CN101056704B - 使用高密度催化剂的重整方法 - Google Patents
使用高密度催化剂的重整方法 Download PDFInfo
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- CN101056704B CN101056704B CN2005800388425A CN200580038842A CN101056704B CN 101056704 B CN101056704 B CN 101056704B CN 2005800388425 A CN2005800388425 A CN 2005800388425A CN 200580038842 A CN200580038842 A CN 200580038842A CN 101056704 B CN101056704 B CN 101056704B
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- 238000000034 method Methods 0.000 title claims abstract description 35
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- 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 106
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052718 tin Inorganic materials 0.000 claims abstract description 45
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 29
- 229910052736 halogen Inorganic materials 0.000 claims description 26
- 150000002367 halogens Chemical class 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 9
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001228 spectrum Methods 0.000 claims description 6
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- 239000003795 chemical substances by application Substances 0.000 claims description 3
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011733 molybdenum Substances 0.000 claims description 2
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- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 230000001131 transforming effect Effects 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
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- 229910052783 alkali metal Inorganic materials 0.000 claims 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
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- 238000007598 dipping method Methods 0.000 description 7
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- 238000002360 preparation method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000001935 peptisation Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 2
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- NGXWSRYOFVTCCT-UHFFFAOYSA-L lead(2+);dichlorate Chemical compound [Pb+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NGXWSRYOFVTCCT-UHFFFAOYSA-L 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 229910001630 radium chloride Inorganic materials 0.000 description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- 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
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 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
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
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- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
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- FHFOQXYFWKSNNF-UHFFFAOYSA-N [N+](=O)([O-])[Ir]([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-] Chemical compound [N+](=O)([O-])[Ir]([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-] FHFOQXYFWKSNNF-UHFFFAOYSA-N 0.000 description 1
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- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000012798 spherical particle Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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Abstract
本发明提供通常用于烃转化的催化剂和使用该催化剂的方法。该催化剂具有增加的平均体密度及减少的铂族金属质量比。对于石脑油范围烃的重整而言，使用该催化剂的方法获得意想不到的高活性和稳定性。使用穆斯堡尔谱表征锡与铂的缔合程度且测定对于具有大于0.6g/cc的密度的氧化铝承载而言适当的有效摩尔锡比率。
Description
技术领域
本发明涉及关于具有指定高密度且具有铂族组份对锡组份的指定的低比率的经成型的催化剂，并涉及使用该催化剂用于烃转化的方法，例如将石脑油范围原料重整为高辛烷芳族物。
