CN103638943A - Cobalt-based Fischer-Tropsch fixed bed catalyst used for biomass synthetic gas and preparation method therefor - Google Patents
Cobalt-based Fischer-Tropsch fixed bed catalyst used for biomass synthetic gas and preparation method therefor Download PDFInfo
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Abstract
The invention belongs to the biomass energy utilization technology field, and discloses a cobalt-based Fischer-Tropsch fixed bed catalyst used for biomass synthetic gas and a preparation method therefor. The catalyst is composed of the following materials, by weight, 5-15% of Co3O4, CuO with a content of being more than 0 and less than or equal to 5%, 0.1-1% of RuO2, 3-20% of ZrO2, and the balance being gamma-aluminum oxide. The preparation method is as follows: first, gamma-aluminum oxide with a BET specific area of 180-210 m<2>/g and an average pore size of 14-16 nm is weighed according to required weight, the gamma-aluminum is peptized with 1-3wt% of concentrated nitric acid, then 0.5-2wt% of a pore forming agent CMC and 0.5-2wt% of auxiliary extruding agent sesbania powder are added, after the above mixture is mixed, pinched, ground and agglomerated, strip extrusion molding is carried out, after drying and calcinations, an alumina carrier is obtained; second, ZrO2 component is loaded through a saturation impregnation method, and a catalyst carrier is obtained after drying and calcination; third, Co3O4, CuO and RuO2 components are loaded through a saturation impregnation method, and a catalyst is obtained after drying and calcination. The catalyst has high CO hydrogenation catalytic activity and C<+5> selectivity, and low CH4 and CO2 selectivity.
Description
Technical field
The invention belongs to Biomass Energy Utilization technical field, relate in particular to a kind of co-based fischer-tropsch fixed bde catalyst for biomass synthesis gas and preparation method thereof.
Background technology
For a long time, the utilization of Biomass Energy Resources be take and directly burnt as main, not only inefficiency, and contaminated environment.Along with scientific and technical development, Biomass Energy Resources can be transformed and efficient utilization by various technology, produces electric power and heating power, or produces bio-fuel, as ethanol, biodiesel and biogas.Gasification of biomass synthesis clean fuel technology, is being stored in living beings, utilizes sun photosynthesis and the C, H component and the heat energy that obtain, by the synthetic method of gasification of biomass-Fischer-Tropsch, obtains high-quality, super clean liquid fuel.In this technique, for the fischer-tropsch synthetic catalyst of biomass synthesis gas, obtain extensive concern and research.
Fischer-tropsch synthetic catalyst generally includes following component: active metal (Co, Fe etc.), oxide carrier or structural promoter (SiO
2, Al
2o
3deng), chemical assistant (alkali metal oxide) and precious metal additive (Ru, Re, Pt etc.).Cobalt-base catalyst, for the synthetic hydrocarbon of CO hydrogenation, has the advantages such as chain growth ability is strong, course of reaction stable, the oxygenatedchemicals of generation is few, is comparatively ideal, rising FT synthetic catalyst.At present, the research catalyst based to Co, substantially around how further improving its catalytic activity and C
5+the selective expansion of hydrocarbon.Co precursor, preparation method, carrier, precious metal additive and rare metal oxide auxiliary agent etc. are very large on the interaction impact between active component Co and carrier, between metal and carrier, the interaction of appropriateness is conducive to reduction and the dispersion of Co, be conducive to improve the density of metallic state Co active sites, thereby make the synthetic hydrocarbon process of CO hydrogenation there is higher reaction rate and C
5+hydrocarbon selective.
US Patent No. 6537945 B2 provide a kind of Heat stability is good, active high Co base aluminium oxide catalyst and preparation method thereof.Its feature is with γ-Al
2o
3be carrier, Co
3o
4for active component, by adding noble metal and alkaline-earth metal, improve catalyst performance, catalyst is mainly adapted to slurry reactor.
US Patent No. 7939699 B2 provide the Co based titanium dioxide Catalysts and its preparation method that a kind of activity is high.Its feature is to adopt TiO
2for carrier, because itself and Co have stronger interaction, can make Co and carrier surface form new active sites, thereby make catalyst there is higher activity and C
5+selectively.
Chinese patent CN 102962066 discloses Co based Fischer-Tropsch synthesis catalyst of a kind of alumina load and preparation method thereof.This catalyst is introduced microwave technology in catalyst preparation process.Catalyst is used γ-Al
2o
3as carrier, with Co
3o
4for active component, the oxides such as noble ruthenium, rhodium, palladium of take are auxiliary agent.It is good that this catalyst has reactivity, stability high.Above-mentioned catalyst is mainly studied is that to take the synthesis gas that coal and natural gas prepared as raw material be Fischer-Tropsch synthesis material, special less for the research of biomass synthesis gas, Catalyst for CO high active of hydrogenation catalysis, C
5+selective and heat endurance needs further to be improved, CH
4and CO
2selectively need further to be reduced.
Summary of the invention
One of object of the present invention is to provide a kind of co-based fischer-tropsch fixed bde catalyst for biomass synthesis gas, and two of object is to provide its preparation method, and this catalyst has higher CO high active of hydrogenation catalysis, C
5+selective and low CH
4and CO
2selectively.
The technical scheme that realizes one of the object of the invention is: a kind of co-based fischer-tropsch fixed bde catalyst for biomass synthesis gas, is comprised of the following material that accounts for catalyst weight percentage composition: Co
3o
45-15%, 0 < CuO≤5%, RuO
20.1-1%, ZrO
23-20%, all the other are gama-alumina.Catalyst of the present invention is comprised of carrier, active component and auxiliary agent, wherein, and ZrO
2with gama-alumina be carrier, Co
3o
4for active component, RuO
2and ZrO
2for auxiliary agent.
Preferably, by the following material that accounts for catalyst weight percentage composition, formed: Co
3o
410-15%, CuO 3-5%, RuO
20.1-0.5%, ZrO
23-10%, all the other are gama-alumina.
Two the technical scheme that realizes the object of the invention is: the steps include: 1. by required weight, to take BET method specific area 180-210m
2the gama-alumina of/g, average pore size 14-16nm, with 1-3 wt% red fuming nitric acid (RFNA) peptization, add afterwards the pore creating material CMC(carboxymethyl cellulose of 0.5-2 wt%) and the extrusion aid sesbania powder of 0.5-2 wt%, kneading, roll agglomerating after, extruded moulding, obtains alumina support through super-dry, roasting; Described wt% all be take gama-alumina weight as calculating basis; 2. the alumina support that adopts saturated infusion process 1. to make by zirconium nitrate aqueous solution room temperature impregnation steps, obtains catalyst carrier through super-dry, roasting; 3. the catalyst carrier that adopts saturated infusion process 2. to make by the mixed solution room temperature impregnation steps that is dissolved with ruthenium trichloride, cobalt nitrate and copper nitrate, obtains catalyst through super-dry, roasting.
Preferably, step 1. in, in 100-130 ℃ of air drying 8-24h, in 500-750 ℃ of roasting 5-8h; Step 2. in, dipping 12-20h, in 100-130 ℃ of air drying 6-12h, in 600-800 ℃ of roasting 5-8h; Step 3. in, dipping 18-24h, in 100-130 ℃ of air drying 6-12h, in 300-500 ℃ of roasting 3-8h.
Preferably, step 1. in, extruded moulding is to the hollow stripe shape of peripheral diameter 1.6-3.5mm.
Catalyst of the present invention has higher CO high active of hydrogenation catalysis, C
5+selective and low CH
4and CO
2selectively.In addition, advantage of the present invention also shows: 1. compared with prior art, due to the meso-hole structure carrier that has adopted high surface and average pore size at 14-16nm, the polymolecularity of active component and good reactant mass transfer have been guaranteed, simultaneously, the type of the selecting effect in duct causes the concentrated 6-14nm that is distributed in of cobalt granule particle diameter, is applicable to Fischer-Tropsch synthesis.2. due at γ-Al
2o
3carrier surface load high dispersive ZrO
2coating, has stoped the synthetic middle steam producing of Fischer-Tropsch and the interaction of cobalt, has improved the hydrothermal stability of catalyst, stops to form to be difficult to reduction and the lower cobalt surface aluminate species of activity simultaneously, thereby improves the reducing degree of Co.ZrO
2there is oxidisability and reproducibility, acidity and alkaline simultaneously, can form the Co-Zr species of easy reduction with Co, improved the decentralization of Co, promoted the increase of catalyst activity.3. because catalyst has formed Co-Cu-Ru alloy catalyst, brought into play the synergy of metallic catalyst, the hydrogen overflow of noble metal has simultaneously guaranteed the reducing activity of metal.4. this catalyst carrier adopts hollow stripe shape carrier, and carrier center has formed reaction district, microchannel, causes catalyst to have higher mass transfer and heat transfer property, improves the activity and selectivity of catalyst.
The specific embodiment
Below by specific embodiment, the present invention is further described, but is not limited to this.
The catalyst A that embodiment 1 is prepared with the inventive method
1. getting a kind of BET method specific area is 210m
2the gama-alumina 300g of/g, average pore size 15.2nm, add 5ml red fuming nitric acid (RFNA) (65%, quality, following examples are same) peptization, add afterwards 3.0g sesbania powder and 3.0gCMC to mix kneading agglomerating, put into banded extruder and extrude hollow flute profile irregular bar, peripheral maximum gauge is 3.5mm, after 110 ℃ of air drying 10h, in 600 ℃ of roasting temperature 8h, obtain gamma-aluminium oxide carrier afterwards.
2. getting gamma-aluminium oxide carrier 90g that 1. step obtained, to impregnated in 75ml concentration be 1.08mol/L zirconium nitrate solution, and under room temperature, dip time is 16h, after 110 ℃ of air drying 10h, in 750 ℃ of roasting temperature 6h, obtains catalyst carrier.
3. getting catalyst carrier 10g that 2. step obtained impregnated in and be dissolved with 0.056g ruthenium trichloride (RuCl
33H
2o), 8.62g cobalt nitrate (Co (NO
3)
36H
2o) and 1.58g copper nitrate (Cu (NO
3)
23H
2o) mixed solution 10ml, under room temperature, dip time is 20h, after 110 ℃ of air drying 10h, in 400 ℃ of roasting temperature 5h, makes catalyst A.The active component Co of catalyst A load
3o
4content is the 15wt% of catalyst total amount, and CuO content is 4.5 wt %, RuO
2content is 0.30 wt %, ZrO
2content is 10 wt %, and surplus is gama-alumina.
The catalyst B that embodiment 2 is prepared with the inventive method
1. getting a kind of BET method specific area is 182m
2the gama-alumina 300g of/g, average pore size 14.4nm, add 6ml red fuming nitric acid (RFNA) peptization, add afterwards 3.0g sesbania powder and 4.0gCMC to mix kneading agglomerating, put into banded extruder and extrude hollow cylinder shape bar, peripheral maximum gauge is 1.8mm, after 110 ℃ of air drying 12h, in 650 ℃ of roasting temperature 6h, obtain gamma-aluminium oxide carrier afterwards.
2. getting gamma-aluminium oxide carrier 90g that 1. step obtained, to impregnated in 70ml concentration be 1.16mol/L zirconium nitrate solution, and under room temperature, dip time is 12h, after 110 ℃ of air drying 10h, in 700 ℃ of roasting temperature 8h, obtains catalyst carrier.
3. getting catalyst carrier 10g that 2. step obtained impregnated in and be dissolved with 0.056g ruthenium trichloride (RuCl
33H
2o), 8.62g cobalt nitrate (Co (NO
3)
36H
2o) and 1.58g copper nitrate (Cu (NO
3)
23H
2o) mixed solution 8ml, under room temperature, dip time is 20h, after 110 ℃ of air drying 10h, in 450 ℃ of roasting temperature 5h, makes catalyst B.The active component Co of catalyst B load
3o
4content is 15 wt % of catalyst total amount, and CuO content is 4.5 wt %, RuO
2content is 0.30 wt %, ZrO
2content is 10 wt %, and surplus is gama-alumina.
The catalyst C that embodiment 3 is prepared with the inventive method
1. with embodiment 1.
2. getting gamma-aluminium oxide carrier 90g that 1. step obtained, to impregnated in 75ml concentration be 0.32mol/L zirconium nitrate solution, and under room temperature, dip time is 16h, after 110 ℃ of air drying 10h, in 750 ℃ of roasting temperature 6h, obtains catalyst carrier.
3. getting catalyst carrier 10g that 2. step obtained impregnated in and be dissolved with 0.056g ruthenium trichloride (RuCl
33H
2o), 8.62g cobalt nitrate (Co (NO
3)
36H
2o) and 1.58g copper nitrate (Cu (NO
3)
23H
2o) mixed solution 11ml, under room temperature, dip time is 20h, after 110 ℃ of air drying 10h, in 400 ℃ of roasting temperature 5h, makes catalyst C.The active component Co of catalyst C load
3o
4content is 15 wt % of catalyst total amount, and CuO content is 4.5 wt %, RuO
2content is 0.30 wt %, ZrO
2content is 3.0 wt %, and surplus is gama-alumina.
The catalyst D that embodiment 4 is prepared with the inventive method
1. with embodiment 1.
2. with embodiment 1.
3. getting catalyst carrier 10g that 2. step obtained impregnated in and be dissolved with 0.019g ruthenium trichloride (RuCl
33H
2o), 5.48g cobalt nitrate (Co (NO
3)
36H
2o) and 1.0g copper nitrate (Cu (NO
3)
23H
2o) mixed solution 10ml, under room temperature, dip time is 20h, after 110 ℃ of air drying 10h, in 400 ℃ of roasting temperature 5h, makes catalyst D.The active component Co of catalyst D load
3o
4content is the 10wt% of catalyst total amount, and CuO content is 3 wt %, RuO
2content is 0.1 wt %, ZrO
2content is 10 wt %, and surplus is gama-alumina.
Application example
1. get above-mentioned catalyst A, B, C, each 2g of D and reduce in fixed bed with pure hydrogen, reducing condition is: 250 ℃, and normal pressure, 1.8L/g.cat.h, constant temperature 14h.
2. react in fixed bed reactors and carry out, reaction condition is: 250 ℃, and 2.0MPa, 1.8L/g.cat.h, biomass synthesis gas volume consists of: N
2: 49.1%, CO:13.07%, CO
2: 10.65%, H
2: 25.78%, CH
4: 1.40%.Reaction 24h the results are shown in Table 1.As seen from table: this catalyst has higher CO high active of hydrogenation catalysis, C
5+selective and low CH
4and CO
2selectively.
Table 1 catalyst reaction result
| Catalyst | CO conversion ratio/% | CO 2Selectively/% | CH 4Selectively/% | C 2H 6Selectively/% | C 3H 8Selectively/% | C 4H 10Selectively/% | C 5+Selectively/% |
| Catalyst A | 99.00 | 9.09 | 20.78 | 3.88 | 3.97 | 2.39 | 59.89 |
| Catalyst B | 98.75 | 8.79 | 20.35 | 3.75 | 3.86 | 2.28 | 60.97 |
| Catalyst C | 96.01 | 6.08 | 19.46 | 3.81 | 4.18 | 2.42 | 64.06 |
| Catalyst D | 94.43 | 10.32 | 25.97 | 3.02 | 2.34 | 1.87 | 56.48 |
Claims (5)
1. for a co-based fischer-tropsch fixed bde catalyst for biomass synthesis gas, it is characterized in that being formed by the following material that accounts for catalyst weight percentage composition: Co
3o
45-15%, 0 < CuO≤5%, RuO
20.1-1%, ZrO
23-20%, all the other are gama-alumina.
2. the co-based fischer-tropsch fixed bde catalyst for biomass synthesis gas as claimed in claim 1, is characterized in that being comprised of the following material that accounts for catalyst weight percentage composition: Co
3o
410-15%, CuO 3-5%, RuO
20.1-0.5%, ZrO
23-10%, all the other are gama-alumina.
3. a method of preparing the co-based fischer-tropsch fixed bde catalyst for biomass synthesis gas as claimed in claim 1, is characterized in that step is as follows:
1. by required weight, take BET method specific area 180-210m
2the gama-alumina of/g, average pore size 14-16nm, with 1-3 wt% red fuming nitric acid (RFNA) peptization, add afterwards the pore creating material CMC of 0.5-2 wt% and the extrusion aid sesbania powder of 0.5-2 wt%, kneading, roll agglomerating after, extruded moulding, obtains alumina support through super-dry, roasting; Described wt% all be take gama-alumina weight as calculating basis;
2. the alumina support that adopts saturated infusion process 1. to make by zirconium nitrate aqueous solution room temperature impregnation steps, obtains catalyst carrier through super-dry, roasting;
3. the catalyst carrier that adopts saturated infusion process 2. to make by the mixed solution room temperature impregnation steps that is dissolved with ruthenium trichloride, cobalt nitrate and copper nitrate, obtains catalyst through super-dry, roasting.
4. preparation method as claimed in claim 3, is characterized in that: step 1. in, in 100-130 ℃ of air drying 8-24h, in 500-750 ℃ of roasting 5-8h; Step 2. in, dipping 12-20h, in 100-130 ℃ of air drying 6-12h, in 600-800 ℃ of roasting 5-8h; Step 3. in, dipping 18-24h, in 100-130 ℃ of air drying 6-12h, in 300-500 ℃ of roasting 3-8h.
5. preparation method as claimed in claim 3, is characterized in that: step 1. in, extruded moulding is to the hollow stripe shape of peripheral diameter 1.6-3.5mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376937A (en) * | 2017-08-14 | 2017-11-24 | 河南省科学院能源研究所有限公司 | A kind of order mesoporous composite catalyst and its preparation method and application |
| CN107913708A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | HCN-containing gases catalyst for catalytic oxidation and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010049715A1 (en) * | 2008-10-30 | 2010-05-06 | Johnson Matthey Plc | Cobalt catalyst precursor |
| CN102962077A (en) * | 2012-11-26 | 2013-03-13 | 中国科学院山西煤炭化学研究所 | Cobalt-based Fischer-Tropsch synthetic catalyst as well as preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010049715A1 (en) * | 2008-10-30 | 2010-05-06 | Johnson Matthey Plc | Cobalt catalyst precursor |
| CN102962077A (en) * | 2012-11-26 | 2013-03-13 | 中国科学院山西煤炭化学研究所 | Cobalt-based Fischer-Tropsch synthetic catalyst as well as preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| 厉衡隆等: "《铝冶炼生产技术手册（上册）》", 31 July 2011, article "催化剂及其载体", pages: 952 * |
| 史建文等: ""挤出成型过程中得各种因素对氧化铝载体物性的影响"", 《石油化工》, vol. 14, 31 December 1985 (1985-12-31), pages 322 - 328 * |
| 徐承恩: "《催化重整工艺与工程》", 31 December 2006, article ""载体成型"", pages: 316 * |
| 朱洪法等: "《催化剂制备及应用技术》", 30 June 2011, article "成型助剂", pages: 244-248 * |
| 熊海峰: ""SBA-15负载的钴、钌费-托合成催化剂结构及性能的研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 4, 15 April 2010 (2010-04-15) * |
| 赵骧: "《催化剂》", 31 January 2001, article "催化剂", pages: 102 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107913708A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | HCN-containing gases catalyst for catalytic oxidation and preparation method thereof |
| CN107376937A (en) * | 2017-08-14 | 2017-11-24 | 河南省科学院能源研究所有限公司 | A kind of order mesoporous composite catalyst and its preparation method and application |
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