CN112010327A - Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material - Google Patents
Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material Download PDFInfo
- Publication number
- CN112010327A CN112010327A CN202010951796.4A CN202010951796A CN112010327A CN 112010327 A CN112010327 A CN 112010327A CN 202010951796 A CN202010951796 A CN 202010951796A CN 112010327 A CN112010327 A CN 112010327A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sapo
- mother liquor
- source
- crystallization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 47
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000012452 mother liquor Substances 0.000 title claims abstract description 43
- 239000002994 raw material Substances 0.000 title claims abstract description 27
- 238000002425 crystallisation Methods 0.000 claims abstract description 37
- 230000008025 crystallization Effects 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000499 gel Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 235000011007 phosphoric acid Nutrition 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 239000013589 supplement Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000009718 spray deposition Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the technical field of molecular sieve synthesis, and particularly relates to a method for preparing an SAPO-34 molecular sieve by using a crystallization mother liquor as a raw material. The invention takes the crystallized mother liquor obtained after the synthesis of the SAPO-34 molecular sieve as a raw material component to replace an organic template agent and partial raw materials in the synthesis process, supplements phosphorus, silicon, an aluminum source and water into the crystallized mother liquor, and synthesizes the SAPO-34 molecular sieve by a one-step hydrothermal crystallization method after aging. The method has the advantages of no need of additionally adding an organic template in the synthesis process, reduction of the pollution problem caused by direct discharge of mother liquor, simple process, greenness and environmental protection, improvement of the comprehensive utilization rate of synthesis raw materials, and reduction of the production cost.
Description
Technical Field
The invention belongs to the technical field of molecular sieve synthesis, and particularly relates to a method for preparing an SAPO-34 molecular sieve by using a crystallization mother liquor as a raw material.
Background
With the development of industrial civilization, the energy demand is continuously increased, fossil fuels are gradually reduced, and the search for new petroleum substitute raw materials in the chemical industry becomes the subject of numerous studies at present. The methanol to low-carbon olefin (MTO) reaction provides a new way for synthesizing low-carbon olefins such as ethylene, propylene and the like without depending on petroleum, and is considered as a possible raw material source. Among them, SAPO-34 molecular sieve is considered as a catalyst excellent in MTO reaction. SAPO-34 molecular sieve is made of SiO2、AlO2 -、PO2 +The tetrahedral unit is composed of 8-membered ring chabazite CHA spherical cage and three-dimensional pore channel structure, the diameter of the pore opening is 0.43-0.50nm, and the catalyst has medium-strength acidity and good hydrothermal stability. At present, the synthesis of SAPO-34 is mainly carried out by a one-step hydrothermal crystallization method, however, the hydrothermal crystallization method has low utilization rate of raw materials, a large amount of organic template agents are needed in the synthesis, and the separated crystallization mother liquor contains more unreacted raw materials, residual molecular sieve crystals and residual template agents. The crystallized mother liquor is usually directly discharged after synthesis, which not only causes a great deal of waste of raw materials, but also brings great pollution to the environment. Therefore, how to repeatedly utilize the crystallization mother liquor to synthesize the SAPO-34 molecular sieve is a relatively wide concern.
Chinese patent CN102992349B recovers crystallized mother liquor, supplements silicon source, aluminum source and phosphorus source, adds matrix material, binder, pore-forming agent and the like, prepares microsphere raw powder by spray forming, and prepares SAPO-34 molecular sieve by in-situ crystallization together with organic template agent aqueous solution after roasting, thereby realizing the recycling of the mother liquor. The method supplements raw materials and binders, and the like, then carries out spray forming and roasting crystallization, thereby increasing the process complexity.
Chinese patent CN105668587B considers the crystallization mother liquor as a whole, first preparing a small amount of slurry as "primer", then adding a large amount of concentrated mother liquor and raw materials to prepare a gel mixture. The volume of the concentrated mother liquor is 25-50% of the volume of the recovered mother liquor. The SAPO-34 molecular sieve is synthesized by the circulation. The method concentrates the mother liquor for use, increases energy consumption cost and reduces economy.
