CN101940944B - Method for preparing formed molecular sieve catalyst, and product obtained by method and application thereof - Google Patents
Method for preparing formed molecular sieve catalyst, and product obtained by method and application thereof Download PDFInfo
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- CN101940944B CN101940944B CN2010102180142A CN201010218014A CN101940944B CN 101940944 B CN101940944 B CN 101940944B CN 2010102180142 A CN2010102180142 A CN 2010102180142A CN 201010218014 A CN201010218014 A CN 201010218014A CN 101940944 B CN101940944 B CN 101940944B
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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
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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
- Y02P30/20—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
The invention relates to a method for preparing a formed molecular sieve catalyst from slurry formed by crystallizing a molecular sieve, and a product obtained by the method and application thereof. Particularly, a molecular sieve product and crystallization slurry are separated from the slurry formed by crystallizing the molecular sieve, the crystallization slurry is mixed with a modified molecular sieve crystal and a binder to obtain catalyst slurry, and the catalyst slurry is formed to prepare the formed molecular sieve catalyst. In the method, due to the reutilization of the crystallization slurry, investment is saved, and environment is protected; simultaneously, the molecular sieve crystal is modified before the mixing step, so that a mode of processing the molecular sieve is more flexible.
Description
Technical field
The present invention relates to the molecular sieve field, product that relate more specifically to a kind of method of utilizing molecular sieve crystallization slurries, obtains through this method and uses thereof.
Background technology
The crystallization slurries of molecular sieve are generally discarded or wherein individual substance reclaimed by directly, and this has caused the very big wasting of resources and environmental pollution.If can utilize again, then not only have economic interests, and environmental protection is also had contribution it.
Chinese patent ZL98119914 discloses a kind of preparation method of catalyst of cracking petroleum, and this method comprises molecular sieve pulp, aluminium colloidal sol, boehmite, clay and inorganic acid making beating mixed processes catalyst slurry, then spray-drying.Chinese patent ZL00103386 discloses a kind of preparation method of catalytic cracking catalyst, and this method comprises molecular sieve pulp, aluminium colloidal sol, boehmite, clay and inorganic acid mixed processes catalyst slurry, then spray-drying.Chinese patent ZL01100019 discloses a kind of preparation method of catalytic cracking catalyst, and this method comprises molecular sieve pulp, boehmite, clay and inorganic acid making beating mixed processes catalyst slurry, then spray-drying.In the above-mentioned several patents, the molecular sieve pulp of indication is the molecular sieve pulp of molecular sieve solid powder and water making beating preparation, is not the slurries of the synthetic usefulness of molecular sieve itself.
Chinese patent ZL 00137233 discloses a kind of preparation method of zeolite catalyst, and this method is not for separating catalyst with slurries, and the suspension and the oligomeric Ludox that form during directly with synthetic zeolite are mixed with aqueous dispersions, carry out spray-drying then.Patent application CN 101121148A discloses a kind of direct forming method of fluidized reaction catalyst that contains molecular sieve; Slurries when this method adopts molecular sieve synthetic; Do not carry out molecular sieve and separate, directly in slurries, add materials such as binding agent, matrix and mix, then spray-drying.Above-mentioned prior art has all adopted the synthetic slurries of molecular sieve itself, has not all directly carried out molecular sieve moldedly through separating, and this straight forming method owing to do not separate template expensive in the crystallization slurries, causes production cost high on the one hand; Owing to do not isolate synthetic molecular sieve, cause to carry out modification to it and handle on the other hand, as carry out roasting, metal-modified and/or hydrogen modification processing.
Therefore, need a kind of slurries that can either utilize again after the molecular sieve crystallization, can carry out the method that modification is in advance handled to molecular sieve as required again simultaneously.
Summary of the invention
An object of the present invention is to provide a kind of can carrying out molecular sieve as required after modification handles, utilize slurries after the molecular sieve crystallization to be used for the method for shaping of catalyst, this method has been saved resource, has protected environment, has reduced cost.
In one aspect, the invention provides a kind of method of utilizing the slurry preparation molded molecular sieve catalyst after the molecular sieve crystallization, this method may further comprise the steps:
A) isolated molecule sieve from the slurries after the molecular sieve crystallization is to obtain molecular sieve and crystallization slurries;
B) isolated molecular sieve being carried out modification handles;
C) molecular sieve after crystallization slurries and modification are handled mixes, and adds binding agent, to obtain catalyst pulp;
D) catalyst pulp is carried out moulding and obtains molded molecular sieve catalyst.
In a preferred implementation, molecular sieve is aluminium silicophosphate (SAPO) molecular sieve.
In further preferred embodiment, the SAPO molecular sieve is SAPO-34, SAPO-5, SAPO-18, SAPO-44, SAPO-56 molecular sieve or their homobium.
In a preferred implementation, the crystallization slurries are to separate the upper strata suspension that obtains after the molecular sieve crystallization.
In a preferred implementation, molecular sieve content is 0-50%.
In a preferred implementation, the molecular sieve modified processing in the step b) is to carry out metal-modified or the hydrogen modification.
In a preferred implementation, the forming method in the step d) is a spray-drying.
In a preferred implementation, binding agent is oxide, the colloidal sol of silicon, aluminium, magnesium or zirconium, or their mixture.
In a preferred implementation, before step c), further comprise the crystallization slurries are handled to reclaim template.
In further preferred embodiment, be to carry out rectifying or distillation to the processing of crystallization slurries.
In a preferred implementation, comprise that further the preformed catalyst that step d) is obtained carries out roasting to obtain removing the preformed catalyst of template.
In further preferred embodiment, roasting is under 500-600 ℃, to carry out 3-6 hour.
In a preferred implementation, in the blend step of step c), also add matrix.
In further preferred embodiment, matrix is a kind of in amorphous silicon aluminium oxide, unformed phosphorus sieve and silica-sesquioxide, kaolin, metakaolin, carclazyte or their mixture.
On the other hand, the invention provides molecular sieve molded catalyst through method for preparing.
In yet another aspect, the invention provides the purposes of above-mentioned preformed catalyst, as the catalyst in the reaction of producing low-carbon alkene with oxygen-containing compound material.
In a preferred implementation, contain the oxygen raw material and be selected from methyl alcohol, dimethyl ether or its mixture any.
In a preferred implementation, low-carbon alkene is ethene and/or propylene.
In the present invention,, not only saved processing again, and saved the consumption of inorganic acid or inorganic base, saved investment, protected environment the crystallization slurries owing to utilize crystallization slurries behind the isolated molecule sieve as the bulking agent of molecular sieve and binding agent, matrix.
The molecular sieve that in blend step, uses can be this area molecular sieve commonly used, for example, and SAPO-34; SAPO-5, SAPO-18, SAPO-44; SAPO-56 and their homobium etc.; And can handle before the blend step, like processing such as washing, dry, roasting or metal-modified, hydrogen modifications, it is more flexible to handle the processing mode that makes to molecular sieve in advance.
Description of drawings
Fig. 1 is the XRD figure spectrum according to the synthetic molecular sieve ML-0 of one embodiment of the invention.
The SEM picture of the molecular sieve ML-0 that Fig. 2 synthesizes for the present invention.
Fig. 3 is the stereoscan photograph of synthetic according to a further embodiment of the invention molecular sieve ML-3.
The specific embodiment
The present invention utilizes to prepare the method for molecular sieve catalyst the slurries after the molecular sieve crystallization again.In the inventive method; Mix by a certain percentage with the remaining suspension liquid after the molecular sieve crystallization (being the crystallization slurries) and through molecular sieve crystal, binding agent and matrix components after the modification processing, for example the shared mass ratio of molecular sieve crystal is 0-40%; The binding agent proportion is about 5-20%; The matrix proportion is 40-80%, carries out spray-drying after mixing, and obtains molded molecular sieve catalyst.
Owing to contain the component of periodic arrangement in sial phosphorus molecular sieve skeleton in the crystallization slurries that molecular sieve is produced when synthetic; Can have good compatibility with it with molecular sieve as solvent, guarantee that also molecular sieve has good dispersiveness in mixed solution simultaneously.The crystallization slurries contain all or part of component like materials such as aluminium colloidal sol, boehmite, clays as binding agent, carrier in addition; This also makes crystallization slurries and binding agent, carrier have compatibility preferably, can guarantee that also binding agent, carrier have good dispersiveness in mixed solution simultaneously.The crystallization slurries play increase-volume or compatible role between molecular sieve and binding agent, carrier, increased the active force between binding agent and the molecular sieve.The crystallization slurries that the inventive method is produced when utilizing molecular sieve synthetic are as the bulking agent of molecular sieve and binding agent, carrier; Realized the recycle of unreacting material on the one hand; Avoided the discharging of crystallization slurries; Realized the zero-emission of catalyst preparation process wastewater treatment, saved postprocessing working procedures the crystallization slurries; Saved the practicality of binding agent and inorganic acid on the other hand.
More specifically; Contain and unreacted Ludox and aluminium colloidal sol in crystallization slurries when the inventive method utilizes molecular sieve synthetic; Make the crystallization slurries have simultaneously binding agent and dispersant effect; Help the even dispersion to molecular sieve and matrix, the binding agent in the slurries helps strengthening the wear resistance of molecular sieve.Because the aluminium silicophosphate molecular sieve skeleton is the AlO of periodic arrangement
2 -, PO
2 +, SiO
2, having good similar compatibility property with composition in the crystallization slurries, the active force between binding agent and the molecular sieve is stronger, helps the spray drying forming catalyst and has than uniform grain sizes and distribute and sphericity preferably.On the other hand, this method has been saved the postprocessing working procedures to the crystallization slurries, has saved investment, has reduced environmental pollution.
Make more flexible through separation, drying, roasting to the processing mode of catalyst; Such as modification to molecular sieve; Not only can adopt metal salt solution is joined the isomorphous replacement of in hydrothermal crystallization process, carrying out metal oxide in the crystallization stoste, also can prepare molecular sieve earlier and carry out modification through the impregnating method again.
After molecular sieve crystal separates, can accurately control the composition of molecular screen primary powder, crystallization slurries, binding agent and matrix components when mixing with the crystallization slurries again.
In the present invention; The crystallization slurries that use can be that molecular sieve prepares the crystallization slurries that obtain in the process, for example, and the upper strata suspension after the molecular sieve crystallization; The cleaning solutions that obtain during the molecular sieve crystal washing etc., preferred crystallization slurries are the upper strata suspension through separating after the molecular sieve crystallization.
In the present invention, synthetic molecular sieve is preferably aluminium silicophosphate molecular sieve or its metal-modified, hydrogen modified molecular screen, SAPO-34 more preferably, SAPO-5, SAPO-18, SAPO-44, SAPO-56 molecular sieve or their homobium.
In the present invention, molecular sieve content is preferably 0-50%, and more preferably 10-40% most preferably is 20-40%, is preferably 30-40% especially.
In the present invention, before molecular sieve being carried out the modification processing, can wash drying and roasting to the molecular sieve crystal after separating.Its modification is handled for example for carrying out metal-modified to molecular sieve crystal or carrying out the hydrogen modification.
After molecular sieve crystal separates, can also handle the crystallization slurries, such as isolating template, can reclaim the template of high price like this through processing, practiced thrift cost.In addition, after handling crystallization slurries recovery template, can avoid the nitrogen oxides pollution environment that the template decomposition is produced when roasting.To the recovery to template that is treated to of crystallization slurries, the recovery method that is adopted is rectifying or distillation.
In the present invention, the binding agent of use can be mentioned the oxide of silicon, aluminium, magnesium or zirconium, or their colloidal sol; Or their mixture; For example be the oxide of colloidal sol or silicon, the oxide of aluminium colloidal sol or aluminium, for example boehmite, magnesia or zirconia.
In the present invention, when adding bonding, can add matrix, use therein matrix can be mentioned amorphous silicon aluminium oxide, unformed phosphorus sieve and silica-sesquioxide, kaolin, metakaolin, carclazyte or their mixture.
In the present invention, after 500-600 ℃ of roasting of the preformed catalyst of preparation process, as containing the catalyst that oxygen raw material such as methyl alcohol or dimethyl ether are produced low-carbon alkene.
Enumerate embodiment below the present invention is explained, but the present invention does not receive the restriction of following instantiation.
Embodiment
Synthesizing of embodiment 1:SAPO-34 molecular sieve
With triethylamine (TEA) is template, with 3.0TEA: 0.6SiO
2: P
2O
5: Al
2O
3: 50H
2O mole proportioning is mixed each component according to a definite sequence, and the 200mL liner of packing into after fully stirring is in the crystallizing kettle of PPL (contraposition polyphenyl), under self pressure, 200 ℃ of following crystallization 48 hours, obtains the SAPO-34 molecular sieve pulp.After separating, obtain molecular sieve crystal and crystallization slurries.Molecular sieve crystal is carried out XRD determining (referring to Fig. 1), confirm as the SAPO-34 molecular sieve, it is numbered ML-0.
Embodiment 2: the preparation of molded molecular sieve catalyst ML-1
Crystallization slurries among the embodiment 1 distill processing, to reclaim template wherein.Molecular sieve crystal among the embodiment 1 washs, drying and roasting, obtains pure SAPO-34 molecular sieve crystal.The crystallization slurries of handling are mixed in following ratio with molecular sieve crystal, boehmite (as binding agent) and carclazyte (as matrix); Mixed proportion is the crystallization slurries: molecular sieve: boehmite: carclazyte=6: 1: 0.8: 2; Carry out spray-drying after stirring; Obtain the molecular sieve catalyst of moulding, it is numbered ML-1.
Embodiment 3: the preparation of molded molecular sieve catalyst ML-2
Molecular sieve crystal among the embodiment 1 washs, drying and roasting, obtains pure SAPO-34 molecular sieve crystal.The molecular sieve crystal that obtains is mixed with crystallization slurries, Ludox and kaolin among the embodiment 1; Mixed proportion is the crystallization slurries: molecular sieve: Ludox: kaolin=6: 1.2: 0.8: 2; Carry out spray-drying after stirring; Obtain the molecular sieve catalyst of moulding, it is numbered ML-2.
Embodiment 4: the preparation of molded molecular sieve catalyst ML-3
Molecular sieve crystal among the embodiment 1 washs, drying and roasting, obtains pure SAPO-34 molecular sieve crystal.This molecular sieve crystal was flooded in zinc nitrate solution 24 hours, take out the ZnSAPO-34 that the back roasting obtains the Metal Zn modification.Crystallization slurries among the embodiment 1 carry out rectifying, reclaim template wherein.Crystallization slurries, aluminium colloidal sol and diatomite after the metal modified molecular screen crystal that obtains and the processing are mixed; Mixed proportion is the crystallization slurries: molecular sieve: aluminium colloidal sol: diatomite=7: 1.2: 0.8: 2.2 stir the back spray-drying; Obtain the molecular sieve catalyst of moulding, it is numbered ML-3.
Embodiment 5: the preparation of molded molecular sieve catalyst ML-4
Molecular sieve crystal among the embodiment 1 washs, drying and roasting, obtains pure SAPO-34 molecular sieve crystal.This molecular sieve crystal was flooded 24 hours in the nitric acid ammonia solution, take out the HSAPO-34 that the back roasting obtains the hydrogen modification.Crystallization slurries among the embodiment 1 carry out rectifying, reclaim template wherein.Crystallization slurries, aluminium colloidal sol and diatomite after the hydrogen modified molecular screen crystal that obtains and the processing are mixed; Mixed proportion is the crystallization slurries: molecular sieve: aluminium colloidal sol: diatomite=7: 1: 0.8: 2.2; The back spray-drying stirs; Obtain the molecular sieve catalyst of moulding, it is numbered ML-4.
Embodiment 6: the evaluation of molecular sieve molded catalyst
Above-mentioned molecular sieve molded catalyst ML-1～4 usefulness micro anti-evaluation devices are estimated.Loaded catalyst is 1g, and mass space velocity is 3h
-1, reactant is a methyl alcohol, nitrogen is done carrier gas.450 ℃ of reaction temperatures, pressure is 0.2Mpa, product gas is formed with gas chromatographic analysis.Evaluation result is seen table 1.
Table 1
Can find out that in the evaluation result of last table 1 adopt the used forming method of the present invention, (C2～C4) olefine selective is good, and is equal or higher with the performance of existing product for total low-carbon (LC) of the catalyst of acquisition.And the present invention has carried out utilizing to this material of regarding waste disposal before of crystallization slurry again, has not only practiced thrift cost of material, has more reduced the expense of environmental treatment, says it also is to have improved environment from another aspect.And method of the present invention has not only been utilized the slurries after the molecular sieve crystallization again, can carry out modification in advance to molecular sieve as required again simultaneously and handle.
Though illustrated and described these embodiments of the present invention, the present invention is not limited to these specific embodiment, under the situation that does not deviate from scope of the present invention, those skilled in the art can form various distortion and/or be equal to replacement.
Claims (14)
1. method of utilizing the slurry preparation molded molecular sieve catalyst after the molecular sieve crystallization said method comprising the steps of:
A) isolated molecule sieve from the slurries after the said molecular sieve crystallization is to obtain molecular sieve and crystallization slurries;
B) isolated molecular sieve being carried out modification handles;
C) molecular sieve after said crystallization slurries and modification are handled mixes, and adds binding agent, to obtain catalyst pulp;
D) said catalyst pulp is carried out moulding and obtains molded molecular sieve catalyst,
Wherein, before step c), further comprise said crystallization slurries are handled to reclaim template wherein.
2. method according to claim 1, wherein, isolated molecular sieve is the SAPO molecular sieve.
3. method according to claim 2, wherein, said SAPO molecular sieve is SAPO-34, SAPO-5, SAPO-18, SAPO-44, SAPO-56 molecular sieve or their homobium.
4. method according to claim 1, wherein, said crystallization slurries are to separate the upper strata suspension that obtains after the molecular sieve crystallization.
5. method according to claim 1, wherein, the molecular sieve modified processing in the said step b) is to carry out metal-modified or the hydrogen modification.
6. method according to claim 1, wherein, the forming method in the said step d) is a spray-drying.
7. method according to claim 1, wherein, said binding agent is the oxide of silicon, aluminium, magnesium, zirconium or the colloidal sol that is formed by its oxide.
8. method according to claim 1, wherein, said processing to the crystallization slurries is to carry out rectifying or distillation.
9. method according to claim 1 wherein, comprises that further the molded molecular sieve catalyst that step d) is obtained carries out roasting, to obtain removing the molded molecular sieve catalyst of template.
10. method according to claim 9, wherein, said roasting is under 500-600 ℃, to carry out 3-6 hour.
11. method according to claim 1 wherein, in the blend step of step c), also adds matrix.
12. method according to claim 11, wherein, said matrix is a kind of in amorphous silicon aluminium oxide, unformed phosphorus sieve and silica-sesquioxide, kaolin, metakaolin, carclazyte or their mixture.
13. molded molecular sieve catalyst through each described method preparation among the claim 1-12.
14. the application of molded molecular sieve catalyst according to claim 13; Produce the catalyst in the reaction of low-carbon alkene as containing the oxygen raw material; Wherein, the said oxygen raw material that contains is to be selected from methyl alcohol, dimethyl ether or its mixture any, and said low-carbon alkene is ethene and propylene.
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| CN102430425A (en) * | 2011-09-01 | 2012-05-02 | 神华集团有限责任公司 | Pre-treatment method for molecular sieve catalyst forming, forming method and catalyst product |
| CN103170361B (en) * | 2011-12-23 | 2015-09-23 | 正大能源材料(大连)有限公司 | SAPO-34 Zeolite synthesis liquid is for the production of the method for methanol-to-olefin catalyst |
| CN103833047B (en) * | 2014-03-28 | 2015-06-24 | 神华集团有限责任公司 | SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same |
| CN110314699B (en) * | 2018-03-30 | 2021-11-16 | 中国石油化工股份有限公司 | Preparation method of titanium silicalite molecular sieve catalyst |
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| US6864202B2 (en) * | 2002-09-16 | 2005-03-08 | Indian Oil Corporation Limited | Process for preparing sodium silicate alkali solution depleted of sodium salt and enriched in silica |
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