CN102992349B - Recycling method of mother liquor for SAPO-34 molecular sieve synthesis - Google Patents
Recycling method of mother liquor for SAPO-34 molecular sieve synthesis Download PDFInfo
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- 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 38
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 24
- 239000012452 mother liquor Substances 0.000 title abstract description 25
- 238000004064 recycling Methods 0.000 title abstract description 4
- 238000002425 crystallisation Methods 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- 239000004411 aluminium Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000007493 shaping process Methods 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000009415 formwork Methods 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- -1 silicon ester Chemical class 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000008247 solid mixture Substances 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 8
- 239000010935 stainless steel Substances 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a recycling method of mother liquor for SAPO-34 molecular sieve hydro-thermal synthesis, and relates to the technical field of molecular sieve synthesis. The method comprises the following steps: recovering mother liquor obtained by SAPO-34 molecular sieve hydro-thermal synthesis crystallization and separation, additionally adding a silicon source, an aluminium source, and a phosphorus source into the mother liquor used as a raw material, mixing, adding a substrate material, a binder, and a pore forming agent, preparing microsphere raw powder by spraying molding, putting the roasted microspheres and an aqueous solution of an organic template together into a stainless steel reaction vessel, performing in-situ crystallization to prepare a spherical SAPO-34 molecular sieve catalyst which can be used directly in a fluidized bed device.
Description
Technical field
The invention belongs to Zeolite synthesis technical field, relate to a kind of circulation utilization method of synthesis mother liquid, especially a kind of circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid.
Background technology
SAPO-34 molecular sieve is owing to having chemistry and the physical propertys such as suitable acidity, suitable pore passage structure, less aperture, larger specific surface area, good absorption property and good thermostability and hydrothermal stability, in methanol-to-olefins (MTO) reaction, show excellent catalytic performance.At present SAPO-34's is synthetic taking hydrothermal synthesis method as main, but in current hydrothermal synthesis method, the utilization ratio of raw material is lower, isolating the water that contains more unreacted raw material in the synthesis mother liquid forming after molecular sieve and contain in a large number organic formwork agent.The direct discharge of mother liquor causes the waste of raw material on the one hand, can cause larger pollution to environment on the other hand.Therefore obtained paying close attention to widely for the utilization of synthesis mother liquid.
Chinese patent CN200610152274.8 reclaims by the mother liquor that phosphor-silicon-aluminum molecular sieve crystallization is filtered, a part using mother liquor as Zeolite synthesis raw material of the same type, add corresponding new raw material according to proportioning again and prepare synthesis of molecular sieve initial gel mixture, obtain the former powder of SAPO molecular sieve analog through hydrothermal crystallizing, filtration, the operation such as dry again, realize the recycling of mother liquor.
Aluminium source and deionized water or aluminium source and crystallization mother liquor are mixed to form suspension liquid A by Chinese patent CN201010280116.7; Phosphorus source and deionized water or phosphorus source and crystallization mother liquor are mixed to form solution B; After being mixed with solution B, suspension liquid A add template, silicon source, crystal seed and crystallization mother liquor to form initial gel mixture; Then hydrothermal crystallizing, filtration, washing, oven dry, roasting obtain silicoaluminophosphamolecular molecular sieves; Filtrate is reclaimed.
Chinese patent CN101121148B proposes, and after Hydrothermal Synthesis SAPO-34 molecular sieve, without filtration washing step, directly the synthetic slurry that contains molecular sieve is carried out to spray shaping step, thereby avoids producing the discharging of waste liquid problem that contains unreacting material.
In the method for above-mentioned recycling, the one, consider to utilize the unreacting material in mother liquor to return to synthetic system, utilize hydrothermal crystallizing to produce molecular screen material of the same type, but in utilizing mother liquor, also produced new need crystallization mother liquor to be processed.Directly synthetic slurry is carried out to moulding process easily forms unreacted material accumulation and covering on molecular sieve surface, cause gained catalyst performance to be affected.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid is provided, the method is in the mother liquor reclaiming, add corresponding raw material spray shaping to form after microballoon, the synthetic microspherical catalyst that contains SAPO-34 molecular sieve of direct in situ crystallization.It has on the one hand realized the complete-reclaiming of water in mother liquor and unreacted material, and the method for in-situ crystallization can avoid forming new need mother liquor to be processed; Simultaneously, by utilizing the cohesive action of superfine reaction mass, required binding agent can partly replace traditional first synthesis of molecular sieve and carry out moulding again time, reduce production costs, and ultra-fine zeolite crystal has also played the inducing action of crystal seed in follow-up crystallization process in mother liquor, can the higher molecular sieve catalytic agent material of synthetic crystallization degree.
The object of the invention is to solve by the following technical programs:
The circulation utilization method of this SAPO-34 molecular sieve synthesis mother liquid, comprises the following steps:
1) filtrate of the synthetic SAPO-34 molecular sieve of hydrothermal crystallizing is reclaimed as synthesis mother liquid, add wherein phosphorus source, He Gui source, aluminium source, under room temperature, stir 2-24h, gained slurry is designated as A, silicon wherein: phosphorus: the atomic ratio of aluminium is (0.2 ~ 1.5): (0.2 ~ 3.0): (0.2 ~ 3.0); In slurry, solid mixture is designated as M-A;
2) in above-mentioned slurry A, add deionized water, matrix, binding agent, pore-forming material is also uniformly mixed, and final gained mixture is designated as B, and the solid matter in mixture B is designated as M-B; In mixture B, the mass content of water is 60-80%; In solid matter M-B, the shared mass ratio of M-A is 25-50%, the mass ratio 30-60% that matrix is shared, and the shared mass ratio of binding agent is 0-15%, the shared mass ratio of pore-forming material is 0-5%;
3) after gained mixed solution is mixed, utilize colloidal mill shear disperse after carry out spray shaping, obtain spheroidal particle;
4) will after the roasting of gained spheroidal particle, in sealed vessel, carry out hydrothermal crystallizing with together with the aqueous solution of organic formwork agent;
5) crystallization complete after filtration drying obtain the spherical catalytic material containing SAPO-34 molecular sieve.
In step 1), described phosphorus source is phosphoric acid, ammonium phosphate, the mixing of one or more in ammonium hydrogen phosphate and Secondary ammonium phosphate; Aluminium source is aluminium colloidal sol, pseudo-boehmite, aluminum oxide, aluminium hydroxide, the mixing of one or more in aluminum isopropylate; Silicon source is silicon oxide, silicon sol, silicon ester, or one or more mixing in the kaolin that contains soluble silicon component.
Step 2) in, described substrate material is kaolin, polynite, the mixing of one or more in aluminum oxide; Binding agent is aluminium colloidal sol, silicon sol, the mixing of one or more in aluminum phosphate; Pore-forming material is graphite, sesbania powder, starch, the mixing of one or more in poly-methylcellulose gum.
In step 3), shear particle diameter in disposed slurry and be not more than 4 μ m, spraying gained spherical particle diameters is between 20-300 μ m, and meso-position radius is between 40-100 μ m.
In step 4), described organic formwork agent is triethylamine, diethylamine, ethamine, morpholine, tetraethyl ammonium hydroxide, Isopropylamine, the mixing of one or more in di-n-propylamine; The molar ratio of organic formwork agent and water is 1:(2 ~ 17), the mass ratio of solid and liquid is 1:(0.5 ~ 15).Described spraying gained spheroidal particle maturing temperature is 0 ~ 400 DEG C, and roasting time is 0-20h.In step 4), crystallization temperature is 100-250 DEG C, crystallization time 1-90h.
Compared with prior art, the present invention has following beneficial effect:
1,, by enforcement of the present invention, water and the unreacted raw material etc. that can realize in mother liquor are recycled completely.
2,, by enforcement of the present invention, mother liquor is binding agent when alternative catalysts grain forming partly or entirely, has reduced production cost.
3, by enforcement of the present invention, the ultra-fine molecular sieve crystal particle in mother liquor in crystallization process, has played crystal seed inducing action in position, and the degree of crystallinity of resulting materials is higher.
4, by enforcement of the present invention, can in-situ crystallization syntheticly contain the spherical catalyzer of SAPO-34 molecular sieve, avoid producing new need mother liquor to be processed simultaneously.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram of embodiments of the invention 1-8 resulting materials.
Embodiment
The circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid of the present invention, specifically according to following steps:
1) filtrate of the synthetic SAPO-34 molecular sieve of hydrothermal crystallizing is reclaimed as synthesis mother liquid, add wherein phosphorus source, He Gui source, aluminium source, under room temperature, stir 2-24h, gained slurry is designated as A, silicon wherein: phosphorus: the atomic ratio of aluminium is (0.2 ~ 1.5): (0.2 ~ 3.0): (0.2 ~ 3.0); In slurry, solid mixture is designated as M-A.Wherein said phosphorus source is phosphoric acid, ammonium phosphate, the mixing of one or more in ammonium hydrogen phosphate and Secondary ammonium phosphate; Aluminium source is aluminium colloidal sol, pseudo-boehmite, aluminum oxide, aluminium hydroxide, the mixing of one or more in aluminum isopropylate; Silicon source is silicon oxide, silicon sol, silicon ester, or one or more mixing in the kaolin that contains soluble silicon component.
2) in above-mentioned slurry A, add deionized water, matrix, binding agent, pore-forming material is also uniformly mixed, and final gained mixture is designated as B, and the solid matter in mixture B is designated as M-B; In mixture B, the mass content of water is 60-80%; In solid matter M-B, the shared mass ratio of M-A is 25-50%, the mass ratio 30-60% that matrix is shared, and the shared mass ratio of binding agent is 0-15%, the shared mass ratio of pore-forming material is 0-5%.Described substrate material is kaolin, polynite, the mixing of one or more in aluminum oxide; Binding agent is aluminium colloidal sol, silicon sol, the mixing of one or more in aluminum phosphate; Pore-forming material is graphite, sesbania powder, starch, the mixing of one or more in poly-methylcellulose gum.
3) after gained mixed solution is mixed, utilize colloidal mill to shear dispersion, shear particle diameter in disposed slurry and be not more than 4 μ m, after carry out spray shaping, obtain spheroidal particle.Spraying gained spherical particle diameters is between 20-300 μ m, and meso-position radius is between 40-100 μ m.
4) will after the roasting of gained spheroidal particle, in sealed vessel, carry out hydrothermal crystallizing with together with the aqueous solution of organic formwork agent; Described organic formwork agent is triethylamine, diethylamine, ethamine, morpholine, tetraethyl ammonium hydroxide, Isopropylamine, the mixing of one or more in di-n-propylamine; The molar ratio of organic formwork agent and water is 1:(2 ~ 17), the mass ratio of solid and liquid is 1:(0.5 ~ 15).Described spraying gained spheroidal particle maturing temperature is 0 ~ 400 DEG C, and roasting time is 0-20h.In step 4), crystallization temperature is 100-250 DEG C, crystallization time 1-90h.
5) crystallization complete after filtration drying obtain the spherical catalytic material containing SAPO-34 molecular sieve.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.All inventions of doing under thought enlightenment of the present invention all belong to the scope of protection of the invention.
Embodiment 1
After Hydrothermal Synthesis SAPO-34, crystallization adds kaolin after 1.07kg pseudo-boehmite, 0.41kg phosphoric acid, 0.22kg roasting, 11.9kg water in proportion successively under separating in the 12kg mother liquor obtaining and stirring, stir after 2h, add 4.5kg kaolin, 3.2kg silicon sol, 0.5kg Graphite Powder 99 and 1.3kg water, after mixing, shear after spray shaping, obtain microspheres with solid.33.75g microspheres with solid, 33g triethylamine and 35.35g water are joined in stainless steel cauldron, still is placed in to 200 DEG C of crystallization 24h in homogeneous reactor, cooling, centrifugation, the dry catalyst microspheres that obtains.
Embodiment 2
The present embodiment is identical with embodiment 1 preparation technology, and wherein difference is: the microballoon of spray shaping is carried out at 300 DEG C again to hydrothermal crystallizing processing after roasting 2h.
Embodiment 3
The present embodiment is identical with embodiment 1 preparation technology, wherein difference is: in 13 kilograms of mother liquors, add successively 1.07kg aluminum oxide, 0.61kg phosphoric acid, 0.4kg silicon oxide, 13.5kg water, stir after 10h, add 5.7kg kaolin, 2.6kg silicon sol, 0.2kg starch, shears after spray shaping after mixing, by the microballoon of spray shaping roasting 6h at 400 DEG C, obtain microspheres with solid.30g microspheres with solid, 68g diethylamine and 60g water are joined in stainless steel cauldron, still is placed in homogeneous reactor and at 200 DEG C, stirs crystallization 48h, after separation, obtain spherical catalyst particle.
Embodiment 4
The present embodiment is identical with embodiment 3 preparation technologies, wherein difference is: by the microballoon of spray shaping roasting 12h at 200 DEG C, 9.75g microspheres with solid, 8.12g Tri N-Propyl Amine and 138.13g water are joined in stainless steel cauldron, crystallization 60h at 200 DEG C, separates and obtains spherical catalyst particle.
Embodiment 5
The present embodiment is identical with embodiment 1 preparation technology, wherein difference is: after Hydrothermal Synthesis SAPO-34, crystallization separates in the 13kg mother liquor obtaining and adds successively in proportion 2.37kg pseudo-boehmite, 0.69kg phosphoric acid, 1.42kg tetraethyl orthosilicate, 12kg water under stirring, stir after 16h, add 5.5kg kaolin, 0.3kg Graphite Powder 99 and 3.3kg water, after mixing, shear after spray shaping, obtain microspheres with solid.30g microspheres with solid, 42g triethylamine and 38g water are joined in stainless steel cauldron, in 200 DEG C of crystallization 24h, separate and obtain catalyst microspheres.
Embodiment 6
The present embodiment is identical with embodiment 1 preparation technology, wherein difference is: crystallization 4.07kg pseudo-boehmite, 0.81kg primary ammonium phosphate, 1.21kg silicon sol, 10.5kg water successively in proportion under separating in the 13kg mother liquor obtaining and stirring after Hydrothermal Synthesis SAPO-34, stir after 10h, add 7.4kg kaolin, 3.6kg aluminium colloidal sol, 0.5kg sesbania powder, shears after spray shaping after mixing, by the microballoon of spray shaping roasting 6h at 400 DEG C, obtain microspheres with solid.30g microspheres with solid, 78g diethylamine and 100g water are joined in stainless steel cauldron, still is placed in and in homogeneous reactor, at 200 DEG C, stirs crystallization 48h, cooling, centrifugation, dry.
Embodiment 7
The present embodiment is identical with embodiment 1 preparation technology, wherein difference is: by the microballoon of spray shaping roasting 2h at 300 DEG C, 30g microspheres with solid, 12.4g ethamine and 16.35g water are joined in stainless steel cauldron, still is placed in and in homogeneous reactor, at 150 DEG C, stirs crystallization 72h.
Embodiment 8
The present embodiment is identical with embodiment 1 preparation technology, wherein difference is: by the microballoon of spray shaping roasting 12h at 200 DEG C, 33.75g microspheres with solid, 33g morpholine and 38.84g water are joined in stainless steel cauldron to crystallization 72h at 180 DEG C, separate and obtain spherical catalyst particle.
Embodiment 9
Above embodiment 1-8 resulting materials is carried out respectively to X-ray diffraction analysis.Resulting materials is the SAPO-34 molecular sieve catalytic agent material that contains well-crystallized.
Claims (7)
1. a circulation utilization method for SAPO-34 molecular sieve synthesis mother liquid, is characterized in that, comprises the following steps:
1) filtrate of the synthetic SAPO-34 molecular sieve of hydrothermal crystallizing is reclaimed as synthesis mother liquid, add wherein phosphorus source, He Gui source, aluminium source, under room temperature, stir 2-24h, gained slurry is designated as A, silicon wherein: phosphorus: the atomic ratio of aluminium is (0.2～1.5): (0.2～3.0): (0.2～3.0); In slurry, solid mixture is designated as M-A;
2) in above-mentioned slurry A, add deionized water, matrix, binding agent, pore-forming material is also uniformly mixed, and final gained mixture is designated as B, and the solid matter in mixture B is designated as M-B; In mixture B, the mass content of water is 60-80%; In solid matter M-B, the shared mass ratio of M-A is 25-50%, the mass ratio 30-60% that matrix is shared, and the shared mass ratio of binding agent is 0-15%, the shared mass ratio of pore-forming material is 0-5%;
3) after gained mixed solution is mixed, utilize colloidal mill shear disperse after carry out spray shaping, obtain spheroidal particle;
4) will after the roasting of gained spheroidal particle, in sealed vessel, carry out hydrothermal crystallizing with together with the aqueous solution of organic formwork agent;
5) crystallization complete after filtration drying obtain the spherical catalytic material containing SAPO-34 molecular sieve.
2. the circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid according to claim 1, is characterized in that step 1) in, described phosphorus source is phosphoric acid, ammonium phosphate, the mixing of one or more in ammonium hydrogen phosphate and Secondary ammonium phosphate; Aluminium source is aluminium colloidal sol, pseudo-boehmite, aluminum oxide, aluminium hydroxide, the mixing of one or more in aluminum isopropylate; Silicon source is silicon oxide, silicon sol, silicon ester, or one or more mixing in the kaolin that contains soluble silicon component.
3. the circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid according to claim 1, is characterized in that step 2) in, described substrate material is kaolin, polynite, the mixing of one or more in aluminum oxide; Binding agent is aluminium colloidal sol, silicon sol, the mixing of one or more in aluminum phosphate; Pore-forming material is graphite, sesbania powder, starch, the mixing of one or more in poly-methylcellulose gum.
4. the circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid according to claim 1, it is characterized in that step 3) in, shear particle diameter in disposed slurry and be not more than 4 μ m, spraying gained spherical particle diameters is between 20-300 μ m, and meso-position radius is between 40-100 μ m.
5. the circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid according to claim 1, is characterized in that step 4) in, described organic formwork agent is triethylamine, diethylamine, ethamine, morpholine, tetraethyl ammonium hydroxide, Isopropylamine, the mixing of one or more in di-n-propylamine; The molar ratio of organic formwork agent and water is 1:(2～17), the mass ratio of solid and liquid is 1:(0.5～15).
6. the circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid according to claim 1, is characterized in that step 4) in, by step 3) spraying gained spheroidal particle maturing temperature is 0～400 DEG C, roasting time is 0-20h.
7. the circulation utilization method of SAPO-34 molecular sieve synthesis mother liquid according to claim 1, is characterized in that step 4) in, crystallization temperature is 100-250 DEG C, crystallization time 1-90h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210531673.0A CN102992349B (en) | 2012-12-11 | 2012-12-11 | Recycling method of mother liquor for SAPO-34 molecular sieve synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210531673.0A CN102992349B (en) | 2012-12-11 | 2012-12-11 | Recycling method of mother liquor for SAPO-34 molecular sieve synthesis |
Publications (2)
| Publication Number | Publication Date |
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| CN104445245A (en) * | 2013-09-25 | 2015-03-25 | 天津神能科技有限公司 | Synthesis method of silicoaluminophosphate molecular sieve SAPO-34 |
| CN106540744A (en) * | 2015-09-22 | 2017-03-29 | 正大能源材料(大连)有限公司 | A kind of reuse method of sial phosphorus molecular sieve catalyst |
| CN105668587B (en) * | 2016-02-23 | 2018-06-22 | 山东齐鲁华信高科有限公司 | The circulation utilization method of SAPO-34 molecular sieve synthesis mother liquids |
| CN106830009A (en) * | 2017-01-25 | 2017-06-13 | 中国天辰工程有限公司 | A kind of method of reuse sial phosphorus molecular sieve filtered fluid and molecular sieve device is prepared again |
| CN108067300B (en) * | 2017-12-20 | 2021-01-26 | 卓悦环保新材料（上海）有限公司 | Method for forming SAPO-34 molecular sieve catalyst |
| CN110217804B (en) * | 2018-03-01 | 2021-01-22 | 国家能源投资集团有限责任公司 | ZSM-5 molecular sieve and preparation method thereof, hydrogen type ZSM-5 molecular sieve and application thereof, and methanol conversion method |
| CN109225318B (en) * | 2018-07-30 | 2022-01-18 | 中国华能集团有限公司 | Multistage recycling method for methanol-to-olefin catalyst synthesis wastewater |
| CN110665538B (en) * | 2019-12-06 | 2020-10-16 | 山东国瓷功能材料股份有限公司 | Modified CHA type molecular sieve and preparation method and application thereof |
| CN112062138B (en) * | 2020-09-08 | 2022-04-15 | 正大能源材料(大连)有限公司 | Catalyst for preparing olefin from methanol and preparation method and application thereof |
| CN112010327A (en) * | 2020-09-11 | 2020-12-01 | 上海第二工业大学 | Method for preparing SAPO-34 molecular sieve by taking crystallized mother liquor as raw material |
| CN113562739A (en) * | 2021-08-06 | 2021-10-29 | 中海油天津化工研究设计院有限公司 | Method for fully crystallizing SAPO-34 molecular sieve balls by using aluminophosphate molecular sieve mother liquor |
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| CN101121531A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Phosphorus modifying method for pinhole phosphorus-silicon-aluminum molecular sieve |
| CN100584758C (en) * | 2006-08-08 | 2010-01-27 | 中国科学院大连化学物理研究所 | Fast synthetic method for phosphorus-silicon-aluminum molecular sieve |
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| CN101121533B (en) * | 2006-08-08 | 2010-05-19 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve with micropore and mesopore structure and synthetic method thereof |
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