CN105749958A - Movable bed methanol to olefin arene spherical catalyst and preparation method of movable bed methanol to olefin arene spherical catalyst - Google Patents
Movable bed methanol to olefin arene spherical catalyst and preparation method of movable bed methanol to olefin arene spherical catalyst Download PDFInfo
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- CN105749958A CN105749958A CN201610080460.9A CN201610080460A CN105749958A CN 105749958 A CN105749958 A CN 105749958A CN 201610080460 A CN201610080460 A CN 201610080460A CN 105749958 A CN105749958 A CN 105749958A
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- 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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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
- B01J29/46—Iron group metals or copper
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- 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
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- 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
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- 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
- C07C2529/46—Iron group metals or copper
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- 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
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- 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
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- 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 invention relates to a movable bed methanol to olefin arene spherical catalyst and a preparation method of the movable bed methanol to olefin arene spherical catalyst. The catalyst provided by the invention is prepared from the following components in percentage by weight: (1) 30 percent to 70 percent of a hydrogen type ZSM-5 molecular sieve; (2) 20 percent to 60 percent of binding agent oxide; (3) 0 to 10 percent of metal oxide, wherein a metal element is selected from at least one of La, Ce, Fe, Ni, V, Mo, Pt, Zn, Co and Ag; the catalyst is spherical; the sphericility degree is more than 90 percent, the grain diameter is 0.5mm to 4.0mm, the strength of the catalyst is 30N/grain to 80N/grain and the abrasion rate is smaller than 1 percent. According to the catalyst provided by the invention, the hydrogen type ZSM-5 molecular sieve, a binding agent and an auxiliary extruding agent are mixed; in a kneading process, an inorganic acid solution is added to peptize, and the mixture is extruded into a strip shape through a pore plate with a certain pore diameter; after pre-drying is carried out, the mixture is shaped into a spherical carrier with the size of 0.5mm to 4mm through a cutting machine and a shaping machine; 0 to 10 percent of the metal element is loaded on the carrier and modification is carried out to prepare a methanol to olefin arene spherical catalyst. The catalyst has the advantages of uniform pelletizing granularity, high strength, high yield and small loss, and can be applied to a methanol to olefin arene movable bed process.
Description
Technical field
The present invention relates to catalyst preparation technical field, particularly relate to that a kind of moving bed methanol aromatic hydrocarbons is spherical urges
Agent and preparation method thereof.
Background technology
Light aromatics BTX (benzene,toluene,xylene) is important Organic Chemicals, is chemical fibre, engineering plastics
And the critical materials of high performance plastics etc., be widely used in garment material, Aero-Space, transportation, decorations,
The field such as electric equipment products and mobile communication, current China aromatic hydrocarbons Year's consumption more than 20,000,000 tons, wherein xylol
(PX) about the 45% of BTX total quantity consumed is accounted for, mainly for the production of p-phthalic acid (PTA).At present, 85%
Above aromatics production depends on the catalytic reforming in petroleum path and catalytic pyrolysis, along with consumption and the state of petroleum resources
The rise of border oil price, aromatic hydrocarbons production capacity certainly will be restricted.In view of the current resources situation of China's " few gas richness coal of oil starvation ",
Coal is then an Aromatics Production Technology route the most promising through methanol aromatic hydrocarbons.
MTA technique is broadly divided into fixed bed, moving bed and fluid bed three class, due to severe reaction conditions, catalyst
Easily coking and deactivation, fixed-bed process is difficult to meet requirement, and current studies in China mechanism is substantially carried out moving bed and fluidisation
The exploitation of bed process and popularization.Fluid bed can realize input continuously and the output of solid material, but methanol hydrocarbon process is
Strong exothermal reaction, gas, solid, liquid three-phase back-mixing in reactor are serious, and catalyst is prone to wear out, to catalyst with anti-
The requirement answering device is higher.Moving bed then combines fixed bed bed and stablizes easy to control and regenerating catalyst in fluidized bed and give birth to continuously
The advantage produced, due to the cyclic regeneration of moving bed, it is adaptable to the catalyst of moving bed needs possess preferable mobility
And wearability, it is necessary to the strict forming process of spheric catalyst that controls is to carrier roundness and mean intensity.
CN200710010378 discloses the preparation method of a kind of micro-spherical catalyst carrier, by catalysis suitable for humidity
Agent carrier material produces granule by screen cloth under mechanical action, and granule is rolled at the low rotational speed by bowling machine and is a granulated into
Ball, the method can only prepare below 1mm for spheric catalyst.
CN201110313806 discloses the preparation method of a kind of spherical carrier of catalyst, uses spherical granulate method to pass through
Add surfactant to aluminium oxide, improve the physical property of alumina carrier surface, have adjusted carrier forming process
Adhesive and the rheological characteristic of middle material, improves the yield of ball type carrier, but the ball type carrier intensity that the method is prepared
Typically.
Summary of the invention
The present invention relates to the preparation method of a kind of methanol arenes catalytic agent, it is therefore intended that overcome the deficiencies in the prior art,
Thering is provided the preparation method of a kind of spheric catalyst being applicable to methanol aromatic hydrocarbons moving bed process, it is technically characterized in that
A kind of moving bed methanol aromatic hydrocarbons spheric catalyst, it is characterised in that include in terms of catalyst weight percent:
(1) 30～the Hydrogen ZSM-5 molecular sieve of 70%；
(2) 20～the oxide of binding agent of 60%；
(3) 0～the metallic element of 10%, described metallic element selected from La, Ce, Fe, Ni, V, Mo, Pt,
At least one in Zn, Co, Ag, is preferably selected from La, Ce, Ni, V, Mo, Pt, Zn, Ag at least
A kind of；
Wherein spheric catalyst particle diameter is 0.5～4.0mm, and catalyst strength is 30～80N/ grains, sphericity ＞ 90%,
Rate of wear ＜ 1%.
The preparation method of a kind of moving bed methanol aromatic hydrocarbons spheric catalyst of the present invention, comprises following step
Rapid:
(1) weigh Hydrogen ZSM-5 molecular sieve to mix homogeneously with binding agent, extrusion aid, carry out by adding mineral acid
Mediating, the water content adjusting butt is 40～60%, and described binding agent is molten selected from boehmite, Ludox, aluminum
At least one in glue, gama-alumina, Kaolin, extrusion aid is selected from sesbania powder, methylcellulose, benzene sulfonamide
At least one in hydrochlorate, liquid paraffin, fatty alcohol-polyoxyethylene ether, mineral acid is in hydrochloric acid, nitric acid, phosphoric acid
At least one；
(2) orifice plate of material warp is extruded into strip, then puts into after being cut into bar columnar product by slitting device whole
Shape machine is carried out shear, rounding, be dried, roasting prepares catalyst carrier；
(3) by the salt solution impregnation of metallic element on a catalyst support, being dried, roasting prepares methanol aromatic hydrocarbons ball
Shape catalyst, described metallic element is selected from La, Ce, Fe, Ni, V, Mo, Pt, Zn, Co, Ag extremely
Few one.
The preparation method of moving bed methanol aromatic hydrocarbons spheric catalyst of the present invention, wherein said binding agent is preferred
At least one in boehmite, Ludox, Alumina gel, Kaolin, extrusion aid be preferably selected from sesbania powder,
At least one in methylcellulose, liquid paraffin, fatty alcohol-polyoxyethylene ether, mineral acid is preferably selected from nitric acid, phosphorus
At least one in acid；Described metallic element is selected from La, Ce, Ni, V, Mo, Pt, Zn, Ag at least
A kind of.
Compared with prior art, the present invention has following innovative point and advantage is:
1) using extruding pelletization method to prepare spheric catalyst in the preparation method that the present invention provides, the method balling-up granularity is equal
One, intensity is high, and yield is high, loses little, arenes selectivity is greatly improved by supported active metals.
2) spheric catalyst that the present invention provides carries out reactivity worth evaluation by fixed-bed reactor, due to spherical catalyst
The mobility of agent and recyclability, this catalyst possesses higher intensity (30～80N/ grain) and relatively low abrasion (＜
1%), can apply and methanol aromatic hydrocarbons moving bed process.
Detailed description of the invention
For the technological means making the present invention realize, character of innovation, reach purpose and be easy to understand with effect, below
The present invention is expanded on further.
Embodiment 1
Weigh 133g Hydrogen ZSM-5 molecular sieve, add 120g boehmite, 3g sesbania powder, be sufficiently mixed all
After even, add 1g liquid paraffin and 117g dilute nitric acid solution, be extruded into after being kneaded into plastic shape bar shaped (bar shaped orifice plate
A diameter of 2.0mm).It is then passed through Spheroidgranulatemachine cutting, balling-up, in 30 DEG C of baking ovens after predrying 20 minutes,
The bar cylindrical particle of gained is put in trimmer carry out shearing, rounding, be dried 4 hours at 110 DEG C, at 550 DEG C
Lower constant temperature calcining 4 hours, obtains spherical carrier of catalyst.Carrier is sampled 100 and is tested by radial strength instrument, and it is put down
All intensity is 50N/ grain, sphericity ＞ 92%, adds 2000g ball type carrier in abrasion instrument, and 1 as a child took out, sieve
Point, remaining 1995g, rate of wear is 0.25%.By carrier loaded 3%ZnO and 3%Ce2O3, it is dried, 550 DEG C of roastings
Burn 4h, prepare methanol arenes catalytic agent, be loaded in fixed bed reactors carrying out methanol aromatic hydrocarbons reaction evaluating,
Wherein methanol air speed is 2h-1, reaction pressure 1.0MPa, reaction temperature 450 DEG C, its aromatics yield is 20%, aromatic hydrocarbons
Selectivity is 65%.
Embodiment 2
Weigh 266g Hydrogen ZSM-5 molecular sieve, add 260g Alumina gel, 3g sesbania powder, after being sufficiently mixed uniformly,
Add 1g liquid paraffin and 125g dilute phosphoric acid solution, after being kneaded into plastic shape, be extruded into bar shaped (bar shaped orifice plate a diameter of
2.5mm).It is then passed through Spheroidgranulatemachine cutting, balling-up, in 30 DEG C of baking ovens after predrying 20 minutes, by institute
Bar cylindrical particle put in trimmer carry out shearing, rounding, be dried 4 hours at 110 DEG C, at 550 DEG C
Constant temperature calcining 4 hours, obtains spherical carrier of catalyst.Carrier is sampled 100 and is tested by radial strength instrument, and it is average
Intensity is 55N/ grain, sphericity ＞ 94%, adds 2000g ball type carrier in abrasion instrument, and 1 as a child took out, screening,
Residue 1990g, rate of wear is 0.5%.By carrier loaded 3%NiO and 2%La2O3, it is dried, 550 DEG C of roasting 4h,
Prepare methanol arenes catalytic agent, be loaded in fixed bed reactors carrying out methanol aromatic hydrocarbons reaction evaluating, Qi Zhongjia
Alcohol air speed is 3h-1, reaction pressure 1.0MPa, reaction temperature 450 DEG C, its aromatics yield is 19.4%, aromatic selective
Property is 66.5%.
Embodiment 3
Weigh 266g Hydrogen ZSM-5 molecular sieve, add 200g Ludox, 4g methylcellulose, be sufficiently mixed all
After even, add 1g liquid paraffin and 260g Alumina gel, after being kneaded into plastic shape, be extruded into the bar shaped (diameter of bar shaped orifice plate
For 1.6mm).It is then passed through Spheroidgranulatemachine cutting, balling-up, in 30 DEG C of baking ovens after predrying 20 minutes, will
The bar cylindrical particle of gained put into trimmer is carried out shear, rounding, be dried 4 hours at 110 DEG C, at 550 DEG C
Lower constant temperature calcining 4 hours, obtains spherical carrier of catalyst.Carrier is sampled 100 and is tested by radial strength instrument, and it is put down
All intensity is 42N/ grain, sphericity ＞ 91%, adds 2000g ball type carrier in abrasion instrument, and 1 as a child took out, sieve
Point, remaining 1994g, rate of wear is 0.3%.By carrier loaded 3%NiO and 5%ZnO, it is dried, 550 DEG C of roastings
4h, prepares methanol arenes catalytic agent, is loaded in fixed bed reactors carrying out methanol aromatic hydrocarbons reaction evaluating, its
Middle methanol air speed is 4h-1, reaction pressure 1.0MPa, reaction temperature 450 DEG C, its aromatics yield is 19.4%, aromatic hydrocarbons
Selectivity is 65.2%.
Embodiment 4
Weigh 198g Hydrogen ZSM-5 molecular sieve, add 182g boehmite, 4g methylcellulose, the most mixed
After closing uniformly, add 1g fatty alcohol-polyoxyethylene ether and 195 grams of dilute nitric acid solutions, after being kneaded into plastic shape, be extruded into bar
Shape (a diameter of 1.8mm of bar shaped orifice plate).It is then passed through Spheroidgranulatemachine cutting, balling-up, pre-in 30 DEG C of baking ovens
Be dried after 20 minutes, the bar cylindrical particle of gained is put in trimmer carry out shearing, rounding, dry at 110 DEG C
Dry 4 hours, at 550 DEG C, constant temperature calcining 4 hours, obtained spherical carrier of catalyst.Carrier samples 100 by footpath
Testing to intensity meter, its mean intensity is 45N/ grain, sphericity ＞ 93%, adds 2000g ball type carrier in abrasion instrument,
1 as a child took out, screening, remained 1984g, and rate of wear is 0.8%.By carrier loaded 2%PtO and 6%V2O5,
It is dried, 550 DEG C of roasting 4h, prepares methanol arenes catalytic agent, be loaded in fixed bed reactors carrying out methanol system
Aromatic hydrocarbons reaction evaluating, wherein methanol air speed is 3h-1, reaction pressure 1.0MPa, reaction temperature 450 DEG C, its aromatic hydrocarbons is received
Rate is 21.6%, and arenes selectivity is 67.2%.
Embodiment 5
Weigh 253g Hydrogen ZSM-5 molecular sieve, add 60g Kaolin, 4g sesbania powder, after being sufficiently mixed uniformly,
Add 195g dilute nitric acid solution, after being kneaded into plastic shape, be extruded into bar shaped (a diameter of 1.9mm of bar shaped orifice plate).Then
Through Spheroidgranulatemachine cutting, balling-up, in 30 DEG C of baking ovens after predrying 20 minutes, by the bar cylindrical particle of gained
Put in trimmer carry out shearing, rounding, be dried 4 hours at 110 DEG C, constant temperature calcining 4 hours at 550 DEG C,
Obtain spherical carrier of catalyst.Carrier is sampled 100 and is tested by radial strength instrument, and its mean intensity is 45N/ grain,
Sphericity ＞ 95%, adds 2000g ball type carrier in abrasion instrument, 1 as a child took out, screening, remained 1982g,
Rate of wear is 0.9%.By carrier loaded 8%MoO and 2%Ag2O, is dried, 550 DEG C of roasting 4h, prepares methanol system
Arenes catalytic agent, is loaded in fixed bed reactors carrying out methanol aromatic hydrocarbons reaction evaluating, and wherein methanol air speed is
3h-1, reaction pressure 1.0MPa, reaction temperature 450 DEG C, its aromatics yield is 20.3%, and arenes selectivity is 68.2%.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned exemplary embodiment, and
Without departing from the spirit or essential characteristics of the present invention, it is possible to realize the present invention in other specific forms.Cause
This, no matter from the point of view of which point, all should regard embodiment as exemplary, and be nonrestrictive.
Claims (5)
1. a moving bed methanol aromatic hydrocarbons spheric catalyst, it is characterised in that with catalyst weight percent
Meter includes:
1) 30～the Hydrogen ZSM-5 molecular sieve of 70%；
2) 20～the oxide of binding agent of 60%；
3) 0～the metal-oxide of 10%, described metal selected from La, Ce, Fe, Ni, V, Mo, Pt,
At least one in Zn, Co, Ag；
Wherein said catalyst is spherical in shape, sphericity ＞ 90%, and particle diameter is 0.5～4.0mm, and catalyst strength is
30～80N/ grains, rate of wear ＜ 1%.
Moving bed methanol aromatic hydrocarbons spheric catalyst the most according to claim 1, it is characterised in that institute
At least one in La, Ce, Ni, V, Mo, Pt, Zn, Ag of the metallic element stated.
3. a preparation method for the moving bed methanol aromatic hydrocarbons spheric catalyst described in claim 1, it is special
Levy and be, comprise following step:
(1) weigh Hydrogen ZSM-5 molecular sieve to mix homogeneously with binding agent, extrusion aid, by adding mineral acid
Mediating, the water content adjusting butt is 40～60%, and described binding agent is molten selected from boehmite, silicon
At least one in glue, Alumina gel, gama-alumina, Kaolin, extrusion aid is selected from sesbania powder, Methyl cellulose
At least one in element, alkylbenzenesulfonate, liquid paraffin, fatty alcohol-polyoxyethylene ether, mineral acid is selected from salt
At least one in acid, nitric acid, phosphoric acid；
(2) material is extruded into strip through orifice plate, then puts into after being cut into bar columnar product by slitting device
Trimmer is carried out shear, rounding, be dried, roasting prepares catalyst carrier；
(3) by the salt solution impregnation of metallic element on a catalyst support, being dried, roasting prepares methanol system virtue
Hydrocarbon spheric catalyst, described metallic element selected from La, Ce, Fe, Ni, V, Mo, Pt, Zn, Co,
At least one in Ag.
The preparation method of moving bed methanol aromatic hydrocarbons spheric catalyst the most according to claim 3, it is special
Levy and be:
At least one in boehmite, Ludox, Alumina gel, Kaolin of described binding agent, helps
Squeeze at least one in sesbania powder, methylcellulose, liquid paraffin, fatty alcohol-polyoxyethylene ether of agent, nothing
At least one in nitric acid, phosphoric acid of machine acid；Described metallic element selected from La, Ce, Ni, V, Mo,
At least one in Pt, Zn, Ag.
5. the moving bed methanol aromatic hydrocarbons spheric catalyst moving bed methanol aromatic hydrocarbons described in a claim 1
Application in technique.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631676A (en) * | 2016-12-09 | 2017-05-10 | 中国科学院大连化学物理研究所 | Moving bed method for co-producing low-carbon olefin during p-xylene preparation through toluene alkylation |
| CN107497477A (en) * | 2017-08-07 | 2017-12-22 | 刘博男 | A kind of methanol aromatic hydrocarbons coproduction alkene catalyst and preparation method thereof |
| CN113477247A (en) * | 2021-09-07 | 2021-10-08 | 中海油天津化工研究设计院有限公司 | High-activity hydrothermal-resistant stable catalyst and preparation method thereof |
| CN115487795A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Spherical alumina carrier and preparation method thereof, dehydrogenation catalyst and application |
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| CN115487795A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Spherical alumina carrier and preparation method thereof, dehydrogenation catalyst and application |
| CN113477247A (en) * | 2021-09-07 | 2021-10-08 | 中海油天津化工研究设计院有限公司 | High-activity hydrothermal-resistant stable catalyst and preparation method thereof |
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