Chinese patent CN106542548A takes crystallized mother liquor as a base, adds a silicon source, an aluminum source, triethylamine and water, prepares gel according to a certain proportion, controls pH to be 6.5-7.5 by adding acid, and crystallizes at a constant temperature of 180-200 ℃ under self pressure for 3-24 hours to synthesize the SAPO-34 molecular sieve. The method strictly regulates and controls pH, and introduces unnecessary substances by adding acid.
In addition, the above methods require the addition of organic templates again, which still increases environmental pollution to some extent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing the SAPO-34 molecular sieve by taking the crystallization mother liquor as a raw material, which has simple process and is green and environment-friendly. In the method, after the crystallization mother liquor is recovered, a silicon source, an aluminum source, a phosphorus source and deionized water are added, and after the mixture is fully stirred and aged, the SAPO-34 molecular sieve is directly synthesized by in-situ crystallization. On one hand, the recycling of unreacted components in the crystallization mother liquor is realized, and the overall utilization rate of raw materials is improved; on the other hand, the residual template agent and the superfine molecular sieve in the crystallization mother liquor can play a role of inducing seed crystals without additionally adding an organic template agent. In addition, no new substance or treatment procedure is introduced in the method, the whole process is simple, and the method is green and environment-friendly.
The technical scheme adopted by the invention is as follows.
A method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material comprises the following steps:
(1) synthesizing the SAPO-34 molecular sieve by using a one-step hydrothermal crystallization method, carrying out simple precipitation separation on the obtained solid product, and recovering to obtain crystallized mother liquor;
(2) supplementing and adding a silicon source, an aluminum source, a phosphorus source and deionized water into the crystallized mother liquor obtained in the step (1) to prepare initial gel of the SAPO-34 molecular sieve;
(3) fully stirring the initial gel obtained in the step (2), and then aging to obtain an SAPO-34 molecular sieve crystallization liquid;
(4) preparing SAPO-34 molecular sieve coarse powder from the SAPO-34 molecular sieve crystallization liquid obtained in the step (3) by using a one-step hydrothermal crystallization method;
(5) and (4) precipitating and separating the SAPO-34 molecular sieve obtained in the step (4), drying, calcining at 480-650 ℃ for 6-8 hours, and removing organic impurities to obtain the pure SAPO-34 molecular sieve.
In the step (1), the silicon source used in the one-step hydrothermal crystallization method is one or more of silica sol, silica gel or tetraethoxysilane; the aluminum source is one or more of pseudo-boehmite, aluminum oxide or aluminum hydroxide; the phosphorus source is one or more of orthophosphoric acid or metaphosphoric acid; the template agent is one or more of diethylamine, triethylamine and tetraethyl ammonium hydroxide.
In the step (1), the crystallized mother liquor is Al2O3:H2O:P2O5:SiO2The template agent is prepared by performing a one-step hydrothermal crystallization reaction on a silicon source, an aluminum source, a phosphorus source, deionized water and the template agent according to the molar ratio of (0.5-2.0) to (40-80) to (0.5-3.0) to (0.4-2.0) to (1.5-4.0) and then separating the reaction product.
In the step (1), the recovered crystallization mother liquor accounts for 10-20 wt% of the evaporated solid component, based on 100% of the total mass.
In the step (2), when the initial gel of the SAPO-34 molecular sieve is prepared, the additionally added silicon source is one or more of silica sol, silica gel or tetraethoxysilane, the aluminum source is one or more of pseudo-boehmite, alumina or aluminum hydroxide, and the phosphorus source is one or more of orthophosphoric acid or metaphosphoric acid.
