CN108883401A - 硫化铅作为烷烃脱氢催化剂 - Google Patents
硫化铅作为烷烃脱氢催化剂 Download PDFInfo
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- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 23
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- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 9
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
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- 206010037660 Pyrexia Diseases 0.000 description 1
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- 229940056932 lead sulfide Drugs 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
用于将烷烃脱氢成烯烃的催化剂包括负载在载体上作为催化活性材料的硫化铅(II)(PbS)。脱氢在500至650℃的温度和低于环境压力0.5巴至高于环境压力5巴的压力下进行。
Description
本发明涉及使用硫化铅作为在将烷烃脱氢成相应烯烃的方法中的催化剂。
基本上,低级烷烃的催化脱氢是一种简单但重要的反应,其可以通过根据以下反应将丙烷脱氢成丙烯来说明:
C3H8<->C3H6+H2
随着对轻质烯烃,即具有碳-碳双键的低级脂族开链烃的不断增长的需求,催化脱氢的重要性日益增加。特别是丙烷和异丁烷的脱氢是商业上用于分别生产丙烯和异丁烯的重要反应。丙烯是塑料和树脂的重要基础化学结构单元,全球对丙烯的需求几十年来一直在稳步增长。预计丙烯的需求增长将很快等于或甚至高于对乙烯的需求增长。异丁烯的主要应用之一是作为甲基叔丁基醚(MTBE)制造中的原料。
上面所示的方法是吸热的并且需要约125kJ/mol的反应热。因此,为了实现合理的转化率,脱氢过程在约600℃的温度下进行。除了需要稍低的温度之外,异丁烷的脱氢在各方面都与丙烷的脱氢相似。
使用3种不同的催化剂,存在3至4种用于烷烃脱氢的商业方法。这些方法之间的差异主要涉及反应热的供应。下面将简要描述这些方法和催化剂。
a)Catofin(Houdry)法
该方法的特征在于通过预热催化剂提供反应热。Catofin法在3至8个固定床绝热反应器中进行,使用含有约20wt%氧化铬的氧化铬/氧化铝催化剂。催化剂可以补充有具有高热容的惰性材料,或者可备选地用选择性燃烧或与形成的氢反应的材料,即所谓的发热材料(HGM)。可以添加助催化剂如钾。
Catofin法是非常成熟的方法,仍然是主要的工业脱氢方法。由于反应热由催化剂提供,因此使用顺序操作,在此期间催化剂床用于脱氢。然后吹扫掉气体,将催化剂再生/加热,用氢气还原氧化铬(VI)。最后,在另一次脱氢之前用蒸汽吹扫床。
b)Snamprogetti-Yarzintez法
该方法是上述方法的流化床形式,使用双流化床,每个流化床负责处理和再生,催化剂在它们之间循环。许多车间正在运作中,例如在前苏联和沙特阿拉伯。
催化剂失活可能是由于机械原因、在加热-冷却循环期间引起的应力和固态反应,例如铬扩散到氧化铝晶格中。然而,这与除去铬的需要相比是次要的,除去铬是该方法中的真正挑战,因为铬的毒性是一个问题。更具体地,催化剂中铬的存在使因对环境和健康有害而被处理。这特别是这种情况,因为氧化铬(VI)、CrO3和氧化态VI的相关铬的化合物易于通过催化剂的氧化形成。因此,在制造、运输、装载和卸载过程中对催化剂的各种处理都是潜在的危害,并且随着对脱氢方法的需求的增加,期望找到有效的、毒性较小的脱氢催化剂。
c)Oleflex法
Oleflex法在3至4个移动床反应器的反应系统中使用贵金属催化剂,尤其是促进的Pt/Al2O3催化剂,催化剂在单独的再生回路中连续再生。通过预热烃流来提供反应热。贵金属催化剂经历缓慢失活。因此,在Oleflex法中,催化剂在径向流动床中向下移动。在底部,催化剂被输送到再生反应器,其中催化剂上的碳被烧掉,并且铂通过氯处理再次分散。将再生的催化剂再循环回到脱氢反应器的顶部。循环时间长达一周。
贵金属负载在氧化铝载体上,并通过锡和可能的其它助催化剂稳定。从技术角度来看,铂是一种很好的催化剂选择,并且它与锡形成稳定的合金。这种催化剂的主要问题是高价格,目前通过旨在降低铂负载来抵消。
d)STAR法
