CN105800647B - Recover the method for the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve - Google Patents
Recover the method for the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve Download PDFInfo
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- CN105800647B CN105800647B CN201610098819.5A CN201610098819A CN105800647B CN 105800647 B CN105800647 B CN 105800647B CN 201610098819 A CN201610098819 A CN 201610098819A CN 105800647 B CN105800647 B CN 105800647B
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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
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Abstract
The invention belongs to Zeolite synthesis technical field, and in particular to a kind of method for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve.Hydrothermal Synthesiss are carried out by the synthesis technique of preparing light olefins from methanol molecular sieve, after crystallization is complete, reclaim volatility template, mother liquor and filter cake must be reclaimed by carrying out separation of solid and liquid to crystallization magma afterwards, be preserved after filter cake is scrubbed；After filter cake is rotten, rotten filter cake is added in mother liquor, is eventually adding volatility template, prepares initial gel mixture；Initial gel mixture is placed in crystallization in high pressure crystallizing kettle, obtains Crystallization of Zeolite liquid；Crystallization of Zeolite liquid is obtained into filter cake through separation of solid and liquid, Washing of Filter Cake must recover the molecular sieve filter cake of crystallinity, dry molecular sieve.By the implementation of the present invention, rotten molecular sieve filter cake crystallinity can recover the level to before going bad substantially, greatly reduce production loss, be effectively guaranteed the continuity of molecular sieve production.
Description
Technical field
The invention belongs to Zeolite synthesis technical field, and in particular to one kind is recovered preparing light olefins from methanol molecular sieve and gone bad
The method of filter cake crystallinity.
Background technology
The energy crisis faced in recent years around the whole world, it is proposed that the new ideas of a solution energy problem：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, it is that the powerful measure of solution China's oil scarcity of resources and path, its core are MTO catalyst
Research and development.
At present, industrialized MTO catalyst is most of with SAPO-34 molecular sieves or SAPO-34 and compound point of SAPO-18
Son sieve is used as former powder, and the synthesis technique about above two molecular sieve, researcher has done a lot of work, including optimised process bar
The exploration, the recycling of mother liquor etc. of part.In the industrial operation of reality, for various reasons, the complete molecule of crystallization
The filter cake that screening the pulp liquid is formed after separation of solid and liquid and washing, is not dried in time, after a period of time is placed, the crystallization of molecular sieve
The decline of cliff of displacement formula occurs in degree, and the character of molecular sieve filter cake with good thixotropic white filter cake also by going bad as crystalline substance
The transparent yellowish color substance of jade-like stone, and with the extension of time, the crystallinity decline of molecular sieve filter cake can be more and more faster.We know
Road, molecular sieve are a kind of metasable state materials, have the trend changed to stable state under suitable conditions, molecular sieve pulp is through solid
The filter cake formed after liquid separation, washing need to be passed through and remove the mother liquor remained in filter cake, and in actual industrial production, it is impossible to
A small amount of residual mother liquor in filter cake is thoroughly removed, which forms the necessary condition for the steady opposite stable inversion of phases that is situated between, Zhi Houhui
Gradually sprawling, until most of filter cake goes bad.These rotten filter cake crystallinity are changed into less than 50% before going bad, and physical property has been sent out
The change of matter is given birth to, performance also significantly declines, and immeasurable loss is brought to production.
The content of the invention
A kind of method for the filter cake crystallinity that goes bad it is an object of the invention to provide recovery preparing light olefins from methanol molecular sieve, greatly
Production loss is reduced greatly, is effectively guaranteed the continuity of molecular sieve production.
The method of the present invention for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve, step are as follows：
(1) Hydrothermal Synthesiss are carried out by the synthesis technique of preparing light olefins from methanol molecular sieve, after crystallization is complete, reclaims volatility
Template, mother liquor and filter cake must be reclaimed by carrying out separation of solid and liquid to crystallization magma afterwards, be preserved after filter cake is scrubbed；
(2) after filter cake is rotten, rotten filter cake is added in mother liquor, is eventually adding volatility template, is prepared initial
Gel mixture；
(3) initial gel mixture is placed in crystallization in high pressure crystallizing kettle, obtains Crystallization of Zeolite liquid；
(4) Crystallization of Zeolite liquid is obtained into filter cake through separation of solid and liquid, Washing of Filter Cake must recover the molecular sieve filter cake of crystallinity, do
It is dry to obtain molecular sieve.
Preparing light olefins from methanol molecular sieve described in step (1) is SAPO-18 molecular sieves, SAPO-34 molecular sieves or
One kind in SAPO-34/SAPO-18 composite molecular screens.
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 plus the deionized water of 3 times of Crystallization of Zeolite liquid products is washed.
Drying 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 the 5-50% that crystallinity is dropped to before going bad.
Mother liquor source：Hydrothermal synthesis method prepares the filtrate of preparing light olefins from methanol molecular sieve recovery as mother liquor.
Reclaim volatility template source：Hydrothermal synthesis method is prepared after preparing light olefins from methanol Crystallization of Zeolite terminates,
The liquid mixture of condensed device recovery is as the volatility template reclaimed during 120 DEG C of crystallizing kettle kettle temperature.
The present invention is directed to filter cake in actual industrial production and places the problem of perishable for a long time, there is provided one kind recovers methanol system
The method of the rotten filter cake crystallinity of low-carbon alkene molecular sieve.Using the inventive method, rotten filter cake crystallinity can be recovered to becoming
95-100% before matter.
The present invention compared with prior art, has the advantages that：
By the implementation of the present invention, rotten molecular sieve filter cake crystallinity can recover the level to before going bad substantially, greatly
Production loss is reduced greatly, is effectively guaranteed the continuity of molecular sieve production.In addition, in the implementation process of the present invention, adopt
It is the volatility template for the mother liquor and recovery reclaimed after Crystallization of Zeolite, the cost of crystallization substantially reduces again.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of SAPO-34 molecular sieves in embodiment 1.
Fig. 2 is the X-ray diffractogram of SAPO-18 molecular sieves in embodiment 2.
Fig. 3 is the X-ray diffractogram of SAPO-34/SAPO-18 composite molecular screens in embodiment 3.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
(1) synthesis of SAPO-34 molecular sieves
With Primogel mol ratio 2TEAOH：0.4SiO2：P2O5：Al2O3：40H2O is by meter feedstock by deionized water, aluminium
Source, TEAOH, phosphorus source, the order of silicon source sequentially add mixing, are sufficiently stirred into gel, are then charged into stainless steel high pressure crystallizing kettle
In, the crystallization 48h at 172 DEG C.After crystallization terminates, when kettle temperature is down to 120 DEG C, thief hatch is slowly opened, will be volatilizable in kettle
Property material import condenser in, weighed after collection；After kettle temperature is down to room temperature, using sheet frame by crystallization magma separation of solid and liquid, receive
Collection mother liquor is simultaneously weighed, and the filter cake on sheet frame is washed till into neutrality with deionized water, is weighed after removing the filter cake on sheet frame, takes a small amount of filter
Cake is dried at 120 DEG C, and X-ray diffraction analysis result is as shown in a in Fig. 1, crystallinity 105%.
(2) recovery of SAPO-34 molecular sieve crystallinities
81.6g recovery mother liquors are weighed, add the rotten rear filter cakes of 30.6g, are eventually adding the volatile thing of 22.8g recovery
Matter, 20min is stirred, is placed in stainless steel high pressure crystallizing kettle, 172 DEG C of crystallization 24h.After separation of solid and liquid, with deionized water by solid
Product is washed till neutrality, is dried at 120 DEG C, X-ray diffraction analysis result is as shown in b in Fig. 1, crystallinity 104%.
Embodiment 2
(1) synthesis of SAPO-18 molecular sieves
With Primogel mol ratio 1.6R：0.5SiO2：0.9P2O5：Al2O3：50H2O (R N, N- diisopropylethylamine) will
Meter feedstock sequentially adds mixing by deionized water, silicon source, DIPEA, phosphorus source, the order of silicon source, is sufficiently stirred
Into gel, it is then charged into stainless steel high pressure crystallizing kettle, the crystallization 72h at 180 DEG C.After crystallization terminates, 120 DEG C are down in kettle temperature
When, thief hatch is slowly opened, volatile material in kettle is imported in condenser, weighed after collection；After kettle temperature is down to room temperature,
Crystallization magma separation of solid and liquid, collection mother liquor are simultaneously weighed, the filter cake on sheet frame are washed till into neutrality with deionized water, taken using sheet frame
Weighed after filter cake on lower sheet frame, take a small amount of filter cake to be dried at 120 DEG C, X-ray diffraction analysis result is as shown in a in Fig. 2, knot
Brilliant degree is 100%.
(2) recovery of SAPO-18 molecular sieve crystallinities
89.5g recovery mother liquors are weighed, add the rotten rear filter cakes of 30.6g, are eventually adding the volatile thing of 24.5g recovery
Matter, 30min is stirred, is placed in stainless steel high pressure crystallizing kettle, 180 DEG C of crystallization 30h.After separation of solid and liquid, with deionized water by solid
Product is washed till neutrality, is dried at 120 DEG C, X-ray diffraction analysis result is as shown in b in Fig. 2, crystallinity 96%.
Embodiment 3
(1) synthesis of SAPO-34/SAPO-18 composite molecular screens
With Primogel mol ratio 2TEAOH：0.4SiO2：P2O5：Al2O3：40H2O is by meter feedstock by deionized water, aluminium
Source, TEAOH, phosphorus source, the order of silicon source sequentially add, and stir 30min, add 20% SAPO-18 points of silicon source quality afterwards
Son sieve (is made) in embodiment 2, continues stirring 20min and obtains crystallization gel, is loaded into stainless steel high pressure crystallizing kettle, in 175
Crystallization 36h at DEG C.After crystallization terminates, when kettle temperature is down to 120 DEG C, thief hatch is slowly opened, volatile material in kettle is led
Enter in condenser, weighed after collection；After kettle temperature is down to room temperature, using sheet frame by crystallization magma separation of solid and liquid, mother liquor is collected simultaneously
Weigh, the filter cake on sheet frame is washed till neutrality with deionized water, weighed after removing the filter cake on sheet frame, takes a small amount of filter cake 120
Dried at DEG C, X-ray diffraction analysis result is as shown in a in Fig. 3, crystallinity 98%.
(2) recovery of SAPO-34/SAPO-18 composite molecular screens crystallinity
90g recovery mother liquors are weighed, add the rotten rear filter cakes of 28.5g, are eventually adding the volatile material of 23.4g recovery,
30min is stirred, is placed in stainless steel high pressure crystallizing kettle, 175 DEG C of crystallization 24h.After separation of solid and liquid, with deionized water by solid product
Neutrality is washed till, is dried at 120 DEG C, X-ray diffraction analysis result is as shown in b in Fig. 3, crystallinity 94%.
Claims (7)
- A kind of 1. method for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve, it is characterised in that step is as follows：(1) Hydrothermal Synthesiss are carried out by the synthesis technique of preparing light olefins from methanol molecular sieve, after crystallization is complete, reclaims volatility template Agent, mother liquor and filter cake must be reclaimed by carrying out separation of solid and liquid to crystallization magma afterwards, be preserved after filter cake is scrubbed；(2) after filter cake is rotten, rotten filter cake is added in mother liquor, volatility template is eventually adding, prepares Primogel Mixture；(3) initial gel mixture is placed in crystallization in high pressure crystallizing kettle, obtains Crystallization of Zeolite liquid；(4) Crystallization of Zeolite liquid being obtained into filter cake through separation of solid and liquid, Washing of Filter Cake must recover the molecular sieve filter cake of crystallinity, dry Molecular sieve.
- 2. the method according to claim 1 for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve, its feature It is SAPO-18 molecular sieves, SAPO-34 molecular sieves or SAPO- to be the preparing light olefins from methanol molecular sieve described in step (1) One kind in 34/SAPO-18 composite molecular screens.
- 3. the method according to claim 1 for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve, its feature It is 170-190 DEG C to be the crystallization temperature described in step (3).
- 4. the method according to claim 1 for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve, its feature It is 12-36h to be the crystallization time described in step (3).
- 5. the method according to claim 1 for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve, its feature It is that the washing described in step (4) is plus the deionized water of 3 times of Crystallization of Zeolite liquid products is washed.
- 6. the method according to claim 1 for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve, its feature It is 120 DEG C to be the drying temperature described in step (4).
- 7. the method according to claim 1 for recovering the rotten filter cake crystallinity of preparing light olefins from methanol molecular sieve, its feature It is 12h to be the drying time described in step (4).
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