CN1025865C - Reforming catalyst containing beta zeolite - Google Patents
Reforming catalyst containing beta zeolite Download PDFInfo
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- CN1025865C CN1025865C CN 90106023 CN90106023A CN1025865C CN 1025865 C CN1025865 C CN 1025865C CN 90106023 CN90106023 CN 90106023 CN 90106023 A CN90106023 A CN 90106023A CN 1025865 C CN1025865 C CN 1025865C
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- 239000010457 zeolite Substances 0.000 title claims abstract description 65
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 59
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002407 reforming Methods 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 60
- 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 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 239000011591 potassium Substances 0.000 claims abstract description 15
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 17
- 102000040350 B family Human genes 0.000 claims description 16
- 108091072128 B family Proteins 0.000 claims description 16
- 239000010970 precious metal Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 11
- 239000000969 carrier Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 48
- 239000005864 Sulphur Substances 0.000 description 45
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 38
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 22
- 230000000694 effects Effects 0.000 description 20
- 241001120493 Arene Species 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000010926 purge Methods 0.000 description 14
- 229910052702 rhenium Inorganic materials 0.000 description 12
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 12
- 238000000748 compression moulding Methods 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000012974 tin catalyst Substances 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- DBJYYRBULROVQT-UHFFFAOYSA-N platinum rhenium Chemical class [Re].[Pt] DBJYYRBULROVQT-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000005899 aromatization reaction Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 230000007096 poisonous effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
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- 239000012467 final product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
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- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101100004286 Caenorhabditis elegans best-5 gene Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WKWAYZMEWWWCMS-UHFFFAOYSA-N platinum plutonium Chemical compound [Pt][Pu] WKWAYZMEWWWCMS-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a reforming catalyst containing beta zeolite, which contains 0.04-2.0 wt% of a VIII group noble metal or 0.04-2.0 wt% of a VIII group noble metal and 0.04-2.7 wt% of a VIIB group metal or 0.04-1.8 wt% of an IVA group metal and the balance of a carrier, wherein the carrier contains beta zeolite and alumina with the ratio of silicon to aluminum of potassium and phosphorus being more than 40.
Description
The present invention relates to modified beta zeolite and aluminum oxide is the reforming catalyst of carrier.
Catalytic reforming is an important technological process in oil refining and the petrochemical complex industry, and it not only can provide industrial chemicals such as stop bracket gasoline, production aromatic hydrocarbons, but also can pay hydrogen producing.Both at home and abroad to the environmental protection requirement increasingly stringent, motor spirit is progressively to unleaded development in recent years.In addition,, therefore must constantly improve existing reforming catalyst along with the development volume increase aromatic hydrocarbons of chemical industry and chemical fibre industry is also very urgent, or the development of new catalyzer, satisfy requirement to volume increase aromatic hydrocarbons and production high octane gasoline component.
The catalyzer that extensively adopts in the catalytic reforming process is platinum rhenium series and platinum tin catalyst series at present, and its carrier all is ν-Al
2O
3, the metal constituent element in the catalyzer provides the hydrogenation dehydrogenation functionality, and carrier provides acid function, and the common weakness of this class dual-function catalyst is relatively poor to the aromatization activity of low-carbon paraffin, especially to C
6The transformation ratio of alkane is difficulty.
In order further to improve the activity and the selectivity of reforming catalyst, all carried out the research of the reforming catalyst that contains molecular sieve now both at home and abroad, Chevron company has developed reforming catalyst (the GB Z114150A of year platinum L type molecular sieve, USP4448841), this catalyzer is fine to low-carbon paraffin aromatization activity and selectivity, but sulfur resistance is poor, and stability is not ideal enough.
At problems of the prior art, the purpose of this invention is to provide a kind of aromatization activity height, the reforming catalyst that sulfur resistance is good.
Reforming catalyst provided by the invention contains 0.04~2.0 heavy %, best 0.3~0.8 heavy % VIII family precious metal and 0.04~2.7 heavy %, best 0.1~1.4 heavy % VII B family's metal or 0.04~1.8 heavy %, best 0.1~0.8 heavy % IV A family metal, and balance carriers; Carrier contains (being benchmark with the vehicle weight) 20~80 heavy %, best 30~70 heavy % modified beta zeolites and 80~20 heavy %, best 70~30 heavy % aluminum oxide; Modified beta zeolite is for containing 0.5~2.5 heavy %, and best 1.0~2.0 heavy % potassium and 0.01~0.5 heavy %, the silica alumina ratio of best 0.03~0.3 heavy % phosphorus be greater than 40, best 50~100 β zeolite.
Catalyzer provided by the invention also can be by 0.04~2.0 heavy %, best 0.3~0.8 heavy % VIII family precious metal and balance carriers are formed, carrier contains the aluminum oxide of (being benchmark with the vehicle weight) 45~20 heavy % modified beta zeolites and 55~80 heavy %, modified beta zeolite is to contain (is benchmark with zeolite weight) 0.5~2.5 heavy %, best 1.0~2.0 heavy % potassium and 0.01~0.5 heavy %, the silica alumina ratio of best 0.03~0.3 heavy % phosphorus is greater than 40, best 50~100 β zeolite.
Said VIII family precious metal is platinum preferably, and VII B family metal is rhenium preferably, and IV A family metal is tin preferably, and aluminum oxide can be η-Al
2O
3Or ν-Al
2O
3, ν-Al preferably
2O
3, catalyzer can also contain 0.1~2.0 heavy % halogen, and halogen can be chlorine or fluorine, chlorine preferably, when the catalyzer rhenium-containing, catalyzer also contains 0.01~0.5 heavy %, best 0.02~0.24 heavy % sulphur.
Catalyzer provided by the invention can be made by following method:
The method I:
1, contains potassium 0.5~2.5 heavy % by method among the CN1043450A by the preparation of Na β zeolite, best 1.0~2.0 heavy % and phosphorus 0.01~0.5 heavy %, the silica alumina ratio of best 0.03~0.3 heavy % is greater than 40 β zeolite, just in this method behind the dealuminzation silica alumina ratio of gained H β zeolite get final product greater than 40.
2, the conventional preparation method who presses reforming catalyst is with 0.2~1.5 heavy % in the gains load of I step, and best 0.2~1.4 heavy % VII B family's metal or 0.2~1.0 weighs %, best 0.2~0.8 heavy % IV A family metal.
3, the solution of the diacyloxy four ammino type compounds of a kind of VIII family precious metal of the 1st step gains and proper concn is pressed 20~2: 1, best 5~3: the liquid-solid ratio 1(weight ratio) mixes, reacted 1~72 hour down in 15~80 ℃, the concentration of noble metal compound solution so that on the zeolite noble metal support amount be 0.2~2.0 heavy %, best 0.3~0.8 heavy % is advisable, and is dry then, 200~500 ℃, best 260~400 ℃ of roastings 2~5 hours, reduction.
4, the 2nd step gains are pressed the method in the 3rd step and the solution reaction of VIII family precious metal chemical complex, drying, roasting, reduction.
5, the conventional preparation method by reforming catalyst prepares a kind of VIII of load family precious metal 0.2~2.0 heavy %, best 0.2~0.8 heavy % and a kind of VII B metal 0.2~3.0 heavy % of family, best 0.2~1.4 heavy % or a kind of IV A metal 0.2~2.0 heavy % of family, best 0.2~0.8 heavy %, perhaps a kind of VII B of load family metal 0.2~3.0 weighs %, best 0.2~1.4 heavy % or a kind of IV A metal 0.2~2.0 heavy % of family, the aluminum oxide of best 0.2~0.8 heavy %.
6, by 2~8: 8~2, best 3~7: ratio 7~3(weight ratio) is with the 3rd step gains and the 5th step gains, the 4th step gains and the 5th step gains or the aluminum oxide that contains VII B family metal that perhaps will contain VII B family metal, the 4th step gains that perhaps will contain IV A family metal mix with the 5th step gains or the aluminum oxide that contain IV A family metal, or in 4.5~2: ratio 5.5~8(weight ratio) mixes moulding with the 3rd step gains and aluminum oxide.
The method II:
1, contains potassium 0.5~2.5 heavy % by method among the CN1043450A by the preparation of Na β zeolite, best 1.0~2.0 heavy % and phosphorus 0.01~0.5 heavy %, the silica alumina ratio of best 0.03~0.3 heavy % is greater than 40 β zeolite, just in this method behind the dealuminzation silica alumina ratio of gained H β zeolite get final product greater than 40.
2, go on foot gained β zeolite with the 1st and press 0.2~1.5 heavy % in conventional preparation method's load of reforming catalyst, best 0.2~1.4 heavy % VII B family's metal or 0.2~1.0 heavy %, best 0.2~0.8 heavy % IV A family metal.
3, the conventional preparation method by reforming catalyst prepares a kind of VII B of load family metal 0.2~3.0 heavy %, best 0.2~1.4 heavy % or a kind of IV A metal 0.2~2.0 heavy % of family, the aluminum oxide precursor of best 0.2~0.8 heavy %.
4, by 2~8: 8~2, best 3~7: ratio 7~3(weight ratio) is mixed the 1st step gains with the 3rd step gains, the 2nd step gains that maybe will contain VII B family metal mix with the 3rd step gains or the aluminum oxide precursor that contain VII B family, and the 2nd step gains that maybe will contain IV A family metal mix with the 3rd step gains or the aluminum oxide precursor that contain IV A family metal; Perhaps in 4.5~2: ratio 5.5~8(weight ratio) is mixed the 1st step gains with the aluminum oxide precursor, after mixing, moulding, dry, roasting, with the solution of the diacyloxy four ammino type compounds of a kind of VIII family precious metal of proper concn by 15~1: 1, best 4~2: the liquid-solid ratio 1(weight ratio) mixes, reacted 1~72 hour in 15~80 ℃, the concentration of noble metal compound solution so that on the gained catalyzer bullion content be 0.04~2.0 heavy %, best 0.3~0.8 heavy % is advisable, dry then, 200~500 ℃, best 260~400 ℃ of roastings 2~5 hours, reduction.
In the 2nd step and the 3rd step of said the 2nd step of method I and the 5th step and method II, when β zeolite or aluminum oxide are loaded with rhenium, to carry out sulfidizing by the conventional preparation method who contains rhenium reforming catalyst, the sulphur content of this step products therefrom depends on the content of its rhenium metal, can be 0.01~0.5 heavy %, best 0.02~0.24 heavy %, said aluminum oxide and aluminum oxide precursor can be aluminum oxide and the aluminum oxide precursor that is usually used in the reforming catalyst preparation, aluminum oxide can be η-or ν-Al
2O
3, the aluminum oxide precursor can be an aluminium hydroxide, said reduction step is carried out according to conventional reduction method in the reforming catalyst preparation.Said forming step carries out according to conventional forming method in the reforming catalyst preparation, can be extruded moulding, compression molding and ball forming or the like.Roasting process during said method II the 4th goes on foot after the moulding is to be undertaken by the ordinary method in the reforming catalyst preparation.
Catalyzer provided by the invention is compared with platinum-tin catalyst with present industrial platinum rhenium, has higher aromatization activity, also has sulfur poisoning-resistant ability preferably simultaneously.
Below will the present invention will be further described by embodiment.
Example 1
1, preparing the modified beta zeolite that contains potassium 1.8 heavy % and phosphorus 0.08 heavy % by the method for example among the CN1043450A 1, is the Pt(NH of 2 mg/ml (in Pt) with modified beta zeolite and concentration
3)
4Cl
2Solution mixes by 3: 1 liquid-solid ratio, and dipping is 24 hours under the room temperature, drying, and 300 ℃ of following roastings 2 hours, 500 ℃ down with hydrogen reducing 4 hours, promptly get the modified beta zeolite of platiniferous 0.6 weight %, is designated as Pt β-1.
2, get CB-6 platinum-rhenium catalyst (platiniferous 0.3 heavy %, rhenium 0.3 heavy %, chlorine 1.1 heavy % and surplus ν-Al
2O
3, the Chang Ling refinery is produced) in 500 ℃ down with hydrogen reducing 4 hours, be 0.05 heavy % with hydrogen sulfide sulfuration sulphur content to this catalyzer again.
3, the 1st step gains and the 2nd step gains are ground to respectively below 100 orders, with 1: the mixed 1(weight ratio) is even, compression molding, promptly get the catalyzer of platiniferous 0.45 heavy %, rhenium 0.15 heavy % and balance carriers, carrier contain (being benchmark with the vehicle weight) 50 heavy % to contain potassium 1.8 heavy % and phosphorus 0.08 heavy %(be benchmark with β zeolite weight) modified beta zeolite and ν-aluminum oxide of 50 heavy %, this catalyzer is designated as A.
Example 2
1, identical with the 1st step of example 1.
2, get 3861-I industry platinum-tin catalyst (oil three factories produce, platiniferous 0.37 heavy %, tin 0.3 heavy %, chlorine 1.1 heavy % and surplus aluminum oxide) and under 500 ℃, use hydrogen reducing.
3, the 1st step and the 2nd step gains are ground to respectively below 100 orders, then with 1: the mixed 2(weight ratio) is even, compression molding promptly gets the catalyst B that platiniferous 0.45 heavy % and tin 0.2 weigh %, contains modified beta zeolite 33 heavy % and aluminum oxide 67 heavy % in the carrier.
Example 3
1, identical with the 1st step of example 1.
2, getting SB aluminium hydroxide (West Germany's import) is the HReO of 2.5 mg/ml (in Re) with concentration
4Solution mixes with liquid-solid ratio (weight ratio) at 2: 1, and dipping is 24 hours under room temperature, filter, washing, 500 ℃ of following roastings 4 hours, in 500 ℃ down with hydrogen reducing 4 hours, use H
2It is that 0.08 heavy %(is with Al that S vulcanizes to sulphur content
2O
3Weight is benchmark), can get rhenium-containing 0.5 heavy %(with Al
2O
3Weight is benchmark) aluminum oxide.
3, the 1st step and the 2nd step gains are ground to below 100 orders, then with 3: the mixed 1(weight ratio) is even, and compression molding promptly gets the catalyzer C that platiniferous 0.45 heavy % and rhenium 0.13 weigh %, contains modified beta zeolite 75 heavy % and aluminum oxide 25 heavy % in its carrier.
Example 4
1, identical with the 1st step of example 1.
2, get that to contain the heavy %(of Sn0.5 be benchmark with the alumina weight) aluminium hydroxide (Fushun No.3 Petroleum Factory's productions), 500 ℃ of roastings 4 hours, 500 ℃ with hydrogen reduction 4 hours, promptly gets the aluminum oxide that contains Sn0.5 weight %.
3, the 1st step and the 2nd step gains are ground to respectively below 100 orders, then with 3: the 1(weight ratio) mixed is even, compression molding promptly gets the catalyzer D that platiniferous 0.45 heavy % and tin 0.13 weigh %, contains modified beta zeolite 75 heavy % and aluminum oxide 25 heavy % in its carrier.
Example 5
1, with silica alumina ratio be 29 Na β (Fushun No.3 Petroleum Factory's production) and 0.5NHCl(analytical pure) refluxed 1.5 hours down at 100 ℃, its liquid-solid ratio is 4: 1, being washed till filtrate pH with deionized water after filtering is 6~7,110 ℃ of dryings are 2 hours then, 500 ℃ of roastings 2 hours promptly get silica alumina ratio and are 66 H β zeolite.
By the method for example among the CN1043450A 1 above-mentioned H β zeolite is carried out the modification processing and promptly get the modified beta zeolite that contains potassium 1.8 heavy % and phosphorus 0.08 heavy %.
With modified beta zeolite and concentration is the Pt(NH of 2 mg/ml (in Pt)
3)
4Cl
2Solution mixes by 3: 1 liquid-solid ratio, soaked under the room temperature 24 hours, and drying, 300 ℃ of following roastings 3 hours, 500 ℃ down with hydrogen reducing 4 hours, promptly get the modified beta zeolite of platiniferous 0.6 weight %.
ν-the Al that 2, will contain the heavy % of Sn0.5
2O
3(identical with the 2nd step of example 4 gains) presses Pt β with the 1st step products therefrom: stanniferous Al
2O
3Weight ratio is that 3: 7 mixed is even, grinds, and compression molding promptly gets catalyzer E, and catalyzer contains the heavy % of Pt0.2, and tin 0.35 heavy % and balance carriers contains modified beta zeolite 30 heavy % and ν-Al in the carrier
2O
370 heavy %.
Example 6
1, modified beta zeolite (same with example 5) and stanniferous aluminium hydroxide (same with example 4) are pressed 7: the mixed 3(weight ratio) is even, add 0.4 milliliter of acetic acid (chemical pure by per 10 gram materials, the Beijing Chemical Plant) and the consumption of 6 milliliters of deionized waters add acetic acid and deionized water, mediate extrusion, 120 ℃ of dryings 5 hours, 550 ℃ of roastings 3 hours.
2, be the Pt(NH of 2.5 mg/ml (in Pt) with the 1st step gains and concentration
3)
4Cl
2Solution is by 4: the mixed 1(weight ratio) is even, soaks 28 hours under the room temperature, and dry 320 ℃ of roastings 3 hours are used hydrogen reducing 4 hours down for 500 ℃, promptly get the catalyzer F that contains 0.15 heavy % tin and 1.0 heavy % platinum.
With the 1st step gains and concentration is the Pt(NH of 2.5 mg/ml (in Pt)
3)
4Cl
2Solution is by 2: the mixed 1(weight ratio) is even, 40 ℃ of reactions 18 hours down, and drying, 400 ℃ of roastings 3 hours, 540 ℃ down with hydrogen reducing 4 hours, promptly get the catalyzer G that stanniferous 0.15 heavy % and platinum 0.5 weigh %.
Example 7
1, identical with the 1st step of example 5.
2, the 1st step gains and SB aluminum oxide (West Germany's import) are pressed 3: the mixed 7(weight ratio) is even, grinds, and compression molding promptly gets the catalyzer H that platiniferous 0.18 weighs %.
3, the 1st step gains and SB aluminum oxide are pressed 4: the mixed 6(weight ratio) is even, grinds, and compression molding promptly gets the catalyzer I that platiniferous 0.24 weighs %.
4, the 1st step gains and SB aluminum oxide are pressed 1: the mixed 1(weight ratio) is even, grinds, and compression molding promptly gets the comparative catalyst that platiniferous 0.3 weighs %, is designated as contrast-1.
Example 8
1, get the H β zeolite of example 5 the 1st gained in the step, making the silica alumina ratio that contains potassium 1.5 heavy % and phosphorus 0.12 heavy % by the method for example among the CN1043450A 3 is 66 modified beta zeolite, is the Pt(NH of 2 mg/ml (in Pt) with modified beta zeolite and concentration
3)
4Cl
2Solution is by 6: the mixed 1(weight ratio) is even, and 60 ℃ of reactions 10 hours are down stirred down in 100 ℃ of slow evaporate to dryness solution, 250 ℃ of roastings 5 hours, and 500 ℃ of reduction 4 hours promptly get the β zeolite that platiniferous 1.2 weighs %.
2, the aluminum oxide for preparing rhenium-containing 1.5 heavy % by example 3 the 2nd one step process, just HReO
4Strength of solution is 3.75 mg/ml (in Re), and liquid-solid ratio is 4: the 1(weight ratio).
3, the 1st step and the 2nd step gains are pressed 4: the mixed 6(weight ratio) is even, grinds, and compression molding promptly gets the catalyzer J that platiniferous 0.48 and rhenium 0.9 weigh %.
Example 9
1, by example 5 the 1st in the step method preparation contain the heavy modified beta zeolite of the heavy and phosphorus of potassium 1.8 0.08 (just the silica alumina ratio of H β zeolite be 60 get final product), be the Pt(NH of 1.5 mg/ml (in Pt) with this β zeolite and concentration again
3)
4Cl
2Solution is by 2: the liquid-solid ratio 1(weight ratio) mixes, and reaction is 30 hours under the room temperature, 100 ℃ of evaporate to dryness solution then, 320 ℃ of roastings 3 hours, 500 ℃ down the reduction β zeolites that promptly get platiniferous 0.3 heavy % be designated as Pt β-2 zeolite.
2, the 1st step gained Pt β zeolite and CB-6 catalyzer are pressed 1: the 1(weight ratio) mixed is even, grinds, and compression molding promptly gets the catalyzer K that platiniferous 0.3 heavy % and rhenium 0.15 weigh %.
Example 10
The dehydrocyclization activity and the selectivity of evaluate catalysts on the continuous micro-reactor of pressurization, reaction conditions is: reaction raw materials is a normal hexane, and temperature of reaction is 480 ℃, and reaction pressure is 9.81 * 10
5Handkerchief, weight space velocity are 13.6 hours
-1, reaction result sees Table 1.
By table 1 as seen, the aromatization activity of catalyzer provided by the invention all is higher than industrial platinum rhenium and platinum-tin catalyst, and its selectivity also has raising by a relatively large margin.
Example 11
The anti-sulfur poisonous performance of evaluate catalysts A and B on normal pressure pulse micro-inverse device, and and industrial platinum-rhenium catalyst CB-6 and platinum-tin catalyst 3861-I and carry a platinum L zeolite and make comparisons, reaction conditions: with thiophene (Beijing Chemical Plant, chemical pure) is poisonous substance, and reaction raw materials is a normal hexane, temperature of reaction is 490 ℃, hydrogen flowing quantity is 60 ml/min, catalyzer loading amount 0.1 gram, and the thiophene of 2 microlitres injects in elder generation on catalyzer, metal center is poisoned, remove the sulphur of reversible adsorption then with hydrogen purge.Reaction result sees Table 2, has listed before annotating sulphur in the table, has annotated behind the sulphur and purge activity and the selectivity of 70 minutes rear catalysts with hydrogen.
Carry platinum L zeolite catalyst and be by document (petroleum journal, 4(4), 15,1988) method preparation, platinum containing amount is 0.6 heavy %, is designated as the PtL catalyzer.
As shown in Table 2, behind the notes sulphur, the activity of catalyst A and B and aromatics yield decline degree are less, and its activity and arenes selectivity all recover better behind hydrogen purge, and the anti-sulfur poisonous performance of PtL catalyzer is relatively poor.
Example 12
The dehydroisomerization activity and the selectivity of evaluate catalysts on normal pressure pulse micro-inverse device, reaction conditions is: raw material is a methylcyclopentane, 490 ℃ of temperature, catalyst-assembly 0.1 gram, hydrogen flowing quantity is 60 ml/min, inlet amount is 2 microlitres.Simultaneously also estimated the anti-sulphur ability of catalyzer, poisonous substance is a thiophene, and sample size is 2 microlitres.Reaction result sees Table 3.
Can see that the dehydroisomerization activity of catalyzer provided by the invention is higher than industrial platinum rhenium and platinum-tin catalyst from table, aromatization activity has the trend of increase behind the sulfur poisoning.
Example 13
Evaluate catalysts dehydrocyclization activity and selectivity under the condition identical with example 10 the results are shown in Table 4, and as seen from the table, the dehydrocyclization activity of catalyzer of the present invention all is higher than carries a platinum β zeolite; Its selectivity and stability also increase.
Example 14
The anti-sulphur ability of evaluate catalysts under the condition identical with example 11.Reaction result sees Table 5, can see that by table 5 this catalyzer has anti-preferably sulphur ability, and active and selectivity all is higher than industrial platinum rhenium and platinum-tin catalyst.
Example 15
The dehydroisomerization activity of evaluate catalysts under the condition identical with example 12.Reaction result sees Table 6, and by table 6 as seen, activity of such catalysts provided by the invention is higher than industrial platinum plutonium and platinum-tin catalyst, and arenes selectivity has the trend of increase behind the sulfur poisoning.
Example 16
Dehydrocyclization activity and the selectivity of evaluate catalysts E, F, G, H and I under raw material identical and pressure condition with example 10, and make comparisons with CB-6 and 3861-I catalyzer, it the results are shown in Table 7.
Can see from table that catalyzer provided by the invention has than the worker and come platinum rhenium and platinum-tin catalyst to want high aromatics yield, transformation efficiency and arenes selectivity.The arenes selectivity of catalyzer H and I and contrast-1 catalyzer is suitable, although the Pt β content in contrast-1 catalyzer is than catalyzer H and I height.
Example 17
Evaluate catalysts K active and compare under the condition identical with CB-6 and Pt β-2 with example 10.The results are shown in Table 8.
As seen from Table 8, catalyzer provided by the invention has than CB-6 and Pt β-2 catalyzer wants high aromatics yield, arenes selectivity and total conversion rate, and its activity stability is also better.
Table 1
Reaction times
Urge hours 0.5 1357
Change reactivity worth
Agent
Aromatics yield, heavy % 11.64 11.71 11.85 11.38 11.87
The A total conversion rate, heavy % 85.38 85.37 84.06 83.97 83.86
Arenes selectivity, % 13.6 13.7 14.1 13.6 14.2
Aromatics yield, heavy % 3.13 2.73 2.84 2.86
The CB-6 total conversion rate, heavy % 54.83 55.23 56.63 57.03
Arenes selectivity, % 5.7 4.9 5.0 5.0
Aromatics yield, heavy % 8.90 9.22 9.75 9.14 8.97
The B total conversion rate, heavy % 83.4 83.13 82.53 82.33 81.45
Arenes selectivity, % 10.7 11.1 11.8 11.1 11.0
Aromatics yield, heavy % 0,53 0.61 0.72 0.62
The 3861-1 total conversion rate, heavy % 31.49 36.61 38.27 37.53
Arenes selectivity, % 1.7 1.7 1.9 1.7
Table 2
Aromatics yield total conversion rate aromatic selective purges the back choosing
The recovery of selecting property of catalyzer
Heavy % is heavy, and % % leads %
Annotate sulphur preceding 32.46 98.26 33.0
A annotates behind the sulphur 15.03 81.83 18.4
Purge back 29.06 89.14 32.6 98.8
Annotate sulphur preceding 16.21 66.61 24.3
CB-6 annotates behind the sulphur 7.42 50.82 14.6
Purge back 15.51 69.33 22.4 92.2
Annotate sulphur preceding 31.05 90.25 34.4
B annotates behind the sulphur 11.66 80.14 14.5
Purge back 29.69 87.60 33.9 98.5
Annotate sulphur preceding 16.70 70.30 23.8
The 3861-I annotates behind the sulphur 4.56 44.08 10.3
Purge back 12.27 61.79 19.9 83.6
Annotate sulphur preceding 62.5 99.1
63.1
Annotate behind the sulphur 7.5 30.7
24.4
PtL* purges back 17.2 52.0 52.4
** 33.1
* annotate: temperature of reaction is 500 ℃, and the thiophene injection rate is 1 microlitre.
* annotates: purge 80 minutes rear catalyst activity and selectivity.
Table 3
Aromatics yield total conversion rate arenes selectivity
Catalyzer
The heavy % % of heavy %
Annotate sulphur preceding 71.48 99.11 72.1
A
Annotate behind the sulphur 76.05 98.21 77.4
Annotate sulphur preceding 48.99 71.51 68.5
CB-6
Annotate behind the sulphur 50.19 65.05 77.2
Annotate sulphur preceding 74.91 99.19 75.5
B
Annotate behind the sulphur 78.46 98.26 79.8
Annotate sulphur preceding 47.53 74.65 63.7
3861-Ⅰ
Annotate behind the sulphur 49.08 67.02 73.2
Table 4
Reaction times,
Urge hours 0.5 1357
Change reactivity worth
Agent
Aromatics yield, heavy % 10.14 9.52 9.51 8.71 8.14
P+ β-1 total conversion rate, heavy % 84.63 83.60 82.30 80.38 80.31
Arenes selectivity, % 12.0 11.4 11.6 10.8 10.1
Aromatics yield, heavy % 14.41 13.94 13.78 13.32 12.51
The C total conversion rate, heavy % 85.72 85.71 84.93 84.28 83.60
Arenes selectivity, % 16.8 16.3 16.2 15.8 14.9
Aromatics yield, heavy % 10.68 10.69 10.18 9.91 10.47
The D total conversion rate, heavy % 83.79 84.47 83.33 83.30 83.59
Arenes selectivity, % 12.7 12.7 12.2 11.8 12.5
Table 5
Aromatics yield total conversion rate arenes selectivity
Catalyzer
The heavy % % of heavy %
Annotate sulphur preceding 33.59 94.93 35.4
C annotates behind the sulphur 13.74 77.68 17.7
Purge back 26.21 85.15 30.8
Annotate sulphur preceding 16.21 66.61 24.3
CB-6 annotates behind the sulphur 7.42 50.82 14.6
Purge back 15.51 69.33 22.4
Annotate sulphur preceding 33.77 91.88 36.8
Behind the D stream sulphur 10.63 74.07 14.4
Purge back 24.56 85.78 28.6
Annotate sulphur preceding 16.70 70.30 23.8
The 3861-I annotates behind the sulphur 4.56 44.08 10.3
Purge back 12.27 61.79 19.9
Table 6
Aromatics yield total conversion rate arenes selectivity
Catalyzer
The heavy % % of heavy %
Annotate sulphur preceding 52.02 97.07 53.6
C
Annotate behind the sulphur 75.16 97.48 77.1
Annotate sulphur preceding 48.99 71.51 68.5
CB-6
Annotate behind the sulphur 50.19 65.05 77.2
Annotate sulphur preceding 66.85 99.22 67.4
D
Annotate behind the sulphur 75.02 96.98 77.4
Annotate sulphur preceding 47.53 74.65 63.7
3861-I
Annotate behind the sulphur 49.08 67.02 73.2
Table 7
Catalyst reaction weight space velocity aromatics yield total conversion rate aromatic hydrocarbons
Catalyzer platinum containing amount temperature selectivity
The heavy % ℃ hour heavy % of heavy %
E 0.2 480 5.3 11.13 87.22 12.8
F 1.0 480 13.6 8.75 82.11 10.7
500 13.6 13.86 84.87 16.3
G 0.5 480 13.6 4.28 72.1 5.9
500 13.6 5.87 75.92 7.7
520 13.6 8.11 78.81 10.3
H 0.18 480 5.3 16.52 93.0 17.7
I 0.24 480 7.0 15.47 88.6 17.5
CB-6 0.30 480 6.6 4.39 70.82 6.2
480 13.2 2.82 57.59 4.92
3861-I 0.37 480 13.6 0.61 36.61 1.7
Contrast-1 0.3 480 8.8 14.3 84.1 17.0
Table 8
Reaction times,
Urge hours 0.5 13579
Change reactivity worth
Agent
Aromatics yield, heavy % 12.91 9.89 12.21 10.19 10.77 11.13
The K total conversion rate, heavy % 83.05 83.2 83.27 83.13 83.01 82.7
Arenes selectivity, % 15.5 11.9 14.7 12.3 13.0 13.5
Aromatics yield, heavy % 7.25 7.52 7.81 7.65 7.45 7.73
Pt β-2 total conversion rate, heavy % 83.7 80.34 79.23 79.06 78.42 77.84
Arenes selectivity, % 8.7 9.4 9.9 9.7 9.5 9.9
Aromatics yield, heavy % 3.13 2.73 2.84 2.86
The CB-6 total conversion rate, heavy % 54.83 55.23 56.63 57.03
Arenes selectivity, % 5.7 4.9 5.0 5.0
Claims (10)
1, the reforming catalyst that contains the β zeolite, it is characterized in that: catalyzer contains 0.04~2.0 heavy %, a kind of VIII family's precious metals pt and 0.04~2.7 heavy % metal Re of a VIII family or 0.04~1.8 heavy %, a kind of IV A family's metal Sn and balance carriers, carrier comprises (being benchmark with the vehicle weight) 20~80 heavy % modified beta zeolites and 80~20 heavy % aluminum oxide, modified beta zeolite for the silica alumina ratio that contains (is benchmark with zeolite weight) 0.5~2.5 heavy % potassium and 0.01~0.5 heavy % phosphorus greater than 40 β zeolite.
2, the reforming catalyst that contains the β zeolite, it is characterized in that: catalyzer comprises 0.04~2.0 heavy % VIII family precious metals pt and balance carriers, carrier contains (being benchmark with the vehicle weight) 45~20 heavy % modified beta zeolites and 55~80 heavy % aluminum oxide, and modified beta zeolite is the silica alumina ratio that contains (is benchmark with zeolite weight) 0.5~2.5 heavy % potassium and 0.01~0.5 heavy % phosphorus greater than 40 β zeolite.
3, by claim 1 or 2 described catalyzer, it is characterized in that:
(1) the Preparation of catalysts method is (a method I):
A. the preparation silica alumina ratio that contains potassium 0.5~2.5 heavy % and phosphorus 0.01~0.5 heavy % is greater than 40 β zeolite.
B. with 0.2~1.5 heavy % VII B metal Re of family or 0.2~1.0 heavy % IV A family metal Sn in a step gains load.
C. with the solution of the diacyloxy four ammino type compounds of a step gains and a kind of VIII of proper concn family precious metals pt by 20~2: the liquid-solid ratio 1(weight ratio) mixes, under 15~80 ℃, reacted 1~72 hour, the concentration of noble metal compound solution so that on the zeolite bullion content be that 0.2~2.0 heavy % is advisable, dry then, 200~500 ℃ of roastings 2~5 hours, reduction
D. b step gains are pressed the c method and the VIII family precious metals pt solution reaction in step, drying, roasting, reduction.
E. prepare precious metals pt 0.2~2.0 heavy % of a kind of VIII of load family and a kind of VII B metal Re0.2 of family~3.0 heavy % or a kind of IV A metal Sn 0.2~2.0 heavy % of family, the perhaps aluminum oxide of the metal Re0.2 of a kind of VII B of load family~3.0 heavy % or a kind of IV A metal Sn 0.2~2.0 heavy % of family.
F. in 2~8: ratio 8~2(weight ratio) is with c step gains and e step gains, the d step gains and the e step gains or the aluminum oxide that contain the metal Re of VIII B family that perhaps will contain the metal Re of VII B family, the d step gains that perhaps will contain IV A family metal Sn mix with the e step gains or the aluminum oxide that contain IV A family metal Sn, or in 4.5~2: ratio 5.5~8(weight ratio) mixes moulding with c step gains and aluminum oxide;
(2) the Preparation of catalysts method can also be (a method II):
A. the preparation silica alumina ratio that contains potassium 0.5~2.5 heavy % and phosphorus 0.01~0.5 heavy % is greater than 40 β zeolite.
B. a is gone on foot gained β zeolite-loaded last 0.2~1.5 heavy % VII B metal Re of family or 0.2~1.0 heavy % IV A family metal Sn,
C. the aluminum oxide precursor for preparing a kind of VII B of load metal Re0.2 of family~3.0 heavy % or a kind of IV A metal Sn 0.2~2.0 heavy % of family.
D. in 2~8: ratio 8~2(weight ratio) is mixed a step gains with c step gains, the b step gains that maybe will contain the metal Re of VII B family mix with the c step gains or the aluminum oxide precursor that contain the metal Re of VII B family, the b step gains that maybe will close IV A family metal Sn mix with the c step gains or the aluminum oxide precursor that contain IV A family metal Sn, perhaps in 4.5~2: ratio 5.5~8(weight ratio) is mixed a step gains with the aluminum oxide precursor, after mixing, moulding, dry, roasting, then with the diacyloxy four ammino type compound solutions of a kind of VIII family precious metals pt of proper concn by 15~1: the liquid-solid ratio 1(weight ratio) mixes, under 15~80 ℃, reacted 1~72 hour, the concentration of noble metal compound solution so that on the gained catalyzer bullion content be that 0.04~2.0 heavy % is advisable, dry again, 200~500 ℃ of roastings 2~5 hours, reduction.
4, by the described catalyzer of claim 1, it is characterized in that this catalyzer contains 0.3~0.8 heavy % VIII family precious metals pt, 0.1~1.4 heavy % VII B metal Re of family or 0.1~0.8 heavy % IV A family's metal Sn and balance carriers, carrier comprises 30~70 heavy % modified beta zeolites and 70~30 heavy % aluminum oxide, this modified beta zeolite contains 1.0~2.0 heavy % potassium and 0.03~0.3 heavy % phosphorus, and its silica alumina ratio is 50~100.
5, by the described catalyzer of claim 3, it is characterized in that liquid-solid ratio is 5~3: 1 in said method I c and the d step, maturing temperature is 260~400 ℃, these step gains contain a kind of VIII family precious metals pt of 0.3~0.8 heavy %.
6, by the described catalyzer of claim 3, it is characterized in that aluminum oxide contains 0.2~0.8 heavy % VIII family precious metals pt and 0.2~1.4 heavy % VII B metal Re of family or 0.2~0.8 weight % IV A family metal Sn in the said method I e step, perhaps contain 0.2~1.4 heavy % VII B metal Re of family or 0.2~0.8 and weigh % IV A family metal Sn.
7, by the described catalyzer of claim 3, it is characterized in that said method I f in the step c step gains go on foot gains with e, or contain the d step gains and the e step gains or the aluminum oxide that contain the metal Re of VII B family of the metal Re of VII B family, or the d step gains that contain the IV A Sn of family are by 3~7 with the e step gains or the aluminum oxide that contain IV A family metal Sn: mixed 7~3(weight ratio).
8, by the described catalyzer of claim 3, it is characterized in that the aluminum oxide precursor is an aluminium hydroxide in the said method II, the aluminum oxide precursor contained 0.2~1.4 heavy % VII B metal Re of family or 0.2~0.8 heavy % IV A family metal Sn during said method II c went on foot.
9, by the described catalyzer of claim 3, it is characterized in that said method II d in the step a step gains go on foot gains with c, or contain the b step gains and the c step gains or the aluminum oxide precursor that contain the metal Re of VII B family of the metal Re of VII B family, or the b step gains that contain IV A family metal Sn are in 3~7 with the c step gains or the aluminum oxide precursor that contain IV A family metal Sn: 7~3 ratio (weight ratio) blended.
10, by the described catalyzer of claim 3, it is characterized in that said method II d in the step liquid-solid ratio be 4~2: 1, maturing temperature is 260~400 ℃.
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WO2016205441A1 (en) * | 2015-06-18 | 2016-12-22 | Johnson Matthey Public Limited Company | Nh3 overdosing-tolerant scr catalyst |
CN114653395B (en) * | 2022-03-09 | 2024-05-24 | 中科合成油技术股份有限公司 | Naphtha reforming catalyst and preparation method and application thereof |
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