CN106890672B - A kind of methanol conversion light olefin catalyst processed and its preparation method and application - Google Patents
A kind of methanol conversion light olefin catalyst processed and its preparation method and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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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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- 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
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
A kind of methanol light olefin catalyst, it is characterized in that becoming sodium oxide molybdena < 0.1m%, silica 25m%~40m%, aluminium oxide 40m%~60m%, phosphorous oxide 10m%~20m%, boron oxide 0.01m%~1m% with the group of inorganic matter dry basis；Its 85~95% acid amount is distributed in the Hammett acid strength function range of Ho+4.8~-3.0；Ten-ring/twelve-ring duct volumetric ratio is 10~20: 1 in catalyst；It is with < 5 mesoporous nano in aperture abundant and step Jie's micropore distributed architecture；Catalyst is Chabazite-type (CHA) molecular sieve [mRAl by hydrothermal crystallizing and modified through secondary synthesis17P12Si7O72], with the synthesis of its mother liquor and modified obtained bi-five-member cycle configuration (MFI) type molecular sieve [R of boron compoundnAln‑BnSi96‑2nO192, n < 27], aluminium sol adhesive and kaolin group at；And with after remaining mother liquor and the mashing of condensate liquid mixed grinding, spray shaping is 55~75 microns of average grain diameter and the microspherical catalyst of abrasion index 0.5m%~1.8m%；After washed and oxidizing atmosphere calcination activation, there is preferably activity, selectivity and stability in MTO reaction；Make easy preparation process, environmental protection and low cost due to recycling.
Description
Technical field
It is light more particularly to a kind of methanol system the present invention relates to a kind of catalyst of transforming oxygenated organic compound process
Alkene catalyst and its preparation method and application belongs to petrochemical industry catalysis technical field.
Background technique
Light olefin (C2 =~C4 =) it is especially ethylene and propylene is that demand is greatly and the base that has many uses in petro chemical industry
This Organic Ingredients, since the seventies, many industrially developed country concentrate strength on exploitation non-petroleum feedstocks and produce the new of light olefin
Technology path, in case substitute technology when not supplying insufficient as petroleum resources.It is opposite to such a petroleum resources in China
Few big country is even more to have positive effect.Coal or natural gas via process of preparing low carbon olefinic hydrocarbon with methanol (MTO) research and development,
Being one produces the process route that chemical products are concerned from non-oil resource, wherein the performance of catalyst is without being suspected to have
Important influence.
Mobil company, the U.S. most earlier than 1977 reports are urged using ZSM-5 zeolite molecular sieve as methanol-to-olefins (MTO)
Agent (USP5367100)；U.S. combinating carbide company (UCC) develops novel phosphoric acid sial Series Molecules sieve for 1984
SAPO-n (USP4440871, US4499327), wherein SAPO-34 molecular sieve is due to having the acidity for being suitable for and cellular structure to exist
Excellent catalytic performance is showed in MTO reaction.
The catalyst used in the process of methanol-to-olefins generallys use SAPO molecular sieve and ZSM-5 molecular sieve at present, and
It is all had been reported that in prior art, as USP5248647, USP6153552, USP6787501 are reported SAPO-34 molecular sieve, height
Methanol conversion catalyst is made in ridge soil, binder spray drying；CN102029181B,CN102029182B,
CN102294262A etc. also discloses the preparation method of SAPO silicoaluminophosphamolecular molecular sieves type methanol-to-olefin catalyst.In addition,
CN102380414A also discloses a kind of AlPO-18 and AlPO-34 molecular sieve without element silicon of hydro-thermal method synthesis, for making
The preparing olefin by conversion of methanol catalyst method of standby low in acidity, high stability.
Last century the nineties, German Lurgi company develop the methanol of complete set based on modified ZSM-5 molecular sieve
Propylene (MTP) technique processed, the Propylene Selectivity under Product olefins circular response reach 71.2%, therefore ZSM-5 molecular sieve type
The another degree of methanol light olefin technology causes to pay close attention to, and has a large amount of reports in prior art, as US4238631B1,
US4328384B1, US4423274B1 and CN104056654A etc., wherein to increase light olefin and reducing C5 +Byproduct is also boiling
It deposited coke on stone；A kind of high C containing ZSM-5 molecular sieve is disclosed in CN103962170A4The catalysis of olefine selective microballoon
Agent, for the methanol conversion > 99% in fluidized bed, C4Selectivity can reach 32%；And CN1352627A is also disclosed
It is the method for light olefin by methanol or dimethyl ether conversion using the ZSM-5 zeolite catalyst of P Modification.
Being related to MTO catalyst atomizing preparing technique has many reports, as USP6153552, USP6787501,
USP5248647, CN1341584A etc. disclose the spray with SAPO-34, inorganic oxide adhesive and clay class matrix fill
Mist preparation method.Since the content of molecular sieve often produces bigger effect the catalytic performance of MTO catalyst, and macromolecule sieve contains
Microspherical catalyst abrasion strength resistance problem is always again a difficult point when amount, therefore the prior art of this respect is concerned, such as
Prepared by the wear-resistant methanol conversion catalyst of CN01132533A, really played and mentioned by molecular sieve content in reduction catalyst
The effect of high catalyst abrasion index；It is also common method that slurry before spraying is levigate and improves binder, such as
CN102284302A carries out particle refinement after mixing the slurry of methanol-to-olefin catalyst, thus living with excellent catalysis
Property, selectivity, especially excellent attrition resistance energy；And CN104162448A is then in the light alkene of the methanol system of molecular sieve containing SAPO-34
Hydrocarbon catalyst prepare when boehmite in reinforce acid and phosphoric acid method, come solve molecular sieve content it is low, it is not wear-resisting, catalysis
The defects of performance is unstable.
In addition to above-mentioned conventional method, the mother liquor of synthesis of molecular sieve is used for catalyst preparation attention, such as
CN103170361A uses the liquid generated in SAPO-34 Zeolite synthesis to prepare methanol-to-olefin catalyst as raw material, reduces
Raw material additional amount reduces production cost and realizes recycling；CN103706393A is then to be added to close after the stirring of material homogeneous
It is mother liquid obtained at molecular sieve, wear-resisting methanol-to-olefin catalyst microballoon is produced, reduces costs and refers to attrition of catalyst
Number drops to 0.5m%/h-1Below.
