CN102942971B - Application of raney nickel as slurry reactor to synthesize methane catalyst - Google Patents
Application of raney nickel as slurry reactor to synthesize methane catalyst Download PDFInfo
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- CN102942971B CN102942971B CN201210382659.9A CN201210382659A CN102942971B CN 102942971 B CN102942971 B CN 102942971B CN 201210382659 A CN201210382659 A CN 201210382659A CN 102942971 B CN102942971 B CN 102942971B
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Abstract
The invention provides the application of raney nickel as a slurry reactor to synthesize a methane catalyst, including: adding a raney nickel catalyst dispersed in an inert liquid medium to a reactor for a methanation reaction, feeding product gas and raw material gas to a separator, discharging a liquid phase component I composed of the liquid phase component and the catalyst component in the product gas from the bottom of the separator I, discharging gas phase I from the top of the separator, discharging a part of the inert liquid medium containing the catalyst from the middle of the reactor into a separator II, discharging gas phase II from the top of the separator II, mixing the gas phase II with the gas phase I to get a natural gas product, discharging the inert liquid medium of the catalyst from the bottom of the separator II to mix with the liquid phase component I to get a mixture, and feeding the mixture and the fresh methanation catalyst dispersed in the inert liquid medium together into the reactor for the methanation reaction. The application has the advantages that the raney nickel catalyst does not need reduction, has high mechanical strength and good wear resistance, and can satisfy the requirement of slurry reactor methanation process for low temperature activity.
Description
Technical field
The invention belongs to the purposes of Raney's nickel (Raney-Ni), relate in particular to Raney's nickel as the application of slurry state bed methanation catalyst.
Background technology
China has the Energy Situation of rich coal, oil-poor, weak breath, therefore the complex optimum utilization of coal resources is compeled as pressing as a fire singeing one's eyebrows.Coal synthetic natural gas processed not only can meet current growing clean energy demand, also to the reasonable utilization of domestic coal resources with distribute the irreplaceable effect of playing rationally.Methanation is the core technology of coal preparing natural gas, and this reaction refers to CO or CO
2the synthetic CH of hydrogenation under the effect of catalyzer
4and H
2o, reaction formula is as follows:
CO+3H
2＝CH
4+H
2O+206KJ/mol (1)
CO
2+4H
2＝CH
4+2H
2O+165KJ/mol (2)
At present, coal preparing natural gas technology mainly contains German Shandong strange (LURGI) in the world, Britain wears dimension (DAVY) and Denmark Top rope
three kinds, above-mentioned technology all adopts fixed bed methanation process, and catalyzer is that loading type Ni is catalyst based.Because methane turns to strong exothermal reaction, therefore all adopt many fixed bed methanator series connection, and with complex appts such as many interchanger and gas circulators, control temperature, adopt up to the circulation gas more than 5 times simultaneously and have 25% to be diluted to 2%～4% the CO in producing synthesis gas from coal.Not only increase facility investment, also significantly increased circulation gas power consumption.
For the strong exothermicity of methanation reaction and the shortcoming of existing fixed bed methanation process, SaiDing Engineering Co., Ltd and Institutes Of Technology Of Taiyuan's joint development go out a kind of slurry state bed methanation process (CN101979476A and CN101979475A).Slurry state bed methanation process refers to introduces the inert liquid phase component that thermal conductivity is large, hot melt is large in the process of methanation reaction, methanation catalyst is dispersed in inert liq uniformly, realized the isothermal of bed, thereby avoided the temperature runaway problem occurring in conventional fixed bed methanation method, the adaptability that makes to starch state bed methanation unstripped gas due to slurry state bed good heat transfer property is stronger, in unstripped gas, the concentration of CO can regulate in 2%～30% large concentration range, and without CO/CO in dilution unstripped gas
2concentration, and this technique one way CO transformation efficiency reaches more than 90%, greatly reduces facility investment and circulating consumption, for coal preparing natural gas provides a kind of new thinking.
In above-mentioned two patents, disclosed slurry state bed methanation process catalyzer used is commercial fixed bed catalyzer.But slurry state bed methanation process is different to the requirement of catalyzer with fixed-bed process, therefore being used for starching state bed methanation reaction, commercial fixed bed catalyzer there are many shortcomings, be embodied in: (1) slurry state bed requires the granularity of catalyzer less more even, but fixed bed methanation catalyst granularity is larger, therefore need carry out fragmentation to commercial catalysts, and then can cause the pore passage structure of catalyzer destroyed; (2) commercial fixed bed methanation catalyst is loading type nickel-based catalyst, before reaction, must pass through H
2reduce, reduction temperature is up to 400～600 ℃, but the inert component boiling point of starching in state bed methanation process is lower, and high temperature easily decomposes; (3) owing to being subject to the restriction of inert component boiling point, slurry state bed methanation process requires catalyzer to have higher low temperature active, but the temperature of reaction of fixed bed methanation catalysis is all higher; (4) slurry state bed methanator needs peripheral equipment stir or mix by unstripped gas turbulent flow, has increased the wearing and tearing of catalyzer, therefore higher to the requirement of mechanical strength of catalyzer.
Summary of the invention
The object of the invention is to overcome the shortcoming of fixed bed catalyst in slurry state bed methanation process, provide a kind of Raney's nickel as starching state bed synthetic methane catalyst in the application of passing through slurry state bed methanation synthetic natural gas.
Technical scheme of the present invention is as follows:
(1) coal produces coal gas through gasification, then through purifying and convert to obtain methanation unstripped gas.
(2) Raney's nickel (Raney-Ni) catalyzer is dispersed in inert liquid phase medium and forms finite concentration, and be added to paste state bed reactor, then by slurry state bed bottom, pass into methanation unstripped gas, be warming up to temperature of reaction, after boosting to reaction pressure, carry out methanation reaction simultaneously, after gas product and unstripped gas heat exchange, enter gas-liquid separator I, the slurry state liquid phase component I that in gas product, liquid phase component and catalyzer form is discharged by gas-liquid separator I bottom, and gas phase I is discharged by gas-liquid separator top;
(3) in methanation reaction process, part is discharged from paste state bed reactor middle part containing the inert liquid phase medium of catalyzer, enter into gas-liquid separator II, wherein gas phase II is discharged by gas-liquid separator II top, and merge with the gas phase I being discharged by gas-liquid separator I top, afterwards by obtaining gas product after cooling and separated; And discharged by gas-liquid separator II bottom containing the inert liquid phase medium of methanation catalyst, and merge with discharge slurry state liquid phase component I bottom gas-liquid separator I, then after filtration the large granular catalyst below 300 orders is leached, and more than 300 orders thin catalyzer is discharged after separated with inert liquid phase medium, isolated inert liquid phase medium is mixed with large granular catalyst, through with unstripped gas heat exchange after carry out coolingly, and jointly enter and in paste state bed reactor, carry out methanation reaction with the fresh methanation catalyst being dispersed in inert liquid phase medium.
Inert liquid phase medium as above is paraffinic hydrocarbon, thermal oil (as
vP-1 type) and the inert liquid phase component that thermal conductivity is large, thermal capacitance is large, boiling point is high such as hydrogenated terphenyl (as SHHG-340).
Raney's nickel catalyst as above is alloy powder or the catalyzer of industrial Ni-auxiliary agent-Al, if industrial alloy powder, the NaOH that is 16wt% with concentration by it mixes with the ratio of 1: 4, and react 1h under the water bath condition of 60 ℃, then after washing three times, obtain finished catalyst, finished catalyst consists of: Ni 90～93wt%, Al5～7wt%, Mo0～2wt%, Fe0～2wt%, Cr0～2wt%, Ti0～2wt%, Cr wherein, Mo, Fe and Ti auxiliary agent at least one, catalyst grain size is 80～200 orders.
Raney's nickel catalyst as above is that the good rainbow chemical industry in JH-15 or JH-19 Mai Zi“ Shandong is limited "; RTH-2161, RTH3110, RTH4110, RTH-5110 catalyzer or RTH-4010 alloy powder are bought from " Yixing City rich metallurgical company limited in morning "; YL-211, YL-31 or YL-312 Mai Zi“ Jiangsu You Lian metal products company limited ".
The concentration of Raney's nickel catalyst as above in inert liquid phase medium is 2～40wt%.
The temperature of methanation reaction as above is 250 ℃～320 ℃, and more excellent is 280 ℃～300 ℃, and reaction pressure is 1～6MPa, and unstripped gas air speed is 1000～12000L/ (hkg).
CO/CO in methanation unstripped gas as above
2volumetric concentration between 2%～30%, (H
2-CO
2)/(CO+CO
2) mol ratio be 2.5～3.7, more excellent is 2.8～3.3.
The present invention
compared with prior artthe substantive distinguishing features and the marked improvement that have are:
(1) Raney's nickel is first by melting, to prepare Ni-Al alloy, then a kind of skeleton nickel with pore passage structure of through NaOH being prepared by the Al extracting in alloy, therefore this catalyzer is without reduction, not only overcome loading type nickel-based catalyst because reduction temperature is higher, and inert component high-boiling in the paste state bed reactor causing or the problem of decomposition, and avoided the energy consumption of slurry state bed process reduction operation.
(2) in preparing Raney's nickel catalyst process, by regulating the granularity of Ni-Al alloy powder to realize the control to Raney's nickel catalyst granularity.First by means such as grinding or fragmentations, choose the alloy powder of certain particle size, the Raney's nickel catalyst of the corresponding granularity of then making after aluminium extracting, therefore Raney's nickel catalyst not only can be realized the control to catalyst grain size, and can not affect the Catalytic Hydrogenation Properties of pore passage structure and the catalyzer of finished catalyst.
(3) slurry state bed methanation process, owing to thering is good heat transfer property, therefore in the situation that the per pass conversion of CO concentration and CO is higher, can in time reaction heat be shifted out to realize the isothermal of bed, therefore this processing requirement catalyzer has higher Catalytic Hydrogenation Properties.Raney's nickel catalyst has spongiform cavernous structure, and catalyst surface exists distortion or the dislocation of many crystallites, causes Raney's nickel catalyst to have extremely strong absorption H
2performance and high low-temperature catalytic activity, be widely used in the Chemical Manufacture such as hydrogenation, dehydrogenation and dehalogenation; Catalyst performance due to Ni active component content Geng Gao， unit catalyzer in Raney's nickel catalyst is obviously better than loading type nickel-based catalyst simultaneously, therefore Raney's nickel catalyst can meet the requirement of slurry state bed methanation process to low temperature active.
(4) Raney's nickel catalyst is prepared after aluminium extracting by Ni-Al alloy powder, Ni in finished catalyst mainly exists with metallic state, therefore this catalyzer has higher physical strength and better wear resisting property, meet slurry state bed owing to stirring or turbulent flow is mixed and requirement to catalyst strength.
(5) Raney's nickel catalyst technology maturation is reliable, and in numerous hydrogenation reactions, all realized industrialization, and the industrialization technology with the recycling of spent catalyst, has reliable industry experience therefore Raney's nickel catalyst is used for starching state bed methanation reaction.
Accompanying drawing explanation
Fig. 1 be take the schema of Raney's nickel as catalyst slurry state bed methanation process
As shown in the figure, 1 slurry state bed methanator, 2 interchanger I, 3 gas-liquid separator I, 4 gas-liquid separator II, 5 live catalyst storage tanks, 6 interchanger II, the 7th, recycle pump; P1, p2, p3, p4, p5, p6, p7, p8 and p9 are pipelines.
Embodiment
In slurry state bed methanation process, mechanical wear is to cause the major cause of catalyst deactivation, therefore the catalyzer occurring in specific embodiments of the invention and comparative example, during small-particle more than granularity wears up to 300 orders, catalyzer is defined as inactivation.Therefore, in order better to describe the stability of the catalyzer providing in the specific embodiment of present disclosure and comparative example, contriver represents with catalyst abrasion rate, and catalyzer wears up to more than 300 orders catalyzer every day and accounts for the percentage ratio of participating in catalyzer total mass and represent, unit is wt%/h.
The catalyzer that this patent is used is industrial alloy powder or the Raney's nickel catalyst through screening, if alloy powder, the NaOH that is 16wt% with concentration by it mixes with the ratio of 1: 4, and react 1h under the water bath condition of 60 ℃, then after washing three times, obtain finished catalyst, for simplicity, the catalyzer providing is in the following embodiments the finished catalyst of seeing after drawer, and replaces catalyzer model with alloy powder model.
Below by specific embodiment, the specific embodiment of the present invention is further described in detail, but this should be interpreted as to the scope of theme of the present invention only limits to following embodiment.
