CN113694943A - Semi-regenerated reforming catalyst with shell-core structure and preparation method and evaluation method thereof - Google Patents
Semi-regenerated reforming catalyst with shell-core structure and preparation method and evaluation method thereof Download PDFInfo
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- CN113694943A CN113694943A CN202110991035.6A CN202110991035A CN113694943A CN 113694943 A CN113694943 A CN 113694943A CN 202110991035 A CN202110991035 A CN 202110991035A CN 113694943 A CN113694943 A CN 113694943A
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- reforming catalyst
- platinum
- rhenium
- lanthanum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000002407 reforming Methods 0.000 title claims abstract description 54
- 238000011156 evaluation Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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 39
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 29
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 15
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- 239000011241 protective layer Substances 0.000 claims abstract description 10
- NNCOOIBIVIODKO-UHFFFAOYSA-N aluminum;hypochlorous acid Chemical compound [Al].ClO NNCOOIBIVIODKO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008188 pellet Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000004073 vulcanization Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 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 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 150000003058 platinum compounds Chemical class 0.000 claims description 2
- 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 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 150000003282 rhenium compounds Chemical class 0.000 claims description 2
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- 150000003748 yttrium compounds Chemical class 0.000 claims description 2
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 description 24
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- DBJYYRBULROVQT-UHFFFAOYSA-N platinum rhenium Chemical compound [Re].[Pt] DBJYYRBULROVQT-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 208000035874 Excoriation Diseases 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- -1 nitrogen-containing compound Chemical class 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction 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
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 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
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a semi-regenerative reforming catalyst with a shell-core structure and a preparation method and an evaluation method thereof, wherein the semi-regenerative reforming catalyst with the shell-core structure comprises platinum and rhenium-containing high-pore-volume alumina pellets, a protective layer containing rare earth elements is coated outside the platinum and rhenium-containing high-pore-volume alumina pellets, and the protective layer containing the rare earth elements is formed by lanthanum and yttrium-containing aluminum hydroxychloride sol; the semi-regenerative reforming catalyst comprises 0.1-0.65 wt% of platinum, 0.1-0.65 wt% of rhenium, 0.1-0.4 wt% of lanthanum, 0.1-0.4 wt% of yttrium, 0.5-1.5 wt% of chlorine and the balance of alumina; the protective layer containing rare earth elements is coated on the surface of the original semi-regenerated reforming catalyst, so that the hydrogenolysis activity of rhenium, namely the carbon deposition occurrence rate, is mainly reduced, and the selectivity and the activity of the semi-regenerated reforming catalyst are improved.
Description
Technical Field
The invention belongs to the technical field of catalytic reforming, relates to a semi-regenerative reforming catalyst, and more particularly relates to a semi-regenerative reforming catalyst with a shell layer of a rare earth metal coating layer and an alumina core, and a preparation method and an evaluation method thereof.
Background
Catalytic reforming is an important production process for chemical refining, and aims to produce high-octane gasoline, high-content aromatic hydrocarbon and cheap hydrogen. In recent years, with the progress of industry, the demand for reformed gasoline and aromatic hydrocarbon raw materials is gradually increased, and the search for a catalyst with better performance is one of the main methods for solving the problem.
The reforming process is mainly divided into continuous reforming and semi-regenerative reforming, wherein the continuous reforming mainly uses a platinum-tin alumina series catalyst, and the semi-regenerative reforming mainly uses a platinum-rhenium alumina series catalyst. The platinum-tin bimetallic catalyst used for continuous reforming has the characteristics of high initial activity and good selectivity, but has poor stability, needs continuous regeneration to maintain the performance of the catalyst, and needs to be activated and reduced before use; the platinum-rhenium catalyst used for semi-regenerative reforming has the advantages of high stability and long service life, but has poor selectivity.
USP 3415737 discloses platinum-rhenium bimetallic catalysts that significantly improve the stability of semi-regenerated reforming catalysts, increasing the life cycle, but the selectivity has yet to be improved.
CN 1388218A discloses a platinum-rhenium reforming catalyst and a preparation method thereof, the catalyst is a reforming catalyst prepared from 0.1-2.0 wt% of platinum, 0.1-2.0 wt% of rhenium, 0.1-0.98 wt% of yttrium, 0.1-0.5 wt% of chlorine and the rest of alumina carriers, the catalyst adopts a saturated impregnation method to impregnate yttrium into the carriers, and then adopts an impregnation-filtration method to impregnate platinum and rhenium elements on the carriers, the selectivity of the prepared reforming catalyst is improved, but the selectivity is still required to be improved.
