CN103934039A - Method of enhancing strength of molecular sieve catalyst - Google Patents
Method of enhancing strength of molecular sieve catalyst Download PDFInfo
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- CN103934039A CN103934039A CN201310023136.XA CN201310023136A CN103934039A CN 103934039 A CN103934039 A CN 103934039A CN 201310023136 A CN201310023136 A CN 201310023136A CN 103934039 A CN103934039 A CN 103934039A
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Abstract
The invention relates to a method of enhancing strength of a molecular sieve catalyst, mainly solving a problem of low strength of molecular sieve catalysts in molding technologies in the past. According to a technical scheme adopted by the method, silica sol is added into a molecular sieve, mixed, extruded or subjected to roll molding, dried and calcinated to obtain a molded molecular sieve catalyst; the method of enhancing the strength of the molecular sieve catalyst includes a step of processing the molded molecular sieve catalyst with an acid solution having a pH value of 0.5-4 at 100-300 DEG C for 1-200 h, with the weight ratio of the acid solution to the molded molecular sieve being 3-100:1, and a step of drying and calcinating the processed molded molecular sieve catalyst to obtain a finished catalyst product. By adoption of the technical scheme, the problem is solved well. The method can be used for industrial production of the molecular sieve catalyst.
Description
Technical field
The present invention relates to improve the method for molecular sieve catalyst intensity.
Background technology
Zeolite molecular sieve is due to its unique pore passage structure feature and have higher heat endurance and hydrothermal stability, thereby is widely applied in the petrochemical industries such as the shape slective cracking of hydro carbons, alkylation, isomerization, disproportionation, etherificate, dewaxing.
Artificial synthetic molecular sieve is white powder, can not in industry, directly use, and need to add a certain amount of binding agent, is moulded suitable shape.The selection of binding agent should change to meet and requires: (1) caking property is good, with a small amount of binding agent just can be strong the molecular sieve powder that bonds; (2) do not affect absorption and the catalytic property of molecular sieve; (3) in the various application of molecular sieve, do not produce harmful side reaction.Thereby, binding agent polyphyly inert substance, or organic binder bond, after activation by burn off; (4) adherend is stable, is not easy to be sprinkled picture in various processing; (5) there is plasticity, easily moulding; (6) solidify or phase transition temperature lower than the fail temperature of zeolite molecular sieve lattice; (7) cost is low, easily obtains.The main binding agent adopting is clay and various silica-alumina gel at present.
In the commercial Application process of catalyst, for fixed bed reaction technique, not only require catalyst to there is certain active and higher target product selectivity, and require catalyst to there is certain compressive resistance.Catalyst strength is too low, and catalyst is easily broken, will cause reactor bed pressure drop to increase, and affects the distribution of catalytic reaction products, reduces target product selectivity, has a strong impact on the economic benefit of device.The factor that affects molecular sieve catalyst intensity is a lot, comprises binding agent kind, extrusion aid kind, kind of peptizator, zeolite type, zeolite grain size, zeolite crystallinity, zeolite powder granularity and various binding agent, extrusion aid, addition of peptizing agent etc.
CN 86101315A discloses a kind of catalyst carrier with suitable high strength and high surface.Described catalyst carrier can at least reach the porous oxides of 20 meters squared per gram by surface area by heating and prepared by the mixture through being shaped that forms for the inorganic bond precursor of this porous oxides.Described adhesive is the precursor of aluminium oxide, silica or titanium dioxide, and this adhesive can be given the intensity that carrier is high at lower sintering temperature.
CN 1854258A discloses a kind of fluid cracking catalyst, this catalyst is mainly by the cracking activity constituent element of 5～70 heavy %, the binding agent of the clay of 5～80 heavy % and 10～60 heavy % forms, it is characterized in that containing Y zeolite in said cracking activity constituent element and take catalyst as benchmark, content be a kind of mesoporous silica-alumina materials through acidification of 3～20 heavy %, said mesoporous silica-alumina materials, the phase structure with boehmite, the anhydrous chemical expression of oxide weight of take is (0-0.3) Na
2o (40-90) Al
2o
3(10-60) SiO
2, its specific area is 200～400m
2/ g, pore volume is 0.5～2.0ml/g, and average pore size is 8～20nm, and most probable aperture is 5～15nm, and said acidification is, under room temperature to 80 ℃, 0.1～0.3 sour aluminum ratio condition, mesoporous silica-alumina materials is contacted to 0.5～3 hour with inorganic acid.This catalyst not only has good intensity, and has advantages of that activity stability is high, heavy oil yield is low and crude oil conversion capability is strong.
CN102211023A discloses a kind of be suitable for commercial Application, high-intensity Carbon Nanotubes Supported Platinum Catalysts preparation method; comprise: pre-treatment step: primary CNT is in the nitration mixture (volume ratio 3: 1) of the concentrated sulfuric acid (mass concentration 98%) and red fuming nitric acid (RFNA) (mass concentration 60-63%); in 100-130 ℃ of temperature range, add hot reflux, filter afterwards, wash, dry; Impregnation steps: pretreated CNT mixes with platinum acid chloride solution, placed after 24 hours, added the absolute ethyl alcohol that is no more than cumulative volume 50%, and recycling Rotary Evaporators is by solvent evaporate to dryness, and fragmentation obtains 80-100 object particle; Reduction step: process 2 hours for 350 ℃ in hydrogen stream, be down to after room temperature, in 20% nitrogen-air, passivation is 1 hour.Gained catalyst p-nitrophenyl hydrogenation reaction performance good catalytic activity, and crushing strength reaches 20Nmm
-1.
CN1506157 discloses a kind of solid phosphoric acid catalyst and preparation method thereof, mainly solve and in conventional art, do not relate to catalyst water resistance, the defect that the crush strength of catalyst is desirable not enough, solid phosphoric acid catalyst of the present invention forms and is represented by following chemical general formula with molar ratio computing: A1BaWb (P
2o
5) c (H2O) d, in formula, A is Si, B is selected from boron, antimony, bismuth, magnesium or its mixture, W is tungsten, a, b, c, d are the molal quantity that A component equals 1 o'clock corresponding component, and method for preparing catalyst is first made polyphosphate by the polyphosphoric acids of preheating and B component, then with the mixture blend that contains A and W component, the material forming is through moulding, dry, roasting, activation, obtain catalyst finished product, wherein W component induces one with the heteropoly acid form of tungsten.It is good that this catalyst has water resistance, the feature that crush strength is high, and catalyst still keeps higher catalytic activity simultaneously.Can be used in industrial production.
CN201110257159 discloses pre-treating method, forming method and the catalyst prod of molecular sieve based catalyst forming.More specifically, relate to a kind of forming method that comprises the molecular sieve catalyst of pre-treatment, this pre-treating method comprises that the catalyst slurry for the treatment of moulding carries out Fruit storage to discharge the gas in this catalyst slurry, after described pre-treatment, again molecular sieve slurry is carried out to moulding and post processing, the intensity of the molecular sieve catalyst that obtains after moulding is obviously improved.
In foregoing invention, all deposit and do not relate to the method that preformed catalyst acid treatment improves catalyst strength.
Summary of the invention
Technical problem to be solved by this invention is the problem that preformed catalyst acid treatment improves catalyst strength that do not relate to existing in conventional art, a kind of method that improves molecular sieve catalyst intensity is provided, when the method is used for the production of preformed catalyst, have advantages of that catalyst strength is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that improves molecular sieve catalyst intensity, comprises the following steps successively:
1) acid solution that is 0.5～4.0 by pH value is processed molded molecular sieve catalyst, and treatment temperature is 100～300 ℃, and the processing time is 1-200 hour, and the weight ratio of acid solution and molded molecular sieve catalyst is 3～100:1;
2) to the molded molecular sieve catalyst after processing be dried, after roasting finished catalyst.
