CN1265340A - 新型无铬铁系一氧化碳高温变换催化剂及其制备 - Google Patents

新型无铬铁系一氧化碳高温变换催化剂及其制备 Download PDF

Info

Publication number
CN1265340A
CN1265340A CN00105435A CN00105435A CN1265340A CN 1265340 A CN1265340 A CN 1265340A CN 00105435 A CN00105435 A CN 00105435A CN 00105435 A CN00105435 A CN 00105435A CN 1265340 A CN1265340 A CN 1265340A
Authority
CN
China
Prior art keywords
oxide
solution
qualified
high temperature
base catalyst
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.)
Granted
Application number
CN00105435A
Other languages
English (en)
Other versions
CN1097483C (zh
Inventor
魏可镁
郑起
徐建本
林性怡
魏明灯
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.)
CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
Original Assignee
CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
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 CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV filed Critical CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
Priority to CN00105435A priority Critical patent/CN1097483C/zh
Publication of CN1265340A publication Critical patent/CN1265340A/zh
Priority to US09/670,586 priority patent/US6569804B1/en
Application granted granted Critical
Publication of CN1097483C publication Critical patent/CN1097483C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • B01J23/745—Iron
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • 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
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • 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)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

本发明公开了一种用于合成氨及制氨工业中一氧化碳加水蒸气变换反应制取氢气的新型无铬铁系一氧化碳高温变换催化剂及其制备方法。它由氧化铁、铝铁硅复合氧化物或铝硅胶、钒氧化物、镁氧化物、镍氧化物、氧化钾等化学组份组成,分别采用混沉淀和混碾法两种工艺制备方法,制得该种无铬高变催化剂产品。

Description

新型无铬铁系一氧化碳高温变换催化剂及其制备
本发明涉及一种用于合成氨及制氢工业中一氧化碳加水蒸汽变换反应制取氢气的催化剂及其制备方法，具体地说是一种新型无铬铁系一氧化碳高温变换催化剂。
传统的一氧化碳高变催化剂为铁铬系变换催化剂，铬是该催化剂重要的助剂，它可大幅度提高催化剂的活性、耐热性和使用寿命。但它又是一种很强的致癌物质，在催化剂制造、使用过程及废弃后都给人体和环境带来严重的危害。因此，无铬铁系高变催化剂的研制，已引起国内外学者的极大关注。
自七十年代以来，世界各国开展无铬高变催化剂的研究工作的有：
前苏联伊凡诺夫化工研究所研制的CTK-＞KC型铁铅系高变催化剂，含PbO10％～14％，引入了新的污染物铅。
英国ICI公司开发无铬71-1和71-2型催化剂，其主要成份为CaO、CeO2、ZrO2或HfO2等。但制造困难，价格昂贵。
日本日产公司采用Fe2O3、Al2O3、CuO、K2O及Pt组份制备的无铬催化剂。
中国内蒙古工业大学申请的专利《铁系无铬型高(中)温变换催化剂及其生产方法》(申请号：95121834.4)是采用Fe2O3、CeO2、Al2O3、K2O组份开展NBC型无铬催化剂的研制。
上述研究工作不同程度存在着制造困难、成本高、产生新污染源等问题，致使研究进展缓慢。
本发明的目的是制造一种能彻底消除铬的污染，且不增加新的污染源，原料易得，制备工艺简单，可在现行高变催化剂生产线上实现规模生产的，由氧化铁、铝铁硅复合氧化物或铝硅胶、钒氧化物、镁氧化物、镍氧化物、氧化钾等的化学组份组成的新型的无铬铁系一氧化碳高温变换催化剂。
本发明的目的是这样实现的：一种新型无铬铁系一氧化碳高温变换催化剂及其制备其特征由氧化铁：65％～90％，铝铁硅复合氧化物(Al∶Fe∶Si＝6∶2∶1)或铝硅胶(Al∶Si＝8∶2)：1％～10％，钒氧化物：0.5％～2.0％，镁氧化物：0.5％～3.0％，镍氧化物：0.5％～5.0％，氧化钾：0.1％～0.6％组成。
将固体硫酸亚铁FeSO4.7H2O在30℃～50℃下溶化为合格的硫酸亚铁溶液，溶液比重为1.2～1.35，将固体碳酸氢铵溶化为溶液并通液氨调节为合格的碳酸溶液，其中(NH4)2CO3浓度为180g/L～280g/L，NH4OH浓度20g/L～100g/L。合格的硫酸亚铁液和碳酸铵液在中和罐中并流中和沉淀，中和温度为65℃～75℃，PH值为6.5～7.5，时间180min，沉淀液经90℃～95℃热煮60min后，用40℃～60℃清水洗涤4～6次，澄清液用10％的BaCl2溶液滴定，无白色沉淀，为洗涤合格。洗涤合格的料浆由下面两种工艺流程完成催化剂制备：
方法一：按配料比配入铝铁硅复合氧化物、镁氧化物、钒氧化物、镍氧化物，打浆30min，打浆后的料浆经压滤得到滤饼，滤饼经烘干后按配料比配入KOH，在碾磨机中碾压60min，碾压后的物料经造粒、300℃～350℃焙烧90～120min后，再配入0.5％～1.0％石墨粉进行打片，即得圆柱状无铬催化剂产品。
方法二：洗涤合格的料浆经压滤、烘干后按配料比配入所有助剂，在碾压机中碾压1小时。碾压后的物料经造粒、并经300℃～350℃焙烧90～120min，再配入0.5％～1.0％的石墨粉进行打片，即得圆柱状产品。
本发明由于通过深入的基础理论研究和大量性能测定、表征，发现铬在高变催化剂中不仅起结构助剂作用，而且还起电子助剂作用。在此理论指导下，经过大量的配方筛选，工艺改革，应用特殊工艺加工形成铝铁硅复合氧化物或铝硅胶，通过制造、还原进入Fe3O4晶格，使晶粒度变小，比表面增大，取代氧化铬的骨架助剂作用提高了催化剂的稳定性；加入钒氧化物在反应体系中以V4+存在于Fe3O4的A位(正四面体位)代替Cr6+起电子助剂作用，从XPS和穆斯堡尔谱证实了这点；镍氧化物的加入提高了催化剂表面富集OH-基团的能力，使催化剂在低水碳比下(～1.85)仍具有高活性和高抗硫能力。为此，本发明无铬铁系高变催化剂的性能达到传统铁铬系催化剂的水平。
本发明的具体制备方法由以下的实施例及其附图给出：
图1是本发明方法1的工艺流程图。
图2是本发明方法2的工艺流程图。
图1中将固体硫酸亚铁溶化为合格的硫酸亚铁液，将固体碳酸氢铵溶化为溶液并通入氨调节为合格的铵液。硫酸亚铁液和碳酸铵液在中和罐中并流中和沉淀，沉淀经热煮、洗涤后按配料比加入助剂进行打浆，打浆后物料经压滤后得到滤饼。滤饼经烘干、加入KOH碾压、造粒、加石墨混合、打片，即得成品。
图2中将固体硫酸亚铁溶化为合格的硫酸亚铁液，将固体碳酸氢铵溶化为溶液并通入氨调节为合格的铵液。硫酸亚铁液和碳酸氨液在中和罐中并流中和沉淀，沉淀经热煮、洗涤、压滤、烘干、按配料比加入各种助剂碾压、造粒、加石墨混合、打片，即得成品。
实例1：
以生产1000Kg催化剂为基准，需90％的七水合硫酸亚铁3100Kg，碳酸氢铵1200Kg，液氨200Kg，铝铁硅复合氧化物60Kg，钒氧化物15Kg，镁氧化物20Kg，镍氧化物45Kg，氢氧化钾5Kg，石墨8Kg。
将FeSO4.7H2O在30℃～50℃下溶化为合格的硫酸亚铁溶液，溶液比重为1.2～1.35，将碳酸氢铵溶解并通液氨调节为合格的碳酸铵溶液，其中(NH4)2CO3浓度为180g/L～280g/L，NH4OH浓度20g/L～100g/L。当反应罐的底水温度达60℃时，将合格的硫酸亚铁液和碳酸铵液并流加入反应罐起中和反应，起始小流量，逐渐加大。中和温度65℃～75℃，PH控制在6.5～7.5，时间约为180min。中和结束前半小时，溶液进行返酸处理，调节流量使PH控制在6.5，维持15min后返碱，PH调至7.2搅拌15min后，结束中和。中和后沉淀物料提温至90℃～95℃热煮60min。沉淀物料用40℃～60℃清水洗涤4～6次，洗涤液用10％的BaCl2溶液滴定，无白色沉淀，为洗涤合格，得到氧化铁料浆。
在合格的氧化铁料浆中按配料比配入铝铁硅复合氧化物、镁氧化物、钒氧化物、镍氧化物，打浆30min，打浆后的料浆经压滤得到滤饼，滤饼经烘干后按配料比配入氢氧化钾溶液，在碾磨机中碾压60min，碾压后的物料经造粒、300℃～350℃焙烧90～120min后，再配入0.5％～1.0％石墨粉进行打片，即得φ9mm×(6～8)mm圆柱状无铬催化剂产品。
该成品按ZBG74001-89标准检测，耐热后CO转化率为55.7％，平均颗粒径向抗压碎强度275N/cm，低强度百分率2.5％，磨耗率3.6％，烧失重2.5％。
实例2：
氧化铁料浆的制备方法同实例1，洗涤合格后的氧化铁料浆经压滤、烘干后按配料比配入所有助剂，在碾压机中碾压1小时。碾压后的物料经造粒、300℃～350℃焙烧90～120min，再配入0.5％～1.0％的石墨粉进行打片，即得成品。
该成品按ZBG74001-89标准检测条件进行检测，耐热后CO转化率为52.3％，平均颗粒径向抗压碎强度325N/cm，低强度百分率0％，磨耗率3.3％，烧失重5.1％。
该批样在工业试用，效果良好，寿命达3年以上。
实例3：
以生产1000Kg催化剂为基准，需90％的七水合硫酸亚铁3100Kg，碳酸氢铵1200Kg，液氨200Kg，铝硅胶(含硅铝40％，硅铝比2∶8)100Kg，钒氧化物15Kg，镁氧化物20Kg，镍氧化物45Kg，氢氧化钾5Kg，石墨8Kg。生产方法同实例2。
该成品按ZBG74001-89标准检测条件进行检测，耐热后CO转化率为49.3％，平均颗粒径向抗压碎强度360N/cm，低强度百分率0％，磨耗率4.5％，烧失重6.1％。

Claims (4)

1.一种新型无铬铁系一氧化碳高温变换催化剂及其制备其特征由氧化铁：65％～90％，铝铁硅复合氧化物(Al∶Fe∶Si＝6∶2∶1)或铝硅胶(Al∶Si＝8∶2)：1％～10％，钒氧化物：0.5％～2.0％，镁氧化物：0.5％～3.0％，镍氧化物：0.5％～5.0％，氧化钾：0.1％～0.6％组成。
2.一种新型无铬铁系一氧化碳高温变换催化剂及其制备其特征是将固体硫酸亚铁FeSO4.7H2O在30℃～50℃下溶化为合格的硫酸亚铁溶液，溶液比重为1.2～1.35，将固体碳酸氢铵溶化为溶液并通液氨调节为合格的碳铵溶液，合格的硫酸亚铁液和碳酸铵液在中和罐中并流中和沉淀，沉淀液经90℃～95℃热煮60min后，用40℃～60℃清水洗涤4～6次，澄清液用10％的BaCl2溶液滴定，无白色沉淀，为洗涤合格。
3.根据权利要求2所述的一种新型无铬铁系一氧化碳高温变换催化剂及其制备其特征是(NH4)2CO3浓度为180g/L～280g/L，NH4OH浓度20g/L～100g/L。
4.根据权利要求2所述的一种新型无铬铁系一氧化碳高温变换催化剂及其制备其特征是，中和温度为65℃～75℃，PH值为6.5～7.5，时间180min。
CN00105435A 2000-03-29 2000-03-29 新型无铬铁系一氧化碳高温变换催化剂及其制备 Expired - Fee Related CN1097483C (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN00105435A CN1097483C (zh) 2000-03-29 2000-03-29 新型无铬铁系一氧化碳高温变换催化剂及其制备
US09/670,586 US6569804B1 (en) 2000-03-29 2000-09-28 Chromium-free Fe-based catalyst for CO high-temperature-shift reaction and its preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN00105435A CN1097483C (zh) 2000-03-29 2000-03-29 新型无铬铁系一氧化碳高温变换催化剂及其制备

Publications (2)

Publication Number Publication Date
CN1265340A true CN1265340A (zh) 2000-09-06
CN1097483C CN1097483C (zh) 2003-01-01

Family

ID=4577697

Family Applications (1)

Application Number Title Priority Date Filing Date
CN00105435A Expired - Fee Related CN1097483C (zh) 2000-03-29 2000-03-29 新型无铬铁系一氧化碳高温变换催化剂及其制备

Country Status (2)

Country Link
US (1) US6569804B1 (zh)
CN (1) CN1097483C (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102164879A (zh) * 2008-09-30 2011-08-24 弗纳技术股份有限公司 半负载的脱氢催化剂
CN109364941A (zh) * 2018-12-07 2019-02-22 中国石油天然气股份有限公司乌鲁木齐石化分公司 一种耐高温高压的铜系变换催化剂及其制备方法
CN116251614A (zh) * 2023-05-09 2023-06-13 山东秋水化学科技有限公司 一种co变换反应用催化剂及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070249953A1 (en) * 2006-04-21 2007-10-25 Medtronic, Inc. Method and apparatus for detection of nervous system disorders
KR100847443B1 (ko) * 2007-02-23 2008-07-22 고려대학교 산학협력단 일산화탄소를 제거하기 위한 비-크롬계 고온 수성가스전환반응용 촉매
US7964114B2 (en) * 2007-12-17 2011-06-21 Sud-Chemie Inc. Iron-based water gas shift catalyst
KR101098602B1 (ko) 2009-09-21 2011-12-23 에스케이이노베이션 주식회사 일산화탄소 제거에 높은 활성을 나타내는 비-크롬계 수성가스 전환반응용 촉매

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872027A (en) * 1970-02-13 1975-03-18 Petro Tex Chem Corp Oxidative dehydrogenation catalysts and their method of preparation
US3686347A (en) * 1970-04-16 1972-08-22 Petro Tex Corp Oxidative dehydrogenation of organic compounds
US4256654A (en) * 1977-12-29 1981-03-17 Texaco Inc. Conversion of hydrogen and carbon monoxide into C1 -C4 range hydrocarbons
US4234461A (en) * 1978-03-30 1980-11-18 Standard Oil Company (Ohio) Oxidation catalysts
US4329517A (en) * 1979-05-16 1982-05-11 Mitsui Petrochemical Industries Ltd. Process for production of mono- or di-ortho-methyl-substituted phenols by catalytic methylation and catalyst therefor
US4235749A (en) * 1979-09-17 1980-11-25 Indianapolis Center For Advanced Research Ammonia synthesis catalysts and process of making and using them
US5118715A (en) * 1983-12-20 1992-06-02 Exxon Research And Engineering Company Selective fixed-bed fischer-tropsch synthesis with high surface area Cu and K promoted, iron/manganese spinels
IT1174207B (it) * 1984-06-19 1987-07-01 Fertimont Spa Processo per la preparazione di catalizzatori a base di ferro per la sintesi dell'ammoniaca e catalizzatori cosi'ottenuti
US5543437A (en) * 1986-05-08 1996-08-06 Rentech, Inc. Process for the production of hydrocarbons
US4968661A (en) * 1988-01-15 1990-11-06 The Standard Oil Company Oxidation catalyst amended by examiner
US4912077A (en) * 1988-07-15 1990-03-27 Corning Incorporated Catalytically active materials and method for their preparation
US4861745A (en) * 1988-08-03 1989-08-29 United Catalyst Inc. High temperature shift catalyst and process for its manufacture
US5243095A (en) * 1992-04-24 1993-09-07 Engelhard Corporation Hydrogenation catalyst, process for preparing and process for using said catalyst
US6235677B1 (en) * 1998-08-20 2001-05-22 Conoco Inc. Fischer-Tropsch processes using xerogel and aerogel catalysts by destabilizing aqueous colloids

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102164879A (zh) * 2008-09-30 2011-08-24 弗纳技术股份有限公司 半负载的脱氢催化剂
CN109364941A (zh) * 2018-12-07 2019-02-22 中国石油天然气股份有限公司乌鲁木齐石化分公司 一种耐高温高压的铜系变换催化剂及其制备方法
CN109364941B (zh) * 2018-12-07 2021-08-06 中国石油天然气股份有限公司乌鲁木齐石化分公司 一种耐高温高压的铜系变换催化剂及其制备方法
CN116251614A (zh) * 2023-05-09 2023-06-13 山东秋水化学科技有限公司 一种co变换反应用催化剂及其制备方法

Also Published As

Publication number Publication date
US6569804B1 (en) 2003-05-27
CN1097483C (zh) 2003-01-01

Similar Documents

Publication Publication Date Title
CN103395796B (zh) 蛇纹石的综合利用方法及其所用的设备
Fang et al. A novel method to remove chromium, vanadium and ammonium from vanadium industrial wastewater using a byproduct of magnesium-based wet flue gas desulfurization
CN104445311B (zh) 高含量二氧化硅质粉煤灰多联产洁净制备方法
CN102583575B (zh) 利用钛白废渣硫酸亚铁生产颜料级铁红的方法
CN1097483C (zh) 新型无铬铁系一氧化碳高温变换催化剂及其制备
CN101760641A (zh) 从硫酸镁溶液中回收镁的工艺
CN112441621A (zh) 富锰渣的综合利用方法
CN102616867B (zh) 一种由蛇纹石及其尾矿中提取制备碳酸镍、硫酸镍和氧化铁红的方法
Abu-Zied et al. An investigation on the N2O decomposition activity of MnxCo1− xCo2O4 nanorods prepared by the thermal decomposition of their oxalate precursors
CN109622055B (zh) 一种基于碳化铁基mofs的铁锰双金属催化剂及其制备方法
CN113385139B (zh) 一种碱中和方法制备的施威特曼石及其应用
CN110306065A (zh) 一种钒渣制备偏钒酸铵的方法
CN104973627B (zh) 一种以碳素铬铁为原料生产三氧化二铬的方法
CN107649142A (zh) 一种低密度铁铬系co变换催化剂
CN106185988B (zh) 一种制备高比表面羟基氧化铁并联产硫酸铵的工艺
Li et al. In-situ synthesis of CrOx (OH) 3-2x for synchronous adsorption of Si and V from high concentration Cr (VI) solution and converted to excellent Cr2O3 pigment
CN1046640C (zh) 铁系无铬型高(中)温变换催化剂及其生产方法
CN101618894B (zh) 三氯化铁的制备方法
CN110015689B (zh) 高碳铬铁清洁生产羟基氧化铬、铬盐系列产品的生产工艺
CN1065815A (zh) 新型高温变换催化剂的制造方法
CN106241874A (zh) 利用生产萘醌所得残液制备氧化铬绿的方法
DE2107844B2 (de) Verfahren zur großtechnischen Herstellung von Magnesiumoxyd hoher Reinheit
CN1022987C (zh) 稀土低铬中温变换催化剂
CN114477280B (zh) 一种氟化法制备纳米二氧化钛的方法
CN1052922C (zh) 低水/碳比高温变换催化剂及制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20030101