CN 110064414A discloses a semi-regenerated reforming catalyst containing rare earth, which is mainly characterized in that gamma-alumina is used for dipping platinum, rhenium, rare earth elements, competitive adsorbent and nitrogen-containing compound; the alumina carrier is impregnated and the impregnation solution is evaporated to dryness, and the catalyst is used for hydrocarbon catalytic reforming reaction and has better activity and selectivity, but the selectivity is still to be improved.
Disclosure of Invention
Aiming at the problem that the selectivity of the existing semi-regenerative reforming catalyst is still to be improved, the invention provides a semi-regenerative reforming catalyst with a shell layer of a rare earth metal coating layer and an alumina core, and a preparation method and an evaluation method thereof.
The invention adopts the following technical scheme: a semi-regenerated reforming catalyst with a shell-core structure,
the high-porosity alumina pellet containing platinum and rhenium is coated with a protective layer containing rare earth elements, and the protective layer containing the rare earth elements is formed by aluminum hydroxychloride sol containing lanthanum and yttrium;
the semi-regenerative reforming catalyst comprises 0.1-0.65 wt% of platinum, 0.1-0.65 wt% of rhenium, 0.1-0.4 wt% of lanthanum, 0.1-0.4 wt% of yttrium, 0.5-1.5 wt% of chlorine and the balance of alumina;
the semi-regenerated reforming catalyst has a pore volume of 0.4 to 1.0ml/g and a specific surface area of 100 to 400m2A density of 0.6 to 0.8g/ml, and a particle diameter of 1.0 to 2.0 mm. .
Further, the platinum is selected from one or more of chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate, platinum tetrachloride, platinum nitrate, tetraammineplatinum chloride and tetraammineplatinum hydroxide, and is preferably chloroplatinic acid.
Further defined, the rhenium is derived from perrhenic acid or ammonium perrhenate, preferably ammonium perrhenate.
The lanthanum is derived from one or more of lanthanum chloride, lanthanum nitrate, lanthanum acetate and lanthanum oxide, and the lanthanum nitrate is preferred.
Further defined, the yttrium is derived from yttrium carbonate or yttrium chloride.
The invention also discloses a preparation method of the semi-regenerative reforming catalyst, which comprises the following steps:
dropwise adding and mixing an alkaline aluminum salt solution and an acidic aluminum salt solution under the condition of pH 7.5-10.5, and then roasting to obtain a high-pore-volume alumina precursor, dissolving the high-pore-volume alumina precursor with acid colloid, and preparing a microspherical alumina blank by one of an oil ammonia column method, a hot oil column method, a rolling ball method or a micro-flow forming method;
drying the alumina blank, and carrying out hydrothermal roasting treatment at 400-700 ℃ for 0.1-20 h to obtain an alumina carrier core;
dipping an alumina inner core by using a solution containing a platinum compound and a rhenium compound, aging at room temperature for 2-12 h, drying at 80-200 ℃ for 2-12 h, evaporating the rest dipping solution to dryness, and roasting at 400-700 ℃ for 4-8 h to obtain an intermediate catalyst containing platinum and rhenium;
coating a platinum and rhenium-containing intermediate catalyst with aluminum hydroxychloride sol containing lanthanum and yttrium compounds, and drying at 80-200 ℃ for 0.5-12 h to obtain the semi-regenerative reforming catalyst with a shell-core structure.
Further limiting the pH value to be 8.5-9.5.
The invention also discloses an evaluation method of the semi-regenerated reforming catalyst with the shell structure, which is characterized in that water and hydrogen chloride are adopted to activate the semi-regenerated reforming catalyst with the shell-core structure in a reducing gas atmosphere, and the mass ratio of the water to the hydrogen chloride is 5-100: 1, the temperature is 450-600 ℃, and the activation time is 0.5-10 h;
after activation, pre-vulcanizing at 350-450 ℃ for 0.5-10 h;
after the pre-vulcanization is finished, the pre-vulcanization and naphtha are subjected to the conditions of 400-600 ℃, 0.15-3.0 MPa and the volume space velocity of the naphtha is 0.1-10 h-1And performing contact reaction, wherein the volume ratio of hydrogen to hydrocarbon is 700-1200: 1.
