CN103785435A - Multi-component composite catalyst used for catalytic coal gasification, and preparation method and use thereof - Google Patents
Multi-component composite catalyst used for catalytic coal gasification, and preparation method and use thereof Download PDFInfo
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- CN103785435A CN103785435A CN201210420994.3A CN201210420994A CN103785435A CN 103785435 A CN103785435 A CN 103785435A CN 201210420994 A CN201210420994 A CN 201210420994A CN 103785435 A CN103785435 A CN 103785435A
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Abstract
The invention provides a multi-component composite catalyst used for catalytic coal gasification, and pa reparation method and a use thereof. The multi-component composite catalyst contains a potassium-containing substance, a sodium-containing substance and a nickel-containing substance, wherein a molar ratio of potassium atom/sodium atom/nickel atom is between 0.63:0.27:9 and 6.3:2.7:1, and a ratio of the total mole of the potassium atom, the sodium atom and the nickel atom to the mole of the carbon atom in used coal is between 0.0125 and 0.05. The multi-component composite catalyst containing a calcium substance can obviously improve the methane yield of high-sulfur coal. The multi-component composite catalyst can catalyze coal gasification, has a very strong catalysis effect on synthetic gas methanation reactions, and has a very good catalysis performance under low addition, so compared with present catalysts, the multi-component composite catalyst has the advantages of excellent catalysis effect and low cost.
Description
Technical field
The present invention relates to a kind of multiplex catalyst and its production and use, particularly, relate to multiplex catalyst of a kind of catalysis coal gasification reaction simultaneously and synthesis gas methanation reaction and its production and use.
Background technology
The energy feature of China is " rich coal, few oil, deficency ", and coal is changed into top quality fuel one methane in fossil energy, is a shortcut that is applicable to China's national situation, clean environment firendly and guarantees energy security.
The catalytic gasification of coal refers to that coal is in middle cryogenic conditions (700 ℃ of left and right or lower), and by the catalytic action of catalyst, coal is vaporized as CO, H
2, CH
4deng gas.The research of typical case's catalytic coal gasifaction has the catalytic coal gasifaction of EXXON methane research processed (proposing for 1976) and Japanese catalytic coal gasifaction hydrogen producing technology (HyPr-RING technology is implemented for 1999) (referring to non-patent literature 1-4).The common feature of these two researchs is on catalytic coal gasifaction basis, reduces coal gasification reaction temperature; Difference is the difference of target product, the one, and methane, another is hydrogen.As catalyzed carbon water gasification reaction (C+H
2o=CO+H
2) catalyst, scientist has tested almost all elements in periodic table for many years, find after deliberation wherein alkali metal, alkaline-earth metal catalyst, and take iron, nickel as the catalytic activity of the 8th family's element of representative best, wherein alkali-metal best performance, and do not exist hydrogen sulfide in gasification product gas to make it poisoning phenomenon.Comparatively speaking, as catalytic activity is close with it the element such as iron, nickel but because very responsive to hydrogen sulfide, can very fast poisoning and deactivation and activity is significantly reduced.
In existing catalytic gasification technology, using maximum is potassium carbonate catalyst, but this catalyst is expensive, easily reacts the water-fast lithium aluminium silicate (KAISiO of generation with coal mineral
4) etc. material, simultaneously along with the carrying out of coal gasification reaction, potassium carbonate catalyst activity significantly reduces, and has lost the carrying out that catalyzes and synthesizes gas methanation reaction.So the subject matter that uses at present potassium carbonate catalyst to face is the increase of catalyst cost, and the makings generating is poor, and calorific value is on the low side.
In order to research and develop cheap catalyst system, Y.D.Yeboah etc. have carried out system research to multiple binary, ternary base metal catalysts, and result shows at binary catalyst Na
2cO
3-K
2cO
3in, two kinds of components by mass fraction be respectively 29%, more satisfactory when 71% proportioning, main cause is that two kinds of components have lower eutectic temperature under this proportioning, in loading process, mobility is better, easily be uniformly dispersed, form more active site (referring to non-patent literature 5).Described catalyst activity site refers to that catalyst passes through the mode load of chemisorbed on coal surface, has the site quantity of high-efficiency catalytic activity.Although use this kind of catalyst to reduce catalyst input cost, in gasification, base metal catalysts is easily caused catalytic action to weaken by mineral matter passivation and the methane content problem on the low side in gas that generates does not still solve.