诸如催化石脑油重整器的烃转化单元需要对于清洁燃料提供较大数量的氢，对于汽油提供高辛烷产物及对于石化产品提供芳族物。具有较高密度及较低铂-锡比的改良的催化剂允许重整单元增加氢、C5 +及/或芳族产物的量的增大产生的生产量。与低密度催化剂相比，新催化剂具有较高活性且允许较高的堵塞极限。堵塞极限指这样的极限，即在此极限移动床催化剂由此流过工艺反应器，相对于若非如此催化剂将停止移动并有效地堵塞或粘在反应器壁或中心管上的烃流动条件。较低的堵塞极限通常与移动催化剂流的分布问题关联，从而导致不均匀的反应器效能。对于已将较高速率的进料推动通过其重整单元的精制器而言，加载较高密度催化剂可为进一步增加进料烃生产量的简单有效方式。对于恒定的再循环氢气流而言，许多重整单元中的烃液压容量可增加多达20％或更多。较高密度催化剂的较低焦炭产生对于焦炭产生受限于连续再生能力且需要增加进料速率、但不能增加再循环气体速率的精制器而言特别重要。
在现有技术中提供许多用于石脑油重整的含有铂及锡的催化剂。
US3,745,112提供基于均一分散的铂-锡复合物的烃转化催化剂和方法。所提供催化剂的特定实例为铂族金属、氧化锡和卤素与氧化铝载体材料的组合，其中氧化锡组份以相对小的粒度均一分散在氧化铝载体材料中。
US3,920,615提供用于减少氧化铝催化剂的表面积至10与150m2/gm之间的至少800℃的煅烧处理。催化剂含有具有诸如铜的第二金属的铂族金属，且在作为生产烷基-芳基磺酸酯的一部分的长链单烯烃自石蜡的脱氢工艺中展示改良的选择性。
加拿大专利第1,020,958号提供由至少一种铂族组份组成的催化剂，其在导致焦炭沉积在催化剂上的条件下在烃与氢的反应区中使用。催化剂借助湿氧化而重生且重复该工艺直至表面积介于初始值的20与90％之间。接着处理催化剂以并入至少一种诸如锡的促进剂金属。所得催化剂在使用中展示增加的稳定性，因此不需太频繁地再生或置换。
US6,514,904提供通常用于烃转化并特别用于石脑油重整的催化剂及使用该催化剂的方法。
US6,600,082及US6,605,566提供使用锡的基于有机物的浸渍以达成与铂的高的相互作用所制备的重整及脱氢催化剂，该相互作用如基于穆斯堡尔谱的表征所测定。
发明内容
申请人现在已经发现具有增大的氧化铝密度及减少的铂对锡比率的催化剂在诸如石脑油的烃原料的转化中提供显著的方法优点。特别是，申请人已经发现，荸荠其他重整方法中所预期的，具有增大的氧化铝密度的催化剂提供较低焦炭产生、较好稳定性或较高活性。
本发明的广泛实施方案为烃转化催化剂，其包含具有高于0.6g/cc的平均体密度的载体，该载体上分散有铂族组份及锡组份，其中铂族对锡的体质量比低于0.9。载体优选氧化铝组份，其具有的X光粉末衍射图案2-θ布拉格角值34.0的峰强度与2-θ布拉格角值32.5的峰强度之比至少为1.2，并且2-θ布拉格角值46.0的峰强度与2-θ布拉格角值45.5的峰强度之比至多为1.1。此外，优选用穆斯堡尔谱测定特定铂族锡簇(platinum-group tin cluster)内与铂族金属缔合的锡的量来对锡进行表征。
另一个实施方案为特别在小于1ppm硫存在下在用于转化汽油范围烃的催化重整工艺中使用催化剂的方法。当催化剂含有碱或碱土金属时，该催化剂适用于脱氢工艺。
本发明的一个目的是提供具有低的铂族对锡比率的高密度催化剂，其适用于烃转化作用。另一个目的是提供适于重整的催化剂，其允许增加的堵塞极限，低焦炭产生及极好的活性。
本发明的额外目的、实施方案及细节可自本发明的以下详细描述中获得。
发明详述
因此，本发明的一个广泛实施方案为使用平均体密度高于0.6g/cc的载体颗粒所制备的经成型的催化剂。优选平均体密度较高于0.65g/cc。载体在组成上应是均一的且在烃转化工艺中所使用的条件下应是相对耐熔的。适当的载体包括无机氧化物，例如氧化铝、氧化镁、氧化锆、氧化铬、氧化钛、氧化硼、氧化钍、磷酸盐、氧化锌及二氧化硅中的一种或多种。氧化铝为优选的载体。
适当的氧化铝材料为被称为γ、η及θ相氧化铝的结晶氧化铝，其中γ或η相氧化铝给出最佳结果。优选的氧化铝为已在US3,852,190及US4,012,313中作为齐格勒(Ziegler)的US2,892,858中所述的齐格勒高级醇合成反应的副产物而得以表征的氧化铝。为简化的目的，该氧化铝在下文中将被称为“齐格勒氧化铝”。齐格勒氧化铝目前可在商标“Catapal”下自Vista Chemical Company获得或在商标“Pural”下自Condea Chemie GmbH获得。此材料为非常高纯度的假勃姆石，其在高温下煅烧后已展示生成高纯度γ氧化铝。
