CN117884125A - 催化气化方法、催化剂、催化剂的用途和用于制备催化剂的方法 - Google Patents
催化气化方法、催化剂、催化剂的用途和用于制备催化剂的方法 Download PDFInfo
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- CN117884125A CN117884125A CN202311718250.4A CN202311718250A CN117884125A CN 117884125 A CN117884125 A CN 117884125A CN 202311718250 A CN202311718250 A CN 202311718250A CN 117884125 A CN117884125 A CN 117884125A
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- Prior art keywords
- catalyst
- catalytic gasification
- coke
- petroleum coke
- gasification
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 238000002309 gasification Methods 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 67
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 59
- 230000008569 process Effects 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000002006 petroleum coke Substances 0.000 claims abstract description 47
- 239000000571 coke Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000003245 coal Substances 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000006004 Quartz sand Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
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- 150000003624 transition metals Chemical class 0.000 claims description 6
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FBKLJOCLOTZNGP-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[V+5].[Ce+3] Chemical compound [O--].[O--].[O--].[O--].[V+5].[Ce+3] FBKLJOCLOTZNGP-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 239000002009 anode grade coke Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 244000038293 primary consumers Species 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 229910001923 silver oxide Inorganic materials 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 238000009865 steel metallurgy Methods 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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Classifications
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- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
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- C10J3/48—Apparatus; Plants
- C10J3/482—Gasifiers with stationary fluidised bed
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及催化气化方法、催化剂、催化剂的用途和用于制备催化剂的方法,尤其是应用于焦炭或煤单独或以混合物的气化方法的催化剂,以及制备所述催化剂的方法,所述催化剂可用于获得更高水平的氢气和一氧化碳,所述催化剂允许将焦炭转化为更高附加价值的副产物(富氢合成气)。本发明还涉及用于通过使用根据本发明的催化剂转化石油焦炭的方法。
Description
本申请是申请日为2020年11月17日、申请号为“202080089856.4”、发明名称为“催化气化方法、催化剂、催化剂的用途和用于制备催化剂的方法”的中国专利申请的分案申请,原申请是国际申请PCT/BR2020/050478的中国国家阶段申请。
技术领域
本发明涉及焦炭或煤单独或以混合物的催化气化方法。气化方法使用允许将焦炭转化为更高附加价值的副产物(富氢合成气)的催化剂。
本发明还涉及获得应用于石油焦炭的催化转化过程的所述催化剂的方法,和催化剂本身。
背景技术
众所周知,油在很大程度上推动了19世纪初的工业发展,直到今天,它仍是地球上的主要能源。事实上,它是一种可耗尽的资源,加上其重要的经济价值,使得这种燃料成为导致世界各地重大的地缘政治和社会经济变化的要素。
通常,可以将石油描述为一种在地下不同深度处发现的油性和易燃物质。其主要由烃类,主要是脂族烃、无环烃、脂环族烃和芳族烃的复杂组合组成。
在从沉积物中提取出石油的方式,其实际上没有应用,只有在经历在精炼厂中进行的其组分的分馏或分离的过程之后,才能使其可用于最大程度地利用其能源潜力。
从油精炼中通过蒸馏分离烃类,并且在另一些过程中去除其杂质,使得可以提取各种产品,包括:柴油、汽油、石脑油、煤油、沥青、润滑剂、石蜡、液化石油气、溶剂、塑料和聚合物、一般的焦油和焦炭,更准确地为石油焦炭(本专利中描述的催化剂的主要目标)。
石油焦炭由具有高分子量和高碳浓度的聚合物链组成。虽然焦炭产品被认为是一种低附加价值副产物,但是根据其纯度,其可以具有一定价值,在用于铁和钢冶金的冶金等级焦炭与用作制造用于生产铝或二氧化钛的阳极的原材料的阳极等级焦炭之间存在差别。
目前,世界上生产的石油焦炭以燃料的形式被消耗,并且主要消耗者是炼油厂本身,炼油厂优先在其炉内部使用商业价值低的燃料,从而使其他更高价值产物的生产和商业化最大化。
被认为是固体燃料的石油焦炭具有高热值、低灰分含量、低购买成本、低挥发性材料含量、高硫含量、含有重金属的灰分和低燃烧效率。
应强调的是,石油焦炭来自为低附加价值油流(高密度、富含硫和杂质)的热裂解过程的延迟焦化。产生的焦炭的特性取决于油的来源和操作条件,并且除了粘度增加之外,还可能在其最终组成中存在大量硫、低挥发性内容物。
因此,由于其特别的特性,石油焦炭被认为是煤的使用的令人感兴趣的替代品。其在炼油厂中的广泛可用性使其成为一种可行且低成本的替代品,石油焦炭通过其气化引起产生气体、氢气、甲烷和电力。
进而,气化可以定义为通过热化学反应将有机物质转化为气态产物,涉及量低于化学计量(燃烧的理论最小值)的蒸汽、空气或氧气。
无论装料的性质如何,构成烃类的混合物的主要元素碳、氢、氧和硫都会转化为热力学稳定的物质,其为一氧化碳、二氧化碳、氢气、水、甲烷、硫化氢和硫化羰,其比例根据过程条件(特别地在氧化中使用的是空气还是氧气)而变化。
因此,气化允许将不能汽化的烃类转化,伴随着碳-碳键的断裂,这导致存在单一所得的烃,即甲烷。
用于气化过程的最常见原材料是煤、油及其残渣、天然气、生物质或其混合物。由合成气获得的产物用于各种应用,例如发电、氢气生产、甲醇生产和液体燃料合成。
以这种方式,由煤、石油焦炭、精炼厂残渣的气化获得的合成气通常在其组成中存在25%至30%H2(体积/体积)、30%至60%CO(体积/体积)、5%至15%CO2(体积/体积)和2%至3%H2O(体积/体积)。还发现了较低水平的CH4、H2S、N2、NH3、HCN、Ar、COS、Ni和Fe。产生的气体的量和组成与所使用的原材料的特性各不相同地相关。
为了使反应发生,典型的加工温度为1600℃至1350℃,并且压力可以达到150kgf/cm2(14.710MPa)。过程的基本反应为:
在这种情况下,可以注意到,发生反应所需的氧气的最小量由方程式(1)表示,每1kmol/h的碳需要0.5kmol/h的氧气。
一氧化碳和氢气气是主要产物,直到所有的烃都被转化;然后才会由额外提供的氧气形成二氧化碳和水。然而,反应的顺序仍然不确定。一些作者认为CO2和H2O是反应的主要产物。
根据方程式(2),为了防止不受控的温度升高,有时添加蒸汽,与烃类发生吸热反应。这导致形成比方程式(1)所预期的更多的氢气。
保留在混合物中的组分的比例由平衡确定,除了一氧化碳氧化反应(7)和甲烷干重整(8)之外,所述平衡还包括水置换(5)、蒸汽重整(4)和由硫化氢到硫化羰的反应(6),如下:
平衡建立在1500℃至1350℃的反应器中。低于900℃,只有借助长的停留时间或借助使用催化剂才能达到接近平衡。由于煤烟形成,并未在商业上应用催化剂的使用。
因此,油残渣,特别是石油焦炭主要由于其在炼油厂中的广泛可用性,已成为对于气化过程有前途的原材料。作为主要特性,在与煤相比时,石油焦炭的反应性较低,具有较低量的碳和低量的挥发性物质,这导致需要1400℃至1500℃的高温使得可以气化。此外,由于高硫含量,因此需要采取额外的步骤以去除不期望的化合物例如H2S、COS和S2。
为了改善和优化气化过程,存在待考虑的数个策略,其中可以提及:经由膜的空气分离、新的气化器配置、热气净化、新溶剂、提高变换反应中的转化率的膜、氢气分离以及在过程中应用催化剂。按照这种推理路线,寻找新的催化剂可以允许以更温和的条件和/或伴随形成更少的副产物来操作,甚至降低反应的温度和能量消耗,这导致过程效率的提高。
相关文献描述了升高操作温度提高了焦炭与作为气化剂的CO2的转化率,并导致反应时间的减少。因此,温度越高,石油焦炭转化为气态产物所需的时间越短。此外,转化速率随着转化率的提高而提高,然后下降。
在焦炭与CO2的气化中观察到的这种反应行为是由于温度影响在气化期间石油焦炭的石墨化过程的事实。在这种情况下,值得注意的是,在与煤相比时,焦炭具有高结晶度和高结构组织,这是随着温度升高而形成石墨碳的理想条件。
专业文献中描述的另一点涉及木质素对石油焦炭的气化的影响。木质素具有高反应性,这是由于存在碱性物质和高表面积。所述描述指出了以下事实:焦炭与木质素的混合物提供了焦炭的反应性的优化,因为在研磨步骤中其促进了物质之间的密切接触,因此存在于木质素中的碱性物质的接近将能够加速石油焦炭的气化。
关于专利文献,文献US20150299588描述了焦炭与浸渍在煤中的催化剂在蒸汽的存在下的气化反应。所提出的催化剂由煤和钾组成,该催化剂与焦炭的比例为1:1,呈现出88.4%的转化率。在氩气气氛中,反应温度范围为700℃至900℃。
文献US20070083072描述了用于焦炭气化过程的碱金属催化剂。催化剂选自以下物质:Na2CO3、K2CO3、Rb2CO3、LiCO3、CsCO3、NaOH、KOH、RbOH或CsOH,焦炭预先用新鲜溶液和回收溶液的混合物浸渍。反应在580℃至816℃的温度范围下进行。转化率高达97%,产生甲烷、二氧化碳、一氧化碳和氢气,后两者在过程中被回收。
文献US6585883涉及去除或减少流化床焦化单元中的焦炭。在该过程中,提出了烷氧基化或未烷氧基化的含有铈、钛和锆的氧化物催化剂;钴氧化物、钒氧化物和银氧化物;金属碳酸盐、碱金属氢氧化物和碱土金属氢氧化物;第VIII族过渡金属氧化物、铈钒氧化物和氯化钾的混合物或者Cu-K-V-Cl催化剂或其混合物,这些溶液预先浸渍在焦炭中。在该描述中,反应在500℃至700℃下发生。
文献US20090165380描述了用蒸汽以及由碱金属氢氧化物和一种或更多种另外的碱金属的组合组成的催化剂使焦炭气化,催化剂浸渍在焦炭中,产生甲烷、氢气、一氧化碳和其他较大的烃。焦炭气化在700℃下进行。
文献CN108587687公开了一种通过使用催化剂使石油焦炭气化的方法,所述方法包括机械混合、浸渍或直接喷洒基于镁的催化剂,其中可以将以下引以为例:MgO、MgCl2、MgSO4和Mg(NO3)2。
以另外的方式,文献CN108641752涉及一种通过以下催化剂优化石油焦炭气化反应的方法:CaO、ZrO2、Ba2TiO4、Li2O、Li2ZrO3、Li2SiO3、Li4SiO4,其大大提高了气化的反应速率并减少了该反应所需的时间。
从本公开内容中可以注意到,现有技术描述了在实践中具有改善和优化过程的功能的催化剂,但是所有实例都存在在反应之前的步骤,其中催化相必须与焦炭混合或浸渍在焦炭中,或仍然浸渍在煤中,然后得到其与焦炭的混合物,需要重复该步骤,因为材料必须随着焦炭的消耗而重新供应到该过程中。
因此,仍然需要描述一种催化剂,该催化剂能够优化过程,而不需要随着每次新的焦炭供应进行用以形成催化剂的先前的混合阶段或焦炭浸渍阶段;以这种方式,旨在公开一种传统描述中的催化剂,该催化剂不与焦炭一起消耗并且不需要与焦炭高度相关地重新供应,而是仅需要更换损失,这减少了步骤的数量并因此降低了过程的成本。
为了解决这个问题,本发明提出了能够通过消除用以引入催化功能的焦炭预处理步骤并采用低成本的金属和载体来优化焦炭气化过程、降低成本的催化剂。消除上述步骤是指不需要将催化剂与焦炭混合或将催化剂预先浸渍在焦炭中的事实。应进一步强调的是,与目前描述的方法相比,本申请中描述的方法以非常低的加工成本产生了具有高浓度的氢气的高附加价值的合成气。
发明内容
本发明涉及一种通过热化学反应将有机物质,特别是石油焦炭转化为气态产物(气化)的催化剂,涉及量低于化学计量的蒸汽、空气或氧气。无论装料的性质如何,主要的转化元素是一氧化碳、二氧化碳、氢气、水、甲烷、硫化氢和硫化羰。
根据本发明的一个方面,提出了三种催化剂,衍生自硝酸盐的Fe/SiO2-NO3、来源于氯化物的Fe/SiO2-Cl、或衍生自硫酸盐的Fe/SiO2-SO4。本发明提出优先使用Fe/SiO2-Cl催化剂,与在热气化中和在使用催化剂Fe/SiO2-NO3和Fe/SiO2-SO4进行的反应中所需的6小时相比,该催化剂在4小时的反应中达到了全部转化。
根据同一个方面,相对于不存在催化剂的纯热反应,Fe/SiO2-Cl催化剂在相同温度下减少了反应时间。当与现有技术相比时,所述催化剂的应用产生更高水平的H2,促进石油焦炭转化为更高附加价值的副产物(富氢合成气)。
附图说明
下面将参照附图更详细地描述本发明,以示意性方式且不限制本发明范围的附图代表其实施方案的实例。在附图中,存在:
-图1示出了在热气化以及使用由氯化物、硝酸盐和硫酸盐制备的Fe/SiO2催化剂在800℃下的催化气化中作为时间的函数的石油焦炭的转化率。
-图2示出了在使用Fe/SiO2-Cl催化剂在800℃下进行的测试中气化器输出流的摩尔组成(在无水和无氮气的基础上)。
-图3示出了使用Fe/SiO2-Cl催化剂在800℃、750℃和700℃下气化器输出流的摩尔组成(在无水和无氮气的基础上)。
具体实施方式
本发明涉及石油焦炭、煤或其混合物的催化气化方法,以产生富氢合成气。催化剂的使用为加工上述装料提供了更温和的条件。此外,本发明中所需的催化剂可以与待加工的材料一起供应,而不需要在焦炭中的浸渍步骤或者与焦炭或其他材料预先混合。
本发明提出的催化气化方法通过以下步骤进行:
a)用催化剂、惰性材料或两者的混合物装载反应器;
b)在室温下以10Nl/分钟的空气流量使步骤(a)中装载的床流态化;
c)以20℃/分钟的速率将步骤(b)中流态化的床从室温加热至800℃;d)开始向步骤(c)中加热的体系中引入蒸汽;
e)在达到气化温度,所述床和所述体系的温度稳定之后,开始引入石油焦炭;
f)将来自气化器的气体从步骤(e)注入到色谱仪中;
g)在空气流下将所述体系冷却;
h)将所述床卸载;
i)称量步骤(h)中卸载的床、旋风分离器和过滤器;
j)进行单元的质量平衡。
在本发明的一个方面中,用1kg二氧化硅和1kg催化剂装载反应器床以进行石油焦炭或煤的催化气化过程。相反,在热气化中,将用2kg二氧化硅(这种材料是惰性的)装载反应器。
在本发明的另一个方面中,应强调的是,在使床流态化之后,达到500℃的温度,开始向体系中引入蒸汽,其中将液体泵校准为5ml/分钟的供应量。
在另一个方面中,当达到体系中的气化温度时,发生床稳定化以及以0.366kg/小时的速率引入石油焦炭。
在又一个方面中,应强调的是,在固体供应开始五分钟之后,将来自气化器的气体注入到在线色谱仪中以确定其组成。每三十分钟注入一次气体流样品。在供应全部焦炭物料之后,继续注入直到不再检测到CO和H2产物的存在,表明气化结束。
当气化结束并达到室温时,将床卸载,然后称量卸载的床、旋风分离器和过滤器。根据情况,进行称量以确定是否存在颗粒从床,从石油焦炭或煤中带出。
关于催化气化方法的一个方面,应强调的是,所述方法产生富氢合成气。
在催化气化方法的另一个方面中,所述方法允许反应在温和的条件下并以更高的转化速率发生。
除了所述方面之外,催化剂被供应到体系中而不需要在焦炭、煤或其他类似材料中浸渍并且无需与装料预先混合。
本发明的第二变体涉及用于制备催化气化用催化剂的方法,在数个相关方面中描述该方法,其中包括以下制备步骤:
a)称量100g载体(石英砂);
b)称量铁盐以得到期望的铁含量%(重量/重量);
c)向所述铁盐中添加150ml水;
d)向所述石英砂中添加制备的溶液;
e)静置16小时;
f)使所述溶液缓慢蒸发;
g)在100℃的烘箱中干燥16小时;
h)在550℃下煅烧5小时。
在该变体中,催化剂通过浆料法制备,其中将确定质量的载体与构成期望金属浓度的溶液一起混合来形成悬浮体。将形成的呈悬浮体的溶液静置,然后干燥和煅烧。
在本发明的所有变体中,用于获得富氢合成气所使用的原材料优选为最大颗粒尺寸为177μm的石油焦炭。然而,可以将催化剂用于煤的气化。
还要求本发明的前述变体中提及的催化剂作为创新产品。以这种方式,获得的催化气化用催化剂包含:
a)载体,优选石英砂;
b)第VIII族的过渡金属;
c)在550℃下煅烧所述化合物5小时。
应强调的是,在本发明的该第三变体中,催化气化用催化剂包含第VIII族的过渡金属,即铁。在本发明中要求三种形式的催化剂:FeSiO2-Cl、FeSiO2-NO3和第三种FeSiO2-SO4。
在提及的种类中,与热转化相比,FeSiO2-Cl在反应中表现出转化时间的减少以及提高的CO2和H2水平。因此,催化气化用催化剂FeSiO2-Cl允许在更温和的条件下并且以更高的石油焦炭转化速率并且以与煤类似的方式发生催化气化。
以另一种方式,催化气化用催化剂还具有另外的优点,因为其被供应到体系中而不需要在焦炭、煤或其他类似材料中浸渍并且不需要与装料预先混合,从而减少了加工步骤、加工时间和能量消耗。
因此,使用催化气化用催化剂优化并改善了石油焦炭或煤的催化气化方法,产生了高附加价值的富氢合成气。此外,由于使用的材料和制备方法,其为一种低成本催化剂。
实施例
如在进行的测试中可以看出,通过浆料法制备催化剂,所述方法包括向确定质量的载体中添加具有期望金属浓度的溶液。将形成的悬浮体静置,然后干燥并煅烧。用于制备的步骤为:
a)称量100g载体(石英砂);
b)称量铁盐至期望的铁含量%(重量/重量);
c)向所述铁盐中添加150ml水;
d)向所述石英砂中添加制备的溶液;
e)静置16小时;
f)使所述溶液缓慢蒸发;
g)在100℃的烘箱中干燥16小时;
h)在550℃下煅烧5小时。
将测试中使用的焦炭研磨并使用一组筛进行粒度分级,收集并储存最大颗粒尺寸为177μm的部分。表1涉及通过X射线荧光(FRX)确定的所制备的各种催化剂的组成。
表1–-通过FRX获得的数种制备的催化剂的组成。
图1示出了在使用由使用氯化物、硫酸盐和硝酸盐制备的Fe/SiO2催化剂时在800℃的温度下作为气化时间的函数的石油焦炭的转化率。为了比较目的,包括在不存在催化剂的情况下由热气化获得的焦炭转化率曲线。
通过测试以下方案来进行空白测试以及用以测试各种催化剂的转化有效性而进行的测试:
a)装载反应器床,其可以包含2kg二氧化硅(热气化测试)或者1kg二氧化硅和1kg催化剂(催化气化测试);
b)在室温下使用10Nl/分钟的空气流量使床流态化;
c)使用20℃/分钟的速率将床从室温加热至800℃;
d)当达到500℃的温度时,开始向体系中引入蒸汽,并将液体泵校准为5mL/分钟的供应量;
e)当达到期望的气化温度时,等待稳定。一旦床温度稳定,就开始以0.366kg/小时的速率引入石油焦炭;
f)在固体供应开始五分钟之后,将来自气化器的气体注入到在线色谱仪中以确定其组成。每三十分钟注入一次气体流样品。在供应全部焦炭物料之后,继续注入直到不再检测到CO和H2产物的存在,表明气化结束;g)将体系在空气流下冷却,并且一旦达到室温,就将床卸载并称量。还称量旋风分离器和过滤器以确定颗粒是否从床或从石油焦炭中带出,因此闭合单元的质量平衡。
在进行的测试之后,可以观察到由硫酸盐制备的Fe/SiO2催化剂呈现出与在热气化中观察到的性能类似的性能。该结果可以解释为,如果考虑到当使用硫酸盐作为金属源时,并入到二氧化硅中的铁含量低于其他情况。这样的信息可以由表1证实。
在使用硝酸盐作为铁源制备的催化剂的情况下,并入的含量高于其他两者,但在这种情况下,与热气化相比,石油焦炭的转化率也没有显著改善。特别地,由硝酸盐制备的催化剂表现出与由硫酸盐制备的催化剂类似的性能,直到约100分钟由硝酸盐制备的催化剂的性能开始下降时,即使对于热气化也是如此。
使用Fe/SiO2-Cl催化剂似乎影响了石油焦炭的气化动力学,因为与在热气化中以及在通过使用Fe/SiO2-NO3和Fe/SiO2-SO4催化剂进行的反应中所需的6小时相比,在4小时的反应中达到了全部转化。
图2示出了在使用FeSiO2-Cl催化剂在800℃下进行的测试中气化器输出流的摩尔组成(在无水和无氮气的基础上)。在使用Fe/SiO2-Cl催化剂的实验中,获得了更高含量的CO2和H2,如图2所示。该结果表明,除了有效减少总气化时间之外,该催化剂还极大地促进了气-水的置换反应,因此增加了氢气的产量。
如可以在图3中所见,存在在800℃、750℃和700℃下进行的测试中气化器输出流的摩尔组成(在无水和无氮气的基础上)。这样的数据证明,在图3中引用的附加测试中,转化率在较低温度下降低,并且达到最终转化的气化时间也逐渐增加。另一方面,在750℃下观察到的转化率接近于不存在催化剂的纯热转化率,如图1所示。因此,可以注意到,在存在本发明的催化剂对象的情况下,需要较低的温度来实现与纯热反应的转化率相当的转化率,从而使整个过程能耗较少。
应注意,虽然已经相对于附图描述了本发明,但是本主题技术人员可以根据具体情况进行修改和调整,但条件是其在本文所限定的发明范围内。
以下内容对应于母案申请中的原始权利要求书,现作为说明书的一部分并入此处:
1.一种催化气化方法,特征在于其包括以下步骤:
a)装载反应器床;
b)在室温下以10Nl/分钟的空气流量使步骤(a)中装载的所述床流态化;
c)以20℃/分钟的速率将步骤(b)中流态化的床从室温加热至800℃;
d)开始将向步骤(c)中加热的体系中引入蒸汽;
e)在达到气化温度,所述床和所述体系的温度稳定之后,开始引入石油焦炭;
f)将来自气化器的气体从步骤(e)注入到色谱仪中;
g)在空气流下将所述体系冷却;
h)将所述床卸载;
i)称量步骤(g)中卸载的所述床、旋风分离器和过滤器;
j)进行单元的质量平衡。
2.根据项1所述的催化气化方法,特征在于当进行石油焦炭、煤或其混合物的催化气化时,用比例为10:90的催化剂和惰性材料的混合物装载所述反应器床,其中所述催化剂和惰性材料的混合物的比例优选地选择为50:50的二氧化硅和催化剂。
3.根据项1所述的催化气化方法,特征在于在达到300℃至700℃,优选500℃的温度之后,用被校准为5ml/分钟的供应量或者与所使用的设备的零件的尺寸相匹配的液体泵将蒸汽开始引入。
4.根据项1所述的催化气化方法,特征在于在达到所述气化温度之后,发生床稳定化,以及以0.366kg/小时或与所使用的设备的零件和原材料的质量相匹配的速率引入石油焦炭。
5.根据项1所述的催化气化方法,特征在于所述方法产生高附加价值的富氢合成气。
6.根据项1所述的催化气化方法,特征在于所述方法允许反应在温和的条件下并且以更高的转化速率发生。
7.根据项1所述的催化气化方法,特征在于将所述催化剂供应到所述方法而无需预先浸渍步骤或者无需与装料预先混合。
8.一种用于制备催化气化用催化剂的方法,特征在于进行以下制备步骤:
a)称量100g载体(石英砂);
b)称量铁盐以具有期望的铁含量%(重量/重量);
c)向所述铁盐中添加150ml水;
d)向所述石英砂添加制备的溶液;
e)静置16小时;
f)使所述溶液缓慢蒸发;
g)在100℃的烘箱中干燥16小时;
h)在550℃下煅烧5小时。
9.根据项8所述的用于制备催化气化用催化剂的方法,特征在于通过浆料法制备所述催化剂。
10.根据项8所述的用于制备催化气化用催化剂的方法,特征在于以确定的载体质量用具有期望的金属浓度的溶液制备所述催化剂。
11.根据项8所述的用于制备催化气化用催化剂的方法,特征在于由形成的悬浮体并将其静置,然后干燥并煅烧来制备所述催化剂。
12.根据项8所述的用于制备催化气化用催化剂的方法,特征在于所使用的原材料优选为石油焦炭,其中最大颗粒尺寸为177μm。
13.一种通过根据项8至12所述的方法获得的催化气化用催化剂,特征在于其包含:
a)载体,优选石英砂;
b)第VIII族的过渡金属;
c)在400℃至700℃下,优选在550℃下煅烧所述化合物持续范围为2至10小时的时间,并且优选5小时以内。
14.根据项13所述的催化气化用催化剂,特征在于所述第VIII族的过渡金属包括铁。
15.根据项13所述的催化气化用催化剂,特征在于所述催化剂能够为以下种类:Fe/SiO2-NO3和Fe/SiO2-SO4。
16.根据项13所述的催化气化用催化剂,特征在于其用于石油焦炭、煤和两者的混合物的催化气化,其中优选使用的原材料为石油焦炭。
17.根据项13所述的催化气化用催化剂,特征在于其允许催化气化在更温和的条件下并且以石油焦炭和煤的更高的转化速率发生。
18.根据项13所述的催化气化用催化剂,特征在于所述催化剂被供应到方法而无需预先浸渍步骤或者无需与装料预先混合。
19.根据项13至18中任一项所述的催化剂的用途,特征在于其用于石油焦炭、煤或两者的混合物的催化气化方法的优化和改善,其中优选使用的原材料为焦炭。
20.根据项19所述的催化剂的用途,特征在于其产生具有高附加价值的富氢合成气。
Claims (13)
1.一种用于制备催化气化用催化剂的方法,特征在于进行以下制备步骤:
a)称量100g载体(石英砂);
b)称量铁盐以具有期望的铁含量%(重量/重量);
c)向所述铁盐中添加150ml水;
d)向所述石英砂添加制备的溶液;
e)静置16小时;
f)使所述溶液缓慢蒸发;
g)在100℃的烘箱中干燥16小时;
h)在550℃下煅烧5小时。
2.根据权利要求1所述的用于制备催化气化用催化剂的方法,特征在于通过浆料法制备所述催化剂。
3.根据权利要求1所述的用于制备催化气化用催化剂的方法,特征在于以确定的载体质量用具有期望的金属浓度的溶液制备所述催化剂。
4.根据权利要求1所述的用于制备催化气化用催化剂的方法,特征在于由形成的悬浮体并将其静置,然后干燥并煅烧来制备所述催化剂。
5.根据权利要求1所述的用于制备催化气化用催化剂的方法,特征在于所使用的原材料优选为石油焦炭,其中最大颗粒尺寸为177μm。
6.一种通过根据权利要求1至5所述的方法获得的催化气化用催化剂,特征在于其包含:
a)载体,优选石英砂;
b)第VIII族的过渡金属;
c)在400℃至700℃下,优选在550℃下煅烧所述化合物持续范围为2至10小时的时间,并且优选5小时以内。
7.根据权利要求6所述的催化气化用催化剂,特征在于所述第VIII族的过渡金属包括铁。
8.根据权利要求6所述的催化气化用催化剂,特征在于所述催化剂能够为以下种类:Fe/SiO2-NO3和Fe/SiO2-SO4。
9.根据权利要求6所述的催化气化用催化剂,特征在于其用于石油焦炭、煤和两者的混合物的催化气化,其中优选使用的原材料为石油焦炭。
10.根据权利要求6所述的催化气化用催化剂,特征在于其允许催化气化在更温和的条件下并且以石油焦炭和煤的更高的转化速率发生。
11.根据权利要求6所述的催化气化用催化剂,特征在于所述催化剂被供应到方法而无需预先浸渍步骤或者无需与装料预先混合。
12.根据权利要求6至11中任一项所述的催化剂的用途,特征在于其用于石油焦炭、煤或两者的混合物的催化气化方法的优化和改善,其中优选使用的原材料为焦炭。
13.根据权利要求12所述的催化剂的用途,特征在于其产生具有高附加价值的富氢合成气。
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