Since SAPO type molecular sieve coke selectivity is higher and causes catalyst inactivation very fast, and ZSM-5 molecular sieve C4With
The selectivity of upper alkene and aromatic hydrocarbons is higher, in order to further increase the catalytic performance of MTO catalyst, it is therefore desirable to carry out further
Study on the modification.Being modified using metal or nonmetalloid to molecular sieve active component is common method, such as
The modification to SAPO molecular sieve such as USP4752651, CN1128676C, CN101555022A.There is series report to draw transition metal
Entering the MeAPSO molecular sieve formed into SAPO molecular sieve skeleton has higher light olefin selectivity to MTO reaction, such as
J.Mol.Catal.A 160(2000)437、CN1108867、CN1108868、CN1108869、CN1108870、CN1111091、
CN1132698 etc. discloses related content；In CN101121145B in addition to using transition metal, alkaline-earth metal is also used
It is modified；Also have more report for MTO catalyst using the modified SAPO-34 system with molecular sieve for preparing of Zn, as USP7119242,
USP6759360, CN1704390A, CN1683079A, to solve catalyst activity, the problems such as selectivity and yield are low；
With rare earth modified SAPO-34 molecular sieve catalyst, methanol conversion 100%, ethylene+propylene total recovery in CN104096591A
> 80%, triolefin total recovery > 90% and propylene/ethylene > 0.9.
Equally, the modification technology of ZSM-5 molecular sieve is also had been reported that, USP4480145 using -5 zeolite of large crystal ZSM-5 and
The diffusivity that the silica filling of zeolite pores reduces zeolite improves the ethylene yield of methanol conversion；USP3911041 uses P Modification
ZSM-5 zeolite so that methanol is converted into alkene, USP4049573 and USP4088706 are by boron or the oxide of magnesium, or further
Phosphorous oxides modified ZSM-5 zeolite is added, methanol is made to be converted into alkene；CN102259013A is then added boron source in synthesis and obtains
The ZSM-5 zeolite catalyst of skeleton boracic is improved with effectively controlling the medium acid strength and strong acidic site ratio of molecular sieve surface
The catalytic activity and stability of MTO reaction.But the acid regulation of this unimolecule sieve will affect catalyst conversion activity.
For solve unimolecule sieve improve MTO catalyst performance on limitation, US2007/0100188A1,
AEI the and CHA skeleton class such as CN101214089A, CN101450806A, CN97180440, CN02805772, CN1525940A
The silicoaluminophosphamolecular molecular sieves of the intergrowth phase of type molecular sieve, for MTO catalysis reaction；CN102430424A is with the ZSM- first prepared
5 and aluminium phosphate molecular sieve complex type molecular sieve, then the catalyst of phosphorus modification preparation is carried out, when methanol conversion 100%
C2 =~C4 =Total low-carbon alkene and Propylene Selectivity are better than the catalyst individually with ZSM-5 up to 82% and 50% or more；
CN104107720A also with the complex type molecular sieve catalysis containing metallic element, improves MTO catalyst stability, selectivity and receipts
Rate.Though complex type molecular sieve performance is good, it is neither easy to control when preparing, it is also inconvenient steadily to produce and apply.
It is also had been reported that with the catalyst of silicon phosphorus aluminium profiles and Si-Al molecular sieve simultaneously, as CN102389833A uses SAPO-
34 molecular sieves and nitric acid or rare earth nitrades treated NaY type molecular sieve, while being catalyzed lighter hydrocarbons steam cracking alkene and first
Alcohol converts alkene processed, solves steam cracking heat supply and methanol-to-olefins heat dissipation problem；CN101676028B, CN102814194B etc.
It is prepared for the MTO catalyst containing Y class, ZSM-5 class and SAPO-34 molecular sieve simultaneously, but the Y molecular sieve analog of highly acid will affect
The selectivity of MTO reaction.
Multistage pore canal in MTO catalyst also has an impact to catalytic performance, if CN104525250A is to using triethylamine mould
Alkali process after the SAPO-34 molecular sieve that plate agent and same type molecular sieve seed synthesize is roasted obtains very regular more
The catalyst of grade pore structure type methanol-to-olefins, activity and selectivity of light olefin are high, reproducible；CN101157057B is then
The catalyst that in-situ crystallization SAPO-34 molecular sieve is prepared on microsphere particle also has multistage pore canal.But not modulated is more
Grade duct, aperture and pore capacities distribution are uncontrolled, are also extremely limited to the diffusion and reactivity worth that improve MTO catalyst, special
It is not the intensity that catalyst had both been damaged in excessive aperture (5 nanometers of >), is distributed to improving catalytic performance and obtaining ideal product
Also effect is had no, is in addition introduced on unimolecule sieve catalyst mesoporous, practical application effect is not also significant.
Although the catalyst patented technology report of MTO involved in the prior art is more, according to MTO response characteristic, for
The requirement of active component, with suitable condition is separately synthesized and modified SAPO-34 and ZSM-5 molecular sieve, composition are conducive to reactant
It is distributed with the acid strength after the step Jie's microcellular structure system and modulation of product diffusion-acid amount, to improve the reaction during MTO
Object-product diffusion, catalytic reaction activity, the technology of selectivity and stability, there is not been reported；During the preparation process, for MTO
Reacting middle catalyst carrier diffusion needs, and the preparation method that organic mould pulls agent and mother liquor, condensate circulation utilize makes to make
Standby easier reasonable, the environmentally protective and inexpensive prior art of process also has not been reported.
Summary of the invention
In the presence of overcoming the shortcomings of the prior art, a kind of oxygen-containing organic compound turn is provided
The catalyst of change process is especially to provide a kind of catalyst and preparation method thereof of methanol light olefin for improving catalytic performance
And application, belong to petrochemical catalyst technology and petrochemical industry reaction process field.
Usual faujasite (such as Y zeolite, X zeolite), Beta zeolite and modenite large pore zeolite, being capable of catalysis methanol
It is converted into hydrocarbon, but often C5 +The selectivity of product of hydro carbons is high, and the selectivity of low-carbon alkene is low；And erionite, T zeolite, chabasie
Equal pore zeolites, though the selectivity of alkene can be improved, coking and deactivation is very fast.Therefore many researchs concentrate on ZSM-5 zeolite
The zeolite in aperture in, excellent shape selective catalysis performance can no doubt obtain higher yield of light olefin, but too due to acidity
By force, the selectivity of ethylene is to be improved, C5 +The product distribution of hydro carbons is also unsatisfactory.And SAPO molecular sieve is a kind of crystalline silico-alumino
Phosphate, three dimensional skeletal structure is made of phosphorus oxygen, alumina and oxygen-octahedron, and this aperture is about the aperture and acid of 0.43nm
Property moderate molecular sieve be a kind of preferable shape-selective catalyst.Especially SAPO-34 molecular sieve catalysts, methanol conversion life
It to be substantially better than ZSM-5 zeolite at the selectivity of ethylene, P/E is than low in product component, catalyst aperture little Yi coking, so that again
Raw process becomes frequent.
To the modification of silicoaluminophosphate and Si-Al molecular sieve in prior art, the selectivity of light olefin in MTO has been only focused on, compared with
Few complex relationship paid close attention between diffusion, activity of conversion, selectivity, by-product alkane and coke etc. on the whole, uses
Method it is also more single and linear, it is difficult to obtain ideal effect.And pass through addition CMC, starch, surface-active in prior art
Agent, sesbania powder etc. make the MTO catalyst of preparation obtain multipole hole and enrich mesoporous method, it is excessive to expansion often to there is aperture
It dissipates and catalytic performance improvement result is lower, and the defects of the abrasion strength resistance of damage catalyst and higher cost etc..
