CN103706366A - Novel methanation catalyst and preparation method thereof - Google Patents
Novel methanation catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a novel methanation catalyst and a preparation method thereof, which can solve the problems that a current high temperature resistant methanation catalyst comes mainly from import, and the price of the methanation catalyst is high, but the high temperature resistant methanation catalyst is urgently required in China. The novel methanation catalyst comprises an active component, a carrier, a first auxiliary, and a second auxiliary. The raw materials and the preparation method of the catalyst are obviously different from those of the prior art, the novel catalyst can be used for producing synthetic natural gas from coal gas at high temperature and high pressure, and be used for methanation preparation of gas rich in CO, CO2 and H2. The catalyst comprises the active component, the carrier, the first auxiliary and the second auxiliary, is suitable for production of synthetic natural gas from coal gas at high temperature and high pressure, is high in high-temperature activity, stability and carbon deposit prevention so as to fully satisfy the production requirements of high temperature resistant methanation catalysts and has important significance in domestication of similar catalysts and reduction of production costs.
Description
Technical field
The present invention relates to chemical field, especially coal chemical technology, is specially a kind of novel methanation catalyst and preparation method thereof.
Background technology
Along with the fast development of China's economy, growing for the demand of the energy, the fast-developing phase of China's natural gas market access.2012, China's natural gas import volume (containing liquefied natural gas) was 425 billion cubic meters, compared with 2011 year-on-years, increases by 31.1%, and the external interdependency of natural gas reaches 28.9%, than 2011, increases by 5 percentage points; 2015, the domestic natural gas demand of China will reach 2,000 hundred million Nm
3, market has openings approximately 40,000,000,000 Nm
3; During 2016～the year two thousand twenty, Natural Gas Demand speedup will remain on annual 8% left and right, and to the year two thousand twenty, natural gas demand is expected to surpass 300,000,000,000 Nm
3, market has openings will reach 90,000,000,000 Nm
3, when the time comes by the natural gas dependence on import that has 40%.For the growing situation of natural gas demand, China is in the urgent need to increasing the output of natural gas, to reduce the dependence to inlet natural gas.
Compare with oil equal energy source, China's coal reserves is relatively abundant, therefore, utilizes coal preparing natural gas or synthesis gas to have broad prospects.The energy conversion efficiency of coal preparing natural gas is higher, can reach 50%, its efficiency than ICL for Indirect Coal Liquefaction (transformation efficiency is 32%) and DCL/Direct coal liquefaction (transformation efficiency is 38%) is all high, from energy, utilizes angle, and coal preparing natural gas is a kind of approach that utilizes preferably that utilizes coal.
Utilizing high-temperature heat insulation technique to carry out the capacity usage ratio of methanation process design high, is also the technology of current main flow, and in conjunction with this technology, rope company of at present external Top, Dai Wei company have ripe high-temperature methanation catalyst technology.At present, such catalyst mainly relies on import, and corresponding license fee is higher, and the domestic catalyst that there is no industrial applications.Therefore, domestic in the urgent need to this type of high temperature resistant methanation catalyst.
Summary of the invention
Goal of the invention of the present invention is: for current high temperature resistant methanation catalyst, mainly rely on import, expense is higher, and the domestic problem in the urgent need to this type of high temperature resistant methanation catalyst of China provides a kind of novel methanation catalyst and preparation method thereof.The raw material of catalyst of the present invention, preparation method all have remarkable difference with prior art, and this catalyst can be used in coal gas HTHP production synthetic natural gas, and other is rich in CO, CO
2and H
2the methanation preparation of gas.This catalyst comprises active component, carrier, the first auxiliary agent, the second auxiliary agent etc., and this catalyst is suitable for coal gas HTHP production synthetic natural gas.It has good high temperature active, stability and anti-carbon, can meet the need of production of high temperature resistant methanation catalyst completely, and the production domesticization for such catalyst, reduces production costs, and has great importance.
To achieve these goals, the present invention adopts following technical scheme:
A novel methanation catalyst, comprises active component, carrier, the first auxiliary agent, the second auxiliary agent, take Ni as active component, with Al
2o
3for carrier, the first auxiliary agent is a kind of in the oxide of lanthanum, cerium, samarium, and the second auxiliary agent is one or more in the oxide of magnesium, manganese, iron, zirconium; Active component, carrier, the first auxiliary agent, the second auxiliary agent are all present in this catalyst with the form of oxide.