本催化剂的优选形式为球体。氧化铝球体可由熟知的油滴方法连续制造，该方法包含：由本领域中所教示的任何技术用齐格勒氧化铝或氧化铝水溶胶形成氧化铝浆液，且优选使铝金属与盐酸反应来形成氧化铝浆液；将所得水溶胶或浆液与适当的胶凝剂组合；及将所得混合物滴入保持在升高的温度下的油浴中。混合物的液滴停留在油浴中直至其凝固且形成胶凝球体。接着自油浴中连续取出球体且通常在油及氨溶液中经受特定老化及干燥处理以进一步改良其物理特征。接着将所得经老化及胶凝的颗粒洗涤并在150℃至205℃的相对低温下干燥，且在450℃至700℃的温度下经受1至20小时的时间的煅烧程序。此处理实现氧化铝水凝胶至相应的结晶γ氧化铝的转化。US2,620,314提供额外细节且以引用的方式并入本文。术语“大体上球体”的使用是指大多数球体的几何性质是圆的且包括微小偏差。
本催化剂的替代形式为圆柱形挤出物。“大体上圆柱形”催化剂是定义为大多数圆柱的几何性质在一个方向上是圆的且在另一个方向上是线状的，且包括与其的微小偏差，该催化剂可由本领域中熟知的任何形成方法(例如挤出法)制备。优选的挤出物形式是借助将齐格勒氧化铝粉末与水及适当的胶溶剂(例如硝酸、乙酸、硝酸铝及其类似材料)混合以形成在500℃下具有45至65质量％的燃烧损失(LOI)的可挤出膏团而得以制备。所得膏团经由适当形状及大小的模具挤出以形成挤出颗粒，其可在150℃至205℃的相对低温下干燥且在450℃至700℃的温度下经受1至20小时的时的煅烧程序。
此外，也可借助在旋转圆盘上滚动挤出颗粒而自挤出物形成球体颗粒。平均颗粒直径可自1mm至10mm变化，其中优选颗粒直径为约3mm。
在成形之后，催化剂经受至少一个煅烧处理。此煅烧优选在经选择用以产生包含经煅烧氧化铝的产物催化剂的条件下进行，该经煅烧氧化铝具有特征性X光图案及就表面积而言的所要物理性质。此煅烧通常在700℃至900℃的温度、低于4质量％蒸汽的湿气含量及15分钟至20小时的时间下发生。煅烧条件更优选包含800℃至900℃的温度、低于3质量％蒸汽的湿气含量及30分钟至6小时的时限。所应用的氧气氛通常包含干燥空气。干燥空气被视为未添加湿气或蒸汽的空气，其在已使用诸如分子筛或氧化硅的化学方式加以干燥的空气至环境湿气含量的范围内。准确时间通常为达到所要求的经煅烧氧化铝的表面积及块压碎强度的物理性质所需的时间。表面积减少的相对量将大约介于5至30％之间。另外，块压碎强度将至多减少至初始值的95％。归因于此煅烧，块强度也可增加，因此可获得高于初始值100％的值。
因此，若在此煅烧处理之前氧化铝具有介于200与220m2/gm之间的表面积，则经煅烧的氧化铝将具有介于140与210m2/gm之间的表面积(由BET/N2方法、ASTM D3037或相当方法测定)。经煅烧的氧化铝优选将具有介于150与180m2/gm之间的表面积。注意此时要求当然将随着所应用的煅烧温度及所用气氛的氧含量而变化。也注意在此煅烧处理之前的氧化铝可具有介于180与240m2/gm之间的表面积范围，如上文所说明其中优选范围为200至m2/gm。
当催化剂具有在指定布拉格角位置展示特征性的峰强度的X光衍射图案时，获得极好结果。具体而言，优选催化剂具有这样的X光粉末衍射图案，即2-θ布拉格角值34.0的峰强度与2-θ布拉格角值32.5的峰强度之比至少为1.2，并且2-θ布拉格角值46.0的峰强度与2-θ布拉格角值45.5的峰强度之比至多为1.1。X光图案可由标准X光粉末衍射技术获得，其一个适当实例在下文描述。辐射源通常为在45KV及35mA下操作的高强度、铜靶X光管。说明性地用连续模式以0.030°的步长及9.0秒的停留时间在计算机控制器衍射计上扫描扁平压制的粉末样本。来自铜K辐射的衍射图案可以帕耳贴效应冷却固态检测器(Peltier effect cooled solid-state detector)记录。资料适当地以数字形式储存在控制计算机中。峰高度及峰位置作为两倍θ(2-θ)的函数自计算机图线读取，其中θ为布拉格角。
催化剂的一种成份为铂族金属组分。此组份包含铂、钯、钌、铑、铱、锇或其混合物，其中铂为优选。铂族金属可作为诸如氧化物、硫化物、卤化物、氧卤化物等的化合物与复合物的其他成份中的一种或多种的化学组合或作为元素金属存在于最终催化复合物中。当大体上所有铂族金属组份均以元素状态存在且其均匀地分散在载体材料中时可获得最佳结果。铂族金属组份可以任何催化有效量存在于最终催化剂复合物中；在元素基础上计算，铂族金属通常将构成最终催化复合物的0.01至2质量％。当催化剂含有0.05至1质量％的铂时获得极好结果。
