CN104226318A - High-space-velocity honeycombed methanation catalyst and preparation method thereof - Google Patents
High-space-velocity honeycombed methanation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104226318A CN104226318A CN201410514216.XA CN201410514216A CN104226318A CN 104226318 A CN104226318 A CN 104226318A CN 201410514216 A CN201410514216 A CN 201410514216A CN 104226318 A CN104226318 A CN 104226318A
- Authority
- CN
- China
- Prior art keywords
- auxiliary agent
- carrier
- methanation catalyst
- cellular
- 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.)
- Pending
Links
Abstract
The invention discloses a high-space-velocity honeycombed methanation catalyst. The high-space-velocity honeycombed methanation catalyst comprises a carrier, an active component and auxiliary agents, wherein the carrier is honeycombed ceramic cordierite coated with an Al2O3 film; the active component is Ni; the first auxiliary agent is one of alkaline earth metal oxides CaO and MgO; the second auxiliary agent is rare earth oxide La2O3. The catalyst is high space velocity (50000-100000h<-1>) and small in using amount; the active component is dispersed on the honeycombed carrier and is high in utilization ratio and low in content, so that the production cost of the catalyst is reduced; through a honeycombed structure, resistance to synthesis gas is low, and pressure drop of the synthesis gas after passing through a catalyst bed is low; the alkaline earth metal oxide CaO or MgO is used as the first auxiliary agent, so that the surface acidity of the carrier is improved, and resistance to carbon deposition is improved; the La2O3 is used as the second auxiliary agent, so that the dispersibility of NiO particles can be improved easily to promote NiO reduction, thereby improving the activity of the catalyst.
Description
Technical field
The invention belongs to chemical field, relate to the preparation of methanation catalyst, be specially a kind of cellular methanation catalyst being applicable to high-speed and preparation method thereof.
Background technology
Current China's natural gas inadequate resource, electric power and domestic gas consumption constantly increase, and cause imbalance between supply and demand to give prominence to, the problems such as peak regulation pressure increase.According to the prediction data that industry is generally admitted, to the year two thousand twenty, China's natural gas market demand is about 3000 billion cubic meters, and about domestic amount of natural gas 1500 billion cubic meter, natural gas external dependence degree may reach 50% when the time comes.
Utilize the coal resources of China's abundant, develop actively coal based synthetic gas preparing natural gas, deliver to national consumption market from remote rich coal district long-distance transport pipes, the imbalance between supply and demand of natural gas can be alleviated, there is good economic and social benefit.
Current National Development and Reform Committee have approved continuously and comprises 15 coal preparing natural gas projects such as CNOOC's Ordos, inner Mongolia, Datang international Chifeng, Fuxin, Liaoning, Qing Hua group Xinjiang Yili of China, aggregated capacity reaches 660 billion cubic meters, also has multiple project to plan in addition.The coal preparing natural gas project gone into operation is all adopt external methanation technology.External methanation technology mainly contains the methanation circulation technology (TREMPTM) of rope company of Top exploitation and the gas methanation technology (CRG technology) of Dai Wei company at present.The transfer fee of external methanation process technology and supporting catalyst selling price are all quite expensive.Given this, China is in the urgent need to developing the methanation technology of production domesticization.
In recent years, studies in China mechanism has carried out research work in the preparation of methanation catalyst and performance study field.CN101468311 provides a kind of catalyst for methanation of coal gas, and take Ni as main active component, Rare earth (based on La) is as the first auxiliary agent, Sr is Cr, V, the W of advocating peace, in Mo, at least one is as the second auxiliary agent, and the catalyst obtained belongs to stratified material; CN102114425A reports a kind of methanation of coal gas Catalysts and its preparation method, and this catalyst is the γ-A1 in two mesoporous distribution
2o
3carrier is loaded with NiO and La
2o
3, transmit resistance little, be beneficial to the diffusion of reactant and product, be not easy to produce carbon distribution; It is carrier with aluminium oxide that CN102513119A reports a kind of, and nickel is main active component, and rare earth is the methanation catalyst of auxiliary agent, has intensity high, active good, has the excellent properties such as conversion simultaneously.
With the catalyst Patents information analysis delivered at present, the active constituent of methanation catalyst is Ni; Common carrier is generally Al
2o
3, ZrO
2, TiO
2, SiO
2deng; Auxiliary agent relates to Li, K, Mg, Ca, Al, Sr, Ba, Ti, Cr, Mn, Fe, Co, Cu, Zr, Mo, La, Ce, Sm etc.Catalyst preparing mode is mainly the precipitation method and infusion process, and adopt different preparation conditions, active component and auxiliary agent feed postition etc., the catalyst microscopic pattern obtained is different, and target is high activity and stability.
But the research report at present about minimizing catalyst amount, reduction Catalyst Production cost is less.There is not yet high-speed (>=50000h
-1) and the report of cellular methanation catalyst.High-speed condition is run, can less catalyst amount; The resistance of alveolate texture to synthesis gas is little, and synthesis gas is low by the pressure drop of beds.
Summary of the invention
The object of the invention is to for above technical problem, provide a kind of cellular methanation catalyst for the high-speed in coal preparing natural gas process, this catalyst uses air speed high, is 50000h
-1~ 150000h
-1, active good, production cost is low.
Another object of the present invention is the preparation method providing a kind of above-mentioned catalyst.
The object of the invention is realized by following technical proposals:
Be applicable to a cellular methanation catalyst for high-speed, comprise carrier, active component and auxiliary agent, described carrier is coating Al
2o
3the cordierite honeycomb ceramics of film, described active constituent is Ni, described auxiliary agent comprises the first auxiliary agent and the second auxiliary agent, and wherein the first auxiliary agent is the mixture of any one or two kinds in alkaline earth oxide CaO and MgO, and the second auxiliary agent is rare-earth oxide La
2o
3.
Be applicable to the cellular methanation catalyst of high-speed, each component by percentage to the quality, cordierite honeycomb ceramics: 65% ~ 85%, NiO:5% ~ 15%, Al
2o
3: 2% ~ 7%, CaO or MgO:2% ~ 5%, La
2o
3: 2% ~ 8%, the mass percentage sum of each component is 100%.
The method of the cellular methanation catalyst of described high-speed, the method adopts infusion process preparation coating Al
2o
3the cordierite honeycomb ceramics carrier of film, recycling infusion process by active constituent, auxiliary agent load on carrier.
Preferably, above-mentioned preparation method comprises:
(1) infusion process preparation coating Al
2o
3the cordierite honeycomb ceramics carrier of film: cordierite is flooded in aluminum nitrate solution, dry, roasting obtained coating Al
2o
3the cordierite honeycomb ceramics carrier of film.
(2) preparation catalyst: the carrier obtained by step (1) is flooded in the nitrate solution containing a kind of, the lanthanum in nickel, calcium and magnesium, dry, calcine and get final product.
The cellular methanation catalyst preparation method of air speed, specifically comprises the following steps:
(1) Al
2o
3the preparation of film immersion liquid: aluminum nitrate is dissolved in distilled water and is mixed with maceration extract A; Described aluminum nitrate is (Al (NO
3)
39H
2o, concentration is 267.0g/L-935.5g/L.
(2) Al
2o
3the load of film: be impregnated in by cordierite honeycomb ceramics in maceration extract A, after dipping terminates, through super-dry and calcination process obtained coating Al
2o
3the cordierite honeycomb ceramics carrier B of film; The pore structure of cordierite honeycomb ceramics is 50-150 hole/square inch.
(3) preparation of active constituent and auxiliary agent maceration extract: the nitrate of nickel, lanthanum and calcium or magnesium is dissolved in distilled water and is mixed with maceration extract C; The nitrate of described nickel is Ni (NO
3)
26H
2o, concentration is 316.0g/L-698.5g/L; The nitrate of lanthanum is La (NO
3) 6H
2o, concentration is 57.3g/L-230.6g/L; The nitrate of calcium is Ca (NO
3)
24H
2o, concentration is 91.3g/L-228.3g/L; The nitrate of magnesium is Mg (NO
3)
26H
2o, concentration is 161.3g/L-403.6g/L.
(4) load of active constituent and auxiliary agent: carrier B be impregnated in maceration extract C, then take out drying, after dry, sample floods again, and the sample after dipping terminates obtains described methanation catalyst through super-dry and calcination process.
Step (2) and the dipping temperature described in (4) are 50-90 DEG C, and the time is 2h-6h; Step (2) and the baking temperature described in (4) are 60-100 DEG C, and the time is 12-24h; Calcining heat is 400 DEG C-600 DEG C, and the time is 4h-6h.
Compared with prior art, beneficial effect of the present invention is:
(1) this catalyst uses the high (50000h of air speed
-1~ 100000h
-1), catalyst amount is few;
(2) active constituent is dispersed on honeycomb support, and utilization rate is high, content is low, thus reduces the production cost of catalyst;
(3) resistance of alveolate texture to synthesis gas is little, and synthesis gas is low by the pressure drop of beds.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of methanation catalyst
Fig. 2 is methanation catalyst evaluation experimental device schematic diagram.
Wherein, 1-1,1-2 and 1-3 are flowmeter; 2-1 and 2-2 is voltage-stablizer; 3-evaporation mixer; 4-reactor; 5-water storing tank; 6-water pump; 7-refrigerated separation; 8-wet flow indicator; 9-transfer valve
Detailed description of the invention
Arbitrary feature disclosed in this description (comprising any accessory claim, summary), unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
All features disclosed in this description, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Embodiment 1:
Prepare cellular methanation catalyst I
(1) 0.2L is contained 160.2g Al (NO
3)
39H
2the aqueous solution of O adds in constant temperature dipping tank, and control temperature is 70 DEG C, adds 75.0g cordierite, dipping 2.0h.Impregnated carrier is in 80 DEG C of dry 18h, and 450 DEG C of calcining 5h, obtain coating Al
2o
3the cordierite honeycomb ceramics carrier of film.
(2) 0.2L is contained 111.6g Ni (NO
3)
26H
2o, 15.8g La (NO
3) 6H
2o, 64.5g Mg (NO
3)
26H
2the mixed aqueous solution of O adds in constant temperature dipping tank, and control temperature is 70 DEG C, adds the carrier obtained by step (1), dipping 2.5h, then takes out the carrier after dipping, in 100 DEG C of dry 12h.After dry, constant temperature dipping tank put into again by sample, in 70 DEG C of dipping 2.5h, then at 100 DEG C of dry 12h, and 450 DEG C of calcining 5h, obtained described methanation catalyst I.
Embodiment 2:
Prepare cellular methanation catalyst II
(1) 0.2L is contained 187.1g Al (NO
3)
39H
2the aqueous solution of O adds in constant temperature dipping tank, and control temperature is 75 DEG C, adds 70g cordierite, dipping 3.0h.Impregnated carrier is in 70 DEG C of dry 24h, and 450 DEG C of calcining 5h, obtain coating Al
2o
3the cordierite honeycomb ceramics carrier of film
(2) 0.2L is contained 120.9g Ni (NO
3)
26H
2o, 28.6g La (NO
3) 6H
2o, 80.8g Mg (NO
3)
26H
2the mixed aqueous solution of O adds in constant temperature dipping tank, and control temperature is 70 DEG C, adds the carrier obtained by step (1), dipping 3.5h, then takes out the carrier after dipping, in 100 DEG C of dry 12h.After dry, constant temperature dipping tank put into again by sample, in 70 DEG C of dipping 3.5h, then at 100 DEG C of dry 12h, and 450 DEG C of calcining 5h, obtained described methanation catalyst II.
