CN115734997A - 用于去除原料中杂质的多孔材料 - Google Patents
用于去除原料中杂质的多孔材料 Download PDFInfo
- Publication number
- CN115734997A CN115734997A CN202180046007.5A CN202180046007A CN115734997A CN 115734997 A CN115734997 A CN 115734997A CN 202180046007 A CN202180046007 A CN 202180046007A CN 115734997 A CN115734997 A CN 115734997A
- Authority
- CN
- China
- Prior art keywords
- porous material
- alumina
- feedstock
- pores
- hydroprocessing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000011148 porous material Substances 0.000 title claims abstract description 180
- 239000012535 impurity Substances 0.000 title claims abstract description 36
- 239000002994 raw material Substances 0.000 title claims description 13
- 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 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 26
- 150000002739 metals Chemical class 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002803 fossil fuel Substances 0.000 claims description 7
- -1 silicon aluminate Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
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- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 6
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
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- 241000251468 Actinopterygii Species 0.000 claims description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
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- 230000000694 effects Effects 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000000523 sample Substances 0.000 description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
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- 239000013074 reference sample Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 235000019737 Animal fat Nutrition 0.000 description 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000007866 anti-wear additive Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
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Abstract
本发明涉及一种包含氧化铝的多孔材料,所述氧化铝包括α‑氧化铝,所述多孔材料包括一种或多种选自Co、Mo、Ni、W及其组合的金属,并且所述多孔材料具有1‑110m2/g的BET表面积、0.50‑0.80ml/g的总孔隙体积(如通过压汞法测量的),和孔径分布(PSD),其中总孔隙体积的至少30vol%为半径的孔隙,适当地为半径的孔隙,例如半径至多的孔隙。本发明还涉及一种通过使所述原料与包括上述多孔材料的保护床接触,从原料(如可再生进料)中去除杂质(例如磷(P))的方法。本发明还涉及一种用于加氢处理系统的包含多孔材料的保护床;一种加氢处理系统,其包括包含多孔材料的保护床,位于下游的包含至少一种加氢处理催化剂的加氢处理段;还涉及多孔材料在加氢处理方法中作为磷防护剂的用途。
Description
技术领域
本发明涉及包含氧化铝的多孔材料,特别是用于去除原料中杂质的多孔材料。多孔材料包括氧化铝,氧化铝包括α氧化铝和任选的θ氧化铝。多孔材料还包括选自Co、Mo、Ni、W及其组合的至少一种金属,并且具有1-110m2/g的BET表面积。多孔材料具有0.50-0.80ml/g,例如0.50-0.75ml/g,或0.55-0.70ml/g,或0.60-0.70ml/g(如通过压汞法测量的)的总孔隙体积,和孔径分布(PSD),其中总孔隙体积的至少30vol%,例如至少40vol%,至少50vol%,或至少60vol%为半径≥(40nm)的孔隙,适当地为半径≥(50nm)的孔隙,例如半径至多(500nm)的孔隙。本发明还涉及一种通过使所述原料与包括上述多孔材料的保护床接触,从含有杂质的原料(如可再生进料)中去除一种或多种杂质(例如磷(P))的方法。本发明还涉及一种用于加氢处理系统的包括多孔材料的保护床,一种包括包含多孔材料的保护床和包含至少一种加氢处理催化剂的位于下游的加氢处理段(加氢处理阶段)的加氢处理系统,还涉及多孔材料在加氢处理方法中作为磷防护剂的用途。本发明还涉及所述多孔材料,但不包括金属及其在加氢处理方法中作为磷防护剂的用途。
背景技术
可再生燃料可以从多种来源生产,包括动物脂肪和植物油,也包括妥尔油、热解油和其他非食用化合物。在由可再生有机材料衍生的原料能够用于常规汽车发动机、航空涡轮机、船用发动机或其他发动机,并使用现有燃料基础设施进行分配之前,希望将该材料转化为与石油衍生运输燃料中存在的那些材料类似的烃类。为此目的,一种完善的方法是采用加氢处理工艺将植物油转化为汽油、喷气燃料或柴油沸程内的正常链烷烃。
在加氢处理方法中,可再生有机材料在催化反应器中在高温高压下与氢气反应。
诸如可再生原料的原料的一个特殊问题是,它们含有诸如含磷或含硅物质的杂质。含磷物质可能以磷脂的形式存在,如从种子油中提取的卵磷脂。废润滑油还可含有诸如二烷基二硫代磷酸锌(ZDDP)的物质,其在此类润滑剂中充当抗磨损添加剂。磷(P)快速钝化用于加氢处理的传统催化剂,并显著缩短循环时间。与基于化石燃料的炼油工艺相比,加工可再生原料的精炼器被迫装载更多的材料来保护加氢处理催化剂。该装置通常使用洗涤和/或吸附剂对原料进行预处理,以将P从10-20ppm降至1-2ppm,但即使在1-2ppm下,也需要防护材料。
因此,加工可再生能源的精炼器,无论是仅使用可再生能源作为原料,还是可再生能源和化石燃料的混合物作为原料,即共同加工,都一致表示需要更好的防护材料,特别是P捕获剂,以防止其本体催化剂的压降和失活。因此,在到达本体催化剂之前,减少或(如果可能)去除杂质(特别是含磷物质)至关重要。
催化过程的“保护床”概念是已知的。例如,从美国专利号5,879,642已知。上游催化剂床用作保护性催化剂床,用于从烃进料流中去除大部分杂质,以延长位于催化剂保护床下方(下游)的一个或多个催化剂床的寿命。
US 9,447,334(US 2011/138680)公开了一种利用进料预处理转化衍生自可再生来源的进料的方法,其中在加氢处理步骤的上游,进行用于消除在加氢处理条件下不溶的杂元素如磷的强化预处理步骤。该步骤包括使用不含催化材料(不含催化金属)的吸附剂,该吸附剂具有高的表面积(例如140m2/g)和高的总孔隙体积(例如1.2ml/g)。
US 2004/077737公开了一种用于费托合成的催化剂,其包含3-35wt%的负载在氧化铝上的钴,氧化铝载体具有小于50m2/g的表面积和/或是至少10%的α-氧化铝。钴(Co)适当地与金属助催化剂Re或Pt结合。特别地,当Co通过Re或Pt促进时,催化剂中Co的含量为5wt%或更高。当催化剂中仅使用Co时,其含量为12wt%或更高。
US 4,510,092公开了一种在表面积小于10m2/g、微孔隙体积小于0.1ml/g且大孔隙体积小于0.6ml/g、优选小于0.3ml/g的镍/α-氧化铝催化剂上连续氢化脂肪材料(特别是液体植物油)的方法。微孔隙体积是指尺寸小于约的孔的总体积;而大孔隙体积是指尺寸大于约的孔的总体积。镍含量很高,为1-25%。
US 4,587,012公开了一种使用包含大于80%的α-氧化铝的催化剂对含烃流进行提质以去除金属杂质镍、钒和铁的方法。催化剂材料具有仅为约500ml/kg(0.5ml/g)的孔隙体积(PV)和不大于10%的大孔,即不超过10%的PV为半径大于(直径大于)的孔。
用于P捕获的常规和市售保护床材料是由高孔隙体积γ-氧化铝载体制成的催化剂形式,其具有用于提供加氢处理活性的低金属含量。
通常,在防护材料中使用金属,特别是具有加氢处理活性的金属(如Mo或Ni),导致不希望的焦化,这会导致保护床堵塞,从而导致不合适的压降。高的金属含量或促进达到的过高活性导致催化剂周围缺乏氢而焦化,并且由于放热而导致高温。
尽管该领域最近取得了进展,但仍需要改进的材料,特别是用于保护床中以去除杂质(如P)的多孔材料,特别是需要包含大量可再生能源的原料,包括具有100%可再生能源的原料,即100%可再生进料。
发明内容
本发明的一个目的是提供一种包含一种或多种具有加氢处理活性的金属的材料,该材料能够捕获烃原料中的杂质(特别是P),并且其使操作期间的焦化最小化。
本发明的另一个目的是提供一种具有比常规材料更高的P渗透性并由此具有改善的P捕获的材料。
本发明的另一个目的是提供一种具有高容量的材料,用于捕获源自可再生源的原料或可再生源与化石燃料组合的原料中的杂质(特别是P)。
本发明解决了这些和其他目的。
因此,在本发明的第一方面中是一种多孔材料,特别是用于从原料中去除一种或多种杂质的多孔材料,该多孔材料包含氧化铝,
-所述氧化铝包括α-氧化铝,
-所述多孔材料包括一种或多种选自Co、Mo、Ni、W及其组合的金属,
-所述多孔材料具有1-110m2/g的BET表面积,
其中,
-多孔材料具有的总孔隙体积为0.50-0.80ml/g,例如0.50-0.750ml/g,或0.55-0.70ml/g,或0.60-0.7ml/g(600-700ml/kg),(如通过压汞法测量的),
且
-多孔材料具有孔径分布(PSD),其中总孔隙体积的至少30vol%,例如至少40vol%,至少50vol%,或至少60vol%为半径≥(40nm)的孔隙,适当地为半径≥(50nm)的孔隙,例如半径至多(500nm)的孔隙。
根据ASTM D4284进行压汞法。
当半径等于或大于或等于或大于的较大孔隙用于P捕获时,半径小于的较小孔能够更好地利用多孔材料中的一种或多种金属来提供加氢处理活性。例如,多孔材料可以表现出单峰孔体系的宽峰,或者表现出双峰或甚至三峰孔体系的宽峰,其中特别地,较小的孔使得可以增加多孔材料的加氢处理活性。
BET表面积根据ASTM D4567-19测量,即通过BET方程单点测定表面积。
在根据本发明第一方面的实施方案中,α-氧化铝的含量为50-100wt%,如65-95wt%,或60-80wt%(如通过XRD测定的)。
在根据本发明第一方面的实施方案中,氧化铝还包括θ-氧化铝和任选的γ-氧化铝。
在根据本发明第一方面的实施方案中,θ-氧化铝的含量为0-50wt%,如35-45wt%,或30-40wt%(如通过XRD测定的)。
在根据本发明第一方面的实施方案中,γ-氧化铝的含量为0-10wt%,如5wt%或更少(如1wt%)(如通过XRD测定的)。因此,在特定实施方案中,γ-氧化铝的含量为0wt%,即多孔材料不含γ-氧化铝。
在根据本发明第一方面的实施方案中,一种或多种金属的含量为0.25-20wt%,例如0.25-15wt%、0.25-10wt%或0.25-5wt%。
还包括上述特征的组合。因此,在根据第一方面的实施方案中,α-氧化铝的含量为50-100wt%,例如65-95wt%;θ-氧化铝的含量为0-50wt%,例如35-45wt%,且γ-氧化铝的含量为0-10wt%,例如5wt%或更少(如1wt%)(如通过XRD测定的),并且一种或多种金属的含量为0.25-20wt%,例如0.25-15wt%、0.25-10wt%、或0.25-5wt%。
XRD(X射线衍射)根据标准XRD分析进行,其中粉末X射线衍射图案在使用CuKα辐射以布拉格-布伦塔诺模式配置的XPertPro仪器上收集,并且使用TOPAS软件的Rietveld分析用于量化相组成。
在不受任何理论约束的情况下,认为与例如常规材料或催化剂中主要的γ-氧化铝相相比,作为多孔材料的主要氧化铝相的α-氧化铝和任选的θ-氧化铝的形成导致多孔材料对P物质的表面反应性显著降低。因此,对P物质的反应性也降低,使得P不仅被捕获在多孔材料的表面上。同时,显示出增加的孔径的多孔材料允许更好渗透进料,特别是可再生进料,从而渗透P物质。此外,还发现使用一种或多种具有加氢处理活性的金属在多孔材料上显示出显著较少的焦化,同样不受任何理论的约束,这可以归因于金属(例如Mo)阻挡了剩余的酸性位点,或者归因于当存在金属时多孔材料的一些低的氢化活性。
在根据第一方面的实施方案中,多孔材料还包括选自硼酸铝如Al5BO9、铝酸钙、铝酸硅及其组合的化合物。这些化合物可以晶体形式存在。
在一个特定的实施方案中,θ-、α-和γ-氧化铝和以晶体形式存在的任何任选的上述化合物如铝酸钙的总和为100wt%(如通过XRD测定的)。
在另一特定实施方案中,多孔材料不含所述化合物。因此,θ-、α-和γ-氧化铝的总和(如通过XRD测定的)为100wt%。
在多孔材料的制备过程中,在1050℃或更高的温度(例如1100℃或1200℃或1300℃或1400℃)下,在空气中煅烧包含氧化铝且特别是具有大量γ-氧化铝(例如50wt%或更高(如通过XRD测量的))的起始(前体)材料,持续1-10小时,例如4、6或8小时;例如,在1100℃下持续2小时,从而将γ-氧化铝转化为α-氧化铝和θ-氧化铝。在制备中还可以使用其他氧化铝前体如勃姆石,例如作为粘合剂。
在材料制备过程中,即在起始材料中添加添加剂如硼酸(H3BO3)、含钙化合物如硝酸钙(Ca(NO3)2)或二氧化硅(SiO2),可以更好地控制煅烧过程中尤其是氧化铝相的烧结和/或转变,从而实现更平稳和稳健的转变。由此也实现了对表面积和孔径的更好控制。因此,添加剂在多孔材料的制备过程中充当稳定剂。
当使用这样的添加剂时,这些添加剂随后以例如SiO2的形式存在于多孔材料中和/或以例如硼酸铝、铝酸钙或铝酸硅的形式存在氧化铝中。
在另一个实施方案中,包含氧化铝的起始材料,例如氧化铝载体,是在450-850℃,优选450-750℃的温度下预煅烧的材料。
当进料与用于加氢处理的主要下游催化剂床接触时,防护材料具有一些(尽管很低的)加氢处理活性以避免焦化和高放热性。进料中最具反应性的分子被转化,从而降低了可能导致结胶的温度升高过度的风险。因此,通过本发明实现了权衡:没有金属会导致材料焦化,过多的金属活性将由于过高的温升而导致焦化和结胶。低金属含量,例如15wt%的Mo、10wt%的Mo、5wt%的Mo或更低,例如3wt%的Mo、1wt%的Mo或0.5wt%的Mo,适当地在如下所述的相应范围内,似乎正好可以平衡这两种失活效应。此外,还实现了在进料到达本体催化剂之前的一些预热。
在根据第一方面的实施方案中,一种或多种金属包括Mo,其含量为0.5-15wt%,例如0.5-10wt%、或0.5-5wt%、或0.5-3wt%,例如0.5-1.5wt%或0.5-1wt%如0.7wt%或0.9wt%、或1-2wt%;并且任选地还包括0.1-5wt%,例如0.1-3wt%、0.1-1wt%、0.1-0.5wt%、或0.1-0.2wt%的至少一种Ni、Co、和W。在根据第一方面的另一实施方案中,一种或多种金属包括Mo,其含量为0.5-15wt%,例如0.5-10wt%、或0.5-5wt%、或0.5-3wt%,例如0.5-1.5wt%如0.7wt%或0.9wt%、或1-2wt%,并且任选地还包括0.05-0.5wt%的Ni;此外,任选地,多孔材料不包含一种或多种选自Co、W的金属,即多孔材料不含Co和/或W。
在特定实施方案中,至少一种或多种金属是Mo。在另一特定实施方案中,一种或多种金属是Mo和Ni。因此,多孔材料不包含一种或多种选自Co、W的金属。例如,多孔材料可包含0.5-1.5wt%的Mo,例如1wt%的Mo和0.1-0.2wt%的Ni。由于孔材料的低表面积,Mo负载量(Mo含量)降低,但是例如通过添加Ni作为助催化剂,可以补偿低金属含量。此外,尽管本发明的多孔材料的表面积低,但少量钼,例如0.5-3wt%的Mo,例如约1wt%,导致显著更低的焦炭形成。当使用100%可再生原料操作时,钼的使用特别有利,因为相对于多孔材料中不存在钼时,P捕获显著增加。此外,少量镍(例如0.05-0.5wt%的Ni,例如约0.1wt%的Ni)的存在进一步减少了焦炭形成。
本发明不需要使用任何金属来提供P捕获,然而证明了添加Mo显著减少焦化,并且无论如何,还使得在包含多孔材料的装置中实现活性梯度的期望效果。此外,虽然添加Co或Ni作为助催化剂可能是可取的,因为它显著增加了活性,但这可能对包括至少一种加氢处理催化剂的下游加氢处理段确实有害。更具体地,在处理可再生原料时,它可能对加氢处理/加氢脱氧(HDO)选择性(产率损失)非常不利。虽然期望在HDO中从可再生原料中去除氧主要通过去除H2O进行,但特别是镍含量高于约0.5wt%导致不期望的脱羧化,从而降低HDO选择性。
在加氢处理/HDO中具有催化活性的材料通常包括活性金属(硫化的碱金属如镍、钴、钨和/或钼,但也可能是单质贵金属如铂和/或钯)和耐火载体(如氧化铝、二氧化硅或二氧化钛,或其组合)。
加氢处理条件包括250-400℃范围内的温度、30-150巴范围内的压力和0.1-2范围内的液时空速(LHSV),任选地与通过用冷氢气、进料或产物的猝灭进行的中间冷却联用。
在根据第一方面的实施方案中,BET表面积为1-70m2/g,例如1-60m2/g、或1-30m2/g,例如10-30m2/g,例如15-25m2/g、或1-28m2/g、5-28m2/g、10-28m2/g、15-28m2/g、20-28m2/g、20-25m2/g、5-20m2/g、或其组合。特定的实施方案是3-15m2/g,例如9-10m2/g;或25-30m2/g、40-45m2/g、或50-55m2/g。
在根据第一方面的实施方案中,至少一种金属是氧化物或硫化物的形式。
在根据第一方面的实施方案中,多孔材料是挤出的或片剂化颗粒,其形状选自三叶形、四叶形、五叶形、圆柱形、球形、中空(例如中空环或中空圆柱体)及其组合。例如,如图4所示,具有四叶形状的颗粒因为改善了外表面积/体积比而特别有利。
在第二方面,本发明还包括一种从原料中去除一种或多种杂质的方法,所述方法包括使所述原料与保护床接触的步骤,从而提供经纯化的原料,所述保护床包含根据前述任一实施方案所述的多孔材料。
在根据本发明第二方面的实施方案中,一种或多种杂质选自含钒杂质、含硅杂质、含卤化物杂质、含铁杂质、含磷杂质及其组合。优选地,一种或多种杂质是含磷(P)杂质。
在根据本发明第二方面的实施方案中,该方法在高温下进行,例如100-400℃,例如250-350℃,任选地在还原剂如氢气的存在下进行。
在根据本发明第二方面的实施方案中,原料是:
i)从可再生来源的原料获得的可再生源,例如源自植物、藻类、动物、鱼类、精制植物油、生活垃圾、富含塑料的垃圾、工业有机废物(如妥尔油或黑液),或衍生自一种或多种含氧化合物的原料,所述含氧化合物取自甘油三酯、脂肪酸、树脂酸、酮、醛或醇的组,其中所述含氧化合物源自生物源、气化过程、热解过程、费托合成或基于甲醇的合成中的一种或多种。所述含氧化合物还可以源自其他合成过程。其中一些原料可能含有芳族化合物;尤其是来自热解过程的产物或来自例如煎炸油的废物。还设想了上述原料的任何组合。
原料也可以是:
ii)源自化石燃料的原料,例如柴油、煤油、石脑油、真空瓦斯油(VGO)、废润滑油或其组合;
或
iii)源自根据i)的可再生源和源自根据ii)的化石燃料的原料的组合的原料
在本发明的上下文中,术语“可再生源”和“可再生进料”可互换使用。
在特定实施方案中,源自可再生源的原料部分为5-60wt%,例如10wt%或50wt%。在另一特定实施方案中,源自可再生源的原料部分高于60wt%,例如70-90wt%。
在根据本发明第二方面的实施方案中,一种或多种杂质是含磷(P)杂质,并且所述原料含有0.5-1000ppm的P。P的含量可根据原料显著变化。例如,源自热解过程(例如热解油)的含氧化合物衍生的油中,P为50-60ppm;或源自动物(特别是动物脂肪)的原料中,P为100-300ppm(例如200ppm)。
在根据本发明第二方面的实施方案中,随后在加氢处理阶段中在加氢催化剂的存在下处理经纯化的原料。在一个特定实施方案中,加氢处理阶段直接位于下游,其间任选具有加热/冷却。在另一特定实施方案中,加氢处理催化剂优选包含选自Co、Mo、Ni、W及其组合的至少一种金属。
在第三方面,本发明包括用于加氢处理系统的保护床,所述保护床包括根据本发明第一方面的多孔材料。
在第四方面,本发明包括用于对原料进行加氢处理的加氢处理系统,所述加氢处理系统包括:
保护床,其包括根据本发明第一方面的多孔材料;和
加氢处理段,其布置在所述保护床下游且包括至少一种加氢处理催化剂。
在第五方面,本发明还包括根据本发明第一方面的多孔材料在加氢处理方法中作为磷防护剂的用途。
在第六方面,多孔材料是无金属的,例如多孔材料不包括选自Co、Mo、Ni、W及其组合的一种或多种金属。本发明不需要使用任何金属来提供P捕获。
因此,还提供了一种包括氧化铝的多孔材料,
-所述氧化铝包括α-氧化铝,
-所述多孔材料不包括一种或多种选自Co、Mo、Ni、W及其组合的金属,
-所述多孔材料具有1-110m2/g的BET表面积,
其中
-多孔材料具有的总孔隙体积为0.50-0.80ml/g,例如0.50-0.75ml/g,或0.55-0.70ml/g,或0.60-0.70ml/g(如通过压汞法测量的),
且
根据本发明第一方面的任何实施方案可以与根据本发明第二、第三、第四、第五和第六方面的任何实施方案一起使用,反之亦然。还应理解,根据第一至第五方面的实施方案涉及一种或多种选自Co、Mo、Ni、W及其组合的金属的用途,这些实施方案不与本发明的第六方面一起使用。
附图简要说明
图1显示了根据本发明的多孔材料的孔径分布(PSD)(通过压汞法测定)。
图2显示了根据本发明的多孔材料的孔体积分布和总孔隙体积(通过压汞法测定)。
图4显示了根据现有技术(低P渗透)和根据本发明(深P渗透)的样品中P捕获的SEM(扫描电子显微镜)照片。
详细说明
实施例
将根据本发明的多孔材料与参考多孔材料(即,主要具有用3wt%的Mo浸渍的γ-氧化铝载体的常规市售精制催化剂)一起填充在单独的隔室中,并在加氢处理条件下,与50%可再生进料和50%化石进料的混合物以及100%可再生进料接触一段时间(通常为8-12个月)。在测试之前,通过XRD分析样品以例如测定氧化铝相。测试结束时,样品冲洗并通过二甲苯萃取,真空干燥,并分析金属/P捕获(XRF,根据EN ISO 12677:2011的X射线荧光分析)、SEM、碳和硫(C+S;LECO分析,ASTM E1915-13)和BET表面积(ASTM D4567-19)。
使用XRD测定氧化铝相。因此,使用CuKα辐射在配置为布拉格-布伦塔诺模式的XPertPro仪器上收集粉末X射线衍射图。使用TOPAS软件进行Rietveld分析并用于量化相组成。
为了测定总孔隙体积和孔径分布,根据ASTM D4284进行压汞法。
多孔材料如下制备:不添加用作催化剂载体的氧化铝材料作为添加剂,包括50wt%或更多γ-氧化铝,在1100-1200℃的高温下在空气中煅烧2-3小时。
图1显示了测试中使用的四个样品的PSD。注意,X轴是对数的。样品1是根据现有技术的参考,即主要具有γ-氧化铝载体的上述常规市售的精制催化剂。样品2-4是根据本发明的多孔材料。观察到,对于根据本发明的样品,大部分孔隙的孔半径为及更大,或及更大。这些用于P捕获的大孔隙的形成归因于α-氧化铝和任选的θ-氧化铝的形成。
找到多孔材料的平衡是非常微妙的,该多孔材料具有高的杂质捕获能力,特别是P捕获能力,同时能够容纳用于加氢处理的金属,但不促进焦化。如此大的孔隙并不能保证更好的保护。例如,图1中高于至约的孔隙区域中的峰并不一定会使相应的多孔材料(样品2至4)成为比类似多孔材料(即至少30vol%的总孔隙体积为半径等于或大于或半径等于或大于的孔隙,且在的孔隙区域中没有显示峰值,或者在该的区域没有孔隙的多孔材料)更好的防护材料。同时,简单地使多孔材料具有大量的微孔或低于约或低于的孔隙(因为通常希望为金属沉积提供高表面积并由此提供催化加氢处理活性)会由于微孔阻塞进入更大孔隙的通道而削弱多孔材料作为P防护剂的能力。
图2和图3显示了总孔隙体积(PV)和相应的孔隙分布。对应于根据本发明的样品2至4的多孔材料显示总孔隙体积在0.50-0.80ml/g范围内,更具体地约0.60ml/g,其中半径大于的孔隙占总孔隙体积的至少30%。例如,样品2为约90wt%的α-氧化铝和约10wt%的θ-氧化铝,显示大于的孔隙占总孔隙体积的99%,而参考样品1显示大于的孔隙仅占总孔隙体积的约20%。
表1显示了通过XRD测量的样品中氧化铝相的含量。制备中未使用添加剂作为稳定剂,因此未检测到硼酸铝、铝酸钙或铝酸硅结晶相。
表1
下表2显示了原料为50%可再生来源和100%可再生来源的多孔材料的杂质捕获结果,特别是P和Fe,以及焦化(C wt%)情况。
使用50%可再生来源运行的样品显示,P捕获比参考(样品1)高出高达600%。使用100%可再生来源运行的样品显示,磷捕获增加高达51%。还表明,如果新鲜多孔材料中存在少量Mo,例如约1wt%的Mo,则与不含金属的相应样品(3'、4')相比,焦化显著减少(见下划线值)。令人惊讶的是,尽管本发明样品的表面积较低,但例如添加0.9wt%和0.7wt%的Mo导致显著更低的焦炭形成。
图4显示了参考样品1(顶部)和样品2(底部)的以P地图形式(更亮意味着更多P)表示的P渗透到具有四叶形形状的多孔材料中的SEM照片。对于参考样品,观察到P仅存在于材料表面上,而在样品2中,发生高水平的P渗透。
表2
用另一种100wt%的可再生原料进行其他实验,新鲜多孔材料(样品5、6、7;见下表3)中氧化铝相的含量(如通过XRD测量的)为约70wt%的α-氧化铝和30wt%的θ-氧化铝,且表面积在25-40m2/g的范围内。样品1'(参考样品)是与样品5-7一起测试的新参考样品。样品1'(参考样品)具有100wt%的γ-氧化铝,表面积为约150m2/g,并且含有比样品1(参考样品)稍多的钼(约3.1wt%)。同样,在制备中没有使用添加剂作为稳定剂,因此没有检测到硼酸铝、铝酸钙或铝酸硅结晶相。样品5不含钼和镍。样品6含有约1wt%的钼。样品7含有约1.2wt%的钼和另外约0.1wt%的镍,更具体地,0.14wt%的Ni。所有新鲜多孔材料(样品1-7)均不含Co和/或W。样品的结果如表3所示。
再次实现了显著的P捕获。尽管本发明样品的表面积较低,但添加约1wt%的Mo导致显著更低的焦炭形成。通过进一步添加少量镍(约0.1wt%),进一步减少焦炭形成,而不会显著损害P捕获。
当使用100%可再生原料操作时,钼任选地与镍一起使用尤其更有利,因为相对于不使用钼的样品,P捕获显著增加。
表3
*样品7是含有0.14wt%的镍的NiMo多孔材料。
Claims (21)
3.根据权利要求1-2中任一项所述的多孔材料,其中所述α-氧化铝的含量为50-100wt%。
4.根据权利要求1-2中任一项所述的多孔材料,所述氧化铝还包括θ-氧化铝和任选的γ-氧化铝。
5.根据权利要求1-4中任一项所述的多孔材料,其中所述一种或多种金属的含量为0.25-20wt%。
6.根据权利要求1-5中任一项所述的多孔材料,还包括选自硼酸铝、铝酸钙、铝酸硅及其组合的化合物。
7.根据权利要求1-6中任一项所述的多孔材料,其中所述一种或多种金属包括Mo,并且其含量为0.5-15wt%,例如0.5-10wt%、或0.5-5wt%、或0.5-3wt%、或0.5-1.5wt%。
8.根据权利要求7所述的多孔材料,还包括0.1-5wt%的Ni、Co和W中的至少一种。
9.根据权利要求7所述的多孔材料,还包括0.05-0.5wt%的Ni;此外任选地,所述多孔材料不包括选自Co、W的一种或多种金属,即所述多孔材料不含Co和/或W。
10.根据权利要求1-9中任一项所述的多孔材料,其中所述BET表面积为1-70m2/g,例如1-60m2/g、或1-30m2/g,如10-30m2/g,例如15-25m2/g。
11.根据权利要求1-10中任一项所述的多孔材料,其中所述多孔材料是挤出的或片剂化颗粒,其形状选自三叶形、四叶形、五叶形、圆柱形、球形、中空,例如中空环或中空圆柱体,及其组合。
12.一种从原料中去除一种或多种杂质的方法,所述方法包括使所述原料与保护床接触的步骤,从而提供经纯化的原料,所述保护床包含根据前述权利要求中任一项所述的多孔材料。
13.根据权利要求12所述的方法,其中所述一种或多种杂质选自含钒杂质、含硅杂质、含卤化物杂质、含铁杂质、含磷杂质及其组合。
14.根据权利要求12-13中任一项所述的方法,所述方法在高温如100-400℃下,任选地在还原剂如氢气的存在下进行。
15.根据权利要求12-14中任一项所述的方法,其中所述原料是:
i)从可再生来源的原料获得的可再生源,例如源自植物、藻类、动物、鱼类、精制植物油、生活垃圾、富含塑料的垃圾、工业有机废物(如妥尔油或黑液),或衍生自一种或多种含氧化合物的原料,所述含氧化合物取自甘油三酯、脂肪酸、树脂酸、酮、醛或醇的组,其中所述含氧化合物源自生物源、气化过程、热解过程、费托合成或基于甲醇的合成中的一种或多种;或
ii)源自化石燃料的原料,例如柴油、煤油、石脑油、真空瓦斯油(VGO)、废润滑油、或其组合;或
