CN1351954A - 一种用于甲烷与二氧化碳重整反应的微波催化剂 - Google Patents
一种用于甲烷与二氧化碳重整反应的微波催化剂 Download PDFInfo
- Publication number
- CN1351954A CN1351954A CN00123255A CN00123255A CN1351954A CN 1351954 A CN1351954 A CN 1351954A CN 00123255 A CN00123255 A CN 00123255A CN 00123255 A CN00123255 A CN 00123255A CN 1351954 A CN1351954 A CN 1351954A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- microwave
- hours
- methane
- carrier
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000006057 reforming reaction Methods 0.000 title claims description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011358 absorbing material Substances 0.000 claims abstract description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 23
- 238000011161 development Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000006260 foam Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- 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
- B01J23/755—Nickel
-
- 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
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0892—Materials to be treated involving catalytically active material
-
- 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
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming 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
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0855—Methods of heating the process for making hydrogen or synthesis gas by electromagnetic heating
-
- 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
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1029—Catalysts in the form of a foam
-
- 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
- C01B2203/1058—Nickel 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
- Y02P20/141—Feedstock
-
- 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
一种用于甲烷与二氧化碳重整反应的微波催化剂,由载体和活性成分组成,其特征在于:催化剂活性组分为氧化镍,其担载量为3～20%重量;所用的催化剂载体为表面涂覆γ－Al2O3的泡沫陶瓷,泡沫陶瓷的主组分为碳化硅、铁氧体的吸波材料,次组分为用作粘接剂的二氧化硅,载体的重量组成为2～25%的粘接剂,70～90%的吸波材料,5～25%的γ－Al2O3。本发明可以使反应在温和的条件下进行,并且具有较高的合成气收率,很低的反应积炭。
Description
本发明涉及甲烷与二氧化碳重整反应，特别提供了一种用于甲烷与二氧化碳重整反应的微波催化剂。
甲烷与二氧化碳重整反应是有效利用储量丰富的天然气与二氧化碳的最有效途径之一。该反应以其生成低H2/CO比的合成气而倍受研究者重视。为克服该反应反应温度高、积炭严重的缺点，采用微波强化该反应不失为一条有效的途径。微波能在化学中的应用近年来取得了很大的进展，利用其快速、选择性加热的特点，可以得到许多常规加热所不能得到的结果，尤其是在催化反面的研究，更是取得了许多很好的结果，由此微波催化作为一门交叉学科应运而生。微波催化发展的关键问题是寻找具有良好的微波可加热性的微波催化剂，近几年的实践也证明微波催化剂已越来越成为制约微波催化发展的瓶颈问题。开发研制微波催化剂的关键是寻找吸波性能良好的催化剂或催化剂载体，由于在多数催化剂中活性组分所占的比例很小，尤其是在贵金属催化剂中表现更为突出，载体的微波吸收能力将对整个催化剂的吸波能力起到关键作用。传统催化剂中用作载体的氧化铝、二氧化硅及多数碱土金属和过渡金属氧化物的吸波能力都是很弱的。据B.Vos等报道对Ni/Al2O催化剂采用微波加热，难以加热到300℃以上，这将难以达到使用要求。为此开发研制全新具有强吸波能力的催化剂就显的极为重要。
本发明的目的在于提供一种用于甲烷与二氧化碳重整反应的微波催化剂，其可以使反应在温和的条件下进行，并且具有较高的合成气收率，很低反应积炭。
本发明提供了一种用于甲烷与二氧化碳重整反应的微波催化剂，由载体和活性成分组成，其特征在于：催化剂活性组分为氧化镍，其担载量为3～20％重量；所用的催化剂载体为表面涂覆γ-Al2O3的泡沫陶瓷，泡沫陶瓷的主组分为碳化硅、铁氧体的吸波材料，次组分为用作粘接剂的二氧化硅，载体的重量组成为2～25％的粘接剂，70～90％的吸波材料，5～25％的γ-Al2O3。
本发明还提供了上述用于甲烷与二氧化碳重整反应的微波催化剂的制备方法，其特征在于：
载体的制备：
(1)将正硅酸乙酯、酒精、水、冰醋酸和盐酸按一定比例配制成水解液，水解液的重量份数组成为：100正硅酸乙酯，50～90酒精，5～25水，1～5冰醋酸，0.1～2浓盐酸；
(2)将80～200目的吸波材料与过程1中配制的水解液按比例混合均匀，二者重量比为100碳化硅，20～50水解液，并将其挂在泡沫塑料上，然后置于烘箱中60～120℃烘干固化，再在1000～2200℃下焙烧处理2～10小时，即可制得具有超强吸波能力的泡沫陶瓷；
(3)用水解液在过程(2)制成的泡沫陶瓷表面浸渍、涂覆一层γ-Al2O3，然后置于烘箱中120℃，8～24小时烘干，再在400～800℃下焙烧处理2～10小时，即可制得具有超强吸波能力的泡沫状催化剂载体。
催化剂的制备：
将Ni(NO3)2配成溶液，将过程(3)制成的催化剂载体浸渍于Ni(NO3)2溶液中，取出后吹扫掉悬浮的Ni(NO3)2溶液，置于烘箱中120℃，8～24小时烘干，再在400～800℃下焙烧处理2～10小时，即可制得具有超强吸波能力的泡沫状催化剂。
本发明通过强吸波泡沫陶瓷的研制，制得了具有超强吸波能力的泡沫状陶瓷作为催化剂基体，通过在泡沫陶瓷表面涂覆γ-Al2O3，有效的增加了泡沫陶瓷的比表面积，使其适合于用作催化剂载体，最后用浸渍法制备成泡沫陶瓷担载的镍催化剂。
本发明研制的泡沫状吸波催化剂为三维连通网络结构。其连通结构使催化剂床整体连续，从而克服了传统颗粒状催化剂微波加热时的颗粒间放电导致加热不均匀现象，使催化剂床加热更均匀；泡沫陶瓷所独有的三维手性特征使其具有更优异的电损耗和磁损耗，更有利于微波加热；所选用泡沫陶瓷材料原有的高热导率，更有利于催化剂床层的温度内外均一。总之，吸波泡沫状催化剂所特有的结构，使其具有更优异的微波可加热性和微波加热均匀性。
本发明研制的泡沫状吸波催化剂用于甲烷与二氧化碳重整制合成气反应，采用微波辐照进行该反应时实现了温和反应条件下，高合成气收率，很低反应积炭的目的。
总之，本发明具有下述技术特点：
1.本发明研制的吸波泡沫状催化剂载体，基体为碳化硅、铁氧体等吸波材料，孔径均匀，强度高。
2.本发明研制的吸波泡沫状催化剂载体，具有低比重和高热导率。
3.本发明研制的吸波泡沫状催化剂载体，在碳化硅表面涂覆一层γ-Al2O3，涂层均匀，有效的增加了载体的比表面积。
4.本发明研制的吸波泡沫状催化剂，具有超强的吸收微波能力和微波加热均匀性。
5.本发明研制的吸波泡沫状催化剂，具有生产过程简单，成本低，易于工业化等特点。
6.采用微波辐照本发明研制的吸波泡沫状催化剂，进行甲烷与二氧化碳重整制合成气反应，具有反应温度低，合成气收率高，合成气中CO/H2比合理等优点。
附图1为泡沫碳化硅SEM照片；
附图2为催化剂载体A的SEM照片；
附图3为催化剂载体B2的SEM照片；
附图4为催化剂载体B2微波加热红外热像图；
附图5为泡沫吸波催化剂在微波场中的升温曲线；
附图6为不同加热方式下合成气收率随温度变化曲线(B2催化剂，空速为2000h-1)；
附图7为不同加热方式下产物中H2/CO随温度变化曲线(B2催化剂，空速为2000h-1)；
附图8为不同加热方式下空速对合成气受率的影响(B2催化剂，T＝1073K)；
附图9为B2催化剂常规反应后SEM照片；
附图10为B2催化剂微波反应后SEM照片；
附图11为B2催化剂反应前后X-Ray衍射图。
实施例1：高比表面泡沫吸波催化剂载体的制备
将SiC粉500克与50克二氧化硅混合均匀后，制成泡沫状，经1800℃焙烧3小时，再用由正硅酸乙酯配制的粘接剂在其表面涂覆55克γ-Al2O3，并于600℃下焙烧处理6小时，即得催化剂载体A。正硅酸乙酯配制的粘接剂的组成重量比为：(100)正硅酸乙酯，(70)酒精，(12)水，(4)冰醋酸，(1.2)浓盐酸。
该催化剂载体的BET比表面积可达46m2/g。由扫描电子显微镜也可以看出涂覆γ-Al2O3前后泡沫陶瓷表面有明显变化(如图1、2所示)。
实施例2：
将实施例1中碳化硅和二氧化硅分别换作锰锌铁氧体，然后按照实施例1的制备过程，制备出催化剂载体B。
实施例3：泡沫吸波催化剂的制备
用实施例1所述催化剂载体A，抽真空浸渍Ni(NO3)2溶液，然后120℃烘干16小时，经600℃焙烧6小时，所得催化剂称为催化剂An。其活性组分以NiO计为3～20％。其中NiO含量为5％、9％和17％的催化剂分别称为催化剂A1、A2、和A3。催化剂A2的SEM照片如图3所示，X-Ray衍射图谱如图11所示。
实施例4：泡沫吸波催化剂的微波加热性实验
用实施例2制备的泡沫吸波催化剂A2、B2，置于石英管中，用单模微波谐振腔进行微波加热实验，微波功率为2～30W/ml催化剂。采用红外热像仪对加热温度和加热均匀性进行观测。从图5所示的催化剂升温曲线可以看出，催化剂温度随微波功率的变化基本呈线性变化；从图4所示的红外热像图可以看出泡沫吸波催化剂具有很好的微波加热均匀性。
实施例5～7：用甲烷与二氧化碳重整反应表征催化剂的反应性能
在连续流动固定床反应装置上分别装填4ml实施例2所制的B2催化剂，在0.1Mpa，750～900℃，2000～6000h-1，CO2/CH4＝1的反应条件下，分别采用常规和连续微波加热进行催化剂反应性能评价实验1～3，其反应结果如图6--8所示。微波源为2450MHz，800W连续微波源，实验用微波功率为6W/ml催化剂。实验结果表明采用微波时可以明显降低反应温度，提高合成气收率，优化H2/CO比。
实施例10：反应后催化剂表征
对微波及常规加热反应后的催化剂B2进行了SEM(图9～10)及X-Ray衍射(图11)表征。通过对反应前及反应后催化剂X-Ray衍射的结果进行对比表明，用微波加热本发明研制的微波催化剂进行甲烷与二氧化碳重整反应，对反应积炭有很明显的抑制作用。
Claims (2)
1、一种用于甲烷与二氧化碳重整反应的微波催化剂，由载体和活性成分组成，其特征在于：催化剂活性组分为氧化镍，其担载量为3～20％重量；所用的催化剂载体为表面涂覆γ-Al2O3的泡沫陶瓷，泡沫陶瓷的主组分为碳化硅、铁氧体的吸波材料，次组分为用作粘接剂的二氧化硅，载体的重量组成为2～25％的粘接剂，70～90％的吸波材料，5～25％的γ-Al2O3。
2、一种权利要求1所述用于甲烷与二氧化碳重整反应的微波催化剂的制备方法，其特征在于：
载体的制备：
(1)将正硅酸乙酯、酒精、水、冰醋酸和盐酸按比例配制成水解液，水解液的重量份数组成为：100正硅酸乙酯，50～90酒精，5～25水，1～5冰醋酸，0.1～2浓盐酸；
(2)将80～200目的吸波材料与过程1中配制的水解液按比例混合均匀，二者重量比为100碳化硅，20～50水解液，并将其挂在泡沫塑料上，然后置于烘箱中60～120℃烘干固化，再在1000～2200℃下焙烧处理2～10小时，即可制得具有超强吸波能力的泡沫陶瓷；
(3)用水解液在过程(2)制成的泡沫陶瓷表面浸渍、涂覆一层γ-Al2O3，然后置于烘箱中120℃，8～24小时烘干，再在400～800℃下焙烧处理2～10小时，即可制得具有超强吸波能力的泡沫状催化剂载体。
催化剂的制备：
将Ni(NO3)2配成溶液，将过程(3)制成的催化剂载体浸渍于Ni(NO3)2溶液中，取出后吹扫掉悬浮的Ni(NO3)2溶液，置于烘箱中120℃，8～24小时烘干，再在400～800℃下焙烧处理2～10小时，即可制得具有超强吸波能力的泡沫状催化剂。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00123255XA CN1142086C (zh) | 2000-11-15 | 2000-11-15 | 一种用于甲烷与二氧化碳重整反应的微波催化剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00123255XA CN1142086C (zh) | 2000-11-15 | 2000-11-15 | 一种用于甲烷与二氧化碳重整反应的微波催化剂及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1351954A true CN1351954A (zh) | 2002-06-05 |
| CN1142086C CN1142086C (zh) | 2004-03-17 |
Family
ID=4589719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB00123255XA Expired - Fee Related CN1142086C (zh) | 2000-11-15 | 2000-11-15 | 一种用于甲烷与二氧化碳重整反应的微波催化剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142086C (zh) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2864528A1 (fr) * | 2003-12-31 | 2005-07-01 | Total France | Procede de traitement des melanges methane/dioxyde de carbone |
| CN100388975C (zh) * | 2005-09-29 | 2008-05-21 | 北京化工大学 | 一种甲烷二氧化碳重整制合成气的金属载体催化剂及其制备方法 |
| US7393877B2 (en) | 2003-12-31 | 2008-07-01 | Total France | Process for the conversion of a synthesis gas to hydrocarbons in the presence of beta-SiC and effluent from this process |
| WO2011035852A3 (de) * | 2009-09-22 | 2011-05-19 | Clariant International Ltd | Vorrichtung zur kontinuierlichen durchführung heterogen katalysierter chemischer reaktionen bei hohen temperaturen |
| CN101757919B (zh) * | 2009-12-28 | 2012-12-26 | 中国科学院广州能源研究所 | 一种应用于生物油重整制氢的整体型催化剂及其制备方法和用途 |
| US8884040B2 (en) | 2008-04-04 | 2014-11-11 | Clariant Finance (Bvi) Limited | Continuous method for producing fatty acid amides |
| US8974743B2 (en) | 2009-06-30 | 2015-03-10 | Clariant Finance (Bvi) Limited | Device for continuously carrying out chemical reactions at high temperatures |
| US9000197B2 (en) | 2009-09-22 | 2015-04-07 | Clariant Finance (Bvi) Limited | Continuous transesterification method |
| US9039870B2 (en) | 2006-10-09 | 2015-05-26 | Clariant Finance (Bvi) Limited | Method for producing alkaline (meth)acrylamides |
| US9221938B2 (en) | 2010-12-30 | 2015-12-29 | Clariant Finance (Bvi) Limited | Polymers carrying hydroxyl groups and ester groups and method for the production thereof |
| US9243116B2 (en) | 2010-12-30 | 2016-01-26 | Clariant International Ltd. | Method for modifying polymers comprising hydroxyl groups |
| CN106008188A (zh) * | 2016-05-30 | 2016-10-12 | 浙江工业大学 | 一种甘油催化脱水制备丙烯醛的新方法 |
| CN107337446A (zh) * | 2017-07-07 | 2017-11-10 | 福建省德化县联达陶瓷有限公司 | 一种功能性陶瓷产品及其制作工艺 |
| CN110772890A (zh) * | 2018-07-30 | 2020-02-11 | 天津大学 | 一种负载四氧化三铁的SiC泡沫陶瓷及其制备方法和应用 |
| CN110772911A (zh) * | 2018-07-30 | 2020-02-11 | 天津大学 | 一种去除生物气溶胶的微波反应装置、反应***及其应用 |
| CN112604702A (zh) * | 2020-12-10 | 2021-04-06 | 南昌大学 | 一种微波驱动型催化剂的制备方法及应用 |
| CN116253288A (zh) * | 2023-01-17 | 2023-06-13 | 中国林业科学研究院林产化学工业研究所 | 一种变频微波催化甲烷裂解制氢的方法 |
-
2000
- 2000-11-15 CN CNB00123255XA patent/CN1142086C/zh not_active Expired - Fee Related
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005072867A1 (fr) * | 2003-12-31 | 2005-08-11 | Total France | Procede de traitement des melanges methane/dioxyde de carbone |
| US7393877B2 (en) | 2003-12-31 | 2008-07-01 | Total France | Process for the conversion of a synthesis gas to hydrocarbons in the presence of beta-SiC and effluent from this process |
| FR2864528A1 (fr) * | 2003-12-31 | 2005-07-01 | Total France | Procede de traitement des melanges methane/dioxyde de carbone |
| CN100388975C (zh) * | 2005-09-29 | 2008-05-21 | 北京化工大学 | 一种甲烷二氧化碳重整制合成气的金属载体催化剂及其制备方法 |
| US9039870B2 (en) | 2006-10-09 | 2015-05-26 | Clariant Finance (Bvi) Limited | Method for producing alkaline (meth)acrylamides |
| US8884040B2 (en) | 2008-04-04 | 2014-11-11 | Clariant Finance (Bvi) Limited | Continuous method for producing fatty acid amides |
| US8974743B2 (en) | 2009-06-30 | 2015-03-10 | Clariant Finance (Bvi) Limited | Device for continuously carrying out chemical reactions at high temperatures |
| US9302245B2 (en) | 2009-09-22 | 2016-04-05 | Clariant International Ltd. | Apparatus for continuously carrying out heterogeneously catalyzed chemical reactions at elevated temperatures |
| WO2011035852A3 (de) * | 2009-09-22 | 2011-05-19 | Clariant International Ltd | Vorrichtung zur kontinuierlichen durchführung heterogen katalysierter chemischer reaktionen bei hohen temperaturen |
| US9000197B2 (en) | 2009-09-22 | 2015-04-07 | Clariant Finance (Bvi) Limited | Continuous transesterification method |
| CN101757919B (zh) * | 2009-12-28 | 2012-12-26 | 中国科学院广州能源研究所 | 一种应用于生物油重整制氢的整体型催化剂及其制备方法和用途 |
| US9221938B2 (en) | 2010-12-30 | 2015-12-29 | Clariant Finance (Bvi) Limited | Polymers carrying hydroxyl groups and ester groups and method for the production thereof |
| US9243116B2 (en) | 2010-12-30 | 2016-01-26 | Clariant International Ltd. | Method for modifying polymers comprising hydroxyl groups |
| CN106008188A (zh) * | 2016-05-30 | 2016-10-12 | 浙江工业大学 | 一种甘油催化脱水制备丙烯醛的新方法 |
| CN106008188B (zh) * | 2016-05-30 | 2018-05-29 | 浙江工业大学 | 一种甘油催化脱水制备丙烯醛的新方法 |
| CN107337446A (zh) * | 2017-07-07 | 2017-11-10 | 福建省德化县联达陶瓷有限公司 | 一种功能性陶瓷产品及其制作工艺 |
| CN110772890A (zh) * | 2018-07-30 | 2020-02-11 | 天津大学 | 一种负载四氧化三铁的SiC泡沫陶瓷及其制备方法和应用 |
| CN110772911A (zh) * | 2018-07-30 | 2020-02-11 | 天津大学 | 一种去除生物气溶胶的微波反应装置、反应***及其应用 |
| CN110772911B (zh) * | 2018-07-30 | 2021-11-09 | 天津大学 | 一种去除生物气溶胶的微波反应装置、反应***及其应用 |
| CN110772890B (zh) * | 2018-07-30 | 2021-11-19 | 天津大学 | 一种负载四氧化三铁的SiC泡沫陶瓷及其制备方法和应用 |
| CN112604702A (zh) * | 2020-12-10 | 2021-04-06 | 南昌大学 | 一种微波驱动型催化剂的制备方法及应用 |
| CN112604702B (zh) * | 2020-12-10 | 2022-06-14 | 南昌大学 | 一种微波驱动型催化剂的制备方法及应用 |
| CN116253288A (zh) * | 2023-01-17 | 2023-06-13 | 中国林业科学研究院林产化学工业研究所 | 一种变频微波催化甲烷裂解制氢的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1142086C (zh) | 2004-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1142086C (zh) | 一种用于甲烷与二氧化碳重整反应的微波催化剂及其制备方法 | |
| EP3053880B1 (en) | Method for controlling bulk density of carbon nanotube agglomerate | |
| WO2009140791A1 (en) | Process for producing silicon carbide | |
| CN103908976B (zh) | 选择性可调的金属有机骨架zif-8膜包覆负载型贵金属高效核壳催化剂的制备方法 | |
| Zhao et al. | The synergistic catalytic effect between graphene oxide and three-dimensional ordered mesoporous Co3O4 nanoparticles for low-temperature CO oxidation | |
| CN108355668B (zh) | 一种甲烷化催化剂及其制备方法和应用 | |
| CN1038412A (zh) | 蒸汽转化催化剂 | |
| JP2012000614A (ja) | タングステン酸塩含有触媒の製造方法 | |
| CN109665512A (zh) | 一种多壁碳纳米管的制备方法 | |
| CN114249300A (zh) | 一种特定微观结构氧化铝负载Ni催化剂在等离子体催化甲烷干重整制合成气中的应用 | |
| WO2010115320A1 (zh) | 一种整体式多孔吸附剂及其制备方法 | |
| Lu et al. | Preparation of meso-macroporous carbon nanotube-alumina composite monoliths and their application to the preferential oxidation of CO in hydrogen-rich gases | |
| CN110885069A (zh) | 一种三维大孔超轻氮化碳材料及其制备方法 | |
| CN1301793C (zh) | 一种纳米碳材料改性的铜基催化剂及其制备方法 | |
| KR101466125B1 (ko) | 메조-마크로 기공을 갖는 산화마그네슘 구조체의 제조방법 | |
| CN118384887A (zh) | 一种用于微波驱动的甲醇-水重整制氢催化剂 | |
| CN113600223B (zh) | 一种Fe2P/氮空位g-C3N4纳米片光催化剂的制备方法与用途 | |
| KR20130081921A (ko) | 카본나노튜브용 균질 담지 촉매의 제조방법 및 이에 사용되는 장치 | |
| CN1736558A (zh) | 微波催化净化氮氧化物的新型催化剂及其制备方法和应用 | |
| CN115041230B (zh) | 一种金属负载型镍锰尖晶石纳米球气凝胶及其制备方法及应用 | |
| CN110961109A (zh) | 一种超声-微波协同辅助制备Ni-Al2O3催化剂的方法及其在CO2加氢中的应用 | |
| CN1131170C (zh) | 一种微波强化甲烷与二氧化碳重整制合成气的方法 | |
| CN114984997B (zh) | 一种三维多孔氮化碳基Zn单原子光催化剂、制备方法和应用 | |
| KR100962062B1 (ko) | 나노 결정질의 나노 다공성 전이금속 산화물의 제조 방법 | |
| Yao et al. | Vapor phase transport synthesis of SAPO-34 films on cordierite honeycombs |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |