CN110064417B - Continuous reforming catalyst and preparation method thereof - Google Patents
Continuous reforming catalyst and preparation method thereof Download PDFInfo
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- CN110064417B CN110064417B CN201810063490.8A CN201810063490A CN110064417B CN 110064417 B CN110064417 B CN 110064417B CN 201810063490 A CN201810063490 A CN 201810063490A CN 110064417 B CN110064417 B CN 110064417B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 238000002407 reforming Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 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 78
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims abstract description 35
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003213 activating effect Effects 0.000 claims abstract description 18
- 239000003463 adsorbent Substances 0.000 claims abstract description 12
- 230000002860 competitive effect Effects 0.000 claims abstract description 11
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004448 titration Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims description 115
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 114
- 239000007788 liquid Substances 0.000 claims description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 35
- 239000004202 carbamide Substances 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 35
- 229910001868 water Inorganic materials 0.000 claims description 31
- 239000000460 chlorine Substances 0.000 claims description 27
- 230000004913 activation Effects 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 150000003058 platinum compounds Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052718 tin Inorganic materials 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000001833 catalytic reforming Methods 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 43
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 238000001994 activation Methods 0.000 description 23
- 239000008188 pellet Substances 0.000 description 16
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 15
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 14
- 229910021529 ammonia Inorganic materials 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- 239000012018 catalyst precursor Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 238000002803 maceration Methods 0.000 description 14
- 239000001119 stannous chloride Substances 0.000 description 14
- 235000011150 stannous chloride Nutrition 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- 238000007598 dipping method Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 229910002846 Pt–Sn Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- 229910008839 Sn—Ti Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KVIPHDKUOLVVQN-UHFFFAOYSA-N ethene;hydrate Chemical compound O.C=C KVIPHDKUOLVVQN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a continuous reforming catalyst and a preparation method thereof, wherein the method comprises the following steps: step 1, preparing a tin-containing alumina carrier; step 2, preparing an impregnating solution, wherein the impregnating solution comprises a platinum-containing compound, a competitive adsorbent and a nitrogen-containing compound; and 3, impregnating the carrier in the step 1 and evaporating the impregnating solution to dryness at the temperature of 50-60 ℃, and 4, drying, activating and reducing the catalyst to obtain the multi-metal reforming catalyst. The obtained reforming catalyst comprises the following components in percentage by weight based on the carrier: 0.01-0.4 mass% of Pt, 0.01-0.6 mass% of Sn, 0.3-3.0 mass% of Cl, and the dispersion degree of Pt measured by a hydrogen titration method of the catalyst is more than or equal to 90%. The catalyst is used for hydrocarbon catalytic reforming reaction, and has good activity and selectivity and low carbon deposition rate.
Description
Technical Field
The invention relates to a reforming catalyst and a preparation method thereof, in particular to a Pt-Sn continuous reforming catalyst and a preparation method thereof.
Background
Catalytic reforming is one of the important production processes for petroleum processing, with the main objective of producing high octane gasoline, BTX aromatics, and inexpensive hydrogen. With the upgrading of gasoline and diesel oil quality and the rapid development of hydrogenation technology, the catalyst is heavyThe whole position in the oil refining chemical industry is more and more important. Currently, the most commonly used reforming catalyst in the industry is Pt-Re/A1 for semi-regenerative reforming processes2O3Catalyst and Pt-Sn/A1 for continuous regenerative reforming process2O3. The reforming catalyst is a bifunctional catalyst having both a metal function of hydrogenation-dehydrogenation and an acidic function. Pt in the reforming catalyst is a metal functional active center, Cl enhances the surface acidity of alumina through an induction effect, and Sn has a modulation effect on the carrier acidity and the electronic property of Pt.
Typical metrics for catalyst performance include activity, selectivity, and stability. For reforming catalysts, the activity is the magnitude of the octane number of the product obtained at a given feed and reaction conditions, or the magnitude of the reaction temperature at a given octane number; selectivity refers to the yield of aromatics or C at a given activity level5 +Yield of gasoline product; stability refers to the change in catalyst activity or selectivity per unit time or unit throughput. High performance reforming catalysts should have high activity and selectivity, as well as high stability.
The preparation of Pt-Sn catalysts by a stepwise impregnation method is described in US 3883419.
US3929683 describes the preparation of Pt-Sn catalysts using Sn-containing alumina carriers.
CN95117453 discloses the preparation of Pt-Sn-Ti catalysts using Sn-containing alumina carriers.
CN200780047703, US4964975, US6600082B2 and US6605566B2 describe platinum and tin containing catalysts that can be used in catalytic reforming or dehydrogenation processes.
CN201410532430 discloses a Pt-Sn bimetal reforming catalyst and a preparation method, wherein the average tin concentration in the shell region of the catalyst is 1.0-2.0 times of the average tin concentration in the central region, namely, tin elements are non-uniformly distributed in the catalyst.
CN200910157856 discloses a preparation method of a bimetallic reforming catalyst, which takes polycarboxylic acid such as citric acid as a competitive adsorbent, Pt in the catalyst is distributed in yolk, and Sn is uniformly distributed.
Disclosure of Invention
The invention aims to provide a continuous reforming catalyst and a preparation method thereof, and aims to solve the problems that in the prior art, the interaction between metal components and a carrier is not strong, and the metal components are easy to aggregate. The catalyst has better activity, selectivity and stability.
In order to achieve the above object, the present invention provides a method for preparing a continuous reforming catalyst, comprising the steps of:
step 1, preparing a tin-containing alumina carrier;
step 2, preparing an impregnating solution, wherein the impregnating solution comprises a platinum-containing compound, a competitive adsorbent and a nitrogen-containing compound;
step 3, impregnating the carrier of step 1 and evaporating the impregnating solution to dryness at a temperature of 50-60 ℃, and
and 4, drying, activating and reducing the catalyst.
In the preparation method of the continuous reforming catalyst, in the step 1, the content of Sn is 0.01-0.6 mass% based on dry-based alumina.
In the step 2 of the preparation method of the continuous reforming catalyst, the platinum compound is one or more of chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate, platinum tetrachloride, platinum nitrate, tetraammineplatinum chloride and tetraammineplatinum hydroxide, and the platinum content in the platinum compound is 0.01-0.4 mass% based on dry-based alumina.
In the step 2 of the preparation method of the continuous reforming catalyst, the competitive adsorbent is one or more of hydrochloric acid, nitric acid, hydrofluoric acid, trichloroacetic acid and citric acid, and the chlorine content in the competitive adsorbent is 0.3-3.0 mass% based on dry alumina.
In the preparation method of the continuous reforming catalyst, in the step 2, the nitrogen-containing compound is urea, and the content of the nitrogen-containing compound is 0.01-5.0 mass% based on the total mass of the alumina carrier.
In the step 3, the impregnation is saturated impregnation or supersaturated impregnation, the liquid-solid volume ratio of the impregnation liquid to the carrier is 0.5-3, the impregnation process is static or dynamic, the impregnation temperature is 10-50 ℃, and the impregnation time is 0.1-4 hours.
In the step 3, the impregnation liquid is evaporated by a vacuum drying method, the vacuum drying pressure is 0.001-0.08 MPa, and the vacuum drying temperature is 50-60 ℃. According to the preparation method of the continuous reforming catalyst, in the step 4, the activation atmosphere is air, the activation temperature is 200-650 ℃, and the activation time is 0.5-10 hours.
In the step 4, water and chlorine or water and chlorine-containing organic matters are injected into a catalyst bed layer in the activation process, wherein the molar ratio of the water to the chlorine is (10-120): 1.
According to the preparation method of the continuous reforming catalyst, in the step 4, the reducing gas is hydrogen or CO, the reducing temperature is 200-650 ℃, and the reducing time is 0.5-8 hours.
In order to achieve the above object, the present invention also provides a catalyst prepared by the above method for preparing a continuous reforming catalyst, comprising the following components: based on the mass of the carrier, 0.01-0.4% by mass of Pt, 0.01-0.6% by mass of Sn and 0.3-3.0% by mass of Cl, and the dispersion degree of Pt measured by a hydrogen titration method is not less than 90%.
The invention has the beneficial effects that:
according to the invention, urea is introduced into the impregnation liquid, so that the interaction between the metal components and the carrier is enhanced, the metal components are not easy to aggregate, the particle size of a platinum cluster of the catalyst is smaller, the occurrence of hydrogenolysis side reaction in the reforming reaction process is reduced, the hydrogenolysis by-product methane is less, and the selectivity of the product aromatic hydrocarbon is high.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The invention provides a preparation method of a continuous reforming catalyst, which comprises the following steps:
step 1, preparing a tin-containing alumina carrier;
step 2, preparing an impregnating solution, wherein the impregnating solution comprises a platinum-containing compound, a competitive adsorbent and a nitrogen-containing compound;
step 3, impregnating the carrier of step 1 and evaporating the impregnating solution to dryness at a temperature of 50-60 ℃, and
and 4, drying, activating and reducing the catalyst to obtain the multi-metal reforming catalyst.
In the preparation method of the continuous reforming catalyst, in the step 1, the alumina carrier can be prepared by a rolling ball or dropping ball method, a spherical alumina carrier can be prepared firstly, and then Sn element is introduced by an immersion method, or Sn element is introduced in the preparation process of the spherical carrier, such as rolling ball or dropping ball colloid preparation, preferably Sn element is introduced in the dropping ball colloid, and the content of Sn added by taking dry-based alumina as a reference is 0.01-0.6 mass%.
In the step 2 of the preparation method of the continuous reforming catalyst, the platinum compound is one or more of chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate, platinum tetrachloride, platinum nitrate, tetraammineplatinum chloride and tetraammineplatinum hydroxide, and the platinum content in the platinum compound is 0.01-0.4 mass% based on dry-based alumina.
In the step 2 of the preparation method of the continuous reforming catalyst, the competitive adsorbent is one or more of hydrochloric acid, nitric acid, hydrofluoric acid, trichloroacetic acid and citric acid, preferably trichloroacetic acid, hydrochloric acid or a combination of hydrochloric acid and trichloroacetic acid, and the chlorine content in the competitive adsorbent is 0.3-3.0 mass% based on dry alumina.
In the preparation method of the continuous reforming catalyst, in the step 2, the nitrogen-containing compound is urea, and the content of the nitrogen-containing compound is 0.01-5.0 mass% based on the total mass of the alumina carrier.
In the step 3 of the preparation method of the continuous reforming catalyst, the impregnation is saturated impregnation or supersaturated impregnation, the liquid-solid volume ratio of an impregnation liquid to a carrier is 0.5-3, the impregnation process is static or dynamic, and the dynamic refers to a rotary impregnation container in the impregnation process, preferably dynamic impregnation. The dipping temperature is 10-50 ℃, and the dipping time is 0.1-4 hours.
In the preparation method of the continuous reforming catalyst, in the step 3, the impregnation solution is evaporated by a vacuum drying method. The vacuum drying pressure is 0.001-0.08 MPa, and the vacuum drying temperature is 50-60 ℃. The need for strict control of the vacuum drying temperature, which is higher than 75 ℃, can lead to hydrolysis of urea, increase of pH and aggregation of metallic components.
According to the preparation method of the continuous reforming catalyst, in the step 4, the activation atmosphere is air, the activation temperature is 200-650 ℃, preferably 450-550 ℃, and the activation time is 0.5-10 hours, preferably 1-4 hours.
In the step 4, water and chlorine or water and chlorine-containing organic matters are injected into a catalyst bed layer in the activation process, wherein the molar ratio of the water to the chlorine is (10-120): 1.
In the preparation method of the continuous reforming catalyst, in the step 4, the reducing gas is hydrogen or CO, the reducing temperature is 200-650 ℃, preferably 400-580 ℃, and the reducing time is 0.5-8 hours, preferably 1-4 hours.
In order to achieve the above object, the present invention also provides a catalyst prepared by the above method for preparing a continuous reforming catalyst, comprising the following components: based on the mass of the carrier, 0.01-0.4% by mass of Pt, 0.01-0.6% by mass of Sn and 0.3-3.0% by mass of Cl, and the dispersion degree of Pt measured by a hydrogen titration method is not less than 90%.
The catalyst of the invention is suitable for the continuous reforming process of naphtha to produce gasoline blending components with high gasoline octane number or aromatic hydrocarbons. The naphtha is rich in naphthenes and paraffins and is selected from full boiling range gasoline with an initial boiling point of 40-80 ℃ and an end boiling point of 160-220 ℃, light naphtha with a distillation range of 60-150 ℃ or heavy naphtha with a distillation range of 100-200 ℃ measured by an ASTM D-86 method. Suitable reforming raw materials are straight-run gasoline, hydrocracking heavy naphtha, thermal cracking or catalytic cracking gasoline fractions and Fischer-Tropsch synthetic gasoline.
The absolute pressure of the catalyst used in the catalytic reforming reaction process is 100 KPa-7 MPa, preferably 0.35-2.5 MPa; the reaction temperature is 315-600 ℃, preferably 425-565 ℃; the hydrogen/hydrocarbon molar ratio is 1-20, preferably 2-10; the Liquid Hourly Space Velocity (LHSV) is 0.1-10 h-1Preferably 1 to 5 hours-1。
The reforming process is carried out under substantially anhydrous conditions. The water content of the feed as it enters the conversion zone should be less than 50ppm, preferably less than 20 ppm. The water in the reformate may be dried by conventional adsorbents such as molecular sieves or may be conditioned by appropriate stripping by a fractionation unit. Adsorption drying and stripping drying can also be combined to remove water from the feedstock.