Further, the hydrogen chloride is derived from hydrochloric acid or an organic compound capable of decomposing chlorine, preferably hydrochloric acid, and the organic compound capable of decomposing chlorine is selected from tetrachloroethylene, dichloromethane, trichloromethane or carbon tetrachloride.
Further defined, the naphtha is composed of C6-C10 linear alkanes, and the volume ratio of the C6-C10 linear alkanes is 10.5:25.5:27.1:26.9: 10.0.
The invention has the beneficial effects that: the protective layer containing rare earth elements is coated on the surface of the original semi-regenerated reforming catalyst, so that the hydrogenolysis activity of rhenium, namely the carbon deposition occurrence rate, is mainly reduced, and the selectivity and the activity of the semi-regenerated reforming catalyst are improved.
Detailed Description
In the evaluation method of the semi-regenerative reforming catalyst with the shell structure, a mixed solution of C6-C10 with the volume ratio of 10.5:25.5:27.1:26.9:10.0 is used as a reforming raw material, and a high-octane gasoline and BTX aromatic hydrocarbon component are produced in the semi-regenerative reforming process.
In the following examples, platinum, rhenium, lanthanum, yttrium, chlorine in the semi-regenerated reforming catalyst having a shell structure were measured by X-ray fluorescence; measuring the specific surface area and pore volume of the semi-regenerated reforming catalyst with a shell structure by adopting an Autosord IQ full-automatic gas adsorption analyzer of Quantachrome company in the United states; the composition analysis of the reforming raw material and the reaction product is completed by adopting an Agilent 6890N gas chromatograph; the carbon and hydrogen elements on the reforming raw material are measured by a Vario MICRO element instrument of Elementar company of Germany; the mechanical attrition of the reformate while running in the plant was simulated using a catalyst attrition tester from VINCI, france.
The reforming materials prepared in the examples and comparative examples were subjected to abrasion treatment prior to evaluation, simulating the regenerative abrasion loss experienced by the reforming materials in chemical use.
Example 1
S1, adding 2.0L of water into a gelling tank, and dropwise adding 1.0L of sodium aluminate solution (Na) while stirring2O 150g/L、Al2O3100g/L) and 0.9L of aluminum sulfate solution (Al)2O390g/L), and controlling the dropping speed of the material to keep the pH value of the material within the range of 8.5-9.5. Filtering, washing with water, adding 13mL of dilute nitric acid, acidifying for 1 hour, pulping with 0.3L of water to obtain sol, wherein the volume ratio of nitric acid to water in the dilute nitric acid is 1: 1.
S2, dripping the mixture into a small spherical blank in an oil-ammonia column by adopting an oil column forming method, solidifying the small spherical blank in an ammonia water column for 2 hours, filtering, washing the small spherical blank three times by using deionized water, drying the small spherical blank for 4 hours at 80 ℃, drying the small spherical blank for 2 hours at 120 ℃, and roasting the small spherical blank for 4 hours at 500 ℃ to obtain the high-pore-volume alumina sphere carrier core.
S3, preparing 75g of hydrochloric acid solution of chloroplatinic acid with platinum content of 0.05g/g, dissolving 4.32g of ammonium perrhenate in 60g of aqueous solution to obtain impregnation liquid, evaporating redundant impregnation to dryness under the vacuum condition of 70 ℃, wherein the liquid-solid ratio during impregnation is 1.7:1, aging at room temperature for 12h after impregnation, drying at 120 ℃ for 10h, and roasting at 400 ℃ for 4h to obtain the platinum-and-rhenium-containing intermediate catalyst.
S4, dissolving 24.5g of aluminum hydroxychloride sol (the aluminum content is 11-12%), 0.22g of yttrium chloride and 0.31g of lanthanum nitrate in 70g of water to obtain a solution; the semi-regenerated reforming catalyst A with a shell structure is obtained by repeatedly spraying and coating the catalyst on an intermediate catalyst containing platinum and rhenium in a ball roller machine, drying the catalyst for 12 hours at 120 ℃, and roasting the catalyst for 4 hours at 400 ℃.
Comparative example 1
Catalyst a was prepared as in example 1, except that this comparative example employed a commercially available gamma-alumina pellet support of some grade as the inner core.
S1, preparing 75g of hydrochloric acid solution of chloroplatinic acid with platinum content of 0.05g/g, dissolving 4.32g of ammonium perrhenate in 60g of aqueous solution to obtain impregnation liquid, evaporating redundant impregnation to dryness under the vacuum condition of 70 ℃, wherein the liquid-solid ratio during impregnation is 1.7:1, aging at room temperature for 12h after impregnation, drying at 120 ℃ for 10h, and roasting at 400 ℃ for 4h to obtain platinum-and-rhenium-containing pellets.