iii)源自根据i)的可再生源和源自根据ii)的化石燃料的原料的组合的原料。
16.根据权利要求15所述的方法,其中所述原料中源自可再生源的部分为5-60wt%,例如10wt%或50wt%。
17.根据权利要求13-16中任一项所述的方法,其中所述一种或多种杂质是含磷(P)杂质,并且所述原料含有0.5-1000ppm的P。
18.根据权利要求12-17中任一项所述的方法,其中随后在加氢处理阶段中在加氢处理催化剂的存在下处理所述经纯化的原料。
19.一种用于加氢处理系统的保护床,所述保护床包括根据权利要求1-11中任一项所述的多孔材料。
20.一种用于对原料进行加氢处理的加氢处理系统,所述加氢处理系统包括:
保护床,其包括根据权利要求1-11中任一项所述的多孔材料;和
加氢处理段,其布置在所述保护床下游且包括至少一种加氢处理催化剂。
21.根据权利要求1-11中任一项所述的多孔材料在加氢处理方法中作为磷防护剂的用途。
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DE3405858A1 (de) * | 1983-02-16 | 1984-08-16 | Exxon Research And Engineering Co., Florham Park, N.J. | Verfahren zur wiederaufbereitung von altoelen |
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US4510092A (en) | 1982-03-19 | 1985-04-09 | Uop Inc. | Continuous reduction of edible oils |
US5079208A (en) * | 1988-12-30 | 1992-01-07 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Synthetic, macroporous, amorphous alumina silica and a process for refining glyceride oil |
US5879642A (en) | 1996-04-24 | 1999-03-09 | Chevron U.S.A. Inc. | Fixed bed reactor assembly having a guard catalyst bed |
FR2953854B1 (fr) | 2009-12-16 | 2012-12-28 | Inst Francais Du Petrole | Procede de conversion de charges issues de sources renouvelables avec pretraitement des charges par dephosphatation a chaud |
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- 2021-07-06 CN CN202180046007.5A patent/CN115734997A/zh active Pending
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DE3405858A1 (de) * | 1983-02-16 | 1984-08-16 | Exxon Research And Engineering Co., Florham Park, N.J. | Verfahren zur wiederaufbereitung von altoelen |
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JP2023533939A (ja) | 2023-08-07 |
BR112023000207A2 (pt) | 2023-01-31 |
KR20230035246A (ko) | 2023-03-13 |
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WO2022008508A1 (en) | 2022-01-13 |
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