铂族金属组份可以诸如共沉淀、离子交换或浸渍的任何适当方式并入载体中。制备催化剂的优选方法包括使用铂放金属的可溶且可分解的化合物以相对均一的方式浸渍载体材料。例如，可借助将载体与氯铂酸或氯铱酸或氯钯酸的水溶液混合而将组份添加至载体中。铂族金属的其他水溶性化合物或络合物可在浸渍溶液中应用且其包括氯铂酸铵、溴铂酸、三氯化铂、水合四氯化铂、二氯羰基二氯化铂、二硝基二氨基铂、四硝基铂(II)酸钠、氯化钯、硝酸钯、硫酸钯、二胺氢氧化钯(II)、四胺氯化钯(II)、六胺氯化铑、羰基氯化铑、水合三氯化铑、硝酸铑、六氯铑(III)酸钠、六硝基铑(III)酸钠、三溴化铱、二氯化铱、四氯化铱、六硝基铱(III)酸钠、氯铱酸钾或氯铱酸钠、草酸钾铑等。使用诸如氯铂酸、氯铱酸或氯钯酸或水合三氯化铑的氯化铂、铱、铑或钯化合物是优选的，因为其有利于在仅一个步骤中并入铂族金属组份及至少一种较小数量的优选卤素组份。盐酸或其类似酸通常也添加至浸渍溶液中以便进一步有利于并入卤素组份及在载体材料中均一分布金属组份。另外，在煅烧之后浸渍载体材料以便将洗掉有价值的铂族金属的风险减至最小通常是优选的。
铂族金属组份通常均匀地分散在催化剂中。优选地，借助将局部金属浓度与全部催化剂金属含量进行比较的电子微探针分析来测定铂族金属的均匀分散。均匀分布与均一分布是同义的。在一个替代性实施方案中，一种或多种铂族金属组份可作为如US4,677,094中所描述的表面层组份存在，该文献以引用的方式并入本文。“表面层”为邻近颗粒表面的催化剂颗粒的层，且当由催化剂的颗粒表面行进至中心时表面层金属的浓度逐渐减少。
IV A族(IUPAC 14)金属组份为本发明的催化剂的另一种成份。在IV A族金属中，锗及锡是优选的且锡尤其优选。该组份可作为元素金属存在，作为诸如氧化物、硫化物、卤化物、氧氯化物等的化合物存在，或作为与多孔载体材料和/或催化复合物的其他组份的物理或化学组合存在。IVA族金属的实质部分优选以超过元素金属的氧化态存在于所完成的催化剂中。IV A族金属组份最佳是以足以导致含有以元素基础计0.01至5质量％金属的最终催化复合物的量使用，其中在0.1至2质量％的金属含量下获得最佳结果。
IV A族金属组份可以任何适当方式并入催化剂中以达成均匀分散，例如在制备中的任何阶段与多孔载体材料共沉淀、与载体材料离子交换或浸渍载体材料。一种将IV A族金属组份并入催化剂复合物中的方法包括使用IV A族金属的可溶且可分解的化合物将该金属浸渍且分散在多孔载体材料中。IV A族金属组份可在其他组份添加至载体材料中之前、同时或之后浸渍。因此，IVA族金属组份可借助将载体材料与适当的金属盐或可溶性化合物(例如溴化亚锡、氯化亚锡、氯化锡、五水合氯化锡；或氧化锗、四乙醇锗、四氯化锗；或硝酸铅、乙酸铅、氯酸铅及其类似化合物)的水溶液混合而添加至载体材料中。使用诸如氯化锡、四氯化锗或氯酸铅的IVA族金属氯化物化合物是尤其优选的，因为此有利于在仅一个步骤中并入金属组份及至少一种较小量的优选卤素组份。当在上文所述的尤其优选的氧化铝胶溶步骤中与盐酸组合时，根据本发明获得IV A族金属组份的均匀分散。在一个替代性实施方案中，在无机氧化物粘合剂的胶溶作用期间且最佳在氧化铝与盐酸或硝酸的胶溶作用期间将诸如三甲基氯化锡及二甲基二氯化锡的有机金属化合物并入催化剂中。
催化剂也可含有单独或共同充当催化剂改性剂以改良活性、选择性或稳定性的多种IV A族金属组份或其他组份或其混合物。某些其他已知的催化剂改性剂包括铼、镓、铈、镧、铕、铟、磷、镍、铁、钨、钼、锌及镉。催化有效量的这样的组份可以任何适当方式在其制备期间或制备后添加至载体材料中，或在其他组份并入之前、期间或之后添加至催化复合物中。通常，当这样的组份以每一种组份的元素基础计构成复合物的0.01至5质量％时，获得良好结果。
催化剂的另一种可选组份，尤其是适用于包含脱氢反应、脱氢环化反应或加氢反应的烃转化工艺中的，为碱或碱土金属组份。更具体而言，此可选择成份选自由碱金属——铯、铷、钾、钠及锂——的化合物及碱土金属——钙、锶、钡及镁——的化合物组成的组。通常，当以元素基础计此组份构成复合物的0.01至5质量时，获得良好结果。此可选的碱或碱土金属组份可以任何已知方式借助用合适的水溶性、优选水分解性化合物的水溶液浸渍而并入复合物中。
如至今所指出的，在催化剂的制备中希望使用至少一个煅烧步骤。本发明的一个可选步骤为高温煅烧步骤，其也可称为氧化步骤，优选发生在任何金属并入至载体之前，但也可在任何金属并入之后进行。当高温煅烧发生在任何金属并入之前时，当较低温度氧化步骤及可选的卤素调节步骤接在任何金属的添加之后时，获得良好结果。
对用于实现较低温度氧化步骤的条件加以选择以将催化复合物中的所有金属组份大体上转化为其相应氧化物形式。该氧化步骤通常发生在370℃至600℃的温度下。通常应用包含空气的氧气氛。大体而言，该氧化步骤将进行0.5至10小时或更多的时间，准确时间为将所有金属组份大体上转化为其相应氧化物形式所需的时间。当然，此时间将随所应用的温度及所应用气氛中的氧含量而改变。
除氧化步骤外，卤素调节步骤也可应用于制备催化剂。卤素调节步骤可充当双重功能。首先，卤素调节步骤可帮助IV A族金属(IUPAC 14)及任何其他金属组份的均匀分散。此外，卤素调节步骤也可充当将所希望含量的卤素并入至最终催化复合物中的方式。卤素调节步骤在空气或氧气氛中应用卤素或含卤素的化合物。由于用于并入至催化复合物中的优选卤素包含氯，因此在卤素调节步骤中所用的优选卤素不或含卤素化合物为氯、HCl或这样的化合物的前体。在进行卤素调节步骤中，在空气或氧气氛中于370℃至600℃的升高的温度下使催化复合物与卤素或含卤素化合物接触。在接触步骤中可存在水以便帮助调节。特别地，当催化剂的卤素组份包含氯时，使用5∶1至100∶1的水对HCl摩尔比是优选的。卤化步骤的持续时间通常为0.5至5小时或更多。因为条件相似，因此卤素调节步骤可在氧化步骤期间发生。或者，卤素调节步骤可根据用于制备本发明的催化剂的特定方法的需要在煅烧步骤之前或之后进行。以元素基础计，最终催化剂的卤素含量应构成所完成复合物的0.1至10质量％，与所应用的准确卤素调节步骤无关。
在制备催化剂中，也可应用还原步骤。还原步骤是设计为将铂族金属组份大体上还原成相应的元素金属状态且确保该组份遍及难熔无机氧化物中的相对均一及精细分散的分散。还原步骤发生在大体上无水环境下是优选的。还原气体优选大体上纯的干燥氢(意即小于20体积ppm水)。然而，可应用其他还原气体，例如CO、氮等。通常在包括315℃至650℃的还原温度及0.5至10或更多小时的时间的、可有效地将所有铂族金属组份大体上还原为元素金属状态的条件下，将还原气体与氧化的催化复合物接触。还原步骤可在将催化复合物加载至烃转化区域中之前进行或可作为烃转化工艺起始程序的部分原位进行及/或在烃原料的重整期间进行。然而，若应用原位技术，则必须进行适当防范，以预先将烃转化设备干燥至大体上无水状态且应当应用大体上无水的含氢还原气体。
催化复合物也可经受预先硫化步骤。可选的硫组份可以任何已知技术并入催化剂中。
催化剂的临界性质为铂族组份对IV A族(IUPAC 14)金属组份的体质量比。优选IV A族组份为锡，且因此优选的铂族对锡的体质量比小于0.9。尤其优选者为小于0.85的体质量比。
一种可检查本发明中所使用的锡的局部电子结构(氧化态、环境、化学键结)的技术为穆斯堡尔谱。异构体位移测定梅斯堡吸收的能量位置，与源相比较的吸收剂中119Sn原子的核的电子密度的函数，其直接表征锡的氧化态。界定吸收环境的四极分离(quadrupolar splitting)为周围电荷分布的函数，且其表征配位度并因此表征其中包括锡的化学键的类型。穆斯堡尔谱也提供有关有序度及锡所占据的位点的分布的信息。本发明的催化剂优选含有锡，使用穆斯堡尔谱测定特定铂族锡簇内缔合锡的量以对该锡进行表征，其中该缔合锡的有效摩尔比为至少0.65。缔合锡的量适当地将大于全部整体锡的33质量％，其中优选大于35质量％的量。使用此表征工具，已额外地发现本发明的催化剂的特征在于催化剂中所存在的锡的至少10％、优选至少15％为还原态。还原态意谓着Sn0。
本发明的催化剂特别用作烃转化催化剂。在烃转化条件下将待转化的烃与催化剂接触，此类条件包括40℃至550℃的温度，1个大气压至200个大气压(绝对)的压力及0.1至100hr-1的液时空速。该催化剂尤其适于汽油范围原料的催化重整，且也可用于脂族物及芳族物的异构化、脱氢环化、脱氢、加氢裂化、歧化、脱烷基、烷基化、烷基转移、寡聚及其他烃转化。当作为催化重整的催化剂用于处理汽油范围原粒时，本发明提供相对于本领域所已知的其他催化剂而言较高的稳定性及较低的焦炭产生。汽油范围原料优选具有小于百万分之1的硫含量。当在其中的催化剂包含碱或碱土金属组份的脱氢工艺中使用时，本发明也提供相对于本领域所已知的其他催化剂而言较高的稳定性和较低的焦炭产生。