Inventor through a large number of experiments it was unexpectedly observed that overcome limitation in the presence of numerous prior arts,
When preparing MTO catalyst, to the silicoaluminophosphamolecular molecular sieves and Si-Al molecular sieve in catalyst, using specific separately synthesized and change
Property, and the general requirement to catalyst performance is reacted from MTO, pass through nonlinear complicated modulation and both given activities of arranging in pairs or groups
The micropore of constituent element is arranged in pairs or groups and acid distribution, constitutes the step Jie's microcellular structure system for being conducive to reactants and products Reaction-diffusion terms, adjusts
Become the catalyst Hammett acid strength function Ho distribution for being suitable for out, can inhibit catalyst and cross strong acid center to light olefin
Aromatization activity makes catalyst in the reaction process that methanol oxidation converts light olefin processed, obtains high yield of light olefin, especially
It is ethylene, propene yield, reduces by-product and C5 +With the yield of coke, and the activity cycle internal stability having had.
Inventor also found the preparation method by mother liquid recycling, both solve a large amount of mother liquor emission aftertreatments hardly possiblies
It is more easy to be reasonable, environmentally protective and reduce cost to make whole preparation process, and organic formwork contained therein is utilized for problem
Agent makes to form the mesoporous of smaller aperture due abundant (5 nanometers of <) in the preparation of molecular sieve modified and shaping of catalyst, thus further
Jie's micropore distributed architecture system for forming the truly advantageous reactant in MTO reaction process, product diffusion, improves the anti-of catalyst
Activity, selectivity and stability are answered, these inventions and discovery can not obtain direct and specific technology in the prior art
Enlightenment.
Therefore specifically, the present invention provides a kind of catalyst of methanol light olefin, it is characterized in that dry with inorganic matter
The group of base weight meter becomes sodium oxide molybdena < 0.1m%, silica 25m%~40m%, aluminium oxide 40m%~60m%, phosphorous oxide
10m%~20m%, boron oxide 0.1m%~1m%；Its 85~95% acid amount is distributed in acid strength Hammett function Ho+4.8
In~-3.0 ranges；Ten-ring/twelve-ring duct volumetric ratio is 10~20: 1 in catalyst；With aperture < 5 abundant
The mesoporous system and step Jie's micropore distributed architecture of nanometer；The microspherical catalyst is highly suitable to be applied for methanol conversion and produces light alkene
In the reaction process of hydrocarbon.
Acid strength Hammett function Ho is comparable intuitively to reflect molecular sieve and catalyst within the scope of different acid strengths
Acid amount distribution situation can refer to understanding of the professional book acquisition of any catalysis aspect in this field to this respect.Ho is by just
It is worth negative value and shows acid strength from low to high, molecular sieve and catalyst is catalyzed it in the acid amount distribution of different acid strength ranges
Performance often generates most direct influence, but for current technology development level, to its modulation often have it is non-linear and
Unpredictable feature is to constitute one of molecular sieve and the major technique knowhow (tricks of the trade) of catalyst performance.Of the invention
MTO catalyst constitutes the upper and prior art there are dramatically different and in addition to leading to performance difference except composition, also has and the prior art
Very different catalyst acid intensity distribution feature, and its catalytic activity, selectivity and stability are profoundly affected, which constitute this
The core technology content of invention, and direct technical inspiration can not be obtained from prior art and experience.
A kind of methanol light olefin catalyst provided by the present invention, it is characterised in that step Jie's micropore is distributed knot
Structure are as follows: 0.5 nanometer of mesopore volume of 40v%~60v% of 0.43 nanometer of aperture Kong Rongzhan total pore volume of ten-ring, twelve-ring
Account for 1v%~10v% of total pore volume, 2~5 nanometers of smaller aperture due of mesoporous Kong Rong accounts for 30v%~50v% of total pore volume.> 5 receives
The mesoporous Kong Rong of larger aperture of rice accounts for total pore volume 2v%~8v%.
Those skilled in the art are known, pore distribution be influence molecular sieve and catalyst performance another it is important because
Element, and also there is complicated non-linear correlation relationship between catalytic performance, for current catalytic theory and technical level, also
It cannot accomplish that accurate theory deduction or experience speculate, can not be tested by simple condition in pore canal system distribution and catalytic performance
Between establish and be clearly associated with.One of the technology knowhow (tricks of the trade) of catalyst, institute of the present invention are equally constituted to its modulation and composition
The mesoporous distribution of abundant smaller aperture due (5 nanometers of <) in the MTO catalyst of offer and step Jie's micropore different from prior art
Distribution characteristics constitutes one of the core content of catalyst of the present invention, and can not obtain from prior art and experience inference bright
True technical inspiration.
A kind of catalyst of methanol light olefin provided by the present invention, feature there are also the catalyst be by 30m%~
The hydrothermal crystallizing of 40m% and Chabazite-type (CHA topological structure, the chemical formula [mRAl modified through secondary synthesis17P12Si7O72])
Molecular sieve, 5m%~10m% hydrothermal crystallizing and through boron compound it is modified obtain bi-five-member cycle configuration type (MFI topological structure,
Chemical formula [RnAln-BnSi96-2nO192, n < 27]) molecular sieve, the Aluminum sol knot agent of 5m%~20m% and balance kaolin composition,
Wherein R is organic formwork agent；The average grain diameter of catalyst microspheres is 55~75 microns and abrasion index 0.5m%~1.8m%.
Demand of the preparing olefin by conversion of methanol reaction for reply frequent regeneration usually containing SAPO molecular sieve, Yao Caiyong recycle stream
Change bed operation mode, catalyst must be the microspheroidal that there is appropriate particle size to be distributed.Although therefore above-mentioned mentioned molecular sieve
It with preferable MTO catalytic performance, but can not be applied directly in industrial production, need keeping high catalytic as far as possible
Under the premise of energy, there is preferable abrasion strength resistance, more completely miniature spheroidal looks and suitable size distribution.Usual fluidized bed
It is made of with microspherical catalyst active component such as molecular sieve, binder and filler matrix, the latter plays dispersion and dilution activity
Component, improve catalyst abrasion strength resistance, reduce reaction heat effect, but this also bring catalysis composition, constitute, catalytic performance and
Obtaining excellent wear-resistant physical property when complexity when physical property adjustment and change, especially macromolecule sieve content becomes
It is abnormal difficult.Though being improved the various reports of intensity in the prior art, when the catalyst being related to forms, constitutes different, often
It is difficult to obtain direct reference.Therefore, the catalyst in the case of heterogeneity molecular sieve high level provided by the invention, is had
Composition, the feature in composition and chemical and physical features, also constitute catalyst of the present invention technology contents and feature it
One, and direct reference can not be directly obtained from the prior art and experience inference, it is less likely to be those skilled in the art
Member institute is apparent.
The present invention also provides a kind of preparation methods of methanol light olefin catalyst, it is characterized in that the catalyst preparation packet
Include following steps:
(1) mol ratio SiO is pressed2/Al2O3=0.7~1.1, P2O5/SiO2=0.7~1.1, H2O/SiO2=65~80,
Organic formwork agent R/Al2O3=0.5~2.2, first by boehmite and organic formwork agent R hybrid reaction at 90~190 DEG C
0.5~5 hour, then the slurry that pH value 6.4~7.5 is made is mixed with phosphoric acid, silica gel and/or silica solution, through 20 DEG C~50
DEG C after ageing 15~30 hours, then hydrothermal crystallizing 20~100 hours at 170 DEG C~210 DEG C, unmodified chabasie is prepared
Type molecular screen primary powder.
(2) by above-mentioned unmodified Chabazite-type molecular sieve original powder after 400 DEG C~650 DEG C roast 0.5~6 hour, with
The resulting crystallization mother liquor of above-mentioned steps (1), organic formwork agent and deionized water, by molecular screen primary powder: organic formwork agent R: water=1
: 0.01~1: 5~20 weight proportion mixing, hydro-thermal process 15~30 hours, obtains through secondary conjunction at 170 DEG C~210 DEG C
At modified Chabazite-type molecular sieve.
(3) SiO is pressed2/Al2O3=30~90, organic formwork agent R/Al2O3=0.5~40, H2O/SiO2=5~15 rub
You match, and will react 0.5~5 at 90 DEG C~190 DEG C after the mother liquid obtained mixing with boehmite of above-mentioned steps (1) and (2)
Hour, then obtained unmodified through at 130 DEG C~200 DEG C times hydrothermal crystallizing 10~40 hours after mix with silica gel and/or silica solution
Bi-five-member cycle configuration type molecular screen primary powder.
(4) molecular screen primary powder: boride: water=1: 0.01~0.5: 0.1~2 weight proportion is pressed, it will be obtained by step (3)
Unmodified bi-five-member cycle configuration type molecular screen primary powder hydro-thermal process 0.5~4 hour at 350 DEG C~600 DEG C, obtain through boron
The modified bi-five-member cycle configuration type molecular sieve of compound.
(5) by modified molecular sieve obtained by step (2) and step (4), with aluminium sol adhesive, kaolin and deionization
Water, by the mother liquor after the concentration of slurry of dry weight content 25m%~40m%, with the crystallization and secondary synthesis of above-mentioned molecular sieve
And the condensate liquid in crystallization, modification, roasting and spray process is sufficiently mixed, grinding mashing consolidating to 90v%~95v%
Behind body object partial size≤2 micron, 350 DEG C~650 DEG C of intake air temperature, 150 DEG C~350 DEG C of exhaust temperature spray drying tower at
Type is microballoon.
(6) catalyst microspheres after spray shaping are washed with 30 DEG C~90 DEG C of deionized water to the Na of microspheres with solid2O
After < 0.1m%, the calcination activation 0.5~4 hour under 400 DEG C~650 DEG C of oxidizing atmosphere.
Wherein, the template is nitrogen-containing organic compound: diethylamine, triethylamine, n-propylamine, isopropylamine, three positive third
Amine, tri-isopropyl amine, di-n-propylamine, diisopropylamine, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, 1,
6- hexamethylene diamine, cyclohexylamine, beautiful jade, ethanol amine, diethanol amine, triethanolamine, N ', N ', N, in N- tetramethyl -1,6- hexamethylene diamine
The mixture of one or any of several；Preferred organic amine R is diethylamine, in triethylamine, di-n-propylamine, tetraethyl ammonium hydroxide
It is one or more.These there is nitrogenous compound can be convenient be commercially available.
In a kind of preparation method of methanol light olefin catalyst provided by the present invention, it is characterized in that in preparation step
(4) used boron compound is one of boron oxide, boric acid, ammonium borate, boron phosphate or a variety of, preferably boric acid in,
It can easily be obtained by commercially available.
It is used in each preparation step in a kind of preparation method of methanol light olefin catalyst provided by the present invention
The raw materials such as phosphoric acid, boehmite, silica gel, silica solution can easily be obtained by commercially available.
In a kind of preparation method of methanol light olefin catalyst provided by the present invention, step (1) and step (3) may be used also
Using addition, mutually identical molecular sieve is as crystal seed with synthesized product object, and to improve the crystallinity of synthetic product, additive amount is general
Less than the 20m% of product, preferably less than 10m%, more preferably less than 5m%, cost is reduced with benefit, this method is ability
Field technique personnel are known and apply.
In a kind of preparation process of methanol light olefin catalyst provided by the present invention, material slurry and through spray shaping
When the aqueous degree of catalyst microspheres and contained moisture, most water includes that the water of addition can vapor away in the drying process,
It will not influence the final catalytic performance of catalyst.
In a kind of preparation method of methanol light olefin catalyst provided by the present invention, related hydrothermal synthesis crystallization changes
Property processing and ratio calculating when catalyst preparation, the mixing that feeds intake, the operation of hydro-thermal process be well known to those skilled in the art
Routine operation.Involved noun " butt " is technical term well-known to those skilled in the art, refers to absolute dry condition
When quality of material.The selection for the range that feeds intake and the selection of calcination activation condition, those skilled in the art are according to known special
The industry knowledge combination prior art, can't be particularly restricted.But it is received from height required for catalyst activity constituent element is improved
It carries out using for the purpose of rate, selectivity of product, activity of conversion and stability and be difficult, and cannot be obtained from prior art
It obtains and clearly enlightens.
In a kind of preparation method of methanol light olefin catalyst provided by the present invention, due to raw material type and use
The range selection of amount, ingredient proportion and hydrothermal crystallizing and the temperature of processing, time, pH value, formation and product object to material
Mutually there is significant impact, can also change and influence product physico-chemical property and catalytic performance.Influence factor it is numerous and uncertain, make
It must be suitble to the acquisition of methanol conversion catalyst molecular sieve active component, the preparation including catalyst can only be touched by experimental study
Rope can not obtain specific technical inspiration from the prior art, can not lead in experience and in prior art basis
Cross result needed for simple condition test arrangement obtains.These correlation preparation contents, condition and steps and they to prepared
The physico-chemical property and catalytic performance of molecular sieve, finished catalyst out influence, and all constitute one of core substantive content of the present invention.
The present invention also provides a kind of method of methanol light olefin, light olefin (being defined as ethylene, propylene and butylene) can
Raw material as many chemicals.The present invention is characterized in that in a fluidized bed reactor, methanol 350 DEG C of reaction temperature~
650 DEG C, 0.01~10MPa of reaction pressure, weight space velocity 0.1~50 hour-1Under conditions of urged with one of claims 1 to 3
Agent contact is converted into light olefin, enters in 550 DEG C~850 DEG C of regenerator after catalyst microspheres inactivation and returns after coke-burning regeneration
Reaction is continued to participate in fluidized reactor；Preferred reaction condition are as follows: reaction temperature is 400 DEG C~550 DEG C, reaction pressure is
0.1~2.5MPa, weight space velocity are 1~10 hour-1, 580 DEG C~780 DEG C of regeneration temperature.
The method of a kind of methanol light olefin provided by the present invention, it is further characterized in that addition water vapour or inert gas
It divides, and reaction can be had an impact to adjust methanol charging；Material benzenemethanol used can be water-free methanol, can also be with
It is aqueous methanol, can be easily obtained by commercially available, is converted when metering with purity 100m%, conversion method is with general
Known to the personnel that Tonghua is gained knowledge.
In a kind of method of methanol light olefin provided by the present invention, involved specific reaction process and reaction dress
Set situation are as follows: after the methanol from head tank is preheated, feed flash tank into methanol, the methanol come out from charging flash tank steams
Vapour is further heated with middle pressure steam first, is allowed to become to overheat methanol steam, after being sent into pre-reactor conversion, reaction gas and
The steam of lighter hydrocarbons, methanol stripper tower that follow up device recycles, the methanol merging of recycling are sent into MTO main reactor.
Methanol light olefin MTO main reactor uses fluidized-bed catalytic reactor design and use microspherical catalyst, and MTO is anti-
It should be an exothermic reaction, when material benzenemethanol enters reactor bottom, reaction begins to occur.In reactor methanol with come from
The high-temperature regenerated catalyst of regenerator directly contacts, and carries out exothermic reaction.
MTO temperature of reactor is controlled with reactor catalyst cooler, and the heat of reaction that catalyst cooler removes is used
To generate high steam, coke is the by-product of MTO reaction, it, which is attached to catalyst particle surface, causes catalyst activity to reduce
Or inactivation, therefore, catalyst must be by coke burning regeneration with activity recovery.Catalyst regeneration is a continuous process.It separates
Decaying catalyst catalyst regenerator is entered by decaying catalyst transportation system, the reclaimable catalyst of carbon deposit is again after reaction
Rear Returning reactor is burnt in raw device.Catalyst regeneration is exothermic reaction, and the combustion heat in regenerator catalyst cooler by moving
Out, to generate steam.
Reaction gas is drawn after cyclone separator removes the microspherical catalyst of entrained with, after heat exchanger cools down, is sent to urgency
Cold tower.The admixture of gas come out from chilling top of tower enters product separator, most of product water quilt in admixture of gas
It condenses out and enters product separator bottom.The olefin product come out at the top of from product separator is sent to separation of olefins unit,
It compressed, be fractionated and purified, product separates in recovery unit, takes off minor amount of water, methanol and DME.Propylene, ethylene are main produce
Product, byproduct are liquid fuel and gasoline.
Methanol light olefin catalyst provided by the present invention by the separately synthesized and modified phosphorus sial of specified conditions and
Borosilicate aluminum molecular screen makes catalyst have the acid amount distribution in the medium acid strength sum aggregate for being suitable for MTO reaction, has well
MTO catalyzed conversion activity and light olefins product selectivity, overcome catalyst conversion activity in the prior art and selectivity of product
Insufficient inherent shortcoming；It is suitable for ten-ring aperture needed for reaction and the collocation of twelve-ring mesoporous possessed by catalyst, enriches
Smaller aperture due (5 nanometers of <) is mesoporous and Jie's micropore distributed architecture system of step configuration, be conducive in MTO reaction process
In reactant, product and other by-products, organic attachment circulation and diffusion, make catalyst activity, selectivity obtain
Stablize and plays.
Mother liquor iterative cycles in methanol light olefin catalyst preparation process provided by the present invention utilize, and with crystalline substance
Change mother liquor, each process work condensate liquid are mixed with beating the molding method of rear atomized microball, have both been the small-bore of matrix (5 nanometers of <)
Mesoporous system provides contribution, in turn ensures necessary mechanical strength when catalyst uses, due to recycling, mother liquor and
Molecular sieve and sial raw material of organic amine, precipitating in various condensate liquids, recovered liquid etc. have all obtained effective collection and again benefit
With to save these raw material needed for catalyst manufacturing procedures；In combination with eliminating, ion exchange, drying etc. are numerous
General labourer's sequence and step significantly reduce catalyst production cost, and keep entire catalyst preparation process easier to be rationally and green
Colour circle is protected.
Specific embodiment
Following examples will further illustrate the present invention, but not thereby limiting the invention.
In embodiments, using the acid strength of the method for indicator and n-butylamine titration measurement sample and acid amount distribution；
Sample object phase and crystallinity are measured using X-ray diffractometer；The chemical composition of x-ray fluorescence method measurement sample；BET cryogenic nitrogen is inhaled
Specific surface area, pore volume and the mesoporous distribution of attached method measurement sample；The suction of surface weight adsorption balance measurement sample different pore size
Attached capacity and kinetic diameter (adsorbing medium ammonia, n-hexane, iso-butane etc.)；Catalyst grain size is measured using laser particle analyzer；
Microspherical catalyst abrasion strength resistance is measured with gooseneck friabilator；Reaction evaluating divides reaction product gas with gas chromatograph
Analysis.
Other detections are referring to (" petroleum and oil product test method national standard " published by China Standards Press 1989
Year).
Embodiment 1
In the autoclave with stirring, 1 liter of deionized water is added in (1), by 183 grams of boehmites (industrial goods, Al2O3
70m%, Shandong Aluminum Plant) it is (chemical with 225 grams of diethylamine (chemically pure reagent, Beijing chemical reagent company) and 12 grams of di-n-propylamines
Pure reagent, Beijing chemical reagent company) hybrid reaction 2 hours at 95 DEG C, then with 300 grams of phosphoric acid (industrial goods, 85m%, Sichuan
Profit and catalyst plant), 180 grams of silica solution (industrial goods, 25m% SiO2, Haiyang Chemical Plant, Qingdao), pH value is made in mixing
6.7 slurry, after 30 DEG C are aged 24 hours, then hydrothermal crystallizing 80 hours at 185 DEG C, filtering obtain SAPO-34 molecular sieve
Original powder A, crystallization mother liquor are used for the preparation of step (2) and (3).
(2) it by above-mentioned SAPO-34 molecular screen primary powder A after 550 DEG C roast 1 hour, is filtered with above-mentioned steps (1) resulting
In crystallization mother liquor, 20 grams of diethylamine and 700 grams of deionized water mixing are added, hydro-thermal process 24 hours, are filtered at 190 DEG C
It is mother liquid obtained after filtering to be used to prepare step (3) to the modified SAPO-34 molecular sieve B of secondary synthesis.
(3) in above-mentioned steps (1) and (2) are mother liquid obtained, 3 grams of boehmites (ibid) are added, at 150 DEG C after mixing
It is lower reaction 3 hours, then with 50 grams of silica gel (industrial goods, 99m% SiO2, Haiyang Chemical Plant, Qingdao) mixing after through being lauched at 160 DEG C
Thermal crystallisation 30 hours, ZSM-5 molecular sieve original powder C is obtained by filtration, filtered mother liquor is used to prepare step (5).
(4) by the resulting ZSM-5 molecular sieve original powder C of above-mentioned steps (3) and 10 grams of boric acid (chemically pure reagent, 95m%, north
Capital chemical reagent company) after ground and mixed is uniform, in 450 DEG C of tube furnace, 60 Grams Per Hour of water vapour weight flow rate, hydro-thermal
Processing 2 hours, obtains the modified B-ZSM-5 molecular sieve D powder of boron compound, tail gas condensing liquid is used to prepare step (5).
(5) by modified SAPO-34 molecular sieve B powder and B-ZSM-5 molecular sieve D powder obtained by step (2) and step (4),
With 600 grams of aluminium sol adhesives (industrial goods, Al2O320m%, Sichuan profit and catalyst plant), 400 grams of kaolin (industrial goods, Gu
Content 88m%, Kaolin of Suzhou company) with the remaining mother liquor after the crystallization and secondary synthesis of above-mentioned molecular sieve and crystallization, change
Property, the condensate liquid containing organic formwork agent in roasting and spray process be sufficiently mixed, add 700 grams of deionized waters, grind
It is dry in the small spraying of 600 DEG C of intake air temperature, 280 DEG C of exhaust temperature behind mashing to solids partial size≤2 micron of 93v%
Microballoon is shaped in device, tail gas condensing liquid is used for next group of sample mashing preparation.
(6) 15 liters 70 DEG C of deionized water of the catalyst microspheres after above-mentioned spray shaping is respectively washed 10 points in three times
Clock, 110 DEG C after drying 2 hours under 550 DEG C of oxidizing atmosphere calcination activation 2 hours (oxygen volumetric concentration 5v%), obtain
The catalyst of embodiment 1.
Comparative example 1
Using commercially available commodity SAPO-34 molecular sieve (industrial goods, relative crystallinity 90%, phosphorus aluminum ratio 0.5, silica alumina ratio
And ZSM-5 molecular sieve (industrial goods, crystallinity 90% 0.7).Silica alumina ratio 50), can also by USP USP4440871 and
USP3702886 prepares SAPO-34 and ZSM-5 molecular sieve respectively, by the molecular sieve ratio of the embodiment 11 of CN101676028B
Example, method and condition, under molecular sieve total content same as Example 1, spray shaping prepares microspherical catalyst, acquisition pair
The catalyst of ratio 1.
Comparative example 2
The step of according to comparative example 1, the CMC (work of material butt 1m% was added in mashing by identical molecular sieve content
Industry product, Na2O < 0.1m%, her Lipha of Suzhou produce), other conditions are prepared with comparative example 1 with mesoporous comparison
2 catalyst of example.
Comparative example 3
According to the method and steps in the embodiment of CN104525250A, the SAPO- of the multi-stage porous after preparing alkali modification
34 molecular sieves, after SAPO-34 can also being prepared according to the method for USP4440871, the method that refers again to step (2) in embodiment 1
It is modified, obtain the modified SAPO-34 molecular sieve of secondary synthesis；According still further to the method and step of the comparative example 3 of CN101676028B
Suddenly, a kind of molecular sieve of SAPO-34 containing multi-stage porous after alkali modification being only added in mashing by identical molecular sieve content, is prepared
The catalyst of comparative example 3.
Comparative example 4
According to the method and steps in the embodiment of CN102259013A, the B-ZSM-5 molecular sieve of boracic is prepared, it can also
It after preparing ZSM-5 molecular sieve according to the method for USP3702886, then carries out boron compound and is modified, obtain B-ZSM-5；And reference
B-ZSM-5 one kind is only added in mashing by identical molecular sieve content for the method and steps of the comparative example 6 of CN101676028B
Molecular sieve prepares the catalyst of comparative example 4.
Embodiment 2
The step of according to embodiment 1, is replaced real using 240 grams of triethylamines (chemically pure reagent, Beijing chemical reagent company)
Diethylamine in example 1 and di-n-propylamine are applied as organic template agent, to investigate the catalyst performance in the case of single organic formwork agent
With preparation situation, other preparation condition embodiments 1 are identical, obtain the catalyst of embodiment 2.
Embodiment 3
The step of according to embodiment 1, but 16 grams of resulting SAPO-34 molecular sieves of embodiment 1 are added in preparation step (1)
Original powder is as crystal seed；1 gram of resulting ZSM-5 molecular sieve original powder of embodiment 1 of addition is prepared and is adopted as crystal seed in step (3)
The SAPO-34 molecular sieve and ZSM-5 molecular sieve synthesized with crystal seed method, other preparation conditions are same as Example 1, obtain embodiment
3 catalyst.
Embodiment 4
In the autoclave with stirring, 1 liter of deionized water is added in (1), by 200 grams of boehmites (ibid) and 250 grams
Diethylamine (ibid) hybrid reaction 2 hours at 140 DEG C, then with 300 grams of phosphoric acid (ibid), 50 grams of silica gel (ibid), mixing is stirred
Mixing is at the slurry of pH value 6.9, and after 40 DEG C are aged 20 hours, then hydrothermal crystallizing 60 hours at 190 DEG C, filtering obtain
SAPO-34 molecular screen primary powder A, crystallization mother liquor are used for the preparation of step (2) and (3).
(2) it by above-mentioned SAPO-34 molecular screen primary powder A after 500 DEG C roast 2 hours, is filtered with above-mentioned steps (1) resulting
In crystallization mother liquor, 20 grams of tetraethyl ammonium hydroxides (chemically pure reagent, Beijing chemical reagent company) and 1 liter of deionized water are added
Mixing, the modified SAPO-34 molecular sieve B of secondary synthesis, institute after filtering is obtained by filtration in hydro-thermal process 30 hours at 175 DEG C
It obtains mother liquor and is used to prepare step (3).
(3) in above-mentioned steps (1) and (2) are mother liquid obtained, 2 grams of boehmites (ibid) are added, at 140 DEG C after mixing
Lower reaction 4 hours, then ZSM- was obtained by filtration through at 180 DEG C times hydrothermal crystallizing 20 hours after mix with 200 grams of silica solution (ibid)
5 molecular screen primary powder C, filtered mother liquor are used to prepare step (5).
(4) by the resulting ZSM-5 molecular sieve original powder C of above-mentioned steps (3) and 5 grams of boron oxides (chemically pure reagent, Beijing chemical industry
Reagent Company) after ground and mixed is uniform, in 450 DEG C of tube furnace, 50 Grams Per Hour of water vapour weight flow rate, hydro-thermal process 3 is small
When, the modified B-ZSM-5 molecular sieve D powder of boron compound is obtained, tail gas condensing liquid is used to prepare step (5).
(5) by modified SAPO-34 molecular sieve B powder and B-ZSM-5 molecular sieve D powder obtained by step (2) and step (4),
With remaining after 500 grams of aluminium sol adhesives (ibid), the crystallization of 450 grams of kaolin (ibid) and above-mentioned molecular sieve and secondary synthesis
The condensate liquid containing organic formwork agent in remaining mother liquor and crystallization, modification, roasting and spray process is sufficiently mixed, addition
500 grams of deionized waters, after grinding mashing to solids partial size≤2 micron of 92v%, in 620 DEG C of intake air temperature, exhaust temperature
Microballoon is shaped in 285 DEG C of disk-type spray dryer, tail gas condensing liquid is used for next group of sample mashing preparation.
(6) 20 liters 85 DEG C of deionized water of the catalyst microspheres after above-mentioned spray shaping is respectively washed 15 points in two times
Clock, calcination activation 1 hour (oxygen volumetric concentration 15v%) under 600 DEG C of oxidizing atmosphere obtain the catalyst of embodiment 4.
Embodiment 5
The present embodiment compares the catalyst preparation overall process emission behaviour in Examples 1 to 4 and comparative example 1~4,
The catalyst preparation overall process includes synthesis, crystallization, filtering, mashing, the drying of ion exchange and catalyst of molecular sieve
Molding and washing, dry, calcination activation, are shown in Table 1.
The preparation overall process unit product of 1~4 catalyst of table 1, Examples 1 to 4 and comparative example discharges comparison:
By in table 1 as it can be seen that in the catalyst preparation overall process of Examples 1 to 4, except containing micro Na2O and Trace Silicon aluminum precipitation
Object can not discharge the reluctant sewage containing organic matter and salt, ammonia nitrogen outside reuse saliferous washing water substantially, this is subsequent dirt
Water process is brought conveniently, also makes whole preparation process more green, environmentally friendly.
Embodiment 6
The present embodiment is using instrumental analysis characterizing method described in specific embodiment, to above-described embodiment and comparison
The catalyst sample of example carries out analysis detection, with the difference of comparative example 1~4 and 1~4 catalyst of comparative example on physico-chemical property
Data that are different, being shown in Table in 2.
The physico-chemical property comparative situation of 1~4 catalyst of table 2, Examples 1 to 4 and comparative example:
Embodiment 7
Catalyst sample obtained in Examples 1 to 4 and comparative example 1~4 is subjected to the micro- of preparing olefin by conversion of methanol reaction
It is anti-to evaluate, through 600 DEG C before evaluating catalyst, after 100% steam aging is handled 4 hours, respectively by the particle of 5 gram of 20~40 mesh
Catalyst sample is fitted into micro- anti-fixed-bed micro-reactor, is led to nitrogen activation 1 hour at 600 DEG C, is then cooled to
460 DEG C are reacted.It is fed using micro pump, 40% methanol aqueous solution, methanol weight air speed 2.0 hours-1, react 4 hours
Sampling analysis afterwards, the results are shown in Table 3.
The MTO of 1~4 catalyst of table 3, Examples 1 to 4 and comparative example reacts micro anti-evaluation situation:
It can compare and find out from table 3, the catalyst sample of Examples 1 to 4 has more preferable in an activity cycle
Activity stability and selectivity of product, this when using recirculating fluidized bed reaction-regeneration system, is conducive in industrial application
The intensity of circulation for reducing catalyst, reduces the abrasion of catalyst.
Embodiment 8
This example demonstrates that catalyst of the present invention and comparative catalyst are used for the effect of MTO reaction.In small-sized fixed fluidisation
In bed reactor, catalysis methanol is carried out to catalyst sample obtained in above-described embodiment and comparative example and converts light olefin processed
Test.Cracked gas product is measured in reaction evaluating and it is formed with gas chromatographic analysis, and the water sample after gas-liquid separation uses gas phase
Chromatograph measurement methanol and water soluble products content, evaluation result are shown in Table 4.
The fixed fluidized bed reaction evaluating situation of MTO of 1~4 catalyst of table 4, Examples 1 to 4 and comparative example:
Through 600 DEG C before evaluating catalyst, 100% steam aging is handled 4 hours, 200 grams of catalyst sample-loading amount.React item
Part is normal pressure, 460 DEG C of reaction temperature, 680 DEG C of regeneration temperature.Material benzenemethanol is to analyze pure, water vapour stripping charging, water and methanol
Mass ratio is 0.2, and charging methanol weight (hourly) space velocity (WHSV) is 2.0 hours-1。
Moles of methanol/investment reaction moles of methanol of the conversion ratio %=reaction consumption of methanol
It as can be seen from Table 4, can be more effectively using catalyst of the invention compared with the catalyst of the prior art
Catalysis methanol is converted into light olefin, and has higher ethylene+productivity of propylene.
Finally, it should be noted that the above examples are only used to illustrate the technical scheme of the present invention rather than limits, although ginseng
It is described the invention in detail according to preferred embodiment, those skilled in the art should understand that, it can be to the present invention
Technical solution be modified or replaced equivalently, and without departing from the spirit and scope of technical solution of the present invention.
Claims (9)
1. a kind of methanol light olefin catalyst, it is characterized in that becoming sodium oxide molybdena < with the group of inorganic matter dry basis
0.1m%, silica 25m%~40m%, aluminium oxide 40m%~60m%, phosphorous oxide 10m%~20m%, boron oxide 0.01m%
The water of~1m%, 30m%~40m% hydrothermal crystallizing and the Chabazite-type molecular sieve being modified through secondary synthesis, 5m%~10m%
Thermal crystallisation and through the modified bi-five-member cycle configuration type molecular sieve obtained of boron compound, 5m%~20m% aluminium sol adhesive and
Balance kaolin composition, the Chabazite-type are CHA topological structure, chemical formula mRAl17P12Si7O72, the bi-five-member cycle configuration
Type is MFI topological structure, chemical formula RnAln-BnSi96-2nO192, n < 27, wherein R is organic formwork agent, 85~95% acid
Amount is distributed in the Hammett acid strength function range of Ho+4.8~-3.0；Ten-ring/twelve-ring duct volume in catalyst
Than being 10~20: 1；With 5 nanometers of aperture < of mesoporous system abundant and step Jie's micropore distributed architecture, the step is situated between
Micropore distributed architecture are as follows: 40v%~60v% of 0.43 nanometer of aperture Kong Rongzhan total pore volume of ten-ring, the 0.5 of twelve-ring are received
Rice mesopore volume accounts for 1v%~10v% of total pore volume, 2~5 nanometers of smaller aperture due of mesoporous Kong Rong account for the 30v% of total pore volume~
The mesoporous Kong Rong of the larger aperture that 5 nanometers of 50v%, > accounts for 2v%~8v% of total pore volume；The catalyst is applied to the light alkene of methanol system
In the reaction of hydrocarbon.
2. methanol light olefin catalyst according to claim 1, it is characterised in that the average grain diameter of catalyst microspheres is 55
~75 microns and abrasion index are 0.5m%~1.8m%.
3. a kind of preparation method of methanol light olefin catalyst, it is characterized in that the catalyst preparation includes the following steps:
(1) mol ratio SiO is pressed2/Al2O3=0.7~1.1, P2O5/SiO2=0.7~1.1, H2O/SiO2=65~80, organic
Template R/Al2O3=0.5~2.2, first by boehmite and organic formwork agent R hybrid reaction 0.5~5 at 90~190 DEG C
Hour, then the slurry that pH value 6.4~7.5 is made is mixed with phosphoric acid, silica gel and/or silica solution, it is aged through 20 DEG C~50 DEG C
After 15~30 hours, then hydrothermal crystallizing 20~100 hours at 170 DEG C~210 DEG C, prepare unmodified Chabazite-type molecule
Sieve original powder；
(2) and above-mentioned by above-mentioned unmodified Chabazite-type molecular sieve original powder after 400 DEG C~650 DEG C roast 0.5~6 hour
The resulting crystallization mother liquor of step (1), organic formwork agent and deionized water, by molecular screen primary powder: organic formwork agent R: water=1:
0.01~1: 5~20 weight proportion mixing, hydro-thermal process 15~30 hours, obtains through secondary synthesis at 170 DEG C~210 DEG C
Modified Chabazite-type molecular sieve；
(3) SiO is pressed2/Al2O3=30~90, organic formwork agent R/Al2O3=0.5~40, H2O/SiO2=5~15 mole match
Than, it will be reacted 0.5~5 hour at 90 DEG C~190 DEG C after the mother liquid obtained mixing with boehmite of above-mentioned steps (1) and (2),
Through hydrothermal crystallizing 10~40 hours at 130 DEG C~200 DEG C after mixing again with silica gel and/or silica solution, unmodified double five are obtained
Ring structure type molecular screen primary powder；
(4) molecular screen primary powder: boride: water=1: 0.01~0.5: 0.1~2 weight proportion is pressed, step (3) is resulting not
Modified bi-five-member cycle configuration type molecular screen primary powder obtains hydro-thermal process 0.5~4 hour at 350 DEG C~600 DEG C through boride
Modified bi-five-member cycle configuration type molecular sieve；
(5) by modified molecular sieve obtained by step (2) and step (4), and aluminium sol adhesive, kaolin and deionized water,
By after the concentration of slurry of dry weight content 25m%~40m%, with the crystallization and secondary synthesis of above-mentioned molecular sieve mother liquor and
Condensate liquid in crystallization, modification, roasting and spray process is sufficiently mixed, the solids of grinding mashing to 90v%~95v%
Behind partial size≤2 micron, 350 DEG C~650 DEG C of intake air temperature, 150 DEG C~350 DEG C of exhaust temperature spray drying tower in be shaped to
Microballoon；
(6) catalyst microspheres after spray shaping are washed with 30 DEG C~90 DEG C of deionized water to the Na of microspheres with solid2O <
After 0.1m%, the calcination activation 0.5~4 hour under 400 DEG C~650 DEG C of oxidizing atmosphere.
4. a kind of preparation method of methanol light olefin catalyst according to claim 3, it is characterised in that the mould
Plate agent be nitrogen-containing organic compound: diethylamine, triethylamine, n-propylamine, isopropylamine, Tri-n-Propylamine, tri-isopropyl amine, di-n-propylamine,
Diisopropylamine, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, 1,6- hexamethylene diamine, cyclohexylamine, beautiful jade,
Ethanol amine, diethanol amine, triethanolamine, N ', N ', N, one of N- tetramethyl -1,6- hexamethylene diamine or any several mixing
Object.
5. a kind of preparation method of methanol light olefin catalyst according to claim 4, it is characterised in that described has
Machine nitrogenous compound is one of diethylamine, triethylamine, di-n-propylamine, tetraethyl ammonium hydroxide or a variety of.
6. a kind of preparation method of methanol light olefin catalyst according to claim 3, it is characterised in that the boron
Compound is one of boron oxide, boric acid, ammonium borate, boron phosphate or a variety of.
7. a kind of method for carrying out methanol light olefin using catalyst described in claim 1, it is characterised in that anti-in fluidized bed
It answers in device, methanol is in 350 DEG C~650 DEG C of reaction temperature, 0.01~10MPa of reaction pressure, weight space velocity 0.1~50 hour-1's
Under the conditions of contacted with catalyst and be converted into light olefin, into making charcoal in 550 DEG C~850 DEG C of regenerator after catalyst microspheres inactivation
It is returned in fluidized-bed reactor after regeneration and continues to participate in reaction.
8. a kind of method of methanol light olefin according to claim 7, it is characterised in that the reaction temperature is 400
DEG C~550 DEG C, reaction pressure be 0.1~2.5MPa, weight space velocity is 1~10 hour-1, 580 DEG C~780 DEG C of regenerator temperature.
9. a kind of method of methanol light olefin according to claim 7, it is characterised in that addition water vapour or indifferent gas
Body divides to adjust methanol charging.
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| CN108911990B (en) * | 2018-05-09 | 2021-04-06 | 南京圆点环境清洁技术有限公司 | Reduction and recycling treatment process for methanol-to-olefin SMTO catalyst production mother liquor |
| CN109772476B (en) * | 2019-03-18 | 2021-12-03 | 新兴能源科技有限公司 | Method for recovering fine powder of waste molecular sieve catalyst of DMTO device and application |
| CN114433152B (en) * | 2020-10-31 | 2023-09-01 | 中国石油化工股份有限公司 | Grading method of vanadium phosphorus oxide catalyst |
| CN115703071A (en) * | 2021-08-05 | 2023-02-17 | 中国石油化工股份有限公司 | Aromatic methylation catalyst and preparation method and application thereof |
| CN116173934B (en) * | 2023-04-24 | 2023-07-28 | 浙江晟格生物科技有限公司 | Preparation method of silicon-aluminum-boron solid catalyst applied to preparation of plant galactose |
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Effective date of registration: 20210826 Address after: 201208 room 118, building 20, No. 1-42, Lane 83, Hongxiang North Road, Lingang New Area, China (Shanghai) pilot Free Trade Zone, Pudong New Area, Shanghai Patentee after: Runhe Kehua catalyst (Shanghai) Co.,Ltd. Address before: Room 401, unit 1, building 4, Jiangshan Ruicheng garden, Jiangshan Road, Qingdao Economic and Technological Development Zone, Qingdao, Shandong 266500 Patentee before: Zhuo Runsheng |