CN101687660A - 用于还原来自fcc再生器的sox排放物的含添加剂的阴离子粘土及其制备工艺 - Google Patents
用于还原来自fcc再生器的sox排放物的含添加剂的阴离子粘土及其制备工艺 Download PDFInfo
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- CN101687660A CN101687660A CN200880008346A CN200880008346A CN101687660A CN 101687660 A CN101687660 A CN 101687660A CN 200880008346 A CN200880008346 A CN 200880008346A CN 200880008346 A CN200880008346 A CN 200880008346A CN 101687660 A CN101687660 A CN 101687660A
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- 125000000129 anionic group Chemical group 0.000 title claims abstract description 92
- 239000000654 additive Substances 0.000 title claims abstract description 75
- 230000000996 additive effect Effects 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title abstract description 18
- 230000001603 reducing effect Effects 0.000 title description 2
- 239000004927 clay Substances 0.000 claims abstract description 83
- 239000006069 physical mixture Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims description 42
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- 238000005516 engineering process Methods 0.000 claims description 37
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- 239000011777 magnesium Substances 0.000 claims description 19
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- 150000003624 transition metals Chemical class 0.000 claims description 18
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 15
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- 239000002019 doping agent Substances 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
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- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
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- 239000010703 silicon Substances 0.000 claims description 3
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004576 sand Substances 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 6
- 229910052709 silver Inorganic materials 0.000 claims 6
- 239000004332 silver Substances 0.000 claims 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 5
- 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 claims 3
- 238000002360 preparation method Methods 0.000 abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 12
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- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 21
- 229910052815 sulfur oxide Inorganic materials 0.000 description 18
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- 239000003795 chemical substances by application Substances 0.000 description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 9