S2, dissolving 24.5g of aluminum hydroxychloride sol (the aluminum content is 11-12 wt%) and 0.22g of yttrium chloride and 0.31g of lanthanum nitrate in 70g of water to obtain a solution, wherein the aluminum in the solution respectively accounts for 1.0 wt% of the total aluminum content of the catalyst, and the lanthanum and the yttrium account for 0.1 wt% of the total mass of the catalyst; the catalyst a is coated on the small balls containing platinum and rhenium by repeated spraying in a ball rolling machine, dried for 12 hours at 120 ℃ and calcined for 4 hours at 400 ℃.
Comparative example 2
Catalyst b was prepared as in example 1, using commercially available gamma-alumina pellets of comparative example 1 as the core, except that no rare earth-containing alumina coating was added as the protective layer.
75g of hydrochloric acid solution of chloroplatinic acid of 0.05g/g is prepared, 4.32g of ammonium perrhenate is dissolved in 60g of aqueous solution to obtain impregnation liquid, redundant impregnation is evaporated to dryness under the vacuum condition of 70 ℃, the liquid-solid ratio during impregnation is 1.7:1, the impregnation liquid is aged at room temperature for 12 hours, the drying is carried out for 10 hours at the temperature of 120 ℃, and the calcination is carried out for 4 hours at the temperature of 400 ℃, so that the catalyst b only containing platinum, rhenium and chlorine is obtained.
Example 2
Catalyst B was prepared as in example 1, this comparative example using a self-made core, except that no rare earth-containing alumina coating was added as a protective layer
S1, adding 2.0L of water into a gelling tank, and dropwise adding 1.0L of sodium aluminate solution (Na) while stirring2O150g/L、Al2O3100g/L) and 0.9L of aluminum sulfate solution (Al)2O390g/L), and controlling the dropping speed of the material to keep the pH of the material within the range of 9.0-10.0. After filtration and washing with water, 13mL of dilute nitric acid (VHNO) was added3:VH2O ═ 1:1) acidified for 1 hour and slurried with 0.3L of water to a sol.
S2, dripping the mixture into a small spherical blank in an oil-ammonia column by adopting an oil column forming method, solidifying the small spherical blank in an ammonia water column for 2 hours, filtering, washing the small spherical blank three times by using deionized water, drying the small spherical blank at 80 ℃ for 4 hours, drying the small spherical blank at 120 ℃ for 2 hours, and roasting the small spherical blank at 500 ℃ for 4 hours to obtain the high-pore-volume alumina sphere carrier inner core.
S3, preparing 46.8g of ammonium chloroplatinate with platinum content of 0.08g/g, dissolving 4.32g of ammonium perrhenate in 60g of aqueous solution to obtain impregnation liquid, evaporating redundant impregnation under the vacuum condition of 70 ℃, aging at room temperature for 12h after impregnation, drying at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain a catalyst B containing platinum, rhenium and chlorine.
Example 3
S1, adding 2.0 liters of water into a gelling tank, and simultaneously dropwise adding 1.2L of sodium aluminate solution (Na) while stirring2O 150g/L、Al2O3100g/L) and 1.0L of aluminum chloride solution (Al)2O380g/L), and controlling the dropping speed of the material to keep the pH value of the material within the range of 9.0-10.0. After filtration and washing with water, 15mL of dilute nitric acid (VHNO) was added3:VH2O ═ 1:1) acidified for 1 hour and slurried with 0.3L of water to a sol.
S2, dripping the mixture into a small spherical blank in an oil-ammonia column by adopting an oil column forming method, solidifying the small spherical blank in an ammonia water column for 2 hours, filtering, washing the small spherical blank three times by using deionized water, drying the small spherical blank at 80 ℃ for 4 hours, drying the small spherical blank at 120 ℃ for 2 hours, and roasting the small spherical blank at 500 ℃ for 4 hours to obtain the high-pore-volume alumina sphere carrier inner core.
S3, preparing 90g of hydrochloric acid solution with platinum content of 0.04g/g of platinum chloride, dissolving 4.32g of ammonium perrhenate in 60g of aqueous solution to obtain impregnation liquid, evaporating redundant impregnation to dryness under the vacuum condition of 70 ℃, aging at room temperature for 12h after impregnation, drying at 120 ℃ for 10h, and roasting at 400 ℃ for 4h to obtain the catalyst precursor containing platinum and rhenium.
