CN104549285A - Complex nano-catalyst for preparing synthesis gas by reforming methane and carbon dioxide, and preparation method thereof - Google Patents
Complex nano-catalyst for preparing synthesis gas by reforming methane and carbon dioxide, and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of catalyst preparation, and particularly relates to a complex nano-catalyst for preparing synthesis gas by reforming methane and carbon dioxide, and a preparation method thereof. The complex nano-catalyst comprises an active ingredient, an accessory ingredient and a complex carrier, wherein the active ingredient is composed of cobalt oxide and nickel oxide; the accessory ingredient is composed of one or more of potassium oxide, magnesium oxide or lanthanum oxide; the complex carrier is composed of two of nano aluminium oxide, nano zirconium oxide or nano silicon oxide. The preparation method comprises the following steps: preparing a mixed solution; preparing the complex nano-catalyst. The complex nano-catalyst is small in particle diameter of the complex carrier, has high surface energy and surface defects, increases catalyst active sites, activates carbon dioxide to generate active oxygen, assists carbon elimination, reduces the yield of carbon, slightly improves stability of the complex nano-catalyst, and prolongs the use period of the complex nano-catalyst; the preparation method is simple, scientific and reasonable.
Description
Technical field
The invention belongs to field of catalyst preparation, be specifically related to nano-composite catalyst of a kind of synthesizing gas by reforming methane with co 2 and preparation method thereof.
Background technology
Day by day serious along with greenhouse effects, the discharge of restriction greenhouse gases is more and more subject to people's attention.Carbon dioxide causes greenhouse effects, causes the one of the main reasons that global climate worsens.Along with the development of chemical industry, the carbon dioxide content in air will be more and more higher.Carbon dioxide content only in air just reaches 100,000,000,000,000 tons, and the amount of carbon dioxide that the whole world is discharged every year in air reaches 185*10
8ton, and with annual 4% speed increment.Therefore, how to reduce the discharge of carbon dioxide and carry out the huge challenge that Resources of Carbon Dioxide utilization is facing mankind.
Natural gas methane, as industrial chemicals, is mainly used in synthetic ammonia and methanol industry at present.Along with the long-term exploitation of petroleum resources, its reserves are hidden weary increasingly, the primary carbon source that natural gas will be following basic chemicals.According to estimates, to the year two thousand twenty, in world energy sources structure, natural gas proportion rises to 40% by from current 25%, thus petroleum replacing becomes the global topmost energy.
Synthesizing gas by reforming methane with co 2, makes full use of abundant natural gas resource on the one hand, effectively can reduce CO2 emission, have environmental benefit; Methane, carbon dioxide conversion are the chemicals of high added value by another aspect, have huge economic benefit.
In recent years, microwave heating is applied to the broad interest that inorganic porous material synthesis field causes people.Microwave hydrothermal be one prepare fast narrow diameter distribution, good dispersion, reunion less, perfect crystalline and good crystallinity, the new method of the nano particle that form is homogeneous, aggregate velocity and efficiency are also higher than conventional hydrothermal method a lot.
The methane of current patent or bibliographical information, CO 2 reformation catalyst for preparing synthetic gas are mainly divided into two large classes: noble metal catalyst and non-precious metal catalyst.Catalyst activity component is mainly the group VIII metals such as rhodium, ruthenium, platinum, iridium, nickel, cobalt.Wherein noble metal catalyst has the advantage that catalytic activity is high, anti-carbon performance is strong, but the shortcoming of easy-sintering, loss under also there is expensive, hot conditions.Nickel-base catalyst has good catalytic activity, but easily occurs because of carbon monoxide high temperature disproportionation carbon distribution that activity decrease and beds block.Therefore, by improving carrier and method for preparing catalyst, improving dispersiveness and the stability of active component, and then improve activity and the anti-carbon performance of catalyst, is that this research field needs one of key problems-solving at present.
Chinese patent CN201110274705 discloses the catalyst of nickel-loaded, cobalt, copper isoreactivity component on the sial complex carrier of alkalinous metal modification, this catalyst comprises the metallic nickel of 5.0wt% ~ 40.0wt%, second metal M of 0.5wt% ~ 15.0wt% and the carrier of 45.0wt% ~ 94.5wt%, carrier is made up of the sieve and silica-sesquioxide of 50.0wt% ~ 90.0wt% and the alkaline metal oxide of surplus.This catalyst adopts sol-gal process to obtain.US Patent No. 5744419 discloses a kind of method for preparing catalyst producing synthesis gas for methane, natural gas and biogas catalyzed conversion; its technical scheme is that carrier surface passes through to flood or apply and superscribes one deck alkaline-earth metal beryllium, one of the oxide of magnesium or its mixture in advance as protective layer, then by dipping or coating carried upper active component.Carrier is the low specific surface area porous refractory inert solid of sintering, particle diameter 1 ~ 15mm, be selected from silica, aluminium oxide, silica-alumina, carborundum, zirconia, hafnium oxide or its mixture, catalyst activity component is the oxide of cobalt and nickel, contain or do not contain noble metal, active component content take oxide basis as 0.3wt% ~ 30wt%, and the mol ratio of cobalt nickel is 0.01 ~ 2.0; Alkali-metal-oxide content is 0.3wt% ~ 30wt%.
Summary of the invention
The object of this invention is to provide a kind of nano-composite catalyst of synthesizing gas by reforming methane with co 2, activity is high, carbon accumulation resisting ability is strong, stability is high; Invention also provides the preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2, preparation technology is simple, scientific and reasonable.
The nano-composite catalyst of synthesizing gas by reforming methane with co 2 of the present invention, comprise active component, auxiliary agent and complex carrier, active constituent is cobalt oxide and nickel oxide, auxiliary agent is one or more in potassium oxide, magnesia or lanthana, and complex carrier is two kinds in nano aluminium oxide, nano zircite or nano silicon oxide.
By percentage to the quality, catalyst components content is as follows:
The particle diameter of described catalyst is 10-15nm, and average pore size is 4.5-10nm.
The preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2 of the present invention, comprises the following steps:
(1) first configure the homogeneous water solution A of cobalt oxide predecessor, complex carrier predecessor and auxiliary agent predecessor, then configure the solution B of nickel oxide predecessor;
(2) under ultrasonic wave treatment conditions, by solution A and solution B and stream mix, obtain mixed solution C;
(3) mixed solution C heating using microwave, naturally cools to room temperature, washing, dry, adds lubricant and binding agent extruded moulding, roasting and get final product.
Cobalt oxide predecessor described in step (1) is the one in cobalt nitrate, cobaltous sulfate, cobalt chloride or cobalt acetate, preferred cobalt acetate; Complex carrier predecessor is aluminum nitrate, zirconium nitrate and Ludox, and nickel oxide predecessor is basic nickel carbonate, and auxiliary agent predecessor is potassium nitrate, magnesium nitrate and lanthanum nitrate.
The solution of the nickel oxide predecessor described in step (1) is dissolved in ammoniacal liquor and/or urea liquid by nickel oxide predecessor.
Ultrasonic treatment time described in step (2) is 10-25min, preferred 15-20min; Ultrasonic frequency is 25-45kHz.
Microwave heating temperature described in step (3) is 100-200 DEG C, preferred 160-190 DEG C; Microwave heating time is 15-100min, preferred 20-60min.
Drying described in step (3) is vacuum drying, and baking temperature is 80-120 DEG C, and drying time is 24-72 hour.
Roasting described in step (3) is that dried catalyst is warming up to 400 ~ 450 DEG C with 1 ~ 5 DEG C/min speed, constant temperature calcining 1 ~ 2h in atmosphere, is then warming up to 650 ~ 850 DEG C of constant temperature calcining 0.5 ~ 2.5h with 1 ~ 5 DEG C/min speed.
When complex carrier predecessor be aluminum nitrate and zirconium nitrate time, the mol ratio of aluminum nitrate and zirconium nitrate is 0.5-5:1, preferred 1-2:1; When complex carrier predecessor be Ludox and zirconium nitrate time, the mol ratio of Ludox and zirconium nitrate is 0.5-5:1, preferred 1-2:1; When complex carrier predecessor be aluminum nitrate and Ludox time, the mol ratio of aluminum nitrate and Ludox is 1:1.
When auxiliary agent is multiple in potassium oxide, magnesia or lanthana, combine with any proportioning.
Described lubricant is sesbania powder, and binding agent is citric acid.
The preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2 of the present invention, concrete steps are as follows:
(1) by cobalt oxide predecessor, complex carrier predecessor and auxiliary agent predecessor stirring soluble in water 10-30min, solution A is obtained; Again nickel oxide predecessor is dissolved in ammoniacal liquor and/or urea liquid, obtains solution B;
(2) by solution A and solution B in ultrasonic oscillator and stream mix, obtain mixed solution C;
(3) move in microwave reaction kettle by mixed solution C, loading is no more than 80%, and heating using microwave naturally cools to room temperature, takes out, and washing is dry, adds lubricant and binding agent extruded moulding, roasting and get final product.
Catalyst of the present invention is nano-composite catalyst, adopts microwave-hydrothermal method preparation.The nano-metal particle prepared and the interactional nano-composite catalyst of nano-oxide particles, achieve concerted catalysis between metal active constituent and carrier.
The present invention compared with prior art, has following beneficial effect:
Catalyst of the present invention, complex carrier particle diameter little (10-15nm), there is high surface energy and blemish, add catalyst active center, activation carbon dioxide produces active oxygen, and the auxiliary carbon that disappears, decreases the growing amount of carbon, the stability of catalyst is increased, extends the life cycle of catalyst.Catalyst can at methane volumetric air speed 2000-18000h
-1, methane: carbon dioxide=1:1.5(mol ratio), pressure is under condition of normal pressure, and the conversion ratio of methane and carbon dioxide reaches 99% and 90% respectively; Under 1MPa pressure condition, the conversion ratio of methane and carbon dioxide reaches 85% and 83% respectively, and this catalyst has good Activity and stabill.Preparation technology of the present invention is simple, scientific and reasonable.
Accompanying drawing explanation
Fig. 1 is small-sized evaluating apparatus schematic flow sheet,
In figure 1, mass flowmenter; 2, stop valve; 3, preheater; 4, reactor; 5, gas-liquid separator; 6, drier; 7, flowing valve; 8, chromatograph; 9, Pressure gauge.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Take 57g aluminum nitrate, 40.5g zirconium nitrate, 4.1g cobalt acetate, 0.42g lanthanum nitrate be dissolved in 500ml water and stir 10min, obtain solution A.Take 72g urea, 16ml ammoniacal liquor adds 14.2g basic nickel carbonate after being dissolved in 500ml water and obtain solution B.By solution A and solution B in ultrasonic oscillator and stream mix, ultrasonic frequency is 25kHz, and vibration 15min obtains mixed solution C.Solution C moved in microwave reaction kettle, loading is no more than 80%, in 180 DEG C of heating 30min, naturally cools to room temperature, pours centrifuge washing into, 120 DEG C of dry 24h.Gained catalyst fines is mixed with 0.8g sesbania powder, 0.7g citric acid, extruded moulding roasting, be warming up to 400 DEG C with 2 DEG C/min speed, constant temperature calcining 2h, then rise to 850 DEG C of roasting 2.5h with 2 DEG C/min speed, obtain catalyst A.Catalyst A physico-chemical property and composition are in table 1.
Embodiment 2
Take 40.5g zirconium nitrate, 1.1g cobalt acetate, 0.85g lanthanum nitrate, 39.6g Ludox be dissolved in 500ml water and stir 20min, obtain solution A.Take 60g urea, 12ml ammoniacal liquor adds 10.5g basic nickel carbonate after being dissolved in 500ml water and obtain solution B.By solution A and solution B in ultrasonic oscillator and stream mix, ultrasonic frequency is 45kHz, and vibration 20min obtains mixed solution C.Solution C moved in microwave reaction kettle, loading is no more than 80%, in 160 DEG C of heating 15min, naturally cools to room temperature, pours centrifuge washing into, 80 DEG C of vacuum drying 36h.Gained catalyst fines is mixed with 0.7g sesbania powder, 0.6g citric acid, extruded moulding roasting, be warming up to 400 DEG C with 1 DEG C/min speed, constant temperature calcining 2h, then rise to 850 DEG C of roasting 0.5h with 2 DEG C/min speed, obtain catalyst B.Catalyst B physico-chemical property and composition are in table 1.
Embodiment 3
Take 104g aluminum nitrate, 40.5g zirconium nitrate, 5.9g cobaltous sulfate, 2.33g lanthanum nitrate be dissolved in 500ml water and stir 15min, obtain solution A.Take 89.7g urea, 18ml ammoniacal liquor adds 18.2g basic nickel carbonate after being dissolved in 500ml water and obtain solution B.By solution A and solution B in ultrasonic oscillator and stream mix, ultrasonic frequency is 30kHz, and vibration 25min obtains mixed solution C.Solution C moved in microwave reaction kettle, loading is no more than 80%, in 100 DEG C of heating 60min, naturally cools to room temperature, pours centrifuge washing into, 80 DEG C of vacuum drying 72h.Gained catalyst fines is mixed with 1.2g sesbania powder, 0.9g citric acid, extruded moulding roasting, be warming up to 450 DEG C with 2 DEG C/min speed, constant temperature calcining 1h, then rise to 650 DEG C of roasting 2.5h with 1 DEG C/min speed, obtain catalyst C.Catalyst C physico-chemical property and composition are in table 1.
Embodiment 4
Take 57g aluminum nitrate, 40.5g zirconium nitrate, 2.2g cobalt acetate, 11g magnesium nitrate be dissolved in 500ml water and stir 30min, obtain solution A.Take 72g urea, 10ml ammoniacal liquor adds 18.2g basic nickel carbonate after being dissolved in 500ml water and obtain solution B.By solution A and solution B in ultrasonic oscillator and stream mix, ultrasonic frequency is 40kHz, and vibration 20min obtains mixed solution C.Solution C moved in microwave reaction kettle, loading is no more than 80%, in 190 DEG C of heating 25min, naturally cools to room temperature, pours centrifuge washing into, 80 DEG C of vacuum drying 72h.Gained catalyst fines is mixed with 0.8g sesbania powder, 0.7g citric acid, extruded moulding roasting, be warming up to 450 DEG C with 5 DEG C/min speed, constant temperature calcining 2h, then rise to 850 DEG C of roasting 2.5h with 2 DEG C/min speed, obtain catalyst D.Catalyst D physico-chemical property and composition are in table 1.
Embodiment 5
Take 57g aluminum nitrate, 40.5g zirconium nitrate, 2.1g cobalt chloride, 2.2g magnesium nitrate be dissolved in 500ml water and stir 10min, obtain solution A.Take 72g urea, 10ml ammoniacal liquor adds 18.2g basic nickel carbonate after being dissolved in 500ml water and obtain solution B.By solution A and solution B in ultrasonic oscillator and stream mix, ultrasonic frequency is 35kHz, and vibration 10min obtains mixed solution C.Solution C moved in reactor, loading is no more than 80%, in 200 DEG C of heating 30min, naturally cools to room temperature, pours centrifuge washing into, 90 DEG C of vacuum drying 72h.Gained catalyst fines is mixed with 0.8g sesbania powder, 0.7g citric acid, extruded moulding roasting, be warming up to 440 DEG C with 2 DEG C/min speed, constant temperature calcining 1.5h, then rise to 850 DEG C of roasting 2h with 5 DEG C/min speed, obtain catalyst E.Catalyst E physico-chemical property and composition are in table 1.
Embodiment 6
Take 57g aluminum nitrate, 4.1g cobalt acetate, 0.42g potassium nitrate, 40.2g Ludox be dissolved in 500ml water and stir 10min, obtain solution A.Take 72g urea, 16ml ammoniacal liquor adds 14.2g basic nickel carbonate after being dissolved in 500ml water and obtain solution B.By solution A and solution B in ultrasonic oscillator and stream mix, ultrasonic frequency is 30kHz, and vibration 25min obtains mixed solution C.Solution C moved in microwave reaction kettle, loading is no more than 80%, in 180 DEG C of heating 100min, naturally cools to room temperature, pours centrifuge washing into, 120 DEG C of dry 24h.Gained catalyst fines is mixed with 0.8g sesbania powder, 0.7g citric acid, extruded moulding roasting, be warming up to 400 DEG C with 2 DEG C/min speed, constant temperature calcining 2h, then rise to 800 DEG C of roasting 2.5h with 2 DEG C/min speed, obtain catalyst F.Catalyst F physico-chemical property and composition are in table 1.
Table 1 catalyst physico-chemical property and composition
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Catalyst is numbered | A | B | C | D | E | F |
| Ni content, % (weight) | 9 | 6.5 | 11.5 | 11.5 | 11.5 | 9 |
| Co content, % (weight) | 4 | 1 | 5 | 2 | 2 | 4 |
| La content, % (weight) | 1 | 2 | 5.5 | - | - | - |
| K content, % (weight) | - | - | - | - | - | 1 |
| Mg content, % (weight) | - | - | - | 5.5 | 1 | - |
| Catalyst particle size, nm | 10.5 | 14.5 | 12.6 | 13.8 | 14.2 | 11.0 |
Catalyst A-the F for preparing of said method is adopted to measure on small-sized evaluating apparatus, with methane, carbon dioxide conversion and carbon monoxide and hydrogen yield for index.As shown in Figure 1, concrete appreciation condition is the signal of device flow process:
Test raw material is the natural gas of sulfur content <0.2ppm, food-grade carbon-dioxide.
The filling of catalyst: catalyst Φ 2.2 × 5 ~ 10mm bar, loading amount 10mL;
Normal pressure operating condition: methane air speed is 18000h
-1; Carbon dioxide/methane (v/v) is 1.5/1; Reaction temperature is 750 DEG C, and the duration of runs is 100h.
Pressurization operating condition: methane air speed is 6000h
-1; Carbon dioxide/methane (v/v) is 1.5/1; Reaction temperature is entrance 700 DEG C, exports 850 DEG C; Reaction pressure is 1.0MPa, the duration of runs: 100h.Catalyst still keeps good activity and stability after normal pressure and each 100h of pressurization running.
Catalyst A-F normal pressure Activity evaluation is in table 2, and pressurization Activity evaluation is in table 3.
Table 2 normal pressure Activity evaluation
| Catalyst | CH 4Conversion ratio % | CO 2Conversion ratio % | CO yield % | H 2Yield % |
| A | 99.5 | 94.0 | 97.2 | 99 |
| B | 92 | 89.2 | 90.0 | 91.2 |
| C | 98.3 | 90.6 | 94.7 | 93.6 |
| D | 97.5 | 90.1 | 93.5 | 92.0 |
| E | 93.1 | 88.9 | 91.7 | 90.5 |
| F | 99.1 | 90.5 | 95.5 | 94.5 |
Table 3 pressurizes Activity evaluation
| Catalyst | CH 4Conversion ratio % | CO 2Conversion ratio % | CO yield % | H 2Yield % |
| A | 85.6 | 83.4 | 97.2 | 99.0 |
| B | 80.4 | 77.5 | 79.3 | 93.8 |
| C | 84.2 | 75.1 | 90.8 | 92.5 |
| D | 83.9 | 75.3 | 90.4 | 93.1 |
| E | 81.1 | 80.5 | 87.7 | 91.5 |
| F | 84.1 | 78.3 | 80.1 | 92.1 |
Claims (10)
1. the nano-composite catalyst of a synthesizing gas by reforming methane with co 2, comprise active component, auxiliary agent and complex carrier, it is characterized in that active constituent is cobalt oxide and nickel oxide, auxiliary agent is one or more in potassium oxide, magnesia or lanthana, and complex carrier is two kinds in nano aluminium oxide, nano zircite or nano silicon oxide.
2. the nano-composite catalyst of synthesizing gas by reforming methane with co 2 according to claim 1, is characterized in that by percentage to the quality, and catalyst components content is as follows:
3. the nano-composite catalyst of synthesizing gas by reforming methane with co 2 according to claim 1, it is characterized in that the particle diameter of described catalyst is 10-15nm, average pore size is 4.5-10nm.
4. a preparation method for the nano-composite catalyst of the arbitrary described synthesizing gas by reforming methane with co 2 of claim 1-3, is characterized in that comprising the following steps:
(1) first configure the homogeneous water solution A of cobalt oxide predecessor, complex carrier predecessor and auxiliary agent predecessor, then configure the solution B of nickel oxide predecessor;
(2) under ultrasonic wave treatment conditions, by solution A and solution B and stream mix, obtain mixed solution C;
(3) mixed solution C heating using microwave, naturally cools to room temperature, washing, dry, adds lubricant and binding agent extruded moulding, roasting and get final product.
5. the preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2 according to claim 4, it is characterized in that the cobalt oxide predecessor described in step (1) is the one in cobalt nitrate, cobaltous sulfate, cobalt chloride or cobalt acetate, complex carrier predecessor is aluminum nitrate, zirconium nitrate and Ludox, nickel oxide predecessor is basic nickel carbonate, and auxiliary agent predecessor is potassium nitrate, magnesium nitrate and lanthanum nitrate.
6. the preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2 according to claim 4, is characterized in that the solution of the nickel oxide predecessor described in step (1) is dissolved in ammoniacal liquor and/or urea liquid by nickel oxide predecessor.
7. the preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2 according to claim 4, it is characterized in that the ultrasonic treatment time described in step (2) is 10-25min, ultrasonic frequency is 25-45kHz.
8. the preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2 according to claim 4, it is characterized in that the microwave heating temperature described in step (3) is 100-200 DEG C, microwave heating time is 15-100min.
9. the preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2 according to claim 4, it is characterized in that the drying described in step (3) is vacuum drying, baking temperature is 80-120 DEG C, and drying time is 24-72 hour.
10. the preparation method of the nano-composite catalyst of synthesizing gas by reforming methane with co 2 according to claim 4, it is characterized in that the roasting described in step (3) is that dried catalyst is warming up to 400 ~ 450 DEG C with 1 ~ 5 DEG C/min speed in atmosphere, constant temperature calcining 1 ~ 2h, is then warming up to 650 ~ 850 DEG C of constant temperature calcining 0.5 ~ 2.5h with 1 ~ 5 DEG C/min speed.
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| CN105363452A (en) * | 2015-10-20 | 2016-03-02 | 太原理工大学 | Method for preparing bimodal mesoporous structure Ni/SiO2-ZrO2 catalyst used for partial oxidation of methane |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0692451A1 (en) * | 1994-07-13 | 1996-01-17 | Zhaolong Zhang | A stable and active nickel catalyst for carbon dioxide reforming of methane to synthesis gas |
| EP0564526B1 (en) * | 1990-12-24 | 1998-08-19 | BG plc | Process for the conversion of methane to synthesis gas |
| CN1680027A (en) * | 2005-02-03 | 2005-10-12 | 复旦大学 | Copper-base catalyst of methanol steam reintegrating hydrogen manufacturing and preparation thereof |
| CN101352687A (en) * | 2008-08-29 | 2009-01-28 | 同济大学 | Catalyst for carbon dioxide dry-reforming of methane, and preparation method and use thereof |
| CN101584986A (en) * | 2009-07-04 | 2009-11-25 | 太原理工大学 | Method for preparing methanol synthesizing catalyst |
| CN102008962A (en) * | 2009-09-07 | 2011-04-13 | 中国石油化工股份有限公司 | Hydrocarbon pre-converting catalyst for large-scale energy-saving hydrogen production technology |
| CN102380394A (en) * | 2010-08-31 | 2012-03-21 | 中国石油化工股份有限公司 | Catalyst for producing synthesis gas by reforming natural gas and carbon dioxide and preparation method thereof |
| CN103143364A (en) * | 2013-03-12 | 2013-06-12 | 上海中科高等研究院 | High-dispersion nano-composite catalyst, and preparation method and applications thereof |
-
2013
- 2013-10-15 CN CN201310479969.7A patent/CN104549285B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0564526B1 (en) * | 1990-12-24 | 1998-08-19 | BG plc | Process for the conversion of methane to synthesis gas |
| EP0692451A1 (en) * | 1994-07-13 | 1996-01-17 | Zhaolong Zhang | A stable and active nickel catalyst for carbon dioxide reforming of methane to synthesis gas |
| CN1680027A (en) * | 2005-02-03 | 2005-10-12 | 复旦大学 | Copper-base catalyst of methanol steam reintegrating hydrogen manufacturing and preparation thereof |
| CN101352687A (en) * | 2008-08-29 | 2009-01-28 | 同济大学 | Catalyst for carbon dioxide dry-reforming of methane, and preparation method and use thereof |
| CN101584986A (en) * | 2009-07-04 | 2009-11-25 | 太原理工大学 | Method for preparing methanol synthesizing catalyst |
| CN102008962A (en) * | 2009-09-07 | 2011-04-13 | 中国石油化工股份有限公司 | Hydrocarbon pre-converting catalyst for large-scale energy-saving hydrogen production technology |
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