CN106362791A - Mesoporous-microporous composite-pore-channel molecular sieve catalyst used for propane dehydrogenation for conversion into propylene and preparation method thereof - Google Patents
Mesoporous-microporous composite-pore-channel molecular sieve catalyst used for propane dehydrogenation for conversion into propylene and preparation method thereof Download PDFInfo
- Publication number
- CN106362791A CN106362791A CN201610638899.9A CN201610638899A CN106362791A CN 106362791 A CN106362791 A CN 106362791A CN 201610638899 A CN201610638899 A CN 201610638899A CN 106362791 A CN106362791 A CN 106362791A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- mesoporous
- micropore
- preparation
- 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
Classifications
-
- 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
-
- 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
-
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- 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
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention specifically relates to a mesoporous-microporous composite-pore-channel molecular sieve catalyst used for propane dehydrogenation for conversion into propylene and a preparation method thereof, belonging to the field of catalysts. The catalyst contains 0.01 to 0.3% of Pt, 0.01 to 0.3% of Ru or Ir, 0.01 to 3% of Sn and 0.01 to 3% of any one selected from a group consisting of Zr, Nb, Ta and W. The preparation method comprises the following steps: subjecting a Na-ZSM-5 molecular sieve to stirring treatment in an organic mixed alkaline solution; then carrying out washing, filtering and drying; then subjecting the treated Na-ZSM-5 molecular sieve to exchanging with an inorganic acid solution; and carrying out washing, filtering, drying and calcining so as to obtain a HZSM-5 molecular sieve containing mesoporous-microporous composite pore channels. The obtained mesoporous-microporous carrier is subjected to distributed impregnation and extrusion molding so as to obtain the catalyst for propane dehydrogenation. The catalyst has better dehydrogenation activity and stability when applied to propane dehydrogenation; the preparation method is simple; and the catalyst has good strength, low Pt content and good application prospect.
Description
Technical field
The invention belongs to catalyst technical field, specially a kind of multiple for the preparing propylene transformed mesoporous-micropore of dehydrogenating propane
Close duct molecular sieve catalyst and preparation method thereof.
Background technology
Propylene is one of important basic organic chemical industry raw material, mainly in order to produce polypropylene, expoxy propane, acrylonitrile,
Acrylic acid etc., has in occupation of critical role in modern petroleum and chemical industry.70% propylene is derived from steam in the world at present
The side-product of producing ethylene by cracking, 28% is derived from oil plant catalytic cracking (fcc) produces vapour, the side-product of diesel oil.But with right
Being continuously increased of propylene demand, traditional production of propylene ability also much can not meet the rate of increase of demand, so seeking height
The rational plant-scale propylene production-increasing technique of effect, it has also become chemical enterprise for a kind of new technique therein, due to technique
Simply, product is single, low-carbon environment-friendly, is more and more paid attention to.
pt-sn/γ-al2o3Catalyst is used for preparing propylene by dehydrogenating propane and reacts, and comparison system has been carried out both at home and abroad
Research, has obtained many important achievements, and domestic and international Duo Jia research unit has all applied for the dehydrogenating propane patent of correlation.Wherein relate to
And to al2o3For carrier, the patent of the preparation method of the propane dehydrogenation catalyst with pt-sn as active component has
Cn1033949a, cn1265878c, cn102049267a, cn101003458a, cn102698750a etc..
With going deep into of research, cause people's with the material with special structure and property as catalyst carrier
Concern.Hzsm-5 molecular sieve contains the channel system of two kinds of intersections, has higher shape selective catalysis performance, in dehydrogenating propane reaction
Can γ-al2o3 as an alternative excellent carrier: urge as cn101108362a is related to a kind of molecular sieve of preparing propylene by dehydrogenating propane
Agent, the method using branch's dipping adds pt-sn-na tri- component element, conversion of propane 30%, Propylene Selectivity 98%；
Cn101066532a is related to a kind of employing skeleton and contains the zsm-5 molecular sieve of sn as propane dehydrogenation catalyst, Propylene Selectivity
Reach as high as 99%；Being related to a kind of molecular sieve containing rare earth elemental metals for employing skeleton in cn101380587a is the third of carrier
Alkane dehydrogenation, by step impregnation alkali or alkaline-earth metal, pt-sn modifying agent, conversion of propane highest 30.5%, propylene selects
Selecting property 97%；Cn101513613a is related to one kind and adopts multicomponent hetero atom zms-5 molecular sieve, by step impregnation alkali or alkali
Earth metal, pt-sn modifying agent, as propane dehydrogenation catalyst, conversion of propane is 30%, Propylene Selectivity highest 98%.
From the point of view of the patent of above-mentioned current open report, all focus on using the 3rd or the 4th component modification pt-sn/
Hzsm-5 catalyst.Typical zsm-5 molecular sieve pore passage is in range of micropores, and pore passage structure is unfavorable for the expansion of reactant and product
Dissipate, dehydrogenating propane hot environment easily generates carbon distribution and causes catalyst to inactivate, and contain composite holes zsm- of mesoporous-micropore
5 molecular sieves then can strengthen the mass transfer ability of zsm-5 molecular sieve, makes up this defect.Traditional composite holes preparation is mainly passed through
Add mesoporous pore creating material or to prepare mesoporous-micropore by post processing (typically adopt inorganic base naoh process) multiple in building-up process
Close hole zsm-5 molecular sieve；But using mesoporous pore creating material preparation molecular sieve in mesoporous be all distributed from inside to outside, its mfi tie
Structure is destroyed, and this makes the stability of zsm-5 molecular sieve substantially reduce；Using comprehend at inorganic base especially naoh so that
It is distributed and its uneven to mesoporous pore size, outer surface micropore major part is all destroyed simultaneously, and the high thermal stability of molecular sieve is significantly
Reduce.And dehydrogenating propane is pyroreaction, the stability requirement to carrier is very high, and it has one to the uniformity of pore distribution simultaneously
Fixed requirement.The compound porous molecular sieve of therefore above two method preparation is all not suitable for the carrier as dehydrogenating propane reaction.
Additionally, from above-mentioned Patents, in traditional dehydrogenating propane pt-sn System Catalyst, pt content is generally
Between 0.4-0.5%, this makes catalyst overall price expensive.For this reason, we are in above-mentioned regular mesoporous-micro porous molecular sieve carrier
On the basis of, have developed the catalyst of the pt-ru/ir-sn system of high degree of dispersion, wherein pt content is compared to traditional pt-sn
Catalyst is greatly reduced, and reduces the processing cost of catalyst.This catalyst has more preferable dehydrogenation activity for dehydrogenating propane
And stability, and preparation process is simple, intensity are good, and pt content is low, has preferable prospects for commercial application.
Content of the invention
Present invention aims to above technical problem, there is provided one kind is used for preparing propylene transformed Jie of dehydrogenating propane
Hole-micropore is combined duct molecular sieve catalyst.This catalyst has more preferable dehydrogenation activity and stability for dehydrogenating propane, and
And preparation process is simple, intensity are good, pt content is low, has preferable prospects for commercial application.
Another object of the present invention is that offer is above-described multiple for the preparing propylene transformed mesoporous-micropore of dehydrogenating propane
Close the preparation method of duct molecular sieve catalyst.
The object of the invention is realized by following technical proposals:
A kind of preparing propylene transformed mesoporous-micropore of dehydrogenating propane that is used for is combined duct molecular sieve catalyst, the load of this catalyst
Body is the zsm-5 molecular sieve being combined duct containing mesoporous-micropore, and its silica alumina ratio is 100～300.With weight/mass percentage composition
Meter, in this catalyst containing 0.01%～0.3% pt element, 0.01%～0.3% ru or ir element, 0.01%～3%
Sn element and 0.01%～3% zr, nb, ta, w element in any one, gross mass percentage composition be 100%.
The wherein molecular sieve supported preparation of composite holes is as follows: by na-zsm-5 molecular sieve at 60～90 DEG C respectively at one
Determine stir process 6～36h in organic mixed-alkali solution of concentration, molten with appropriate mineral acid after scrubbed, filtration and drying
Liquid exchanges 3 times (each 2h) in 90 DEG C, more scrubbed, filtration and drying obtain containing mesoporous-micropore after 550 DEG C of calcining 4h
Compound duct hzsm-5 molecular sieve.
Above-mentioned organic mixed-alkali solution, is any one in quaternary ammonium base, and Sodium Acetate Trihydrate, triethylamine, pyridine or miaow
Any one in azoles, its mixing alkali concn is 0.6～6.0mol/l, the time-optimized 8～24h of stir process.
The carrier that will be obtained by said method, prepares the modified propane dehydrogenation catalyst of multielement in accordance with the following steps:
1) by load weighted zsm-5 molecular sieve, boehmite mix homogeneously, add the distillation of 10 times of molecular sieve quality
Water forms the gel solution of molecular sieve and boehmite；
2) by load weighted three groups of modifying agent (one group be ru/ir, one group be sn, one group be zr, nb, ta, w in any
A kind of) chloride mixing after, add the distillation water dissolution of 5 times of quality to form three kinds of muriatic mixed solutions；
3) by step 2) solution prepared is added drop-wise to the 1st step and obtains in sol solution, and constantly stir；Stir at 80 DEG C
Mix 4h, be then placed in drying in 90 DEG C in baking oven, and calcine 4h at 500 DEG C；
4) by step 3) after the catalyst precarsor prepared is fully ground, in terms of weight/mass percentage composition, add 5% sesbania
Powder, and Deca weight/mass percentage composition is 3% dilute nitric acid solution extruded moulding, obtains molded molecular sieve, and dry under the conditions of 100 DEG C
Dry standby.
5) by step 4) catalyst prepared calcines 2h at 550 DEG C, then incipient impregnation platinum acid chloride solution, and 100
Dry for standby under the conditions of DEG C.
The positive effect of the present invention is embodied in:
(1), adopt the preparation method of new mesoporous-micropore composite holes zsm-5 molecular sieve, solve the preparation of conventional composite hole
Method leads to the problem of high thermal stability difference and pore-size distribution inhomogeneities so as to can be excellent as propane dehydrogenation catalyst
Carrier.
(2), this catalyst has more preferable dehydrogenation activity and stability for dehydrogenating propane, and preparation process is simple,
Intensity is good, and pt content is low, has preferable prospects for commercial application.
Specific embodiment
All features disclosed in this specification, or disclosed all methods or during step, except mutually exclusive
Feature and/or step beyond, all can combine by any way.
Any feature disclosed in this specification (including any accessory claim, summary), unless specifically stated otherwise,
Replaced by other alternative features equivalent or that there is similar purpose.I.e., unless specifically stated otherwise, each feature is a series of
One of equivalent or similar characteristics example.
Following %, if no special instructions, all represents in terms of catalyst gross mass, its shared weight/mass percentage composition.Implement
Example 1:
Prepare the ratio according to the corresponding 10ml solution of 1g powder for the mesoporous-micropore composite holes molecular sieve carrier, by na-zsm-5
Molecular sieve (sio2/al2o3Mol ratio is 100) at 80 DEG C, in organic mixed-alkali solution, (mixed liquor is the four of 0.8mol/l
Ethyl ammonium hydroxide and 0.6mol/l pyridine) stir process 16h, scrubbed, filter after, in 1mol/l's under the conditions of 90 DEG C
In hcl solution, h exchanges 3 times (each 2h), more scrubbed, filtration and drying obtain containing mesoporous-micro- after 550 DEG C of calcining 4h
Hole is combined duct hzsm-5 molecular sieve.
Embodiment 2:
The molecular sieve supported preparation of this composite holes is as follows: according to the ratio of the corresponding 10ml solution of 1g powder, by na-zsm-
5 molecular sieve (sio2/al2o3Mol ratio is 300) at 60 DEG C, in organic mixed-alkali solution, (mixed liquor is 1.0mol/l's
TPAOH and 1.0mol/l Sodium Acetate Trihydrate) stir process 8h, scrubbed, filter after, in 1mol/l under the conditions of 90 DEG C
Hcl solution in h exchange 3 times (each 2h), more scrubbed, filter and be dried after 550 DEG C calcining 4h after obtain containing mesoporous-
Micropore is combined duct hzsm-5 molecular sieve.
Embodiment 3:
The molecular sieve supported preparation of this composite holes is as follows: according to the ratio of the corresponding 10ml solution of 1g powder, by na-zsm-
5 molecular sieve (sio2/al2o3Mol ratio is 200) at 90 DEG C, in organic mixed-alkali solution, (mixed liquor is 1.6mol/l's
Tetramethylammonium hydroxide and 0.1mol/l Sodium Acetate Trihydrate) stir process 12h, scrubbed, filter after, in 1mol/l under the conditions of 90 DEG C
Hcl solution in h exchange 3 times (each 2h), more scrubbed, filter and be dried after 550 DEG C calcining 4h after obtain containing mesoporous-
Micropore is combined duct hzsm-5 molecular sieve.
Embodiment 4:
The molecular sieve supported preparation of this composite holes is as follows: according to the ratio of the corresponding 10ml solution of 1g powder, by na-zsm-
5 molecular sieve (sio2/al2o3Mol ratio is 180) at 70 DEG C, in organic mixed-alkali solution, (mixed liquor is 2.0mol/l's
TPAOH and 1.0mol/l triethylamine) stir process 6h, scrubbed, filter after, in 1mol/l under the conditions of 90 DEG C
Hcl solution in h exchange 3 times (each 2h), more scrubbed, filter and be dried after 550 DEG C calcining 4h after obtain containing mesoporous-
Micropore is combined duct hzsm-5 molecular sieve.
Embodiment 5:
The molecular sieve supported preparation of this composite holes is as follows: according to the ratio of the corresponding 10ml solution of 1g powder, by na-zsm-
5 molecular sieve (sio2/al2o3Mol ratio is 250) at 70 DEG C, in organic mixed-alkali solution, (mixed liquor is 0.6mol/l's
Tetraethyl ammonium hydroxide and 0.2mol/l imidazoles) stir process 18h, scrubbed, filter after, in 1mol/l's under the conditions of 90 DEG C
In hcl solution, h exchanges 3 times (each 2h), more scrubbed, filtration and drying obtain containing mesoporous-micro- after 550 DEG C of calcining 4h
Hole is combined duct hzsm-5 molecular sieve.
Embodiment 6:
The carrier that embodiment 1～5 is obtained, prepares the modified propane dehydrogenation catalyst of multielement in accordance with the following steps, its
Concrete modified component content is shown in Table 1.
1) by load weighted zsm-5 molecular sieve, boehmite mix homogeneously, add the distillation of 10 times of molecular sieve quality
Water forms the gel solution of molecular sieve and boehmite；
2) by load weighted three groups of modifying agent (one group be ru/ir, one group be sn, one group be one of zr, nb, ta, w)
Chloride mixing after, add 5 times of quality distillation water dissolution formed three kinds of muriatic mixed solutions；
3) by step 2) solution prepared is added drop-wise to the 1st step and obtains in sol solution, and constantly stir；Stir at 80 DEG C
Mix 4h, be then placed in drying in 90 DEG C in baking oven, and calcine 4h at 500 DEG C；
4) by step 3) after the catalyst precarsor prepared is fully ground, in terms of weight/mass percentage composition, add 5% sesbania
Powder, and Deca weight/mass percentage composition is 3% dilute nitric acid solution extruded moulding, obtains molded molecular sieve, and dry under the conditions of 100 DEG C
Dry standby.
5) by step 4) catalyst prepared calcines 2h at 550 DEG C, then incipient impregnation platinum acid chloride solution, and 100
Dry for standby under the conditions of DEG C.
Table 1 catalyst carrier source, elemental constituent and its content
| Carrier is originated | Component and its content (%) | Binding agent and its content (%) | |
| cat-1 | Embodiment 1 | pt(0.3)-ru(0.1)-sn(0.6)-nb(0.5) | Boehmite (10%) |
| cat-2 | Embodiment 2 | pt(0.25)-ir(0.2)-sn(1.0)-w(0.2) | Boehmite (15%) |
| cat-3 | Embodiment 3 | pt(0.3)-ru(0.3)-sn(0.5)-ta(0.3) | Boehmite (15%) |
| cat-4 | Embodiment 4 | pt(0.3)-ir(0.3)-sn(1.5)-zr(0.2) | Boehmite (25%) |
| cat-5 | Embodiment 1 | pt(0.3)-ir(0.01)-sn(3.0)-ta(0.01) | Boehmite (15%) |
| cat-6 | Embodiment 3 | pt(0.3)-ru(0.3)-sn(0.6)-w(0.1) | Boehmite (20%) |
| cat-7 | Embodiment 5 | pt(0.25)-ru(0.2)-sn(0.7)-zr(0.3) | Boehmite (15%) |
Comparative example
Have purchased a collection of hzsm-5 molecular sieve (sio from conventional molecular sieve producer2/al2o3Mol ratio is 200), using enforcement
The preparation step of example 6 plays interpolation modifying element, is prepared for two catalyst of cat-3a and cat-6a respectively, its group is grouped into and is shown in Table 2.
Table 2 comparative example catalyst carrier source, elemental constituent and its content
| Carrier is originated | Component and its content (%) | Binding agent and its content (%) | |
| cat-3a | Buy molecular sieve | pt(0.3)-ru(0.3)-sn(0.5)-ta(0.3) | Boehmite (15%) |
| cat-6a | Buy molecular sieve | pt(0.3)-ru(0.3)-sn(0.6)-w(0.1) | Boehmite (20%) |
Embodiment 7:
Catalyst prepared by comparative example and embodiment 6 through-flow dynamic air calcination 4h first at 500 DEG C, is then filled into
Its dehydrogenating propane activity is evaluated in miniature fixed bed reaction., reaction 550 DEG C of initial temperature, pressure normal pressure, raw materials quality air speed
3h-1, nitrogen/propane initial molar ratio is 2.5:1, and after evaluating 100h, its conversion of propane and Propylene Selectivity are as shown in table 3.
Table 3 embodiment dehydrogenating propane activity
From table 3 it is observed that the basic phase of cat-3a and cat-6a and cat-3 and cat-6 intensity according to tradition preparation
When, but its conversion ratio and selectivity will be less than the catalyst of the preparation of the present invention.
The invention is not limited in aforesaid specific embodiment.The present invention expands to and any discloses in this manual
New feature or any new combination, and the arbitrary new method of disclosure or the step of process or any new combination.
Claims (7)
1. a kind of be combined duct molecular sieve catalyst for the preparing propylene transformed mesoporous-micropore of dehydrogenating propane it is characterised in that: with matter
Amount percentage composition meter, in this catalyst contain 0.01% ~ 0.3% pt element, 0.01% ~ 0.3% ru or ir element, 0.01% ~ 3%
Sn element and 0.01% ~ 3% zr, nb, ta, w element in any one, balance of composite holes molecular sieve carrier, gross mass
Percentage composition is 100%.
2. according to claim 1 be combined duct molecular sieve catalyst for the preparing propylene transformed mesoporous-micropore of dehydrogenating propane,
It is characterized in that: the carrier of this catalyst is the zsm-5 molecular sieve being combined duct containing mesoporous-micropore, and its silica alumina ratio is
100~300.
3. dividing for the compound duct of the preparing propylene transformed mesoporous-micropore of dehydrogenating propane according to claim 1 or claim 2
Sub- sieve catalyst is it is characterised in that the preparation method of described composite holes molecular sieve carrier comprises the following steps: na-zsm-5 is divided
Son sieve at 60 ~ 90 DEG C in certain density organic mixed-alkali solution stir process 6 ~ 36h, scrubbed, filter and
Exchange 3 times in 90 DEG C with appropriate inorganic acid solution after drying, 2 h every time, more scrubbed, filtration and drying are forged after 550 DEG C
Obtain after burning 4h being combined duct hzsm-5 molecular sieve containing mesoporous-micropore.
4. according to claim 3 be combined duct molecular sieve catalyst for the preparing propylene transformed mesoporous-micropore of dehydrogenating propane,
It is characterized in that: described organic mixed-alkali solution be quaternary ammonium base in any one, or Sodium Acetate Trihydrate, triethylamine, pyridine and
Any one in imidazoles.
5. according to claim 3 be combined duct molecular sieve catalyst for the preparing propylene transformed mesoporous-micropore of dehydrogenating propane,
It is characterized in that: the concentration of organic mixed ammonium/alkali solutions is 0.6 ~ 6.0mol/l.
6. according to claim 3 be combined duct molecular sieve catalyst for the preparing propylene transformed mesoporous-micropore of dehydrogenating propane,
It is characterized in that: the described stir process time is 8 ~ 24h.
7. dividing for the compound duct of the preparing propylene transformed mesoporous-micropore of dehydrogenating propane according to claim 1 or claim 2
The preparation method of sub- sieve catalyst is it is characterised in that comprise the following steps:
1) by load weighted zsm-5 molecular sieve, boehmite mix homogeneously, add the distilled water of 10 times of molecular sieve quality
Form the gel solution of molecular sieve and boehmite；
2) by load weighted three groups of modifying agent, one group be ru/ir, one group be sn, one group be zr, nb, ta, w in any one
Chloride mixing after, add 5 times of quality distillation water dissolution formed three kinds of muriatic mixed solutions；
3) by step 2) solution prepared is added drop-wise to step 1) and obtains in sol solution, and constantly stir；Stir at 80 DEG C
4h, is then placed in drying in 90 DEG C in baking oven, and calcines 4h at 500 DEG C；
4) after catalyst precarsor prepared by step 3) being fully ground, in terms of weight/mass percentage composition, add 5% sesbania powder, and
Deca weight/mass percentage composition is 3% dilute nitric acid solution extruded moulding, obtains molded molecular sieve, and dries standby under the conditions of 100 DEG C
With；
5) catalyst preparing step 4) calcines 2h at 550 DEG C, then incipient impregnation platinum acid chloride solution, and in 100 DEG C of bars
Dry under part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610638899.9A CN106362791B (en) | 2016-08-05 | 2016-08-05 | One kind is for compound duct molecular sieve catalyst of the preparing propylene transformed mesoporous-micropore of dehydrogenating propane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610638899.9A CN106362791B (en) | 2016-08-05 | 2016-08-05 | One kind is for compound duct molecular sieve catalyst of the preparing propylene transformed mesoporous-micropore of dehydrogenating propane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106362791A true CN106362791A (en) | 2017-02-01 |
| CN106362791B CN106362791B (en) | 2018-10-26 |
Family
ID=57878663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610638899.9A Active CN106362791B (en) | 2016-08-05 | 2016-08-05 | One kind is for compound duct molecular sieve catalyst of the preparing propylene transformed mesoporous-micropore of dehydrogenating propane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106362791B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108654678A (en) * | 2018-05-31 | 2018-10-16 | 上海绿强新材料有限公司 | One type Fenton oxidation catalyst and its application |
| CN108855066A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108927213A (en) * | 2018-06-26 | 2018-12-04 | 上海绿强新材料有限公司 | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane |
| CN111377461A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Multi-stage hole HZSM-5 zeolite molecular sieve |
| CN111375442A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Hierarchical pore HZSM-5 zeolite molecular sieve |
| CN112206816A (en) * | 2020-10-13 | 2021-01-12 | 西南化工研究设计院有限公司 | Composite molecular sieve catalyst for preparing olefin by propane dehydrogenation and preparation method thereof |
| CN112619686A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Supported non-noble metal dehydrogenation catalyst and preparation method and application thereof |
| CN113457654A (en) * | 2021-06-02 | 2021-10-01 | 江西省科学院应用化学研究所 | Carbon-based solid acid catalyst, and preparation method and use method thereof |
| CN115591574A (en) * | 2022-10-08 | 2023-01-13 | 扬州晨化新材料股份有限公司（Cn） | Porous alumina-supported metal copper catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1430949A1 (en) * | 2002-12-10 | 2004-06-23 | Haldor Topsoe A/S | Process for catalytic dehydrogenation and catalyst therefore |
| CN101066532A (en) * | 2007-06-04 | 2007-11-07 | 南京大学 | Catalyst with ZSM5 molecular sieve containing Sn in skeleton as carrier for dehydrogenating propane to prepare propylene |
-
2016
- 2016-08-05 CN CN201610638899.9A patent/CN106362791B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1430949A1 (en) * | 2002-12-10 | 2004-06-23 | Haldor Topsoe A/S | Process for catalytic dehydrogenation and catalyst therefore |
| CN101066532A (en) * | 2007-06-04 | 2007-11-07 | 南京大学 | Catalyst with ZSM5 molecular sieve containing Sn in skeleton as carrier for dehydrogenating propane to prepare propylene |
Non-Patent Citations (2)
| Title |
|---|
| SÒNIA ABELLÓ等: ""Mesoporous ZSM-5 zeolite catalysts prepared by desilication with organic hydroxides and comparison with NaOH leaching"", 《APPLIED CATALYSIS A: GENERAL》 * |
| 崔生航等: ""多级孔道ZSM-5分子筛的合成及其催化应用"", 《化工进展》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855066A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108855066B (en) * | 2017-05-10 | 2019-09-27 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108654678A (en) * | 2018-05-31 | 2018-10-16 | 上海绿强新材料有限公司 | One type Fenton oxidation catalyst and its application |
| CN108927213A (en) * | 2018-06-26 | 2018-12-04 | 上海绿强新材料有限公司 | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane |
| CN111377461B (en) * | 2018-12-28 | 2022-07-12 | 中国石油化工股份有限公司 | Multi-stage hole HZSM-5 zeolite molecular sieve |
| CN111375442A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Hierarchical pore HZSM-5 zeolite molecular sieve |
| CN111377461A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Multi-stage hole HZSM-5 zeolite molecular sieve |
| CN111375442B (en) * | 2018-12-28 | 2023-05-05 | 中国石油化工股份有限公司 | Hierarchical pore HZSM-5 zeolite molecular sieve |
| CN112619686A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Supported non-noble metal dehydrogenation catalyst and preparation method and application thereof |
| CN112619686B (en) * | 2019-10-09 | 2024-01-30 | 中国石油化工股份有限公司 | Supported non-noble metal dehydrogenation catalyst and preparation method and application thereof |
| CN112206816A (en) * | 2020-10-13 | 2021-01-12 | 西南化工研究设计院有限公司 | Composite molecular sieve catalyst for preparing olefin by propane dehydrogenation and preparation method thereof |
| CN113457654A (en) * | 2021-06-02 | 2021-10-01 | 江西省科学院应用化学研究所 | Carbon-based solid acid catalyst, and preparation method and use method thereof |
| CN115591574A (en) * | 2022-10-08 | 2023-01-13 | 扬州晨化新材料股份有限公司（Cn） | Porous alumina-supported metal copper catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106362791B (en) | 2018-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106362791A (en) | Mesoporous-microporous composite-pore-channel molecular sieve catalyst used for propane dehydrogenation for conversion into propylene and preparation method thereof | |
| CN104646050B (en) | Hydrogenation catalyst, preparation and application thereof | |
| CN108002402A (en) | A kind of middle micro-diplopore MFI type nano molecular sieve with multi-layer steamed bread shape pattern and its preparation method and application | |
| CN103539152B (en) | Core-shell molecular sieve of Si modification and preparation method thereof | |
| CN109985659A (en) | A kind of CO2Orientation conversion prepares catalyst of aromatic hydrocarbons and preparation method thereof | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN101157050A (en) | A Ti/MCM-22/MCM-41 composite material as well as preparing method and application | |
| US20230132229A1 (en) | Composite zsm-5 molecular sieve, preparation method therefor, catalyst and use thereof | |
| CN108654594B (en) | Solid acid catalyst, preparation method and application thereof | |
| CN104117386A (en) | Catalyst used for hydrogenation ring opening reaction of polycyclic aromatic hydrocarbon, and preparation method and application thereof | |
| JP7032612B2 (en) | Catalyst for producing isoprene glycol and method for producing isoprene glycol | |
| CN107349956B (en) | Catalyst for hydrogen production by reforming ethanol steam and preparation method thereof | |
| CN102872903A (en) | Preparation method of in-process shape-selective catalyst for para-xylene synthesis | |
| CN103028430B (en) | MWW type molecular sieve carrier catalyst, and preparation method and application thereof | |
| CN106040289B (en) | A kind of preparation method and application of isobutene direct aminatin production tert-butylamine catalyst | |
| CN102806085B (en) | Preparation method of catalyst for co-generating of isopropanol and diisobutyl ketone through acetone hydrogenation and application | |
| CN101003376A (en) | Method for synthesizing alkali modified molecular sieve containing titanium | |
| CN102276412B (en) | Method for producing ethylbenzene from ethanol and benzene | |
| CN102274746B (en) | Catalyst for preparing ethylbenzene by vapor-phase alkylation of ethanol and benzene | |
| CN112206811A (en) | Catalyst for preparing propylene by methanol conversion and preparation method and application thereof | |
| CN106890669A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN113198527B (en) | Composite hierarchical pore molecular sieve catalyst for preparing aromatic hydrocarbon from low-carbon alkane and preparation method thereof | |
| CN112675902B (en) | Catalyst for preparing propylene by inverse disproportionation of ethylene and butene and preparation method thereof | |
| KR101633985B1 (en) | Supported mixed metal oxide catalyst for dehydrogenation of buthane and preparing method of the same | |
| CN103447077B (en) | In situ modification method of zeolite socony mobil-five (ZSM-5)/foam silicon carbide structured catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |