CN114100670B - 耐硫变换催化剂及其制备方法 - Google Patents

耐硫变换催化剂及其制备方法 Download PDF

Info

Publication number
CN114100670B
CN114100670B CN202010900141.4A CN202010900141A CN114100670B CN 114100670 B CN114100670 B CN 114100670B CN 202010900141 A CN202010900141 A CN 202010900141A CN 114100670 B CN114100670 B CN 114100670B
Authority
CN
China
Prior art keywords
catalyst
sulfur
tolerant shift
shift catalyst
zeolite
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.)
Active
Application number
CN202010900141.4A
Other languages
English (en)
Other versions
CN114100670A (zh
Inventor
白志敏
王民
王昊
余汉涛
赵庆鲁
姜建波
薛红霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
Original Assignee
China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Qilu Petrochemical Co of Sinopec filed Critical China Petroleum and Chemical Corp
Priority to CN202010900141.4A priority Critical patent/CN114100670B/zh
Publication of CN114100670A publication Critical patent/CN114100670A/zh
Application granted granted Critical
Publication of CN114100670B publication Critical patent/CN114100670B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B01J29/58—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/783—CHA-type, e.g. Chabazite, LZ-218
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

本发明涉及一种耐硫变换催化剂及其制备方法，属于耐硫变换催化剂技术领域。本发明所述的耐硫变换催化剂，包括载体和活性组分，载体成分包括氧化铝和天然沸石，活性组分为钴钼氧化物。本发明所述的耐硫变换催化剂，具有抑制甲烷化副反应的性能；本发明同时提供了简单易行的制备方法。

Description

耐硫变换催化剂及其制备方法
技术领域
本发明涉及一种耐硫变换催化剂及其制备方法，属于耐硫变换催化剂技术领域。
背景技术
CO变换技术及变换催化剂的应用已有近百年的历史，主要用于制氢、合成氨、合成甲醇、合成汽油以及城市煤气等生产中。由于原油的短缺与价格的上涨，煤及各种形式的渣油、石油焦等高含硫物质作为轻烃的替代原料也逐步引起人们的重视，而随着渣油、煤造气工艺的日臻完善，特别是新型加压气化技术的大规模工业应用，改变了合成氨及羰基合成气原料的格局，重质含硫原料(如煤及渣油等)在合成氨原料中所占的比例逐年上升，这些都进一步促进了耐硫变换催化剂的研究开发。
钴钼系耐硫宽温变换催化剂主要是为满足以重油、渣油、煤等重质原料制取原料气的需要，它比铁系高温变换催化剂起活温度低，与铜系低温变换催化剂相当，且其耐热性不低于铁铬系高温变换催化剂，具有很宽的活性温区，几乎覆盖了铁系高温变换催化剂和铜系低温变换催化剂整个活性温区。此外，其最突出的优点是耐硫和抗毒性能强，强度高、使用寿命长等。对于耐硫变换催化剂的载体和助剂研究很多，常用的载体组分主要有Mg、Al、Ti、Si、Ca、Zr等其中的一种或多种。已工业化应用最多的是氧化铝、氧化锆、镁铝尖晶石、镁铝钛复合载体等，常用的助剂主要有碱金属、碱土金属、Mn、Cu、稀土等。
随煤气化工艺发展，工艺气中有效气组成CO含量也越来越高。在高CO含量，低水气比工艺条件下，当催化剂床层温度高于350℃时，会出现甲烷化副反应，且随床层温度增加，甲烷化副反应逐步加剧，带来产氢量降低以及超温的危险。目前，耐硫变换工艺主要依靠调整工艺参数来减缓和抑制甲烷化副反应发生，但收效甚微，如控制床层温度、配水或蒸汽提高水气比等。
发明内容
本发明要解决的技术问题是，克服现有技术中的不足，提供一种耐硫变换催化剂，其具有抑制甲烷化副反应的性能；本发明同时提供了简单易行的制备方法。
本发明所述的耐硫变换催化剂，包括载体和活性组分，载体成分包括氧化铝和天然沸石，活性组分为钴钼氧化物。
优选的，载体包括以下质量百分含量的组分：天然沸石10～25wt.％，氧化铝60～80wt.％；
优选的，活性组分包括以下质量百分含量的组分：氧化钼6～12wt.％，氧化钴2.0～4.0wt.％，助剂氧化钙1.0～10.0wt.％；
均以催化剂的总质量为100％计量。
所述天然沸石为斜发沸石、丝光沸石、菱沸石或毛沸石，优选为斜发沸石。
所述天然沸石阳离子交换量≥150mmol/100g，沸石含量≥68％。
所述的耐硫变换催化剂的制备方法，包括以下步骤：
(1)将活性含铝化合物、天然沸石干粉以及碳酸钙混合研磨；
(2)向步骤(1)研磨得到的混合物中加入粘结剂和助挤剂，混合，挤条成型、干燥、焙烧，得到催化剂载体；
(3)用含活性组分的碱性复合络合溶液浸渍一段时间，将活性组份均匀负载在催化剂孔道内部，然后经过干燥、焙烧，得到催化剂。
所述粘结剂为醋酸、柠檬酸、草酸或硝酸中的一种或多种。进一步优选为柠檬酸。加入量为1～6％(m/m)，进一步优选为2～4％(m/m)。加入量以催化剂质量为基准。
所述助挤剂为田箐粉或淀粉。进一步优选为田菁粉。用量为1～4％(m/m)，优选为2～3％(m/m)。用量以催化剂质量为基准。
步骤(2)中，焙烧温度为400～600℃，优选为450℃；步骤(3)中，焙烧温度为400～600℃，优选为500℃。
步骤(3)中，含活性组分的碱性复合络合溶液的配制过程如下：
称取含钴金属元素化合物和含钼金属元素化合物，加入氨水及乙醇胺混合水溶液，加热使其溶解，得到含活性组分的碱性复合络合溶液，其温度为不低于60℃，优选为70-80℃，测得pH值大于10，优选为11-12。
制备得到的催化剂的比表面积为200m2/g～250m2/g，孔容不低于0.50mL/g，催化剂外观可为条形、三叶草、四叶草型和球形等。
沸石是一种架状构造的含水铝硅酸盐矿物，其化学组成十分复杂，因种类不同有很大差异，主要含Na和Ca及少数的Sr、Br、K、Mg等金属离子。目前已知的天然沸石有80多种，分布最广的有方沸石、斜发沸石、片沸石、浊沸石、交沸石、毛沸石、丝光沸石、钠沸石和斜钙沸石等。沸石的性能与沸石的结构和组成密切相关，沸石晶格中的阳离子可被其它金属离子置换，受沸石结构(与孔径大小、阳离子位置有关)、交换阳离子的性能以及交换条件的影响，使沸石的离子交换具有选择性。当沸石与气体混合物接触时，吸引强的组分被吸附，吸引力弱的仍留在气体中，从而使沸石具备吸附分离的作用。此外，比沸石孔径小的分子可进出，因此沸石还具备了选择性吸附功能。并且由于沸石的表面大部分是在晶穴的内表面，因此沸石的催化活性也具有选择性催化的特点。
本发明在耐硫变换催化剂氧化铝载体结构中引入天然沸石，在催化剂制备过程中，沸石中的阳离子可与活性组分溶液中的阳离子互相交换，易于活性组分的添加，且活性组分进入沸石晶格中，不但易于活性组分的负载，且不易流失，增加其活性稳定性；同时还在催化剂内孔形成较高密度阳离子活性位点，在水煤气变换反应过程中，载体中沸石结构可吸附容纳更多的水分子，由于水分子不是载体结构中固有的组分，而是被吸附在晶体的微孔中，在催化剂使用过程中可局部提高孔道内含水量，进而抑制内孔活性位上的甲烷化副反应；同时天然沸石的加入还可调整催化剂孔结构，使反应产生的热量快速传递，一定程度上降低了催化剂内部的热点温度，进一步抑制甲烷化连锁反应，确保催化剂结构更稳定，延长催化剂使用寿命。
与现有技术相比，本发明具有以下有益效果：
(1)本发明以氧化铝和天然沸石作为载体的主要结构，以钴钼氧化物为活性组分，添加适宜的碱性助剂，由此制得具有抑制甲烷化副反应性能的耐硫变换催化剂，可用于较低水气比和高CO原料气工艺中；
(2)在工业变换装置中，使用本发明所述的催化剂可以防止变换炉因为较低水气比发生甲烷化副反应而超温，进一步稳定变换温度，减少甲烷化副反应和氢气消耗，提高装置产氢率，具有良好的经济效益和环保效益。
附图说明
图1是加压评价装置流程示意图；
图中：1、原料气净化器；2、减压器；3、混合器；4、压力表；5、停工阀；6、加热炉；7、反应管；8、管内热偶管；9、冷凝器；10、分离器；11、排液器；12、湿式流量计；13、汽化器；14、水槽；15、水计量泵。
具体实施方式
下面结合实施例对本发明作进一步的说明，但其并不限制本发明的实施。
实施例1
称取7.8g硝酸钴和9.8g钼酸铵，加入40mL氨水及3mL乙二醇胺混合溶液，加热至70℃，测得pH值为12，得到透亮的溶液A。将3g柠檬酸和1mL稀硝酸加入去35mL去离子水中得到溶液B。
取沸石含量68％的20g天然沸石、64g活性氧化铝和10.7g碳酸钙混合研磨0.5h，加入4g田箐粉和2g淀粉混合均匀，加入溶液B捏合均匀，经成型、自然晾干，然后600℃焙烧3h，制得催化剂载体，倒入溶液A中，浸泡2h，100℃烘干后，500℃焙烧2h得到成品C1。
实施例2
称取11.7硝酸钴和7.4g钼酸铵，加入50mL氨水及2mL乙二醇胺，加热至80℃，测得pH值为11.5，得到透亮的溶液A。将3g柠檬酸和2mL草酸分别加入去40mL离子水中得到溶液B。
取沸石含量72％的10g天然沸石、114.3g拟薄水铝石和1.8g碳酸钙混合研磨1.5h，加入5g田箐粉混合均匀，加入溶液B，捏合均匀，经成型、自然晾干，然后550℃焙烧3h，制得催化剂载体，倒入溶液A中，浸泡4h，120℃烘干后，450℃焙烧3h得到成品C2。
实施例3
称取15.5g硝酸钴和12.3g钼酸铵，然后加入30mL氨水及1mL乙二醇胺，加热至75℃，测得pH值为13，得到透亮的溶液A。将3g草酸和2g柠檬酸分别加入去35mL去离子水中得到溶液B。
取沸石含量70％的14g天然沸石、70g活性氧化铝和3.6g碳酸钙混合研磨1h，加入4g田箐粉和4g淀粉混合均匀，加入溶液B捏合均匀，经成型、自然晾干，然后450℃焙烧3h，制得催化剂载体，倒入溶液A中，浸泡1h，120℃烘干后，500℃焙烧3h得到成品C3。
实施例4
称取7.8g硝酸钴和14.7g钼酸铵，加入45mL氨水及1mL乙二醇胺，加热至80℃，测得pH值为12，得到透亮的溶液A。将3g柠檬酸和2mL稀硝酸分别加入去30mL去离子水中得到溶液B。
取沸石含量74％的的25g天然沸石、51g活性氧化铝和17.9g碳酸钙混合研磨3h，加入6g田箐粉混合均匀，加入溶液B，捏合均匀，经成型、自然晾干，然后600℃焙烧3h，制得催化剂载体，倒入溶液A中，浸泡2h，60℃烘干后，450℃焙烧3h得到成品C4。
对比例1
称取7.8g硝酸钴和9.8g钼酸铵，加入40mL氨水及3mL乙二醇胺混合溶液，加热至70℃，测得pH值为12，得到透亮的溶液A。将3g柠檬酸和1mL稀硝酸加入去35mL去离子水中得到溶液B。
取沸石含量60％的20g天然沸石、64g活性氧化铝和10.7g碳酸钙混合研磨0.5h，加入4g田箐粉和2g淀粉混合均匀，加入溶液B捏合均匀，经成型、自然晾干，然后600℃焙烧3h，制得催化剂载体，倒入溶液A中，浸泡2h，100℃烘干后，500℃焙烧2h得到成品D1。
对比例2
称取7.8g硝酸钴和9.8g钼酸铵，加入40mL氨水及3mL乙二醇胺混合溶液，加热至70℃，测得pH值为12，得到透亮的溶液A。将3g柠檬酸和1mL稀硝酸加入去35mL去离子水中得到溶液B。
取沸石含量68％的50g天然沸石、34g活性氧化铝和10.7g碳酸钙混合研磨0.5h，加入4g田箐粉和2g淀粉混合均匀，加入溶液B捏合均匀，经成型、自然晾干，然后600℃焙烧3h，制得催化剂载体，倒入溶液A中，浸泡2h，100℃烘干后，500℃焙烧2h得到成品D2。
对比例3
称取7.8g硝酸钴和9.8g钼酸铵，加入40mL氨水及3mL乙二醇胺混合溶液，加热至70℃，测得pH值为12，得到透亮的溶液A。将3g柠檬酸和1mL稀硝酸加入去35mL去离子水中得到溶液B。
取沸石含量68％的5g天然沸石、79g活性氧化铝和10.7g碳酸钙混合研磨0.5h，加入4g田箐粉和2g淀粉混合均匀，加入溶液B捏合均匀，经成型、自然晾干，然后600℃焙烧3h，制得催化剂载体，倒入溶液A中，浸泡2h，100℃烘干后，500℃焙烧2h得到成品D3。
对比例4
称取7.8g硝酸钴和9.8g钼酸铵，加入40mL氨水及3mL乙二醇胺混合溶液，加热至70℃，测得pH值为12，得到透亮的溶液A。将3g柠檬酸和1mL稀硝酸加入去35mL去离子水中得到溶液B。
取沸石含量68％的20g天然沸石、70g活性氧化铝混合研磨0.5h，加入4g田箐粉和2g淀粉混合均匀，加入溶液B捏合均匀，经成型、自然晾干，然后600℃焙烧3h，制得催化剂载体，倒入溶液A中，浸泡2h，100℃烘干后，500℃焙烧2h得到成品D4。
如图1所示，该装置用于模拟工业条件，测定“原粒度”催化剂在不同条件下尾气一氧化碳浓度及其变化，比较催化剂的变换活性和稳定性等性能，综合评价催化剂的各项性能。反应管为不锈钢管，中央有热偶管。按照不同水气比的要求配入一定量的水，经高温气化后，与原料气一起进入反应管进行水煤气变换反应，反应后尾气用色谱分析。
采用加压评价装置测试本发明实施例及对比例中催化剂的物化性能及400℃时的CO变换率结果见表1。
其中原料气组成：
CO含量：50.0％；
CO2含量：3.0％；
H2S含量：＞0.2％；
余量：H2；
催化剂装填量：50mL；
硫化条件：
温度：300℃；压力：2.0MPa；干气空速：2000h-1；
H2S含量：0.3％；时间：20h；
耐硫变换催化剂加压初评价条件：
入口温度：400℃；压力：4.0MPa；水/气：0.3；
干气空速：3000h-1；H2S含量：0.2％～0.4％；时间：40h；
表1催化剂强度及加压活性
从表1的评价结果可以看出，本申请催化剂的综合物化性能及400℃时CO变换率及出口甲烷含量等综合效果要明显好于对比例。

Claims (8)

1.一种耐硫变换催化剂，包括载体和活性组分，其特征在于：载体成分包括氧化铝和天然沸石，活性组分为钴钼氧化物；
载体包括以下质量百分含量的组分：天然沸石10～25wt.%，氧化铝60～80wt. %；
活性组分包括以下质量百分含量的组分：氧化钼6～12wt.%，氧化钴2.0～4.0wt. %，助剂氧化钙1.0~10.0wt.％；
均以催化剂的总质量为100%计量；
天然沸石阳离子交换量≥150mmol/100g，沸石含量≥68%。
2.根据权利要求1所述的耐硫变换催化剂，其特征在于：天然沸石为斜发沸石、丝光沸石、菱沸石或毛沸石。
3.一种权利要求1-2任一所述的耐硫变换催化剂的制备方法，其特征在于：包括以下步骤：
（1）将活性含铝化合物、天然沸石干粉以及碳酸钙混合研磨；
（2）向步骤（1）研磨得到的混合物中加入粘结剂和助挤剂，混合，挤条成型、干燥、焙烧，得到催化剂载体；
（3）用含活性组分的碱性复合络合溶液浸渍一段时间，然后经过干燥、焙烧，得到催化剂。
4.根据权利要求3所述的耐硫变换催化剂的制备方法，其特征在于：粘结剂为醋酸、柠檬酸、草酸或硝酸中的一种或多种。
5.根据权利要求3所述的耐硫变换催化剂的制备方法，其特征在于：助挤剂为田箐粉或淀粉。
6.根据权利要求3所述的耐硫变换催化剂的制备方法，其特征在于：步骤（2）中，焙烧温度为400～600℃；步骤（3）中，焙烧温度为400～600℃。
7.根据权利要求3所述的耐硫变换催化剂的制备方法，其特征在于：步骤（3）中，含活性组分的碱性复合络合溶液的配制过程如下：
称取含钴金属元素化合物和含钼金属元素化合物，加入氨水及乙醇胺混合水溶液，加热使其溶解，得到含活性组分的碱性复合络合溶液。
8.根据权利要求7所述的耐硫变换催化剂的制备方法，其特征在于：得到的含活性组分的碱性复合络合溶液的温度为70-80℃，测得pH值为11-12。
CN202010900141.4A 2020-08-31 2020-08-31 耐硫变换催化剂及其制备方法 Active CN114100670B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010900141.4A CN114100670B (zh) 2020-08-31 2020-08-31 耐硫变换催化剂及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010900141.4A CN114100670B (zh) 2020-08-31 2020-08-31 耐硫变换催化剂及其制备方法

Publications (2)

Publication Number Publication Date
CN114100670A CN114100670A (zh) 2022-03-01
CN114100670B true CN114100670B (zh) 2023-08-11

Family

ID=80360222

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010900141.4A Active CN114100670B (zh) 2020-08-31 2020-08-31 耐硫变换催化剂及其制备方法

Country Status (1)

Country Link
CN (1) CN114100670B (zh)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1213550A (en) * 1982-12-28 1986-11-04 Philip J. Angevine Zeolite containing catalyst support for denitrogenation of oil feedstocks
CN101607207A (zh) * 2008-06-19 2009-12-23 中国石油天然气股份有限公司 一种重质芳烃轻质化催化剂及其制备方法和应用
CN102189002A (zh) * 2010-03-04 2011-09-21 中国石油化工股份有限公司 拟薄水铝石与分子筛的组合物和由其制备的载体
CN103962175A (zh) * 2013-01-24 2014-08-06 中国科学院过程工程研究所 一种重油裂化气化双功能催化剂及其制备方法
EP3375513A1 (fr) * 2017-03-16 2018-09-19 Commissariat à l'Energie Atomique et aux Energies Alternatives Catalyseur pour reaction de gaz a l'eau inverse (rwgs), reaction rwgs associee et procede de regeneration in-situ du catalyseur
CN110237852A (zh) * 2018-03-09 2019-09-17 国家能源投资集团有限责任公司 含硫酸根离子的钛化合物改性的耐硫变换催化剂及其制备方法
CN111097534A (zh) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 一种甲烷化催化剂及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2486354C (en) * 2002-06-12 2013-03-12 Sulzer Metco (Canada) Inc. Hydrometallurgical process for production of supported catalysts

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1213550A (en) * 1982-12-28 1986-11-04 Philip J. Angevine Zeolite containing catalyst support for denitrogenation of oil feedstocks
CN101607207A (zh) * 2008-06-19 2009-12-23 中国石油天然气股份有限公司 一种重质芳烃轻质化催化剂及其制备方法和应用
CN102189002A (zh) * 2010-03-04 2011-09-21 中国石油化工股份有限公司 拟薄水铝石与分子筛的组合物和由其制备的载体
CN103962175A (zh) * 2013-01-24 2014-08-06 中国科学院过程工程研究所 一种重油裂化气化双功能催化剂及其制备方法
EP3375513A1 (fr) * 2017-03-16 2018-09-19 Commissariat à l'Energie Atomique et aux Energies Alternatives Catalyseur pour reaction de gaz a l'eau inverse (rwgs), reaction rwgs associee et procede de regeneration in-situ du catalyseur
CN110237852A (zh) * 2018-03-09 2019-09-17 国家能源投资集团有限责任公司 含硫酸根离子的钛化合物改性的耐硫变换催化剂及其制备方法
CN111097534A (zh) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 一种甲烷化催化剂及其制备方法

Also Published As

Publication number Publication date
CN114100670A (zh) 2022-03-01

Similar Documents

Publication Publication Date Title
CN101054538B (zh) 中低温下催化转化吸收羰基硫的铁基脱硫剂及其制备
CN102083745B (zh) 运行hts反应器的方法
JP5411133B2 (ja) 二酸化炭素の合成ガスへの接触水素化
EP2237882B1 (en) Iron-based water gas shift catalyst
CN101678329B (zh) 将二氧化碳催化加氢成合成气混合物
CN102218323B (zh) 一种不饱和烃加氢催化剂及其制备方法和应用
CN101972656B (zh) 一种乙醇自热重整制取氢气的镍基催化剂及其制备方法
Zuo et al. Highly efficient synthesis of dimethyl ether directly from biomass-derived gas over Li-modified Cu-ZnO-Al2O3/HZSM-5 hybrid catalyst
Huang et al. Effect of pretreatment on the adsorption performance of Ni/ZnO adsorbent for dibenzothiophene desulfurization
Ahmad et al. Synthesis of oxymethylene dimethyl ethers (OMEn) via methanol mediated COx hydrogenation over Ru/BEA catalysts
Yu et al. Hydrogen production from steam reforming of kerosene over Ni–La and Ni–La–K/cordierite catalysts
CN100594061C (zh) 一种含镍的费托合成铁基催化剂及其制备方法
Li et al. Effect of Na promoter on the catalytic performance of Pd-Cu/hydroxyapatite catalyst for room-temperature CO oxidation
JP4990529B2 (ja) 炭化水素ガスからのイオウ化合物の除去
CN102773108B (zh) 一种硫化氢制氢气催化剂的制备方法
CN114100670B (zh) 耐硫变换催化剂及其制备方法
CN105358477A (zh) 预重整含有烯烃的烃料流的方法、预重整催化剂和制备所述催化剂的方法
US20080227631A1 (en) Method for Producing a Catalyst for the Desulfurization of Hydrocarbon Flows
CN114100624B (zh) 高岭土改性耐硫变换催化剂及其制备方法
CN102773109B (zh) 一种由硫化氢制氢气的催化剂及其制备方法
CN102015105A (zh) 液化石油气制造用催化剂及使用了该催化剂的液化石油气的制造方法
US4500646A (en) Conversion catalysts for synthesis gas
CN104248956B (zh) 气态烃类蒸汽预转化催化剂及其制备方法和应用
CN114100695A (zh) 耐硫变换催化剂保护剂及其制备方法
CN112403484B (zh) 耐硫变换催化剂保护剂及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant