CN114425384A - 一种制合成气催化剂及其制备方法和应用 - Google Patents
一种制合成气催化剂及其制备方法和应用 Download PDFInfo
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- CN114425384A CN114425384A CN202011091074.2A CN202011091074A CN114425384A CN 114425384 A CN114425384 A CN 114425384A CN 202011091074 A CN202011091074 A CN 202011091074A CN 114425384 A CN114425384 A CN 114425384A
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- Prior art keywords
- catalyst
- tridymite
- cristobalite
- synthesis gas
- parts
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- 239000003054 catalyst Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000843 powder Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 29
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 29
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 29
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 230000009466 transformation Effects 0.000 claims abstract description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 15
- 238000004898 kneading Methods 0.000 claims abstract description 13
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
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- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 239000000853 adhesive Substances 0.000 abstract description 4
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- 238000005245 sintering Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 241000219782 Sesbania Species 0.000 description 11
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 11
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
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- 238000002407 reforming Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 241001449342 Chlorocrambe hastata Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
本发明涉及一种制合成气催化剂及其制备方法和应用。本发明催化剂以方石英和/或鳞石英作为载体,方石英和/或鳞石英在催化剂中重量含量为25%~99.8%,活性金属及其氧化物在催化剂中重量含量为0.2%~40%。其制备过程为在负载有活性金属的无定形氧化硅基粉体中加入结构助剂、粘合剂等,经过混捏,成型得催化剂前体;催化剂前体进行转晶处理,将催化剂中氧化硅载体转晶为方石英和/或鳞石英载体。本发明催化剂具有更好的抗烧结与机械强度性能的同时仍然保持了高的催化性能和好的催化稳定性。可用于耐高温的制合成气催化剂的工业生产中。
Description
技术领域
本发明属于催化剂制备技术领域,特别涉及一种制合成气的催化剂及其制备方法,可应用于工业制合成气催化反应中。
背景技术
合成气的生产和应用在化学工业中具有极为重要的地位。目前,天然气转化法是合成气的主要生产方法之一,它可通过甲烷与水蒸气、二氧化碳、氧气或其组合等进行重整反应而制得合成气。由于甲烷分子结构稳定,因此该反应需要在较高的温度下进行,例如甲烷与水蒸气或二氧化碳的重整反应通常需达到800℃以上,这对催化剂的耐高温稳定性提出了很高的要求。其中,耐高温稳定性包括高温下的催化性能、抗烧结与机械强度性能等。
甲烷重整制合成气的催化剂活性中心为贵金属(Pt、Pd、Rh、Ru等)、过渡金属(Ni、Co、Fe、Zn、Cu、Mn、W、Mo等)或其氧化物等,它们对甲烷分子有很好的活化作用,而它们一般负载在催化剂载体,如Al2O3、SiO2、ZrO2、MgO和沸石分子筛等上。其中,氧化硅载体由于比表面积大、具有易于负载和稳定活性金属原子或离子的特点,因此氧化硅载体被视为合成气催化剂常用载体之一。例如:CN101773835A中以SiO2为载体,Ni和La为活性组分,采用共同浸渍法制备了Ni-La/SiO2催化剂;CN104475098B公开了一种以CeO2为助剂、Rh负载氧化硅催化剂,用于甲烷部分氧化制合成气;CN105381818B公开了一种高分散Ni负载在介孔SBA-15二氧化硅上的催化剂,用于甲烷二氧化碳重整制合成气;CN103055868B公开了一种镍基负载在介孔二氧化硅上的催化剂及其制备方法;CN103055913B公开了一种采用镍与氧化硅复合氧化物的催化剂。
而通常,这些二氧化硅载体在高温的反应条件下会面临高温熔化或烧结、孔道坍塌等不稳定的问题。
发明内容
本发明所要解决的技术问题是针对现有技术中催化剂氧化硅载体在高温反应环境下的稳定性问题,提供一种制合成气催化剂及其制备方法。以进一步提高催化剂的稳定性。本发明另一目的在于提高制合成气催化剂的抗压强度,以满足苛刻的生产环境要求。
为解决上述技术问题,本发明第一方面在于提供一种制合成气催化剂,催化剂以方石英和/或鳞石英作为载体,方石英和/或鳞石英在催化剂中重量含量为25%~99.8%,活性金属及其氧化物在催化剂中重量含量为0.2%~40%。
上述技术方案中,所述活性金属包含Pt、Pd、Rh、Ru、Ni、Co、Fe、Zn、Cu、Mn、W、Mo等金属中的一种或多种。
上述技术方案中,所述催化剂的XRD图谱,在2θ角为20.77°,21.94°,26.05°,27.61°,28.46°,31.41°,36.13°,42.60°,44.53°,48.58°,51.87°,54.14°,57.16°,60.26°,62.13°,64.97°,76.31°处具有方石英以及鳞石英的特征衍射峰。
上述技术方案中,催化剂径向抗压强度为50N/cm以上,优选为60~250N/cm。
本发明另一方面在于提供一种制合成气催化剂的制备方法,包括以下步骤:
(1)在负载有活性金属的无定形氧化硅基粉体中加入结构助剂、粘合剂、造孔剂、助挤剂、碱或盐溶液,经过混捏,成型得催化剂前体;
(2)将步骤(1)的催化剂前体经过静置养生和烘干后,进行转晶处理,将催化剂中氧化硅载体转晶为方石英和/或鳞石英载体。
上述技术方案中,步骤(1)中各物质的投料量,按重量份计,氧化硅基粉体100份,结构助剂0.05~40份,粘合剂0.05~50份,造孔剂0.5~20份、助挤剂0.05~5份、碱或盐溶液0.05~200份。活性金属的加入量为使其在最终催化剂中的重量含量为0.2%~40%。上述技术方案中,催化剂中进一步包含制备过程中引入的其它成分如:结构助挤剂、粘合剂等。
上述技术方案中,所述结构助剂选自碳化硅粉体和钾霞石粉体中的一种或两种;所述粘合剂选自硅溶胶、水玻璃、拟薄水铝石和氢氧化铝等中的一种或多种;所述造孔剂优选为田菁粉;所述助挤剂优选为羧甲基纤维素钠。
上述技术方案中,步骤(1)中结构助剂优选为5~30份。步骤(1)中所述成型优选为挤条或压片成型。
上述技术方案中,步骤(2)中所述的转晶处理过程为:将成型烘干后的催化剂经过550~1200℃,优选650~1000℃,更优选700~850℃,焙烧处理1~12h;或者将催化剂在制合成气的反应气氛下550~1200℃,优选650~1000℃,更优选700~900℃下反应12~72h。催化剂转晶后优选在氢气气氛下500~800℃还原2~6h。
上述技术方案中,步骤(1)中所述碱或碱金属盐溶液包括氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锂、氨水、氯化钠、氯化钾以及氯化锂等中的一种或多种。
本发明第三方面在于提供一种上述制合成气催化剂在甲烷制合成气反应中的应用。
上述技术方案中,所述的甲烷制合成气反应包括甲烷与CO2反应,甲烷与水蒸气、甲烷与O2部分氧化反应、甲烷与水、CO2和O2三重整反应中的一种或多种。
由于成型催化剂中方石英与鳞石英具有特殊的结构,它的矛头双晶互相交错,形成结晶网络,能获得坚强的骨架,比无定形氧化硅结构更稳定、硬度更高。因此经过转晶处理,该催化剂具有更好的耐高温稳定性,催化剂的强度大大提高。另外,转晶过程中虽然载体发生了晶相转变,但活性中心基本没受影响,因此催化剂的催化活性、选择性与稳定性仍然保持。
本发明提供一种制合成气的催化剂及其制备方法,可应用于工业制合成气技术中。
附图说明
图1为实施例1催化剂的XRD图谱;
图2为对比例1催化剂的XRD图谱;
图3为对比例2催化剂的XRD图谱。
具体实施方式
X-射线多晶粉末衍射(XRD)采用BRUKER公司的D8 Advance SS X射线衍射仪分析样品的晶体结构分析。以Cu靶的Kα1为辐射源,在40kV和40mA,衍射角2θ=5~80°的条件下扫描与记录,得到XRD衍射图谱,以表征晶体物相。
催化剂的径向抗压强度采用大连化工研究设计院生产的KL-II型智能颗粒强度测定仪上测定,测试方法采用国家标准方法GB 3635-1938(化肥催化剂、分子筛、吸附剂颗粒抗压碎强度测定方法),测试精度为一级,加力速度4~10N/s。操作步骤为:取代表性的1~2厘米长度的单颗粒条状催化剂,首先精确测量并记录其长度值,然后将它侧向放置在仪器测试两平台间,均匀对其施加负载直至颗粒破坏,记录其破坏瞬间的压力值。该压力值与长度值的比值即为该颗粒的抗压强度。一共测试的颗粒数为50颗,最后取平均值,即得到该催化剂的平均径向抗压强度。
下面通过具体实施例对本发明作进一步的阐述,但应当理解本发明的保护范围并不受具体实施方式的限制。
【实施例1】
催化剂成型:先将负载有活性金属镍的氧化硅基粉体1.0kg中加入田菁粉50g、碳化硅粉体50g、羧甲基纤维素钠1g、硅溶胶50g、0.5%NaOH碱溶液1.0kg,经过混合、捏合,然后在挤条成型机挤条成型;然后将成型后的催化剂在室温下经过静置养生24h,然后100℃下烘干5h。
催化剂转晶:将成型烘干后的催化剂经过700℃空气下焙烧处理10h,然后将它在氢气下650℃还原3h,得到催化剂C1。
图1为该催化剂的XRD图谱,其中无定形氧化硅载体转晶为方石英与鳞石英晶相。图中下部为方石英、鳞石英、金属镍分别对应的XRD标准PDF卡片峰位。图谱中的XRD衍射峰对应方石英、鳞石英、金属镍的晶相。方石英和/或鳞石英在催化剂中重量含量为94%,活性金属含量为6%。表1为该催化剂的抗压强度与其对甲烷与CO2反应的催化性能。
【实施例2】
催化剂成型:先将负载有活性金属钯的氧化硅基粉体1.0kg中加入田菁粉100g、碳化硅粉体2kg、羧甲基纤维素钠10g、硅溶胶100g、0.5%KOH碱溶液2.0kg,经过混合、捏合,然后在挤条成型机挤条成型;然后将成型后的催化剂在室温下经过静置养生24h,然后100℃下烘干5h。
催化剂转晶:将成型烘干后的催化剂经过550℃空气下焙烧处理6h,然后制合成气的反应气氛(甲烷与二氧化碳)下900℃反应25h,得到催化剂C2。方石英和/或鳞石英在催化剂中重量含量为60%,碳化硅重量含量约为35%,活性金属重量含量为5%。
该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。
【实施例3】
催化剂成型:先将负载有活性金属镍和铁的氧化硅基粉体1.0kg中加入田菁粉200g、钾霞石粉体200g、羧甲基纤维素钠5g、氢氧化铝100g、0.5%LiOH碱溶液2.0kg,经过混合、捏合,然后在挤条成型机挤条成型;然后将成型后的催化剂在室温下经过静置养生24h,然后100℃下烘干5h。
催化剂转晶:将成型烘干后的催化剂经过850℃空气下焙烧处理2h,然后将它在氢气下650℃还原3h,得到催化剂C3。方石英和/或鳞石英在催化剂中重量含量为70%,钾霞石含量约为15%,氧化铝含量约为5%,活性金属及其氧化物含量为10%。
该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。
【实施例4】
催化剂成型:先将负载有活性金属铂的氧化硅基粉体1.0kg中加入田菁粉50g、钾霞石粉体100g、羧甲基纤维素钠2g、拟薄水铝石300g、0.5%NaCl和氨水碱溶液1.2kg,经过混合、捏合,然后在挤条成型机挤条成型;然后将成型后的催化剂在室温下经过静置养生24h,然后100℃下烘干5h。
催化剂转晶:将成型烘干后的催化剂经过950℃空气下焙烧处理1h,然后将它在氢气下600℃还原4h,得到催化剂C4。方石英和/或鳞石英在催化剂中重量含量为75%,钾霞石重量含量约为8%,氧化铝重量含量约为15%,活性金属重量含量为2%。
该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。
【实施例5】
催化剂成型:先将负载有活性金属镍和钴的氧化硅基粉体1.0kg中加入钾霞石粉体2.0kg、田菁粉10g、羧甲基纤维素钠2g、拟薄水铝石50g、0.5%NaOH碱溶液2.2kg,经过混合、捏合,然后在挤条成型机挤条成型;然后将成型后的催化剂在室温下经过静置养生24h,然后100℃下烘干5h。
催化剂转晶:将成型烘干后的催化剂经过550℃空气下焙烧处理4h,然后在制合成气的反应气氛(甲烷与二氧化碳)下900℃反应72h,得到催化剂C5。方石英和/或鳞石英在催化剂中重量含量为28%,钾霞石重量含量约为65%,氧化铝重量含量约为1%,活性金属及其氧化物重量含量为6%。
该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。
【实施例6】
催化剂成型:先将负载有活性金属镍和钨的氧化硅基粉体1.0kg中加入钾霞石粉体1.5kg、田菁粉50g、羧甲基纤维素钠2g、拟薄水铝石10g、0.5%NaOH碱溶液2.0kg,经过混合、捏合,然后在挤条成型机挤条成型;然后将成型后的催化剂在室温下经过静置养生24h,然后100℃下烘干5h。
催化剂转晶:将成型烘干后的催化剂经过550℃空气下焙烧处理5h,然后在制合成气的反应气氛(甲烷与二氧化碳)下850℃反应36h,得到催化剂C6。该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。方石英和/或鳞石英在催化剂中重量含量为24.5%,钾霞石重量含量约为60%,氧化铝重量含量约为0.5%,活性金属及其氧化物重量含量为15%。
【实施例7】
催化剂成型:先将负载有活性金属钴和钼的氧化硅基粉体1.0kg中加入碳化硅粉体2.0kg、田菁粉50g、羧甲基纤维素钠2g、拟薄水铝石10g、0.5%KOH碱溶液2.1kg,经过混合、捏合,然后在挤条成型机挤条成型;然后将成型后的催化剂在室温下经过静置养生24h,然后100℃下烘干5h。
催化剂转晶:将成型烘干后的催化剂在制合成气的反应气氛(甲烷与二氧化碳)下800℃反应48h,得到催化剂C7。方石英和/或鳞石英在催化剂中重量含量为55%,碳化硅重量含量约为27%,氧化铝重量含量约为0.5%,活性金属及其氧化物重量含量为17.5%。
该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。
【实施例8】
催化剂成型:先将负载有活性金属镍、铜和的锌的氧化硅基粉体1.0kg中、碳化硅粉体300g、田菁粉50g、羧甲基纤维素钠2g、拟薄水铝石10g、0.5%NaOH碱溶液1.3kg,经过混合、捏合,然后在挤条成型机挤条成型;然后将成型后的催化剂在室温下经过静置养生24h,然后100℃下烘干5h。
催化剂转晶:将成型烘干后的催化剂在经过700℃空气下焙烧处理10h,然后将它在氢气下700℃还原5h,得到催化剂C8。方石英和/或鳞石英在催化剂中重量含量为62%,碳化硅重量含量约为7%,氧化铝重量含量约为1%,活性金属及其氧化物重量含量为30%。
该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。
【对比例1】
对比例1为常规的以二氧化硅为载体的催化剂。将1.0kg负载有活性金属镍的无定形氧化硅复合粉体中加入田菁粉50g、羧甲基纤维素钠1g、硅溶胶50g、水1.0kg,经过混合、捏合,然后挤条成型;将成型后的催化剂前体经过静置养生和烘干后,550度下焙烧5h。然后将催化剂在氢气气氛下600度还原,得到催化剂D1。
图2给出了对比例1催化剂的XRD图谱,图中下部为金属镍对应的XRD标准PDF卡片峰位;图谱中只有金属镍对应的晶相,图中鼓包线为无定形相,显示了该催化剂中无定形氧化硅载体虽然也经过高温处理但没有转晶。载体在催化剂中重量含量为94%,活性金属重量含量为6%。
该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。该催化剂虽然催化稳定性较好,但催化剂强度较低(见表1)。
【对比例2】
对比例2为用方石英载体浸渍镍盐后,焙烧、还原得到的催化剂。将1.0kg方石英粉体中加入田菁粉50g、羧甲基纤维素钠1g、硅溶胶100g、水1.0kg,经过混合、捏合,然后挤条成型;将成型后的催化剂载体经过晾干、烘干后,550度下焙烧5h。然后将它等体积浸渍硝酸镍溶液,再经过晾干、烘干后,550度下焙烧5h。最后,将催化剂在氢气气氛下600度还原,得到催化剂D2。图3给出了对比例2催化剂的XRD图谱,图中下部为方石英、金属镍分别对应的XRD标准PDF卡片峰位。图谱中的XRD衍射峰对应方石英和金属镍的晶相。方石英在催化剂中重量含量为94%,活性金属重量含量为6%。
该催化剂的抗压强度与其对甲烷与CO2反应的催化性能列于表1。该催化剂反应活性下降较快,催化稳定性较差(见表1)。这说明,以方石英载体直接制得的催化剂的稳定性不好,可能原因是用该方法制得的催化剂,其金属活性中心不能被载体所稳定。
表1本发明材料与对比样的抗压强度与其催化性能
【实施例9】
本实施例为应用实施例。将本发明的实施例1所制备的催化剂用于其它甲烷转化制合成气反应技术中(甲烷水蒸气重整制合成气、甲烷部分氧化制合成气、双重整、三重整反应等)。
表2本发明材料在甲烷转化反应中的催化性能
Claims (10)
1.一种制合成气催化剂,其特征在于,催化剂以方石英和/或鳞石英作为载体,方石英和/或鳞石英在催化剂中重量含量为25%~99.8%,活性金属及其氧化物在催化剂中重量含量为0.2%~40%。
2.根据权利要求1所述催化剂,其特征在于,所述催化剂的XRD图谱,在2θ角为20.77°,21.94°,26.05°,27.61°,28.46°,31.41°,36.13°,42.60°,44.53°,48.58°,51.87°,54.14°,57.16°,60.26°,62.13°,64.97°,76.31°处具有方石英和/或鳞石英的特征衍射峰。
3.根据权利要求1所述催化剂,其特征在于,所述催化剂径向抗压强度为50N/cm以上,优选为60~250N/cm。
4.根据权利要求1所述催化剂,其特征在于,所述活性金属包含Pt、Pd、Rh、Ru、Ni、Co、Fe、Zn、Cu、Mn、W以及Mo活性金属中的一种或多种。
5.一种权利要求1-4任一项所述制合成气催化剂的制备方法,其特征在于,包括以下步骤:
(1)在负载有活性金属的无定形氧化硅基粉体中加入结构助剂、粘合剂、造孔剂、助挤剂、碱或盐溶液,经过混捏,成型得催化剂前体;
(2)将步骤(1)的催化剂前体经过静置养生和烘干后,进行转晶处理,将催化剂中氧化硅载体转晶为方石英和/或鳞石英载体。
6.根据权利要求5所述的制备方法,其特征在于,步骤(1)中各物质的投料量,按重量份计,无定形氧化硅基粉体100份,结构助剂0.05~40份,粘合剂0.05~50份,造孔剂0.5~20份、助挤剂0.05~5份、碱或盐溶液0.05~200份。
7.根据权利要求5或6所述的制备方法,其特征在于,步骤(1)中所述结构助剂选自碳化硅粉体和钾霞石粉体中的一种或两种。
8.根据权利要求5或6所述的制备方法,其特征在于,步骤(1)中所述结构助剂为5~30份。
9.根据权利要求5或6所述的制备方法,其特征在于,步骤(2)中所述的转晶处理过程为:将成型烘干后的催化剂经过550~1200℃,优选650~1000℃,更优选700~850℃,焙烧处理1~12h;或者将催化剂在制合成气的反应气氛下550~1200℃,优选650~1000℃,更优选700~900℃下反应12~72h;或者是两者的结合。
10.一种权利要求1-4所述催化剂或者是权利要求5-9所述制备方法所制备的催化剂在甲烷制合成气反应中的应用。
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