CN1261215C - Nano molecular sieve filtration method - Google Patents
Nano molecular sieve filtration method Download PDFInfo
- Publication number
- CN1261215C CN1261215C CN 03122854 CN03122854A CN1261215C CN 1261215 C CN1261215 C CN 1261215C CN 03122854 CN03122854 CN 03122854 CN 03122854 A CN03122854 A CN 03122854A CN 1261215 C CN1261215 C CN 1261215C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- nano
- sio
- electrolyte
- slurries
- 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.)
- Expired - Lifetime
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 89
- 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 82
- 238000001914 filtration Methods 0.000 title abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000003311 flocculating effect Effects 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 22
- 229910004298 SiO 2 Inorganic materials 0.000 description 20
- 239000000706 filtrate Substances 0.000 description 20
- 239000012065 filter cake Substances 0.000 description 11
- 238000005352 clarification Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000012265 solid product Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- -1 molecular sieve compound Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012224 working solution Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a filtration method of a nanometer molecular sieve. The present invention is characterized in that the method comprises steps of adding alkaline media, non-electrolytes and water into molecular sieve slurry, wherein the addition of the alkaline media makes the pH of the mixture is not smaller than 12, and the volume ratio among the molecular sieve slurry, the non-electrolytes and the water is 1: 1 to 5: 0 to 2. The method can effectively inhibit the flocculating of uncrystallized SiO2.
Description
Technical field
The present invention relates to a kind of filter method of molecular sieve, relate to a kind of filter method of nano molecular sieve furtherly.
Background technology
Nano molecular sieve is meant the molecular sieve of particle size between 1～100nm, its surface atom number and body mutually the ratio of total atom number with the reducing and sharply increase of grain size, thereby nano molecular sieve is become have the new material of unique catalytic performance.The characteristics of nano molecular sieve show: 1) have bigger external surface area, make more activated centre obtain exposing, eliminated diffusion effect effectively, catalyst efficiency is not fully exerted; 2) have the outside apertures that are exposed to more, be difficult for being stopped up, help prolonging and react service cycle by the reactive deposition thing.
But the nano molecular sieve granularity is too small, is difficult to separate with mother liquor, makes filtration and recovery become difficult, thereby has hindered the application of nano molecular sieve in industry.
" Microporous and Mesoporous Materials " 25 (1998) 59～74 " to go out the nano-beta molecular sieve slurries are steady suspension to middle finger, sinking speed is extremely slow, though with its place 1 year can the sedimentation layering yet.This article proposes earlier molecular sieve pulp to be diluted with water to low viscosity and low pH value, adopts the high speed centrifugation partition method to reclaim the method for molecular sieve filter cake then, is to operate 90min under the 16000rpm at rotating speed.This method rotating speed height, the molecular sieve treating capacity is little, and disengaging time is long, thereby can't be applied to large-scale production.
At present existing patent proposes to improve the filter method of nano molecular sieve.
The applicant is to propose to adopt sol-gel (sol-gel) method with nano molecular sieve and SiO in 02100379.3 the Chinese patent at application number
2Or Al
2O
3Or SiO
2/ Al
2O
3Be prepared into the nano molecular sieve compound.Particularly, be 1-4, SiO with pH
2Or Al
2O
3Or SiO
2/ Al
2O
3Content be acidic silicasol or the acidic aluminum sol of 10-50 weight % and contain 10-50 weight % nano molecular sieve, pH is that the molecular sieve pulp of 9-14 is according to (SiO
2Or Al
2O
3The weight ratio of)/molecular sieve=0.2-2 is under agitation mixed, and making the pH that mixes back gained mixture is 7-9.5, thereby forms gel; With gained gel drying and pulverizing or shaping, obtain the nano molecular sieve compound then.This method makes the nano molecular sieve slurries directly mix with the colloidal sol of carrier without filtration, has avoided the most difficult filtration step in the nano molecular sieve preparation; And dried nano molecular sieve compound makes filter operation become easy.
The preparation method of the disclosed a kind of fine-grain superstable Y-molecular sieve of CN1205981A, wherein the filter method of the molecular sieve of Miao Shuing be with average crystal grain be fine-grain NaY type molecular sieve below the 0.5 μ m and water, ammonium salt, and a kind of acidic silicasol according to NaY: ammonium salt: SiO
2: H
2O=1: (0.5～2.5): (0.01～0.20): after the weight ratio of (5～30) mixes, slurry pH value is adjusted to 2.8～3.5, filters then.
In present industrial production, people usually adopt the means of materials such as adding ammonium chloride, ammonium nitrate, ammonium sulfate in molecular sieve pulp to promote the nano molecular sieve flocculation, improve filter efficiency, and it is 9～10 that this method makes molecular sieve pulp pH value.But, the non-crystallized SiO of part is arranged in the crystallization building-up process of nano molecular sieve
2Reside in the mother liquor, in pH＜11 o'clock, the SiO that these are non-crystallized
2Very easily flocculate, be deposited on molecular sieve inside, stop up the aperture, thereby influence the molecular sieve life-span.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of and can suppress non-crystallized SiO effectively
2The filter method of the nano molecular sieve of flocculation takes place.
The filter method of nano molecular sieve provided by the present invention is included in the step that adds alkaline medium, non-electrolyte and water in the molecular sieve pulp, wherein the alkaline medium addition makes mixture pH 〉=12, and the volume ratio of molecular sieve pulp, non-electrolyte and water is 1: (1～5): (0～2).
The kind of said nano molecular sieve has no particular limits in the method provided by the invention, granular size is the various molecular sieves of 1～100nm, and for example beta-molecular sieve, Y zeolite, ZSM-5 molecular sieve, HTS, A type molecular sieve, modenite etc. all are applicable to method provided by the invention.Said molecular sieve pulp both can be the slurries that the finished product nano molecular sieve is dispersed in gained in the water, also can be the molecular sieve pulp that filtered directly obtains behind the synthesis of nano molecular sieve.
In the method provided by the invention, said non-electrolyte can be selected from one of ethanol, propyl alcohol, butanols, glucose or glycerine or its mixture, wherein preferred alcohol; Said alkaline medium can be NaOH, potassium hydroxide, aluminium hydroxide, sodium carbonate or sodium acid carbonate.
In the method provided by the invention, there is no special requirement, can add alkaline medium earlier, add non-electrolyte again for the addition sequence of alkaline medium, non-electrolyte and water; Also can add non-electrolyte earlier, add alkaline medium again, wherein a kind of charging sequence is preferred in the past.
In the method provided by the invention, the volume ratio of molecular sieve pulp, non-electrolyte and water preferred 1: (1～3): (0～1).
The filter method of nano molecular sieve provided by the present invention can make filtering rate accelerate, the filtrate clarification, and have following characteristics:
1, this method is under the alkali condition (pH 〉=12) filtration of nano molecular sieve all the time, has promoted the slurries flocculation, has avoided non-crystallized SiO in the slurries
2Flocculation, thereby can prevent non-crystallized SiO
2Retention is deposited on molecular sieve inside, stops up the molecular sieve aperture and to the influence in molecular sieve life-span.
2, replace water with non-electrolyte, help reducing the surface tension of filtering back dry run medium, reduce the reunion degree of nano molecular sieve, particularly with volatile non-electrolyte, replace water as ethanol, help the recovery of template agent in the filtrate, reduce the nano molecular sieve production cost.
3, the nano molecular sieve that filters through method provided by the invention, the nano molecular sieve that its catalytic perfomance and conventional filtration technology obtain is suitable.
The specific embodiment
Following examples will be further described method provided by the invention, but not thereby limiting the invention.
In each embodiment and Comparative Examples, thing uses X-ray diffraction method (XRD) to measure the SiO in the filtrate mutually
2Be to measure the SiO in the filter cake with plasma emission spectroscopy method (ICP/AES)
2/ Al
2O
3Measure with x ray fluorescence spectrometry (XRF).
In Comparative Examples and embodiment 1～6, used nano-beta molecular sieve is to prepare according to the 7 described methods of the embodiment among the CN1324762A, and concrete steps are: boehmite (is contained Al
2O
356.6 weight %, Zhou village catalyst plant product), NaOH (chemical pure, Beijing Chemical Plant's product), tetraethyl ammonium hydroxide solution (2.633N, go in in a big way emerging good fortune fine chemistry industry research institute) add deionized water, heating for dissolving stirs, and makes working solution, with silochrom (80-120 order, igloss 3.7%, Haiyang Chemical Plant, Qingdao) mix with above-mentioned working solution, make the silica gel surface wetting by working solution, obtain reactant mixture, wherein the mol ratio of each component is SiO
2/ Al
2O
3=30, Na
2O/SiO
2=0.075, TEAOH/SiO
2=0.09, H
2O/SiO
2=6.5, (wherein SY1634-70 is a kind of commercially available pumping fluid to add additive SY1634-70 (50% weight)+Tween-65 (50% weight) then, seven factories of Dalian Petrochemical Industry Company produce, molecular weight 800-1000, and polyoxyethylene groups shared weight ratio in said polyalkylene ether is 25%; Tween-65 is Farco company commodity, molecular weight 800-1000, HLB=10.5) and stir additive/SiO
2Weight ratio is 2.5%.With this reactant mixture 120 ℃ of crystallization 24 hours in autoclave,, promptly get the nano-beta molecular sieve slurries after being cooled to room temperature again 140 ℃ of crystallization 48 hours.Its molecular sieve granularity＜100nm, SiO
2/ Al
2O
3Mol ratio is 25-26.
The catalytic reaction evaluating data is to be that probe reaction carries out with the n-decane hydroisomerization reaction.
The process that molecular sieve is prepared into catalyst for hydroisomerizing is that the ammonium type product with molecular sieve adopts the equi-volume impregnating and the 0.25% palladium ammino-complex aqueous solution to flood, 550 ℃ of dry then, roastings 3 hours, compressing tablet, pulverizing are the 40-60 order, and Pd content is 0.2-0.3 weight % in the catalyst.
Hydroisomerization reaction carries out in continuous fixed bed stainless steel reactor.Catalyst is in nitrogen atmosphere under the 0.6Mpa, and 375 ℃ are given reductase 12 hour, H
2Flow 110ml/min.Reaction condition is: 0.6Mpa, H
2/ n-decane (mol)=1, WHSV=1 hour
-1, 280 ℃.Reactor product separated through condensation, obtained accumulation sample (the reaction incipient stability is after 2 hours) every 1 hour.Analyze on gas chromatograph (GC8000 that CE company produces), chromatographic column is diameter 0.25mm, the OV-1 chromatographic column of long 30m, fid detector.According to measurement result, carry out mass balance, error is 1～3%.
Comparative Examples
The filter process of nano molecular sieve in this Comparative Examples explanation industrial production.
208 milliliters in nano-beta molecular sieve slurries (butt 50g) and the making beating of 50g ammonium chloride are even, stir always, pH is 7-9, makes the molecular sieve pulp flocculation, promotes to filter, and isolates solid product.Filtration is finished in 8min.The filtrate clarification.Measure the SiO in filtrate, the filter cake respectively
2And SiO
2/ Al
2O
3Do catalytic performance test.Be designated as DB.Performance is listed in table 1.
Embodiment 1
170 milliliters in above-mentioned nano-beta molecular sieve slurries (butt 50g) and 7ml 45%NaOH solution are mixed, stir, it is thick that slurries are; The mixture that adds 220ml ethanol and 70ml water again stirs to slurries and flocculates.PH is 12-13, filters, and isolates solid product.Filtration is finished in 6min, the filtrate clarification.Measure the SiO in filtrate, the filter cake respectively
2And SiO
2/ Al
2O
3Do catalytic performance test.Be designated as A1.Performance is listed in table 1.
Embodiment 2
170 milliliters in above-mentioned nano-beta molecular sieve slurries (butt 50g) and 7ml 45%NaOH solution are mixed, stir, it is thick that slurries are; The mixture that adds 600ml ethanol and 120ml water again stirs to the slurries flocculation, and keeping pH is 12-13, filters and finishes in 30min, and cake moisture is big, the filtrate clarification.Measure the SiO in filtrate, the filter cake respectively
2And SiO
2/ Al
2O
3Do catalytic performance test.Be designated as A2.Performance is listed in table 1.
Embodiment 3
170 milliliters in above-mentioned nano-beta molecular sieve slurries (butt 50g) and 7ml 45%NaOH solution are mixed, stir, it is thick that slurries are; Add 220ml ethanol again, stir to slurries and flocculate.PH is 12-13, filters, and isolates solid product.Filtration is finished in 6min, the filtrate clarification.Measure the SiO in filtrate, the filter cake respectively
2And SiO
2/ Al
2O
3Do catalytic performance test.Be designated as A3.Performance is listed in table 1.
Embodiment 4
170 milliliters in above-mentioned nano-beta molecular sieve slurries (butt 50g) and 7ml 20%KOH solution are mixed, stir, it is thick that slurries are; The mixture that adds 220ml propyl alcohol and 200ml water again stirs to slurries and flocculates.PH is 12-13, filters, and isolates solid product.Filtration is finished in 6min, the filtrate clarification.Measure the SiO in filtrate, the filter cake respectively
2And SiO
2/ Al
2O
3Do catalytic performance test.Be designated as A4.Performance is listed in table 1.
Embodiment 5
170 milliliters in nano-beta molecular sieve slurries (butt 50g) and 7ml 45%NaOH solution are mixed, stir, it is thick that slurries are; The mixture that adds 220ml propyl alcohol and 70ml water again stirs to slurries and flocculates.PH is 12-13, filters, and isolates solid product.Filtration is finished in 6min, the filtrate clarification.Measure the SiO in filtrate, the filter cake respectively
2And SiO
2/ Al
2O
3Do catalytic performance test.Be designated as A5.Performance is listed in table 1.
Embodiment 6
170 milliliters in nano-beta molecular sieve slurries (butt 50g) and 7ml 45%NaOH solution are mixed, stir, it is thick that slurries are; The mixture that adds 104ml glucose and 25ml water again stirs to slurries and flocculates.PH is 12-13, filters, and isolates solid product.Filtration is finished in 6min, the filtrate clarification.Measure the SiO in filtrate, the filter cake respectively
2And SiO
2/ Al
2O
3Do catalytic performance test.Be designated as A6.Performance is listed in table 1.
Table 1
| Numbering | Beta-molecular sieve | SiO in the filtrate 2(mg/L) | The SiO of filter cake 2/Al 2O 3 | C 10Isomerization reaction activity % |
| Comparative Examples | DB | 117.5 | 26.6 | 82％ |
| Embodiment 1 | Al | 2975.0 | 24.9 | 83％ |
| Embodiment 2 | A2 | 3015.4 | 25.1 | 81％ |
| Embodiment 3 | A3 | 2874.1 | 25.7 | 80％ |
| Embodiment 4 | A4 | 3027.8 | 24.7 | 79％ |
| Embodiment 5 | A5 | 2954.9 | 25.3 | 82％ |
| Embodiment 6 | A6 | 3017.4 | 25.6 | 81％ |
As can be seen from Table 1, adopt the method for prior art, non-crystallized SiO
2Still stay in the filter cake (DB), and adopt method provided by the invention can effectively separate non-crystallized SiO
2, make it not stop up the molecular sieve aperture, thereby guaranteeing to prolong the life-span of molecular sieve catalyst under the reactivity condition.
Embodiment 7
Said nanometer Y molecular sieve is to prepare by " the 9th national catalysis academic conference Beijing, 1998, p527 " described method in the present embodiment.Detailed process is: with 45.1g aluminum sulfate (Al
2(SO
4)
318H
2O analyzes the commercial reagent), (Changhong chemical plant, Beijing produces the 232.5g Ludox, contains 25.9 weight % and 0.2 weight %Na
2O), 105.9g NaOH (analyzing pure) and 189.8g deionized water, under room temperature and stirring condition, mix, left standstill 24 hours, obtain directed agents.
Under 0 ℃ and stirring condition, 42.4g NaOH, 138.9g Ludox, 42.3g aluminum sulfate, 28.9g deionized water and 60g directed agents are mixed, add the 29.6g citric acid then, continue to stir 0.5 hour.With the gained mixture stainless steel sealed reactor of packing into, 100 ℃ of following hydrothermal crystallizings 18 hours.The XRD analysis result shows that products therefrom is a Y zeolite.TEM result shows that the mean grain size of products molecule sieve is 70nm.
Nanometer Y molecular sieve slurries 200ml (butt 50g) and 7ml 45%NaOH solution are mixed, stir, it is thick that slurries are; The mixture that adds 220ml ethanol and 70ml water again stirs to slurries and flocculates.PH is 12-13, filters, and isolates solid product.Filtration is finished in 6min, the filtrate clarification.
Embodiment 8
Said nano-ZSM-5 molecular sieve is to prepare by " Zeolites (14), p643-649,1994 " described method in the present embodiment, and the molecular sieve granularity is 30-50nm.
Nano-ZSM-5 molecular sieve slurries 220ml (butt 50g) and 7ml 45%NaOH solution are mixed, stir, it is thick that slurries are; The mixture that adds 220ml ethanol and 70ml water again stirs to slurries and flocculates.PH is 12-13, filters, and isolates solid product.Filtration is finished in 6min, the filtrate clarification.
Claims (7)
1, a kind of filter method of nano molecular sieve, it is characterized in that this method is included in the step that adds alkaline medium, non-electrolyte and water in the molecular sieve pulp, wherein the alkaline medium addition makes mixture pH 〉=12, and the volume ratio of molecular sieve pulp, non-electrolyte and water is 1: (1～5): (0～2).
2, according to the said method of claim 1, wherein said molecular sieve is beta-molecular sieve, Y zeolite, ZSM-5 molecular sieve, HTS, A type molecular sieve or modenite.
3, according to the said method of claim 1, wherein said non-electrolyte is selected from one or more in ethanol, propyl alcohol, butanols, glucose or the glycerine.
4, according to the said method of claim 3, wherein said non-electrolyte is an ethanol.
5, according to the said method of claim 1, wherein said alkaline medium is selected from NaOH, potassium hydroxide, aluminium hydroxide, sodium carbonate or sodium acid carbonate.
6, according to the said method of claim 1, it is characterized in that adding earlier alkaline medium, add non-electrolyte again.
7, according to the said method of claim 1, wherein the volume ratio of molecular sieve pulp, non-electrolyte and water is 1: (1～3): (0～1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03122854 CN1261215C (en) | 2003-04-29 | 2003-04-29 | Nano molecular sieve filtration method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03122854 CN1261215C (en) | 2003-04-29 | 2003-04-29 | Nano molecular sieve filtration method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1541765A CN1541765A (en) | 2004-11-03 |
| CN1261215C true CN1261215C (en) | 2006-06-28 |
Family
ID=34321134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03122854 Expired - Lifetime CN1261215C (en) | 2003-04-29 | 2003-04-29 | Nano molecular sieve filtration method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1261215C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100506345C (en) * | 2007-06-07 | 2009-07-01 | 中国石油化工股份有限公司 | Superfine molecular sieves filtering separating and mother solution recovering method |
| US9133037B2 (en) * | 2010-10-21 | 2015-09-15 | Uop Llc | Processes for making nano zeolites and for recovery of nano zeolites from an aqueous suspension |
| CN104108728B (en) * | 2013-04-18 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of SAPO-11 molecular sieve |
-
2003
- 2003-04-29 CN CN 03122854 patent/CN1261215C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1541765A (en) | 2004-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101376506B (en) | Composite double microporous material and preparation thereof | |
| CN102452663A (en) | Improved preparation method of EU-1 molecular sieve | |
| KR20200039727A (en) | AEI structural molecular sieve and its manufacturing method and use | |
| CN112429749B (en) | Small-grain high-pore-volume CHA zeolite molecular sieve, and synthesis method and catalyst application thereof | |
| CN109569715B (en) | Nanowire composite molecular sieve catalyst and preparation method thereof | |
| CN101209845B (en) | Method for preparing molecular sieve material | |
| CN1314589C (en) | Porous material and its synthesis method | |
| CN116332201A (en) | A method and application of ZSM-48 molecular sieve prepared by in-situ regulation of phenolic molecules | |
| DE69826768T2 (en) | Adsorbent for hydrocarbon and catalyst for exhaust gas purification | |
| CN115872413A (en) | Hierarchical pore molecular sieve and preparation method and application thereof | |
| CN1261215C (en) | Nano molecular sieve filtration method | |
| CN111250154B (en) | Using Al2O3Method for preparing propylene by using Mo-loaded catalytic material of silicon-rich hierarchical pore molecular sieve | |
| CN116689022B (en) | A Pt-encapsulated Beta zeolite molecular sieve, its preparation method and application | |
| CN103011191B (en) | Mordenite and beta zeolite core-shell molecular sieve and preparation method thereof | |
| CN104549459B (en) | Composite molecular sieve, as well as synthesis method and application thereof | |
| CN1051055C (en) | Method for synthesis of beta-zeolite | |
| CN1530322A (en) | A kind of ZSM-5 structure zeolite, its preparation and application | |
| CN111298831B (en) | Preparation method of SSZ-13 molecular sieve for MTO catalytic reaction | |
| CN111302358B (en) | Binder-free FAU type molecular sieve particles and preparation method and application thereof | |
| CN1769169A (en) | Beta zeolite particles with hierarchical pores and preparation method thereof | |
| CN1175935C (en) | Prepn of catalyst material containing nano molecular sieve | |
| CN1100004C (en) | Synthesis of small-crystallite beta zeolite | |
| CN1073968C (en) | Process for preparing fine-grain octahedra zeolite | |
| CN119080015A (en) | Recry-Beta molecular sieve and catalyst and preparation method thereof and their application in hydrocarbon conversion reaction | |
| CN115710002A (en) | Nano molecular sieve and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060628 |