S4, dissolving 24.5g of aluminum hydroxychloride sol (the aluminum content is 11-12 wt%) and 0.44g of yttrium chloride and 0.31g of lanthanum nitrate in 70g of water to obtain a solution, wherein the aluminum in the solution respectively accounts for 1.0% of the total aluminum content of the catalyst, and the lanthanum and the yttrium account for 0.1% of the total mass of the catalyst; the catalyst C is obtained by repeatedly spraying and coating the catalyst on the catalyst intermediate in a ball rolling machine, drying the catalyst for 12 hours at 120 ℃ and roasting the catalyst for 8 hours at 400 ℃.
Example 4
S1, adding 2.0 liters of water into a gelling tank, and simultaneously dropwise adding 1.2L of sodium aluminate solution (Na) while stirring2O 150g/L、Al2O3100g/L) and 1.1L of aluminum sulfate solution (Al)2O390g/L), and controlling the dropping speed of the material to keep the pH of the material within the range of 9.0-10.0. After filtration and washing with water, 13mL of dilute nitric acid (VHNO) was added3:VH2O ═ 1:1) acidified for 1 hour and slurried with 0.3L of water to a sol.
S2, dripping the mixture into a small spherical blank in an oil-ammonia column by adopting an oil column forming method, solidifying the small spherical blank in an ammonia water column for 2 hours, filtering, washing the small spherical blank three times by using deionized water, drying the small spherical blank at 80 ℃ for 4 hours, drying the small spherical blank at 120 ℃ for 2 hours, and roasting the small spherical blank at 500 ℃ for 4 hours to obtain the high-pore-volume alumina sphere carrier inner core.
S3, preparing 75g of mixed solution of chloroplatinic acid and tetrammine platinum chloride with the platinum content of 0.02g/g, dissolving 5.76g of ammonium perrhenate in 60g of aqueous solution to obtain impregnation liquid, wherein the liquid-solid ratio in impregnation is 1.2:1, evaporating redundant impregnation to dryness under the vacuum condition at 70 ℃, aging at room temperature for 12 hours after impregnation, drying at 120 ℃ for 2 hours, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor containing platinum and rhenium.
S4, dissolving 18.5g of aluminum hydroxychloride sol (the aluminum content is 11-12 wt%) and 0.22g of yttrium chloride and 0.46g of lanthanum nitrate in 70g of water to obtain a solution, wherein the aluminum in the solution respectively accounts for 5.0% of the total aluminum content of the catalyst, and the lanthanum and the yttrium account for 0.1% of the total mass of the catalyst; the catalyst D is obtained by repeatedly spraying and coating the catalyst on the catalyst intermediate in a ball rolling machine, drying the catalyst for 8 hours at 120 ℃ and roasting the catalyst for 6 hours at 450 ℃.
The catalysts prepared above were evaluated separately, specifically as follows:
50g of catalyst is loaded in a 150ml device, pure hydrogen is used for reduction for 2h at 510 ℃, hydrogen sulfide is introduced for pre-vulcanization for 2h at 370 ℃, the reaction temperature is 495 ℃, the reaction pressure is 0.70MPa, and the liquid feeding volume space velocity is 2h-1The hydrogen-oil volume ratio was 1000:1, and the results are shown in Table 3.
TABLE 1 elemental composition of the catalyst
| Example number | Platinum/wt.% | Rhenium/wt.% | Lanthanum/wt.% | Yttrium/wt.% | Chlorine/wt.% |
| Example A | 0.3 | 0.3 | 0.1 | 0.1 | 1.0 |
| Example B | 0.23 | 0.25 | / | / | 1.03 |
| Example C | 0.29 | 0.30 | 0.1 | 0.21 | 1.01 |
| Example D | 0.21 | 0.40 | 0.15 | 0.1 | 1.09 |
| Comparative example a | 0.3 | 0.3 | 0.1 | 0.1 | 1.2 |
| Comparative example b | 0.29 | 0.3 | / | / | 1.15 |
TABLE 2 physical Properties of the catalysts
TABLE 3 results of catalytic evaluation of simulated semi-regenerative reforming reaction process
The results in table 3 show that the catalyst of the present invention has improved selectivity and activity, increased yield of the target product, reduced carbon deposition content, improved stability, and relatively increased service life under the same reaction conditions.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The semi-regenerative reforming catalyst with a shell-core structure is characterized by comprising platinum and rhenium-containing high-pore-volume alumina pellets, wherein the platinum and rhenium-containing high-pore-volume alumina pellets are coated with a rare earth element-containing protective layer, and the rare earth element-containing protective layer is formed by lanthanum and yttrium-containing aluminum hydroxychloride sol;
the semi-regenerative reforming catalyst comprises 0.1-0.65 wt% of platinum, 0.1-0.65 wt% of rhenium, 0.1-0.4 wt% of lanthanum, 0.1-0.4 wt% of yttrium, 0.5-1.5 wt% of chlorine and the balance of alumina;
the semi-regenerated reforming catalyst has a pore volume of 0.4 to 1.0ml/g and a specific surface area of 100 to 400m2A density of 0.6 to 0.8g/ml, and a particle diameter of 1.0 to 2.0 mm.