As everyone knows, the 8th unit of family that iron, nickel are representative is usually as the catalyst of synthesis gas methanation reaction.Akira Tomita etc. is devoted to the catalytic action of nickel class catalyst to coal gasification always, experimental results show that nickel-base catalyst can be at lower temperature (600 ℃), make efficiency of carbon con version reach 77%, and methane production higher (referring to non-patent literature 6), but the resistance to sulphur of nickel-base catalyst is poor, easily poisoning and deactivation.
For catalytic coal gasifaction preparing natural gas technology, high methane production is the important indicator that guarantees makings, therefore, be necessary that exploitation one is with low cost, be difficult for inactivation, the Catalysts and its preparation method of catalysis coal gasification reaction and synthesis gas methanation reaction simultaneously, this is also one of key point breaking through catalytic coal gasifaction field industrialization technology bottleneck.
[non-patent literature 1] T.Kalina.Exxon catalytic coal gasification process Predevelopment program.Annual report, July1976-June1977[R] .U.S.:National Technical Information Service.1978.
[non-patent literature 2] T.Kalina, N.C.Nahas.Exxon catalytic coal gasification process Predevelopment program.Final project report[R] .U.S.:National Technical Information Service, 1978.
[non-patent literature 3] N.C.Nahas.Exxon catalytic coal gasification process Predevelopment program.Monthly report, December1977[R] .U.S.:National Technical Information Service, 1978.
[non-patent literature 4] N.C.Nahas.Exxon catalytic coal gasification process Predevelopment program.Quarterly technical progress report, July-September 1977[R] .U.S.:National Technical Information Service, 1978.
[non-patent literature 5] Yaw D.Yeboah, Yong Xu, Atul Sheth, et al.Catalytic gasification of coal using eutectic salts:identification of eutectics[J] .Carbon, 41 (2003): 203-214.
[non-patent literature 6] Akira Tomita, Yoshihiko Watanabe, Takayuki Takarada.Nickel-catalysed gasification of brown coal in a fluidized bed reactor at atmospheric pressure[J] .Fuel, 1985,64:795-800.
Summary of the invention
For solving the problem of catalyst in above-mentioned prior art, in guaranteeing high carbon conversions and high methane production, the invention provides a kind of simple, with low cost, multiplex catalyst that industrialization feasibility is strong and preparation method thereof of preparing.
<1>. the multiplex catalyst for catalytic coal gasifaction, described multiplex catalyst contains containing potassium material, sodium-containing material and nickeliferous material, wherein the mol ratio of potassium atom/sodium atom/nickle atom is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and the ratio of the molal quantity of potassium atom, sodium atom and nickle atom molal quantity summation and carbon content in coal atom to be used is between 0.0125 and 0.05.
<2> is according to the multiplex catalyst for catalytic coal gasifaction described in <1>, wherein said multiplex catalyst also contains calcareous material, and the ratio of the molal quantity of calcium atom in described calcareous material and carbon content in coal atom to be used is between 0.0125 and 0.05.
<3>. according to the multiplex catalyst for catalytic coal gasifaction described in <1> or <2>, the wherein said potassium material that contains is preferably sylvite or potassium hydroxide, more preferably potassium hydroxide, potash, potassium acetate, potassium nitrate, potassium sulfate or potassium chloride, most preferably be potash.
<4>. according to the multiplex catalyst for catalytic coal gasifaction described in <1> or <2>, wherein said sodium-containing material is preferably sodium salt or NaOH, more preferably NaOH, sodium carbonate, sodium acetate, sodium nitrate, sodium sulphate or sodium chloride, most preferably be sodium carbonate.
<5>. according to the multiplex catalyst for catalytic coal gasifaction described in <1> or <2>, wherein said nickeliferous material is at least one of complex that is selected from nickel simple substance, nickel nitrate, nickel chloride and nickel, be preferably nickel nitrate, nickel chloride, most preferably nickel nitrate.
<6>. according to the multiplex catalyst for catalytic coal gasifaction described in <2>, wherein said calcareous material is at least one being selected from quick lime, white lime, calcium oxalate, calcium phosphate and organic calcium salt, preferably at least one in quick lime and white lime.
<7>. according to the multiplex catalyst for catalytic coal gasifaction described in <1> or <2>, wherein said potassium atom/sodium atom/nickle atom mol ratio is preferably between 2.1: 0.9: 7 and 4.9: 2.1: 3.
<8>. according to the multiplex catalyst for catalytic coal gasifaction described in <1> or <2>, wherein the ratio of potassium atom, sodium atom and nickle atom molal quantity summation and carbon content in coal atomic molar number is preferably between 0.0125 and 0.0375.
<9>. according to the multiplex catalyst for catalytic coal gasifaction described in <2>, the ratio of the calcium atom in wherein said calcareous material and carbon content in coal atomic molar number is preferably between 0.0125 and 0.0375.
<10>. a method of preparing the multiplex catalyst for catalytic coal gasifaction described in aforementioned any one, described method comprises the steps:
The first step, according to the water absorption rate of used coal, determines catalyst solution volume according to the method for incipient impregnation supported catalyst;
Second step, by certain load capacity containing potassium material, sodium-containing material and nickeliferous material are according to the liquor capacity obtained aqueous solution of catalyst definite in first step, and flood described coal by incipient impregnation method, after stirring, leave standstill, then dry, obtain the products A that moisture content is 10 % by weight-20 % by weight, wherein in described products A, the mol ratio of potassium atom/sodium atom/nickle atom is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and potassium atom, the ratio of sodium atom and nickle atom molal quantity summation and carbon content in coal atomic molar number is between 0.0125 and 0.05,
Optionally, the 3rd step, calculate the liquor capacity of calcareous material according to the method for the water absorption rate of original coal and incipient impregnation supported catalyst, and make the aqueous solution of corresponding certain load capacity calcareous material, be further used for being immersed in the products A obtaining in second step, after stirring, leave standstill, then dry, obtaining moisture content is the final products below 2 % by weight, wherein potassium atom/sodium atom/nickle atom mol ratio is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and potassium atom, the ratio of sodium atom and nickle atom molal quantity summation and carbon content in coal atomic molar number is between 0.0125 and 0.05, the ratio of the calcium atom in described calcareous material and carbon content in coal atomic molar number is between 0.0125 and 0.05.
<11>. according to the preparation method of the multiplex catalyst for catalytic coal gasifaction described in <10>, the particle diameter of coal used is all between 0.25-2.5mm.
<12>. according to the preparation method of the multiplex catalyst for catalytic coal gasifaction described in <10>, the standing time used is 1 to 48 hour, preferably 1-10 hour.
<13>. according to the preparation method of the multiplex catalyst for catalytic coal gasifaction described in <10>, wherein said oven dry is carried out at the temperature of 80-150 ℃.
<14>. a multiplex catalyst of preparing according to the multiplex catalyst described in any one in <1> to <9> or by the method described in any one in <10> to <13> is applied in catalysis coal gasification reaction and synthesis gas methanation reaction at the same time.
With in prior art for compared with the catalyst of catalytic coal gasifaction, this comprising containing the multiplex catalyst of potassium material, sodium-containing material and nickeliferous material and optional calcareous material and high by the catalytic activity of the prepared multiplex catalyst of preparation method of the present invention of the present invention, but also can improve the methane production in catalytic gasification process.
Accompanying drawing explanation
Fig. 1 is the self-control fixed bed reactors schematic diagram using in experiment of the present invention, wherein: 1-water plunger displacement pump; 2-mass flowmenter; 3-preheater; 4-feeder; 5-reactor; 6-heating furnace; 7-counterbalance valve; 8-knockout drum; 9-wet flow indicator.
The specific embodiment
Term definition
In this article, described methane production refers to and transforms the methane volume that unit kg of carbon is produced.
In this article; for the fixed bed of pyrolysis, there is no particular limitation; as long as meet good sealing effectiveness; bed portion temperature evenly; for example can use the fixed bed that is generally used for pyrolysis in this area; such as the Muffle furnace with inert gas shielding, and structure fixed bed as shown in Figure 1.
In this article, for the fixed bed of char Gasification, also there is no particular limitation, as long as meet good sealing effectiveness, bed portion temperature is even, air-flow is laminar flow state substantially, for example can use the fixed bed that is generally used for char Gasification in this area, such as using structure fixed bed as shown in Figure 1.