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- 150000003839 salts Chemical class 0.000 description 9
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- 239000002002 slurry Substances 0.000 description 8
- -1 Hydroxyl pyrope Chemical compound 0.000 description 7
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 5
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- 241000196324 Embryophyta Species 0.000 description 1
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- 240000004859 Gamochaeta purpurea Species 0.000 description 1
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
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- 150000001553 barium compounds Chemical class 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000000975 co-precipitation Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
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- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
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- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- CUQZAIOPOOUPKG-UHFFFAOYSA-L magnesium;acetate;hydroxide Chemical compound [OH-].[Mg+2].CC([O-])=O CUQZAIOPOOUPKG-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052832 pyrope Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
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Abstract
公开了一种用于制备含添加剂的阴离子粘土的工艺,该工艺一般包括以下步骤:a)研磨二价金属化合物和三价金属化合物的物理混合物,b)在范围为约200℃至约800℃的温度下煅烧研磨过的物理混合物,以及c)使煅烧过的混合物在含水悬浮液中再水合以形成含添加剂的阴离子粘土,其中添加剂任选地存在于步骤(a)的物理混合物中和存在于步骤(c)的含水悬浮液中,且所述添加剂基本上不含钒。
Description
烃可在工艺(流体催化裂化)中被催化地转化,其中使烃与流化催化剂颗粒在反应区中在适宜的条件下接触。在这种工艺中,当焦炭副产物形成并沉淀在催化剂颗粒上时,催化剂颗粒被逐渐失活(deactivate)。将(部分)失活的催化剂颗粒从反应区中去除,从汽提区中的挥发性组分中清除出来,随后传到再生区,且然后它们通过用含氧气体燃烧焦炭而再生,供回到反应区中。
焦炭在再生区中的燃烧导致由来源于烃进料中的含硫化合物并存在于焦炭中的硫生成氧化硫。从环境保护的观点来看,包含于来自再生器的烟道气中的氧化硫的排放是不希望的,且可通过加入适合的氧化硫吸收剂来控制,所述氧化硫吸收剂可用热法或化学法再生并可形成催化剂组合物的一部分。
以SOx转移催化剂和/或添加剂的形式的金属氧化物已用于还原氧化硫排放物。金属氧化物在再生区中与氧化硫反应以形成非挥发性无机硫化合物。在反应区和汽提区中,这些硫化合物随后在烃和蒸汽的影响下被转化,以将无机硫化合物转化成含硫化氢的气体并回收金属氧化物。这些金属氧化物也已经与阴离子粘土结合应用。
阴离子粘土具有晶体结构,它由其间存在阴离子和水分子的二价金属氢氧化物和三价金属氢氧化物的特定组合的带阳电荷层组成。水滑石为天然存在的阴离子粘土的实例,其中Mg为二价金属,Al为三价金属,且碳酸盐为存在的主要阴离子。羟镁铝石(meixnerite)为阴离子粘土,其中Mg为二价金属,Al为三价金属,且羟基为存在的主要阴离子。
阴离子粘土根据组成其晶体结构的原子的特性来进一步细分。例如,鳞镁铁矿-磷铜铁矿-水滑石组中的阴离子粘土基于水镁石样层(其中镁阳离子被羟基八面包围),这种层与水分子和/或各种阴离子(例如碳酸盐离子)的间隙层(interstitial layer)交替。当水镁石样层中的镁中的一些被带更多电荷的阳离子如Al3+同形取代时,然后所得的Mg2+--Al3+--OH层的正电荷增加。因此,需要适合数目的间隙阴离子如上述的那些阴离子,以使整个化合物为电中性。
呈现这些晶体结构的天然矿物包括但是决不限于鳞镁铁矿、磷铜铁矿、水滑石、碳铬镁矿、陨菱铁镍矿、水铝镍石、水镁铝石(mannaseite)、水镁铬矿和水铝钙石。
阴离子粘土也常被称为“混合金属氢氧化物”或“层状双氢氧化物”。如上所述,这种表达源自这样一个事实,即阴离子粘土的带阳电荷的金属氢氧化物片可包含处于不同氧化态的两种金属阳离子(例如Mg2+和Al3+)。此外,因为很多阴离子粘土的XRD图案类似于水滑石Mg6Al2(OH)16(CO3)·4H2O的XRD图案,所以阴离子粘土也通常被称为“水滑石样化合物”。
对于本说明书来说(除非另有说明),术语“水滑石样”化合物和“阴离子粘土”的使用将被认为是可互换的,条件是这些术语应该用于包括阴离子粘土、水滑石本身以及通常被称为“水滑石样化合物”的那类材料的任何成员。
已在很多现有技术出版物中描述了阴离子粘土的制备。阴离子粘土化学的两篇主要综述被发表,其中已经概述了可用于阴离子粘土合成的合成方法:F.Cavani等人“Hydrotalcite-type anionic clays:Preparation,Properties andApplications(水滑石型阴离子粘土:制备、性质和应用)”Catalysis Today,11(1991)Elsevier Science Publishers B.V.Amsterdam;和J P Besse等人“Anionic clays:trends in pillary chemistry,its synthesis and microporous solids(阴离子粘土:柱化学动向、其合成和微孔固体)”(1992),2,108,编辑:M.I.Occelli,H.E.Robson,Van Nostrand Reinhold,N.Y。
在这些综述中,作者们陈述了Mg--Al阴离子粘土的特征是在500℃的温和煅烧导致无序MgO样产物的生成。无序MgO样产物可与尖晶石(其在数次煅烧后产生)和阴离子粘土区分开。在本说明书中,我们把无序MgO样物质称为Mg--Al固溶体。此外,这些Mg--Al固溶体包含众所周知的记忆效应,由此这些煅烧过的材料暴露于水导致阴离子粘土结构的再形成。
这些综述中描述了两种类型的阴离子粘土制备。最常用的方法是可溶性二价金属盐和可溶性三价金属盐的共沉淀(Besse将这种方法称为盐-碱法),任选地随后通过水热处理或陈化(aging)来增加微晶大小。第二种方法为盐-氧化物法,其中二价金属氧化物与可溶性三价金属盐在大气压反应,然后在大气压下陈化。仅已就ZnO和CuO与可溶性三价金属盐组合使用描述了这种方法。
对于有关阴离子粘土的工作,进一步提及下述论文:ChemistryLetters(Japan),843(1973);Clays and Clay Minerals,23,369(1975);Clays andClay Minerals,28,50(1980);Clays and Clay Minerals,34,507(1996)MaterialsChemistry and Physics,14,569(1986)。另外,存在有关阴离子粘土的使用及其制备工艺的大量专利文献。
涉及由廉价的原材料生产阴离子粘土的几个专利申请已被公布。这些材料包括氧化镁和三水合铝。
WO 99/441198涉及由两种类型的铝化合物和镁源生产阴离子粘土。铝源之一为三水合铝(aluminum trihydrate)或其热处理形式。
WO 99/41196公开了用醋酸盐作为电荷平衡阴离子由醋酸镁、另一种镁源和三水合铝制备阴离子粘土。
在WO 99/41195中,描述用来由Mg源和三水合铝生产Mg--Al阴离子粘土的连续工艺。
WO 99/41197公开了含阴离子粘土的组合物的生产,所述组合物包括Mg--Al阴离子粘土和未反应的三水合铝或其热处理形式。
几个专利描述了由氧化镁和过渡型氧化铝以分批方式和在非水热条件下合成水滑石即阴离子粘土:美国专利第5,728,364、5,728,365、5,728,366、5,730,951、5,776,424、5,578,286号。这些专利中给出的比较实施例1-3表明,在将三水合铝用作铝源时未形成阴离子粘土。
当阴离子粘土用于SOx减少化学(abatement chemistry)时,经常在阴离子粘土中使用添加剂。一般而言,这些添加剂通过浸渍沉积在阴离子粘土上,或正如US 7,022,304中所述,阴离子粘土与添加剂掺杂。
SOx转移催化剂和/或添加剂的普遍公认的机理如下:(1)SO2氧化至SO3;(2)在催化剂和/或添加剂上SO3化学吸附为金属硫酸盐;和(3)硫酸盐还原至H2S。步骤1和2在约520℃-530℃、在还原条件下于FCC再生器中发生。由于步骤中的每一个连续发生,所以三个步骤中的任何一个可限制SOx转移添加剂性能。
在SOx转移添加剂的机理中第一步骤是SO2的氧化。在FCC再生器条件下,SO2比SO3更有利。因此,SOx转移催化剂和/或添加剂包含促进SO2氧化的催化成分。期望的用于化学吸附SO3的金属氧化物是对SO3具有大的吸附容量以形成适度稳定的金属硫酸盐的那些金属氧化物,如镁铝尖晶石。而且,SOx转移催化剂和/或添加剂必须包括通常以氧化钒形式的钒,以促进在FCC提升器中将金属硫酸盐和硫化物还原成H2S(Davey,Stephen W.,Environmental FluidCatalytic Cracking(环境流体催化裂化),Petroleum Technology Quarterly,于European Refining Technology Conference(欧洲精炼技术会议)提出,2000年2月)。
然而,由于更严格的政府法规,含钒材料因其对环境的有害作用已受到增强的审查。因此,存在对在FCC再生器中显示良好SOx还原性能的无钒材料的需求。
附图简述
图1:SOx添加剂测试结果在图1中示出。
发明描述
本目的通过依据本发明的工艺来实现。一般地,所述工艺包括以下步骤:a)研磨(milling)二价金属化合物和三价金属化合物的物理混合物(physicalmixture),b)在范围为约200℃至约800℃的温度下煅烧物理混合物,以及c)使煅烧过的混合物在含水悬浮液中再水合以形成含添加剂的阴离子粘土,其中添加剂存在于物理混合物和/或步骤c)的含水悬浮液中。
在本说明书中,术语“研磨”被定义为引起颗粒大小减小的任何方法。这样的颗粒大小减小可同时引起反应性表面的形成和/或颗粒的加热。可用于研磨的仪器包括球磨机、高剪切混合机、胶体混合机和可将超声波引入到浆料(slurry)中的电换能器(electrical transducer)。低剪切混合,即基本上使成分保持处于悬浮液中所进行的搅拌,不被认为是“研磨”。
物理混合物可以以干粉形式被研磨或在悬浮液中被研磨。应该清楚的是,当物理混合物处于悬浮液中时,存在于混合物中的金属化合物中的至少一种(二价金属化合物、三价金属化合物或两者)必须是不溶于水的。
适宜的二价金属包括镁、锌、镍、铜、铁、钴、锰、钙、钡、锶及其组合。优选的二价金属包括镁、锰和铁,或其组合。适宜的锌、镍、铜、铁、钴、锰、钙、锶和钡化合物为它们相应的不溶于水的氧化物、氢氧化物、碳酸盐、碱式碳酸盐(hydroxycarbonate)、碳酸氢盐和粘土以及通常水溶性盐如醋酸盐、羟基乙酸盐(hydroxyacetate)、硝酸盐和氯化物。适宜的不溶于水的镁化合物包括氧化镁或氢氧化镁如MgO、Mg(OH)2、碳酸镁、碱式碳酸镁、碳酸氢镁、水菱镁矿、和含镁粘土如白云石、皂石和海泡石。适宜的水溶性的镁化合物为醋酸镁、甲酸镁、(羟基)乙酸镁、硝酸镁和氯化镁。
优选的二价金属化合物为氧化物、氢氧化物、碳酸盐、碱式碳酸盐、碳酸氢盐、和(羟基)乙酸盐,因为这些材料相对廉价。此外,这些材料在含添加剂的阴离子粘土中不会留下不希望的阴离子,这些阴离子必须被洗掉或将在加热后作为对环境有害的气体被排放。
适宜的三价金属包括铝、镓、铁、铬、钒、钴、锰、镍、铟、铈、铌、镧及其组合。优选的三价金属为铝。适宜的镓、铁、铬、钒、钴、锰、镍和锰化合物为它们相应的不溶于水的氧化物、氢氧化物、碳酸盐、碱式碳酸盐、碳酸氢盐、醇盐和粘土以及通常水溶性盐如醋酸盐、羟基乙酸盐、硝酸盐和氯化物。适宜的不溶于水的铝化合物包括氧化铝和氢氧化铝如过渡型氧化铝、三水合铝(铝土矿精矿、水铝矿、三羟铝石)及其热处理形式(包括快速煅烧的三水合铝)、溶胶、无定形氧化铝和(假)勃姆石、含铝粘土如高岭土、海泡石、膨润土和改性粘土如偏高岭土。适宜的水溶性铝盐为硝酸铝、氯化铝、水合氯化铝(aluminium chlorohydrate)和铝酸钠。
本发明的一个实施方案应用三水合氧化铝(如水铝矿、三羟铝石或诺三水铝石)或其热处理形式的用途。另一个实施方案应用勃姆石或假勃姆石的用途。反应引起阴离子粘土的直接形成,所述阴离子粘土可通过简单干燥从反应器中收回的浆料来获得。没有必要洗涤或过滤,并且在反应产物中各种各样比率的二价金属/三价金属是可能的。
三水合铝包括结晶三水合铝(ATH)。BOC(铝土矿精矿)、三羟铝石或诺三水铝石也为适宜的三水合铝。BOC为最便宜的氧化铝来源。三水合氧化铝优选具有范围为1-150μm、更优选小于20μm的颗粒大小。
可将三水合铝的热处理形式应用于本发明的工艺。通过在高于100℃、优选范围为100℃至800℃的温度下将三水合铝(水铝矿)热处理15分钟至24小时的时间,容易地获得煅烧过的三水合铝。在任何情况下,用于获得煅烧过的三水合铝的煅烧温度和时间应足以使表面积相比于如通过拜耳法(Bayerprocess)产生的水铝矿的表面积(通常在30m2/g和50m2/g之间),可测量地增加。应注意,在本发明的上下文中,快速煅烧过的氧化铝还被认为是三水合铝的热处理形式,尽管通常其被认为是非常特殊的氧化铝。通过在专用的工业装置中在800℃至1000℃之间的温度下将三水合铝处理非常短的时间,来获得快速煅烧过的氧化铝,正如在美国专利第4,051,072和3,222,129号中描述的。还可使用三水合铝和三水合铝的热处理形式的组合,而且还可使用三水合铝的各种热处理形式的组合。
三水合铝或其热处理形式当被使用时,优选地以浆料的形式被加入到反应器中。特别地,强调的是,没有必要使用可胶溶的(peptisable)氧化铝来源(水铝矿不是可胶溶的),且因此没有必要加入无机酸或有机酸来改变混合物的pH。在依据本发明的工艺中,可将除了三水合铝或其热处理形式之外的其他铝源加入到含水悬浮液如铝的氧化物和氢氧化物(例如溶胶、凝胶、假勃姆石、微晶勃姆石)、铝盐如硝酸铝、氯化铝、水合氯化铝和铝酸钠中。其他铝源可以是可溶于水的或不溶于水的,且可以被加入到三水合铝和/或其热处理形式中或可以独立地被以固体、溶液或悬浮液的形式加入到含水悬浮液中。
本发明的另一个实施方案应用勃姆石和/或假勃姆石的用途。勃姆石和假勃姆石的制备通常为但不限于合成途径,其中在受控的pH条件下沉淀可溶性铝盐以形成假勃姆石,然后假勃姆石可进一步被热处理以获得各种量的表面积范围通常为约200m2/g至约350m2/g(如通过氮吸附测量的BET)的结晶勃姆石。所制备的材料可以以单独或与ATH组合的含水浆料形式使用。
优选的三价金属化合物为氧化物、氢氧化物、碳酸盐、碳酸氢盐、碱式碳酸盐和(羟基)乙酸盐,因为这些材料相对廉价。此外,这些材料在含添加剂的阴离子粘土中不会留下不希望的阴离子,这些阴离子必须被洗掉或将在加热后作为对环境有害的气体被排放。
二价金属化合物和/或三价金属化合物可被掺杂,由此制备掺杂的阴离子粘土。
掺杂的金属化合物可用几种方法来制备。一般而言,金属化合物和掺杂剂(dopant)被转化成以均质分散的状态的含掺杂剂的金属化合物。
适宜的掺杂剂为含有选自以下的组的元素的化合物:碱土金属(例如Ca和Ba)、碱金属、过渡金属(例如Mn、Fe、Co、Ti、Zr、Cu、Ni、Zn、Mo、W、V、Sn)、锕系元素、稀土金属(如La、Ce、Nd)、贵金属(如Pt和Pd)、硅、镓、硼、钛和磷。
掺杂剂可以以硝酸盐、硫酸盐、氯化物、甲酸盐、醋酸盐、草酸盐、醇盐、碳酸盐和钨酸盐的形式使用。优选使用具有热可分解的阴离子的化合物,因为当对于催化目的所不希望的阴离子不存在时,不需间歇洗涤就可直接干燥所得的掺杂的金属化合物。
如上所述,本发明工艺中的第一步骤包括研磨二价金属化合物和三价金属化合物的物理混合物。这种物理混合物可用各种方法来制备。二价金属化合物和三价金属化合物可以以干粉形式混合(掺杂或交换)或在(含水)悬浮液中混合,由此形成浆料、溶胶或凝胶。在后者的情况下,将二价金属化合物和三价金属化合物以粉末、溶胶或凝胶的形式加入到悬浮液中,并且在制备以及研磨混合物后干燥。
如果物理混合物在含水悬浮液中制备,那么可将分散剂加入到悬浮液中。适宜的分散剂包括表面活性剂、磷酸盐、糖、淀粉、聚合物、胶凝剂、可膨胀的粘土等。还可将酸或碱加入到悬浮液中。
物理混合物中二价金属与三价金属的摩尔比范围优选为约0.01至约10,更优选为约0.1至约5,且最优选为约1至约3。物理混合物以干粉形式或在悬浮液中被研磨。除了研磨物理混合物之外,在形成物理混合物之前可单独研磨二价金属化合物和三价金属化合物。
当物理混合物在悬浮液中被研磨时,将混合物在室温在例如球磨机、珠磨机、砂磨机、胶体磨、高剪切混合机、捏合机中或通过使用超声波湿式研磨约1分钟至约30分钟。在湿式研磨之后和在煅烧之前,必须干燥物理混合物,例如可应用喷雾干燥。
为了使粘合特性最佳化,除干燥物理混合物之外,可使物理混合物在范围为约20℃至约110℃、更优选为约30℃至约90℃的温度下和在环境压力下陈化约15分钟至约6小时。
在研磨后所获得的颗粒的平均大小优选为约0.1微米至约10微米,更优选为约0.5微米至约5微米,最优选为约1微米至约3微米。研磨过程中的温度可为室温或更高。较高的温度可例如由研磨工艺自然产生或可由外部热源产生。优选地,研磨过程中的温度范围为约20℃至约90℃,更优选为约30℃至约50℃。
将物理混合物在范围为约200℃至约800℃、更优选在范围为约300℃至约700℃、且最优选在范围为约350℃至约600℃的温度下煅烧。煅烧进行约0.25小时至约25小时,优选约1小时至约8小时,且最优选约2小时至约6小时。可使用所有商业类型的煅烧炉,如固定床或旋转煅烧炉。
煅烧可在各种气氛例如空气、氧气、惰性气氛(例如N2)、蒸气或其混合物中进行。
如此获得的煅烧材料应当包含可再水合的(rehydratable)氧化物。所形成的可再水合的氧化物的量取决于所用的二价金属化合物和三价金属化合物的类型以及煅烧温度。优选地,煅烧过的材料包含约10%至100%的可再水合的氧化物,更优选约30%至100%、甚至更优选约50%至100%,且最优选约70%至100%的可再水合的氧化物。在步骤b)中所形成的可再水合的氧化物的量等于在步骤c)中所获得的阴离子粘土的量,并由在步骤c)中所获得的阴离子粘土的量来计算。这种量可通过混合各种已知量的纯阴离子粘土与步骤c)的再水合产物的样品来确定。然后,在这些混合样品中阴离子粘土与非阴离子粘土的相对强度的外推法-如用粉末X射线衍射法(PXRD)测量的-可用于确定再水合产物中阴离子粘土的量。不可再水合的氧化物的实例为尖晶石型氧化物。
煅烧过的材料的再水合通过使煅烧过的混合物与水或阴离子的水溶液接触来进行。这可通过使煅烧过的混合物穿过含有充足的液体喷雾的滤床或者通过将煅烧过的混合物悬浮在液体中来进行。在再水合过程中,液体的温度优选为约25℃和约350℃之间,更优选为约25℃和约200℃之间,最优选为约50℃和约150℃之间,选择的温度取决于所用的二价金属化合物和三价金属化合物的性质。再水合进行约20分钟至约24小时,优选约30分钟至约8小时,更优选约1小时至约4小时。
在再水合过程中,可通过使用高剪切混合机、胶体混合机、球磨机、捏合机、超声波等来研磨悬浮液。任选地在依据预先公布的第2003-0003035号美国专利申请的连续多步骤操作中,可分批地或连续地进行再水合。例如,在进料制备容器中制备再水合悬浮液,然后将悬浮液连续泵送通过两个或更多个转换容器(conversion vessel)。如果需要的话,可将添加剂、酸或碱加入至转换容器中的任一个中的悬浮液中。可将容器中的每一个调节至其自身期望的温度。
在再水合过程中,可将阴离子加入到液体中。适宜的阴离子的实例包括无机阴离子如NO3 -、NO2 -、CO3 2-、HCO3 -、SO4 2-、SO3NH2、SCN-、S2O6 2-、SeO4 -、F-、Cl-、Br-、I-、ClO3 -、ClO4 -、BrO3 -和IO3 -、硅酸盐、铝酸盐和偏硅酸盐,有机阴离子如醋酸盐、草酸盐、甲酸盐、长链羧酸盐(例如癸二酸盐、癸酸盐和辛酸盐(CPL))、烷基磺酸盐(例如十二烷基磺酸盐(DS)和十二烷基苯磺酸盐)、硬脂酸盐、苯甲酸盐、四磺酸酞菁(phthalocyanine tetrasulfonate),和聚合阴离子如聚苯乙烯磺酸盐、聚酰亚胺、苯甲酸乙烯酯和乙烯基二丙烯酸酯,以及pH依赖型的含硼阴离子、含铋阴离子、含铊阴离子、含磷阴离子、含硅阴离子、含铬阴离子、含钨阴离子、含钼阴离子、含铁阴离子、含铌阴离子、含钽阴离子、含锰阴离子、含铝阴离子和含镓阴离子。
在本发明的一个实施方案中,可溶性SO4 2-阴离子材料用于实现改善的颗粒完整性,这使得最终产物的物理性质改善。可将阴离子材料加入到正被使用的阴离子盐之上,或作为正被使用的阴离子盐的一部分加入。优选的是,阴离子在再水合过程中保持为可溶性形式。
用于依据本发明的工艺的添加剂为包含选自以下的组的元素的化合物:碱土金属(例如Mg、Ca和Ba)、IIIB族过渡金属、IVB族过渡金属(例如Ti、Zr)、VB族过渡金属(钒除外)(例如Nb)、VIB族过渡金属(例如Cr、Mo、W)、VIIB族过渡金属(例如Mn)、VIII族过渡金属(例如Fe、Co、Ni、Ru、Rh、Pd、Pt)、IB族过渡金属(例如Cu、Ag)、IIB族过渡金属(例如Zn)、IIIA族元素(例如B、Al、Ga)、IVA族元素(例如Si、Sn)、VA族元素(例如P)、镧系元素(例如La、Ce)及其混合物,条件是所述元素不同于构成步骤a)的二价金属化合物和三价金属化合物的金属。优选的元素为Fe、Zn、Zr、Nb、Ag、Mn、Cu、Cr、Rh或其组合。添加剂优选为所需元素的氧化物、氢氧化物、碳酸盐或碱式碳酸盐。一种或多种添加剂可存在于物理混合物和/或步骤c)的含水悬浮液中。
如果添加剂存在于物理混合物中,那么在研磨步骤a)之前或之中、在煅烧步骤b)之中、或在研磨步骤a)与煅烧步骤b)之间将它加入到物理混合物中。煅烧过程中的添加需要使用具有充足混合能力的煅烧炉,这种煅烧炉可有效地用作混合机以及煅烧炉。可将添加剂以固体粉末形式、以悬浮液或优选地以溶液的形式加入到步骤a)的物理混合物和步骤c)的悬浮液中。如果在煅烧过程中加入,那么以粉末的形式加入。
所得的含添加剂的阴离子粘土可经受额外的煅烧和任选的额外的再水合步骤。如果煅烧之后接着进行再水合,那么形成类似于第一再水合步骤之后所形成的含添加剂的阴离子粘土的含添加剂的阴离子粘土,但是机械强度增加。这些第二煅烧和再水合步骤可在与第一煅烧和再水合步骤相同或不同的条件下进行。可将额外的添加剂在额外的煅烧步骤之中和/或在再水合步骤之中加入。这些额外的添加剂可与存在于物理混合物和/或步骤c)的含水悬浮液中的添加剂相同或不同。
此外,在额外的再水合步骤期间,可加入阴离子。适宜的阴离子为与第一再水合步骤有关的上述阴离子。在第一再水合步骤和额外的再水合步骤期间加入的阴离子可以是相同或不同的。
如果需要的话,依据本发明的工艺制备的含添加剂的阴离子粘土可与常规催化剂或吸附剂成分混合,所述常规催化剂或吸附剂成分如二氧化硅、氧化铝、铝硅酸盐、氧化锆、二氧化钛、氧化硼(boria);(改性)粘土如高岭土、酸沥滤的高岭土、脱铝高岭土、蒙脱石和膨润土;(改性或掺杂的)磷酸铝;沸石(例如沸石X、Y、REY、USY、RE-USY或ZSM-5、沸石β、硅沸石(silicalite));磷酸盐(例如间位或对位磷酸盐);调孔剂(例如糖、表面活性剂、聚合物)、粘合剂、填充剂及其组合。任选地与上述常规催化剂组分中的一种或多种混合的含添加剂的阴离子粘土可被成形以形成成形体(shaped body)。适宜的成形方法包括喷雾干燥、制粒(pelletising)、挤压(任选地与捏合组合)、形成珠状或用于催化剂和吸收剂领域的任何其他常规的成形方法或其组合。
实施例
实施例1:
SOx添加剂制备
将氧化镁和氧化铝的4∶1摩尔混合物以15%固体在水中浆化并研磨至3微米。随后在50℃将研磨过的浆料陈化2小时,并加入硝酸铈的溶液。然后将粘稠的浆料喷雾干燥。在550℃将经喷雾干燥的材料煅烧2小时,且然后在50℃以30%固体在水中再浆化30分钟。在再水合过程中作为可溶性盐加入各种添加剂如铁和锌。
添加剂的周期性失活(cyclic deactivation)
商业废的(结焦的)催化剂(下文称为废催化剂)从商业FCC单元获得。这种结焦的催化剂包含0.91wt%碳、470ppm硫和220ppm氮。在用于周期性失活研究之前,在788℃将FCC催化剂在固定的流化床反应器中在100%蒸汽下预先蒸煮20小时。Kuwait真空瓦斯油用于周期性失活工艺。这种原料具有3.1wt%硫含量、1027ppm的总氮浓度和301ppm的碱性氮浓度。
详细的周期性失活(CD)方法已在下述文献中描述:(1)Efthimiadis,E.A.,Iliopoulou,E.F.,Lappas,A.A.,Iatridis,D.K.和Vasalos I.A.Ind.Eng.Chem.Res.41(22),5401-5409,(2002);和(2)Dishman,K.L.,Doolin,P.K.和Tullock,L.D.,Ind.Eng.Chem.Res.,37,4631-4636,(1998)。示例性的SOx还原添加剂的失活通过使用Kuwait VGO将添加剂和预先蒸煮的FCC催化剂(PST FCCBase)的混合物周期性失活来进行。没有将额外的金属加入到进料(feed)中。混合物中的添加剂水平为5wt%。失活经历裂化、汽提、再生循环并在催化剂再生步骤后结束。这样的最后再生步骤将在失活的添加剂/催化剂混合物上沉积的焦炭除去,忽略由失活工艺对测试本身的任何影响。可调节CD循环的次数来反映不同的失活严重度。在再生循环过程中,所施加的蒸汽分压是低的,以便更好地模拟商业FCCU操作。
在失活后,将10克添加剂/FCC催化剂混合物与49.5克废催化剂混合,以保持总添加剂量0.5g。添加剂水平的变化可通过改变与废催化剂混合的添加剂/FCC催化剂混合物的量来获得。
SOx添加剂测试
在结焦催化剂的模拟再生过程中,在高级添加剂测试单元(AATU)中评价添加剂。反应单元具有供气***、固定的流化床反应器和气体分析***。将基于FTIR的多气体分析仪(MKS 2030)选择为主要的气体分析仪。可被测量的气体包括COx、SOx、NOx(NO、N2O、NO2)和HCN以及一些通常在焦炭燃烧过程中观察到的烃。使用顺磁氧气分析仪(氧分析仪100P型,CaliforniaAnalytical Instruments)进行O2分析。这种反应器可处理10-200g范围的样品大小,允许评价各种各样浓度的排放控制添加剂。
依据有或没有添加剂(基例)时所排放的总气体的差异计算SO2还原,如下:
SOx添加剂评价结果
SOx添加剂测试的结果在图1中示出。上面柱状图表明,根据本发明的工艺制备的无钒SOx添加剂显示了良好的性能,甚至在失活的5个CD循环和9个CD循环之后。KDSOx 2002、DeSOx和Soxgetter为商业可用的SOx添加剂(KDSOx2002用含有11%CeO2和3%V2O5的4∶1MgO/Al2O3比率的HTC材料制备;Soxgetter为含有约相同量的CeO2和V2O5的另一种基于HTC的材料;DeSOx为含有相似量的铈和钒的基于尖晶石的材料)。无钒添加剂与其含钒的对应物相比,具有表征增强的排放功能的优势。这种效应可在下表中所示的TGA测试结果中看出。TGA测试应用具有自动取样器的Perkin Elmer Pyris 1。使20mg样品经受下列方案:1)在80cc/分钟的氮气流下,将样品以20℃/分钟加热至680℃,然后以10℃/分钟加热至725℃;2)将温度保持在725℃达5分钟;3)使样品暴露至SO2气体混合物(0.5%SO2、2%O2、余量的N2)14分钟;4)在N2下将样品冷却至575℃;5)将温度保持在575℃达5分钟,且然后将样品暴露至H2流(5%H2于N2中)10分钟;6)在N2下将样品以20℃/分钟加热至725℃;7)重复步骤2至步骤6;8)重复步骤2至步骤5。使用TGA的软件确定在SO2吸收和H2排放循环的过程中的Wt%变化。Fe-Ce/HTC、Cu-Ce/HTC和Zn-Ce/HTC显示了与含钒材料相比等同的SOx吸收量,但是排放量增加。
TGA结果(%wt变化)
添加剂 | 总吸收量 | 总排放量 |
Fe-Ce/HTC | 28.2 | 24.6 |
Cu-Ce/HTC | 24.8 | 20.0 |
Zn-Ce/HTC | 25.4 | 15.4 |
KDSOx 2002 | 28.4 | 10.1 |
Ce/HTC | 27.0 | 6.0 |
实施例2:
物理性质比较
含有11wt%铈的Ce/HTC如实施例1中所述那样制备。根据在再水合过程中不存在阴离子材料的发明制得的产物的磨损指数(attrition index)经测定为7.0。根据在再水合步骤中包括阴离子材料(20g H2SO4每升再水合体积)的发明制备的相似Ce/HTC(11wt%铈)显示磨损指数为1.0。此实施例中测量的磨损指数被定义为由在ASTM标准测试方法D-5757描述的磨损装置中测试的并在那个方法中描述的相似条件下运行的催化剂在三小时内产生的细屑的百分比的四分之一。
Claims (43)
1.一种用于制备含添加剂的阴离子粘土的工艺,其包括如下步骤:
研磨二价金属化合物和三价金属化合物的物理混合物,
在范围为约200℃至约800℃的温度下煅烧研磨过的物理混合物,以及