2. Semi-regenerative reforming catalyst according to claim 1, characterized in that the platinum is derived from one or more of chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate, platinum tetrachloride, platinum nitrate, tetraammineplatinum chloride and tetraammineplatinum hydroxide, preferably chloroplatinic acid.
3. A semi-regenerative reforming catalyst according to claim 1, wherein the rhenium is derived from perrhenic acid or ammonium perrhenate, preferably ammonium perrhenate.
4. A semi-regenerative reforming catalyst according to claim 1, wherein the lanthanum is derived from one or more of lanthanum chloride, lanthanum nitrate, lanthanum acetate and lanthanum oxide, preferably lanthanum nitrate.
5. The semi-regenerative reforming catalyst of claim 1 wherein the yttrium is derived from yttrium carbonate or yttrium chloride.
6. A method of preparing a semi-regenerative reforming catalyst as defined in claim 1, comprising the steps of:
dropwise adding and mixing an alkaline aluminum salt solution and an acidic aluminum salt solution under the condition of pH 7.5-10.5, and then roasting to obtain a high-pore-volume alumina precursor, dissolving the high-pore-volume alumina precursor with acid colloid, and preparing a microspherical alumina blank by one of an oil ammonia column method, a hot oil column method, a rolling ball method or a micro-flow forming method;
drying the alumina blank, and carrying out hydrothermal roasting treatment at 400-700 ℃ for 0.1-20 h to obtain an alumina carrier core;
dipping an alumina inner core by using a solution containing a platinum compound and a rhenium compound, aging at room temperature for 2-12 h, drying at 80-200 ℃ for 2-12 h, evaporating the rest dipping solution to dryness, and roasting at 400-700 ℃ for 4-8 h to obtain an intermediate catalyst containing platinum and rhenium;
coating a platinum and rhenium-containing intermediate catalyst with aluminum hydroxychloride sol containing lanthanum and yttrium compounds, and drying at 80-200 ℃ for 0.5-12 h to obtain the semi-regenerative reforming catalyst with a shell-core structure.
7. The method according to claim 6, wherein the pH is 8.5 to 9.5.
8. A method for evaluating a semi-regenerated reforming catalyst according to any one of claims 1 to 5 or a semi-regenerated reforming catalyst prepared by the preparation method according to claim 6 or 7, characterized in that the semi-regenerated reforming catalyst with a shell-core structure is activated by using water and hydrogen chloride in a reducing gas atmosphere, wherein the mass ratio of the water to the hydrogen chloride is 5-100: 1, the temperature is 450-600 ℃, and the activation time is 0.5-10 h;
after activation, pre-vulcanizing at 350-450 ℃ for 0.5-10 h;
after the pre-vulcanization is finished, the pre-vulcanization and naphtha are subjected to the conditions of 400-600 ℃, 0.15-3.0 MPa and the volume space velocity of the naphtha is 0.1-10 h-1And performing contact reaction, wherein the volume ratio of hydrogen to hydrocarbon is 700-1200: 1.
9. The evaluation method according to claim 8, wherein the hydrogen chloride is derived from hydrochloric acid or an organic compound capable of decomposing chlorine, preferably hydrochloric acid, and the organic compound capable of decomposing chlorine is selected from tetrachloroethylene, dichloromethane, trichloromethane or carbon tetrachloride.
10. The evaluation method according to claim 8, wherein the naphtha is composed of C6-C10 linear paraffins, and the volume ratio of the C6-C10 linear paraffins is 10.5:25.5:27.1:26.9: 10.0.
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