In oxidation state, the mass percent of active component is that the mass percent of the 15～55%, first auxiliary agent is that the mass percent of the 1～6%, second auxiliary agent is 3～15%, and surplus is carrier.
In oxidation state, the mass percent of active component is that the mass percent of the 25～45%, first auxiliary agent is that the mass percent of the 2～5%, second auxiliary agent is 7～11%, and surplus is carrier.
The oxide that described the first auxiliary agent is lanthanum.
The preparation method of aforementioned novel methanation catalyst, comprises the steps:
(1) prepare reducing solution: reducing agent is soluble in water, obtain reducing solution;
(2) raw materials liquid: get respectively nickel nitrate, aluminum nitrate, the first slaine, the second slaine, nickel nitrate, aluminum nitrate, the first slaine, the second slaine are mixed with water, obtain material liquid;
(3) hybrid reaction: reducing solution is added in isopyknic material liquid, stir, obtain solution one, again under vigorous stirring, in solution one, add and the isopyknic alkaline solution of solution one, obtain solution two, solution two is transferred in reactor, by after reactor sealing, put into baking oven, the temperature in baking oven is warming up to 100 ~ 200 ℃, after constant temperature 10 ~ 15h, be cooled to room temperature, finally reactor taken out from baking oven;
(4) post processing: product in the reactor taking out from baking oven is filtered, is washed to pH value to 6～7, obtain washings, washings is dried after 4 ~ 30h at 80 ~ 120 ℃, then at 300 ~ 550 ℃ roasting 2 ~ 12h, obtain novel methanation catalyst;
In described step 1, reducing agent is a kind of in formaldehyde, hydrazine hydrate, inferior sodium phosphate, ascorbic acid; In described reducing solution, the mass concentration of solute is 100 ~ 150g/L;
In described step 2, the first slaine is a kind of in lanthanum nitrate, cerous nitrate, samaric nitrate, and the second slaine is one or more in magnesium nitrate, manganese nitrate, ferric nitrate, zirconium nitrate;
In described material liquid, in nickel ion, in every liter of material liquid, contain 0.15 ~ 0.55mol nickel ion; In aluminium ion, in every liter of material liquid, contain 0.25 ~ 0.60mol; In the metal ion of the first slaine, in every liter of material liquid, contain the metal ion of 0.003 ~ 0.015mol the first slaine; In the metal ion of the second slaine, in every liter of material liquid, contain the metal ion of 0.005 ~ 0.030mol the first slaine;
In described step 3, a kind of and water of alkaline solution in sodium carbonate, NaOH, potash, ammonium carbonate, urea, ammoniacal liquor mixes, and in described alkaline solution, the mass concentration of solute is 15-50g/L.
In described step 1, reducing agent is hydrazine hydrate, and the mass concentration of the hydrazine hydrate in reducing solution is 1.0 ~ 1.5g/L.
In described step 3, alkaline solution is mixed by NaOH and water, and in every liter of alkaline solution, the quality of the NaOH of interpolation is 25g.
In described step 3, by after reactor sealing, put into baking oven, the temperature in baking oven is warming up to 150 ℃, after constant temperature 12h, be cooled to room temperature, finally reactor is taken out from baking oven
In described step 4, by washings at 100 ℃ after dry 12h, then at 400 ℃ roasting 4h, obtain novel methanation catalyst.
The shaped granule of aforementioned novel methanation catalyst, comprises the component of following ratio of weight and number:
100 parts of novel methanation catalysts,
Adhesive 8-12 part,
Lubricant 2-5 part,
Water 8-12 part.
Described adhesive is calcium aluminate, and described lubricant is graphite.
The preparation method of aforementioned shaped granule, comprises the steps: to take each component by proportioning, mixes, and compression molding.
For foregoing problems, the invention discloses a kind of novel methanation catalyst and preparation method thereof.This catalyst comprises active component, carrier, the first auxiliary agent, the second auxiliary agent.Catalyst of the present invention has good high temperature active, stability and anti-carbon, can meet the need of production of high temperature resistant methanation catalyst completely, and the production domesticization for such catalyst, reduces production costs, and has great importance.
Simultaneously, the present invention also provides the preparation method of aforementioned novel methanation catalyst, and the method acts in the solution of active component, the first auxiliary agent, the second auxiliary agent by reducing solution, then regulates pH value by aqueous slkali, pyroreaction, dry, roasting, make catalyst.And by the cooperatively interacting of catalyst, adhesive, lubricant, make shaped granule.
Checking by experiment, the present invention has following beneficial effect: the serviceability temperature of (1) catalyst of the present invention is 240～680 ℃, is applicable to high-temperature methane metallization processes, is conducive to improve capacity usage ratio; (2) catalyst high-temperature stability of the present invention is good, and water resistant vapour erosiveness is strong, and through the examination of 1000h life experiment, the high temperature active of catalyst is stable; (3) the first auxiliary agent in catalyst of the present invention, the second auxiliary agent are conducive to the dispersion of active component, improve the anti-caking power of catalyst; (4) preparation method of the present invention makes active component nickel and the first auxiliary agent, the second auxiliary agent high degree of dispersion, evenly combination, is conducive to improve the stability of catalyst under hot conditions.
The specific embodiment
Disclosed all features 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.
Disclosed arbitrary feature in this description, unless narration especially all can be replaced by other equivalences or the alternative features with similar object.That is,, unless narration especially, each feature is an example in a series of equivalences or similar characteristics.
Embodiment 1
Preparation
1.3g hydrazine hydrate is dissolved in 10mL water, obtains reducing solution.
0.78g nickel nitrate, 0.013g ferric nitrate, 0.013g lanthanum nitrate, 0.041g zirconium nitrate, 0.096g magnesium nitrate, 0.94g aluminum nitrate are dissolved in 10mL distilled water jointly, obtain material liquid.
0.5g NaOH is dissolved in 20mL water, obtains alkaline solution.
Reaction
Under normal temperature, reducing solution is slowly added in material liquid, stir, obtain solution one.Under vigorous stirring, in solution one, add alkaline solution again, obtain solution two.Solution two is transferred in polytetrafluoro inner bag autoclave, by after the sealing of polytetrafluoro inner bag autoclave, puts into baking oven.Temperature in baking oven is warming up to 150 ℃, after constant temperature 12h, is cooled to room temperature, finally reactor is taken out from baking oven.
Product in the reactor taking out from baking oven is filtered, is washed to pH value to 6～7, obtain washings, washings is dried after 12h at 100 ℃, then at 400 ℃ roasting 4h, obtain novel methanation catalyst.
Moulding
Press novel methanation catalyst: the mass ratio of cement, graphite: water=100:10:3:10, these four kinds are mixed, compression molding, obtains product.
Embodiment 2
Preparation
1.3g hydrazine hydrate is dissolved in 10mL water, obtains reducing solution.
0.85g nickel nitrate, 0.014g cerous nitrate, 0.041g zirconium nitrate, 0.096g magnesium nitrate, 0.94g aluminum nitrate are dissolved in 10mL distilled water jointly, obtain material liquid.
0.5g NaOH is dissolved in 20mL water, obtains alkaline solution.
Reaction
Under normal temperature, reducing solution is slowly added in material liquid, stir, obtain solution one.Under vigorous stirring, in solution one, add alkaline solution again, obtain solution two.Solution two is transferred in polytetrafluoro inner bag autoclave, by after the sealing of polytetrafluoro inner bag autoclave, puts into baking oven.Temperature in baking oven is warming up to 150 ℃, after constant temperature 12h, is cooled to room temperature, finally reactor is taken out from baking oven.
Product in the reactor taking out from baking oven is filtered, is washed to pH value to 6～7, obtain washings, washings is dried after 12h at 100 ℃, then at 400 ℃ roasting 4h, obtain novel methanation catalyst.
Moulding
Press novel methanation catalyst: the mass ratio of cement, graphite: water=100:10:3:10, these four kinds are mixed, compression molding, obtains product.
Embodiment 3
Preparation
1.3g hydrazine hydrate is dissolved in 10mL water, obtains reducing solution.
0.78g nickel nitrate, 0.026g lanthanum nitrate, 0.041g zirconium nitrate, 0.096g magnesium nitrate, 0.94g aluminum nitrate are dissolved in 10mL distilled water jointly, obtain material liquid.
0.5g NaOH is dissolved in 20mL water, obtains alkaline solution.
Reaction
Under normal temperature, reducing solution is slowly added in material liquid, stir, obtain solution one.Under vigorous stirring, in solution one, add alkaline solution again, obtain solution two.Solution two is transferred in polytetrafluoro inner bag autoclave, by after the sealing of polytetrafluoro inner bag autoclave, puts into baking oven.Temperature in baking oven is warming up to 150 ℃, after constant temperature 12h, is cooled to room temperature, finally reactor is taken out from baking oven.
Product in the reactor taking out from baking oven is filtered, is washed to pH value to 6～7, obtain washings, washings is dried after 12h at 100 ℃, then at 400 ℃ roasting 4h, obtain novel methanation catalyst.
Moulding
Press novel methanation catalyst: the mass ratio of cement, graphite: water=100:10:3:10, these four kinds are mixed, compression molding, obtains product.
Embodiment 4
Preparation
1.3g hydrazine hydrate is dissolved in 10mL water, obtains reducing solution.
0.78g nickel nitrate, 0.019g samaric nitrate, 0.06g zirconium nitrate, 0.096g magnesium nitrate, 0.94g aluminum nitrate are dissolved in 10mL distilled water jointly, obtain material liquid.
0.5g NaOH is dissolved in 20mL water, obtains alkaline solution.
Reaction
Under normal temperature, reducing solution is slowly added in material liquid, stir, obtain solution one.Under vigorous stirring, in solution one, add alkaline solution again, obtain solution two.Solution two is transferred in polytetrafluoro inner bag autoclave, by after the sealing of polytetrafluoro inner bag autoclave, puts into baking oven.Temperature in baking oven is warming up to 150 ℃, after constant temperature 12h, is cooled to room temperature, finally reactor is taken out from baking oven.
Product in the reactor taking out from baking oven is filtered, is washed to pH value to 6～7, obtain washings, washings is dried after 12h at 100 ℃, then at 400 ℃ roasting 4h, obtain novel methanation catalyst.
Moulding
Press novel methanation catalyst: the mass ratio of cement, graphite: water=100:10:3:10, these four kinds are mixed, compression molding, obtains product.Calcium aluminate is one of main component of cement.
Shaped granule prepared by previous embodiment 1-4 carries out determination of activity, is denoted as respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4.
Adopt with the N in gas chromatographic analysis gas
2, H
2, CH
4, CO, CO
2content.
Reducing condition is as follows.
Medium: H
2; Catalyst packing: 30mL; Reduction temperature: 350 ℃; Recovery time: 4h; Reduction air speed: 4000 h
-1.
Catalyst methane hot operation condition: Catalyst packing: 30mL; Outlet temperature: 630 ℃; Reaction pressure: 3MPa; Air speed: 20000 h
-1.
Unstripped gas is by CH
4, H
2, CO, CO
2, N
2form, the percent by volume of each component is as shown in table 1.
The outlet of table 1 novel methanation catalyst forms (v%)
| CO | CO2 | CH4 | H2 |
| 6 | 7 | 37 | 50 |
Table 2 is corresponding measurement result, and table 2 is as follows.
The outlet of table 2 novel methanation catalyst forms
| ? | CO | CO 2 | CH 4 | H 2 |
| Embodiment 1 | 2.12 | 5.26 | 59.92 | 32.70 |
| Embodiment 2 | 2.07 | 5.30 | 59.87 | 32.76 |
| Embodiment 3 | 2.11 | 5.39 | 59.26 | 33.24 |
| Embodiment 4 | 2.04 | 5.28 | 60.41 | 32.34 |
The present invention is not limited to the aforesaid specific embodiment.The present invention expands to any new feature or any new combination disclosing in this manual, and the arbitrary new method disclosing or step or any new combination of process.
Claims (10)
1. a novel methanation catalyst, is characterized in that, comprises active component, carrier, the first auxiliary agent, the second auxiliary agent, take Ni as active component, with Al
2o
3for carrier, the first auxiliary agent is a kind of in the oxide of lanthanum, cerium, samarium, and the second auxiliary agent is one or more in the oxide of magnesium, manganese, iron, zirconium; Active component, carrier, the first auxiliary agent, the second auxiliary agent are all present in this catalyst with the form of oxide, in oxidation state, the mass percent of active component is that the mass percent of the 15～55%, first auxiliary agent is 1～6%, the mass percent of the second auxiliary agent is 3～15%, and surplus is carrier.
2. novel methanation catalyst according to claim 1, is characterized in that, in oxidation state, the mass percent of active component is that the mass percent of the 25～45%, first auxiliary agent is that the mass percent of the 2～5%, second auxiliary agent is 7～11%, and surplus is carrier.
3. according to novel methanation catalyst described in claim 1 or 2, it is characterized in that the oxide that described the first auxiliary agent is lanthanum.
4. according to the preparation method of novel methanation catalyst described in claim 1-3 any one, it is characterized in that, comprise the steps:
(1) prepare reducing solution: reducing agent is soluble in water, obtain reducing solution;
(2) raw materials liquid: get respectively nickel nitrate, aluminum nitrate, the first slaine, the second slaine, nickel nitrate, aluminum nitrate, the first slaine, the second slaine are mixed with water, obtain material liquid;
(3) hybrid reaction: reducing solution is added in isopyknic material liquid, stir, obtain solution one, again under vigorous stirring, in solution one, add and the isopyknic alkaline solution of solution one, obtain solution two, solution two is transferred in reactor, by after reactor sealing, put into baking oven, the temperature in baking oven is warming up to 100 ~ 200 ℃, after constant temperature 10 ~ 15h, be cooled to room temperature, finally reactor taken out from baking oven;
(4) post processing: product in the reactor taking out from baking oven is filtered, is washed to pH value to 6～7, obtain washings, washings is dried after 4 ~ 30h at 80 ~ 120 ℃, then at 300 ~ 550 ℃ roasting 2 ~ 12h, obtain novel methanation catalyst;
In described step 1, reducing agent is a kind of in formaldehyde, hydrazine hydrate, inferior sodium phosphate, ascorbic acid; In described reducing solution, the mass concentration of solute is 100 ~ 150g/L;
In described step 2, the first slaine is a kind of in lanthanum nitrate, cerous nitrate, samaric nitrate, and the second slaine is one or more in magnesium nitrate, manganese nitrate, ferric nitrate, zirconium nitrate;
In described material liquid, in nickel ion, in every liter of material liquid, contain 0.15 ~ 0.55mol nickel ion; In aluminium ion, in every liter of material liquid, contain 0.25 ~ 0.60mol; In the metal ion of the first slaine, in every liter of material liquid, contain the metal ion of 0.003 ~ 0.015mol the first slaine; In the metal ion of the second slaine, in every liter of material liquid, contain the metal ion of 0.005 ~ 0.030mol the first slaine;
In described step 3, a kind of and water of alkaline solution in sodium carbonate, NaOH, potash, ammonium carbonate, urea, ammoniacal liquor mixes, and in described alkaline solution, the mass concentration of solute is 15-50g/L.
5. the preparation method of novel methanation catalyst according to claim 4, is characterized in that, in described step 1, reducing agent is hydrazine hydrate, and the mass concentration of the hydrazine hydrate in reducing solution is 1.0 ~ 1.5g/L.
6. the preparation method of novel methanation catalyst according to claim 4, is characterized in that, in described step 3, alkaline solution is mixed by NaOH and water, and in every liter of alkaline solution, the quality of the NaOH of interpolation is 25g.
7. the preparation method of novel methanation catalyst according to claim 4, is characterized in that, in described step 3, by after reactor sealing, put into baking oven, the temperature in baking oven is warming up to 150 ℃, after constant temperature 12h, be cooled to room temperature, finally reactor taken out from baking oven.
8. according to the preparation method of novel methanation catalyst described in claim 4-7 any one, it is characterized in that, in described step 4, by washings at 100 ℃ after dry 12h, then at 400 ℃ roasting 4h, obtain novel methanation catalyst.
9. according to the shaped granule of novel methanation catalyst described in claim 1-3 any one, it is characterized in that, comprise the component of following ratio of weight and number:
100 parts of novel methanation catalysts,
Adhesive 8-12 part,
Lubricant 2-5 part,
Water 8-12 part.
10. the preparation method of the shaped granule of novel methanation catalyst according to claim 9, is characterized in that, comprises the steps: to take each component by proportioning, mix, and compression molding.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707621A (en) * | 2015-04-02 | 2015-06-17 | 西南化工研究设计院有限公司 | Novel coal-produced natural gas catalyst and preparation method thereof |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| WO2018141649A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| WO2018141648A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Iron-doped nickel methanation catalysts |
| CN111495384A (en) * | 2020-04-24 | 2020-08-07 | 东南大学 | Carbon dioxide hydromethanation catalyst, preparation method and application |
| CN111760576A (en) * | 2019-04-02 | 2020-10-13 | 宁夏大学 | Preparation method of catalyst for methane synthesis from coal gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104707621A (en) * | 2015-04-02 | 2015-06-17 | 西南化工研究设计院有限公司 | Novel coal-produced natural gas catalyst and preparation method thereof |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| WO2018141649A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| WO2018141648A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Iron-doped nickel methanation catalysts |
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| CN111760576A (en) * | 2019-04-02 | 2020-10-13 | 宁夏大学 | Preparation method of catalyst for methane synthesis from coal gas |
| CN111495384A (en) * | 2020-04-24 | 2020-08-07 | 东南大学 | Carbon dioxide hydromethanation catalyst, preparation method and application |
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