CN115279492B - 由烷烃族气体制备烯烃的脱氢催化剂及其制备方法 - Google Patents
由烷烃族气体制备烯烃的脱氢催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 160
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000006356 dehydrogenation reaction Methods 0.000 title description 24
- 150000001335 aliphatic alkanes Chemical class 0.000 title description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 54
- 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 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 22
- 239000010941 cobalt Substances 0.000 claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 description 4
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- 239000012298 atmosphere Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
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- HCQUEFDOQAHXLH-UHFFFAOYSA-N cobalt platinum zinc Chemical compound [Co][Zn][Pt] HCQUEFDOQAHXLH-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 3
- 229910003446 platinum oxide Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- GUBSQCSIIDQXLB-UHFFFAOYSA-N cobalt platinum Chemical compound [Co].[Pt].[Pt].[Pt] GUBSQCSIIDQXLB-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- SKJKDBIPDZJBPK-UHFFFAOYSA-N platinum zinc Chemical compound [Zn].[Pt] SKJKDBIPDZJBPK-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910020707 Co—Pt Inorganic materials 0.000 description 1
- 229910019923 CrOx Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- BFACTPHLVMSVAB-UHFFFAOYSA-N [Co][Zn]O[Pt] Chemical compound [Co][Zn]O[Pt] BFACTPHLVMSVAB-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 230000008025 crystallization Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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Abstract
本发明提供一种用于制备烯烃的催化剂及其制备方法,其环保且转换率及选择性优异。根据本发明,用于制备烯烃的催化剂是氧化铝浸泡钴和锌制成。特别是,根据本发明,催化剂相较于传统催化剂,铂的用量降至1/400左右,无需进一步实施氢还原工艺,在可连续反应‑再生条件下,具有高转换率及选择性。
Description
技术领域
本发明涉及一种制备烯烃的催化剂及其制备方法,其由乙烷、丙烷、丁烷等烷烃族气体制备烯烃,相较于传统技术,选择性和转换率得到了提升。
背景技术
乙烯、丙烯等烯烃正在广泛应用于石化工业。通常,这种烯烃从石脑油的热分解工艺中制得。但,石化工业需要更多烯烃,因此,通过利用催化剂的低级烃脱氢工艺也可以生产出烯烃。
现有丙烷脱氢(PDH,Propane dehydrogenation)常用工艺中,具有代表性的有固定床反应器及移动床反应器。
与此相反,利用高速流化床(以下,流化床)反应器的PDH技术(FPDH,Fast-fluidized Propane dehydrogenation)至今仍然未能实现商业化。
所述固定床反应器和流化床反应器的最大区别在于,催化剂和反应物(丙烷)的相遇时间。即,流化床反应器实施以下工艺:以极快的速度,将丙烷和催化剂一同注入到流化床反应器,使其发生反应,然后,使催化剂进入再生部,使生成物进入分离部。
以往开发的FPDH工艺要达到的目标为:使催化剂的停留时间(Residence time)在10秒以内。催化剂的停留时间短时,与其相应地,丙烷输送量的注入速度也快,可立即再生催化剂,重新参与到反应中,因此,当开发成商业化工艺时,相较于固定床工艺,丙烯产量极其增多。
但,与其相应地,催化剂和丙烷的相遇时间短,因此,催化剂的效率变得极其重要。即,选择性和转换率作为恒量催化剂效率的两个标准,分别达到最高很重要。
进一步,当前应用的丙烷脱氢工艺技术是基于贵金属催化剂或间断性工艺创建,由于贵金属催化剂过度活跃(焦炭生成)出现反应器堵塞现象或者固定床反应器阀顺序(Sequence)起冲突等,使丙烯的生产运营存在难度。
并且,丙烷脱氢反应由于可逆反应,在热力学方面限制丙烷转换率。为了解决这种问题,大部分工艺采用氧、卤素、硫化合物、二氧化碳、水蒸气等外部氧化剂,将氢转换成水。
因此,为了丙烯的有效批量生产,需要开发出解决上述连续工艺中存在的问题,无需使用氧化剂而直接使用脱氢催化剂,节省生产费用的新型丙烷脱氢工艺。
用于丙烷脱氢的催化剂中,贵金属催化剂通过活性点吸附氢的直接脱氢机制进行反应,但实际上,过渡金属氧化物由于电子移动性引起的活性点缺陷,始终未能切实查明其机制。
在这种情况下,通常最多用作PDH催化剂的催化剂有Pt-Sn、VOx、CrOx催化剂。虽然CrOx催化剂在丙烷的转换率和选择性方面极其优异,但,由于环境污染和有害于人体等问题以及反应初期难以控制氧化反应,其的使用受到限制。铂催化剂选择性优异,但,价格昂贵,焦炭生成速度极快,对其需要进行精细控制。并且,随着与助催化剂成分Sn以及其他金属之间的结合导致催化剂固有活性发生变化,以及Sn的环境有害性变强,铂催化剂也同样持续要求开发出新型多组分催化剂。
并且,传统的铂基脱氢催化剂工艺使用Pt-Sn系催化剂,据悉,约含0.4重量%(4,000ppm)铂。图1示出了在作为流化床循环工艺的FPDH条件下,对于浸泡相似量的Pt-Sn催化剂进行试验的结果。用空气再生之后,观察催化剂活性可知,初始转换率为100%,但,其反应进行至甲烷、一氧化碳、乙烷等副产物的生成。反应之前添加氢还原预处理工艺实施约1小时左右时,如果以适用于FPDH工艺的标准进行至约5秒,就显示出转换率为51%,丙烯选择性为87%。
另外,专利文献1及2揭示了Zn-Pt系催化剂相关技术,采用了过量铂,且还原工艺必不可少。
本发明人对其进行了长时间的研究,引进了包含极少量铂的新催化剂,从而开发出了相较于传统技术,催化剂的转换率和选择性均优异的用于制备烯烃的催化剂及其制备方法。
【先行技术文献】
【专利文献】
(专利文献1)日本注册专利第3908314号
(专利文献2)中国注册专利第105438568号
发明内容
所要解决的课题
本发明的目的在于,提供一种由乙烷、丙烷、丁烷等烷烃族气体制备烯烃且转换率和选择性优异的用于制备烯烃的催化剂及其制备方法。
课题解决方案
根据本发明,由烷烃族气体制备烯烃的催化剂是采用共沉淀法,用钴、锌及铂前驱体溶液浸泡氧化铝而成。
优选地,所述催化剂在700℃~900℃下进行焙烧。
优选地,所述钴的浸泡比为催化剂总重量的1~5重量%。
优选地,所述锌的浸泡比为催化剂总重量的2~10重量%。
优选地,所述铂的浸泡比为催化剂总重量的0.001~0.05重量%。
优选地,根据本发明,由烷烃族气体制备烯烃的催化剂的制备方法包括:
将钴、锌及铂前驱体与水混合,制备混合溶液的步骤;
用所述混合溶液浸渍氧化铝,制备浸泡催化剂的步骤;
对于所述浸泡催化剂进行烘干的步骤;以及
将所述烘干的浸泡催化剂在700℃~900℃进行焙烧的步骤。
优选地,根据本发明,由烷烃族气体制备烯烃的催化剂的又另一制备方法包括:
将钴及锌前驱体与水混合,制备混合溶液的步骤;
用所述混合溶液浸渍氧化铝,制备浸泡催化剂A的步骤;
制备铂前驱体溶液的步骤;
将所述浸泡催化剂A浸渍于铂前驱体溶液,制备浸泡催化剂B的步骤;
对于所述浸泡催化剂B进行烘干的步骤;以及
将所述烘干的浸泡催化剂B在700℃~900℃进行焙烧的步骤。
本发明在另一方面,提供一种连续反应-再生烯烃制备方法,其包括:根据本发明制成的由烷烃族气体制备烯烃的催化剂。
优选地,所述连续反应-再生烯烃制备方法中,反应温度为560~620℃。
优选地,所述连续反应-再生烯烃制备方法中,烷烃用作原料,其流量(WHSV)为4~16h-1。
发明效果
根据本发明的由乙烷、丙烷、丁烷等烷烃族气体制备烯烃的催化剂及其制备方法转换率及选择性优异,对于固定床反应器及流化床反应器均有效,特别是,可以实现传统技术未能实现商业化的FPDH工艺。特别是,根据本发明的催化剂相较于传统催化剂,铂的用量降至1/400左右,无需进一步实施氢还原工艺,在可连续反应-再生条件下,具有高转换率及选择性。
附图说明
图1大概示出了对于含0.42重量%铂的Pt-Sn催化剂是否实施一小时氢还原预处理,在流化床循环工艺的FPDH条件下显示出的不同试验结果。
图2大概示出了分别浸泡钴、锌、铂、钴-锌-铂的催化剂的转换率及选择性。
图3大概示出了分别浸泡钴-锌和钴-锌-铂的催化剂的转换率及选择性。
图4大概示出了改变Co-Zn催化剂中铂浸泡量的催化剂的转换率、选择性及产率。
图5大概示出了根据本发明两种制备方法制成的催化剂的转换率及选择性。
图6大概示出了基于4Co-8Zn-0.01Pt催化剂反应温度的转换率、选择性及产率。
图7大概示出了根据原料流量的4Co-8Zn-0.01Pt催化剂的转换率、选择性及产率。
图8大概示出了根据连续反应-再生再循环(Recycle)数量的催化剂的转换率、选择性及产率。
*附图标记*
具体实施方式
根据本发明,由烷烃族气体制备烯烃的催化剂是采用共沉淀法,用钴、锌及铂前驱体溶液浸泡氧化铝而成。
发明的实施形态
以下,参考附图描述本发明的优选实施形态。但,本发明的实施形态可以变形为各种不同形态,本发明的范围不受下述实施形态的限定。
描述本实施例时,对于形同构成应用相同的名称和符号,以下省略重复的附加说明。以下参考附图不适用缩尺比例。
根据本发明,由烷烃族气体制备烯烃的催化剂是采用共沉淀法,用钴、锌及铂前驱体溶液浸泡氧化铝而成。
优选地,所述氧化铝载体在脱氢反应温度以上的550~850℃制备温度下,具有γ~θ相,在该范围内,具有80~300m2/g表面积。
在低于脱氢反应温度的温度下制备所述载体时,如果进行脱氢反应,就会出现催化剂的热变形,在高于900℃的温度下进行制备时,由于载体的晶化,会具有小的催化剂表面积,因此,与反应物相遇时,会阻碍催化剂活性所需物质的传递。
常规脱氢催化剂所需活性金属有多种,但,作为FPDH工艺的特性,要想在数秒内的反应极早期获得高选择性,优选采用钴,进一步,要想保持钴基催化剂高选择性属性的同时,提高转换率,优选添加锌和铂。
如图2所示,在丙烷脱氢反应的TOS1-3秒内,铂对于转换率发挥了最大功效,钴催化剂显示出了最高选择性。因此,4Co-8Zn-0.01Pt催化剂系中,应该是首先进行了基于铂金属金属的丙烷转换,经预测,通过钴催化剂补救了由于铂催化剂中副反应导致丙烯具有低选择性的问题。进一步,通过锌的添加,可以实现更高的转换率和选择性。
并且,如图3所示,对于4Co-8Zn催化剂的活性与用添加0.01重量%铂的4Co-8Zn-0.01Pt浸泡而成的催化剂的活性进行对比时,三种组分均浸泡的催化剂的转换率为24%以上,增加了约2倍,而丙烯选择性则降低幅度甚微,为1%左右。
优选地,所述催化剂在700℃~900℃进行焙烧。根据焙烧温度,催化剂的催化剂相(phase)发生变化。由于在所述温度范围以外形成纳米大小的结晶相,主要引起氧化还原反应,不适宜采用脱氢催化剂。
优选地,所述钴的浸泡比为催化剂总重量的1~5重量%,催化剂量超出所述范围时,将脱离可以从商业化层面适用于FPDH的范围。并且,催化剂量大时,会形成结晶性氧化物,因此,采用脱氢催化剂会产生负面效应。进一步,超出所述范围增加催化剂量时,产率会显著降低。
优选地,所述锌的浸泡比为催化剂总重量的2~10重量%。越增大锌的用量,选择性不改变,但,转换率增加,并且,超出10重量%时,会减少转换率,因此,从商业化角度,优选适用所述范围。
优选地,所述铂的浸泡比为催化剂总重量的0.001~0.05重量%。
如图4所示,改变Co-Zn催化剂中铂的浸泡量时,如果将铂的用量增大至10~100ppm,急剧增大了丙烷转换率,而100ppm之后,转换率的上升呈现出缓慢增高的趋势。随着增加铂的用量,丙烯选择性则持续降低。
具体地,应该可以了解,随着增加铂的用量,丙烷转换率得到增加的同时,丙烯总产率也得到增加。但,越增加铂的用量,副反应也持续增加,主要副产物为甲烷和乙烷。这表示铂催化剂不仅在脱氢反应,还在氢解(Hydrogenolysis)反应液具有极高的活性,该氢解(Hydrogenolysis)反应使生成的氢与丙烷相遇形成甲烷和乙烷。
因此,考虑到基于铂引入量的转换率上升区间及选择性持续减少,应该可以了解,0.01重量%(100ppm)左右的铂与4Co-8Zn催化剂形成的催化剂最适合应用在快速循环流化床工艺。
另外,优选地,根据本发明,由烷烃族气体制备烯烃的催化剂的制备方法包括:
将钴、锌及铂前驱体与水混合,制备混合溶液的步骤;
用所述混合溶液浸渍氧化铝,制备浸泡催化剂的步骤;
对于所述浸泡催化剂进行烘干的步骤;以及
将所述烘干的浸泡催化剂在700℃~900℃进行焙烧的步骤。
优选地,根据本发明,由烷烃族气体制备烯烃的催化剂的又另一制备方法包括:
将钴及锌前驱体与水混合,制备混合溶液的步骤;
用所述混合溶液浸渍氧化铝,制备浸泡催化剂A的步骤;
制备铂前驱体溶液的步骤;
将所述浸泡催化剂A浸渍于铂前驱体溶液,制备浸泡催化剂B的步骤;对于所述浸泡催化剂B进行烘干的步骤;以及
将所述烘干的浸泡催化剂B在700℃~900℃进行焙烧的步骤。
传统催化剂采用结晶度高的溶胶凝胶法和沉淀法进行合成而成,其相较于脱氢反应,主要是通过氧化反应生成CO2,因此,不宜采用。与此相反,通过高纯氧化铝合成法EISA法制成的中型气孔催化剂,或者,在氧化铝固体浆料上实施沉淀法合成的催化剂可以妥当控制氧化铝载体散点,提高脱氢反应的选择性。
图5示出了根据上述两种本发明制备方法制成的催化剂的转换率和选择性。如图所示,4Co-8Zn+0.01Pt(Post)催化剂为制备钴-锌系催化剂之后,进一步浸泡铂的催化剂,4Co-8Zn-0.01Pt催化剂为共同采用钴-锌-铂制备水溶液前驱体之后,浸泡在氧化铝载体上制成的催化剂。后续添加铂的催化剂可以提升钴-锌系催化剂的活性,进一步实现铂的高活性,呈现出最优异的转换率,但,未能显著改善起初选择性。应当可以理解,其结果,同时浸泡三种金属前驱体时,将大幅改善选择性。
本发明在另一方面,提供一种连续反应-再生烯烃制备方法,其包括:根据本发明制成的由烷烃族气体制备烯烃的催化剂。更优选地,由丙烷制备丙烯。
优选地,所述连续反应-再生烯烃制备方法中,反应温度为560~620℃。
如图6所示,随着反应温度的增加,反应活性和产率也同时增加,但,甲烷和乙烷的生成量也得到增加,呈现出了选择性持续降低的趋势。因此,在610℃下,转换率为约49%,选择性为93%,认为其状态最适合于FPDH工艺。
优选地,所述连续反应-再生烯烃制备方法中,烷烃用作原料,其流量(WHSV)为4~16h-1。
如图7所示,随着流量(WHSV)从16h-1减至4h-1,与催化剂之间的相遇时间会增加,转换率线性增加。丙烯选择性线性减少至WSHV 8h-1,自从4h-1起,急剧减少,经预测,这是由于生成了铂基副产物甲烷及乙烷。
以下,通过制备例及实施例进一步具体描述本发明。
<制备例>
1、铂-氧化铝催化剂的制备(Pt/Alumina)
为了制备金属氧化物溶液,准备水,水的体积与氧化铝的气孔体积相同。将H2PtCl6·xH2O(氯铂酸)溶于备好的水中,制备铂氧化物溶液,该H2PtCl6·xH2O(氯铂酸)含有的铂与氧化铝的重量比值为10ppm~1000ppm(0.001~0.1重量%)。将制备的金属氧化物溶液添加到氧化铝,采用初湿含浸法(incipient wetness impregnation)进行浸渍,在50~75℃下烘干12小时,然后,以每分钟1℃的升温速度,在700℃~900℃焙烧温度下焙烧6小时,制备铂-氧化铝催化剂。
2、采用共沉淀法制备钴-锌-铂-氧化铝催化剂(Co-Pt/Alumina、Zn-Pt、Co-Zn-Pt/Alumina)
为了制备金属氧化物溶液,准备水,水的体积与氧化铝的气孔体积相同。共沉淀(co-impregnation)Co(NO3)2·6H2O(硝酸钴六水合物)、含有0~20重量%锌金属的Zn(NO3)2·6H2O(硝酸锌六水合物)以及含有0~100ppm(0~0.01重量%)铂的H 2PtCl6·xH2O(氯铂酸),制备钴-铂、锌-铂、钴-锌-铂氧化物溶剂,所述Co(NO3)2·6H2O(硝酸钴六水合物)含有与氧化铝的重量比值为0~10重量%的钴。
将所述制备的金属氧化物溶剂分别添加到氧化铝,采用初湿含浸法(incipientwetness impregnation)进行浸渍,在50~75℃下烘干12小时,然后,然后,以每分钟1℃的升温速度,在700℃~900℃焙烧温度下焙烧6小时,分别制备钴-锌(0重量%铂)、钴-铂(0重量%锌)、锌-铂(0重量%钴)、钴-锌-铂-氧化铝催化剂。
3、制备添加铂的钴-锌-氧化铝催化剂(Co-Zn/Alumina+Pt)
为了了解基于铂浸渍顺序的催化剂活性,与制备例2中制备采用的共沉淀法不同,钴-锌-氧化铝催化剂分别浸渍铂。首先,为了制备金属氧化物溶液,准备水,水的体积与氧化铝的气孔体积相同。将H2PtCl6·xH2O(氯铂酸)溶于水,制备铂氧化物溶液,该H2PtCl6·xH2O(氯铂酸)含有的铂与所述制备例2通过共沉淀法制备的钴-锌-氧化铝催化剂的重量比值为10~100ppm(0.001~0.01重量%)。
将制备的铂氧化物溶液添加到制备例2通过共沉淀法制备的钴-锌-氧化铝催化剂中,采用初湿含浸法(incipient wetness impregnation)进行浸渍,在50~75℃下烘干12小时,然后,以每分钟1℃的升温速度,在700℃~900℃焙烧温度下焙烧6小时,制备钴-锌-铂-氧化铝催化剂。
<连续反应再生试验方法(Recycle Test)及活性评测>
采用为连续反应再生设置的自动连续反应系统,将制备的催化剂注入到固定床(Fixed-bed)型式反应器中,然后,在作为惰性气体的氮气氛围中,以每分钟10℃的升温速度达到作为反应及再生温度的600℃。反应器的温度达到600℃之后,实施连续反应再生试验。将氮气以100mL/min的流量通入反应器,通入时间为5分钟,然后,以50mL/min的流量,还原为50%丙烷/50%氮气混合气体,还原时间为30秒。再次,将氮气通入反应器中,通入时间为5分钟,然后,在流量为100mL/min的空气氛围中,进行再生过程,再生时间为9分钟30秒。以此作为一次反应再生试验,实施1~1000次连续再生。
从连续反应再生器回收催化剂,向固定床(Fixed-bed)型式反应器注入0.4g制备的催化剂,然后,在作为惰性气体的氦气氛围中,以每分钟10℃的升温速度达到作为反应及再生温度的600℃。然后,以105mL/min的流量,还原为50%丙烷/50%氮气混合气体,还原时间为16秒。在流量为30mL/min的空气氛围中,进行再生过程。其次,利用氦气,清除反应器和催化剂上吸附的氧气,清除时间为20分钟,然后,以105mL/min流量,注入50%丙烷/氮气混合气体,16h-1的WHSV进行反应。每隔一秒,将反应产物收集到16通阀,通过气体色谱进行分析。
图1至图8大概示出了通过连续反应-再生工艺,对于所述制备的催化剂进行试验的结果。
特别是,如图8所示,根据连续反应-再生再循环(Recycle)数量观察催化剂的活性可知,直到再循环约200次,并没有观察到转换率和选择性出现了大的变化(转换率范围为46~47%,选择性范围为93~94%)。但,自从300次起,转换率降低3%左右,选择性提高至95%。然后,直到500次,保持了转换率和选择性。自从300次起进行了催化剂的去活化,但,经确认,转换率和选择性始终保持了其状态。
与传统催化剂相比,本发明的催化剂相较于传统催化剂,铂的添加量只有1/40,经确认,无需实施进一步的氢还原工艺,在可连续反应-再生的条件下,转换率为约48%,选择性为93%。
这表示反应工艺中,即使脱氢催化剂的金属成分相同,但,依据最佳组合催化剂的构成及浸泡量,其效果会不同。由此可知,FPDH工艺所需铂的用量远少于移动床型式工艺所需用量,也可以达到优异的效果。丙烯选择性也由于引入钴-锌系和极少量使用铂,得到了大幅提升。
以上内容详细描述了本发明的实施例,但,这种实施例仅用于举例说明,本发明的权利范围不受其限定,显而易见,本技术领域的技术人员在不脱离权利要求范围所述的本发明技术思想的范围内,可以进行多种修改和变形。
Claims (7)
1.一种高速流化床反应器中的连续反应-再生烯烃制备方法,其特征在于:采用共沉淀法,用钴、锌及铂前驱体溶液浸泡氧化铝而成;催化剂在700℃~900℃下进行焙烧;
所述锌的重量占催化剂总重量的2~10重量%;
反应温度为560~620℃,丙烷流量为4~16h-1。
2.根据权利要求1所述的高速流化床反应器中的连续反应-再生烯烃制备方法,其特征在于:所述钴的重量占催化剂总重量的1~5重量%。
3.根据权利要求1所述的高速流化床反应器中的连续反应-再生烯烃制备方法,其特征在于:所述铂的重量占催化剂总重量的0.01~0.05重量%。
4.一种高速流化床反应器中的连续反应-再生烯烃制备方法,其包括如下步骤来制备:
将钴、锌及铂前驱体与水混合,制备混合溶液的步骤;
用所述混合溶液浸渍氧化铝,制备浸泡催化剂的步骤;
对于所述浸泡催化剂进行烘干的步骤;以及
将所述烘干的浸泡催化剂在700℃~900℃进行焙烧的步骤;
所述锌的重量占催化剂总重量的2~10重量%;
反应温度为560~620℃,丙烷流量为4~16h-1。
5.一种高速流化床反应器中的连续反应-再生烯烃制备方法,其包括如下步骤来制备:
将钴及锌前驱体与水混合,制备混合溶液的步骤;
用所述混合溶液浸渍氧化铝,制备浸泡催化剂A的步骤;
制备铂前驱体溶液的步骤;
将所述浸泡催化剂A浸渍于铂前驱体溶液,制备浸泡催化剂B的步骤;
对于所述浸泡催化剂B进行烘干的步骤;以及
将所述烘干的浸泡催化剂B在700℃~900℃进行焙烧的步骤;
所述锌的重量占催化剂总重量的2~10重量%;
反应温度为560~620℃,丙烷流量为4~16h-1。
6.根据权利要求4或5所述的高速流化床反应器中的连续反应-再生烯烃制备方法,其特征在于:所述钴的重量占催化剂总重量的1~5重量%。
7.根据权利要求4或5所述的高速流化床反应器中的连续反应-再生烯烃制备方法,其特征在于:所述铂的重量占催化剂总重量的0.01~0.05重量%。
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