CN104841435A - Alkali metal-doped modified coal-to-natural gas methane synthesis catalyst and preparation method thereof - Google Patents
Alkali metal-doped modified coal-to-natural gas methane synthesis catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention belongs to the technical field of catalysts and preparation thereof, and relates to an alkali metal-doped modified coal-to-natural gas methane synthesis catalyst and a preparation method thereof. According to the present invention, the catalyst comprises nickel, a co-catalyst, aluminum or magnesium-aluminum, and an alkali metal; a catalyst semi-finished product is prepared by using a precipitation method and then is modified by using a doped alkali metal, the doped alkali metal comprises one or two selected from lithium, sodium, potassium, and rubidium, the alkali metal soluble salt is loaded on the catalyst by using an impregnation method, and draining, drying and calcining are performed to obtain the catalyst finished product; and the catalyst prepared through the method of the present invention has characteristics of high temperature thermal stability, carbon deposition resistance, wide reaction temperature zone (200-800 DEG C), wide raw material gas adaptability, and the like, and can be used for raw material gas purification and other processes in coal-to-natural gas, coke oven gas and coal gas methanation, and ammonia and ethylene synthesis apparatuses.
Description
Technical field
The invention belongs to catalysis technical field, relate to a kind of coal preparing natural gas methane synthesizing catalyst and preparation method thereof.
Background technology
The clean energy resource that natural gas is a kind of practicality and high efficiency safety, calorific value is high, compared with the coal of equal in quality, the CO of burning and exhausting
2be only 40% of coal, do not have waste water, waste residue to produce.Therefore, natural gas is widely used in the industries such as generating, chemical industry, gas, motor vehicle fuel, is one of main in the world clean energy resource.Along with developing rapidly of China's national economy, the demand of natural gas resource is also continued to increase.According to the statistics of National Energy Board, the output of domestic natural gas in 2012 is 1,077 hundred million Nm
3, domestic Apparent con-sumption is 1,471 hundred million Nm
3, nearly 40,000,000,000 Nm of natural gas consumption breach
3.According to " natural gas development " the 12 " planning " of National Energy Board's establishment, expect that China's natural gas consumption figure in 2015 is 2,300 hundred million Nm
3left and right, and the same period, natural gas supply ability only had 1,760 hundred million Nm
3left and right.Natural gas will become the important pushing hands of energy structure in China transition visible coming years.
The breach of current domestic natural gas supply strengthens just year by year, and external dependence degree nearly 2 years is the gesture of rising fast especially.2011, China's natural gas external dependence degree reached 24%, compared with 2010 12.8%, in the situation that is doubled and redoubled.According to relevant data prediction, to the year two thousand twenty, domestic natural gas breach will reach 1,000 hundred million Nm
3.
" rich coal, oil-poor, weak breath " is the characteristic distributions of Chinese energy, and the natural gas resource of China is rare, 1/15 of the average occupancy volume of Jin Zhan world natural gas.Relevant expert represents, this objectively increases the demand dynamics to Unconventional forage and alternative natural gas, and coal preparing natural gas has also been sent to great expectations in country's " 12 " strategical planning.
" Coal Chemical Industry " 12 " program for the development of science and technology " is pointed out, between " 12 ", country will give special assistance to the application of coal preparing natural gas technology, and expand pilot scope in this respect." Dissertation of Development of Coal Industry " 12 " planning " represents, emphasis supports that large enterprise carries out the construction of coal preparing natural gas upgrading demonstration project, accelerates advanced technology commercial application.Coal preparing natural gas project is also classified as one of Coal Chemical Industry five class demonstration project by " petrochemical industry adjustment and development planning ".
Up to now, domesticly to plan, building with built coal preparing natural gas project more than 40, production capacity amounts to 1,618 hundred million Nm
3/ a, estimates to use catalyst to be about 10800t/a.Wherein, start the coal preparing natural gas project 9 of construction, add up to production capacity 34,600,000,000 Nm
3/ a; Obtain the project 4 that National Development and Reform Committee checks and approves, add up to production capacity 15,100,000,000 Nm
3/ a.Domestic and international each scientific research institutions Devoting Major Efforts To Developing methane synthesizing catalyst, to the active demand of methane synthesizing catalyst, is impelled in the good prospect of coal preparing natural gas and future market.
Coal process for producing natural technology is comparatively ripe, and coal based synthetic gas obtains a certain proportion of H after conversion, purification
2, CO, CO
2, after regulating suitable hydrogen-carbon ratio, under methane synthesizing catalyst effect, obtain through methanation reaction the SNG being rich in methane.The key technology of coal preparing natural gas is process for synthesizing methane technology, and one of its core technology is methane synthesizing catalyst.
On thermodynamics, methanation reaction is strong exothermal reaction.The reaction heat of methanation is 2 times of synthesizing methanol reaction heat.In common gas component, the CO methanation of every 1 percentage point can produce the adiabatic temperature rise of 74 DEG C; The CO of every 1 percentage point
2methanation can produce the adiabatic temperature rise of 60 DEG C.Therefore, catalyst of good performance must require to have high high-temp stability and anti-carbon performance simultaneously.
At present, coal based synthetic gas preparing natural gas methanation catalyst used is main active component with nickel, generally uses Al
2o
3, magnesium aluminate spinel etc. as carrier, typical catalyst representative has Britain Dai Wei company CRG type, BASF Aktiengesellschaft H1 type and Top of Denmark rope company MCR type.From the situation that existing catalyst runs, under high temperature, sintering and carbon distribution become two large main causes of catalysqt deactivation.The present invention intends and surface acidic-basic property energy inner by alkali-metal-doped modified catalyst, improves catalyst high temperature carbon distribution.
Patent CN102189004 discloses a kind of preparation method of high-temperature methanation catalyst, by dipping by active constituent loading in magnesia alumina spinel carrier, the catalytic mechanical intensity of preparation is high, the thermally-stabilised feature such as to act charitably; Patent CN102335608A discloses a kind of method adding dispersant Kaolinite Preparation of Catalyst reactive precursor, improves grain size and the dispersive property of catalyst, and catalyst has good wide warm nature energy (220 DEG C ~ 700 DEG C); Patent CN102189003A discloses a kind of rare earth modified methanation catalyst carrier, and obtained catalyst support surface acidity reduces, thus reduces the formation of carbon distribution.
On the basis of above-mentioned patented technology, we will continue optimization of catalysts correlated performance, develop a kind of methane synthesizing catalyst of high temperature anti-carbon performance, be applicable to high-temperature coal preparing natural gas process for synthesizing methane, and its preparation possesses good anti-carbon performance.
Summary of the invention
The invention provides a kind of coal preparing natural gas methane synthesizing catalyst, object improves coal preparing natural gas methanation catalyst high temperature anti-carbon performance, improves the average life span of methane synthesizing catalyst further.This catalyst is mainly used in the high temperature methanations such as coal substitute natural gas (SNG), also goes for low temperature methanation in coke-oven gas methanation, town gas methanation and synthetic ammonia installation, the purification of Ethylene Unit Feedstocks gas etc.
For solving the problems of the technologies described above, technical solution of the present invention is as follows:
The invention provides a kind of preparation method of coal preparing natural gas methane synthesizing catalyst, this catalyst is made up of active component, carrier, auxiliary agent and alkali metal.Alkali-metal-doped mainly plays the effect improving catalyst surface Acidity of Aikalinity and concerted catalysis, has electron type or structural type modifying function concurrently.
A kind of coal preparing natural gas methane synthesizing catalyst provided by the invention, its main active component is nickel, and carrier is aluminium oxide, magnesia, boehmite, boehmite or magnesium aluminate spinel, adopts the preparation of precipitation-mixing method; Alkali doped be in lithium, sodium, potassium, rubidium, caesium one or both, adopt infusion process load.
Consisting of based on catalyst components oxide mass:
Active component: nickel 10% ~ 70%, preferably 20% ~ 40%.
Co-catalyst: 1%-10%
Carrier: 20% ~ 75%.
Alkali-metal-doped amount: 0.1% ~ 15%, preferably 2% ~ 10%.
For achieving the above object, the present invention adopts following preparation process:
1. first active component nickel, co-catalyst soluble-salt are mixed with mixed solution, with NaOH or NaHCO
3or Na
2cO
3or K
2cO
3or ammoniacal liquor carries out co-precipitation as precipitating reagent, the rear obtained catalyst activity parent slurry of aging, washing.
2. one or both powder wherein such as aluminium oxide, magnesia, boehmite, boehmite or magnesium aluminate spinel are carried out mixing with reactive precursor slurry in step 1 and pull an oar, obtain catalyst precursor.
3. this catalyst precursor press filtration, drying, roasting, granulation, compressing tablet are obtained catalyst semi-finished product.
4. prepare alkali doped soluble salt solutions, be immersed on above-mentioned catalyst semi-finished product by certain dipping content, drain rear drying and roasting and obtain finished catalyst.
In above-mentioned preparation process 1, control speed of agitator is 100 ~ 3000r/min, and preferably 500 ~ 2500r/min adopts heating water bath precipitation temperature to control at 50 DEG C ~ 90 DEG C, and endpoint pH controls 7.0 ~ 9.0, preferably between 7.2 ~ 8.0, in alkalescent, measure qualified rear stopping and stirring, aging 1 ~ 3h.
In above-mentioned preparation process 2, support powder must through sieving, and sieve number is not less than 100 orders, and support powder is more thin better.
In above-mentioned preparation process 3, catalyst semi-finished product baking temperature is 100 DEG C ~ 120 DEG C, and control drying time is 1 ~ 3h; Sintering temperature is 350 DEG C ~ 650 DEG C, and roasting time is 3 ~ 5h; Strength of pressed pieces is 120 ~ 300N/cm.
In above-mentioned preparation process 3, catalyst shape, size are determined by reactor real needs, be preferably moulded as honeycombed catalyst, be conducive to reactor feed gas and gas product spreads rapidly, widen and methanation reaction high temperature distributed area occurs, can prevent high-temperature region from too concentrating to greatest extent and cause catalyst carbon deposition, sintering.
In above-mentioned preparation process 4, alkali doped to comprise in lithium, sodium, potassium, rubidium, caesium one or both, and be the soluble-salt of tie substance, obtain solution concentration is 0.5 ~ 2mol/L, control temperature during dipping.
Compared with prior art, the present invention can produce following good effect:
1. catalyst pore passage structure and specific area can suitably add alkali metal according to the actual requirements and regulate, and active component, co-catalyst and alkali doped can be uniformly distributed on carrier, can improve high-temperature stability and the anti-carbon performance of catalyst;
2. catalyst has meso-hole structure, and average pore size is much larger than H
2, CO, CO
2, CH
4molecular diameter, away from Knudsen diffusion model, can overcome transmission resistance, is conducive to diffusion and diffusion into the surface in reactant and product catalyst, the Carbon deposition that minimizing methane and many carbon hydrocarbon residence time are grown and caused;
3. active component exists with NiO form, and alkali doped is alkalescence and is uniformly distributed on carrier, can reduce the formation of acid intensity and quantity, reduces the cracking probability of methane and many carbon hydro carbons, thus suppresses catalyst carbon distribution on a large scale.
Accompanying drawing explanation
Fig. 1 is coal preparing natural gas methane synthesizing catalyst preparation technology general flow chart of the present invention.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the inventive method is described in detail.
Following examples as shown in Figure 1.
Embodiment 1: take Ni (NO
3)
26H
2o 389.38 grams, takes Re (NO
3)
36H
2o 33.32 grams is mixed with mixing 2 ~ 3mol/L solution, and above-mentioned two kinds of solution are fully uniformly mixed 30 ~ 60min.Take about 954.35 grams of NaHCO
3be mixed with saturated solution, join in above-mentioned mixed solution, carry out neutralization precipitation under adding thermal agitation, precipitation temperature is 50 DEG C ~ 90 DEG C, and it is 7.2 ~ 8.0 that terminal pH controls, and obtains reactive precursor slurry.By aluminium oxide ball milling, sieve with 100 eye mesh screens, obtain support powder.This support powder is mixed with above-mentioned reactive precursor slurry and pulls an oar, through press filtration, drying, roasting, shaping after obtain catalyst semi-finished product.Take LiNO
325.24 grams, preparation 1 ~ 2mol/L solution, impregnated catalyst semi-finished product, drain rear drying and roasting and obtain finished catalyst.
Embodiment 2: take Ni (NO
3)
26H
2o 389.38 grams, takes Re (NO
3)
36H
2o 33.23 grams is mixed with mixing 2 ~ 3mol/L solution, and above-mentioned two kinds of solution are fully uniformly mixed 30 ~ 60min.Take about 600.16 grams of Na
2cO
3be mixed with saturated solution, join in above-mentioned mixed solution, carry out neutralization precipitation under adding thermal agitation, precipitation temperature is 50 ~ 90 DEG C, and it is 7.2 ~ 8.0 that terminal pH controls, and obtains reactive precursor slurry.By magnesia ball milling, sieve with 100 eye mesh screens, obtain support powder.This support powder is mixed with above-mentioned reactive precursor slurry and pulls an oar, through press filtration, drying, roasting, shaping after obtain catalyst semi-finished product.Take NaNO
325.24 grams, preparation 1 ~ 2mol/L solution, impregnated catalyst semi-finished product, drain rear drying and roasting and obtain finished catalyst.
Embodiment 3: take Ni (NO
3)
26H
2o 389.38 grams, takes Re (NO
3)
36H
2o 33.23 grams is mixed with mixing 2 ~ 3mol/L solution, and above-mentioned two kinds of solution are fully uniformly mixed 30 ~ 60min.Take about 600.16 grams of Na
2cO
3be mixed with saturated solution, join in above-mentioned mixed solution, carry out neutralization precipitation under adding thermal agitation, precipitation temperature is 50 ~ 90 DEG C, and it is 7.2 ~ 8.0 that terminal pH controls, and obtains reactive precursor slurry.By boehmite ball milling, sieve with 100 eye mesh screens, obtain support powder.This support powder is mixed with above-mentioned reactive precursor slurry and pulls an oar, through press filtration, drying, roasting, shaping after obtain catalyst semi-finished product.Take K
2cO
325.24 grams, preparation 1 ~ 2mol/L solution, impregnated catalyst semi-finished product, drain rear drying and roasting and obtain finished catalyst.
Embodiment 4: take Ni (NO
3)
26H
2o 389.38 grams, takes Re (NO
3)
326.16 grams are mixed with mixing 2 ~ 3mol/L solution, and above-mentioned two kinds of solution are fully uniformly mixed 30 ~ 60min.Take about 785.03 grams of K
2cO
3be mixed with saturated solution, join in above-mentioned mixed solution, carry out neutralization precipitation under adding thermal agitation, precipitation temperature is 50 ~ 90 DEG C, and it is 7.2 ~ 8.0 that terminal pH controls, and obtains reactive precursor slurry.By boehmite ball milling, sieve with 100 eye mesh screens, obtain support powder.This support powder is mixed with above-mentioned reactive precursor slurry and pulls an oar, through press filtration, drying, roasting, shaping after obtain catalyst semi-finished product.Take RbNO
325.24 grams, preparation 1 ~ 2mol/L solution, impregnated catalyst semi-finished product, drain rear drying and roasting and obtain finished catalyst.
Embodiment 5: take Ni (NO
3)
26H
2o 389.38 grams, takes Re (NO
3)
36H
2o 35.07 grams is mixed with mixing 2 ~ 3mol/L solution, and above-mentioned two kinds of solution are fully uniformly mixed 30 ~ 60min.Take about 600.16 grams of Na
2cO
3be mixed with saturated solution, join in above-mentioned mixed solution, carry out neutralization precipitation under adding thermal agitation, precipitation temperature is 50 ~ 90 DEG C, and it is 7.2 ~ 8.0 that terminal pH controls, and obtains reactive precursor slurry.By magnesium aluminate spinel ball milling, sieve with 100 eye mesh screens, obtain support powder.This support powder is mixed with above-mentioned reactive precursor slurry and pulls an oar, through press filtration, drying, roasting, shaping after obtain catalyst semi-finished product.Take CsNO
325.24 grams, preparation 1 ~ 2mol/L solution, impregnated catalyst semi-finished product, drain rear drying and roasting and obtain finished catalyst.
Claims (10)
1. an alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst, is characterized in that: this catalyst composition comprises active component nickel, co-catalyst, carrier and alkali doped, and component is with each component oxide mass percent:
Active component: nickel 10% ~ 70%
Co-catalyst: 1% ~ 10%
Carrier: 20% ~ 75%
Alkali-metal-doped amount: 0.1% ~ 15%.
2. alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst according to claim 1, is characterized in that active component nickel 20% ~ 40%.
3. alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst according to claim 1, is characterized in that alkali-metal-doped amount 2% ~ 10%.
4. the preparation method of alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst according to claim 1, is characterized in that comprising following several step:
A) first the soluble-salt of active component nickel, co-catalyst is mixed with mixed solution, with NaOH, NaHCO
3, Na
2cO
3, K
2cO
3or ammoniacal liquor carries out co-precipitation as precipitating reagent, aging washing is obtained catalyst activity parent afterwards;
B) pulverizer after one or both mixing in aluminium oxide, magnesia, boehmite, boehmite or magnesium aluminate spinel is pulverized;
C) in proportion by step a), b) in two components be mixed together making beating, suction filtration, drying, roasting, compression molding obtain catalyst semi-finished product;
D) Alkali-soluble salt is mixed with solution, makes it dissolve cmpletely;
E) soluble-salt in step d) being immersed in c) on catalyst semi-finished product by dipping content composition, obtaining finished catalyst through draining, after dry, roasting.
5. alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst preparation method according to claim 4, it is characterized in that in above-mentioned preparation process a, control speed of agitator is 100 ~ 3000r/min, heating water bath precipitation temperature is adopted to control at 50 DEG C ~ 90 DEG C, endpoint pH controls 7.0 ~ 9.0, in alkalescent, measure qualified rear stopping to stir, aging 1 ~ 3h.
6. alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst preparation method according to claim 5, it is characterized in that in above-mentioned preparation process a, control speed of agitator is 500 ~ 2500r/min, endpoint pH controls between 7.2 ~ 8.0.
7. alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst preparation method according to claim 4, it is characterized in that support powder is through sieving in above-mentioned preparation process b, sieve number is not less than 100 orders.
8. alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst preparation method according to claim 4, is characterized in that catalyst semi-finished product baking temperature is 100 DEG C ~ 120 DEG C in above-mentioned preparation process c, and control drying time is 1 ~ 3h; Sintering temperature is 350 DEG C ~ 650 DEG C, and roasting time is 3 ~ 5h; Strength of pressed pieces is 120 ~ 300N/cm.
9. alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst preparation method according to claim 4, is characterized in that the catalyst prepared is cellular.
10. alkali-metal-doped modified coal preparing natural gas methane synthesizing catalyst preparation method according to claim 1, it is characterized in that the alkali metal adulterated comprises in lithium, sodium, potassium, rubidium, caesium one or both.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126805A (en) * | 2018-09-06 | 2019-01-04 | 鄂尔多斯应用技术学院 | A kind of low temperature high activity gas employing methanation of coke oven catalyst and preparation method thereof |
| CN109821543A (en) * | 2019-01-25 | 2019-05-31 | 西安向阳航天材料股份有限公司 | A kind of methanation catalyst of alkali metals modified and preparation method thereof |
| CN110327953A (en) * | 2019-07-29 | 2019-10-15 | 安徽工业大学 | A kind of pair of caking coal carries out brokenly the viscous preparation method with the dual-component catalyst of gasification |
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| WO2012168690A1 (en) * | 2011-06-06 | 2012-12-13 | Johnson Matthey Public Limited Company | Water-gas shift catalyst |
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| CN101380581A (en) * | 2007-09-07 | 2009-03-11 | 新奥科技发展有限公司 | Novel methanation catalyst and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109126805A (en) * | 2018-09-06 | 2019-01-04 | 鄂尔多斯应用技术学院 | A kind of low temperature high activity gas employing methanation of coke oven catalyst and preparation method thereof |
| CN109821543A (en) * | 2019-01-25 | 2019-05-31 | 西安向阳航天材料股份有限公司 | A kind of methanation catalyst of alkali metals modified and preparation method thereof |
| CN110327953A (en) * | 2019-07-29 | 2019-10-15 | 安徽工业大学 | A kind of pair of caking coal carries out brokenly the viscous preparation method with the dual-component catalyst of gasification |
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Application publication date: 20150819 |