以下实施例将用以说明本发明的某些特定实施方案。然而，这样的实例不应解释为对权利要求中所提出的本发明范畴构成限制。如本领域技术人员将认识到，存在许多其他在本发明的精神内的可能变化。
实施例1
在860℃下于含有约2.5质量％水的空气中用干燥高温煅烧将经由油滴方法而商业制造的两种球形催化剂A及B处理45分钟。接着在煅烧之后自氯铂酸及HCl的水溶液将铂浸渍在油滴落的载体上。注意在油滴落之前将锡添加至氧化铝溶胶中。接着在510℃下于1000hr-1的气时空度(GHSV)的气流中将催化剂制剂氧化8小时，同时注入HCl溶液及氯气。在氮与15摩尔％氢的425GHSV混合物中还原催化剂。还原温度为565℃且保持2小时。催化剂的性质为：
获得每一种催化剂的重整效能。在三个独立床中在反应器中加载60cc体积的每一种催化剂以代表一系列重整反应器。测试条件为：517kPa(75psig)的压力，1.7hr-1的液时空速(LHSV)，2.0的氢/烃摩尔比。该测试使用具有58.7/30.6/10.7液体体积％的块状石蜡/环烷烃/芳族组合物的石脑油原料及自68.3℃的初始沸点至160℃的最终沸点的ASTM D-86蒸馏。经分析石脑油原料含有0.4重量ppm硫。对于每一次操作，获得105的目标研究辛烷值(RON)，且接着温度持续增加以保持恒定的RON。每一次操作在时间长度上是相等的。在每一次操作之后，在保持每一个床独立下倾卸掉失去效能的试验设备催化剂。来自每一个床的样本经受碳燃烧且对结果进行重量平均以计算平均碳。在每Ft3催化剂7进料桶[或39.3m3进料/m3催化剂]及105RON下，重整效能为：
| 样本 | 温度，℃ | C5 +产率，重量 | 催化剂上的平均碳，g/100cc |
| A | 517 | 86.7 | 1.75 |
| B | 519 | 86.8 | 2.14 |
用穆斯堡尔谱分析此类样本以测定Sn与Pt金属缔合的程度。有效Sn/Pt比代表与Pt缔合的Sn的量且该比不同于包括样本中所有Sn和Pt的整体Sn/Pt比。有效Sn/Pt摩尔比是借助整体Sn/Pt摩尔比乘以来自梅斯堡分析的与Pt缔合的Sn的分数计算而来，发现催化剂A和B的梅斯堡结果和有效Sn/Pt比为：
实施例2
借助使用氯铂酸浸渍商业制造的载体(通过油滴方法)来制备含有0.256和0.375重量％Pt的另外两种催化剂C和D。此类催化剂在高温下于含有HCl、水及Cl2的流动空气中氧氯化且随后在高温下于流动氢中用实施例1的相同条件还原2小时。此类催化剂的性质为：
用如实施例1所描述的相同程序获得催化剂C和D的重整效能。在7BPCF[或39.3m3进料/m3催化剂]及105RON下重整效能为：
用穆斯堡尔谱分析样本以测定Sn与Pt金属缔合的程度。发现催化剂C和D的梅斯堡结果和有效Sn/Pt比为：
催化剂A、B、C和D的梅斯堡结果展示，对于高密度及高度含铂的催化剂D(33％Sn缔合度)而言，％Sn缔合度并不像基于低密度及高度含铂的催化剂B(47％Sn缔合度)所预斯的那样增加。根据重整效能测试，催化剂D展示显著较高的碳产生，此对于商业重整单元是不利的。该碳产生增加反映较差的稳定性且引起在催化剂操作中燃烧相对较高的碳含量所需的再生器负荷的显著相对增加。高碳也可导致再生器限制，使得精制器可能不得不降低转化和/或进料速率以便降低碳产生。此外，催化剂C因在最低温度下达成目标RON而展示最好的活性。因此，对于本发明的高密度催化剂而言，具有保持可接受的重整效能并允许用高密度催化剂进行操作从而可以在烃转化条件下操作具有增加的堵塞极限的移动床的有效的铂族对锡比率是关键的。
实施例3
由标准X光粉末技术获得先前实施例的催化剂的代表性X光衍射图案。该衍射图案展示此类催化剂与US6,514,904所提供的材料类似，该文献以引用的方式并入本文。峰值是借助将峰强度比与常规γ氧化铝进行比较来表征。在2-θ布拉格角值34.0和2-θ布拉格角值32.5以及2-θ布拉格角值46.0和2-θ布拉格角值45.5下，测定常规γ氧化铝的峰强度比为1.0和1.1，且本发明的催化剂为1.4和1.0。
Claims (18)
1.一种经成型的烃转化催化剂，其包含铂族组份、锡组份及具有高于0.6g/cc的平均体密度的载体组份，其中铂族对锡的体质量比小于0.9，其中该铂族组份为以元素基础计以该催化剂的0.01至2.0质量％的量存在的铂，并且其中该催化剂含有特定铂-锡簇内的缔合锡，其中缔合锡以锡组份的至少33质量％的量存在，且以穆斯堡尔谱表征在此类簇内的缔合锡对铂的有效摩尔比至少为0.65。
2.权利要求1的催化剂，其中载体组份具有高于0.65g/cc的平均体密度。
3.权利要求1的催化剂，其中载体组份为选自由氧化铝、氧化镁、氧化锆、氧化铬、氧化钛、氧化硼、氧化钍、氧化锌、二氧化硅及其混合物组成的组的无机氧化物。
4.权利要求2的催化剂，其中载体组份为选自由氧化铝、氧化镁、氧化锆、氧化铬、氧化钛、氧化硼、氧化钍、氧化锌、二氧化硅及其混合物组成的组的无机氧化物。
5.权利要求3的催化剂，其中载体组份为氧化铝。
6.权利要求4的催化剂，其中载体组份为氧化铝。
7.权利要求3的催化剂，其中该无机氧化物为氧化铝且其进一步特征为2-θ布拉格角值34.0的峰强度与2-θ布拉格角值32.5的峰强度之比至少为1.2且2-θ布拉格角值46.0的峰强度与2-θ布拉格角值45.5的峰强度之比至多为1.1的X光粉末衍射图案。
8.权利要求4的催化剂，其中该无机氧化物为氧化铝且其进一步特征为2-θ布拉格角值34.0的峰强度与2-θ布拉格角值32.5的峰强度之比至少为1.2且2-θ布拉格角值46.0的峰强度与2-θ布拉格角值45.5的峰强度之比至多为1.1的X光粉末衍射图案。
9.权利要求5的催化剂，其中该无机氧化物为氧化铝且其进一步特征为2-θ布拉格角值34.0的峰强度与2-θ布拉格角值32.5的峰强度之比至少为1.2且2-θ布拉格角值46.0的峰强度与2-θ布拉格角值45.5的峰强度之比至多为1.1的X光粉末衍射图案。
10.权利要求6的催化剂，其中该无机氧化物为氧化铝且其进一步特征为2-θ布拉格角值34.0的峰强度与2-θ布拉格角值32.5的峰强度之比至少为1.2且2-θ布拉格角值46.0的峰强度与2-θ布拉格角值45.5的峰强度之比至多为1.1的X光粉末衍射图案。
11.权利要求1至10中任一项的催化剂，其进一步包含选自由锗、铼、镓、铈、镧、铕、铟、磷、镍、铁、钨、钼、锌、镉及其混合物组成的组的金属促进剂组份，其中以元素基础计该金属促进剂构成该催化剂的0.01至5.0质量％。
12.权利要求1至10中任一项的催化剂，其进一步包含以该催化剂的0.1至10质量％的量存在的卤素组份。
13.权利要求5至10中任一项的催化剂，其中该氧化铝具有140至210m2/gm的表面积。
14.权利要求13的催化剂，其中该氧化铝具有150至180m2/gm的表面积。
15.权利要求1至10中任一项的催化剂，其中铂族对锡的体质量比小于0.85。
16.一种烃转化方法，其包括在烃转化条件下将烃原料与权利要求1至15中任一项的催化剂接触而生成经转化的烃，该催化剂包含铂族组份、锡组份及具有高于0.6g/cc的平均体密度的载体组份，其中铂族对锡的体质量比小于0.9。
17.权利要求16的方法，其中该烃原料为石脑油范围原料且该方法为催化重整方法。
18.权利要求16的方法，其中该方法为脱氢方法且该催化剂进一步包含分散于经成型的催化剂上的碱金属或碱土金属，其量以元素基础计为该催化剂的0.01至5.0质量％。
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| CA2586727C (en) | 2013-01-22 |
| MY142468A (en) | 2010-11-30 |
| ATE427158T1 (de) | 2009-04-15 |
| ZA200703790B (en) | 2008-08-27 |
| AU2005306957B2 (en) | 2010-11-18 |
| AU2005306957A1 (en) | 2006-05-26 |
| DE602005013629D1 (de) | 2009-05-14 |
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