Embodiment 3:
Prepare cellular methanation catalyst III
(1) 0.2L is contained 181.5g Al (NO
3)
39H
2the aqueous solution of O adds in constant temperature dipping tank, and control temperature is 70 DEG C, adds 72g cordierite, dipping 3.0h.Impregnated carrier is in 80 DEG C of dry 24h, and 500 DEG C of calcining 4h, obtain coating Al
2o
3the cordierite honeycomb ceramics carrier of film
(2) 0.2L is contained 116.3g Ni (NO
3)
26H
2o, 22.9g La (NO
3) 6H
2o, 42.9g Ca (NO
3)
24H
2the mixed aqueous solution of O adds in constant temperature dipping tank, and control temperature is 80 DEG C, adds the carrier obtained by step (1), dipping 3.0h, then takes out the carrier after dipping, in 100 DEG C of dry 12h.After dry, constant temperature dipping tank put into again by sample, in 80 DEG C of dipping 3.0h, then at 100 DEG C of dry 12h, and 500 DEG C of calcining 4h, obtained described methanation catalyst III.
Embodiment 4:
Prepare cellular methanation catalyst IV
(1) 0.2L is contained 173.5g Al (NO
3)
39H
2the aqueous solution of O adds in constant temperature dipping tank, and control temperature is 70 DEG C, adds 75g cordierite, dipping 4.0h.Impregnated carrier is in 80 DEG C of dry 24h, and 450 DEG C of calcining 5h, obtain coating Al
2o
3the cordierite honeycomb ceramics carrier of film.
(2) 0.2L is contained 102.3g Ni (NO
3)
26H
2o, 25.8g La (NO
3) 6H
2o, 48.4g Mg (NO
3)
26H
2the mixed aqueous solution of O adds in constant temperature dipping tank, and control temperature is 80 DEG C, adds the carrier obtained by step (1), dipping 2.0h, then takes out the carrier after dipping, in 100 DEG C of dry 16h.After dry, constant temperature dipping tank put into again by sample, in 80 DEG C of dipping 2.0h, then at 100 DEG C of dry 16h, and 450 DEG C of calcining 5h, obtained described methanation catalyst IV.
Embodiment 5:
Prepare cellular methanation catalyst V
(1) 0.2L is contained 146.8g Al (NO
3)
39H
2the aqueous solution of O adds in constant temperature dipping tank, and control temperature is 70 DEG C, adds 72g cordierite, dipping 2.5h.Impregnated carrier is in 80 DEG C of dry 24h, and 500 DEG C of calcining 4h, obtain coating Al
2o
3the cordierite honeycomb ceramics carrier of film.
(2) 0.2L is contained 116.5g Ni (NO
3)
26H
2o, 34.4g La (NO
3) 6H
2o, 41.1g Ca (NO
3)
24H
2the mixed aqueous solution of O adds in constant temperature dipping tank, and control temperature is 70 DEG C, adds the carrier obtained by step (1), dipping 2.5h, then takes out the carrier after dipping, in 100 DEG C of dry 18h.After dry, constant temperature dipping tank put into again by sample, in 70 DEG C of dipping 2.5h, then at 100 DEG C of dry 18h, and 500 DEG C of calcining 4h, obtained described methanation catalyst V.
The methanation activity test of each catalyst that embodiment 1-5 is obtained under high-speed condition
Methanation catalyst I, II, III, IV and V is crushed to the granule of 3.2mm ~ 4.0mm, get the reaction tube that 10mL loads Φ 25 × 3.5 respectively, loading height is 30mm, tests by following condition.
A) test adopts the steel cylinder gas of preparation with unstripped gas, through decompression metering laggard enter evaporimeter, raw water enters evaporator evaporation through constant-flux pump pressurization, enter reactor after fully mixing with unstripped gas to react simultaneously, reactor adopts external heat form control outlet temperature, exit gas through cooling, be separated, metering rear portion spectrum of discoloring carries out component analysis, another part is emptying (methanation experimental provision as shown in Figure 2) directly.
B) test unstripped gas composition and see the following form 1:
Table 1 raw material coal gas composition v%
| Unstripped gas | CO | CO 2 | CH 4 | H 2 | N 2 |
| Content | 19.63 | 1.32 | 14.87 | 64.16 | 0.02 |
C) catalyst reduction: at temperature 350 DEG C, with hydrogen pressure-raising to 0.5MPa, reductase 12 hour, reduction air speed 2000h
-1;
D) high-speed methanation activity test: after reduction terminates, disconnects hydrogen, and pass into water vapour and coal gas pressure-raising to 2.0MPa, temperature is increased to 500 DEG C, coal gas air speed 50000 ~ 100000h
-1, steam-to-gas ratio 0.17, carries out coal gas high-speed methanation reaction;
E) component analysis: component analysis adopts gas-chromatography to test, and selected chromatogram condition of work should ensure that each component in sample can be efficiently separated.Table 2 gives analyzes H
2, N
2, CO, CO
2, CH
4agilent 7820 gas-chromatography condition of work.
Table 2 chromatogram condition of work
G) CO and CO
2total conversion computing formula is:
Wherein:
for CO and CO
2total conversion;
V
cO entrancefor CO entrance butt volume fraction;
for CO
2entrance butt volume fraction;
V
entrancefor butt feed(raw material)inlet flow, L/h;
V
cO exportsfor CO exports butt volume fraction;
for CO
2outlet butt volume fraction;
V
outletfor butt material outlet flow, L/h;
Test result is as shown in table 3.
Table 3CO and CO
2total conversion (%)
As can be seen from the above results, honeycombed catalyst I-V of the present invention can run under high-speed condition.Be 50000h in air speed
-1under condition, CO and CO of catalyst I-V
2total conversion is 50% ~ 53%; Be 70000h in air speed
-1under condition, CO and CO of catalyst I-V
2total conversion is 31% ~ 36%; When air speed is increased to 100000h
-1time, CO and CO of catalyst I-V
2total conversion is 16% ~ 19%.
This catalyst can be used as pre-methanation catalyst, uses under high-speed condition, and make synthesis gas generating portion methanation reaction, after pre-methanation reaction, gas enters main methanator again.By the change of air speed, adjust the pre-methanation reaction degree of depth, and then the load of the pre-methanation of controlled adjustment and main methanation.
Claims (9)
1. be applicable to a cellular methanation catalyst for high-speed, comprise carrier, active component and auxiliary agent, it is characterized in that, described carrier is coating Al
2o
3the cordierite honeycomb ceramics of film, described active constituent is Ni, described auxiliary agent comprises the first auxiliary agent and the second auxiliary agent, and wherein the first auxiliary agent is the mixture of any one or two kinds in alkaline earth oxide CaO and MgO, and the second auxiliary agent is rare-earth oxide La
2o
3.
2. be applicable to the cellular methanation catalyst of high-speed as claimed in claim 1, it is characterized in that in mass percentage, the mass percentage shared by each component is: cordierite honeycomb ceramics: 65% ~ 85%, NiO:5% ~ 15%, Al
2o
3: 2% ~ 7%, CaO or MgO:2% ~ 5%, La
2o
3: 2% ~ 8%, the mass percentage sum of each component is 100%.
3. prepare a method for the cellular methanation catalyst of high-speed as described in claim arbitrary in claim 1-2, it is characterized in that: with infusion process preparation coating Al
2o
3the cordierite honeycomb ceramics carrier of film, recycling infusion process by active constituent, auxiliary agent load on carrier.
4. the cellular methanation catalyst preparation method of air speed as claimed in claim 3, is characterized in that comprising the following steps:
(1) Al
2o
3the preparation of film immersion liquid: aluminum nitrate is dissolved in distilled water and is mixed with maceration extract A;
(2) Al
2o
3the load of film: be impregnated in by cordierite honeycomb ceramics in maceration extract A, after dipping terminates, through super-dry and calcination process obtained coating Al
2o
3the cordierite honeycomb ceramics carrier B of film;
(3) preparation of active constituent and auxiliary agent maceration extract: the nitrate of nickel, lanthanum and calcium or magnesium is dissolved in distilled water and is mixed with maceration extract C;
(4) load of active constituent and auxiliary agent: carrier B be impregnated in maceration extract C, then take out drying, after dry, sample floods again, and the sample after dipping terminates obtains described methanation catalyst through super-dry and calcination process.
5. the cellular methanation catalyst preparation method of high-speed as claimed in claim 4, is characterized in that: the aluminum nitrate described in step (1) is (Al (NO
3)
39H
2o, concentration is 267.0 g/L-935.5 g/L.
6. the cellular methanation catalyst preparation method of high-speed as claimed in claim 4, is characterized in that: the pore structure of the cordierite honeycomb ceramics described in step (2) is 50-150 hole/square inch.
7. the cellular methanation catalyst preparation method of high-speed as claimed in claim 4, is characterized in that: the nitrate of the nickel described in step (3) is Ni (NO
3)
26H
2o, concentration is 316.0 g/L-698.5g/L; The nitrate of lanthanum is La (NO
3) 6H
2o, concentration is 57.3 g/L-230.6g/L; The nitrate of calcium is Ca (NO
3)
24H
2o, concentration is 91.3 g/L-228.3g/L; The nitrate of magnesium is Mg (NO
3)
26H
2o, concentration is 161.3 g/L-403.6g/L.
8. the cellular methanation catalyst preparation method of high-speed as claimed in claim 4, it is characterized in that: step (2) and the dipping temperature described in (4) are 50-90 DEG C, the time is 2 h-6h.
9. the cellular methanation catalyst preparation method of high-speed as claimed in claim 4, it is characterized in that: step (2) and the baking temperature described in (4) they are 60-100 DEG C, the time is 12-24h; Calcining heat is 400 DEG C-600 DEG C, and the time is 4h-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514216.XA CN104226318A (en) | 2014-09-29 | 2014-09-29 | High-space-velocity honeycombed methanation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514216.XA CN104226318A (en) | 2014-09-29 | 2014-09-29 | High-space-velocity honeycombed methanation catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104226318A true CN104226318A (en) | 2014-12-24 |
Family
ID=52215741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410514216.XA Pending CN104226318A (en) | 2014-09-29 | 2014-09-29 | High-space-velocity honeycombed methanation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104226318A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987907A (en) * | 2016-10-26 | 2018-05-04 | 中国石油天然气股份有限公司 | It is a kind of that the method rich in methane gas is prepared by synthesis gas |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043639A (en) * | 1988-12-23 | 1990-07-11 | 四川大学 | Low-nickel methenyl catalyst and preparation method thereof |
| CN101607199A (en) * | 2008-06-19 | 2009-12-23 | 汉能科技有限公司 | A kind of CO selective methanation monolithic catalyst and preparation method thereof |
| CN101733104A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for methanation of carbon dioxide-containing synthesis gas, preparation method and application |
| US20100168257A1 (en) * | 2007-03-13 | 2010-07-01 | Matthias Duisberg | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
| CN103127939A (en) * | 2011-11-24 | 2013-06-05 | 新奥科技发展有限公司 | Cellular integral sulfur-tolerant methanation catalyst and preparation method thereof |
-
2014
- 2014-09-29 CN CN201410514216.XA patent/CN104226318A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043639A (en) * | 1988-12-23 | 1990-07-11 | 四川大学 | Low-nickel methenyl catalyst and preparation method thereof |
| US20100168257A1 (en) * | 2007-03-13 | 2010-07-01 | Matthias Duisberg | Metal-doped nickel oxides as catalysts for the methanation of carbon monoxide |
| CN101607199A (en) * | 2008-06-19 | 2009-12-23 | 汉能科技有限公司 | A kind of CO selective methanation monolithic catalyst and preparation method thereof |
| CN101733104A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for methanation of carbon dioxide-containing synthesis gas, preparation method and application |
| CN103127939A (en) * | 2011-11-24 | 2013-06-05 | 新奥科技发展有限公司 | Cellular integral sulfur-tolerant methanation catalyst and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 周世忠等: ""在Ni-MgO-La2O3-Al2O3催化剂上CO2、CO加氢甲烷化反应动力学研究"", 《化学工程》, vol. 19, no. 2, 25 April 1991 (1991-04-25), pages 24 - 28 * |
| 张鹤凌等: "《中国化工产品大全》", 31 January 2005, article ""甲烷化催化剂"", pages: 209 * |
| 徐亚荣等: ""合成气完全甲烷化催化剂研究"", 《天然气化工》, vol. 36, no. 4, 31 December 2011 (2011-12-31) * |
| 邵潜等: "《规整结构催化剂及反应器》", 31 August 2005, article ""甲烷化作用"", pages: 122-124 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987907A (en) * | 2016-10-26 | 2018-05-04 | 中国石油天然气股份有限公司 | It is a kind of that the method rich in methane gas is prepared by synthesis gas |
| CN107987907B (en) * | 2016-10-26 | 2020-07-10 | 中国石油天然气股份有限公司 | Method for preparing methane-rich gas from synthesis gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104043454B (en) | A kind of nano combined methanation catalyst and preparation method thereof | |
| CN103706370B (en) | A kind of coal gas high-temperature methanation catalyst and preparation method thereof | |
| CN104028270A (en) | Methanation catalyst and preparation method thereof | |
| CN105777480B (en) | Method for ethyl benzene dehydrogenation preparation of styrene | |
| CN102600860B (en) | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof | |
| CN104399491B (en) | A kind of high temperature resistant methanation catalyst and preparation method thereof | |
| CN103182311B (en) | Preparation method of sulfur-resistant carbon monoxide shift catalyst carrier | |
| CN103611538B (en) | For the multifunction catalyst and preparation method thereof of hydrogen production from methane vapor reforming | |
| CN106582687B (en) | Catalyst of low-water ratio ethylbenzene dehydrogenation and preparation method thereof | |
| CN108203365B (en) | Method for preparing styrene by ethylbenzene dehydrogenation | |
| CN103769151B (en) | High activity ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof | |
| CN103977808A (en) | Nickel cerium catalyst as well as preparation method and application thereof | |
| CN103537288A (en) | Method for preparing methanation catalyst by adopting urea combustion method | |
| CN103447042B (en) | Preparation method of anti-carbon deposition and anti-sintering monolithic methane dry reforming catalyst | |
| CN103170338B (en) | A kind of catalyst for being used for 1,2 propane diols and preparation method thereof | |
| CN103464164B (en) | Tartaric acid complexometry prepares the method for methanation catalyst | |
| CN105833878A (en) | Preparation method of Fe2O3-CeO2 nano-composite catalyst | |
| CN109569652A (en) | A kind of catalyst and its preparation method and application for syngas catalytic conversion | |
| CN104226318A (en) | High-space-velocity honeycombed methanation catalyst and preparation method thereof | |
| CN101623642B (en) | Ethylbenzene dehydrogenation catalyst with low water ratio | |
| CN103028418A (en) | High-activity low-water ratio ethylbenzene dehydrogenation catalyst and preparation method | |
| CN106064089B (en) | A kind of Regenrable catalyzed and preparation method thereof for catalyzing and reforming biologic oil hydrogen manufacturing | |
| CN104667925A (en) | Copper-based catalyst for preparing ethanol by acetate hydrogenation and preparation method | |
| CN105749934B (en) | A kind of production of phenylethylene catalyst by low-water ratio ethylbenzene dehydrogenation and preparation method | |
| CN105478131B (en) | CO mesohigh low temperature resistant to sulfur pre-transform catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141224 |