The present invention will be specifically described below with reference to specific examples.
The content of Pt and Sn in the catalyst is measured by an X-ray fluorescence method, and the content of chlorine is measured by an electrode method.
Example 1
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.30 mass% with respect to the dry alumina, and the solution was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, the content of hydrochloric acid and the content of urea in the impregnation liquid are respectively 0.28 percent, 3 percent and 0.6 percent relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.5, the impregnation temperature is 25 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 60 ℃ under vacuum and dried at 120 ℃ for 2 hours. The dried catalyst precursor was activated in air at 520 ℃ for 6 hours and reduced with hydrogen at 500 ℃ for 2 hours to give catalyst A, the composition of which is shown in Table 1.
Example 2
Catalyst B was prepared by the method of example 1 except that the Sn content in the carrier was 0.24% by mass relative to the dry alumina, and the platinum content, the hydrochloric acid content and the urea content in the impregnating solution were 0.25%, 1.9% and 1.2% respectively relative to the dry alumina. The method specifically comprises the following steps:
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.24 mass% with respect to the dry alumina, and the solution was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, the content of hydrochloric acid and the content of urea in the impregnation liquid are respectively 0.25 percent, 1.9 percent and 1.2 percent relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.5, the impregnation temperature is 25 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 60 ℃ under vacuum and dried at 120 ℃ for 2 hours. The dried catalyst precursor was activated in air at 520 ℃ for 6 hours and reduced with hydrogen at 500 ℃ for 2 hours to give catalyst B, the composition of which is shown in Table 1.
Example 3
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.41 mass% with respect to the dry alumina, and the mixture was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, trichloroacetic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, trichloroacetic acid, hydrochloric acid and urea in the impregnation liquid is respectively 0.35%, 5%, 1.2% and 4% relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.8, the impregnation temperature is 15 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 50 ℃ under vacuum and dried at 120 ℃ for 2 hours. Activating the dried catalyst precursor in air atmosphere at 220 deg.C for 7 hr, at 480 deg.C for 3 hr, and activating at 480 deg.C in air atmosphere according to H2O: the Cl molar ratio is 20: 1 proportion of water and carbon tetrachloride were injected, and after the air activation was completed, the catalyst C was reduced with hydrogen at 480 ℃ for 4 hours to obtain a catalyst C, the composition of which is shown in Table 1.
Example 4
Catalyst D was prepared as in example 2, except that the impregnation solution contained 0.15%, 1.5% and 0.02% of platinum, hydrochloric acid and urea, respectively, based on the amount of dry alumina. The liquid/solid ratio of the impregnating solution to the carrier was 1.1. The impregnation temperature was 45 ℃ and the impregnation time was 2 hours. The air activation temperature was 550 ℃ and the activation time was 2 hours. The hydrogen reduction temperature is 300 ℃, and the reduction time is 6 hours. The method specifically comprises the following steps:
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.24 mass% with respect to the dry alumina, and the solution was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, the content of hydrochloric acid and the content of urea in the impregnation liquid are respectively 0.15 percent, 1.5 percent and 0.02 percent relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.1, the impregnation temperature is 45 ℃, and the impregnation time is 2 hours later. The excess of the maceration extract was evaporated to dryness at 60 ℃ under vacuum and dried at 120 ℃ for 2 hours. The dried catalyst precursor was activated in air at 550 ℃ for 2 hours and reduced with hydrogen at 300 ℃ for 6 hours to give catalyst D, the composition of which is shown in Table 1.
Example 5
Catalyst E was prepared as in example 1, except that the Sn content in the carrier was 0.12% by mass relative to the dry alumina, and the platinum content, the hydrochloric acid content and the urea content in the impregnating solution were 0.12%, 3% and 3.2% respectively relative to the dry alumina. The liquid/solid ratio of the impregnating solution to the carrier was 1.4. The impregnation temperature was 30 ℃ and the impregnation time was 1 hour. Air activation temperature of 560 ℃, activation time of 4 hours, air activation period of 560 ℃ according to H2O: the Cl molar ratio is 40: water and tetrachloroethylene were injected in a ratio of 1. The hydrogen reduction temperature is 560 ℃, and the reduction time is 0.5 hour. The method specifically comprises the following steps:
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.12 mass% with respect to the dry alumina, and the solution was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, the content of hydrochloric acid and the content of urea in the impregnation liquid are respectively 0.12 percent, 3 percent and 3.2 percent relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.4, the impregnation temperature is 30 ℃, and the impregnation time is 1 hour later. The excess of the maceration extract was evaporated to dryness at 60 ℃ under vacuum and dried at 120 ℃ for 2 hours. The dried catalyst precursor was activated in air at 560 ℃ for 4 hours, as H, during the air activation at 560 ℃2O: the Cl molar ratio is 40: 1Water and tetrachloroethylene were injected in proportion. Reduction with hydrogen at 560 ℃ for 0.5 h gave catalyst E, the composition of E being given in Table 1.
Example 6
Catalyst F was prepared as in example 1, except that the Sn content in the carrier was 0.05% by mass relative to the dry alumina, and the platinum content, the hydrochloric acid content and the urea content in the impregnating solution were 0.04%, 1% and 1% respectively relative to the dry alumina. The liquid/solid ratio of the impregnating solution to the carrier was 2.5. The impregnation temperature was 50 ℃ and the impregnation time was 1.5 hours. The method specifically comprises the following steps:
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.05 mass% with respect to the dry alumina, and the solution was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, the content of hydrochloric acid and the content of urea in the impregnation liquid are respectively 0.04 percent, 1 percent and 1 percent relative to the content of dry-based alumina. The carrier prepared in the previous step is soaked by the soaking liquid, the liquid/solid ratio of the soaking liquid to the carrier is 2.5, the soaking temperature is 50 ℃, and the soaking time is 1.5 hours later. The excess of the maceration extract was evaporated to dryness at 60 ℃ under vacuum and dried at 120 ℃ for 2 hours. The dried catalyst precursor was activated in air at 520 ℃ for 6 hours and reduced with hydrogen at 500 ℃ for 2 hours to give catalyst F, the composition of which is shown in Table 1.
Example 7
Catalyst G was prepared as in example 5, except that the impregnation solution contained 0.08%, 1.4% and 0.17% of platinum, hydrochloric acid and urea, respectively, based on the amount of dry alumina. The liquid/solid ratio of the impregnation liquid to the carrier was 3. Air activation temperature is 500 ℃, activation time is 8 hours, and the air activation period at 500 ℃ is H2O: the Cl molar ratio is 110: 1 ratio of water and dichloroEthane. The method specifically comprises the following steps:
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.12 mass% with respect to the dry alumina, and the solution was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, the content of hydrochloric acid and the content of urea in the impregnation liquid are respectively 0.08 percent, 1.4 percent and 0.17 percent relative to the content of dry-based alumina. And (3) dipping the carrier prepared in the previous step by the dipping solution, wherein the liquid/solid ratio of the dipping solution to the carrier is 3, the dipping temperature is 30 ℃, and the dipping time is 1 hour later. The excess of the maceration extract was evaporated to dryness at 60 ℃ under vacuum and dried at 120 ℃ for 2 hours. The dried catalyst precursor was activated in 500 ℃ air for 8 hours at 500 ℃ as H during the 500 ℃ air activation2O: the Cl molar ratio is 110: water and dichloroethane were injected in a ratio of 1. Reduction with hydrogen at 560 ℃ for 0.5 h gave catalyst G, the composition of which is given in Table 1.
Example 8
Catalyst H was prepared as in example 2, except that the impregnation solution contained 0.18%, 2.7% and 0.07% of platinum, hydrochloric acid and urea, respectively, based on the amount of dry alumina. The method specifically comprises the following steps:
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.24 mass% with respect to the dry alumina, and the solution was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, the content of hydrochloric acid and the content of urea in the impregnation liquid are respectively 0.18 percent, 2.7 percent and 0.07 percent relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.5, the impregnation temperature is 25 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 60 ℃ under vacuum and dried at 120 ℃ for 2 hours. The dried catalyst precursor was activated in air at 520 ℃ for 6 hours and reduced with hydrogen at 500 ℃ for 2 hours to give catalyst H, the composition of which is shown in Table 1.
Example 9
Catalyst I was prepared as in example 2, except that the impregnation solution contained 0.21%, 2.2% and 2.3% of platinum, hydrochloric acid and urea, respectively, based on the amount of dry alumina. The method specifically comprises the following steps:
100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.24 mass% with respect to the dry alumina, and the solution was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, the content of hydrochloric acid and the content of urea in the impregnation liquid are respectively 0.21 percent, 2.2 percent and 2.3 percent relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.5, the impregnation temperature is 25 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 60 ℃ under vacuum and dried at 120 ℃ for 2 hours. The dried catalyst precursor was activated in air at 520 ℃ for 6 hours and reduced with hydrogen at 500 ℃ for 2 hours to give catalyst I, the composition of which is shown in Table 1.