In this article, term " incipient impregnation " refers to that the volume ratio of the volume of the catalytic component aqueous solution (to contain quick lime, white lime, calcium oxalate, calcium phosphate etc. water insoluble or be turbid liquid while being slightly soluble in the component of water when catalytic component, and the present invention is called slurries) and the water absorption rate of respective load coal is 1: 1.For example, the ature of coal amount of load is 100 grams, and its water absorption rate is 30g water/100g coal after measured, the volume of 30g water is about 30mL, want " incipient impregnation " these coals, the volume of the catalytic component aqueous solution needing is just 30mL, and the catalyst solution that will configure should be just 30mL.
In addition, in this article, secondary incipient impregnation refers to and carries out for the second time incipient impregnation, and now to calculate the required related absorptivity of aqueous solution volume of calcareous material be to calculate by the water absorption rate of the coal of initial load.
In this article, term " initially enters steam/hydrocarbons ratio " and refers to the ratio of carbonaceous amount in water flow velocity/original coal, can in the unit of account time, add thus the molal quantity and the ratio of molal quantity that reacts initial carbon content in coal of the water of reaction system.
In the present invention, term " M
1/ C " ratio of the molal quantity summation that refers to potassium atom in multiplex catalyst of the present invention, sodium atom and nickle atom and used carbon content in coal atomic molar number.In comparative example of the present invention, owing to only using K
2cO
3, therefore M now
1it is only the molal quantity of potassium atom." M
2/ C " ratio of the molal quantity that refers to calcium atom in quaternary composite catalyst of the present invention and used carbon content in coal atomic molar number.
At present catalytic gasification technology catalyst used mostly is potash, but due to expensive and easily react inactivation with the mineral matter in coal ash in course of reaction.And K-Na binary catalyst, (mol ratio of potassium atom/sodium atom is to have lowest total of the melting point at 71: 29 o'clock, is easy to catalyst flow best results in course of reaction), proves that this catalyst exists lower gaseous product mostly to be CO and H by experiment
2.Therefore, goal in research of the present invention is catalytic coal gasifaction one-step method CH processed
4the catalyst of (natural gas), can be in a reactor C+H of catalysis simultaneously
2o=CO+H
2reaction (1), CO+H
2o=CO
2+ H
2reaction (2), CO+H
2=CH
4+ H
2the catalyst of O reaction (3).Composite catalyst containing potassium material and sodium-containing material composition is obvious to the catalytic effect of the first two reaction in course of reaction, but have little effect for the 3rd reaction (methanation reaction), therefore need to supplement the catalyst of synthesis gas methanation reaction.
The present invention through carefully research after, utilize nickel-containing catalyst for methanation reaction successful, so developmental research a kind of ternary complex catalyst comprising containing potassium material, sodium-containing material and nickeliferous material.Experiment finds, this composite catalyst can be realized goal of the invention of the present invention, can be in a reactor C+H of catalysis simultaneously
2o=CO+H
2reaction (1), CO+H
2o=CO
2+ H
2reaction (2), CO+H
2=CH
4+ H
2o reacts (3)., realized the catalyst that does not need to supplement synthesis gas methanation reaction in course of reaction.And this ternary complex catalyst, also significantly efficiency of carbon con version is improved to about 5-20%.
But for the higher coal of sulfur content; the easy sulfur poisoning of nickel-containing catalyst; after calcareous material adds as solid sulphur protective agent; to a certain degree alleviate the intoxicating phenomenon of nickel-containing catalyst; also find the mineral matter in calcareous material energy passivation coal ash simultaneously, avoid and react containing base metal catalysts such as potassium material, sodium-containing materials.Therefore, the present invention has further developed so a kind of quaternary composite catalyst by being composited containing potassium material, sodium-containing material and nickeliferous material and calcareous material.This quaternary composite catalyst has not only been realized one-step method CH processed
4(natural gas) completes C+H in a reactor simultaneously
2o=CO+H
2reaction (1), CO+H
2o=CO
2+ H
2reaction (2), CO+H
2=CH
4+ H
2o reacts (3), realized and in course of reaction, do not need to supplement the catalyst of synthesis gas methanation reaction, and this quaternary composite catalyst has also been realized the raising of efficiency of carbon con version and methane production in coal gasification course.
Especially in the case of lower catalyst loadings, polynary (ternary or quaternary) of the present invention composite catalyst is all than prior art catalyst K
2cO
3catalytic effect significantly improve, in the time reaching identical catalytic effect, polynary (ternary or quaternary) of the present invention composite catalyst input cost is lower, thereby has certain cost advantage compared with prior art catalyst.In the situation that multiplex catalyst of the present invention contains calcareous material, especially for the higher coal of sulfur content, its methane production improves more obvious.
Therefore, one aspect of the present invention is to provide a kind of multiplex catalyst for catalytic coal gasifaction, described multiplex catalyst contains containing potassium material, sodium-containing material and nickeliferous material, wherein potassium atom/sodium atom/nickle atom mol ratio is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and the ratio of potassium atom, sodium atom and nickle atom molal quantity summation and carbon content in coal atomic molar number is between 0.0125 and 0.05.Further, multiplex catalyst of the present invention can also comprise calcareous material, and the ratio of calcium atom in described calcareous material and carbon content in coal atomic molar number is between 0.0125 and 0.05.
In multiplex catalyst of the present invention, under the condition that the mol ratio of described potassium atom/sodium atom/nickle atom is is 7: 3 based on fixing potassium atom/sodium atom mol ratio, it is 1 that the proportioning of three kinds of atoms of adjusting makes its mole of sum, determines by evaluation experimental.At the multiplex catalyst for catalytic coal gasifaction of the present invention, potassium atom/sodium atom/nickle atom mol ratio is preferably between 2.1: 0.9: 7 and 4.9: 2.1: 3.Can catalysis coal gasification reaction at the multiplex catalyst that meets this potassium atom/sodium atom/nickle atom molar ratio range of the present invention, also can catalyze and synthesize gas methanation reaction.
Be applicable to using in the present invention containing potassium material, preferably sylvite or potassium hydroxide, is more preferably potassium hydroxide, potash, potassium acetate, potassium nitrate, potassium sulfate or potassium chloride, is most preferably potash.
Be applicable to the sodium-containing material using in the present invention, preferably sodium salt or NaOH, is more preferably NaOH, sodium carbonate, sodium acetate, sodium nitrate, sodium sulphate or sodium chloride, is most preferably sodium carbonate.
The calcareous material that is applicable to using is in the present invention at least one being selected from quick lime, white lime, calcium oxalate, calcium phosphate and organic calcium salt, preferably at least one in quick lime and white lime.
The nickeliferous material that is applicable to using is in the present invention at least one of complex that is selected from nickel simple substance, nickel nitrate, nickel chloride and nickel, and preferably nickel nitrate or nickel chloride, is most preferably nickel nitrate.
At the multiplex catalyst for catalytic coal gasifaction of the present invention, potassium atom, sodium atom are M with nickle atom molal quantity summation with the ratio of carbon content in coal atomic molar number
1/ C is preferably 0.0125 to 0.0375.This ratio is to determine under the prerequisite of the reactivity of comprehensive selected coal, evaluation experimental catalytic effect and catalyst input cost, if be less than 0.0125, catalytic effect is not obvious, be greater than 0.0375 o'clock catalyst in saturated load capacity, catalytic effect promotes not obvious and catalyst cost increase.
At the multiplex catalyst for catalytic coal gasifaction of the present invention, the calcium atom in the calcareous material adding is M with the ratio of carbon content in coal atomic molar number
2/ C is preferably between 0.0125 and 0.0375.This ratio is determined according to evaluation experimental catalytic effect and catalyst cost on the one hand, is to determine according to the coal analysis of selected coal on the other hand, and when as high in sulfur content, this ratio will improve.
It is worthy of note, the aqueous solution mentioned in the present invention, the not necessarily proper aqueous solution, it also can comprise aqueous slurry, for example, in the time selecting calcium oxalate as calcareous material of the present invention, what now formed should be aqueous slurry.
As for the coal using in the present invention, be not specifically limited for its particle diameter, but consider the easy degree of supported catalyst component, the particle diameter of coal used all 0.25 and 2.5mm between.Normally, the pretreatment operation that coal can be pulverized and sieve etc., can make the particle diameter of coal reach 0.25 and 2.5mm between scope in.