使煅烧过的混合物在含水悬浮液中再水合以形成所述含添加剂的阴离子粘土,
其中添加剂任选地存在于所述步骤(a)的物理混合物中,添加剂存在于所述步骤(c)的含水悬浮液中,并且所述含添加剂的阴离子粘土基本上不含钒。
2.根据权利要求1所述的工艺,其中所述研磨在球磨机、珠磨机、砂磨机、胶体磨、捏合机或高剪切混合机中进行,或者通过使用超声波来进行。
3.根据权利要求1所述的工艺,其中煅烧温度的范围为约300℃至约700℃。
4.根据权利要求3所述的工艺,其中所述煅烧温度的范围为约350℃至约600℃。
5.根据权利要求1所述的工艺,其进一步包括陈化所述步骤a)的物理混合物的步骤。
6.根据权利要求5所述的工艺,其中所述陈化在范围为约20℃至约110℃的温度下进行约15分钟至约6小时。
7.根据权利要求1所述的工艺,其中所述二价金属为镁、锌、镍、铜、铁、钴、锰、钙、钡、锶及其组合。
8.根据权利要求7所述的工艺,其中所述二价金属为镁、锰、铁或其组合。
9.根据权利要求1所述的工艺,其中所述三价金属为铝、镓、铁、铬、钒、钴、锰、镍、铟、铈、铌、镧及其组合。
10.根据权利要求9所述的工艺,其中所述三价金属为铝。
11.根据权利要求1所述的工艺,其中所述添加剂为包含选自由以下组成的组的元素的化合物:碱土金属、IIIB族过渡金属、IVB族过渡金属、除钒之外的VB族过渡金属、VIB族过渡金属、VIIB族过渡金属、VIII族过渡金属、IB族过渡金属、IIB族过渡金属、IIIA族元素、IVA族元素、VA族元素、镧系元素及其混合物,条件是所述元素不同于构成所述步骤a)的二价金属化合物和三价金属化合物的金属。
12.根据权利要求11所述的工艺,其中所述添加剂为包含选自由以下组成的组的元素的化合物:铁、锌、锆、铌、银、锰、铜、铬、铑及其组合。
13.根据权利要求12所述的工艺,其中所述添加剂为氧化物、氢氧化物、碳酸盐或碱式碳酸盐。
14.根据权利要求1所述的工艺,其进一步包括随后煅烧所形成的含添加剂的阴离子粘土的步骤。
15.根据权利要求14所述的工艺,其进一步包括使随后煅烧过的含添加剂的阴离子粘土再水合的步骤。
16.根据权利要求1所述的工艺,其中阴离子材料存在于所述步骤(c)中。
17.根据权利要求16所述的工艺,其中所述阴离子材料提供选自由无机阴离子、有机阴离子和聚合阴离子组成的组的阴离子。
18.根据权利要求17所述的工艺,其中所提供的阴离子为SO4 2-。
19.根据权利要求1所述的工艺,其中所述二价金属化合物和/或所述三价金属化合物为含掺杂剂的金属化合物。
20.根据权利要求19所述的工艺,其中所述掺杂剂为含有选自由以下组成的组的元素的化合物:碱土金属、碱金属、过渡金属、锕系元素、稀土金属、贵金属、硅、镓、硼、钛和磷。
21.根据权利要求20所述的工艺,其中所述掺杂剂为含有选自由以下组成的组的元素的化合物:铁、锌、锆、铌、银、锰、铜、铬、铑及其组合。
22.根据权利要求21所述的工艺,其中所述掺杂剂为硝酸盐、硫酸盐、氯化物、甲酸盐、醋酸盐、草酸盐、醇盐、碳酸盐或钨酸盐。
23.一种阴离子粘土,其由包括以下步骤的工艺制得:
研磨二价金属化合物和三价金属化合物的物理混合物,
在范围为约200℃至约800℃的温度下煅烧研磨过的物理混合物,以及
使煅烧过的混合物在含水悬浮液中再水合以形成含添加剂的阴离子粘土,
其中添加剂任选地存在于所述步骤(a)的物理混合物中,添加剂存在于所述步骤(c)的含水悬浮液中,并且所述阴离子粘土基本上不含钒。
24.根据权利要求23所述的阴离子粘土,其进一步包括陈化所述步骤a)的物理混合物的步骤。
25.根据权利要求24所述的工艺,其中所述陈化在范围为约20℃至约90℃的温度下进行约15分钟至约6小时。
26.根据权利要求23所述的阴离子粘土,其中所述二价金属为镁、锰、铁或其组合。
27.根据权利要求23所述的阴离子粘土,其中所述三价金属为铝。
28.根据权利要求23所述的阴离子粘土,其中所述添加剂为包含选自由以下组成的组的元素的化合物:铁、锌、锆、铌、银、锰、铜、铬、铑及其组合。
29.根据权利要求23所述的阴离子粘土,其中所述二价金属化合物和/或所述三价金属化合物与含有选自由以下组成的组的元素的化合物掺杂:铁、锌、锆、铌、银、锰、铜、铬、铑及其组合。
30.根据权利要求23所述的阴离子粘土,其中所述二价金属化合物包括铈。
31.根据权利要求23所述的阴离子粘土,其中阴离子材料存在于所述步骤(c)中。
32.根据权利要求31所述的阴离子粘土,其中所述阴离子材料提供选自由无机阴离子、有机阴离子和聚合阴离子组成的组的阴离子。
33.根据权利要求32所述的阴离子粘土,其中所提供的阴离子为SO4 2-。
34.一种用于还原来自FCC再生器的SOx排放物的方法,所述方法包括向所述FCC再生器加入由包括以下步骤的工艺制得的阴离子粘土的步骤:研磨二价金属化合物和三价金属化合物的物理混合物,在范围为约200℃至约800℃的温度下煅烧研磨过的物理混合物,以及使煅烧过的混合物在含水悬浮液中再水合以形成含添加剂的阴离子粘土,其中添加剂任选地存在于所述物理混合物中,添加剂存在于所述含水悬浮液中,且所述阴离子粘土基本上不含钒。
35.根据权利要求34所述的方法,其进一步包括在范围为约20℃至约90℃的温度下将所述物理混合物陈化约15分钟至约6小时的步骤。
36.根据权利要求34所述的方法,其中所述二价金属为镁、锰、铁或其组合。
37.根据权利要求34所述的方法,其中所述三价金属为铝。
38.根据权利要求34所述的方法,其中所述添加剂为包含选自由以下组成的组的元素的化合物:铁、锌、锆、铌、银、锰、铜、铬、铑及其组合。
39.根据权利要求34所述的方法,其中所述二价金属化合物和/或所述三价金属化合物与含有选自由以下组成的组的元素的化合物掺杂:铁、锌、锆、铌、银、锰、铜、铬、铑及其组合。
40.根据权利要求34所述的方法,其中所述二价金属化合物包括铈。
41.根据权利要求34所述的阴离子粘土,其中阴离子材料存在于步骤(c)中。
42.根据权利要求41所述的阴离子粘土,其中所述阴离子材料提供选自由无机阴离子、有机阴离子和聚合阴离子组成的组的阴离子。
43.根据权利要求42所述的阴离子粘土,其中所提供的阴离子为SO4 2-。
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CN200880008346A Pending CN101687660A (zh) | 2007-03-20 | 2008-03-20 | 用于还原来自fcc再生器的sox排放物的含添加剂的阴离子粘土及其制备工艺 |
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EP (1) | EP2134651B1 (zh) |
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CN102627304A (zh) * | 2012-05-08 | 2012-08-08 | 山东大学 | 一种镁铝类水滑石的制备方法 |
CN104662270A (zh) * | 2012-09-21 | 2015-05-27 | 排放技术有限公司 | 用于液体添加剂的输送单元 |
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US4774212A (en) * | 1987-12-22 | 1988-09-27 | Amoco Corporation | Pillared hydrotalcites |
US7008896B2 (en) * | 1998-10-08 | 2006-03-07 | Akzo Nobel Nv | Situ formed anionic clay-containing bodies |
ES2239030T3 (es) * | 1999-08-11 | 2005-09-16 | Akzo Nobel N.V. | Cuerpos cristalinos conformados resistentes al desgaste que contienen arcilla que contiene mg-al-si. |
DE60037519T2 (de) * | 1999-08-11 | 2008-12-24 | Akzo Nobel N.V. | Abriebfeste formkörper, die anionische, kristalline tonerden enthalten |
CN1260004C (zh) * | 1999-08-11 | 2006-06-21 | 阿克佐诺贝尔公司 | 多型Mg-Al水滑石 |
BR0207022B1 (pt) * | 2001-02-09 | 2012-06-26 | processos para a preparação de argila aniÈnica dopada e de uma solução sólida de mg/al e/ou um espinel. | |
DK1358128T3 (da) * | 2001-02-09 | 2005-11-28 | Akzo Nobel Nv | Fremgangsmåde til fremstilling af anionisk ler |
JP4293791B2 (ja) * | 2001-02-09 | 2009-07-08 | アクゾ ノーベル ナムローゼ フェンノートシャップ | インシチュー(insitu)で生成されるアニオン性粘土を含有する物体 |
CN100509634C (zh) * | 2002-06-25 | 2009-07-08 | 阿尔伯麦尔荷兰有限公司 | 阳离子层状材料的用途,含有这些材料的组合物以及阳离子层状材料的制备方法 |
EP1682633A1 (en) * | 2003-10-15 | 2006-07-26 | Albemarle Netherlands B.V. | Composition for reducing nox emissions in fcc regeneration process |
EP1899436A1 (en) * | 2005-07-01 | 2008-03-19 | Albemarle Netherlands BV | Use of anionic clay in an fcc process |
EP2032254A2 (en) * | 2006-06-29 | 2009-03-11 | Albemarle Netherlands BV | Additives for removal of metals poisonous to catalysts during fluidized catalytic cracking of hydrocarbons |
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CN102627304A (zh) * | 2012-05-08 | 2012-08-08 | 山东大学 | 一种镁铝类水滑石的制备方法 |
CN104662270A (zh) * | 2012-09-21 | 2015-05-27 | 排放技术有限公司 | 用于液体添加剂的输送单元 |
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US20100111797A1 (en) | 2010-05-06 |
EP2134651A1 (en) | 2009-12-23 |
CN108160063A (zh) | 2018-06-15 |
JP2015063457A (ja) | 2015-04-09 |
BRPI0809610B1 (pt) | 2018-08-28 |
EP2134651B1 (en) | 2018-02-14 |
CA2679477C (en) | 2016-08-16 |
WO2008116076A1 (en) | 2008-09-25 |
JP5706155B2 (ja) | 2015-04-22 |
BRPI0809610A2 (pt) | 2014-10-29 |
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CA2679477A1 (en) | 2008-09-25 |
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