CN103706366B - A kind of novel methanation catalyst and preparation method thereof - Google Patents
A kind of novel methanation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of novel methanation catalyst and preparation method thereof, object is that solving current high temperature resistant methanation catalyst mainly relies on import, costly, and the domestic problem in the urgent need to this type of high temperature resistant methanation catalyst of China, this catalyst comprises active component, carrier, the first auxiliary agent, the second auxiliary agent.Raw material, the preparation method of catalyst of the present invention 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 of gas is standby.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, for the production domesticization of such catalyst, reduces production cost, has great importance.
Description
Technical field
The present invention relates to chemical field, especially coal chemical technology, be specially a kind of novel methanation catalyst and preparation method thereof.
Background technology
Along with the fast development of China's economy, the demand for the energy is growing, the China's natural gas market access fast-developing phase.2012, China's natural gas import volume (containing liquefied natural gas) was 425 billion cubic meters, and comparatively 2011 year-on-years increase by 31.1%, and natural gas external dependence degree reaches 28.9%, increased by 5 percentage points than 2011; 2015, China's domestic natural gas demand will reach 2,000 hundred million Nm
3, market has openings about 40,000,000,000 Nm
3; During 2016 ~ the year two thousand twenty, Natural Gas Demand speedup will remain on annual about 8%, and to the year two thousand twenty, natural gas demand is expected more than 300,000,000,000 Nm
3, market has openings will reach 90,000,000,000 Nm
3, will the natural gas dependence on import of 40% be had when the time comes.For the situation that natural gas demand is growing, China in the urgent need to increasing the output of natural gas, to reduce the dependence to inlet natural gas.
Compared with oil equal energy source, China's coal reserves relative abundance, therefore, utilizes coal preparing natural gas or synthesis gas to have broad prospects.The efficient energy conversion of coal preparing natural gas is higher, can 50% be reached, it is all higher than the efficiency of ICL for Indirect Coal Liquefaction (transformation efficiency is 32%) and DCL/Direct coal liquefaction (transformation efficiency is 38%), and from Energy harvesting angle, coal preparing natural gas utilizes the good utilization ways of the one of coal.
Utilize high-temperature heat insulation technique to carry out the capacity usage ratio of methanation process design high, be also the technology of current main flow, in conjunction with this technology, rope company of external Top, Dai Wei company have ripe high-temperature methanation catalyst technology at present.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: mainly rely on import for current high temperature resistant methanation catalyst, costly, and the domestic problem in the urgent need to this type of high temperature resistant methanation catalyst of China, a kind of novel methanation catalyst and preparation method thereof is provided.Raw material, the preparation method of catalyst of the present invention 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 of gas is standby.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, for the production domesticization of such catalyst, reduces production cost, has great importance.
To achieve these goals, the present invention adopts following technical scheme:
A kind of novel methanation catalyst, comprising active component, carrier, the first auxiliary agent, the second auxiliary agent, is active component with Ni, with Al
2o
3for carrier, the first auxiliary agent is the one 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 present in this catalyst all in the form of the oxide.
In oxidation state, the mass percent of the mass percent of active component to be the mass percent of the 15 ~ 55%, first auxiliary agent be the 1 ~ 6%, second auxiliary agent is 3 ~ 15%, and surplus is carrier.
In oxidation state, the mass percent of the mass percent of active component to be the mass percent of the 25 ~ 45%, first auxiliary agent be the 2 ~ 5%, second auxiliary agent is 7 ~ 11%, and surplus is carrier.
Described first auxiliary agent is the oxide of 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 nickel nitrate, aluminum nitrate, the first slaine, the second slaine respectively, mixes nickel nitrate, aluminum nitrate, the first slaine, the second slaine with water, obtains material liquid;
(3) hybrid reaction: added in isopyknic material liquid by reducing solution, stir, obtains solution one, again with vigorous stirring, in solution one, add alkaline solution isopyknic with solution one, obtain solution two, solution two is transferred in reactor, after reactor is sealed, put into baking oven, by the temperature to 100 in baking oven ~ 200 DEG C, after constant temperature 10 ~ 15h, be cooled to room temperature, finally reactor taken out from baking oven;
(4) post processing: the product in the reactor taken out from baking oven is filtered, washed to pH value to 6 ~ 7, obtains washings, by washings at 80 ~ 120 DEG C after dry 4 ~ 30h, then at 300 ~ 550 DEG C roasting 2 ~ 12h, obtain novel methanation catalyst;
In described step 1, reducing agent is the one 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 the one 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, containing 0.15 ~ 0.55mol nickel ion in often liter of material liquid; In aluminium ion, containing 0.25 ~ 0.60mol in often liter of material liquid; With the metal ion of the first slaine, the metal ion containing 0.003 ~ 0.015mol first slaine in often liter of material liquid; With the metal ion of the second slaine, the metal ion containing 0.005 ~ 0.030mol first slaine in often liter of material liquid;
In described step 3, alkaline solution is mixed by the one in sodium carbonate, NaOH, potash, ammonium carbonate, urea, ammoniacal liquor and water, 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 often liter of alkaline solution, the quality of the NaOH of interpolation is 25g.
In described step 3, after reactor is sealed, put into baking oven, by the temperature to 150 in baking oven DEG C, after constant temperature 12h, be cooled to room temperature, finally reactor taken out from baking oven
In described step 4, by washings at 100 DEG C after dry 12h, then at 400 DEG C roasting 4h, obtain novel methanation catalyst.
The shaped granule of aforementioned novel methanation catalyst, comprises the component of following ratio of weight and number:
Novel methanation catalyst 100 parts,
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, 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, for the production domesticization of such catalyst, reduces production cost, has great importance.
Simultaneously, the present invention also provides the preparation method of aforementioned novel methanation catalyst, and the method is acted in the solution of active component, the first auxiliary agent, the second auxiliary agent by reducing solution, then by aqueous slkali adjust ph, pyroreaction, drying, roasting, make catalyst.And by catalyst, adhesive, the cooperatively interacting of lubricant, make shaped granule.
Verify by experiment, the present invention has following beneficial effect: the serviceability temperature of (1) catalyst of the present invention is 240 ~ 680 DEG C, is applicable to high-temperature methane metallization processes, is conducive to improving capacity usage ratio; (2) catalyst high-temperature stability of the present invention is good, and water vapor erosiveness is strong, and through the examination of 1000h life experiment, the high temperature active of catalyst is stablized; (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 with the first auxiliary agent, the second auxiliary agent high degree of dispersion, is evenly combined, and is conducive to improving catalyst stability under the high temperature conditions.
Detailed description of the invention
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.
Arbitrary feature disclosed in this description, 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.
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, stirs, obtain solution one.Again with vigorous stirring, in solution one, add alkaline solution, obtain solution two.Solution two is transferred in polytetrafluoro inner bag autoclave, after being sealed by polytetrafluoro inner bag autoclave, puts into baking oven.By the temperature to 150 in baking oven DEG C, after constant temperature 12h, be cooled to room temperature, finally reactor taken out from baking oven.
Product in the reactor taken out from baking oven is filtered, is washed to pH value to 6 ~ 7, obtains washings, by washings at 100 DEG C after dry 12h, then at 400 DEG C roasting 4h, obtain novel methanation catalyst.
Shaping
By novel methanation catalyst: cement, graphite: the mass ratio of water=100:10:3:10, mix these four kinds, compression molding, namely 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, stirs, obtain solution one.Again with vigorous stirring, in solution one, add alkaline solution, obtain solution two.Solution two is transferred in polytetrafluoro inner bag autoclave, after being sealed by polytetrafluoro inner bag autoclave, puts into baking oven.By the temperature to 150 in baking oven DEG C, after constant temperature 12h, be cooled to room temperature, finally reactor taken out from baking oven.
Product in the reactor taken out from baking oven is filtered, is washed to pH value to 6 ~ 7, obtains washings, by washings at 100 DEG C after dry 12h, then at 400 DEG C roasting 4h, obtain novel methanation catalyst.
Shaping
By novel methanation catalyst: cement, graphite: the mass ratio of water=100:10:3:10, mix these four kinds, compression molding, namely 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, stirs, obtain solution one.Again with vigorous stirring, in solution one, add alkaline solution, obtain solution two.Solution two is transferred in polytetrafluoro inner bag autoclave, after being sealed by polytetrafluoro inner bag autoclave, puts into baking oven.By the temperature to 150 in baking oven DEG C, after constant temperature 12h, be cooled to room temperature, finally reactor taken out from baking oven.
Product in the reactor taken out from baking oven is filtered, is washed to pH value to 6 ~ 7, obtains washings, by washings at 100 DEG C after dry 12h, then at 400 DEG C roasting 4h, obtain novel methanation catalyst.
Shaping
By novel methanation catalyst: cement, graphite: the mass ratio of water=100:10:3:10, mix these four kinds, compression molding, namely 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, stirs, obtain solution one.Again with vigorous stirring, in solution one, add alkaline solution, obtain solution two.Solution two is transferred in polytetrafluoro inner bag autoclave, after being sealed by polytetrafluoro inner bag autoclave, puts into baking oven.By the temperature to 150 in baking oven DEG C, after constant temperature 12h, be cooled to room temperature, finally reactor taken out from baking oven.
Product in the reactor taken out from baking oven is filtered, is washed to pH value to 6 ~ 7, obtains washings, by washings at 100 DEG C after dry 12h, then at 400 DEG C roasting 4h, obtain novel methanation catalyst.
Shaping
By novel methanation catalyst: cement, graphite: the mass ratio of water=100:10:3:10, mix these four kinds, compression molding, namely obtains product.Calcium aluminate is one of main component of cement.
Determination of activity is carried out to shaped granule prepared by previous embodiment 1-4, is denoted as embodiment 1, embodiment 2, embodiment 3, embodiment 4 respectively.
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 DEG C; Recovery time: 4h; Reduction air speed: 4000h
-1.
Catalyst methane hot operation condition: Catalyst packing: 30mL; Outlet temperature: 630 DEG C; Reaction pressure: 3MPa; Air speed: 20000h
-1.
Unstripped gas is by CH
4, H
2, CO, CO
2, N
2composition, the percent by volume of each component is as shown in table 1.
Table 1 novel methanation catalyst outlet composition (v%)
| CO | CO2 | CH4 | H2 |
| 6 | 7 | 37 | 50 |
Table 2 is corresponding measurement result, and table 2 is as follows.
Table 2 novel methanation catalyst outlet composition
| 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 aforesaid detailed description of the invention.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (10)
1. a methanation catalyst, is characterized in that, comprises active component, carrier, the first auxiliary agent, the second auxiliary agent, is active component, with Al with Ni
2o
3for carrier, the first auxiliary agent is the one 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 present in this catalyst all in the form of the oxide, in oxidation state, the mass percent of active component is 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;
Described catalyst adopts the method comprised the steps to be prepared from:
(1) prepare reducing solution: reducing agent is soluble in water, obtain reducing solution;
(2) raw materials liquid: get nickel nitrate, aluminum nitrate, the first slaine, the second slaine respectively, mixes nickel nitrate, aluminum nitrate, the first slaine, the second slaine with water, obtains material liquid;
(3) hybrid reaction: added in isopyknic material liquid by reducing solution, stir, obtains solution one, again with vigorous stirring, in solution one, add alkaline solution isopyknic with solution one, obtain solution two, solution two is transferred in reactor, after reactor is sealed, put into baking oven, by the temperature to 100 in baking oven ~ 200 DEG C, after constant temperature 10 ~ 15h, be cooled to room temperature, finally reactor taken out from baking oven;
(4) post processing: the product in the reactor taken out from baking oven is filtered, washed to pH value to 6 ~ 7, obtains washings, by washings at 80 ~ 120 DEG C after dry 4 ~ 30h, then at 300 ~ 550 DEG C roasting 2 ~ 12h, obtain methanation catalyst;
In described step (1), reducing agent is the one 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 the one 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, containing 0.15 ~ 0.55mol nickel ion in often liter of material liquid; In aluminium ion, containing 0.25 ~ 0.60mol aluminium ion in often liter of material liquid; With the metal ion of the first slaine, the metal ion containing 0.003 ~ 0.015mol first slaine in often liter of material liquid; With the metal ion of the second slaine, the metal ion containing 0.005 ~ 0.030mol second slaine in often liter of material liquid;
In described step (3), alkaline solution is mixed by the one in sodium carbonate, NaOH, potash, ammonium carbonate, urea, ammoniacal liquor and water, and in described alkaline solution, the mass concentration of solute is 15-50g/L.
2. methanation catalyst according to claim 1, is characterized in that, in oxidation state, the mass percent of the mass percent of active component to be the mass percent of the 25 ~ 45%, first auxiliary agent be the 2 ~ 5%, second auxiliary agent is 7 ~ 11%, and surplus is carrier.
3. methanation catalyst according to claim 1 or 2, is characterized in that, described first auxiliary agent is the oxide of lanthanum.
4. the preparation method of methanation catalyst according to any one of claim 1-3, 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 nickel nitrate, aluminum nitrate, the first slaine, the second slaine respectively, mixes nickel nitrate, aluminum nitrate, the first slaine, the second slaine with water, obtains material liquid;
(3) hybrid reaction: added in isopyknic material liquid by reducing solution, stir, obtains solution one, again with vigorous stirring, in solution one, add alkaline solution isopyknic with solution one, obtain solution two, solution two is transferred in reactor, after reactor is sealed, put into baking oven, by the temperature to 100 in baking oven ~ 200 DEG C, after constant temperature 10 ~ 15h, be cooled to room temperature, finally reactor taken out from baking oven;
(4) post processing: the product in the reactor taken out from baking oven is filtered, washed to pH value to 6 ~ 7, obtains washings, by washings at 80 ~ 120 DEG C after dry 4 ~ 30h, then at 300 ~ 550 DEG C roasting 2 ~ 12h, obtain methanation catalyst;
In described step (1), reducing agent is the one 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 the one 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, containing 0.15 ~ 0.55mol nickel ion in often liter of material liquid; In aluminium ion, containing 0.25 ~ 0.60mol aluminium ion in often liter of material liquid; With the metal ion of the first slaine, the metal ion containing 0.003 ~ 0.015mol first slaine in often liter of material liquid; With the metal ion of the second slaine, the metal ion containing 0.005 ~ 0.030mol second slaine in often liter of material liquid;
In described step (3), alkaline solution is mixed by the one in sodium carbonate, NaOH, potash, ammonium carbonate, urea, ammoniacal liquor and water, and in described alkaline solution, the mass concentration of solute is 15-50g/L.
5. the preparation method of methanation catalyst according to claim 4, it 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 methanation catalyst according to claim 4, it is characterized in that, in described step (3), alkaline solution is mixed by NaOH and water, and in often liter of alkaline solution, the quality of the NaOH of interpolation is 25g.
7. the preparation method of methanation catalyst according to claim 4, is characterized in that, in described step (3), after being sealed by reactor, put into baking oven, by the temperature to 150 in baking oven DEG C, after constant temperature 12h, be cooled to room temperature, finally reactor taken out from baking oven.
8. the preparation method of methanation catalyst according to any one of claim 4-7, is characterized in that, in described step (4), by washings at 100 DEG C after dry 12h, then at 400 DEG C roasting 4h, obtain methanation catalyst.
9. the shaped granule of methanation catalyst according to any one of claim 1-3, is characterized in that, comprise the component of following ratio of weight and number:
Methanation catalyst 100 parts,
Adhesive 8-12 part,
Lubricant 2-5 part,
Water 8-12 part.
10. the preparation method of the shaped granule of methanation catalyst according to claim 9, is characterized in that, comprise the steps: to take each component by proportioning, mix, compression molding.
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| CN104707621B (en) * | 2015-04-02 | 2017-10-27 | 西南化工研究设计院有限公司 | A kind of natural gas catalyst manufactured by coal and preparation method thereof |
| 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 |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| CN111760576B (en) * | 2019-04-02 | 2022-12-02 | 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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| CN102424570A (en) * | 2011-09-01 | 2012-04-25 | 上海大学 | Preparation method of NiFe2O4 magnetic material |
| CN102921429A (en) * | 2012-11-09 | 2013-02-13 | 西南化工研究设计院有限公司 | Coal-derived natural gas catalytic agent and preparation method thereof |
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