First by Ni
93al
5mo
2raney's nickel catalyst mixes with paraffinic hydrocarbon in catalyzer storage tank, and controlling Raney's nickel concentration is 2wt%, and through pipeline p1, by recycle pump 7, from bottom, is pressed into slurry state bed methanator, then passes into (V%): H
266.53%, CH
412%, N
21%,, CO 19.47%, CO
21% synthetic gas, pressure is risen to 1Mpa, temperature starts reaction after rising to 250 ℃, unstripped gas air speed is 1000L/ (hkg), tail gas autoreactor top enters in gas-liquid separator I through pipeline p3, the liquid phase component of carrying secretly in tail gas and catalyzer are discharged by separator I bottom, and merge through pipeline p5 and pipeline p8, and tail gas is discharged by obtaining synthetic natural gas cooling and purification from gas-liquid separator I top.In methanation reaction process, to account for the speed of the 3wt%/min of the inert liquid phase medium that contains catalyzer in reactor, through pipeline p6, pass in gas-liquid separator II, wherein gas phase is discharged and is merged through pipeline p7 and exhaust pipe p4 by gas-liquid separator II5 top, and from gas-liquid separator II5 bottom, discharge through pipeline p8 containing the inert media of catalyzer, and merge with the catalyzer from pipe p5, then after filtration the large granular catalyst below 300 orders is leached, and more than 300 orders thin catalyzer separates and discharges with inert liquid phase medium after separation, and isolated inert liquid phase medium mixes with large granular catalyst, through cooling by water cooler 6 with unstripped gas heat exchange, and jointly enter in slurry state bed methanator 2 and carry out methanation reaction with the fresh methanation catalyst being dispersed in inert liquid phase medium, reaction times is 30 days.
On the basis of embodiment 1,2～11 pairs of catalyst type of embodiment, the concentration of catalyzer in slurry state bed methanator, inert liquid phase medium kind, reaction gas air speed, temperature of reaction, reaction pressure factor is adjusted, concrete data and the results are shown in subordinate list 1, unstripped gas and gas product form and see attached list 2.
Comparative example 1
The ICI11-3 industry methanation catalyst that the catalyzer that this comparative example is used is BASF, the evaluation procedure of catalyzer and condition are identical with embodiment 1, and concrete outcome sees attached list 3.
Comparative example 2
The catalyzer that this comparative example is used is U.S. G-65 industry methanation catalyst, and the evaluation procedure of catalyzer and condition are identical with embodiment 1, and concrete outcome sees attached list 3
Note: the good rainbow chemical industry in JH-15 and JH-19 Mai Zi“ Shandong is limited "; RTH-2161, RTH3110, RTH4110, RTH-5110 catalyzer and RTH-4010 alloy powder are bought from " Yixing City rich metallurgical company limited in morning "; YL-211, YL-311, YL-312 Mai Zi“ Jiangsu You Lian metal products company limited ".
Note: reaction times unit is sky, with d, represents; Wear rate is the per-cent that catalyzer more than catalyst abrasion to 300 order every day accounts for catalyzer total mass, and unit is wt%/d.
Claims (6)
1. Raney's nickel is as an application for slurry state bed synthetic methane catalyst,, it is characterized in that comprising the steps:
(1) coal produces coal gas through gasification, then through purifying and convert to obtain methanation unstripped gas;
(2) Raney's nickel catalyst is dispersed in inert liquid phase medium and forms finite concentration, and be added to paste state bed reactor, then by slurry state bed bottom, pass into methanation unstripped gas, be warming up to temperature of reaction, after boosting to reaction pressure, carry out methanation reaction simultaneously, after gas product and unstripped gas heat exchange, enter gas-liquid separator I, the slurry state liquid phase component I that in gas product, liquid phase component and catalyzer form is discharged by gas-liquid separator I bottom, and gas phase I is discharged by gas-liquid separator top;
(3) in methanation reaction process, part is discharged from paste state bed reactor middle part containing the inert liquid phase medium of catalyzer, enter into gas-liquid separator II, wherein gas phase II is discharged by gas-liquid separator II top, and merge with the gas phase I being discharged by gas-liquid separator I top, afterwards by obtaining gas product after cooling and separated; And discharged by gas-liquid separator II bottom containing the inert liquid phase medium of methanation catalyst, and merge with discharge slurry state liquid phase component I bottom gas-liquid separator I, then after filtration the large granular catalyst below 300 orders is leached, and more than 300 orders thin catalyzer is discharged after separated with inert liquid phase medium, isolated inert liquid phase medium is mixed with large granular catalyst, through with unstripped gas heat exchange after carry out coolingly, and jointly enter and in paste state bed reactor, carry out methanation reaction with the fresh methanation catalyst being dispersed in inert liquid phase medium;
Described Raney's nickel catalyst is the alloy powder of industrial Ni-auxiliary agent-Al, is by industrial alloy powder, to be 16wt% with concentration NaOH mixes with the ratio of 1:4, and reacts 1h under the water bath condition of 60 ℃, then after washing three times, obtain finished catalyst, finished catalyst consists of: Ni90～93wt%, Al5～7wt%, Mo0～2wt%, Fe0～2wt%, Cr0～2wt%, Ti0～2wt%, Cr wherein, Mo, Fe and Ti auxiliary agent at least one, catalyst grain size is 80～200 orders;
The temperature of described methanation reaction is 250 ℃～320 ℃, and reaction pressure is 1～6MPa, and unstripped gas air speed is 1000～12000L/hkg;
CO/CO in described methanation unstripped gas
2volumetric concentration between 2%～30%, (H
2-CO
2)/(CO+CO
2) mol ratio be 2.5～3.7.
As claimed in claim 1 a kind of Raney's nickel as the application of slurry state bed synthetic methane catalyst,, it is characterized in that described inert liquid phase medium is paraffinic hydrocarbon, thermal oil or the inert liquid phase component that hydrogenated terphenyl thermal conductivity is large, thermal capacitance is large, boiling point is high.
3. a kind of Raney's nickel, as the application of slurry state bed synthetic methane catalyst, is characterized in that thermal oil is as claimed in claim 2
vP-1 type, hydrogenated terphenyl is SHHG-340.
4. a kind of Raney's nickel, as the application of slurry state bed synthetic methane catalyst, is characterized in that the concentration of described Raney's nickel catalyst in inert liquid phase medium is 2～40wt% as claimed in claim 1.
5. a kind of Raney's nickel is as the application of slurry state bed synthetic methane catalyst as claimed in claim 1, and the temperature that it is characterized in that described methanation reaction is for being 280 ℃～300 ℃.
6. a kind of Raney's nickel, as the application of slurry state bed synthetic methane catalyst, is characterized in that described (H as claimed in claim 1
2-CO
2)/(CO+CO
2) mol ratio be 2.8～3.3.
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| CN104056634B (en) * | 2014-07-08 | 2016-08-03 | 赛鼎工程有限公司 | A kind of preparation method and application being applicable to fixed bed methanation catalyst |
| CN104084219B (en) * | 2014-07-08 | 2016-02-24 | 赛鼎工程有限公司 | A kind of preparation method and application being applicable to fixed bed methanation Raney's nickel catalyst |
| CN104056641B (en) * | 2014-07-08 | 2016-04-06 | 赛鼎工程有限公司 | A kind of preparation method and application of slurry bed system methanation in presence of sulfur Raney's nickel catalyst |
| CN104069872B (en) * | 2014-07-08 | 2016-04-06 | 赛鼎工程有限公司 | A kind of preparation method and application being suitable for slurry bed system methanation catalyst |
| CN104056640B (en) * | 2014-07-08 | 2016-08-17 | 赛鼎工程有限公司 | A kind of preparation method and application being suitable for slurry bed system methanation Raney's nickel catalyst |
| CN104084220B (en) * | 2014-07-08 | 2016-02-24 | 赛鼎工程有限公司 | A kind of preparation method and application of fixed bed methanation in presence of sulfur Raney's nickel catalyst |
| CN105597788B (en) * | 2016-03-10 | 2017-12-15 | 赛鼎工程有限公司 | The sulfur resistant catalyst and its preparation method of synthesis gas methanation and application |
| WO2020113264A1 (en) * | 2018-12-05 | 2020-06-11 | Robert Louis Clegg | Method and apparatus for mineral processing |
| CN115109616B (en) * | 2021-03-22 | 2024-03-22 | 中国科学院大连化学物理研究所 | Method for producing natural gas |
| CN114011433B (en) * | 2021-12-13 | 2023-12-19 | 万华化学集团股份有限公司 | Preparation method of powder Raney catalyst |
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| CN102600860B (en) * | 2012-02-15 | 2014-06-11 | 华东理工大学 | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof |
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