Comparative example 1
The catalyst was prepared as in example 3, except that no urea was added to the impregnation solution. The composition of the catalyst P obtained is shown in Table 1.
Specifically, 100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and slurried for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.41 mass% with respect to the dry alumina, and the mixture was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, trichloroacetic acid and hydrochloric acid according to a predetermined amount, wherein the content of platinum, trichloroacetic acid and hydrochloric acid in the impregnation liquid is 0.35 percent, 5 percent and 1.2 percent respectively relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.8, the impregnation temperature is 15 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 50 ℃ under vacuum and dried at 120 ℃ for 2 hours. Activating the dried catalyst precursor in air atmosphere at 220 deg.C for 7 hr, at 480 deg.C for 3 hr, and activating at 480 deg.C in air atmosphere according to H2O: the Cl molar ratio is 20: 1 proportion of water and carbon tetrachloride are injected, and after the air activation is finished, the catalyst P is prepared by reducing the mixture by hydrogen for 4 hours at 480 ℃, and the composition of the catalyst P is shown in a table 1.
Comparative examples 2 to 3
The catalyst was prepared as in comparative example 1 except that the vacuum drying temperatures were 80 and 90 c, respectively, to produce catalyst Q, R having the composition shown in table 1. The method specifically comprises the following steps:
catalyst Q: 100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.41 mass% with respect to the dry alumina, and the mixture was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, trichloroacetic acid and hydrochloric acid according to a predetermined amount, wherein the content of platinum, trichloroacetic acid and hydrochloric acid in the impregnation liquid is 0.35 percent, 5 percent and 1.2 percent respectively relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.8, the impregnation temperature is 15 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 80 ℃ under vacuum and dried at 120 ℃ for 2 hours. Activating the dried catalyst precursor in air atmosphere at 220 deg.C for 7 hr, at 480 deg.C for 3 hr, and activating at 480 deg.C in air atmosphere according to H2O: the Cl molar ratio is 20: 1 proportion of water and carbon tetrachloride, and reducing the mixture at 480 ℃ for 4 hours by using hydrogen after the air activation is finished to obtain a catalyst Q, wherein the composition of the catalyst Q is shown in a table 1.
Catalyst Q: 100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.41 mass% with respect to the dry alumina, and the mixture was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, trichloroacetic acid and hydrochloric acid according to a predetermined amount, wherein the content of platinum, trichloroacetic acid and hydrochloric acid in the impregnation liquid is 0.35 percent, 5 percent and 1.2 percent respectively relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.8, the impregnation temperature is 15 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 90 ℃ under vacuum and dried at 120 ℃ for 2 hours. Activating the dried catalyst precursor in air atmosphere at 220 deg.C for 7 hr, at 480 deg.C for 3 hr, and activating at 480 deg.C in air atmosphere according to H2O: the Cl molar ratio is 20: 1, injecting water and carbon tetrachloride in proportion, and activating the knot by airAfter this time, the catalyst Q was obtained by reduction with hydrogen at 480 ℃ for 4 hours, the composition of Q being shown in Table 1.
Comparative examples 4 to 5
Catalyst S, T was prepared by the method of example 3, except that the vacuum drying temperature was 80 ℃ and 90 ℃ respectively. The composition of the resulting catalyst S, T is shown in Table 1. The method specifically comprises the following steps:
catalyst S: 100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.41 mass% with respect to the dry alumina, and the mixture was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, trichloroacetic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, trichloroacetic acid, hydrochloric acid and urea in the impregnation liquid is respectively 0.35%, 5%, 1.2% and 4% relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.8, the impregnation temperature is 15 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 80 ℃ under vacuum and dried at 120 ℃ for 2 hours. Activating the dried catalyst precursor in air atmosphere at 220 deg.C for 7 hr, at 480 deg.C for 3 hr, and activating at 480 deg.C in air atmosphere according to H2O: the Cl molar ratio is 20: 1 proportion of water and carbon tetrachloride are injected, and after the air activation is finished, the catalyst S is prepared by reducing the mixture for 4 hours at 480 ℃ by using hydrogen, and the composition of the S is shown in a table 1.
Catalyst T: 100 g of pseudo-boehmite (manufactured by Sasol company) and a proper amount of deionized water are taken, the liquid/solid mass ratio is 2, and the mixture is stirred and pulped for 0.5 hour at room temperature. Then, 3 ml of nitric acid and a hydrochloric acid solution of stannous chloride in a predetermined amount were added to make the Sn content in the solution 0.41 mass% with respect to the dry alumina, and the mixture was acidified for 2 hours. Then dropping balls in an oil ammonia column for forming, solidifying the wet balls in ammonia water for 1 hour, then filtering, washing with deionized water for three times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 4 hours in a flowing air atmosphere to obtain the Sn-containing alumina pellet carrier.
Preparing impregnation liquid containing chloroplatinic acid, trichloroacetic acid, hydrochloric acid and urea according to a predetermined amount, wherein the content of platinum, trichloroacetic acid, hydrochloric acid and urea in the impregnation liquid is respectively 0.35%, 5%, 1.2% and 4% relative to the content of dry-based alumina. And (3) taking the impregnation liquid to impregnate the carrier prepared in the previous step, wherein the liquid/solid ratio of the impregnation liquid to the carrier is 1.8, the impregnation temperature is 15 ℃, and the impregnation time is 0.5 hour later. The excess of the maceration extract was evaporated to dryness at 90 ℃ under vacuum and dried at 120 ℃ for 2 hours. Activating the dried catalyst precursor in air atmosphere at 220 deg.C for 7 hr, at 480 deg.C for 3 hr, and activating at 480 deg.C in air atmosphere according to H2O: the Cl molar ratio is 20: 1 proportion of water and carbon tetrachloride are injected, and after the air activation is finished, the catalyst S is prepared by reducing the mixture for 4 hours at 480 ℃ by using hydrogen, and the composition of the S is shown in a table 1.
Comparative example 6
An alumina pellet carrier in which the Sn content was 0.20 mass% relative to the dry alumina was prepared by the method of example 1.
Catalyst S was prepared according to the method of patent CN 201410532430. Taking 50 g of the tin-containing alumina pellets and 50 g of SnCl which is obtained by grinding and has the particle size of less than 50um2·2H2Placing O powder in a sealed glass container at 25 deg.C, and rolling the container to make the alumina globules and SnCl2·2H2The O powder was fully contacted for solid phase migration, and the catalyst support was sieved out after 64 hours of contact. Air containing 3 vol% of water was introduced into the sieved carrier, and the carrier was calcined at 550 ℃ for 4 hours.
Impregnating the roasted carrier with a solution of chloroplatinic acid and hydrochloric acid, wherein the platinum content and the hydrochloric acid content in the impregnating solution are respectively 0.29 percent and 1.8 percent relative to the dry-based alumina content. Soaking at 25 deg.C for 4 hr, drying at 120 deg.C for 12 hr, and activating with water and HCl-containing air at 510 deg.C for 4 hr2The mass ratio of O/HCl is 20, then the catalyst U is obtained by reducing the mixture for 4 hours at 500 ℃, and the composition of the catalyst U is shown in the specificationTable 1.
TABLE 1
| Examples | Catalyst and process for preparing same | Pt, mass% | Sn, mass% | Cl, mass% |
| 1 | A | 0.28 | 0.30 | 1.42 |
| 2 | B | 0.25 | 0.24 | 1.01 |
| 3 | C | 0.35 | 0.41 | 1.64 |
| 4 | D | 0.15 | 0.24 | 1.00 |
| 5 | E | 0.12 | 0.12 | 1.16 |
| 6 | F | 0.04 | 0.05 | 0.52 |
| 7 | G | 0.08 | 0.12 | 0.62 |
| 8 | H | 0.18 | 0.24 | 1.35 |
| 9 | I | 0.21 | 0.24 | 1.13 |
| Comparative example 1 | P | 0.35 | 0.41 | 1.47 |
| Comparative example 2 | Q | 0.35 | 0.41 | 1.58 |
| Comparative example 3 | R | 0.35 | 0.41 | 1.45 |
| Comparative example 4 | S | 0.35 | 0.41 | 1.50 |
| Comparative example 5 | T | 0.35 | 0.41 | 1.51 |
| Comparative example 6 | U | 0.29 | 0.31 | 1.45 |
Example 10
This example analyzes the platinum dispersion of the catalyst.
