CN1704163A - Molecular screen microspherical catalyst - Google Patents
Molecular screen microspherical catalyst Download PDFInfo
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- CN1704163A CN1704163A CN 200410024731 CN200410024731A CN1704163A CN 1704163 A CN1704163 A CN 1704163A CN 200410024731 CN200410024731 CN 200410024731 CN 200410024731 A CN200410024731 A CN 200410024731A CN 1704163 A CN1704163 A CN 1704163A
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- catalyst
- molecular sieve
- zeolite catalyst
- silica
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000002808 molecular sieve Substances 0.000 claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004927 clay Substances 0.000 claims abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 15
- 239000004005 microsphere Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 12
- 238000005299 abrasion Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- 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 6
- 239000002994 raw material Substances 0.000 claims description 6
- -1 galapectite Substances 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 4
- 241000269350 Anura Species 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 239000012530 fluid Substances 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract description 2
- 229910052570 clay Inorganic materials 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010009 beating Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102100024304 Protachykinin-1 Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 101800003906 Substance P Proteins 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a molecular sieve micro-balloon catalyst which mainly resolves the problem that the two indexes of macro-mole sieve capacity and good mechanic strength of catalyst can't exist at the same time. It adopts molecular sieve and adds alumina, silicon oxide and clay so that the packing density of catalyst is at 0.6-0.9 gram/milliliter which can be used in industry preparation of fixed bed, fluid bed or moved bend molecular sieve.
Description
Technical field
The present invention relates to microsphere zeolite catalyst, particularly about a kind of high-load microsphere zeolite catalyst of suitable fluidized bed process.
Background technology
Molecular sieve catalyst is because its excellent catalytic performance successfully is applied to the number of chemical course of reaction.Simultaneously, because the highly acid of molecular sieve, when the various organic matters of catalysis reacted, coking especially easily, living carbon made and the very fast inactivation of catalyst can successfully carry out in order to make reaction that catalyst is coke burning regeneration constantly.For this reason, developed various types of reactions-regeneration technology system and corresponding catalyst type, as reactors such as moving bed, fluid bed, risers, its catalyst is a microspheric, and requires to have advantages of good abrasion and fluidizing performance.
The typical catalytic cracking of petroleum refining industry (FCC) catalyst is the microballoon molecular sieve, and molecular sieve content generally is not more than 30%, and the binding agent that the preparation catalyst uses is Ludox, aluminium colloidal sol, silicon gel, alumina gel, silica-alumina gel etc.As:
The acidifying peptization boehmite that Chinese patent CN1240813, CN1311288 provide and the double aluminium binder of aluminium colloidal sol, by steps such as control suitable substance P H values, can be made into molecular sieve content less than 40% microspherical catalyst, have reactivity worth and abrasion strength resistance preferably.
USP3959689 has used the stable Ludox of a kind of aluminium as binding agent, and when molecular sieve content 17%, the microspherical catalyst DAVISON abrasion index that makes is 3% hour
-1
Japanese kokai publication sho 61-215206 adds aluminium colloidal sol with phosphorus compound, and USP3867279 joins phosphate in the microballoon of part combination, is used to improve the mechanical strength of catalyst.
Usually molecular sieve catalyst is when chemical field is used, for improve reactive activity and product once through yield as far as possible, the general catalyst (as greater than 40% weight) that requires to use higher molecular sieve content, but because the catalyst of macromolecule sieve content must cause the reduction of catalyst mechanical strength, particularly use the binding agent and the preparation method of these conventional FCC catalyst, when the preparation macromolecule sieves the microspherical catalyst of content, the non-constant of the mechanical strength of catalyst and wear resistance, be easy to efflorescence, cause cyclonic separation catalyst difficulty, catalyst attrition is serious, and too thin catalyst fines is reunited easily, the catalyst fluidization weak effect causes reaction result (conversion ratio, selectivity) undesirable, thereby can't satisfy the requirement of fluidized-bed reaction technology.General catalyst abrasion index is low more, illustrates that the catalyst wear resistance is good more, and when the polishing machine of catalyst during greater than 4.0 hours-1, then this catalyst just has been difficult to commercial Application.
Summary of the invention
Technical problem to be solved by this invention is to overcome the problem that exists the sieve content of macromolecule in the catalyst and two indexs of catalyst mechanical strength not to possess simultaneously in the conventional art, and a kind of new microsphere zeolite catalyst is provided.This catalyst not only has high molecular sieve content, has the good wear resistance and the characteristics of catalytic activity simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of microsphere zeolite catalyst comprises following component by weight percentage:
A) 40～80% molecular sieve;
B) 10～30% aluminium oxide;
C) 0.5～10% silica;
D) 0～30% clay;
Wherein the bulk density of catalyst is 0.6～0.9 grams per milliliter, and abrasion index is 1.2～4.0 hours
-1
In the technique scheme, the consumption preferable range of molecular sieve is 50～70% by weight percentage, and the consumption preferable range of aluminium oxide is 15～25%, and the consumption preferable range of silica is 0.5～5%.The preferred version of molecular sieve is to be selected from least a in X type molecular sieve, Y zeolite, ZSM type molecular sieve, modenite, beta molecular sieve or the SAPO type molecular sieve; The raw material sources preferred version of aluminium oxide is an aluminium colloidal sol; The raw material sources preferred version of silica is a waterglass; The clay preferred version is for being selected from imvite, tired soil, galapectite, sepiolite or the kaolin of taking off; The catalyst shape preferred version is 20～150 microns a spheric granules.
Method for preparing catalyst:
Its preparation process is basic with the FCC catalyst preparation process of knowing; usually earlier clay being added proper amount of deionized water soaks; stir with the high shear making beating then; the aluminium sol adhesive and the waterglass that add required amount again; the pH value of regulating slurry with acid is 3～10; for the protection molecular sieve is not destroyed by too strong acid or alkali, molecular sieve in the end adds usually.For the intensity of catalyst, the reinforced order of various raw materials changes the influence that there is no greatly, thereby can regulate arbitrarily according to the needs of reaction and preparation.Prepared like this slurry is uniform suspension, generally can place 8～48 hours and not obvious layering.
Usually solid content of slurry is 25～45% (weight), for reducing the evaporation of water amount, reduces energy consumption, and solid content scope preferably is 30～40% (weight).
Slurry under 500～600 ℃ of inlet temperatures, 250～350 ℃ condition of outlet, spray shaping, roasting 0.5～10 hour under 500～650 ℃ of conditions again.
The microsphere particle catalyst that makes, if necessary, can be further at water or exchange of ammonium salt solution intermediate ion or washing several, the dry catalyst sample that gets.
Prepared catalyst is 20～150 microns a spheric granules, and bulk density is 0.6～0.9 grams per milliliter.
This composite binder and method for preparing catalyst can be used for preparing fixed bed or moving bed and FCC catalyst equally, have very high intensity and reactivity worth.
The raw material that the present invention uses can for:
A: molecular sieve as the activity of such catalysts component, can be one or more mixed molecular sieves such as X type, Y type, ZSM series, modenite, β type, SAPO series, and can be the molecular sieve of other ion-exchanges such as ammonium type, Hydrogen, sodium type and rare earth.
The zeolite crystal size requirements is preferably in below 2 microns below 10 microns, and too big zeolite crystal is unfavorable for forming the microspherical catalyst of high mechanical properties.
B: clay is a FCC type commonly used, if you would take off soil, tire out and take off natural claies such as soil, galapectite, sepiolite, and the most frequently used is kaolin.
C: binding agent is aluminium colloidal sol or waterglass and mixture thereof.
D: regulating the used acid of pH value is organic acid or inorganic acid, as nitric acid, hydrochloric acid or formic acid etc., can remove by simple roasting or washing process.
Method for preparing catalyst of the present invention can be used for the differential responses Preparation of catalysts, as the catalyst of olefin cracking propylene enhancing, ethene, and the catalyst of pyridine base-synthesized compounds, and methanol-to-olefins MTO catalyst and preparing gasoline by methanol MTG catalyst etc.
The present invention is by selecting high performance composite binder and corresponding catalyst slurrying, spray art technology, control suitable slurry conditions, overcome the shortcoming in the above-mentioned conventional art, its abrasion index of 50% microsphere zeolite catalyst of preparation can arrive 1.2% hour
-1, (measuring the abrasion index of microspherical catalyst with enterprise of Qilu Petrochemical company mark Q/TSH002.5.125-93 method) has good wear resistance and higher bulk density.Use this composite binder and preparation method, preparation can reach better machinery and fluidizing performance, and can reduce the consumption of binding agent during less than the microballoon of 50% molecular sieve amount, replace cheap filler such as clay, be used for the cost that actual production can reduce catalyst greatly.Because an amount of clay exists, improve the pore size distribution structure of catalyst simultaneously, had unimpeded diffusion duct, can fully effectively utilize the catalytic performance of molecular sieve, made catalyst have good reaction activity, obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With kaolin 68 grams (igloss 15%), adding water 125 grams soaked 10 minutes, then with high shear making beating 10 minutes, the aluminium colloidal sol that adds 300 grams (alumina content 20.6% (weight)) stirred 5 minutes, waterglass 20 grams that add 26% silica again, and adding 20% (weight) nitric acid, to regulate pH value be about 3.5, adds 125 gram HZSM-5 molecular sieves making beating 15 minutes at last, the slurry of 40% (weight) solid content.This slurry spray-drying is shaped, 600 ℃ of import wind-warm syndrome degree, 350 ℃ of outlets, getting particle mean size is the microspherical catalyst of 60 microns molecular sieve content 50% weight.Measure to such an extent that catalyst is piled than 0.83 grams per milliliter abrasion index 1.5% hour
-1
[embodiment 2]
The preparation process condition identical with embodiment 1 changes the consumption of molecular sieve, waterglass and aluminium colloidal sol, and kaolin is poising agent, makes catalyst (when the waterglass consumption is high, with 10% weight nitric acid ammonium salt solution exchange three times and drying, roasting).
And with the catalyst 30 gram fluidized-bed reactor of packing into, the control reaction temperature is at 450～650 ℃, 550, and air speed WHSV1～15 hour
-1, 5, water/molar equivalent 0.5～3,1, under the condition of pressure 0～1.5 atmospheric pressure (gauge pressure), be used to take out the test of surplus mixed c 4 preparing propylene by catalytic cracking, ethene, the reactivity worth of examination catalyst.
Tabulation 1
| Embodiment | Molecular sieve % weight | Aluminium oxide % weight | Silica % weight | Catalyst | Appraisal result | |||
| Heap Bick/milliliter | Abrasion index % hour -1 | ??C 4 ＝Conversion ratio % | Propene yield % | Yield of ethene % | ||||
| ????1 | ????50 | ????25 | ????2 | ??0.83 | ????1.5 | ????72.3 | ????30.5 | ????9.6 |
| ????2 | ????50 | ????25 | ????1 | ??0.72 | ????3.5 | ????73.6 | ????31.2 | ????9.2 |
| ????3 | ????50 | ????25 | ????8 | ??0.85 | ????1.2 | ????65.3 | ????28.4 | ????8.4 |
| ????4 | ????50 | ????10 | ????8 | ??0.78 | ????3.1 | ????63.6 | ????26.5 | ????6.5 |
| ????5 | ????50 | ????15 | ????8 | ??0.81 | ????2.1 | ????67.8 | ????28.5 | ????8.2 |
| ????6 | ????50 | ????15 | ????2 | ??0.68 | ????3.9 | ????68.2 | ????28.9 | ????8.6 |
| ????7 | ????60 | ????25 | ????2 | ??0.70 | ????1.6 | ????74.6 | ????32.1 | ????10.6 |
| ????8 | ????70 | ????25 | ????2 | ??0.65 | ????2.7 | ????76.2 | ????32.6 | ????10.3 |
| ????9 | ????80 | ????15 | ????5 | ??0.61 | ????3.8 | ????75.2 | ????31.5 | ????9.8 |
[comparative example 1]
With kaolin 100 grams (igloss 15%), add water 650 gram making beating 30 minutes, add 20 milliliters of hydrochloric acid (20% weight) and boehmite 128 grams (igloss 20%), pulled an oar 30 minutes, add 250 gram HZSM-5 molecular sieve making beating 15 minutes again, the aluminium colloidal sol and the hydrochloric acid (20% weight) that add 240 grams (alumina content 20.6% weight) at last stirred 20 minutes for 13 milliliters.This slurry spray-drying is shaped, and washs two times, the also roasting in 10 hours of 120 ℃ of dryings with 15～20 times deionized water.Get microspherical catalyst C.Record the catalyst heap than 0.71 grams per milliliter, abrasion index 13.6% hour
-1
Claims (5)
1, a kind of microsphere zeolite catalyst comprises following component by weight percentage:
A) 40～80% molecular sieve;
B) 10～30% aluminium oxide;
C) 0.5～10% silica;
D) 0～30% clay;
Wherein the bulk density of catalyst is 0.6～0.9 grams per milliliter, and abrasion index is 1.2～4.0 hours
-1
2, according to the described microsphere zeolite catalyst of claim 1, it is characterized in that the consumption of molecular sieve is 50～70% by weight percentage, at least a in X type molecular sieve, Y zeolite, ZSM type molecular sieve, modenite, beta molecular sieve or SAPO type molecular sieve of molecular screening.
3, according to the described microsphere zeolite catalyst of claim 1, it is characterized in that the consumption of aluminium oxide is 15～25% by weight percentage, the raw material sources of aluminium oxide are aluminium colloidal sol.
4, according to the described microsphere zeolite catalyst of claim 1, it is characterized in that the consumption of silica is 0.5～5% by weight percentage, the raw material sources of silica are waterglass; Clay is selected from imvite, tired soil, galapectite, sepiolite or the kaolin of taking off.
5,, it is characterized in that catalyst is 20～150 microns a spheric granules according to the described microsphere zeolite catalyst of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100247316A CN100413586C (en) | 2004-05-28 | 2004-05-28 | Molecular screen microspherical catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100247316A CN100413586C (en) | 2004-05-28 | 2004-05-28 | Molecular screen microspherical catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1704163A true CN1704163A (en) | 2005-12-07 |
| CN100413586C CN100413586C (en) | 2008-08-27 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029184A (en) * | 2010-11-04 | 2011-04-27 | 中国天辰工程有限公司 | Catalyst used in process of preparing dimethyl ether from methanol on fluidized bed and preparation method thereof |
| CN102188989A (en) * | 2011-03-24 | 2011-09-21 | 中国天辰工程有限公司 | Fluidized bed catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1046641C (en) * | 1990-12-05 | 1999-11-24 | 中国科学院大连化学物理研究所 | Modified zeolite catalyst for light hydrocardon aromatization reaction |
| US6884744B2 (en) * | 2001-04-13 | 2005-04-26 | W. R. Grace & Co.-Conn. | Zeolite based catalyst of ultra-high kinetic conversion activity |
| CN1199732C (en) * | 2002-06-20 | 2005-05-04 | 中国科学院大连化学物理研究所 | Catalyst for reversal disproportionation preparation of propene from ethylene and butylene |
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2004
- 2004-05-28 CN CNB2004100247316A patent/CN100413586C/en not_active Expired - Lifetime
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