法(STAR是蒸汽辅助重整的首字母缩写)是一种商业化的既有脱氢技术,其具有一些吸引人的特性。
蒸汽用作稀释剂,并且该方法在管式反应器中进行,例如放置在炉中的蒸汽重整器。通过用天然气燃烧来提供反应热。催化剂是负载在ZnAl2O4尖晶石上的铂。锌和铂形成一些非常稳定的合金。发生一些碳沉积,并且催化剂必须每8个小时再生一次。有时在第二反应器中看到该过程,其中进行选择性氢气燃烧连同进一步脱氢。据推测,这里也使用贵金属催化剂。
与上述Oleflex法一样,这里的挑战是贵金属成本。因此,期望用碱金属,即普通且廉价的金属代替贵金属。
现在已经发现,使用新一代金属硫化物催化剂的特定成员可以使烷烃脱氢,这些金属硫化物催化剂易于制造并且在操作期间保持在其活性相中。所讨论的特定金属硫化物是硫化铅(II)(PbS)。
因此,本发明涉及用于将烷烃脱氢成烯烃的催化剂,所述催化剂包含负载在载体上的催化活性材料,其中催化活性材料是硫化铅(II)(PbS),并且其中催化剂在几个步骤中再生。
再生步骤包括(a)在稀释空气中氧化,(b)转化成相应的硫酸盐和(c)通过在含有一些硫化氢的稀释氢气中还原而转化回到硫化物。步骤(a)中的氧化优选在350至750℃的温度下进行,最优选为在400至600℃的温度下进行。
此外,本发明涉及烷烃脱氢成相应的不饱和烯烃和氢气(H2)的方法,包括使烷烃与负载在载体上的催化剂接触,所述催化剂包含硫化铅(II)(PbS)。脱氢优选在500至650℃的温度下进行,最优选为在520至620℃的温度下进行。
脱氢在低于环境压力0.5巴至高于环境压力5巴的压力下进行,优选地在环境压力下或在低于环境压力0.5巴的压力至环境压力下进行。
在该过程中,进料气体含有硫,其量确定为使得平衡反应PbS+H2<->Pb+H2S在整个反应器中向PbS移动。这意味着反应器中必须始终存在足够的H2S以确保PbS的存在。该反应的热力学数据可以在HSC Chemistry for Windows,Outo-kompi,Finland(2002)中获悉。
硫化铅是指含有铅和硫的两种化合物,即含有+2氧化态的铅的硫化铅(II)(PbS)、称为方铅矿的天然存在的矿物,以及含有+4氧化态的铅的硫化铅(IV)(PbS2)。本发明具体地涉及包含PbS的脱氢催化剂。
迄今为止,使用硫化铅作为催化剂非常稀少。然而,早在1930年,镍、镉和铅硫化物就被用作硝基苯气相还原的催化剂(O.W.Brown和R.J.Hartmen,J.Phys.Chem.34,2651-2665(1930)),特别是硫化铅被发现是用于该目的的有效的催化剂。
EP 0 568 303 A2公开了一种用于将有机化合物(例如,烷烃)脱氢成烯烃的催化剂,其包含在碱处理的非酸性载体上的镍和铅的硫化物组合。将硫加入到进料流中以保持催化剂选择性,但没有公开该加入使平衡向金属硫化物移动。
US 2.768.931描述了在称为BenderTM方法的油脱硫方法中使用硫化铅催化剂,其中待脱硫的油在与合适的试剂混合后通过包含负载在惰性载体上的硫化铅(II)的催化剂床。随后,可以如US 3.117.937中所述再生所用的硫化铅催化剂。用于油脱硫方法中的硫化铅(II)催化剂进一步公开于US 3.247.089和US 3.720.627中。这些美国专利都没有将催化剂描述为可用作脱氢催化剂。
除了这些古老的现有技术文献之外,在文献中似乎没有提及使用硫化铅作为催化剂。这可能是由于可以给出不使用铅催化剂的许多环境原因的事实。
从许多现有技术文献中已知广义上使用金属硫化物,即其中金属主要选自Zn、Cu、Mn、Mo、Fe、Co和Ni中,以使异丁烷脱氢成异丁烯。例如,在GB 488.651(1938)和US3.280.210(1966)中描述了使用金属硫化物催化剂由烷烃制备烯烃的方法。最近,GuoweiWang、Chunyi Li和Honghong Shan的一篇文章(ACS Catal.4(4),1139-1143,2014)和许多未决的中国专利申请(CN 104607168 A、CN 104069778 A、CN 104607168 A和CN 103861619A)涉及烷烃脱氢成烯烃和用于该目的的催化剂。
附图显示了使用含有14wt%的作为PbS的Pb(原子量207.2)的催化剂的丙烷脱氢。废催化剂显示出一些非常大的PbS晶体(约)。因此,在表面基础上,PbS可能确实非常活泼。
图中所示的运行显示出130Nl丙烯/千克催化剂/小时的活性和1.6eV的活化能。
使用铅催化剂的重复测试进一步显示出再生后如非常缓慢的再活化的特征,如图中所示。PbSO4是现有最稳定的硫酸盐之一,可能会经历硫酸盐缓慢还原成硫化物。其它非常稳定的硫酸盐是ZnSO4和SnSO4。
在脱氢方法中,例如Oleflex法,通常的做法是在方法中加入大量的硫以保护材料。因此,在基本上标准的设备中,将使用对应于气相中的H2S浓度为20至100ppm的二甲基二硫化物的量。
根据本发明使用的硫化铅催化剂的性质可总结如下:它的熔点为1118℃,且在600℃下的Kp(H2/H2S)值为247。
在下面的实施例中进一步例示本发明。
催化剂测试在专门建立用于高温应用的管式反应器中进行,例如焦油重整,因此它适用于需要含硫化物的气体的测试。反应器的长度为约100cm,内径为10mm。将待测试的催化剂放置在与可移动热电偶连接的栅格上,该热电偶测量入口温度。四个独立的加热区确保等温控制。使用10%丙烷的氮气混合物进行测试,可以向其中加入氢气、氮气和H2S。典型的H2S浓度可以在50ppm直至0.5%之间变化,尽管由于壁效应,低值与一些不确定性相关。这意味着H2S/H2比可以在10-3至10-1之间变化。
典型的测试条件是560至600℃的温度,使用5g的2至5mm的粒级的待测试的催化剂。一些测试气体列于下表中。理想情况下,压力应该很低,但是由于系统中的压降事件,典型的压力在0.2至0.3MPa。测试循环通常以600℃的气体1结束,并且活性的评估将基于他们在这种情况下的性能。
测试气体组成*
气体编号 | 流量 | C3H8% | H2% | H2S% | N2% | H2/H2S i | H2/H2S o |
1 | 55 | 9.1 | 8.7 | 0.36 | bal. | 24 | 29 |
2 | 51 | 9.8 | 1.8 | 0.20 | bal. | 9 | 19 |
3 | 25.5 | 9.8 | 1.8 | 0.20 | bal. | 9 | 19 |
4 | 25.5 | 9.8 | - | 0.004 | bal. | 0 | 500 |
5 | 55 | 9.1 | 8.2 | 0.9 | bal. | 9 | 11 |
6 | 55 | 9.1 | 5.5 | 0.008 | bal. | 0 | 500 |
7 | 51 | 9.8 | - | 0.004 | bal. | 0 | 1000 |
*)流量为Nl/h;bal.是余量;I=入口;o=出口
通过气相色谱测量废气。
用空的反应器和5g的催化剂载体进行的盲测给出了相同的令人惊讶的结果,即CH4、C2H4的形成几乎单独地由于空的反应器,并且还发生了一些脱氢,最可能发生在反应器壁上。对于560至600℃的典型测试条件,丙烯的量以碳为基础对应于C1和C2的量。由反应器中的空白空间引起的解离计算与实验结果非常一致。值得注意的是,这些在高温下发生的均相反应很可能是工业反应的选择性降低的原因,特别是Oleflex法,其中在进入脱氢反应器之前将气体预热至650℃四次。催化反应具有高选择性;实际上,当针对空的反应器贡献校正结果时,实现接近100%的选择性。在催化剂存在下,乙烷的形成是显著的。然而,与形成平衡量时应该存在的量相比,乙烯的氢化远未完全,表明乙烯是来自均相丙烷解离的主要产物。
第一次测试是使用具有由相同材料制成的热电偶套管的反应器完成的。它们表现出严重的硫化物腐蚀。因此,对另一个反应器和热电偶套管进行改变。该反应器的内径为15mm,而前者的直径为10mm。这使得C1和C2的量增加了50%。
报告的结果已通过假设空反应器中的选择性为50%而得到校正。因此,在碳基础上,C1和C2中的碳等于空反应器形成的丙烯。已经针对该贡献校正了催化剂的速率。
实施例1
将15g的Pb(NO3)2溶于37.5g的水中。该溶液用于浸渍50g的载体(pv=1ml/g)。将样品滚动1小时,在100℃下干燥过夜,并在500℃下煅烧2小时(4小时升温)。
然后,将样品在100ml的2%K2CO3溶液中洗涤1小时(滚动板)。然后,用200ml的水(每次1小时,滚动板)洗涤样品两次。将样品过滤并在100℃下干燥过夜。催化剂含有14wt%的Pb和0.8wt%的K。
实施例2
将20g的Pb(CH3COO)2·3H2O溶于37.5g的水中。该溶液用于浸渍50g的载体(pv=1ml/g)。将样品滚动1小时,在100℃下干燥过夜,并在500℃下煅烧2小时(4小时升温)。
然后,将样品在100ml的2%K2CO3溶液中洗涤1小时(滚动板)。然后,用200ml的水(每次1小时,滚动板)洗涤样品两次。将样品过滤并在100℃下干燥过夜。催化剂含有18wt%的Pb和0.8wt%的K。
实施例3
将15g的Pb(NO3)2和1.5g的KNO3溶于37.5g的水中。该溶液用于浸渍50g的载体(pv=1ml/g)。将样品滚动1小时,在100℃下干燥过夜,并在500℃下煅烧2小时(4小时升温)。催化剂含有14wt%的Pb和1wt%的K。
实施例4
将20g的Pb(CH3COO)2·3H2O和1.6g的KNO3溶于37.5g的水中。该溶液用于浸渍50g的载体(pv=1ml/g)。将样品滚动1小时,在100℃下干燥过夜,并在500℃下煅烧2小时(4小时升温)。催化剂含有18wt%的Pb和1wt%的K。
实施例5
将5.0g的实施例1中制备的催化剂置于活塞流管式不锈钢反应器(长度为1.0m,内径为15mm)中。将催化剂置于反应器的中间并支撑在格栅上。在催化剂床的顶部和底部放置热电偶。
通过压力传感器记录入口和出口压力。在催化测试之前,进行盲测,并从后面的催化测试中减去盲测的结果。盲测通常显示在560℃下为4%的转化率,在600℃下为12%的转化率,两者对丙烯的选择性均为50%。
最初,将催化剂还原并在由50Nl/h的N2、4.5Nl/h的H2和0.5Nl/h的H2S组成的气体中硫化,在60分钟时间内,在该气体中从室温加热至600℃的反应温度。
在600℃下,在含有45Nl/h的N2、5Nl/h的C3H8、1.8Nl/h的H2和0.2Nl/h的H2S的气体中测试催化剂。其显示对应于40Nl/h的丙烯/千克催化剂/小时的0.2Nl/h的丙烯的形成(在减去反应器贡献之后)。减去反应器贡献显示在实验误差内为100%的选择性。实验在0.26MPa的压力下进行,并在反应10小时后记录测量结果。
实施例6
反应40小时后,在含有49.5Nl/h的N2和0.5Nl/h的O2的气体存在下,将催化剂在560℃下进行再生6小时。然后,将其还原并在含有50Nl/h的N2、9Nl/h的H2和1Nl/h的H2S的气体中硫化2小时。然后,在560℃下,在含有45Nl/h的N2、5Nl/h的丙烷、0.9Nl/h的H2和0.1Nl/h的H2S的气体中将其测试20小时。以约100%的选择性,对应于124Nl/h的丙烯/千克催化剂/小时,发现0.21Nl/h的丙烯的形成(在减去反应器贡献之后)。压力为0.22MPa。
使用相同的反应混合物将温度升至600℃。在总共85小时的反应时间之后,发现丙烯的形成(在减去反应器贡献之后)为0.62Nl/h,对应于124Nl/h的丙烯/千克催化剂/小时。压力为0.22MPa。
在含丙烷的气体中超过连续50小时后再生催化剂。记录了CO2的量,并得出结论,少于1%的转化丙烷最终作为催化剂和反应器壁上的碳。
将催化剂还原并硫化,然后使用与上述相同的条件在600℃下再次测试。它仍然显示相同的性能。
在氮气中冷却后,通过X射线粉末衍射分析催化剂。除载体材料外,仅观察到PbS。它的平均微晶尺寸为64nm。
本发明的催化剂通过碳沉积缓慢失活,因此需要再生,就像市售的基于铂或氧化铬的催化剂一样。通过在560至600℃下,在稀空气即1%的O2和99%的N2中燃烧进行再生。
使用含有1%的O2的N2再生大多数金属硫化物将导致形成相应的硫酸盐。为了在催化剂上保存硫,再生应从400℃开始,然后在600℃下除去碳。
再生使催化剂通过两个相转变阶段,从硫化物到硫酸盐或氧化物,并再返回到硫化物。相变不仅涉及结构转变,还涉及体积变化。预计在多次再生之后系统的烧结/分散将达到稳定状态。
在脱氢过程中,一些碳沉积在催化剂上,导致缓慢的失活。脱氢发生数小时,然后在含有1%的O2的N2中进行催化剂再生。这通常接着进行硫化或直接返回到脱氢。在这种情况下,发生硫酸盐和丙烷之间的直接反应,导致大量的CO2形成。
用稀碱化合物处理载体,随后洗涤以除去酸性位点。优选地,稀碱化合物是碳酸钾或任何其它钾化合物。
在实验中,将载体浸入稀碳酸钾溶液中,然后在脱矿质水中进行两步洗涤,得到0.15wt%的钾含量。酸性位点已被去除,但不一定全部被去除。结果表明压力对碳形成的影响,并且它们还表明碳的形成是从丙烯而不是丙烷发生的。此外,结果表明在再生期间存在完全的碳去除。
Claims (10)
1.一种用于将烷烃脱氢成烯烃的催化剂,所述催化剂包含负载在载体上的催化活性材料,其中催化活性材料是硫化铅(II)(PbS),并且其中催化剂在几个步骤中再生。
2.根据权利要求1所述的催化剂,其中所述再生步骤包括(a)在稀释空气中氧化,(b)转化成相应的硫酸盐和(c)通过在含有一些硫化氢的稀释氢气中还原而转化回硫化物。
3.根据权利要求2所述的催化剂,其中所述步骤(a)中的氧化在350至750℃的温度下进行,优选为在400至600℃的温度下进行。
4.根据权利要求1至3中任一项所述的催化剂,其中用稀碱化合物处理所述载体,随后洗涤以除去酸性位点。
5.根据权利要求4所述的催化剂,其中所述稀碱化合物是碳酸钾或任何其它钾化合物。
6.一种用于将烷烃脱氢成相应的不饱和烯烃和氢气(H2)的方法,包括使所述烷烃与负载在载体上的根据权利要求1至5中任一项所述的催化剂接触,所述催化剂包含硫化铅(II)(PbS)。
7.根据权利要求6所述的方法,其中所述脱氢在500至650℃的温度下进行,优选为在520至620℃的温度下进行。
8.根据权利要求6或7所述的方法,其中所述脱氢在低于环境压力0.5巴至高于环境压力5巴的压力下进行。
9.根据权利要求8所述的方法,其中所述脱氢在环境压力下或在低于环境压力0.5巴的压力至环境压力下进行。
10.根据权利要求6至9中任一项所述的方法,其中所述进料气体含有硫,其量确定为使得平衡反应PbS+H2<->Pb+H2S在整个反应器中向PbS移动。
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PCT/EP2017/055289 WO2017162431A1 (en) | 2016-03-22 | 2017-03-07 | Lead sulfide as alkane dehydrogenation catalyst |
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US (1) | US20190047921A1 (zh) |
EP (1) | EP3433012B1 (zh) |
KR (1) | KR20180126512A (zh) |
CN (1) | CN108883401A (zh) |
CA (1) | CA3015144A1 (zh) |
ES (1) | ES2822343T3 (zh) |
PL (1) | PL3433012T3 (zh) |
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WO (1) | WO2017162431A1 (zh) |
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US4172853A (en) * | 1973-12-06 | 1979-10-30 | Uop Inc. | Hydrocarbon dehydrogenation with a multimetallic catalytic composite |
EP0568303A2 (en) * | 1992-04-27 | 1993-11-03 | SUN COMPANY, INC. (R&M) | Process and catalyst for dehydrogenation of organic compounds |
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GB488651A (en) | 1936-12-07 | 1938-07-07 | Ig Farbenindustrie Ag | Improvements in or relating to the production of hydrocarbon products of low boilingpoint by the treatment of carbonaceous materials of elevated temperatures |
US2315107A (en) * | 1941-04-29 | 1943-03-30 | Shell Dev | Catalytic dehydrogenation |
US2768931A (en) * | 1954-07-19 | 1956-10-30 | Sinclair Refining Co | In a lead sulfide sweetening process adding dissolved lead oxide to maintain activity of lead sulfide |
US3247089A (en) | 1962-09-05 | 1966-04-19 | Petrolite Corp | Process of sweetening distillates |
US3280210A (en) | 1964-09-08 | 1966-10-18 | Phillips Petroleum Co | Dehydrogenation of paraffins using molybdenum sulfide-alumina catalyst |
US3755480A (en) * | 1969-10-20 | 1973-08-28 | Universal Oil Prod Co | Dehydrogenation with a platinumlead catalytic composite |
US3720627A (en) | 1971-04-15 | 1973-03-13 | Petrolite Corp | Ready-to-use lead sulfide catalyst |
RU2154031C1 (ru) * | 1999-02-15 | 2000-08-10 | Открытое акционерное общество "Органический синтез" | Способ извлечения серебра из сточных вод и отработанных технологических растворов |
RU2488439C1 (ru) * | 2012-04-10 | 2013-07-27 | Леонид Асхатович Мазитов | Способ получения композиционного сорбента на основе сульфида свинца |
CN103861619A (zh) | 2012-12-11 | 2014-06-18 | 江苏省海洋石化股份有限公司 | 一种烷烃脱氢硫化物催化剂及烷烃脱氢的方法 |
CN104069778B (zh) | 2013-03-27 | 2016-08-31 | 中国石油天然气集团公司 | 一种在线硫化烷烃脱氢制烯烃的流化床反应装置和方法 |
CN104607168B (zh) | 2015-01-05 | 2017-11-28 | 中国石油大学(华东) | 一种用于烷烃催化脱氢的催化剂及其制备方法 |
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2017
- 2017-03-07 CA CA3015144A patent/CA3015144A1/en not_active Abandoned
- 2017-03-07 KR KR1020187029388A patent/KR20180126512A/ko not_active Application Discontinuation
- 2017-03-07 PL PL17709424T patent/PL3433012T3/pl unknown
- 2017-03-07 EP EP17709424.0A patent/EP3433012B1/en active Active
- 2017-03-07 CN CN201780018451.XA patent/CN108883401A/zh active Pending
- 2017-03-07 ES ES17709424T patent/ES2822343T3/es active Active
- 2017-03-07 WO PCT/EP2017/055289 patent/WO2017162431A1/en active Application Filing
- 2017-03-07 US US16/079,445 patent/US20190047921A1/en not_active Abandoned
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Patent Citations (3)
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US3117937A (en) * | 1960-02-25 | 1964-01-14 | Petrolite Corp | Production and regeneration of lead sulfide catalyst |
US4172853A (en) * | 1973-12-06 | 1979-10-30 | Uop Inc. | Hydrocarbon dehydrogenation with a multimetallic catalytic composite |
EP0568303A2 (en) * | 1992-04-27 | 1993-11-03 | SUN COMPANY, INC. (R&M) | Process and catalyst for dehydrogenation of organic compounds |
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KR20180126512A (ko) | 2018-11-27 |
CA3015144A1 (en) | 2017-09-28 |
US20190047921A1 (en) | 2019-02-14 |
PL3433012T3 (pl) | 2021-01-11 |
WO2017162431A1 (en) | 2017-09-28 |
EP3433012B1 (en) | 2020-08-05 |
ES2822343T3 (es) | 2021-04-30 |
RU2018136790A3 (zh) | 2020-05-21 |
EP3433012A1 (en) | 2019-01-30 |
RU2018136790A (ru) | 2020-04-22 |
RU2738935C2 (ru) | 2020-12-18 |
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