CN109201092A - 一种多金属连续重整催化剂及其制备 - Google Patents
一种多金属连续重整催化剂及其制备 Download PDFInfo
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- CN109201092A CN109201092A CN201710540737.6A CN201710540737A CN109201092A CN 109201092 A CN109201092 A CN 109201092A CN 201710540737 A CN201710540737 A CN 201710540737A CN 109201092 A CN109201092 A CN 109201092A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000002407 reforming Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 14
- 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 53
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 32
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 31
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 35
- 239000000460 chlorine Substances 0.000 claims description 27
- 229910052801 chlorine Inorganic materials 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 230000004913 activation Effects 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- -1 yttrium compound Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- OPIPOVICJAKBHX-UHFFFAOYSA-N 1,1,1,2,2,3-hexachloropropane Chemical compound ClCC(Cl)(Cl)C(Cl)(Cl)Cl OPIPOVICJAKBHX-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 238000002803 maceration Methods 0.000 description 18
- 229910052718 tin Inorganic materials 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000470 constituent Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000006057 reforming reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 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 1
- 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 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/024—Multiple impregnation or coating
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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
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- 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
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
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- 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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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
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Abstract
一种多金属连续重整催化剂,包括氧化铝载体和以载体为基准计算的含量如下的活性组分:
Description
技术领域
本发明为一种连续重整催化剂及制备,具体地说,是一种含铂锡的多金属连续重整催化剂及制备。
背景技术
催化重整过程是重要的石油加工工艺,在这一过程中石脑油组分在催化剂的作用下转化为芳烃含量较高的产物,可生产高辛烷值汽油、芳烃,同时副产氢气。随着原油品质的劣质化和成品油产品的环保指标升级,炼厂对廉价氢气的需求不断增加,因此催化重整已经成为现代炼油企业必备的工艺过程。按照重整工艺过程的目的产物区分,重整装置可以分为芳烃型装置和汽油型装置两类,前者以生产苯、甲苯和二甲苯等芳烃为目标产物,后者以高辛烷值汽油调和组分为目标产物。对于芳烃型重整装置,在合理的操作条件下获得更高的芳烃产品收率是所追求的目标,特别是获得尽可能高的轻质芳烃─苯、甲苯和二甲苯(BTX)收率,对于装置的整体经济效益至关重要。
重整催化剂是双功能催化剂,必须同时具有异构化酸性功能和加氢-脱氢的金属功能。催化剂的酸性功能一般由多孔的酸性无机氧化物载体,如含氯的氧化铝提供,加氢-脱氢的金属功能由铂族金属提供。为了获得更好的双功能匹配,催化剂中通常还需引入其他金属助剂,如锡、稀土金属等。
CN1181164C公开了一种多金属重整催化剂的制备方法,将铂、铼和镧系金属或钇、氯的水溶性化合物配成浸渍液,浸渍液的量为载体饱和吸附容量的1.1~5.0倍,然后用此浸渍液浸渍载体,随后干燥焙烧,该方法可使多金属组分在催化剂中更均匀分布,提高了催化剂的活性和选择性。所述催化剂适用于半再生重整反应装置。
CN1234455C公开了一种多金属重整催化剂及其制备方法,所述的催化剂包括质量百分数如下的各组分:VIII族金属0.01~2.0,IV族金属0.01~5.0%,Eu 0.01~10.0,Ce0.01~10,卤素0.1~10.0,耐高温无机氧化物63.00~99.86。该催化剂用于石脑油重整反应,具有较高的活性和选择性,积炭速率低,使用寿命长。
CN103372454B公开了一种多金属重整催化剂,包括耐高温无机氧化物载体和以载体为基准计算的含量如下的各组分:VIII族金属0.01~2.0质量%,IVA族金属0.01~5.0质量%,Sm 0.01~3.0质量%,Ce 0.01~3.0质量%,卤素0.1~5.0质量%,所述催化剂中(Sm+Ce)和Pt的原子比为0.2~1.1。该催化剂具有良好的活性稳定性和较高的选择性。
CN104148066A公开了一种多金属重整催化剂,包括耐高温无机氧化物载体和以载体为基准计算的含量如下的各组分:VIII族金属0.01~2.0质量%,IVA族金属0.01~5.0质量%,Y 0.01~3.0质量%,Sm 0.01~3.0质量%,卤素0.1~5.0质量%。该催化剂具有良好的活性稳定性和较高的选择性。
上述专利通过引入稀土金属到重整催化剂中,通常可以获得较好的液体产物选择性,但重整过程中最重要的芳烃产物的收率往往有所降低,特别是轻质芳烃BTX的收率没有获得有效提高。
发明内容
本发明的目的是提供一种多金属连续重整催化剂及其制备方法,该催化剂用于石脑油重整反应,具有较高的活性和芳烃产率,特别是轻质芳烃(BTX)收率提高。
本发明提供的多金属连续重整催化剂,包括氧化铝载体和以载体为基准计算的含量如下的活性组分:
催化剂中钇和铈的含量之和不大于0.5质量%,并且钇与铈的摩尔比大于2。
本发明在常规的连续重整催化剂中引入适量的钇和铈,有效提高了催化剂的活性和活性稳定性,在重整反应过程中可以获得更高的芳烃产率,特别是轻质芳烃─苯、甲苯和二甲苯(BTX)收率。本发明催化剂更适用于以芳烃为目标产物的连续重整装置。
具体实施方式
在催化重整中,衡量催化剂性能的指标包括活性、选择性及稳定性。活性是指在给定的反应条件下,催化剂将反应物转化为目的产物的能力。一般来说,活性表现为在给定原料和反应条件下所得产物辛烷值的大小,或者为在给定液体产品辛烷值下反应温度的高低,在同样的液体产品辛烷值下较低的反应温度说明催化剂活性较高;选择性是指在给定的活性水平下,芳烃的产率或者C5+汽油产品的收率;稳定性是指单位时间或单位处理量下催化剂活性或选择性的变化,变化越小,稳定性越好。
本发明通过同时向催化剂中引入适量的钇和铈,并控制钇与铈的摩尔比,在保证催化剂芳烃产品收率较高的同时,进一步提高了BTX产品收率。
本发明催化剂的活性组分含量优选为:
所述催化剂中钇与铈的摩尔比优选2.3~4.0。催化剂中钇和铈的含量之和优选0.2~0.45质量%。
本发明提供的催化剂的制备方法,包括用含钇化合物和含铈化合物的溶液浸渍含锡的氧化铝载体,经干燥、焙烧后,再用含铂化合物的溶液浸渍,干燥后活化。
本发明催化剂中所述的氧化铝载体为多孔具有吸附性的物质,其比表面积优选30~500米2/克,表观堆密度优选0.4~1.0克/毫升、孔直径优选2~50nm、孔体积优选0.2~1.0毫升/克。其组成应是均匀的,并且在使用的条件下是难熔的。术语“组成均匀”的意思是指载体不分层,没有固有组分的浓度梯度。
本发明所述的氧化铝优选烷氧基铝水解制得的高纯氧化铝,氧化铝结晶形态可为γ-A12O3、η-A12O3或θ-A12O3,优选γ-A12O3或η-A12O3,更优选γ-A12O3。所述A12O3载体型态优选球形,可通过油氨柱法或热油柱法滴球成型,其直径优选1.0~2.5mm。
上述方法所述的含锡的氧化铝载体中的锡组分可采用任何方式引入载体中,并达到均匀分布。如在氧化铝制备过程中通过共沉淀引入,或用含锡化合物通过离子交换或浸渍方法引入。其中浸渍法是用可溶性的含锡化合物溶液浸渍氧化铝载体,使该溶液充满或分散在氧化铝载体中。优选的引入锡的方法是在载体成型前将含锡化合物与氧化铝或其前体混合,然后一起成型,从而使锡在氧化铝载体中分布均匀。适宜的含锡化合物为其氧化物、氯化物、硝酸盐、醇盐或金属有机配合物,如溴化亚锡、氯化亚锡、四氯化锡、四氯化锡五水合物、四丁基锡。
本发明所述催化剂含有的钇和铈可采用任何方式引入到载体中,如采用共沉淀、共胶凝、共挤压、离子交换或浸渍法。优选采用含钇化合物和含铈化合物的溶液浸渍氧化铝载体,浸渍温度优选15~50℃,浸渍液/固比优选0.8~2.0ml/g,浸渍后固体需干燥、焙烧。所述干燥温度优选90~150℃,焙烧温度可为350~850℃、优选620~850℃。为使钇和铈均匀分布于载体上,在浸渍液中加入HCl等酸类。所述的焙烧优选在含水的空气中进行,空气中的水含量优选4~8质量%。
所述含钇化合物和含铈化合物优选其硝酸盐或氯化物,如硝酸钇、硝酸铈、氯化钇或氯化铈。
本发明催化剂中铂的引入可在引入钇和铈之后进行,也可在引入钇和铈之前进行,优选在引入锡、钇和铈之后进行,从而防止铂在浸渍引入其它金属组分过程中流失。优选的方法是采用含铂化合物溶液浸渍载体,所述的含铂化合物优选氯铂酸。在浸渍过程中为了有利于氯的引入并使铂组分在载体上均匀分布,可在浸渍液中加入HCl等酸类。在浸渍引入铂之后,需要进行活化,以使浸渍引入的铂与载体之间更紧密地结合。
浸渍引铂后需进行干燥,活化。所述的活化优选水氯活化,以在催化剂中引入适量的氯。水氯活化所用的介质为含水和HCl的空气,水氯活化的温度为370~700℃,所用空气中水与HCl的摩尔比为5~100:1、优选10~60:1。水氯活化的时间优选2~8小时。水氯活化所用空气中含有的HCl可来源于HCl,也可来源于能分解出氯的有机化合物,如四氯乙烯、二氯甲烷、三氯甲烷、四氯化碳。
本发明方法制备的催化剂在使用前需进行还原,以将铂等金属组元还原成相应的金属态。优选的还原气为氢气,也可采用CO等其他还原气体对催化剂进行还原。还原温度范围是315~650℃,时间优选0.5~10小时。还原可在催化剂装入反应器之前进行,也可在催化剂装入反应器之后重整反应开始前原位进行。
本发明提供的催化剂适用于烃类的重整反应,所述的烃类为石脑油。重整反应的压力为0.20~0.45MPa、优选0.25~0.40MPa,温度为480~540℃,优选490~540℃。反应时进料体积空速为1~5小时-1、更优选1.50~3小时-1,氢/烃摩尔比为1.5~5、优选2~4。
下面通过实例进一步详细说明本发明,但本发明并不限于此。
实例1
(1)制备锡均匀分布的含锡γ-Al2O3小球。
取100克SB氢氧化铝粉(Sasol德国公司生产,氧化铝含量为72质量%)和适量脱离子水搅拌浆化,液/固质量比为2.0。加入7.5毫升体积比为1:1的稀硝酸,30克尿素和预定量的SnCl2的盐酸溶液,使溶液中Sn的含量相对干基氧化铝为0.30质量%,搅拌1小时,加入30克煤油和3克脂肪醇聚氧乙烯醚搅拌1小时,在油氨柱内滴球成型。湿球在氨水中固化1小时,然后过滤,用脱离子水冲洗2~3次,60℃干燥6小时,120℃干燥10小时,600℃焙烧4小时,得含Sn的γ-Al2O3小球,其直径为1.6mm,BET法测定的比表面积为203米2/克、氮气吸附法测定的平均孔直径为8.1nm。
(2)引钇和铈。
取1.077克Y(NO3)3·6H2O和0.3988克CeCl3·7H2O和去离子水配成160毫升的溶液作为浸渍液,在浸渍液中加入适量的盐酸,使得浸渍液中HCl浓度为1.0质量%。将100克按(1)步方法制备的氧化铝小球载体加入浸渍液中于25℃浸渍4小时,然后用旋转蒸发器将浸渍体系蒸干,所得固体于120℃干燥12小时,再通入水含量为5质量%的空气于650℃焙烧4小时。
(3)引铂。
取0.5882克氯铂酸、5.95克浓度为37质量%的盐酸和175克的去离子水配制成溶液,其中HCl的含量相对于干基氧化铝载体为2.2质量%,以配制的溶液为浸渍液于25℃浸渍(2)步制备的载体4小时,浸渍的液/固比为1.8mL/g。浸渍后用旋转蒸发器将浸渍体系蒸干,所得固体于120℃干燥12小时,在510℃水氯活化4小时,水氯活化所用空气中水与HCl的摩尔比为40,然后于500℃用氢气还原4小时,得催化剂A,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Y 0.25质量%,Ce 0.15质量%,Cl 1.15质量%,其中Y/Ce的摩尔比为2.63。各元素含量均采用X射线荧光分析方法测定。
实例2
按实例1的方法制备催化剂,不同的是(2)步配制的浸渍液中,Y(NO3)3·6H2O的加入量为0.8617克,CeCl3·7H2O的加入量为0.2659克。经(3)步引铂,制得催化剂B,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Y 0.20质量%,Ce 0.10质量%,Cl 1.15质量%,其中Y/Ce的摩尔比为3.15。
对比例1
按实例1的方法制备催化剂,不同的是(2)步配制的浸渍液中仅加入Y(NO3)3·6H2O,制得催化剂C,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Y 0.25质量%,Cl 1.15质量%。
对比例2
按实例1的方法制备催化剂,不同的是(2)步配制的浸渍液中仅加入CeCl3·7H2O,制得催化剂D,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Ce0.15质量%,Cl 1.15质量%。
对比例3
按实例1的方法制备催化剂,不同的是(2)步配制的浸渍液中,Y(NO3)3·6H2O的加入量为0.4308克,CeCl3·7H2O的加入量为0.5318克。经(3)步引铂,制得催化剂E,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Y 0.10质量%,Ce 0.20质量%,Cl 1.15质量%,其中Y/Ce的摩尔比为0.79。
对比例4
按实例1的方法制备催化剂,不同的是(2)步中用0.6028克EuCl3·6H2O和0.2659克CeCl3·7H2O配制浸渍液,经(3)步引铂,制得催化剂F,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Eu 0.25质量%,Ce 0.10质量%,Cl 1.15质量%。
对比例5
按实例1的方法制备催化剂,不同的是(2)步中用0.8617克Y(NO3)3·6H2O和0.2426克SmCl3·6H2O配制浸渍液,经(3)步引铂,制得催化剂G,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Y 0.2质量%,Sm 0.10质量%,Cl 1.15质量%。
对比例6
按实例1的方法制备催化剂,不同的是(2)步中用0.6065克SmCl3·6H2O和0.2659克CeCl3·7H2O配制浸渍液,经(3)步引铂,制得催化剂H,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Sm 0.25质量%,Ce 0.10质量%,Cl 1.15质量%。
对比例7
按实例1的方法制备催化剂,不同的是(2)步配制的浸渍液中,Y(NO3)3·6H2O的加入量为1.723克,CeCl3·7H2O的加入量为0.7977克。经(3)步引铂,制得催化剂L,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Y 0.4质量%,Ce 0.3质量%,Cl 1.15质量%。
对比例8
按实例1的方法制备催化剂,不同的是(3)步引铂所用载体为100克按(1)步方法制得的含Sn的γ-Al2O3小球,制得催化剂K,其以氧化铝为基准计算的组分含量为:Pt 0.28质量%,Sn 0.30质量%,Cl 1.15质量%。
实例3~12
以下实例评价催化剂的重整反应性能。
在带有循环压缩机的100毫升中型装置上,以表1所示的直馏石脑油为原料,对本发明催化剂和对比催化剂进行评价。评价条件为反应压力0.35MPa、进料体积空速2.0小时-1,氢/烃摩尔比为4,评价时间为95小时,期间依次调节原料的入口温度为490℃、505℃、520℃和535℃,每一温度反应20小时,每次升温间隔时间为5小时,在相应的反应温度下采样分析液体产品的组成,各实例所用催化剂及在不同反应温度下的芳烃产率见表2,BTX收率见表3。
从表2可以看出,在同样的反应条件下本发明催化剂A和B可以获得更高的芳烃产品收率,而表3则说明本发明催化剂的BTX收率显著高于对比催化剂。表1
表2
表3
Claims (11)
1.一种多金属连续重整催化剂,包括氧化铝载体和以载体为基准计算的含量如下的活性组分:
催化剂中钇和铈的含量之和不大于0.5质量%,并且钇与铈的摩尔比大于2。
2.按照权利要求1所述的催化剂,其特征在于所述催化剂的活性组分含量为:
3.按照权利要求1或2所述的催化剂,其特征在于所述催化剂中钇与铈的摩尔比为2.3~4.0。
4.按照权利要求1所述的催化剂,其特征在于催化剂中钇和铈的含量之和为0.2~0.45质量%。
5.一种权利要求1所述催化剂的制备方法,包括用含钇化合物和含铈化合物的溶液浸渍含锡的氧化铝载体,经干燥、焙烧后,再用含铂化合物的溶液浸渍,干燥后活化。
6.按照权利要求5所述的方法,其特征在于浸渍引铂后的活化为水氯活化,水氯活化所用的介质为含水和HCl的空气,水氯活化的温度为370~700℃,所用空气中水与HCl的摩尔比为5~100:1。
7.按照权利要求5所述的方法,其特征在于所述含钇化合物和含铈化合物为其硝酸盐或氯化物。
8.按照权利要求5所述的方法,其特征在于所述的含铂化合物为氯铂酸。
9.按照权利要求5所述的方法,其特征在于所述浸渍后的焙烧温度为350~850℃。
10.按照权利要求9所述的方法,其特征在于所述的焙烧在含水的空气中进行,空气中的水含量为4~8质量%。
11.按照权利要求6所述的方法,其特征在于水氯活化所用的HCl来自于HCl或能分解出氯的有机化合物,所述有机化合物选自四氯乙烯、二氯甲烷、三氯甲烷或四氯化碳。
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