In technique scheme, the preferred version of the forming method of molded molecular sieve catalyst is: after adding Ludox to mix in molecular sieve, extrude or roller forming, after drying, roasting, obtain molded molecular sieve catalyst.The preferable range of acid solution pH value is 1～3.5, and more preferably scope is 1.5～3.0; 120 ~ 220 ℃ of the preferable range for the treatment of temperature, more preferably scope is 160 ~ 200 ℃; The preferable range in acid solution processing time is 5～100 hours, and more preferably scope is 10～50 hours; The preferable range of the weight ratio of acid solution and molded molecular sieve catalyst is 3～20:1.
Binding agent for molded molecular sieve is that silica content is the silicon sol solution of 40 % by weight, before moulding first by Ludox, molecular screen primary powder, extrusion aid sesbania powder is mediated more than 1 hour, controlling silica binder content in the catalyst after moulding is 20 ~ 50 % by weight, sesbania powder content 2 ~ 10 % by weight.Molecular sieve is micro porous molecular sieve, comprises ZSM-5 type, ZSM-35 type, ZSM-48 type, at least one Si-Al molecular sieve in MCM-22 type molecular sieve.Molecular sieve room temperature after moulding is placed more than 12 hours, is then placed in baking oven 120
odry 12 hours of C, finally in air atmosphere 600
oc roasting 4 hours.What acid solution post processing adopted is citric acid, tartaric acid, a kind of solution in acetic acid or oxalic acid solution or the mixture of several solns.The weight ratio of acid solution and solid particle catalyst is 3 ~ 100:1, and the treatment temperature of acid solution is 100 ~ 300
oc, the processing time is 1-200 hour.Catalyst after processing is through deionized water washes clean, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting was tested crushing strength after 4 hours.The method of testing of crushing strength: strip catalyst is cut into the long segment of 5mm, chooses at random 50 and carry out above crushing strength test, by the results averaged recording.The DLII type intelligence detector for strength of particles that strength tester adopts Dalian Chemical Research &. Design Inst. to produce.
The present invention is by the optimization to treatment temperature, time and formula, compare without acid-treated catalyst and can prepare more than 20% catalyst of compressive resistance raising, method is simple, being easy to industry amplifies, it is generally acknowledged that acid-treated effect is suitable before and after moulding or in forming process, but we are by the acid treatment to moulding rear catalyst, with carrying out two schemes of acid treatment before moulding or in forming process, compare, acid strength can improve 10% left and right, has obtained unexpected technique effect.
Below by embodiment, the invention will be further elaborated.
The specific embodiment
[embodiment 1]
Take 100 grams of silica alumina ratio SiO
2/ Al
2o
3be 20 ZSM-5 molecular sieve, after adding 107 grams of Ludox containing 40 % (weight) silica to mix, extrusion molding, through 120
odry 12 hours of C, 600
oc roasting 4 hours, obtains molded molecular sieve catalyst A-0, and intensity data is as shown in table 1.
[embodiment 2]
Take 50 grams of silica alumina ratio SiO
2/ Al
2o
3being 21.5 ZSM-35 molecular sieve, adding 31 grams of 40%(weight) after Ludox mixes, extrusion molding, through 120
odry 12 hours of C, 600
oc roasting 4 hours, obtains molded molecular sieve catalyst B-0, and intensity data is as shown in table 1.
[embodiment 3]
Take 60 grams of silica alumina ratio SiO
2/ Al
2o
3being 600 ZSM-48 molecular sieve, adding 100 grams of 40%(weight) after Ludox mixes, extrusion molding, through 120
odry 12 hours of C, 600
oc roasting 4 hours, obtains molded molecular sieve catalyst C-0, and intensity data is as shown in table 1.
[embodiment 4]
Take 40 grams of silica alumina ratio SiO
2/ Al
2o
3being 600 ZSM-48 molecular sieve, adding 100 grams of 40%(weight) after Ludox mixes, extrusion molding, through 120
odry 12 hours of C, 600
oc roasting 4 hours, obtains molded molecular sieve catalyst D-0, and intensity data is as shown in table 1.
[embodiment 5 ~ 9]
By oxalic acid, tartaric acid, it is 0.5～2.6 acid solution that citric acid is mixed with pH value, molded molecular sieve catalyst A-0 is added in acid solution and processed, treatment temperature is 100～250 ℃, processing time is 1～100 hour, and the weight ratio of acid solution and molded molecular sieve catalyst is 3～100:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst A1～A5 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[embodiment 10 ~ 13]
By oxalic acid, acetic acid, it is 2.0～3.0 acid solution that tartaric acid is mixed with pH value, molded molecular sieve catalyst B-0 is added in acid solution and processed, treatment temperature is 100～300 ℃, processing time is 2～200 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 10～100:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst B1～B4 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[embodiment 14]
It is 3.0 acid solution that tartaric acid is mixed with to pH value, and molded molecular sieve catalyst C-0 is added in acid solution and processed, and treatment temperature is 180 ℃, and the processing time is 24 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 40:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst C-1 in 4 hours, and crushing strength data are as shown in table 1.
[embodiment 15]
It is 1.5 acid solution that oxalic acid is mixed with to pH value, and molded molecular sieve catalyst C-0 is added in acid solution and processed, and treatment temperature is 160 ℃, and the processing time is 36 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 20:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst C-2 in 4 hours, and crushing strength data are as shown in table 1.
[embodiment 16]
It is 2.1 acid solution that citric acid is mixed with to pH value, and molded molecular sieve catalyst C-0 is added in acid solution and processed, and treatment temperature is 180 ℃, and the processing time is 10 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 20:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst C-3 in 4 hours, and crushing strength data are as shown in table 1.
[embodiment 17]
It is 4.0 acid solution that acetic acid is mixed with to pH value, and molded molecular sieve catalyst C-0 is added in acid solution and processed, and treatment temperature is 120 ℃, and the processing time is 50 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 10:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst C-4 in 4 hours, and crushing strength data are as shown in table 1.
[embodiment 18 ~ 19]
It is 2.0～2.5 acid solution that tartaric acid is mixed with to pH value, molded molecular sieve catalyst D-0 is added in acid solution and processed, treatment temperature is 180 ℃, and the processing time is 30 ~ 40 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 3～30:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst D-1～D-2 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[embodiment 20]
It is 3.0 acidic mixed solution that acetic acid and citric acid are mixed with to pH value, molded molecular sieve catalyst D-0 is added in acid solution and processed, treatment temperature is 200 ℃, and the processing time is 24 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 20:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst D-3 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[embodiment 21]
It is 2.0 acidic mixed solution that tartaric acid and oxalic acid are mixed with to pH value, molded molecular sieve catalyst D-0 is added in acid solution and processed, treatment temperature is 160 ℃, and the processing time is 24 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 20:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst D-4 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[embodiment 22]
It is 2.5 acidic mixed solution that acetic acid is mixed with to pH value, and molded molecular sieve catalyst D-0 is added in acid solution and processed, and treatment temperature is 180 ℃, and the processing time is 20 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 10:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst D-5 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[embodiment 23]
It is 2.5 acidic mixed solution that citric acid is mixed with to pH value, and molded molecular sieve catalyst D-0 is added in acid solution and processed, and treatment temperature is 180 ℃, and the processing time is 20 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 10:1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst D-5 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[comparative example 1]
Take 40 grams of silica alumina ratio SiO
2/ Al
2o
3being 600 ZSM-48 molecular sieve, adding 100 grams of 40%(weight) Ludox obtains the molecular sieve catalyst d-0 in forming process after mixing.
It is 2.5 acid solution that tartaric acid is mixed with to pH value, and molecular sieve catalyst d-0 in forming process is added in acid solution and processed, and treatment temperature is 180 ℃, and the processing time is 40 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 3:1; To the molded molecular sieve catalyst after processing wash, extrusion molding, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst d-1 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[comparative example 2]
Take 40 grams of silica alumina ratio SiO
2/ Al2O
3being 600 ZSM-48 molecular sieve, adding 100 grams of 40%(weight) Ludox obtains the molecular sieve catalyst d-0 in forming process after mixing.
It is 2.0 acid solution that tartaric acid is mixed with to pH value, molecular sieve catalyst d-0 in forming process is added in acid solution and processed, treatment temperature is 180 ℃, and the processing time is 30 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 30:1; To the molded molecular sieve catalyst after processing wash, extrusion molding, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst d-2 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
[comparative example 3]
It is 2.5 acid solution that tartaric acid is mixed with to pH value, by silica alumina ratio SiO
2/ Al
2o
3be that 600 ZSM-48 molecular sieve adds in acid solution and processes, treatment temperature is 180 ℃, and the processing time is 40 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 3:1; To the molecular sieve catalyst after processing wash, 120 ℃ dry 12 hours, and in air atmosphere 600 ℃ of roastings 4 hours ZSM-48 molecular sieves after acid treatment.
Take 40 grams of ZSM-48 molecular sieves after above-mentioned acid treatment, add 100 grams of 40%(weight) after Ludox mixes, extrusion molding, through 120 ℃, be dried 12 hours, 600 ℃ of roastings 4 hours, obtain finished catalyst d-3, and treatment conditions and crushing strength data are as shown in table 1.
[comparative example 4]
It is 2.0 acid solution that tartaric acid is mixed with to pH value, by silica alumina ratio SiO
2/ Al
2o
3be that 600 ZSM-48 molecular sieve adds in acid solution and processes, treatment temperature is 180 ℃, and the processing time is 30 hours, and the weight ratio of acid solution and molded molecular sieve catalyst is 30:1; To the molecular sieve catalyst after processing wash, 120 ℃ dry 12 hours, and in air atmosphere 600 ℃ of roastings 4 hours ZSM-48 molecular sieves after acid treatment.
Take 40 grams of ZSM-48 molecular sieves after above-mentioned acid treatment, add 100 grams of 40%(weight) after Ludox mixes, extrusion molding, through 120 ℃, be dried 12 hours, 600 ℃ of roastings 4 hours, obtain finished catalyst d-3 and d-4, and treatment conditions and crushing strength data are as shown in table 1.
[comparative example 5～8]
Take 40 grams of silica alumina ratio SiO
2/ Al
2o
3being 600 ZSM-48 molecular sieve, adding 100 grams of 40%(weight) after Ludox mixes, extrusion molding, through 120
odry 12 hours of C, 600
oc roasting 4 hours, obtains molded molecular sieve catalyst D-0.
Molded molecular sieve catalyst D-0 is added in acid solution and processed, and treatment conditions are as shown in table 1; To the molded molecular sieve catalyst after processing wash, 120
odry 12 hours of C, and in air atmosphere 600
oc roasting obtains finished catalyst D-7～D-10 in 4 hours, and treatment conditions and crushing strength data are as shown in table 1.
Table 1
Claims (10)
1. a method that improves molecular sieve catalyst intensity, comprises the following steps successively:
1) acid solution that is 0.5～4 by pH value is processed molded molecular sieve catalyst, and treatment temperature is 100～300 ℃, and the processing time is 1～200 hour, and the weight ratio of acid solution and molded molecular sieve catalyst is 3～100:1;
2) to the molded molecular sieve catalyst after processing be dried, after roasting finished catalyst.
2. improve according to claim 1 the method for molecular sieve catalyst intensity, the forming method that it is characterized in that molded molecular sieve catalyst is as follows: after adding Ludox to mix in molecular sieve, extrude or roller forming, after drying, roasting, obtain molded molecular sieve catalyst.
3. improve according to claim 1 the method for molecular sieve catalyst intensity, the pH value that it is characterized in that acid solution is 1～3.5.
4. improve according to claim 3 the method for molecular sieve catalyst intensity, the pH value that it is characterized in that acid solution is 1.5～3.0.
5. improve according to claim 1 the method for molecular sieve catalyst intensity, it is characterized in that treatment temperature is 120～220 ℃, the processing time is 5～100 hours.
6. improve according to claim 5 the method for molecular sieve catalyst intensity, it is characterized in that treatment temperature is 160～200 ℃, the processing time is 10～50 hours.
7. improve according to claim 1 the method for molecular sieve catalyst intensity, it is characterized in that acid solution is citric acid, tartaric acid, the solution of one or more in acetic acid and oxalic acid.
8. improve according to claim 1 the method for molecular sieve catalyst intensity, the weight ratio that it is characterized in that acid solution and molded molecular sieve catalyst is 3～20:1.
9. improve according to claim 2 the method for molecular sieve catalyst intensity, it is characterized in that by weight percentage, in molded molecular sieve catalyst, the content of silica is 20～50 % by weight.
10. improve according to claim 2 the method for molecular sieve catalyst intensity, it is characterized in that molecular sieve is at least one in ZSM-5, ZSM-35, ZSM-48 and MCM-22.
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| CN109731545A (en) * | 2019-03-12 | 2019-05-10 | 太原理工大学 | A kind of forming method of nano molecular sieve |
| CN110072618A (en) * | 2016-12-20 | 2019-07-30 | 巴斯夫欧洲公司 | The method of extrudable composition of the preparation comprising the titanium-containing zeolite material with MWW framework types |
| CN110087768A (en) * | 2016-12-20 | 2019-08-02 | 巴斯夫欧洲公司 | Acid processing is so that the purposes that the plasticity of the composition comprising the titanium-containing zeolite material with MWW framework types reduces |
| CN110342533A (en) * | 2018-04-02 | 2019-10-18 | 国家能源投资集团有限责任公司 | Molecular sieve and its preparation method and application |
| CN112007692A (en) * | 2019-05-31 | 2020-12-01 | 国家能源投资集团有限责任公司 | Catalyst for dewaxing lubricant base oil produced by Fischer-Tropsch wax synthesis and preparation method and application thereof |
| CN112121871A (en) * | 2020-09-11 | 2020-12-25 | 中国天辰工程有限公司 | A processing method for improving the mechanical strength of a shaped titanium-silicon molecular sieve catalyst |
| CN115888803A (en) * | 2022-12-26 | 2023-04-04 | 中触媒新材料股份有限公司 | A kind of preparation method and application of modified ZSM-35 molecular sieve catalyst |
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| CN110072618A (en) * | 2016-12-20 | 2019-07-30 | 巴斯夫欧洲公司 | The method of extrudable composition of the preparation comprising the titanium-containing zeolite material with MWW framework types |
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| CN112007692B (en) * | 2019-05-31 | 2024-03-29 | 国家能源投资集团有限责任公司 | Catalyst for dewaxing lubricating oil base oil for Fischer-Tropsch wax production and preparation method and application thereof |
| CN112121871A (en) * | 2020-09-11 | 2020-12-25 | 中国天辰工程有限公司 | A processing method for improving the mechanical strength of a shaped titanium-silicon molecular sieve catalyst |
| CN112121871B (en) * | 2020-09-11 | 2023-01-10 | 中国天辰工程有限公司 | A treatment method for improving the mechanical strength of a shaped titanium-silicon molecular sieve catalyst |
| CN115888803A (en) * | 2022-12-26 | 2023-04-04 | 中触媒新材料股份有限公司 | A kind of preparation method and application of modified ZSM-35 molecular sieve catalyst |
| CN115888803B (en) * | 2022-12-26 | 2025-01-03 | 中触媒新材料股份有限公司 | Preparation method and application of modified ZSM-35 molecular sieve catalyst |
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