CN102085468A - Pre-fluidizing agent for fluidized bed - Google Patents
Pre-fluidizing agent for fluidized bed Download PDFInfo
- Publication number
- CN102085468A CN102085468A CN200910250081XA CN200910250081A CN102085468A CN 102085468 A CN102085468 A CN 102085468A CN 200910250081X A CN200910250081X A CN 200910250081XA CN 200910250081 A CN200910250081 A CN 200910250081A CN 102085468 A CN102085468 A CN 102085468A
- Authority
- CN
- China
- Prior art keywords
- fluidizing reagent
- strontium
- mixture
- matrix
- fluidizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a pre-fluidizing agent for a fluidized bed, which consists of a base material, a bonder, alkaline-earth metal, alkali metal and a pore-volume regulator. The pre-fluidizing agent provided by the invention can be used in a device for preparing olefin from methanol and dimethyl ether through conversion, has no catalytic activity or only weak catalytic performance to the reaction for preparing olefin from methanol and dimethyl ether through conversion. The pre-fluidizing agent provided by the invention can be used for the fluid-bed processes of all acid catalyzed reactions.
Description
Technical field
The present invention relates to the pre-fluidizing reagent of a kind of fluid bed.
The invention still further relates to above-mentioned pre-fluidizing reagent and transform the application of making in the olefine reaction at methanol and dimethyl ether.
Background technology
Ethene and propylene are important basic chemical industry raw materials, and China mainly adopts the preparation of light oil cracking method at present.Along with the in short supply and rise in price of petroleum resources, it is urgent day by day that non-petroleum path is produced the technology of low-carbon alkene.The research and development of ethene, propylene has become the focus of domestic and international research institution and international each major company's technology input.The technology of single series, heavy industrialization that natural gas or coal are produced methyl alcohol is very ripe, so the research of producing alkene (MTO) by methyl alcohol becomes the key technology that non-petroleum path is produced low-carbon alkene.Pinhole phosphorus-silicon-aluminum molecular sieve has MTO catalytic performance preferably, but has the characteristic of quick carbon distribution in the fixed bed reaction process, thereby causes the rapid deactivation of catalyst and selectivity to reduce, and can not satisfy the industrial continuous production requirement.Fluid bed is a kind of common reactant device form that is applied to chemical industry, adopts the MTO process of the fluidized-bed reactor of successive reaction-regeneration can avoid above problem.The catalyst that is applicable to fluidized-bed reactor should be microspheroidal, and have proper intensity and size distribution under the prerequisite that keeps the greater catalytic performance.
Adopt the MTO process of fluidized bed process pattern with the FCC process of technical maturity similarity to be arranged, but also there are many differences in both, there are differences as both reaction heat, it is strong exothermal reaction that MTO reacts, and FCC then is an endothermic process; The coking yield of two processes and operating temperature are inequality or the like.That is to say that the operating process of MTO commercial plant and regulate and control operation rule must have the characteristics of himself, can not simply use for reference the FCC process.Therefore, the MTO commercial plant catalyst contamination occurs unavoidably from the initial stage stable operation of driving, and runs fortuitous event such as damages grade.
Summary of the invention
In view of the MTO catalyst more valuable, for fear of unnecessary loss, the present invention adopts a kind of and the similarly pre-fluidizing reagent of MTO catalyst physical property replaces catalyst, be used for the debugging at device initial stage, not only can reduce the risk of catalyst breakage, can play simultaneously the fluidization characteristic of understanding microspherical catalyst, the effect of cleaning device etc.But this has also proposed higher requirement to pre-fluidizing reagent, and it must have close size distribution with the MTO catalyst that commercial plant uses, abrasion and bulk density, the device operating condition that only in this way obtains just have higher can be with reference to property.In addition, it is clean to consider that the large scale industry device is difficult to displacement when the catalyst discharging, and pre-fluidizing reagent must be an inertia to the MTO process, or near inertia, remaining so pre-fluidizing reagent just can not have side effects to the MTO reaction, reduces the selectivity of low-carbon alkene.
For this reason, the object of the present invention is to provide the pre-fluidizing reagent of a kind of fluid bed.
For achieving the above object, the pre-fluidizing reagent of fluid bed provided by the invention, by matrix, binding agent, alkaline-earth metal, alkali metal and pore volume conditioning agent constitute; Wherein:
Matrix is selected from aluminum phosphate, aluminium oxide, silica, silica-alumina, clay and their mixture; The mass content of matrix in pre-fluidizing reagent counted 50-85% by oxide;
Binding agent is selected from Ludox, aluminium colloidal sol and their mixture; The mass content of binding agent in pre-fluidizing reagent counted 10-35% by oxide;
Alkaline-earth metal is selected from organic salts of strontium, inorganic strontium salt, organic barium salt, inorganic barium salt and their mixture; The mass content of alkaline-earth metal in pre-fluidizing reagent counted 4-15% by oxide;
Alkali metal is selected from organic cesium salt, inorganic cesium salt and their mixture; The mass content of alkali metal in pre-fluidizing reagent counted 0.05-5% by oxide;
The pore volume conditioning agent is selected from carbon dust, sesbania powder, urea, sucrose, polyvinyl alcohol and their mixture; The mass content of pore volume conditioning agent in pre-fluidizing reagent is 0.05-2%.
Wherein, the clay in the described matrix is selected from kaolin, metakaolin, acid treatment metakaolin, alkali treatment metakaolin, Ai Luoshi, bentonite, illiteracy holder soil and their mixture.
Wherein, having pore volume in the described matrix is that 0.1ml/g counts 10-50% to the mass content of matrix in all matrix of 0.4ml/g by oxide.
Wherein, described inorganic strontium salt is strontium carbonate, strontium nitrate, strontium chloride and their mixture; Inorganic barium salt is brium carbonate, barium nitrate, barium chloride and their mixture.Inorganic strontium salt of the present invention and inorganic barium salt is preferably strontium carbonate or/and brium carbonate; When employing comprises strontium carbonate or/and during the alkaline-earth metal mixture of brium carbonate, derive from strontium carbonate or/and the strontium of brium carbonate or/and barium accounts for strontium in the pre-fluidizing reagent 30-60% of the gross mass of barium.
Pre-fluidizing reagent of the present invention can be used in methanol and dimethyl ether and transform in the application of making alkene, before being used for fluidized bed plant, needs through 500-800 ℃ of roasting, and described fluid bed is the fluid-bed process of acid catalyzed reaction.
The specific embodiment
Technical problem to be solved by this invention is to obtain the pre-fluidizing reagent of a kind of relatively inexpensive fluid bed, this pre-fluidizing reagent and MTO microspherical catalyst have approaching size distribution, bulk density, abrasion index, and pre-fluidizing reagent is not had catalytic activity to methanol and dimethyl ether in the conversion reaction of high temperature, or the faint catalytic performance of tool only.
The MTO catalyst causes it to have bigger specific area and pore volume owing to contain the molecules of active components sieve.In order to make pre-fluidizing reagent and MTO catalyst have approaching bulk density, add the effect that certain pore creating material can effectively play increases pore volume therein, but the addition of pore creating material is limited, slip viscosity and product pattern when too high consumption can influence pre-fluidizing reagent and prepares.Suitable the choosing also of pre-fluidizing reagent matrix components can be played the increase pore volume, reduce the effect of bulk density, as choose the aluminum phosphate that has than large pore volume, aluminium oxide, silica, silica-alumina and through (the Industrial Catalysis V11 N4P49-52 such as metakaolin of acid/alkali treatment; Petrochemical technology and application V20N3P 157-160).Can choose suitable pore creating material consumption and matrix components according to the pore volume and the bulk density of the MTO catalyst of concrete use.But the host material with large pore volume, its price are also higher relatively, and too high consumption also can have a negative impact to the abrasion and the pattern of pre-fluidizing reagent, often are difficult to obtain solid microsphere.How to keep pre-fluidizing reagent to have suitable pore volume simultaneously concurrently, bulk density and abrasion, and relatively inexpensive again be the problem that the present invention wants emphasis to solve.
The MTO reaction is typical acid catalysis process.Though each component is the more weak material of acid strength with molecular sieve than all in the pre-fluidizing reagent, and is very high to the reactivity of methanol and dimethyl ether under higher reaction temperature, so side reaction is difficult to avoid.In order to reduce the side reaction of pre-fluidizing reagent in the MTO process, the present invention adds the effect that alkali metal/alkaline-earth metal can play the side reaction activity of the pre-fluidizing reagent of effective reduction.In addition, the combination of preferentially choosing carbonate and other salt when using alkaline-earth metal is favourable to the intact microballoon pattern maintenance and the follow-up roasting process of pre-fluidizing reagent in spray-drying process, simultaneously also to keeping its inertia in the methanol and dimethyl ether reaction effective.
The microspherical catalyst that is used for fluid bed adopts spray drying process production, and the granularity regulation and control are simple relatively, can realize by the pressure of variation spray-drying installation or the rotating speed of atomizer.
The pre-fluidizing reagent of fluid bed provided by the invention, it is by matrix, binding agent, alkaline-earth metal, alkali metal and pore volume conditioning agent constitute.
Matrix of the present invention is selected from aluminum phosphate, aluminium oxide, silica, silica-alumina, clay and their mixture.Clay in the matrix is selected from kaolin, metakaolin, acid treatment metakaolin, alkali treatment metakaolin, Ai Luoshi, bentonite, illiteracy holder soil and their mixture.In order to effectively reduce the bulk density of pre-fluidizing reagent, can choose pore volume and arrive the material of 0.4ml/g as matrix at 0.1ml/g.The mass content of host material in all matrix with certain pore volume counted 10-50% by oxide.The mass content of matrix in pre-fluidizing reagent counted 50-85% by oxide.
Binding agent of the present invention is selected from Ludox, aluminium colloidal sol and their mixture.The mass content of binding agent in pre-fluidizing reagent counted 10-35% by oxide.
Alkaline-earth metal of the present invention is selected from organic salts of strontium, inorganic strontium salt, organic barium salt, inorganic barium salt and their mixture, wherein derives from the strontium of carbonate or/and barium accounts in the pre-fluidizing reagent 30-60% of the mass content of total strontium and barium.The mass content of alkaline-earth metal in pre-fluidizing reagent counted 4-15% by oxide.Alkali metal is selected from organic cesium salt, inorganic cesium salt and their mixture.The mass content of alkali metal in pre-fluidizing reagent counted 0.05-5% by oxide.
Pore volume conditioning agent of the present invention is selected from carbon dust, sesbania powder, urea, sucrose, polyvinyl alcohol and their mixture.The mass content of pore volume conditioning agent in pre-fluidizing reagent is 0.05-2%.
Pre-fluidizing reagent of the present invention is used for before the fluidized bed plant, needs through high-temperature roasting sintering temperature 500-800 ℃.Pre-fluidizing reagent transforms the system olefine reaction to methanol and dimethyl ether and does not have a catalytic activity, or the faint activity of tool only.
Pre-fluidizing reagent of the present invention is not limited to methanol and dimethyl ether and transforms the system olefin hydrocarbon, and the fluid-bed process of all acid catalyzed reaction principles all can adopt pre-fluidizing reagent of the present invention.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Kaolin (content 85wt%) and the 0.1kg acid treatment metakaolin (pore volume 0.2ml/g) of 0.588kg are mixed with the 1kg deionized water, stir, add 0.667kg Ludox (content 30wt%) and 0.4kg aluminium colloidal sol (20wt%) then successively, stir 30min.Strontium nitrate and 14g cesium nitrate 200g deionized water dissolving with 102g add above-mentioned system.The 71g strontium carbonate is added top system, stir.5g sesbania powder (soaking into small amount of ethanol) is mixed with 100g water, and the system above adding stirs 30min.Feed liquid is crossed colloid mill and is carried out glue mill, makes that particle diameter 70% is less than 3 μ m in the last gained slurry.The slurry room temperature is carried out spray-drying after placing 2h, and the solid microsphere shape spray dried products that obtains is designated as M1, and product roasting 4h in 650 ℃ of air promptly obtains pre-fluidizing reagent, is designated as M1C.
Embodiment 2
Kaolin (content 85wt%) and false boehmite (the pore volume 0.25ml/g of 0.286kg with 0.588kg, content 70wt%) mixes with the 1kg deionized water, stir, add 0.333kg Ludox (content 30wt%) and 0.4kg aluminium colloidal sol (content 20wt%) then successively, stir 30min.Barium chloride and 14g cesium nitrate 200g deionized water dissolving with 68g add above-mentioned system.The 71g strontium carbonate is added top system, stir.The 5g polyvinyl alcohol is mixed with 100g water, and the system above adding stirs 30min.Feed liquid is crossed colloid mill and is carried out glue mill, makes that particle diameter 70% is less than 3 μ m in the last gained slurry.The slurry room temperature is carried out spray-drying after placing 2h, and the solid microsphere shape spray dried products that obtains is designated as M2, and product roasting 4h in 650 ℃ of air promptly obtains pre-fluidizing reagent, is designated as M2C.
Embodiment 3
The preparation of aluminum phosphate: the false boehmite (content 70wt%) of 0.116kg is mixed with the 0.8kg deionized water, stir, add 0.18kg phosphoric acid (content 85wt%), stir 30min, be warming up to 80 degree reaction 6h then.
The imvite (content 80wt%) of 0.125kg is mixed with 0.2kg water, mix in the aluminum phosphate that makes above then, stir, the Ludox (content 30wt%) and the 0.5kg aluminium colloidal sol (content 20wt%) that add 0.3kg porous silica (pore volume 0.3ml/g), 0.167kg then stir 30min.Strontium chloride and 56g cesium nitrate 200g deionized water dissolving with 123g add above-mentioned system.The 81g strontium carbonate is added top system, stir.10g urea is mixed with 100g water, and the system above adding stirs 30min.Feed liquid is crossed colloid mill and is carried out glue mill, makes that particle diameter 70% is less than 3 μ m in the last gained slurry.The slurry room temperature is carried out spray-drying after placing 2h, and the solid microsphere shape spray dried products that obtains is designated as M3, and product roasting 4h in 650 ℃ of air promptly obtains pre-fluidizing reagent, is designated as M3C.
Comparative Examples 1
This experiment batching and process are with embodiment 1, and difference only is that the addition of strontium nitrate is 204g, do not add and there is strontium carbonate.The spray dried products that obtains is designated as M4, and product roasting 4h in 650 ℃ of air promptly obtains pre-fluidizing reagent, is designated as M4C.There is a greater part of amount to be irregular ellipsoid shape among the M4C, the pattern irregularity, and be not solid bead, broken hole is arranged on the ball.
Comparative Examples 2
This experiment batching and process are with embodiment 1, and difference only is that kaolin changes with the relative addition of false thin female stone.The oxide dry basis mass content of the thin female stone of the vacation of pore volume 0.25ml/g in total matrix is 71.4%.
Kaolin (content 85wt%) and false boehmite (the pore volume 0.25ml/g of 0.714kg with 0.235kg, content 70wt%) mixes with the 1kg deionized water, stir, add 0.333kg Ludox (content 30wt%) and 0.4kg aluminium colloidal sol (content 20wt%) then successively, stir 30min.Barium chloride and 14g cesium nitrate 200g deionized water dissolving with 68g add above-mentioned system.The 71g strontium carbonate is added top system, stir.The 5g polyvinyl alcohol is mixed with 100g water, and the system above adding stirs 30min.Feed liquid is crossed colloid mill and is carried out glue mill, makes that particle diameter 70% is less than 3 μ m in the last gained slurry.The slurry room temperature is carried out spray-drying after placing 2h, and the spray dried products that obtains is designated as M5, and product roasting 4h in 650 ℃ of air promptly obtains pre-fluidizing reagent, is designated as M5C.On most balls of M5C large fracture is arranged, and the pattern irregularity.
Comparative Examples 3
This experiment batching and process are with embodiment 1, and difference only is that the addition of strontium nitrate is 142g, and the adding of alkali metal-free salt cesium nitrate.The product that spray-drying obtains is designated as M6, and product roasting 4h in 650 ℃ of air promptly obtains pre-fluidizing reagent, is designated as M6C.
Embodiment 4
The pre-fluidizing reagent sample that obtains among embodiment 1-3 and the Comparative Examples 1-2 is carried out abrasion index measure, be respectively 0.5,0.8,0.9,3.5 and 2.8.
The abrasion index assay method: will the pre-fluidizing reagent sample of about 50g be put in the straight tube about internal diameter 2.5cm, humid air provides a fluidisation environment with the flow velocity of 20L/min by this pipe.The fine powder that therefrom blows out is collected in the special filter bag, and 4h is carried out in test.Calculate abrasion index by the average per hour mass percent of loss of the first loading amount of catalyst.
The pre-fluidizing reagent roasting sample that obtains among the embodiment 1-3 is carried out bulk density measure, the closs packing density of the sample that do not absorb water is respectively 0.90,0.81 and 0.73g/ml.
Embodiment 5
The pre-fluidizing reagent that obtains among the embodiment 1-3 is carried out methanol-to-olefins reaction (MTO) reaction evaluating.
Appreciation condition: take by weighing the 10g sample fixed fluidized-bed reactor of packing into, sample at first rises to 550 ℃ of activation half an hour under the nitrogen of 40ml/min, be cooled to reaction temperature then and carry out chemical reaction.Stop logical nitrogen, use the micro pump charging, 80wt% methanol aqueous solution, weight space velocity WHSV are 2.0h
-1, product is analyzed by online gas-chromatography, the results are shown in Table for 1 (dimethyl ether is regarded reaction raw materials as).Can see that the pre-fluidizing reagent among the embodiment does not have catalytic activity at 400 ℃ to this reaction, only has faint catalytic activity at 500 ℃.The pre-fluidizing reagent M6C of Comparative Examples 3 compares with M1C, and the reactivity of methyl alcohol obviously increases.
Table 1: methanol conversion system olefine reaction result
a
A: dimethyl ether is regarded reaction raw materials as, reaction time 4min
B: 500 ℃ of reaction temperatures
C: 400 ℃ of reaction temperatures
Claims (7)
1. pre-fluidizing reagent, by matrix, binding agent, alkaline-earth metal, alkali metal and pore volume conditioning agent constitute; Wherein:
Matrix is selected from aluminum phosphate, aluminium oxide, silica, silica-alumina, clay and their mixture; The mass content of matrix in pre-fluidizing reagent counted 50-85% by oxide;
Binding agent is selected from Ludox, aluminium colloidal sol and their mixture; The mass content of binding agent in pre-fluidizing reagent counted 10-35% by oxide;
Alkaline-earth metal is selected from organic salts of strontium, inorganic strontium salt, organic barium salt, inorganic barium salt and their mixture; The mass content of alkaline-earth metal in pre-fluidizing reagent counted 4-15% by oxide;
Alkali metal is selected from organic cesium salt, inorganic cesium salt and their mixture; The mass content of alkali metal in pre-fluidizing reagent counted 0.05-5% by oxide;
The pore volume conditioning agent is selected from carbon dust, sesbania powder, urea, sucrose, polyvinyl alcohol and their mixture; The mass content of pore volume conditioning agent in pre-fluidizing reagent is 0.05-2%.
2. according to the described pre-fluidizing reagent of claim 1, wherein, the clay in the described matrix is selected from kaolin, metakaolin, acid treatment metakaolin, alkali treatment metakaolin, Ai Luoshi, bentonite, illiteracy holder soil and their mixture.
3. according to claim 1 or 2 described pre-fluidizing reagents, wherein, having pore volume in the described matrix is that 0.1ml/g counts 10-50% to the mass content of matrix in all matrix of 0.4ml/g by oxide.
4. according to the described pre-fluidizing reagent of claim 1, wherein, described inorganic strontium salt is strontium carbonate, strontium nitrate, strontium chloride and their mixture; Inorganic barium salt is brium carbonate, barium nitrate, barium chloride and their mixture.
5. according to the described pre-fluidizing reagent of claim 4, wherein, derive from strontium carbonate or/and the strontium of brium carbonate or/and barium accounts for strontium in the pre-fluidizing reagent 30-60% of the gross mass of barium.
6. the described pre-fluidizing reagent of claim 1 transforms the application of making in the alkene at methanol and dimethyl ether, before being used for fluidized bed plant, needs through 500-800 ℃ of roasting.
7. according to the described application of claim 6, wherein, described fluid bed is the fluid-bed process of acid catalyzed reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910250081 CN102085468B (en) | 2009-12-04 | 2009-12-04 | Pre-fluidizing agent for fluidized bed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910250081 CN102085468B (en) | 2009-12-04 | 2009-12-04 | Pre-fluidizing agent for fluidized bed |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102085468A true CN102085468A (en) | 2011-06-08 |
| CN102085468B CN102085468B (en) | 2013-02-20 |
Family
ID=44097620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910250081 Active CN102085468B (en) | 2009-12-04 | 2009-12-04 | Pre-fluidizing agent for fluidized bed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102085468B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962012A (en) * | 2012-11-21 | 2013-03-13 | 陕西煤化工技术工程中心有限公司 | Inert agent for fluidized bed as well as preparation and use methods thereof |
| JP2019137854A (en) * | 2018-02-07 | 2019-08-22 | 株式会社ヤノ技研 | Heat storage material composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159102C (en) * | 2000-11-02 | 2004-07-28 | 中国石油化工股份有限公司 | Cocatalyst for cracking hydrocarbons |
| KR100599251B1 (en) * | 2003-09-20 | 2006-07-13 | 에스케이 주식회사 | Catalysts for the dimethyl ether synthesis and its preparation process |
| CN101239870B (en) * | 2007-02-07 | 2011-08-17 | 中国石油化工股份有限公司 | Process for converting methanol or ethanol to preparing low-carbon olefins |
| CN101157051B (en) * | 2007-02-07 | 2010-12-15 | 中国科学院大连化学物理研究所 | Recovery method of microspherical catalyst of fluid bed |
| CN101422690B (en) * | 2007-10-31 | 2011-11-02 | 中国石油化工股份有限公司 | Gas dechlorination agent and preparation method thereof |
-
2009
- 2009-12-04 CN CN 200910250081 patent/CN102085468B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962012A (en) * | 2012-11-21 | 2013-03-13 | 陕西煤化工技术工程中心有限公司 | Inert agent for fluidized bed as well as preparation and use methods thereof |
| JP2019137854A (en) * | 2018-02-07 | 2019-08-22 | 株式会社ヤノ技研 | Heat storage material composition |
| JP7266282B2 (en) | 2018-02-07 | 2023-04-28 | 株式会社ヤノ技研 | Heat storage material composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102085468B (en) | 2013-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101121145B (en) | Catalyst for oxygen-containing compound conversion to produce olefine microshpere and preparing method thereof | |
| CN101773850B (en) | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof | |
| CN102812109B (en) | High light olefins fcc catalyst compositions | |
| CN102389834B (en) | Molecular sieve catalyst micro powder reutilization method as well as obtained product and application thereof | |
| CN1957070A (en) | Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons | |
| CN101157051B (en) | Recovery method of microspherical catalyst of fluid bed | |
| CN102371167A (en) | Fluidized bed catalyst and its preparation method | |
| CN102372571B (en) | Method for producing propylene by oxygen-containing compound conversion | |
| CN104056654B (en) | A kind of ZSM-5 molecular sieve compositions, preparation method and application thereof | |
| CN102371168B (en) | Preparation method of fluid catalyst | |
| CN101337190B (en) | Catalyst for preparing low-carbon olefine by catalytic cracking using fluidized-bed and preparation method and use thereof | |
| CN102085468B (en) | Pre-fluidizing agent for fluidized bed | |
| CN102188989B (en) | Fluidized bed catalyst and preparation method thereof | |
| CN106890672A (en) | A kind of methyl alcohol converts light olefin catalyst processed and its preparation method and application | |
| CN102372553B (en) | Method for producing olefin by catalytically cracking | |
| CN102372534A (en) | Method for preparing light olefins through conversion of oxygen-containing compounds | |
| CN102811812A (en) | Process for making improved catalysts from clay-derived zeolites | |
| CN102371175B (en) | Preparation method for adhesive-free ZSM-5/ mordenite fluidized bed catalyst | |
| CN102371183B (en) | Preparation method for adhesive-free fluidized bed catalyst | |
| CN102372551B (en) | Method for producing light olefin by catalytically cracking | |
| CN102962012B (en) | A kind of fluid bed inert agents and preparation thereof and using method | |
| CN109701633A (en) | Fluid catalyst, preparation method and its usage | |
| CA2899759A1 (en) | Catalyst with high c4 olefin selectivity for preparing olefin from methanol and preparation method thereof | |
| CN102371166A (en) | Preparation method of binder-free ZSM-5 fluidized bed catalyst | |
| CN114425436B (en) | Preparation method of molecular sieve fluidized bed catalyst, prepared catalyst and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |