CN107029783B - A kind of LPG is converted into the catalyst and preparation method thereof of ethylene, propylene - Google Patents
A kind of LPG is converted into the catalyst and preparation method thereof of ethylene, propylene Download PDFInfo
- Publication number
- CN107029783B CN107029783B CN201710315257.XA CN201710315257A CN107029783B CN 107029783 B CN107029783 B CN 107029783B CN 201710315257 A CN201710315257 A CN 201710315257A CN 107029783 B CN107029783 B CN 107029783B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- propylene
- molecular sieve
- lpg
- ethylene
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to liquefied petroleum gas (LPG) conversion ethylene processed, propylene catalyst.The preparation of catalyst of the present invention, use the raw materials such as boehmite, template di-n-propylamine (DPA) and diisopropylamine (DIPA), with the induction of HZSM-5 crystal seed, the hydrothermal synthesis under certain condition, nucleocapsid composite molecular screen is made, wherein catalyst stratum nucleare is the HZSM-5 molecular sieve with microcellular structure, and shell is central hole structure SAPO-11 molecular sieve.Catalyst acid distribution of the present invention and pore size distribution distribution gradient, while the carbon distribution of micropore surface can be reduced, increase the service life, inhibit secondary response, prevent the growth of long chain hydrocarbons, shows high catalytic performance in LPG conversion ethylene processed, propylene reaction.
Description
Technical field
The present invention relates to the methods that by-product LPG in petrochemical industry and coal chemical industry is converted into ethylene, propylene, particularly belong to stone
By-product LPG is converted into the catalyst of ethylene, propylene in oiling work or preparing propylene by coal-based methanol (MTP).
Background technique
Ethylene and propylene are important basic chemical industry raw material, mostly come from naphtha catalytic cracking.Non-petroleum in recent years
Route preparing propylene by coal-based methanol (MTP) and coal oil (CTL) emerge rapidly in China, generated respectively in production process about 31 % and
The liquefied petroleum gas (LPG) of about 8 %, main component are that propane, butane and butylene usually will since boiling point is close, separation is difficult
These hydrocarbon are directly as fuel combustion.In addition, there is also the demands for promoting added value by refinery processes hydro carbons by-product LPG, by these
By-product hydrocarbon mixture is converted into low-carbon alkene, promotes its added value by business circles concern.
HZSM-5 molecular sieve has unique three dimensional intersection cellular structure, biggish surface area and Kong Rong, good hydro-thermal
Stability, is widely used in catalysis and the fields such as adsorbing separation, SAPO-11 have one-dimensional central hole structure and weak acid, in it is strong
Acid activity position belongs to AEL structure, and cellular structure is made of non-crossing oval ten-ring, and duct aperture is 0.39 nm
×0.64 nm.Both molecular sieves all have respective advantage, but there is applications to limit to again the characteristics of due to self structure
Property.HZSM-5 acidity is stronger, and micropore is more, and the side reactions such as polymerization-dehydrocyclization-aromatisation-coking easily occur in reaction process,
C in product5 +Selectivity is higher, and catalyst is easily because carbon distribution inactivates.Low-carbon alkanes chemical property is stablized, and activates at a higher temperature
It can promote a large amount of side reaction of its association, and then reduce the effective rate of utilization of low-carbon alkanes reactant.How low-carbon alkanes are improved
Conversion ratio and the yield for how improving hydrocarbon conversion ethylene, propylene are one of projects urgently to be resolved.
Patent of invention CN101190417 discloses a kind of catalytic pyrolysis preparing ethylene, propylene catalyst, using ZSM-5 and silk
At least one of geolyte, ZSM-5 and β zeolite or ZSM-5 and Y zeolite coexisting molecular sieve and on it supported rare earth element,
In reaction temperature 600~650oC, under conditions of 0.001~0.5 MPa of reaction pressure, catalytic pyrolysis feed naphtha, ethylene
Propylene (diene) yield is up to 55 %.Patent of invention CN101703943A discloses a kind of catalysis of hydrocarbon cracking preparing ethylene and propylene
Agent, using the molecular sieve carried rare-earth oxide of ZRP-1, rare-earth oxide accounts for the 0.1~8.0 of total catalyst weight
% can handle molecular diameter different raw material or mixture material since ZRP-1 molecular sieve has multistage pore canal, and diene is received
Rate is up to 53 %.Invention CN104324747A discloses a kind of HZSM-5 catalyst external surface method of modifying and modified catalysis
Agent and its purposes.Method modified HZSM-5 molecular sieve is modified using outer surface, modified catalysts are used for C4-C5Olefins by catalytic cracking
Prepare ethylene and propylene.The properties such as catalyst aperture and pore volume, energy are not influenced while reducing catalyst external surface acid amount
The yield for enough improving ethylene and propylene in product, up to 55%.Although hole junction structure and surface of these reports around regulating catalyst
Acidity, changed by way of element modification single molecular sieve reacted in catalysis in disadvantage, but molecular sieve is to lower carbon number hydrocarbons
Contact it is poor, due to the presence of diffusional resistance, hardly enter molecule in the duct of molecular sieve, reaction be difficult in duct
Occur, causes many non-shape-selective by-products to generate, and the introducing of modified metal limits reactant and production to a certain extent
Diffusion of the object in duct, is easy to cause coking and deactivation.
In recent years, the dual cellular structure of core-shell molecular sieve can change the diffusion of reactant, intermediate and product
Efficiency, especially for certain special product selectivity with higher, simultaneously because molecular sieve surface acidity and duct knot
The modulation of structure and synergistic effect exist, and core-shell molecular sieve generally possesses more excellent catalytic performance, therefore, nucleocapsid in recent years
Molecular sieve is in petrochemical industry and fine chemistry industry using increase.But there is some disadvantages in such catalyst preparation: preparation
Technique is generally relatively complicated, different kinds of molecules is sieved carry out on nanometer or micron level compound there is still a need for good control ability
Play effective synergistic effect between different molecular sieve.In general, the molecular sieve of core-shell structure is in nuclear phase zeolite molecular sieve
The novel molecular sieve structure that one layer of fine and close shell phase molecular sieve polycrystalline is constituted, referred to as core-shell molecular sieve, shell phase are grown on monocrystalline
Molecular sieve can also protect the catalytic performance of nuclear phase molecular sieve well while retaining acid self-molecules present sieve and architectural characteristic,
Catalytic performance can be preferably overlapped by the two in microstructure, be provided simultaneously in multistage pore canal system and two-part reactive
The heart.But the separation of this molecular sieve analog, roasting, modification it is more demanding, preparing core-shell molecular sieve needs nano molecular sieve
Preparation process, moieties sieve current synthetic technology and are relatively inaccessible to require, and big Crystal-support object are needed, for nuclear phase molecular sieve
Prepare requirement with higher and the defects of mechanical strength does not reach requirement, also limit industrial applications.
Summary of the invention
Object of the present invention is to develop one kind in view of the deficiencies of the prior art with liquefied petroleum gas (LPG) as raw material high yield second
The catalyst of alkene, propylene will be situated between using HZSM-5 molecular sieve and acid adjustable SAPO-11 material with microchannel structure
It is suitable for the catalyst that liquefied petroleum gas Efficient Conversion is ethylene, propylene that hole, which introduces micro porous molecular sieve modulation to go out,.
Core-shell structure copolymer composite molecular sieve catalyst stratum nucleare of the present invention is HZSM-5 molecular sieve, and shell is central hole structure SAPO-11 points
Son sieve.Make shell offer faintly acid position with SAPO-11 and passes through modulation under the premise of not destroying HZSM-5 matrix material structure
SAPO-11 comes regulating catalyst acidity and pore structure, improves the selective activization of its strong and weak acid catalysis and target product,
Keep both HZSM-5 and SAPO-11 molecular sieves compound, and it is innovative combine its advantage that respectively catalytic field is shown, have
Good synergic catalytic effect be distributed catalyst acid of the invention and pore size distribution by the regulation in duct, acidity etc.
Distribution gradient, while the carbon distribution that micro pore volume greatly reduces molecular sieve surface can be reduced, increase the service life, since molecule is spread
Resistance reduces, and can inhibit secondary response, prevent the growth of long chain hydrocarbons, shows in LPG conversion ethylene processed, propylene reaction
High catalytic performance out.
Catalyst of the present invention the preparation method comprises the following steps:
(1) by boehmite room-temperature dissolution in water and phosphoric acid mixed liquor, silica solution, stirring is added, while mould is added
Plate agent di-n-propylamine (DPA) and diisopropylamine (DIPA)；Wherein charge ratio is with molar ratio computing are as follows: SiO2:Al2O3:P2O5:H2O:
DPA:DIPA=0.6:1.0:1.0:50:0.48:0.72~2.5:3.2:3.8:100:1:1.5.
(2) 1~25%HZSM-5 crystal seed of total amount is added, to stir evenly under≤500 r/min revolving speeds；
(3) gained gel being transferred to crystallizing kettle, 120~185 DEG C of crystallization, crystallization time is 6~24 h, be centrifugated,
Deionized water is washed to neutrality, 100~120 DEG C of dryings, 450~550 DEG C of roastings；
(4) using chromic nitrate as raw material, the Cr of 5~10 % is loaded using equi-volume impregnating2O3。
The catalyst prepared through above-mentioned steps is a kind of compound core-shell molecular sieve, nucleocapsid composite molecular sieve catalyst stratum nucleare
For the HZSM-5 molecular sieve with microcellular structure, shell is central hole structure SAPO-11 molecular sieve.It is mesoporous by adjusting in the present invention
The Crystallization of Zeolite time adjusts the shell thickness of composite molecular screen, and such controllability has chemical engineering industryization reaction very much
Benefit, while this technology is utilized into available double mesopore orbit systems on mesopore molecular sieve.
The sequence that raw material is launched in the present invention cannot change, and sequentially be followed successively by boehmite, phosphoric acid solution, silicon is molten
Glue, di-n-propylamine (DPA) and diisopropylamine (DIPA), HZSM-5 crystal seed, final impregnating Cr2O3.This is synthesizing HZSM-5
Occur dealuminzation phenomenon in the Acidic Liquid of SAPO-11, plays an important role to the introducing of mesopore orbit.
HZSM-5 crystal seed is placed in the low temperature crystallized liquid of SAPO-11 by the present invention, in the nanocrystalline developmental process of SAPO-11,
By the modulation of hydrothermal condition, so that the Si content in crystallization liquid meets the acid requirement of composite molecular screen, HZSM-5 is made to exist
SAPO-11 is surface-crosslinked to grow up until covering entire SAPO-11 molecular sieve crystal, and nucleocapsid composite molecular sieve catalyst stratum nucleare is
HZSM-5 molecular sieve with microcellular structure, shell are central hole structure SAPO-11 molecular sieve.Such molecular sieve has duct gradient
With acid gradient, surface faintly acid SAPO-11 reduces the generation of secondary side reaction on the strong acidic site of the surface HZSM-5, simultaneously
Catalyst surface coking carbon distribution can be effectively reduced, extends the molecular sieve service life, enhances its stability.
Catalyst of the invention is applied to that liquefied petroleum gas (LPG) preparing propylene transformed, ethylene, in fixed bed reactors into
Row.Reaction temperature 500~600oC, normal pressure, n (LPG): n (Ar)=1: 2.5~4, W/F=10~20 gh/
Ethylene and propylene are prepared under the conditions of mol.
Detailed description of the invention
Fig. 1 is that the microscopic appearance SEM of sintetics schemes, and wherein a, b are respectively HZSM-5 and SAPO-11 molecular sieve, and c is
HZSM-5 and SAPO-11 molecule screen mechanical is compound, and d is that HZSM-5 and SAPO-11 molecular sieve is compound.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
6 g boehmite room-temperature dissolutions are weighed in the diluted 11.5 g phosphoric acid solution of 39.07 g deionized waters, at a slow speed
Stirring makes it completely dissolved, and 6 g acidic silicasols are added, and stirs 2 h, and 2.478 g DPA and 3.712 g DIPA are added, stir
2 h are mixed, 3.438 g HZSM-5 original powders are added, 2 h, mixing speed 200r/min is stirred, gained gel is transferred to crystallization
Reaction kettle, 185o6 h of C crystallization, centrifuge separation, deionized water are washed to neutrality, through 120oC dries 12 h, 550oC roasting 6
H obtains core~shell composite molecular sieve product.Indicate that SAPO-11, Z indicate ZSM-5 labeled as S@Z-6, S, 6 indicate 6 h of crystallization.Using
Equi-volume impregnating loads the Cr of 10 %2O3, 120oC dry 12 h, 550oC roasts 4 h and obtains catalyst prod.20~40 mesh
It is granulated, takes 1 g to be fitted into micro fixed-bed reactor and evaluate its LPG activity of conversion.The results are shown in Table 1.
Embodiment 2
6 g boehmite room-temperature dissolutions are weighed in the diluted 11.5 g phosphoric acid solution of 39.07 g deionized waters, are stirred
It makes it completely dissolved, 6 g acidic silicasols is added, stir 2 h, 2.478 g DPA and 3.712 g DIPA, stirring 2 is added
3.438 g HZSM-5 original powders are added in h, stir 2 h, and gained gel is transferred to crystallization kettle, and 185o12 h of C crystallization, from
Heart separation, deionized water are washed to neutrality, through 120oC dries 12 h, 550oC roasts 6 h and obtains core~shell composite molecular sieve production
Product.It is denoted as S@Z-12.The Cr of 10 % is loaded using equi-volume impregnating2O3, 120oC dry 12 h, 550oC roasts 4 h and must urge
Agent product.20~40 mesh are granulated, and are taken 1 g to be fitted into micro fixed-bed reactor and are evaluated its LPG activity of conversion.As a result such as table 1
It is shown.
Embodiment 3
6 g boehmite room-temperature dissolutions are weighed in the diluted 11.5 g phosphoric acid solution of 39.07 g deionized waters, are stirred
It makes it completely dissolved, 6 g acidic silicasols is added, stir 2 h, 2.478 g DPA and 3.712 g DIPA, stirring 2 is added
3.438 g HZSM-5 original powders are added in h, stir 2 h, and gained gel is transferred to crystallization kettle, and 185o24 h of C crystallization, from
Heart separation, deionized water are washed to neutrality, through 120oC dries 12 h, 550oC roasts 6 h and obtains core~shell composite molecular sieve production
Product.It is denoted as S@Z-24.The Cr of 10 % is loaded using equi-volume impregnating2O3, 120oC dry 12 h, 550oC roasts 4 h and must urge
Agent product.20~40 mesh are granulated, and are taken 1 g to be fitted into micro fixed-bed reactor and are evaluated its LPG activity of conversion.As a result such as table 1
It is shown.
Embodiment 4
By boehmite room-temperature dissolution in water and phosphoric acid solution, silica solution, stirring is added, while template two is added
N-propylamine (DPA) and diisopropylamine (DIPA)；Wherein charge ratio is with molar ratio computing are as follows: SiO2:Al2O3:P2O5:H2O: DPA:
DIPA=2.5:3.2:3.8:100:1:1.5.The 10gHZSM-5 original powder of total weight is added, 2 h are stirred under 500r/min, by gained
Gel is transferred to crystallization kettle, and 120o20 h of C crystallization, centrifuge separation, deionized water are washed to neutrality, through 100oC dry 12
h、450 oC roasts 6 h and obtains core~shell composite molecular sieve product.It is denoted as S@Z-20.Load 10 %'s using equi-volume impregnating
Cr2O3, 120oC dry 12 h, 550oC roasts 4 h and obtains catalyst prod.20~40 mesh are granulated, and 1 g is taken to be packed into miniature fixation
Its LPG activity of conversion is evaluated in bed reactor.The results are shown in Table 1.
LPG raw material composition is equal in embodiment 1-4 are as follows:
| Component | Propane | Normal butane | Iso-butane | N-butene | Isobutene |
| Content (wt%) | 17.9 | 13.0 | 41.1 | 13.0 | 15.0 |
For embodiment studies have shown that catalyst carries out in fixed bed reactors, loaded catalyst is 1 g, the warp of LPG first
Preheating furnace is pre- thermal evaporation, enters catalyst bed through control system with Ar after preheating with corresponding proportion, in reaction temperature 600oC,
Normal pressure reacts under conditions of n (LPG): n (Ar)=1: 2.5, W/F=15 gh/mol, ethylene, propylene, alkane
And the products such as aromatic hydrocarbons, through gas-chromatography on-line analysis, the more traditional HZSM-5 of diene selective is increased considerably, C5 +Component is seldom.
The molecular sieve catalyst preparation method of this law improvement is simple, is easy to promote and apply in the industry, has potential warp
Ji value.Relative to Mechanical mixture, nuclear phase molecular sieve outer surface is covered by faintly acid shell, it is suppressed that secondary side reaction
Generation, effectively increase the yield of diene.
Comparative example
According to charge ratio: SiO2 : Al2O3 : TPABr : NH3·H2O : H2O = 100 : 1:12 : 100 :
1120 calculate inventory [Y. Wang, S. B. Fan, J. L. Zhang, T. S. Zhao. Effects of
synthesis conditions on the yields and properties of HZSM-5. Cryst. Res.
Technol., 2015, 1-6] .Beaker is added in TPABr, water, ammonium hydroxide, turbine is opened using four oblique leaves under room temperature and stirs
It mixes after paddle keeps 550 r/min rotor speed high-speed stirred, 30 min and aluminum nitrate 1 h of stirring is added, add silica solution stirring 30
Min is eventually adding 4% crystal seed, continues that 1 h is sufficiently stirred, obtains homogeneous gel.Gel solution is transferred to polytetrafluoroethyl-ne
The stainless steel crystallizing kettle of alkene lining, in 180o72 h of C crystallization.It is filtered, washed to neutrality, 120oC dry 12 h, 550oC roasting
It burns 6 h and obtains HZSM-5 original powder, the Cr of 10 % is loaded using equi-volume impregnating2O3, 120oC dry 12 h, 550oC roasts 4 h
Catalyst prod is obtained, 20~40 mesh are granulated, take 1 g to be fitted into micro fixed-bed reactor and evaluate its LPG activity of conversion.As a result such as
Shown in table 1.
The LPG activity of conversion of 1 catalyst sample of table, the catalyst activity prepared as shown in Table 1 are good.
Table 2 is the porous of composite sample.The mesoporous rate of compound rear sample increases as shown in Table 2.
Table 1
Table 2
Claims (4)
1. the catalyst that a kind of LPG is converted into ethylene, propylene, it is characterised in that the catalyst is compound nucleocapsid molecule
Sieve, catalyst stratum nucleare are HZSM-5 molecular sieve, and shell is central hole structure SAPO-11 molecular sieve；Method for preparing catalyst is to lead to
Cross following steps:
(1) by boehmite room-temperature dissolution in water and phosphoric acid solution, silica solution is added, template two positive third is added in stirring
Amine DPA and diisopropylamine DIPA；Wherein charge ratio is with molar ratio computing are as follows: SiO2 : Al2O3 : P2O5 : H2O : DPA:
DIPA=0.6: 1.0: 1.0: 50: 0.48: 0.72~2.5: 3.2: 3.8: 100: 1: 1.5；
(2) HZSM-5 crystal seed is added, to stir evenly under≤500 r/min revolving speeds；
(3) gained gel is transferred to crystallizing kettle, carries out crystallization, separates, washes, dries, roast；
(4) Cr is impregnated using equi-volume impregnating2O3。
2. the catalyst that a kind of LPG according to claim 1 is converted into ethylene, propylene, it is characterised in that described to urge
The sequence that raw material is launched in agent preparation method cannot change, and sequentially be followed successively by boehmite, phosphoric acid solution, silica solution,
Di-n-propylamine and diisopropylamine, HZSM-5 crystal seed, final impregnating Cr2O3。
3. the catalyst that a kind of LPG according to claim 1 is converted into ethylene, propylene, it is characterised in that described to urge
In agent preparation method, the crystallization is 120~185 DEG C of crystallization, and crystallization time is 6~24 h；It is described to be separated into centrifuge separation；
The washing, dry, roasting are as follows: deionized water is washed to neutrality, 100~120 DEG C of dryings, 450~550 DEG C of roastings；It is described
Cr2O3Account for 5~10 % of catalyst quality score.
4. the catalyst that a kind of LPG according to claim 1 is converted into ethylene, propylene, it is characterised in that described to urge
Agent is applied to liquefied petroleum gas conversion ethylene processed, propylene, it is characterised in that the catalyst reacts in fixed bed, reaction temperature
Degree is 500~600 DEG C, normal pressure, and liquefied petroleum gas LPG and argon gas molar ratio are 1: 2.5~4, and air speed is W/F=10~20
Ethylene and propylene are prepared under the conditions of gh/mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710315257.XA CN107029783B (en) | 2017-05-08 | 2017-05-08 | A kind of LPG is converted into the catalyst and preparation method thereof of ethylene, propylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710315257.XA CN107029783B (en) | 2017-05-08 | 2017-05-08 | A kind of LPG is converted into the catalyst and preparation method thereof of ethylene, propylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107029783A CN107029783A (en) | 2017-08-11 |
| CN107029783B true CN107029783B (en) | 2019-05-03 |
Family
ID=59537034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710315257.XA Active CN107029783B (en) | 2017-05-08 | 2017-05-08 | A kind of LPG is converted into the catalyst and preparation method thereof of ethylene, propylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107029783B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530495A (en) * | 2020-06-01 | 2020-08-14 | 宁夏大学 | Method for producing p-xylene |
| CN112322333B (en) * | 2020-10-21 | 2021-11-16 | 中国石油大学(北京) | Alkane-alkene co-cracking catalyst and alkane-alkene mixed catalytic cracking method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711992B (en) * | 2008-09-29 | 2012-05-30 | 宁夏大学 | Catalyst for selectively producing propene by methanol or dimethyl ether and preparation method thereof |
| CN102274748A (en) * | 2011-06-21 | 2011-12-14 | 西北大学 | Catalyst of conversion of ethanol to propylene and propane, preparation method thereof and application thereof |
| CN102266793A (en) * | 2011-06-21 | 2011-12-07 | 西北大学 | Catalyst for producing propylene and producing method and application thereof |
| US9193645B2 (en) * | 2012-08-31 | 2015-11-24 | Exxonmobil Chemical Patents Inc. | Xylene isomerization process and catalyst therefor |
| CN106238093B (en) * | 2016-07-13 | 2018-11-23 | 太原理工大学 | The preparation and application of HZSM-5/SAPO-11 core-shell molecular sieve |
-
2017
- 2017-05-08 CN CN201710315257.XA patent/CN107029783B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107029783A (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102266793A (en) | Catalyst for producing propylene and producing method and application thereof | |
| CN102372277B (en) | Preparation method of binder-free ZSM-5/beta coexisting molecular sieve | |
| CN104226360B (en) | Holocrystalline ZSM-5 molecular sieve catalyst and its production and use | |
| CN105536863B (en) | A kind of molecular sieve catalyst and its preparation method and purposes for methanol conversion for preparing arene | |
| CN101734987A (en) | Method for preparing ethylene and propylene from C4 hydrocarbons | |
| CN107265478B (en) | A kind of boron modification ferrierite molecular sieve catalyst and the preparation method and application thereof | |
| CN105536811A (en) | A core-shell type catalyst for lower-alkene preparation from synthetic gas, a preparing method thereof and applications of the catalyst | |
| CN102302945A (en) | Method for preparing propene by catalytic cracking | |
| CN107442166B (en) | Hydrogenation catalyst suitable for producing biodiesel and preparation method and application thereof | |
| CN107029783B (en) | A kind of LPG is converted into the catalyst and preparation method thereof of ethylene, propylene | |
| CN104192859A (en) | Quick synthesis method of small-crystal-grain ZSM-5 molecular sieve | |
| CN101503201B (en) | Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst | |
| CN106391106B (en) | A kind of preparation method of the core-shell structure molecular sieve containing metal | |
| CN104107713A (en) | Catalyst for preparing propylene through C4 olefin cracking, and preparation method and use thereof | |
| CN103769207A (en) | Catalyst used for production of isobutene via isomerization of n-butene skeleton and combined production of propylene, and preparation method and applications thereof | |
| CN102861604B (en) | Olefin catalytic agent prepared by naphtha catalytic cracking and preparation method and application thereof | |
| KR20150058055A (en) | Bismuth molybdate catalyst having zeolite coating layer, preparation method thereof and method of preparing 1,3-butadiene using the same | |
| CN103263947A (en) | Composite molecular sieve for preparing catalyst for producing light olefins from organic oxygen-containing compound, and preparation method thereof | |
| CN106076401B (en) | Superacid-coated HZSM-5 molecular sieve catalyst, and preparation method and application thereof | |
| CN108097303A (en) | A kind of preparation method of catalytic diesel oil cracking producing light olefins catalyst | |
| CN114100675B (en) | Preparation method of boron-containing molecular sieve and application of molecular sieve in butene double bond isomerization reaction | |
| CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN107803219B (en) | Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application | |
| KR20120117255A (en) | Catalyst for the dehydration of glycerol to acrolein and preparing method of the same | |
| CN110605140A (en) | Nano ZSM-5 catalyst for alkylation of benzene and methanol and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |