CN105800647A - Method for restoring crystallinity of degenerated filter cake of molecular sieve for preparing low-carbon olefin from methanol - Google Patents
Method for restoring crystallinity of degenerated filter cake of molecular sieve for preparing low-carbon olefin from methanol Download PDFInfo
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- CN105800647A CN105800647A CN201610098819.5A CN201610098819A CN105800647A CN 105800647 A CN105800647 A CN 105800647A CN 201610098819 A CN201610098819 A CN 201610098819A CN 105800647 A CN105800647 A CN 105800647A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention belongs to the technical field of molecular sieve synthesis, and in particular relates to a method for restoring the crystallinity of a degenerated filter cake of a molecular sieve for preparing low-carbon olefin from methanol. The method comprises: performing hydro-thermal synthesis according to a synthesis process of the molecular sieve for preparing low-carbon olefin from methanol, recovering a volatile template agent after complete crystallization, then performing solid-liquid separation on a crystallized raw stock to obtain a recovered mother solution and a filter cake, and preserving the filter cake after washing; after the filter cake is degenerated, adding the degenerated filter cake into the mother solution, and finally adding the volatile template agent to prepare an initial gel mixture; crystallizing the initial gel mixture in a high-pressure crystallization kettle to obtain a molecular sieve crystallization solution; and performing solid-liquid separation on the molecular sieve crystallization solution to obtain a filter cake, washing the filter cake to obtain a molecular sieve filter cake with restored crystallinity, and performing drying to obtain the molecular sieve. By implementation of the method provided by the invention, the crystallinity of the degenerated molecular sieve filter cake can be basically restored to the level before degeneration, so that the production loss is greatly reduced, and the continuity of molecular sieve production is effectively guaranteed.
Description
Technical field
The invention belongs to Zeolite synthesis technical field, be specifically related to a kind of method recovering the rotten filter cake degree of crystallinity of preparing light olefins from methanol molecular sieve.
Background technology
The energy crisis faced around the whole world in recent years, it is proposed that one solve energy problem new ideas: methanol economy, using its as reply after the oil gas epoch energy problem a solution route.And coal-based methanol producing light olefins (MTO) technique is the important content of methanol economy, being the powerful measure and the path that solve China's oil scarcity of resources, its core is in that the research and development of MTO catalyst.
At present, industrialized MTO catalyst major part is using SAPO-34 molecular sieve or SAPO-34 and SAPO-18 composite molecular screen as former powder, and about the synthesis technique of above two molecular sieve, researcher is done a lot of work, including the exploration of optimum process condition, recycling of mother solution etc..In actual industrial operation, for various reasons, the filter cake that crystallization molecular sieve pulp completely is formed after solid-liquid separation and washing, do not dry in time, placing after a period of time, the degree of crystallinity of molecular sieve there will be the decline of cliff of displacement formula, and the character of molecular sieve filter cake also goes bad the faint yellow material for crystal clear by having good thixotropic white filter cake, and prolongation over time, the degree of crystallinity of molecular sieve filter cake declines can be more and more faster.It is understood that, molecular sieve is a kind of metasable state material, there is trend under suitable conditions that change to stable state, the filter cake that molecular sieve pulp is formed after solid-liquid separation, need to pass through washing and be removed by the mother solution remained in filter cake, and in the commercial production of reality, a small amount of residual mother liquor in filter cake thoroughly can not be removed, which forms is situated between surely stablizes the essential condition of inversion of phases in opposite directions, can spread gradually afterwards, until major part filter cake goes bad.These rotten filter cake degree of crystallinity become less than 50% before going bad, and physical property there occurs the change of matter, and performance also significantly declines, and brings immeasurable loss to production.
Summary of the invention
It is an object of the invention to provide a kind of method recovering the rotten filter cake degree of crystallinity of preparing light olefins from methanol molecular sieve, greatly reduce production loss, be effectively guaranteed the seriality that molecular sieve produces.
The method of the rotten filter cake degree of crystallinity of recovery preparing light olefins from methanol molecular sieve of the present invention, step is as follows:
(1) carry out Hydrothermal Synthesis by the synthesis technique of preparing light olefins from methanol molecular sieve, after crystallization is complete, reclaims volatility template, afterwards crystallization oleo stock is carried out solid-liquid separation and must reclaim mother solution and filter cake, preserve after filter cake is scrubbed；
(2) after filter cake is rotten, rotten filter cake is joined in mother solution, be eventually adding volatility template, prepare initial gel mixture；
(3) initial gel mixture is placed in crystallization in high pressure crystallizing kettle, obtains Crystallization of Zeolite liquid；
(4) through solid-liquid separation, Crystallization of Zeolite liquid being obtained filter cake, Cake Wash must recover the molecular sieve filter cake of degree of crystallinity, dries to obtain molecular sieve.
Preparing light olefins from methanol molecular sieve described in step (1) is the one in SAPO-18 molecular sieve, SAPO-34 molecular sieve or SAPO-34/SAPO-18 composite molecular screen.
Crystallization temperature described in step (3) is 170-190 DEG C.
Crystallization time described in step (3) is 12-36h.
Washing described in step (4) is to add the deionized water wash that 3 times of Crystallization of Zeolite liquid are long-pending.
Baking temperature described in step (4) is 120 DEG C.
Drying time described in step (4) is 12h.
Rotten filter cake refers to that molecular sieve XRD spectra is normal, but degree of crystallinity drops to the 5-50% before going bad.
Mother solution is originated: hydrothermal synthesis method prepares the filtrate of preparing light olefins from methanol molecular sieve recovery as mother solution.
Reclaim volatility template source: hydrothermal synthesis method is prepared after preparing light olefins from methanol Crystallization of Zeolite terminates, and the liquid mixture that condensed device reclaims when crystallizing kettle still temperature 120 DEG C is as the volatility template of recovery.
The present invention is directed to filter cake in actual industrial production and place perishable problem for a long time, it is provided that a kind of method recovering the rotten filter cake degree of crystallinity of preparing light olefins from methanol molecular sieve.Adopt the inventive method, rotten filter cake degree of crystallinity can recover to the 95-100% before rotten.
The present invention compared with prior art, has the advantages that
By the enforcement of the present invention, rotten molecular sieve filter cake degree of crystallinity can be recovered substantially to the level before rotten, greatly reduces production loss, is effectively guaranteed the seriality that molecular sieve produces.It addition, in the implementation process of the present invention, employing is the volatility template of mother solution and the recovery reclaimed after Crystallization of Zeolite, and the cost of crystallization is substantially reduced again.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of SAPO-34 molecular sieve in embodiment 1.
Fig. 2 is the X-ray diffractogram of SAPO-18 molecular sieve in embodiment 2.
Fig. 3 is the X-ray diffractogram of SAPO-34/SAPO-18 composite molecular screen in embodiment 3.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) synthesis of SAPO-34 molecular sieve
With Primogel mol ratio 2TEAOH:0.4SiO2: P2O5: Al2O3: 40H2O by meter feedstock by deionized water, aluminum source, TEAOH, phosphorus source, silicon source order be sequentially added into mixing, be sufficiently stirred for into gel, be then charged in rustless steel high pressure crystallizing kettle, crystallization 48h at 172 DEG C.After crystallization terminates, when still temperature drop to 120 DEG C, slowly open thief hatch, volatile material in still is imported in condenser, weighs after collection；After still temperature drop to room temperature, adopt sheet frame by crystallization oleo stock solid-liquid separation, collect mother solution and weigh, with deionized water, the filter cake on sheet frame is washed till neutrality, weigh after taking off the filter cake on sheet frame, taking a small amount of filter cake dry at 120 DEG C, in X-ray diffraction analysis result such as Fig. 1 shown in a, degree of crystallinity is 105%.
(2) recovery of SAPO-34 molecular sieve crystallinity
Weigh 81.6g and reclaim mother solution, add the rotten rear filter cake of 30.6g, be eventually adding the 22.8g volatile material reclaimed, stir 20min, be placed in rustless steel high pressure crystallizing kettle, 172 DEG C of crystallization 24h.After solid-liquid separation, with deionized water, solid product being washed till neutrality, dry at 120 DEG C, in X-ray diffraction analysis result such as Fig. 1 shown in b, degree of crystallinity is 104%.
Embodiment 2
(1) synthesis of SAPO-18 molecular sieve
With Primogel mol ratio 1.6R:0.5SiO2: 0.9P2O5: Al2O3: 50H2(R is N to O, N-diisopropylethylamine) by meter feedstock by deionized water, aluminum source, DIPEA, phosphorus source, silicon source order be sequentially added into mixing, be sufficiently stirred for into gel, it is then charged in rustless steel high pressure crystallizing kettle, crystallization 72h at 180 DEG C.After crystallization terminates, when still temperature drop to 120 DEG C, slowly open thief hatch, volatile material in still is imported in condenser, weighs after collection；After still temperature drop to room temperature, adopt sheet frame by crystallization oleo stock solid-liquid separation, collect mother solution and weigh, with deionized water, the filter cake on sheet frame is washed till neutrality, weigh after taking off the filter cake on sheet frame, taking a small amount of filter cake dry at 120 DEG C, in X-ray diffraction analysis result such as Fig. 2 shown in a, degree of crystallinity is 100%.
(2) recovery of SAPO-18 molecular sieve crystallinity
Weigh 89.5g and reclaim mother solution, add the rotten rear filter cake of 30.6g, be eventually adding the 24.5g volatile material reclaimed, stir 30min, be placed in rustless steel high pressure crystallizing kettle, 180 DEG C of crystallization 30h.After solid-liquid separation, with deionized water, solid product being washed till neutrality, dry at 120 DEG C, in X-ray diffraction analysis result such as Fig. 2 shown in b, degree of crystallinity is 96%.
Embodiment 3
(1) synthesis of SAPO-34/SAPO-18 composite molecular screen
With Primogel mol ratio 2TEAOH:0.4SiO2: P2O5: Al2O3: 40H2O by meter feedstock by deionized water, aluminum source, TEAOH, phosphorus source, silicon source order be sequentially added into, stirring 30min, the SAPO-18 molecular sieve (preparing in embodiment 2) of the 20% of addition aluminum source quality afterwards, continue stirring 20min and obtain crystallization gel, it is loaded in rustless steel high pressure crystallizing kettle, crystallization 36h at 175 DEG C.After crystallization terminates, when still temperature drop to 120 DEG C, slowly open thief hatch, volatile material in still is imported in condenser, weighs after collection；After still temperature drop to room temperature, adopt sheet frame by crystallization oleo stock solid-liquid separation, collect mother solution and weigh, with deionized water, the filter cake on sheet frame is washed till neutrality, weigh after taking off the filter cake on sheet frame, taking a small amount of filter cake dry at 120 DEG C, in X-ray diffraction analysis result such as Fig. 3 shown in a, degree of crystallinity is 98%.
(2) recovery of SAPO-34/SAPO-18 composite molecular screen degree of crystallinity
Weigh 90g and reclaim mother solution, add the rotten rear filter cake of 28.5g, be eventually adding the 23.4g volatile material reclaimed, stir 30min, be placed in rustless steel high pressure crystallizing kettle, 175 DEG C of crystallization 24h.After solid-liquid separation, with deionized water, solid product being washed till neutrality, dry at 120 DEG C, in X-ray diffraction analysis result such as Fig. 3 shown in b, degree of crystallinity is 94%.
Claims (7)
1. the method recovering the rotten filter cake degree of crystallinity of preparing light olefins from methanol molecular sieve, it is characterised in that step is as follows:
(1) carry out Hydrothermal Synthesis by the synthesis technique of preparing light olefins from methanol molecular sieve, after crystallization is complete, reclaims volatility template, afterwards crystallization oleo stock is carried out solid-liquid separation and must reclaim mother solution and filter cake, preserve after filter cake is scrubbed；
(2) after filter cake is rotten, rotten filter cake is joined in mother solution, be eventually adding volatility template, prepare initial gel mixture；
(3) initial gel mixture is placed in crystallization in high pressure crystallizing kettle, obtains Crystallization of Zeolite liquid；
(4) through solid-liquid separation, Crystallization of Zeolite liquid being obtained filter cake, Cake Wash must recover the molecular sieve filter cake of degree of crystallinity, dries to obtain molecular sieve.
2. the method for the rotten filter cake degree of crystallinity of recovery preparing light olefins from methanol molecular sieve according to claim 1, it is characterised in that the preparing light olefins from methanol molecular sieve described in step (1) is the one in SAPO-18 molecular sieve, SAPO-34 molecular sieve or SAPO-34/SAPO-18 composite molecular screen.
3. the method for the rotten filter cake degree of crystallinity of recovery preparing light olefins from methanol molecular sieve according to claim 1, it is characterised in that the crystallization temperature described in step (3) is 170-190 DEG C.
4. the method for the rotten filter cake degree of crystallinity of recovery preparing light olefins from methanol molecular sieve according to claim 1, it is characterised in that the crystallization time described in step (3) is 12-36h.
5. the method for the rotten filter cake degree of crystallinity of recovery preparing light olefins from methanol molecular sieve according to claim 1, it is characterised in that the washing described in step (4) is to add the deionized water wash that 3 times of Crystallization of Zeolite liquid are long-pending.
6. the method for the rotten filter cake degree of crystallinity of recovery preparing light olefins from methanol molecular sieve according to claim 1, it is characterised in that the baking temperature described in step (4) is 120 DEG C.
7. the method for the rotten filter cake degree of crystallinity of recovery preparing light olefins from methanol molecular sieve according to claim 1, it is characterised in that the drying time described in step (4) is 12h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795639A (en) * | 2012-07-27 | 2012-11-28 | 大连理工大学 | Utilization method of beta molecular sieve synthetic mother liquid |
| CN103182319A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Regeneration method of deactivated titanium-silicon molecular sieve |
| CN103274430A (en) * | 2013-07-01 | 2013-09-04 | 中国海洋石油总公司 | Method for synthesizing pure phase SAPO-31 molecular sieve by recycling crystallization mother solution |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182319A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Regeneration method of deactivated titanium-silicon molecular sieve |
| CN102795639A (en) * | 2012-07-27 | 2012-11-28 | 大连理工大学 | Utilization method of beta molecular sieve synthetic mother liquid |
| CN103274430A (en) * | 2013-07-01 | 2013-09-04 | 中国海洋石油总公司 | Method for synthesizing pure phase SAPO-31 molecular sieve by recycling crystallization mother solution |
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Effective date of registration: 20180515 Address after: No. 1, Zhoucun District Stadium Road, Zibo, Shandong Patentee after: Shandong Qilu Huaxin Industrial Limited by Share Ltd Address before: 255300 Dongmen Road, Zhoucun District, Zibo, Shandong Province, No. 1688 Patentee before: Shandong Qilu Huaxin High-technology Co., Ltd. |