The platinum dispersion in the catalyst was determined by hydroxide titration using a Micromeritics AutoChem 2920 analytical instrument. Pretreatment conditions of the sample: and (3) loading 0.5 g of catalyst into a U-shaped quartz tube, heating the catalyst to 500 ℃ under a hydrogen flow with the flow rate of 50mL/min (the heating rate is 10 ℃/min), keeping the temperature for 2h, cooling the hydrogen atmosphere to room temperature, and purging with argon for 1h to remove physically adsorbed hydrogen. And (4) carrying out oxygen pulse titration by taking helium as a carrier gas until the peak area is unchanged. And (4) carrying out hydrogen gas pulse titration by taking argon as a carrier gas until the peak area is unchanged. And then carrying out oxygen pulse titration by taking helium as a carrier gas until the peak area is unchanged. The catalyst Pt dispersion analysis results are shown in table 2.
D: degree of Pt dispersion
V: second oxygen titration volume (ml, standard volume)
ω: sample Mass (gram)
p%: pt content in the sample
TABLE 2
As can be seen from the results in Table 4, the Pt in the catalyst prepared by the invention has higher dispersity and smaller Pt cluster particle size.
Example 11
This example evaluates the performance of the catalyst of the invention.
In a micro-reactor, 1ml of a catalyst was charged, and n-heptane was used as a raw material under the following evaluation conditions: the reaction temperature is 510 ℃, the reaction pressure is 0.70MPa, and the volume space velocity is 10.0h-1The hydrogen/hydrocarbon molar ratio was 4.8, the reaction time was 8 hours, and the evaluation results are shown in Table 3.
TABLE 3
As can be seen from Table 3, the aromatic yield and C of the catalyst of the present invention5 +The yield is higher than that of a comparative catalyst, and the carbon deposition amount of the catalyst is lower than that of the comparative catalyst, which shows that the catalyst has better activity, selectivity and stability.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A method for preparing a continuous reforming catalyst, comprising the steps of:
step 1, preparing a tin-containing alumina carrier;
step 2, preparing an impregnating solution, wherein the impregnating solution comprises a platinum-containing compound, a competitive adsorbent and a nitrogen-containing compound;
step 3, impregnating the carrier of step 1 and evaporating the impregnating solution to dryness at a temperature of 50-60 ℃, and
step 4, drying, activating and reducing the catalyst;
the nitrogen-containing compound is urea.
2. The method of producing a continuous reforming catalyst according to claim 1, wherein in step 1, the content of Sn is 0.01 to 0.6 mass% based on dry alumina.
3. The method of preparing a continuous reforming catalyst according to claim 2, wherein in step 2, the platinum compound is one or more selected from chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate, platinum tetrachloride, platinum nitrate, tetraammineplatinum chloride and tetraammineplatinum hydroxide, and the platinum content in the platinum compound is 0.01 to 0.4 mass% based on dry alumina.
4. The method according to claim 1, wherein in step 2, the competitive adsorbent is one or more selected from hydrochloric acid, nitric acid, hydrofluoric acid, trichloroacetic acid and citric acid, and the chlorine content in the competitive adsorbent is 0.3 to 3.0% by mass on a dry basis of alumina.
5. The method of producing a continuous reforming catalyst according to claim 1, wherein the content of the nitrogen-containing compound is 0.01 to 5.0 mass% based on the total mass of the alumina support.
6. The method for preparing a continuous reforming catalyst according to claim 1, wherein the impregnation in step 3 is saturated impregnation or supersaturated impregnation, the liquid-solid volume ratio of the impregnation liquid to the carrier is 0.5 to 3, the impregnation process is static or dynamic, the impregnation temperature is 10 to 50 ℃, and the impregnation time is 0.1 to 4 hours.
7. The method for preparing a continuous reforming catalyst according to claim 1, wherein in the step 3, the impregnation solution is evaporated by a vacuum drying method, the vacuum drying pressure is 0.001-0.08 MPa, and the vacuum drying temperature is 50-60 ℃.
8. The method for preparing a continuous reforming catalyst according to claim 1, wherein the activation atmosphere in step 4 is air, the activation temperature is 200 to 650 ℃, and the activation time is 0.5 to 10 hours.
9. The method for preparing a continuous reforming catalyst according to claim 1, wherein in the step 4, water and chlorine gas or water and chlorine-containing organic substances are injected into the catalyst bed during the activation, and the molar ratio of water to chlorine element is (10-120): 1.
10. The method of claim 1, wherein the reducing gas is hydrogen or CO in the step 4, the reducing temperature is 200 to 650 ℃, and the reducing time is 0.5 to 8 hours.
11. The catalyst produced by the method for producing a continuous reforming catalyst according to any one of claims 1 to 10, comprising the following components: based on the mass of the carrier, 0.01-0.4% by mass of Pt, 0.01-0.6% by mass of Sn and 0.3-3.0% by mass of Cl, and the dispersion degree of Pt measured by a hydrogen titration method is not less than 90%.
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