7%.
Embodiment 2
Repeat embodiment 1, but change micron TS-1 molecular sieve powder into nano-scale TS-1 molecular sieve powder, obtain the preformed catalyst product F, the ratio that its macropore volume accounts for total pore volume is compared with product B and has been increased by 14.6%, and its mechanical strength is compared with product B has increased by 44.1%.
Embodiment 3
Repeat embodiment 1, but the addition of white carbon carrier is changed to accounts for 20% of powder mixture mass percent, obtain the preformed catalyst product G, the ratio that its macropore volume accounts for total pore volume is compared with product A and has been increased by 10.9%, and its mechanical strength is compared with product A has increased by 40.8%.
Embodiment 4
Repeat embodiment 1, but change silica supports wherein into precipitation silicon ball by white carbon, proportion is constant, obtains preformed catalyst product H, the ratio that its macropore volume accounts for total pore volume is compared with product A and has been increased by 9.8%, and its mechanical strength is compared with product A has increased by 46.2%.
Embodiment 5
Repeat embodiment 1, but the addition of polyacrylonitrile radical active carbon fiber become account for 10%, 15% and 20% of powder mixture mass percent, obtain successively preformed catalyst product I, J and K, the ratio that its macropore volume accounts for total pore volume is compared with product A and has been increased respectively 18.1%, 24.3% and 28.6%, and its mechanical strength is compared with product A has increased respectively 42.2%, 40.9% and 38.3%.
Embodiment 6
Repeat embodiment 1, but it is 5%, 15% and 20% that the addition of boric acid is become the mass percent that accounts for adhesive, obtain successively preformed catalyst product L, M and N, the ratio that its macropore volume accounts for total pore volume is compared with product A and has been increased respectively 13.0%, 11.5% and 10.7%, and its mechanical strength is compared with product A has increased respectively 37.5%, 47.4% and 53.3%.
Embodiment 7
Repeat embodiment 1, but the length of polyacrylonitrile radical active carbon fiber is become 2mm, 3mm and 5mm, obtain successively preformed catalyst product L, M and N, the ratio that the macropore volume of products obtained therefrom accounts for total pore volume is compared with product A and has been increased respectively 12.3%, 11.5% and 10.1%, and its mechanical strength is compared with product A has increased respectively 43.2%, 43.9% and 44.3%.
Embodiment 8
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, addition remains unchanged, consistent with embodiment 1, 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.
Embodiment 9
Repeat embodiment 1, but the addition of citric acid 5% is changed to respectively 1% and 10% by what account for the adhesive mass percent, 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.
Embodiment 10
Repeat embodiment 1, but change shaping assistant wherein into glycerine and atoleine, addition is constant, obtains successively the preformed catalyst product, and ratio and mechanical strength that the macropore volume of products obtained therefrom accounts for total pore volume are suitable with product D.
Embodiment 11
Repeat embodiment 1, but the addition of adhesive become account for 8%, 15% and 20% of powder mixture mass percent, obtain successively the preformed catalyst product, the ratio that the macropore volume of products obtained therefrom accounts for total pore volume is suitable with product D, and its mechanical strength is compared with product A has increased respectively 38.4%, 45.7% and 48.9%.
Embodiment 12
Repeat embodiment 1, but the mass percent of Ludox in the adhesive is changed to respectively 20% and 25% by 30%, 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.
Embodiment 13
Repeat embodiment 1, but the temperature of drying is become 40 ℃, 65 ℃ and 80 ℃, the temperature that will further heat up under each baking temperature becomes respectively 100 ℃ and 150 ℃, drying time is constant, 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.
Embodiment 14
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 (10)
1. the roller forming method of a high strength TS-1 titanium-silicon molecular sieve catalyst is characterized in that comprising the steps:
The first step fully stirs described TS-1 HTS powder, active carbon fibre peacekeeping silica supports in mixer, is kneaded into uniform powder mixture; The mass percent that NACF accounts for powder mixture is 1-30%, and the NACF length range is 0.5-10 mm; Silica supports be aluminium content less than the silica supports of 1000ppm, the mass percent that silica supports accounts for powder mixture is 10-40%;
Second step joins the intensity auxiliary agent in the mixed liquor of Ludox and shaping assistant under 60 ℃ in proportion, and fully stirring and dissolving makes forming adhesive; The uniform powder mixture for preparing is joined in the nodulizer, contact with the forming adhesive that atomizing type sprays into, obtain the roller forming thing;
The intensity auxiliary agent is boric acid, and its addition accounts for the 1-30% of the mass percent of forming adhesive;
Ludox is that aluminium content is less than the Ludox of 1000ppm, wherein SiO
2Mass percent content at 5-40%;
The mass percent that shaping assistant accounts for forming adhesive is 0.5-20%, and the mass percent that forming adhesive accounts for powder mixture is 5-30%;
The 3rd step had been no more than 80 ℃ air drying 0-48 hour with the roller forming thing, dried material in 80-200 ℃ air dry 1-24 hour again;
The 4th step, the 3rd roller forming material that goes on foot the drying that obtains is being contained the nitrogen atmosphere Program intensification roasting of oxygen, process making the roller forming catalyst;
The oxygen content that contains oxygen nitrogen is 0.2-21%, and temperature programming speed is 10-100 ℃/hour, and sintering temperature is 200-800 ℃.
2. roller forming 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; The mass percent that NACF accounts for powder mixture is 5-20%, and the NACF length range is 1-5mm.
3. roller forming method according to claim 1 is characterized in that, the mass percent that the addition of described boric acid accounts for forming adhesive is 5-20%.
4. according to claim 1,2 or 3 described roller forming methods, it is characterized in that described silica supports is one or more the mixture in white carbon, solid silicone, the precipitation silicon ball.
5. according to claim 1,2 or 3 described roller forming methods, it is characterized in that described shaping assistant is one or more the mixture in atoleine, glycerine and the citric acid.
6. according to claim 1,2 or 3 described roller forming methods, it is characterized in that the mass percent that silica supports accounts for powder mixture is 20-30%.
7. according to claim 1,2 or 3 described roller forming methods, it is characterized in that the mass percent that forming adhesive accounts for powder mixture is 8-20%.
8. according to claim 1,2 or 3 described roller forming methods, it is characterized in that the mass percent that shaping assistant accounts for forming adhesive is 1-10%.
9. according to claim 1,2 or 3 described roller forming methods, it is characterized in that, the 3rd step, the roller forming thing is being no more than 80 ℃ air drying 0.5-6 hour, dried material was 100-150 ℃ air drying 2-5 hour.
10. according to claim 1,2 or 3 described roller forming methods, it is characterized in that, the 4th the step, sintering temperature is: 350-600 ℃ of lower roasting, heating rate are 20-50 ℃/hour.
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| CN106179482A (en) * | 2016-07-01 | 2016-12-07 | 中国华能集团公司 | A kind of method that can fluidize molecular sieve based on vibrations embedding pelletize preparation |
| 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 |
| CN108126739A (en) * | 2017-12-19 | 2018-06-08 | 济南大学 | Catalyst of COD and preparation method thereof in a kind of ozone heterocatalysis oxidized waste water |
| CN112121871A (en) * | 2020-09-11 | 2020-12-25 | 中国天辰工程有限公司 | Treatment method for improving mechanical strength of formed titanium silicalite molecular sieve catalyst |
| CN115555015A (en) * | 2022-09-16 | 2023-01-03 | 福州大学 | Supported Ru and/or Ni catalyst and preparation method thereof |
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| CN106179482A (en) * | 2016-07-01 | 2016-12-07 | 中国华能集团公司 | A kind of method that can fluidize molecular sieve based on vibrations embedding pelletize preparation |
| CN106179482B (en) * | 2016-07-01 | 2019-05-17 | 中国华能集团公司 | A method of molecular sieve can be fluidized by embedding to be granulated to prepare based on vibration |
| 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 |
| CN108126739A (en) * | 2017-12-19 | 2018-06-08 | 济南大学 | Catalyst of COD and preparation method thereof in a kind of ozone heterocatalysis oxidized waste water |
| CN112121871A (en) * | 2020-09-11 | 2020-12-25 | 中国天辰工程有限公司 | Treatment method for improving mechanical strength of formed titanium silicalite molecular sieve catalyst |
| CN112121871B (en) * | 2020-09-11 | 2023-01-10 | 中国天辰工程有限公司 | Treatment method for improving mechanical strength of formed titanium silicalite molecular sieve catalyst |
| CN115555015A (en) * | 2022-09-16 | 2023-01-03 | 福州大学 | Supported Ru and/or Ni catalyst and preparation method thereof |
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