CN106083509A - The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins - Google Patents
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins Download PDFInfo
- Publication number
- CN106083509A CN106083509A CN201610443593.8A CN201610443593A CN106083509A CN 106083509 A CN106083509 A CN 106083509A CN 201610443593 A CN201610443593 A CN 201610443593A CN 106083509 A CN106083509 A CN 106083509A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- metal skeleton
- crome metal
- normal butane
- light olefins
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/10—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from acyclic hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A kind of method that the invention provides crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins.The method comprises the following steps: makes normal butane contact with crome metal skeleton doping ZSM 5 molecular sieve catalyst under reaction temperature, reaction pressure and in carrier gas atmosphere and reacts, obtains ethylene and propylene；This crome metal skeleton doping ZSM 5 molecular sieve catalyst is that the principle utilizing fabricated in situ prepares, wherein SiO2/(Al2O3+Cr2O3) mol ratio is 80 160, Cr2O3/Al2O3Mol ratio is 0.005 1.0.The present invention utilizes normal butane cheap and easy to get, that added value is low, chemical property is relatively stable, difficulty cracks as raw material, ethylene, propylene is produced as bifunctional catalyst using ZSM 5 molecular sieve of crome metal skeleton doping, normal butane can be efficiently utilized, and the productivity of ethylene, propylene is high, has good prospects for commercial application.
Description
Technical field
The present invention relates to the technology of preparing of low-carbon alkene (i.e. ethylene, propylene), particularly relate to a kind of crome metal skeleton doping
The method of molecular sieve catalytic cracking normal butane producing light olefins, belongs to technical field of petrochemical industry.
Background technology
Ethylene, propylene, as important Elementary Chemical Industry raw material, play the part of important role in national economy.Along with industry
Development, ethylene, the demand of propylene are continuously increased, and existing manufacturing condition can not meet consumption requirement, need a large amount of
Import.At present, ethylene, the main production of propylene are steam cracking, but the reaction temperature of steam cracking is big compared with high, energy consumption,
Harsh and low-carbon alkene the selectivity of requirement to equipment is relatively low.Therefore, ethylene, the propylene technology of developping production receives much concern.
Compared to steam cracking, catalytic pyrolysis is due to the use of catalyst so that reaction temperature is substantially reduced, and can be by regulation
The composition of catalyst improves ethylene, the selectivity of propylene.
On the one hand, along with the development of petroleum refining industry, the C4 hydro carbons of refinery's by-product is continuously increased, and normal butane is due to its chemical bond
Energy is high, character is the most stable, is typically only capable to burn as fuel.On the other hand, in the face of ethylene, the demand gap of propylene, how
Normal butane relatively low for added value is converted into the high ethylene of added value, propylene becomes the focus studied at present.
The alkene that metastable for chemical property normal butane is first converted into correspondence carries out catalytic cracking reaction the most again
It it is one of the approach of currently butane catalytic pyrolysis.Catalyst for dehydrogenation of low-carbon paraffin, a class is with the noble metal of support type as work
Property component, such as CN105363443A, CN105363473A, CN105363447A, CN105363496A, CN105363472A,
In the method for dehydrogenating of the disclosed low-carbon alkanes such as CN105363484A and CN105056990A, with Pt as active component, pass through
Add different auxiliary agents (such as IB race element, Group IIIA element, rare earth element, Sn element or Zn element etc.) and improve lower alkanes
The dehydrogenation activity of hydrocarbon (propane or iso-butane) and the stability of catalyst, Pt series catalysts has preferable low-carbon alkanes and takes off
Hydrogen activity, but owing to active component is noble metal, relatively costly, it is difficult to utilize on a large scale.Another kind of be with base metal or
Its oxide of person is active component, such as VIII element, barium oxide, chromated oxide etc., CN105214657A disclose with
VIII element is as the first active component of the dehydrogenation of C3-C5 alkane, using stannum, germanium etc. as the second metal component, prepared
Catalyst there is higher appearance carbon ability.CN104549415A discloses with vanadium or its oxide as active component, silicon substrate
Material is carrier, CO2Being used for isobutene for oxo-dehydrogenation as oxidant is the process of isobutene., and prepared catalyst has high load
Be uniformly dispersed during amount, active component is difficult to the feature of accumulative crystallization, it is achieved that in course of reaction catalyst stability high and
The purpose that target alkene selectivity is high.CN105312046A, CN104437515A, CN104549321A, CN104549220A with
And CN104549388A etc. discloses the active component with Cr oxide as dehydrogenation, with aluminium oxide or silicon oxide as carrier, use
In the dehydrogenation reaction of propane or iso-butane, show the dehydrogenation of good low-carbon alkanes.Cr is as dehydrogenation activity group
Point, cheap and easy to get compared to noble metal, and the dehydrogenation activity of its low-carbon alkanes can be with the dehydrogenation activity phase of Pt series catalysts
When；Compared to VIII element or vanadium series catalyst, Cr or Cr oxide need not the second affected auxiliary agent of component, exists simultaneously
Still there is under conditions of existing without weak oxidant the activity of higher dehydrogenating low-carbon alkane, it can be seen that Cr is a kind of effective
The active component of low-carbon alkanes anaerobic dehydrogenation.
In terms of catalytic pyrolysis, CN1676499 A discloses and with the mixture of the carbon four without diolefin or carbon five is
Raw material, utilizes the molecular sieve of rare earth metal, rare-earth oxide or phosphorous oxides modification as catalyst, deposits at steam
Under the conditions, catalytic pyrolysis produces ethylene, propylene.CN104557396 A discloses one and utilizes n-butene to split as catalysis
The raw material solved, have employed P Modification SAPO-11 molecular sieve and two kinds of catalyst of ZSM-5 molecular sieve carrys out catalytic pyrolysis and produce propylene.
CN1915924 A discloses a kind of method utilizing C4 olefins by catalytic cracking to produce propylene, wherein uses the ZSM system of high-crystallinity
The molecular sieve of row, as catalyst, is 2～50 hours at mass space velocity-1Under conditions of, reach higher propene yield.
CN101734987 A discloses a kind of with iso-butane, butylene, normal butane mixture as raw material, wherein, and consisting of of raw material: different
The mass fraction of butane is 45.7%, and the mass fraction of butylene is 38.6%, and the mass fraction of normal butane is 15.6%.With expensive
Metal/carrier, molecular sieve are catalyst, through two section reactor, come preparing ethylene, propylene, and its total recovery reaches 38.7%.
In document disclosed above, dehydrogenating low-carbon alkane is made with precious metals pt or base metal or its oxide mostly
For dehydrogenation active component, compared to noble metal or other base metals, it is good and cheap and easy to get that Cr species have dehydrogenation activity
Etc. advantage.C4 hydrocarbon cracking mostly with butylene, iso-butane or their mixture of easily cracking as raw material, with molecular sieve or
The molecular sieve of person's modification, as catalyst, carrys out preparing low-carbon olefins.Normal butane is former as the C4 that a kind of chemical property is relatively stable
Material, is utilized the most efficiently.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of crome metal skeleton doped molecular sieve catalysis and split
The method solving normal butane producing light olefins.The present invention utilize cheap and easy to get, added value is low, chemical property is relatively stable, difficult cracking
Normal butane as raw material, using the ZSM-5 molecular sieve of crome metal skeleton doping as bifunctional catalyst produce ethylene, third
Alkene so that normal butane can be efficiently utilized, and it is low to have energy consumption, ethylene, the productivity advantages of higher of propylene.
In order to achieve the above object, the invention provides a kind of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane system
The method of low-carbon alkene, the method comprises the following steps: make normal butane under reaction temperature, reaction pressure and in carrier gas atmosphere
Contact with crome metal skeleton doping ZSM-5 molecular sieve catalyst and react, obtain ethylene and propylene；Wherein, described crome metal
Skeleton doping ZSM-5 molecular sieve catalyst is through the following steps that prepare:
By silicon source, concentrated sulphuric acid, chromium source, aluminum source, template by certain charging sequence mix homogeneously, obtain a mixed liquor；
With the pH value of the sodium hydroxide described mixed liquor of regulation to 10-13, then after uniform temperature stirs a period of time, obtain a gel group
Compound, the composition of described gel combination includes nSiO2:(1-x)Al2O3:xCr2O3: (8-10) template: (0.125-0.25)
Na2O:(10-12)H2SO4:(2000-3000)H2O；By described gel combination after uniform temperature crystallization a period of time, then warp
Cool down, filter, wash, be dried, roasting；Be then passed through ammonium salt solution ion exchange after, then through filtering, wash, being dried, roasting,
Obtain described crome metal skeleton doping ZSM-5 molecular sieve catalyst, wherein SiO2/(Al2O3+Cr2O3) molar ratio range be
80-160, Cr2O3/Al2O3Molar ratio range be the 0.005-1.0 (SiO in the molecular sieve catalyst finally given2、Al2O3
With Cr2O3Molar ratio relation identical with above-mentioned gel combination, therefore without again to gel combination form in n
Limit further with x).
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
In the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, by silicon source, concentrated sulphuric acid, chromium source, aluminum source, template
The step that agent obtains a mixed liquor by certain charging sequence mix homogeneously includes: is mixed in silicon source and concentrated sulphuric acid, adds chromium
Source, is uniformly mixed, and obtains one first mixed liquor；Aluminum source is dissolved in deionized water, then it is mixed to be added dropwise to described first
Close in liquid, be uniformly mixed, obtain one second mixed liquor；Template is dissolved in deionized water, then is added dropwise to described
In second mixed liquor, it is uniformly mixed, obtains described mixed liquor.Wherein, it is highly preferred that each step stirring mixing
Temperature is 35-60 DEG C (can be constant temperature stirring, more preferably 35 DEG C of constant temperature at a certain temperature of 35-60 DEG C), the time
For 30-40 minute.
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
In the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, described silicon source includes Ludox and/or positive silicic acid
Tetra-ethyl ester etc., it is highly preferred that the Ludox that described Ludox is mass content 40%.
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
In the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, described chromium source includes Chromium nitrate (Cr(NO3)3),nonahydrate etc..
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
Described crome metal skeleton doping ZSM-5 molecular sieve catalyst preparation process in, source of aluminium include Patent alum and/
Or aluminum isopropylate. etc..
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
Described crome metal skeleton doping ZSM-5 molecular sieve catalyst preparation process in, described template include 4-propyl bromide and/
Or TPAOH etc..
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
In the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, regulate the pH of described mixed liquor with sodium hydroxide
Value includes to the step of 10-13: be dissolved in deionized water by sodium hydroxide, then is added dropwise in described mixed liquor, regulates pH
Value is 10-13.
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
In the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, regulate the pH of described mixed liquor with sodium hydroxide
It is worth to 10-13, by prepared gel combination constant temperature stirring, (more preferably 35 DEG C perseverances at a certain temperature of 35-60 DEG C
Temperature), mixing time is 6-10 hour.
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
In the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, the crystallization temperature of gel combination is 150-180
DEG C (more preferably 170 DEG C), crystallization time is 4-6 days (more preferably 4 days)；Gel combination crystallization complete after be dried for
60-100 DEG C dry 6-12 hour, being roasted to 450-600 DEG C of roasting 4-6 hour afterwards.
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that
In the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, described ammonium salt includes ammonium nitrate and/or ammonium chloride
Deng；The concentration of described ammonium salt solution is 1-2M, and described ammonium salt solution and the molecular sieve carrying out ion exchange with ammonium salt solution
Liquid-solid ratio be 10:1-30:1 (mL/g)；The temperature carrying out ion exchange with ammonium salt solution is 60-80 DEG C, and the time is that 2-8 is little
Time；The number of times carrying out ion exchange with ammonium salt solution is 1-3 time；Being dried as at 60-100 after the exchange of ammonium salt solution ion
DEG C dry 6-12 hour, being roasted to 450-600 DEG C of roasting 4-6 hour afterwards.
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that just
Butane contacts, with crome metal skeleton doping ZSM-5 molecular sieve catalyst, the reaction temperature reacted and is 400-700 DEG C, reaction pressure
Power is 0.1MPa (i.e. normal pressure).
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that institute
Stating carrier gas is nitrogen, and the volume flow rate of carrier gas can be 19-190mL min-1。
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that just
The purity of butane is 99.9%, and the volume flow rate of normal butane can be 1-10mL min-1。
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that phase
It is 1-10mL min for normal butane volume flow rate-1, the consumption of described crome metal skeleton doping ZSM-5 molecular sieve catalyst is
0.10-1.00g。
In the method for above-mentioned crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, it is preferable that just
Butane contacts to react with crome metal skeleton doping ZSM-5 molecular sieve catalyst and carries out in fixed bed reactors.
A kind of method that the invention provides crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins.Should
Method use specific preparation process obtain crome metal skeleton doped molecular sieve bifunctional catalyst, then utilize cheap and easy to get,
The normal butane that added value is low, chemical property is relatively stable, difficulty cracks, as raw material, using Cr species as dehydrogenation active component, makes
First there is dehydrogenation reaction in normal butane on dehydrogenation activity position, and then is converted into corresponding alkene, occurs catalytic pyrolysis anti-the most again
Should, generate low-carbon alkene.The side of the crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins that the present invention provides
Method mainly has the advantage that
(1) the crome metal skeleton doping ZSM-5 molecular sieve catalyst that the present invention provides is in the situation without secondary synthesis
Under, crome metal is introduced the skeleton of molecular sieve, regulatory molecule sieve acidity, solves metal component in ion exchange and infusion process
The problem of plug-hole；And the process that the present invention prepares crome metal skeleton doping ZSM-5 molecular sieve catalyst is simple, easily operates,
Low cost；
(2) crome metal skeleton doping ZSM-5 molecular sieve catalyst prepared by the present invention is used, for normal butane catalytic pyrolysis
Course of reaction does not has the requirement of harshness, can realize the Efficient Conversion of normal butane at a lower temperature, and ethylene, propylene have relatively simultaneously
High yield, and there is the advantage that energy consumption is low；Such as, in certain specific embodiments of the invention, it is catalyzed at 650 DEG C
During cracking reaction, the conversion ratio of normal butane has reached 99.5%, and the yield of ethylene has reached 35.1%, ethylene, total receipts of propylene
Rate has reached 53.8%；Therefore, the crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins that the present invention provides
Method there is good prospects for commercial application.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
The invention provides a kind of crome metal skeleton doping ZSM-5 that can be used for normal butane preparing low-carbon olefin by catalytically cracking to divide
Sub-sieve catalyst, in the preferred embodiment of the present invention, this crome metal skeleton doping ZSM-5 molecular sieve catalyst is profit
Prepared by following steps by the principle of fabricated in situ:
(1) silicon source and concentrated sulphuric acid are mixed, be subsequently adding chromium source, constant temperature (preferably 35 ° at a certain temperature of 35-60 DEG C
Constant temperature) stir 30-40 minute, make they mix homogeneously, obtain one first mixed liquor；
(2) aluminum source is dissolved in deionized water, then is added dropwise in described first mixed liquor, a certain at 35-60 DEG C
At a temperature of constant temperature (preferably 35 ° constant temperature) stir 30-40 minute, make they mix homogeneously, obtain one second mixed liquor；
(3) template is dissolved in deionized water, then is added dropwise in described second mixed liquor, certain of 35-60 DEG C
At a temperature of one, constant temperature (preferably 35 ° constant temperature) stirs 30-40 minute, makes they mix homogeneously, obtains one the 3rd mixed liquor；
(4) being dissolved in deionized water by sodium hydroxide, then be added dropwise in described 3rd mixed liquor, regulation pH value is extremely
10-13, then at a certain temperature of 35-60 DEG C, constant temperature (preferably 35 ° constant temperature) stirs 6-10 hour, obtains a Gel Compositions
Thing, the composition of described gel combination includes nSiO2:(1-x)Al2O3:xCr2O3: (8-10) template: (0.125-0.25)
Na2O:(10-12)H2SO4:(2000-3000)H2O；
(5) by described gel combination in 150-180 DEG C of crystallization 4-6 days (preferably in 170 DEG C of crystallization 4 days), cooling, mistake
After filter, washing, dry 6-12 hour in 60-100 DEG C, then 450-600 DEG C of roasting 4-6 hour；Then at 60-80 DEG C through ammonium salt
Solion exchanges 2-8 hour, selectively repeats ammonium salt solution ion and exchanges 1-2 time, then filter, wash after filtration, in
60-100 DEG C dry 6-12 hour, then 450-600 DEG C of roasting 4-6 hour, obtain described crome metal skeleton doping ZSM-5 and divide
Sub-sieve catalyst, wherein SiO2/(Al2O3+Cr2O3) molar ratio range be 80-160, Cr2O3/Al2O3Molar ratio range be
0.005-1.0；
Wherein, described silicon source includes Ludox and/or tetraethyl orthosilicate etc., and described Ludox can be mass content
The Ludox of 40%；
Described chromium source includes Chromium nitrate (Cr(NO3)3),nonahydrate etc.；
Source of aluminium includes Patent alum and/or aluminum isopropylate. etc.；
Described template includes 4-propyl bromide and/or TPAOH etc.；
Described ammonium salt includes ammonium nitrate and/or ammonium chloride etc.；The concentration of described ammonium salt solution is 1-2M, and described ammonium salt
Solution is 10:1-30:1 (mL/g) with the liquid-solid ratio of the molecular sieve carrying out ion exchange with ammonium salt solution.
A kind of method that present invention also offers crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins,
In the preferred embodiment of the present invention, the method comprises the following steps: the above-mentioned crome metal skeleton present invention provided
Doping ZSM-5 molecular sieve catalyst is placed in reactor, and (this reactor can be fixed bed reactors, such as with the stone of bringing-up section
English reaction tube) in, (volume flow rate of carrier gas can be 19-190mL min to be passed through carrier gas nitrogen-1, in the front bearing begun to warm up
The time that is passed through of gas can be 30-50 minute), then reactor is heated to 400-700 DEG C, then is passed through normal butane (normal butane
Purity be 99.9%, the volume flow rate of normal butane can be 1-10mL min-1), make normal butane at 400-700 DEG C, 0.1MPa
Under conditions of and carrier gas atmosphere in contact and reacts (relative with described crome metal skeleton doping ZSM-5 molecular sieve catalyst
It is 1-10mL min in normal butane volume flow rate-1, the consumption of described crome metal skeleton doping ZSM-5 molecular sieve catalyst is
0.10-1.00g), ethylene and propylene are obtained.
Below by specific embodiment, technical scheme is further described.
Embodiment 1
Present embodiments provide a kind of crome metal skeleton doping ZSM-5 molecular sieve catalyst, SiO therein2/(Cr2O3+
Al2O3) mol ratio is 80, Cr2O3/Al2O3Mol ratio is 1/25, and this crome metal skeleton doping ZSM-5 molecular sieve catalyst is logical
Cross what following steps prepared:
(1) by Ludox and the concentrated sulphuric acid mixing of mass content 40%, it is subsequently adding Chromium nitrate (Cr(NO3)3),nonahydrate, at 35 DEG C of constant temperature
Stir 30 minutes, make they mix homogeneously, obtain one first mixed liquor；
(2) Patent alum is dissolved in deionized water, then is added dropwise in described first mixed liquor, at 35 DEG C
Constant temperature stirs 30 minutes, makes they mix homogeneously, obtains one second mixed liquor；
(3) template 4-propyl bromide is dissolved in deionized water, then is added dropwise in described second mixed liquor,
35 DEG C of constant temperature stir 30 minutes, make they mix homogeneously, obtain one the 3rd mixed liquor；
(4) being dissolved in deionized water by sodium hydroxide, then be added dropwise in described 3rd mixed liquor, regulation pH value is extremely
11, then stir 6 hours at 35 DEG C of constant temperature, obtain a gel combination, described gel combination consist of 80SiO2:
0.975Al2O3:0.025Cr2O3:8TPABr:0.125Na2O:10H2SO4:2000H2O；
(5) by described gel combination in 170 DEG C of crystallization 4 days, crystallization is cooled to room temperature after completing, through sucking filtration, washing,
It is dried 12 hours in 100 DEG C, then 550 DEG C of roastings 6 hours to remove template；Then the molecular sieve removing template is placed in
Concentration is the NH of 1M4NO3Exchanging 8 hours in 80 DEG C of ions in solution, repeat ion and exchange 1 time after filtration, ion exchange is complete
After, through sucking filtration, washing, it is dried 12 hours in 100 DEG C, then 550 DEG C of roastings 6 hours, obtains described crome metal skeleton doping
ZSM-5 molecular sieve catalyst, is designated as 1# catalyst.
The present embodiment additionally provides the side of a kind of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins
Method, the method comprises the following steps:
Above-mentioned for 0.3g 1# catalyst is placed in the crystal reaction tube with bringing-up section, is passed through carrier gas nitrogen and regulates carrier gas
Volume flow rate be 57mL min-1, after being continually fed into carrier gas 30 minutes, begin to warm up reaction tube, then passing to purity is
The normal butane of 99.9% volume flow rate regulating normal butane are 3mL min-1, make normal butane at reaction temperature, the bar of 0.1MPa
Contact under part and in carrier gas atmosphere with 1# catalyst and react, obtain ethylene and propylene.
Stepping up reaction temperature, and be analyzed product, the analysis of product uses the micro-inverse of fixed bed
Spectrum on-line detecting system, detection mode is: when reaction temperature is 400-550 DEG C, gathers primary first-order equation system at interval of 50 DEG C
Gaseous products；When reaction temperature is 550-675 DEG C, gather primary first-order equation system gaseous products at interval of 25 DEG C；And it is each
Temperature spot stablize 10-30 minute after sample acquisitions.Reaction result and primary product yield are shown in Table 1, wherein, and " C2 =+C3 =" represent second
Alkene and the total recovery of propylene, " BTX " represents benzene,toluene,xylene, the most identical.
Table 1 normal butane catalytic cracking reaction primary product yield distribution (1#)
Embodiment 2
Present embodiments provide a kind of crome metal skeleton doping ZSM-5 molecular sieve catalyst, be designated as 2# catalyst, therein
SiO2/(Cr2O3+Al2O3) mol ratio is 80, Cr2O3/Al2O3Mol ratio is 1/10, this crome metal skeleton doping ZSM-5 molecular sieve
The preparation process of catalyst is same as in Example 1, and the content differing only in crome metal is different.
The method using this catalyst cracking normal butane producing light olefins, and the determination method of product
The most same as in Example 1.
Catalytic cracking reaction result and the primary product yield of 2# catalyst are shown in Table 2.
Table 2 normal butane catalytic cracking reaction primary product yield distribution (2#)
Embodiment 3
Present embodiments provide a kind of crome metal skeleton doping ZSM-5 molecular sieve catalyst, be designated as 3# catalyst, therein
SiO2/(Cr2O3+Al2O3) mol ratio is 80, Cr2O3/Al2O3Mol ratio is 1/10, this crome metal skeleton doping ZSM-5 molecular sieve
The preparation process of catalyst is same as in Example 1, and the content differing only in crome metal is different.
The method using this catalyst cracking normal butane producing light olefins, and the determination method of product
The most same as in Example 1.
Catalytic cracking reaction result and the primary product yield of 3# catalyst are shown in Table 3.
Table 3 normal butane catalytic cracking reaction primary product yield distribution (3#)
Comparative example 1
This comparative example provides a kind of ZSM-5 molecular sieve catalyst, the preparation process of this ZSM-5 molecular sieve catalyst and reality
Execute example 1 essentially identical, differ only in and be added without chromium source Chromium nitrate (Cr(NO3)3),nonahydrate, the SiO of this ZSM-5 molecular sieve catalyst2/
Al2O3Mol ratio is 80.
The method using this catalyst cracking normal butane producing light olefins, and the determination method of product
The most same as in Example 1.
Catalytic cracking reaction result and the primary product yield of this catalyst are shown in Table 4.
Table 4 normal butane catalytic cracking reaction primary product yield is distributed
Comparative example 2
This comparative example provides a kind of support type Cr/ZSM-5 molecular sieve catalyst, and the preparation method of this catalyst is: (1)
The method of comparative example 1 is first used to prepare SiO2/Al2O3Mol ratio is the ZSM-5 molecular sieve of 80；(2) equal-volume is used to soak again
Stain method prepares Cr2O3/Al2O3Mol ratio is the support type Cr/ZSM-5 molecular sieve catalyst of 1/25.
The method using this catalyst cracking normal butane producing light olefins, and the determination method of product
The most same as in Example 1.
Catalytic cracking reaction result and the primary product yield of this catalyst are shown in Table 5.
Table 5 normal butane catalytic cracking reaction primary product yield is distributed
By the interpretation of result of above-described embodiment and comparative example it can be seen that use the chromium skeleton doping method synthesis of the present invention
ZSM-5 molecular sieve, such as embodiment 1,2 and 3, use it in the reaction of catalyzed conversion normal butane, Cr skeleton doped series sample
The rule of product catalyzed conversion normal butane is: along with the increase of Cr content, the conversion ratio of normal butane and ethylene, propylene yield all in
The most first increasing the trend reduced afterwards, the optimized amount of Cr is Cr2O3/Al2O3=1/25 (mol ratio), contrasts Tables 1 and 2-5, is surveying
Within the temperature range of examination, the either conversion ratio of normal butane or the yield of ethylene, propylene is all higher than Cr content, undoped p Cr
Or the sample of identical Cr content load method synthesis is high.
Claims (10)
1. a method for crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins, the method includes following step
Rapid: to make normal butane be catalyzed with crome metal skeleton doping ZSM-5 molecular sieve under reaction temperature, reaction pressure and in carrier gas atmosphere
Agent contact reacts, and obtains ethylene and propylene；Wherein, described crome metal skeleton doping ZSM-5 molecular sieve catalyst is to pass through
Following steps prepare:
By silicon source, concentrated sulphuric acid, chromium source, aluminum source, template by certain charging sequence mix homogeneously, obtain a mixed liquor；Use hydrogen
The pH value of the sodium oxide described mixed liquor of regulation is to 10-13, then after uniform temperature stirs a period of time, obtains a Gel Compositions
Thing, a mole composition for described gel combination includes nSiO2:(1-x)Al2O3:xCr2O3: (8-10) template: (0.125-
0.25)Na2O:(10-12)H2SO4:(2000-3000)H2O；By described gel combination in uniform temperature crystallization a period of time
After, more cooled, filter, wash, be dried, roasting；Be then passed through ammonium salt solution ion exchange after, then through filtering, washing, do
Dry, roasting, obtains described crome metal skeleton doping ZSM-5 molecular sieve catalyst, wherein SiO2/(Al2O3+Cr2O3) mole
It is 80-160 than scope, Cr2O3/Al2O3Molar ratio range be 0.005-1.0.
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, in the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, by silicon source, concentrated sulphuric acid, chromium source, aluminum
The step that source, template obtain a mixed liquor by certain charging sequence mix homogeneously includes: mixed in silicon source and concentrated sulphuric acid, then
Add chromium source, be uniformly mixed, obtain one first mixed liquor；Aluminum source is dissolved in deionized water, then is added dropwise to described
In first mixed liquor, it is uniformly mixed, obtains one second mixed liquor；Template is dissolved in deionized water, then is added dropwise over
In described second mixed liquor, it is uniformly mixed, obtains described mixed liquor.
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, described crome metal skeleton doping ZSM-5 molecular sieve catalyst preparation process in, described silicon source include Ludox and/
Or tetraethyl orthosilicate, it is preferable that described Ludox is the Ludox of mass content 40%；
Described chromium source includes Chromium nitrate (Cr(NO3)3),nonahydrate；
Source of aluminium includes Patent alum and/or aluminum isopropylate.；
Described template includes 4-propyl bromide and/or TPAOH.
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, in the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, described mixing is regulated with sodium hydroxide
The pH value of liquid is to after 10-13, and by the constant temperature stirring at a certain temperature of 35-60 DEG C of prepared gel combination, mixing time is
6-10 hour.
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, in the preparation process of described crome metal skeleton doping ZSM-5 molecular sieve catalyst, the crystallization temperature of gel combination is
150-180 DEG C, crystallization time is 4-6 days；Gel combination crystallization complete after be dried as dry 6-12 hour at 60-100 DEG C,
Being roasted to 450-600 DEG C of roasting 4-6 hour afterwards.
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, described crome metal skeleton doping ZSM-5 molecular sieve catalyst preparation process in, described ammonium salt include ammonium nitrate and/
Or ammonium chloride；The concentration of described ammonium salt solution is 1-2M, and described ammonium salt solution with carry out ion exchange with ammonium salt solution
The liquid-solid ratio of molecular sieve is 10:1-30:1；The temperature carrying out ion exchange with ammonium salt solution is 60-80 DEG C, and the time is that 2-8 is little
Time；The number of times carrying out ion exchange with ammonium salt solution is 1-3 time；Being dried as at 60-100 after the exchange of ammonium salt solution ion
DEG C dry 6-12 hour, being roasted to 450-600 DEG C of roasting 4-6 hour afterwards.
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, normal butane contacts, with crome metal skeleton doping ZSM-5 molecular sieve catalyst, the reaction temperature reacted is 400-700
DEG C, reaction pressure is 0.1MPa.
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, described carrier gas is nitrogen, and the volume flow rate of carrier gas is 19-190mL min-1。
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, the purity of normal butane is 99.9%, and the volume flow rate of normal butane is 1-10mL min-1。
The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins the most according to claim 1,
Wherein, it is 1-10mL min relative to normal butane volume flow rate-1, described crome metal skeleton doping ZSM-5 molecular sieve catalyst
Consumption is 0.10-1.00g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610443593.8A CN106083509A (en) | 2016-06-20 | 2016-06-20 | The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610443593.8A CN106083509A (en) | 2016-06-20 | 2016-06-20 | The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106083509A true CN106083509A (en) | 2016-11-09 |
Family
ID=57238017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610443593.8A Pending CN106083509A (en) | 2016-06-20 | 2016-06-20 | The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106083509A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529918A (en) * | 2018-11-09 | 2019-03-29 | 南京朗科环保科技有限公司 | A kind of VOCs catalyst for catalytic combustion and its preparation method and application |
| CN115475654A (en) * | 2022-10-12 | 2022-12-16 | 中国科学院山西煤炭化学研究所 | Microcapsule-like modified Zn @ ZSM-5 catalyst and preparation method and application thereof |
| CN116747898A (en) * | 2023-05-16 | 2023-09-15 | 浙江大学 | Lamellar morphology heteroatom zeolite molecular sieve catalyst for catalyzing polyolefin plastic cracking |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065028A (en) * | 1991-03-20 | 1992-10-07 | 中国科学院大连化学物理研究所 | Process for preparing low carbon alkene by catalytic conversion of light hydrocarbon |
| CN1353010A (en) * | 2000-11-02 | 2002-06-12 | 中国石油化工股份有限公司 | Molecular sieve containing heteroatoms and its synthesis |
| CN1806917A (en) * | 2005-01-20 | 2006-07-26 | 石油大学(北京) | Activation of ZSM-5 series catalyst and method for catalytic cracking butane to prepared light olefines thereby |
| CN1911502A (en) * | 2006-09-05 | 2007-02-14 | 大庆石油管理局 | Nanometer grade low carbon paraffin dehydrogen catalyst |
| CN101314135A (en) * | 2008-06-27 | 2008-12-03 | 吉林大学 | Method for preparing double-catalysis center molecular sieve nucleocapsid material with hydrothermal/solvent-thermal system |
| CN101456783A (en) * | 2007-12-13 | 2009-06-17 | 中国石油化工股份有限公司 | Method for improving light olefins output during catalytic cracking process |
| CN101734987A (en) * | 2008-11-07 | 2010-06-16 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene from C4 hydrocarbons |
| CN102198406A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Method for preparing high-content double-transition metal composite molecular sieve |
| CN103159579A (en) * | 2013-02-07 | 2013-06-19 | 大连理工大学 | Method of light alkane catalytic cracking by using modified molecular sieve catalyst |
| CN104326483A (en) * | 2014-10-13 | 2015-02-04 | 天津众智科技有限公司 | Low-silicon composite molecular sieve, and synthetic method and application thereof |
| CN104445255A (en) * | 2014-12-04 | 2015-03-25 | 南京工业大学 | Preparation method of heteroatom MCM-49 zeolite molecular sieve |
| CN105174285A (en) * | 2015-08-21 | 2015-12-23 | 中国石油大学(北京) | Method for modulating aluminum distribution of ZSM-5 molecular sieve skeleton, molecular sieve and application |
| CN105271286A (en) * | 2015-10-10 | 2016-01-27 | 吉林大学 | Method for synthesis of Cr-Al-ZSM-22 molecular sieve from modified diatomite |
-
2016
- 2016-06-20 CN CN201610443593.8A patent/CN106083509A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065028A (en) * | 1991-03-20 | 1992-10-07 | 中国科学院大连化学物理研究所 | Process for preparing low carbon alkene by catalytic conversion of light hydrocarbon |
| CN1353010A (en) * | 2000-11-02 | 2002-06-12 | 中国石油化工股份有限公司 | Molecular sieve containing heteroatoms and its synthesis |
| CN1806917A (en) * | 2005-01-20 | 2006-07-26 | 石油大学(北京) | Activation of ZSM-5 series catalyst and method for catalytic cracking butane to prepared light olefines thereby |
| CN1911502A (en) * | 2006-09-05 | 2007-02-14 | 大庆石油管理局 | Nanometer grade low carbon paraffin dehydrogen catalyst |
| CN101456783A (en) * | 2007-12-13 | 2009-06-17 | 中国石油化工股份有限公司 | Method for improving light olefins output during catalytic cracking process |
| CN101314135A (en) * | 2008-06-27 | 2008-12-03 | 吉林大学 | Method for preparing double-catalysis center molecular sieve nucleocapsid material with hydrothermal/solvent-thermal system |
| CN101734987A (en) * | 2008-11-07 | 2010-06-16 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene from C4 hydrocarbons |
| CN102198406A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Method for preparing high-content double-transition metal composite molecular sieve |
| CN103159579A (en) * | 2013-02-07 | 2013-06-19 | 大连理工大学 | Method of light alkane catalytic cracking by using modified molecular sieve catalyst |
| CN104326483A (en) * | 2014-10-13 | 2015-02-04 | 天津众智科技有限公司 | Low-silicon composite molecular sieve, and synthetic method and application thereof |
| CN104445255A (en) * | 2014-12-04 | 2015-03-25 | 南京工业大学 | Preparation method of heteroatom MCM-49 zeolite molecular sieve |
| CN105174285A (en) * | 2015-08-21 | 2015-12-23 | 中国石油大学(北京) | Method for modulating aluminum distribution of ZSM-5 molecular sieve skeleton, molecular sieve and application |
| CN105271286A (en) * | 2015-10-10 | 2016-01-27 | 吉林大学 | Method for synthesis of Cr-Al-ZSM-22 molecular sieve from modified diatomite |
Non-Patent Citations (1)
| Title |
|---|
| 赵丹等: "Cr掺杂ZSM-5双功能催化剂的制备及其催化裂解正丁烷", 《化工学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529918A (en) * | 2018-11-09 | 2019-03-29 | 南京朗科环保科技有限公司 | A kind of VOCs catalyst for catalytic combustion and its preparation method and application |
| CN109529918B (en) * | 2018-11-09 | 2021-11-30 | 南京朗科环保科技有限公司 | VOCs catalytic combustion catalyst and preparation method and application thereof |
| CN115475654A (en) * | 2022-10-12 | 2022-12-16 | 中国科学院山西煤炭化学研究所 | Microcapsule-like modified Zn @ ZSM-5 catalyst and preparation method and application thereof |
| CN115475654B (en) * | 2022-10-12 | 2023-10-27 | 中国科学院山西煤炭化学研究所 | Microcapsule-shaped modified Zn@ZSM-5 catalyst and preparation method and application thereof |
| CN116747898A (en) * | 2023-05-16 | 2023-09-15 | 浙江大学 | Lamellar morphology heteroatom zeolite molecular sieve catalyst for catalyzing polyolefin plastic cracking |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101279287B (en) | Catalyst for producing olefin hydrocarbon by catalytic pyrolysis | |
| CN103894201B (en) | Catalyst for dehydrogenation of low-carbon paraffin, preparation method and its usage | |
| CN101491772B (en) | Catalyst for naphtha catalytic cracking | |
| CN101108734B (en) | Beta type molecular sieve and method of manufacturing the same | |
| CN107265478B (en) | A kind of boron modification ferrierite molecular sieve catalyst and the preparation method and application thereof | |
| CN106140266B (en) | A kind of metal-modified ZSM-5 molecular sieve catalyst and its preparation method and application | |
| CN102992932A (en) | Method for removing olefin in aromatic hydrocarbon by M-SBA-15 type mesoporous molecular sieve | |
| CN102614864A (en) | Iso-butane dehydrogenation catalyst and preparation method thereof | |
| CN106083509A (en) | The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins | |
| CN111330630A (en) | Molecular sieve catalyst, preparation method thereof and liquefied petroleum gas alkylation reaction method | |
| CN104107712A (en) | Mixed C3/C4 alkane dehydrogenation catalyst and preparation method thereof | |
| CN102633647A (en) | Environment-friendly preparation method of tert-butylamine | |
| CN101279284B (en) | Catalyst for preparing ethylene propylene from catalytic pyrolysis | |
| CN1122572C (en) | Hetero-atom molecular-sieve catalyst for oxygen-free dehydrogenating aromatization of methane and its use | |
| Liu et al. | FeZnK/SAPO-34 catalyst for efficient conversion of CO2 to light olefins | |
| CN101428233B (en) | Catalyst for catalytic pyrolysis | |
| CN101214445A (en) | Catalyst for propane selective oxidation method to prepare propenoic acid and preparation thereof | |
| CN102500413A (en) | n-butane hydroisomerization catalyst, and preparation method and application thereof | |
| CN101190417B (en) | Catalyst for preparing ethylene and propylene by catalytic cracking method | |
| CN103285890A (en) | Cr-doped catalyst for preparing acrylic acid by catalytically oxidizing propane and preparation method of Cr-doped catalyst | |
| CN104226321B (en) | Dehydrogenation catalyst for mixed low carbon alkane and preparation method thereof | |
| Ejtemaei et al. | n-pentane isomerization over Pt-Al promoted sulfated zirconia nanocatalyst | |
| CN103801359B (en) | A kind of catalyst for hydro-upgrading of preparing gasoline by methanol by-product heavy petrol and preparation method thereof | |
| CN1232721A (en) | Synthesis of gallium containing silicate molecular sieve catalyst | |
| CN105521803B (en) | Multiple active components catalyst for preparing propene by oxidative dehydrogenation of propane and the preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161109 |
|
| WD01 | Invention patent application deemed withdrawn after publication |