In the above step (2), according to Al2O3:H2O:P2O5:SiO2The molar ratio of (1.0), (20-80), (0.5-2.0) and (0.6) additionally adding a silicon source, an aluminum source, a phosphorus source and deionized water; in the prepared SAPO-34 molecular sieve initial gel, the crystallized mother liquor accounts for 10-40 wt% of the total mass of 100%.
In the step (3), the aging temperature is 60-90 ℃, and the aging time is 8-12 hours.
In the step (4), the temperature of the hydrothermal crystallization method is 180-200 ℃, and the crystallization time is 48-72 hours.
The invention comprehensively utilizes crystallized mother liquor obtained after the synthesis of the SAPO-34 molecular sieve, takes the crystallized mother liquor as a raw material component to replace an organic template agent and part of raw materials in the synthesis process, supplements phosphorus, silicon, an aluminum source and water into the raw materials, takes residual micro-crystals as crystal seeds, and synthesizes the SAPO-34 molecular sieve by a one-step hydrothermal crystallization method. The template agent and the superfine molecular sieve crystal are remained in the crystallized mother liquor, so that the crystallization can be induced, an organic template agent is not required to be additionally added in the synthesis process, the pollution problem caused by direct discharge of the mother liquor is reduced, the whole process is simple, the environment is protected, the comprehensive utilization rate of the synthesis raw materials is improved, the product yield is increased, and the production cost is reduced. Meanwhile, the SAPO-34 molecular sieve synthesized by the method has higher crystallinity.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a sample obtained in example 1 of the present invention.
FIG. 2 is an X-ray diffraction (XRD) pattern of samples obtained in examples 1 to 5 of the present invention.
Detailed Description
The following examples are given in connection with the accompanying drawings and tables, but the scope of the invention is not limited thereto.
In the examples, the mother liquid for crystallization is Al2O3:H2O:P2O5:SiO2The molar ratio of the template agent is 1.5:60:2.0: 0.6: 2.0 performing one-step hydrothermal crystallization reaction on a silicon source, an aluminum source, a phosphorus source, deionized water and a template agent, and then separating to obtain the product.
Example 1
Taking 27.71g of crystallization mother liquor (the solid component accounts for 16wt percent after evaporation), and proportioning Al according to the raw material2O3:H2O:P2O5:SiO2Pseudo-boehmite, phosphoric acid, silica sol, deionized water were added thereto in order of 1.0:30:1.5:0.6 to give an initial gel having a total mass of 106.58 g. After fully stirring for 8 hours, putting the mixture into a high-pressure crystallization kettle with a polytetrafluoroethylene lining, aging the mixture for 10 hours at 80 ℃, and then heating the mixture to 180 ℃ for crystallization for 48 hours. And centrifuging, washing and drying the product, and calcining the product in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-34 molecular sieve, wherein the sample is recorded as C-1. The Scanning Electron Microscope (SEM) pattern is shown in FIG. 1, and the X-ray diffraction (XRD) pattern is shown in FIG. 2. The relative crystallinity of the initial synthesized SAPO-34 sample is 100%, the relative product yield is 100%, and the crystallinity and yield of the sample C-1 are calculated and shown in Table 1.
TABLE 1 relative crystallinity and product yield for samples obtained in inventive examples 1-5
Example 2
Taking 36.22g of crystallization mother liquor (the solid component accounts for 11 wt% after evaporation), and proportioning Al according to raw material ratio2O3:H2O:P2O5:SiO2Pseudo-boehmite, phosphoric acid, silica sol, deionized water were added thereto in this order to give an initial gel having a total mass of 95.58g ═ 1.0:20:1.0: 0.6. After fully stirring for 8 hours, putting the mixture into a high-pressure crystallization kettle with a polytetrafluoroethylene lining, aging the mixture for 10 hours at 70 ℃, and then heating the mixture to 180 ℃ for crystallization for 72 hours. And centrifuging, washing and drying the product, and calcining the product in a muffle furnace at 490 ℃ for 8 hours to obtain the SAPO-34 molecular sieve, wherein the sample is recorded as C-2. The X-ray diffraction (XRD) pattern is shown in fig. 2. The crystallinity and yield of sample C-2 were calculated and are shown in Table 1.
Example 3
Taking 18.03g of crystallization mother liquor (the solid component accounts for 19wt percent after evaporation), and proportioning Al according to the raw material2O3:H2O:P2O5:SiO2Pseudo-boehmite, phosphoric acid, silica sol, deionized water were added thereto in order of 1.0:80:0.5:0.6 to give an initial gel having a total mass of 82.84 g. After fully stirring for 8 hours, putting the mixture into a high-pressure crystallization kettle with a polytetrafluoroethylene lining, aging the mixture for 10 hours at 80 ℃, and then heating the mixture to 200 ℃ for crystallization for 72 hours. And centrifuging, washing and drying the product, and calcining the product in a muffle furnace at 600 ℃ for 6 hours to obtain the SAPO-34 molecular sieve, wherein the sample is recorded as C-3. The X-ray diffraction (XRD) pattern is shown in fig. 2. The crystallinity and yield of sample C-3 were calculated and are shown in Table 1.
Example 4
Taking 29.66g of crystallization mother liquor (the solid component accounts for 14 wt% after evaporation), and proportioning Al according to the raw material proportion2O3:H2O:P2O5:SiO2Pseudo-boehmite, phosphoric acid, silica sol, deionized water were added thereto in this order to give an initial gel having a total mass of 105.52g ═ 1.0:40:1.0: 0.6. After fully stirring for 8 hours, putting the mixture into a high-pressure crystallization kettle with a polytetrafluoroethylene lining, aging the mixture for 8 hours at 90 ℃, and then heating the mixture to 190 ℃ for crystallization for 48 hours. Centrifuging, washing and drying the product, and calcining the product in a muffle furnace at 650 ℃ for 6 hours to obtain the SAPO-34 molecular sieve sampleIs marked as C-4. The X-ray diffraction (XRD) pattern is shown in fig. 2. The crystallinity of sample C-4 was calculated and the yield is shown in Table 1.
Example 5
Taking 29.81g of crystallization mother liquor (the solid component accounts for 17 wt% after evaporation), and proportioning Al according to raw materials2O3:H2O:P2O5:SiO2Pseudo-boehmite, phosphoric acid, silica sol and deionized water were added thereto in this order to give an initial gel having a total mass of 129.34g ═ 1.0:60:1.5: 0.6. After fully stirring for 8 hours, putting the mixture into a high-pressure crystallization kettle with a polytetrafluoroethylene lining, aging the mixture for 12 hours at the temperature of 60 ℃, and then heating the mixture to 180 ℃ for crystallization for 72 hours. And centrifuging, washing and drying the product, and calcining the product in a muffle furnace at 580 ℃ for 7 hours to obtain the SAPO-34 molecular sieve, wherein the sample is recorded as C-5. The X-ray diffraction (XRD) pattern is shown in fig. 2. The crystallinity of sample C-5 was calculated and the yield is shown in Table 1.
Claims (7)
1. A method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material is characterized by comprising the following steps:
(1) synthesizing the SAPO-34 molecular sieve by using a one-step hydrothermal crystallization method, carrying out simple precipitation separation on the obtained solid product, and recovering to obtain crystallized mother liquor;
(2) supplementing and adding a silicon source, an aluminum source, a phosphorus source and deionized water into the crystallized mother liquor obtained in the step (1) to prepare initial gel of the SAPO-34 molecular sieve;
(3) fully stirring the initial gel obtained in the step (2), and then aging to obtain an SAPO-34 molecular sieve crystallization liquid;
(4) preparing SAPO-34 molecular sieve coarse powder from the SAPO-34 molecular sieve crystallization liquid obtained in the step (3) by using a one-step hydrothermal crystallization method;
(5) and (4) precipitating and separating the SAPO-34 molecular sieve obtained in the step (4), drying, calcining at 480-650 ℃ for 6-8 hours, and removing organic impurities to obtain the pure SAPO-34 molecular sieve.
2. The method of claim 1, wherein: in the step (1), the silicon source used in the one-step hydrothermal crystallization method is one or more of silica sol, silica gel or tetraethoxysilane; the aluminum source is one or more of pseudo-boehmite, aluminum oxide or aluminum hydroxide; the phosphorus source is one or more of orthophosphoric acid or metaphosphoric acid; the template agent is one or more of diethylamine, triethylamine and tetraethyl ammonium hydroxide.
3. The method of claim 1, wherein: in the step (1), the crystallized mother liquor is Al2O3:H2O:P2O5:SiO2The template agent is obtained by performing a one-step hydrothermal crystallization reaction on a silicon source, an aluminum source, a phosphorus source, deionized water and the template agent according to the molar ratio of (0.5-2.0) to (40-80) to (0.5-3.0) to (0.4-2.0) to (1.5-4.0) and then separating; and recovering the obtained crystallization mother liquor, wherein the solid component accounts for 10-20 wt% after evaporation, based on the total mass of 100%.
4. The method of claim 1, wherein: in the step (2), when the initial gel of the SAPO-34 molecular sieve is prepared, the additionally added silicon source is one or more of silica sol, silica gel or tetraethoxysilane, the aluminum source is one or more of pseudo-boehmite, alumina or aluminum hydroxide, and the phosphorus source is one or more of orthophosphoric acid or metaphosphoric acid.
5. The method of claim 1, wherein: in step (2), according to Al2O3:H2O:P2O5:SiO2The molar ratio of (1.0), (20-80), (0.5-2.0) and (0.6) additionally adding a silicon source, an aluminum source, a phosphorus source and deionized water; in the prepared SAPO-34 molecular sieve initial gel, the crystallized mother liquor accounts for 10-40 wt% of the total mass of 100%.
6. The method according to claim 1, wherein in the step (3), the aging temperature is 60 to 90 ℃ and the aging time is 8 to 12 hours.
7. The method according to claim 1, wherein in the step (4), the reaction temperature of the one-step hydrothermal crystallization method is 180-200 ℃ and the crystallization time is 48-72 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010951796.4A CN112010327A (en) | 2020-09-11 | 2020-09-11 | Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010951796.4A CN112010327A (en) | 2020-09-11 | 2020-09-11 | Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112010327A true CN112010327A (en) | 2020-12-01 |
Family
ID=73523117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010951796.4A Pending CN112010327A (en) | 2020-09-11 | 2020-09-11 | Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112010327A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354895A (en) * | 2021-05-10 | 2021-09-07 | 宁波聚才新材料科技有限公司 | High-temperature-resistant polypropylene composite material and preparation method thereof |
| CN114105159A (en) * | 2021-12-21 | 2022-03-01 | 中科催化新技术(大连)股份有限公司 | Preparation method for synthesizing SAPO-34 molecular sieve by using production and recovery mother liquor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121522A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Phosphor-silicon-aluminum molecular sieve synthesis mother liquid utilization method |
| CN101555021A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Method for preparing SAPO-34 molecular sieve by using crystallized residual liquid of SAPO-34 molecular sieve |
| CN101935050A (en) * | 2010-09-10 | 2011-01-05 | 西北化工研究院 | Method for synthesizing silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor |
| CN102992349A (en) * | 2012-12-11 | 2013-03-27 | 陕西煤化工技术工程中心有限公司 | Recycling method of mother liquor for SAPO-34 molecular sieve synthesis |
| CN105668587A (en) * | 2016-02-23 | 2016-06-15 | 山东齐鲁华信高科有限公司 | Recycling method for SAPO-34 molecular-sieve synthesized mother liquid |
-
2020
- 2020-09-11 CN CN202010951796.4A patent/CN112010327A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121522A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Phosphor-silicon-aluminum molecular sieve synthesis mother liquid utilization method |
| WO2008019592A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A method for utilizing mother liquor of synthesizing molecular sieve of silicoaluminum phosphate |
| CN101555021A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Method for preparing SAPO-34 molecular sieve by using crystallized residual liquid of SAPO-34 molecular sieve |
| CN101935050A (en) * | 2010-09-10 | 2011-01-05 | 西北化工研究院 | Method for synthesizing silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor |
| CN102992349A (en) * | 2012-12-11 | 2013-03-27 | 陕西煤化工技术工程中心有限公司 | Recycling method of mother liquor for SAPO-34 molecular sieve synthesis |
| CN105668587A (en) * | 2016-02-23 | 2016-06-15 | 山东齐鲁华信高科有限公司 | Recycling method for SAPO-34 molecular-sieve synthesized mother liquid |
Non-Patent Citations (1)
| Title |
|---|
| 颜婷婷等: "《多级孔沸石分子筛合成及其催化性能研究》", vol. 1, 中国矿业大学出版社, pages: 119 - 127 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354895A (en) * | 2021-05-10 | 2021-09-07 | 宁波聚才新材料科技有限公司 | High-temperature-resistant polypropylene composite material and preparation method thereof |
| CN114105159A (en) * | 2021-12-21 | 2022-03-01 | 中科催化新技术(大连)股份有限公司 | Preparation method for synthesizing SAPO-34 molecular sieve by using production and recovery mother liquor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9963350B2 (en) | ZSM-5 type molecular sieve synthesis method | |
| CN100542961C (en) | A kind of technology of processing bauxite to produce hydroted alumina with sodium hydroxide molten salt growth method | |
| CN107640775B (en) | Method for preparing ZSM-5 molecular sieve by using solid waste | |
| CN112010327A (en) | Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material | |
| CN107434252B (en) | Preparation method of low-silicon nano SAPO-34 molecular sieve | |
| CA2745256C (en) | Process for the preparation of a monovalent succinate salt | |
| CN108928834B (en) | MCM-41 mesoporous molecular sieve, and preparation method and application thereof | |
| CN110937612B (en) | Process for preparing high-quality heavy soda ash by using crude sodium bicarbonate | |
| CN109626388B (en) | Preparation method of nano-layered clinoptilolite molecular sieve | |
| CN107324357B (en) | Method for preparing ZSM-5 molecular sieve by using white mud as raw material and ZSM-5 molecular sieve | |
| CN109928406B (en) | Analcime and its synthesis method | |
| CN110655091A (en) | Preparation method of mordenite molecular sieve | |
| CN108658092B (en) | Method for preparing P-type molecular sieve and high-silicon mordenite from aluminum residue extracted by fly ash acid method and utilization method of fly ash | |
| US10287172B2 (en) | Preparation method for beta zeolite | |
| CN109052446B (en) | Method for preparing calcium-aluminum hydrotalcite by using industrial waste residues as raw materials | |
| CN110844928A (en) | Method for preparing micro-nano aluminum oxide from aluminum alloy hydrolysate | |
| US4051222A (en) | Coarsening of partially calcined alumina dust | |
| CN102050466B (en) | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material | |
| CN112142063A (en) | Preparation method of X molecular sieve | |
| CN109928403B (en) | Large-size analcite and synthesis method thereof | |
| JPH05507054A (en) | A simple method for producing swellable layered silicates | |
| CN108658090B (en) | Method for preparing 13X type molecular sieve and high-silicon mordenite by extracting aluminum residue from fly ash through acid method and utilization method of fly ash | |
| CN101607728B (en) | Method for producing alumina by using sodium bicarbonate to decompose sodium aluminate solution | |
| CN106809850A (en) | A kind of synthetic method of little crystal grain FER molecular sieve | |
| JPH0262487B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201201 |