In situation about not being bound by any theory, the present inventor thinks that the reason that multicomponent catalyst of the present invention can improve the catalytic effect of catalytic coal gasifaction is: be equivalent to based on being major catalyst containing potassium material with the binary catalyst that sodium-containing material forms, add nickeliferous material as co-catalyst, reached the object of one-step method methane processed.And, on above-mentioned three-way catalyst basis, add calcareous material as protective agent, to a certain degree alleviate the inactivation reacting with mineral matter containing base metal catalysts such as potassium material, sodium-containing materials, avoided nickeliferous material sulfur poisoning inactivation simultaneously.Thereby make catalyst of the present invention to coal adaptability grow.In the situation that using multiplex catalyst of the present invention, can regulate according to coal reactivity the addition of major catalyst, co-catalyst, can reach optimum efficiency; For ash content, sulfur content and the catalyst loading of coal used, add calcareous material protective agent, catalyst can adequately protect.
A second aspect of the present invention is to provide a kind of preparation method of the multiplex catalyst for catalytic coal gasifaction, described method comprises the steps: the first step, record in advance the water absorption rate of coal used, and determine catalyst solution volume according to the method for incipient impregnation supported catalyst, second step, by a certain amount of potassium material that contains, sodium-containing material and nickeliferous material are according to catalyst solution volume obtained aqueous solution definite in first step, and flood described coal by incipient impregnation method, after fully stirring, leave standstill for example 3 hours, then dry, obtain the products A that moisture content is 10 % by weight-20 % by weight, the order adding when each component obtain solution in this step does not limit, wherein in described products A, the mol ratio of potassium atom/sodium atom/nickle atom is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and potassium atom, the ratio of sodium atom and nickle atom molal quantity summation and carbon content in coal atomic molar number is between 0.0125 and 0.05, optionally, the 3rd step, calculate the liquor capacity of calcareous material according to the method for the water absorption rate of original coal and incipient impregnation supported catalyst, and make the aqueous solution of corresponding a certain amount of calcareous material, further use equi-volume impregnating, be that secondary equi-volume impregnating is immersed in the products A obtaining in second step, stir, leave standstill for example 3 hours, then dry, obtaining moisture content is the final products below 2 % by weight, wherein potassium atom/sodium atom/nickle atom mol ratio is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and potassium atom, the ratio of sodium atom and nickle atom molal quantity summation and carbon content in coal atomic molar number is between 0.0125 and 0.05, the ratio of the calcium atom in described calcareous material and carbon content in coal atomic molar number is between 0.0125 and 0.05.
In order to investigate multiplex catalyst of the present invention at the catalytic effect aspect catalytic coal gasifaction and methane production, the inventor has adopted multiplex catalyst and the prior art catalyst K under different proportionings
2cO
3as a comparison, respectively they and king family's tower bituminous coal, Erdos bituminous coal are prepared after investigation sample, carry out pyrolysis at the homemade structure in laboratory, inventor place fixed bed as shown in Figure 1, then being to carry out char Gasification experiment in by the homemade structure in laboratory at inventor place small fixed as shown in Figure 1 equally.Between pneumatolytic stage, take per half an hour airbag to collect gas, and carry out component analysis by gas-chromatography, can obtain thus the performance of multiplex catalyst of the present invention.
Specific experiment process can be referring to the record in embodiment part.
The efficiency of carbon con version of the coal obtaining from above-mentioned experiment and methane production aspect can be found out, the catalyst that is all better than prior art containing the performance of the multiplex catalyst of potassium material, sodium-containing material and nickeliferous material and optional calcareous material that relates to of the present invention, and the quaternary composite catalyst that contains calcareous material is the in the situation that of low load capacity, has especially significantly improvement effect for conversion ratio and the methane production of coal.
In addition multiplex catalyst by being composited containing potassium material, sodium-containing material, nickeliferous material and optional calcareous material of the present invention and the catalyst K of prior art,
2cO
3compare, multiplex catalyst of the present invention not only can catalysis coal gasification course, also there is very strong catalytic action for synthesis gas methanation reaction, and when addition is very low, just there is good catalytic performance, therefore to have catalytic effect than prior art good for multiplex catalyst of the present invention, the advantage that cost is low.For example,, in traditional catalyst, as load capacity M
1/ C is that traditional catalyst catalytic action in 0.0125 o'clock is not obvious, and in the time using multiplex catalyst of the present invention, still can obtain good catalytic effect.This can be confirmed by the result of the test of recording in embodiment part.
To be described in more detail the present invention by embodiment below, but these embodiment are not limitation of the scope of the invention, scope of the present invention should be defined by the claims.
Embodiment
Selecting coal is that (phosphorus content is about 70 quality % to king family's tower bituminous coal, water absorption rate is 30g water/100g coal, total sulphur content is about 0.60 quality %), raw coal is through crushing and screening, make its particle diameter between 0.25-2.5mm, investigate the multiplex catalyst of the present invention of different loads amount and (select K
2cO
3-Na
2cO
3-Ni (NO
3)
2and K
2cO
3-Na
2cO
3-Ni (NO
3)
2-Ca (OH)
2, K/Na/Ni mol ratio is 3.5: 1.5: 5) and the most normally used in the art existing catalyst K
2cO
3impact on conversion ratio and methane production in coal gasification course.
Sample one: by 100 grams of incipient impregnations of the coal dust of described particle diameter 0.25-2.5mm in the K of 30mL
2cO
3in catalyst (Beijing Chemical Plant analyzes pure) solution, wherein M
1the mol ratio of (potassium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, puts into oven drying for subsequent use;
Sample two: according to the method for sample one, preparation M
1the sample that the mol ratio of (potassium atom)/C (carbon atom) is 0.025;
Sample three: according to the method for sample one, preparation M
1the sample that the mol ratio of (potassium atom)/C (carbon atom) is 0.050;
Sample four: by 100 grams of incipient impregnations of the coal dust of described particle diameter 0.25-2.5mm in the K of 30mL
2cO
3, Na
2cO
3and Ni (NO
3)
26H
2in the aqueous solution of O catalyst (Beijing Chemical Plant analyzes pure), wherein M
1the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) be 0.0125 and the aqueous solution in K/Na/Ni mol ratio be 3.5: 1.5: 5, leave standstill 3 hours, put into the dry sample that makes of baking oven.
Wherein the concrete configuration step of catalyst solution is according to M
1/ C is that 0.0125, K/Na/Ni mol ratio is 3.5: 1.5: 5, accurately takes K
2cO
31.76g, Na
2cO
30.58g and Ni (NO
3)
26H
2o10.60g, by three kinds of catalyst dissolution in 30mL water.
Sample five: the sample (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) that sample four is made is put into the Ca (OH) of 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample six: according to sample four, preparation M
1the sample that the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) is 0.025;
Sample seven: the sample that sample six is made, put into the Ca (OH) of 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample eight: according to sample four, preparation M
1the sample that the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) is 0.050;
Sample nine: the sample that sample eight is made, put into the Ca (OH) of 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Nine parts of samples producing are put into respectively to fixed bed (laboratory self-control, the structure of this fixed bed is as shown in Figure 1) in carry out pyrolysis, carry out gasification experiment with the semicoke after pyrolysis (semicoke is coal through pyrolysis, gets rid of the remainder of fugitive constituent and moisture).Pyrolytical condition: under nitrogen atmosphere (nitrogen flow rate is 150mL/min), with the firing rate to 700 ℃ of 10 ℃/min, stop after 90min at 700 ℃, close thermal source, nitrogen protection is down to normal temperature.
Char Gasification experiment: install as (the laboratory self-control of laboratory room small-sized fixed bed, the structure of this fixed bed is as shown in Figure 1) reactor, get 10g semicoke, pressure is 3.5MPa, initially entering steam/hydrocarbons ratio is 0.68mL/h/g, and nitrogen, using the flow velocity of 300mL/min as blowing gas, reacts six hours, take middle per half an hour airbag to collect gas, and carry out component analysis by gas-chromatography.
Experimental result: with existing catalyst K
2cO
3compare K of the present invention under the same terms
2cO
3-Na
2cO
3-Ni (NO
3)
2three-way catalyst, K
2cO
3-Na
2cO
3-Ni (NO
3)
2-Ca (OH)
2the efficiency of carbon con version of quaternary composite catalyst improves about 5-20%, and particularly, under low load capacity condition, quaternary composite catalyst shows good catalyst effect, has occupied advantage from cost.Methane production in table 1 refers to and transforms the methane volume that unit kg of carbon is produced, as can be seen from the table, the catalytic production of methane reaction better of the more existing catalyst of multiplex catalyst of the present invention, simultaneously along with the increase methane content of load capacity improves constantly, particularly the effect of quaternary composite catalyst is better, fully shows the synergy between each component.
Embodiment 2
Selecting coal is that (phosphorus content is about 70 quality % to king family's tower bituminous coal, water absorption rate is 30g water/100g coal, total sulphur content is about 0.60 quality %), raw coal is through crushing and screening, make its particle diameter between 0.25-2.5mm, investigate the multiplex catalyst of the present invention of different loads amount and (select K
2cO
3-Na
2cO
3-Ni (NO
3)
2and K
2cO
3-Na
2cO
3-Ni (NO
3)
2-Ca (OH)
2, K/Na/Ni mol ratio is 2.1: 0.9: 7) and the most normally used in the art existing catalyst K
2cO
3impact on conversion ratio and methane production in coal gasification course.
Sample one: by 100 grams of incipient impregnations of the coal dust of described particle diameter 0.25-2.5mm in the K of 30mL
2cO
3in catalyst (Beijing Chemical Plant analyzes pure) solution, wherein M
1the mol ratio of (potassium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, puts into oven drying for subsequent use;
Sample two: according to the method for sample one, preparation M
1the sample that the mol ratio of (potassium atom)/C (carbon atom) is 0.025;
Sample three: according to the method for sample one, preparation M
1the sample that the mol ratio of (potassium atom)/C (carbon atom) is 0.050;
Sample four: by 100 grams of incipient impregnations of the coal dust of described particle diameter 0.25-2.5mm in the K of 30ml
2cO
3, Na
2cO
3and Ni (NO
3)
26H
2in O catalyst (Beijing Chemical Plant the analyzes pure) aqueous solution, wherein M
1the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) be 0.0125 and the aqueous solution in K/Na/Ni mol ratio be 2.1: 0.9: 7, leave standstill after 3 hours, put into the dry sample that makes of baking oven;
Sample five: the sample (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) that sample four is made is put into the Ca (OH) of 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample six: according to sample four, preparation M
1the sample that the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) is 0.025;
Sample seven: the sample that sample six is made, put into the Ca (OH) of 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample eight: according to sample four, preparation M
1the sample that the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) is 0.050;
Sample nine: the sample that sample eight is made, put into the Ca (OH) of 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Nine parts of samples producing are put into respectively to fixed bed (laboratory self-control, the structure of this fixed bed is as shown in Figure 1) in carry out pyrolysis, carry out gasification experiment with the semicoke after pyrolysis (semicoke is coal through pyrolysis, gets rid of the remainder of fugitive constituent and moisture).Pyrolytical condition: under nitrogen atmosphere (nitrogen flow rate is 150mL/min), with the firing rate to 700 ℃ of 10 ℃/min, stop after 90min at 700 ℃, close thermal source, nitrogen protection is down to normal temperature.
Char Gasification experiment: install as (the laboratory self-control of laboratory room small-sized fixed bed, the structure of this fixed bed is as shown in Figure 1) reactor, get 10g semicoke, pressure is 3.5MPa, initially entering steam/hydrocarbons ratio is 0.68mL/h/g, and nitrogen, using the flow velocity of 300mL/min as blowing gas, reacts six hours, take middle per half an hour airbag to collect gas, and carry out component analysis by gas-chromatography.
Experimental result: find by analytical table 2 and table 1 data, adjust K/Na/Ni molar ratio in the present invention's four multiplex catalysts, can to a certain degree change efficiency of carbon con version and methane production.The present embodiment is compared with embodiment 1, reduces the molar ratio containing potassium material and sodium-containing material, and the molar ratio that improves nickeliferous material can promote to generate more methane by the carrying out of methanation reaction, very micro-on the impact of efficiency of carbon con version.Similarly, from sample four and five, sample six and seven and the contrast of sample eight and nine can find out, a small amount of interpolation of calcium, can improve efficiency of carbon con version and methane production effectively, especially in low load capacity as M
1in the situation of/C=0.0125, efficiency of carbon con version and methane production have all obtained significantly improving.
Embodiment 3
Selecting coal is that (phosphorus content is about 70 quality % to king family's tower bituminous coal, water absorption rate is 30g water/100g coal, total sulphur content is about 0.60 quality %), raw coal is through crushing and screening, make its particle diameter between 0.25-2.5mm, investigate the multiplex catalyst of the present invention of different loads amount and (select K
2sO
4-Na
2sO
4-Ni (NO
3)
2and K
2sO
4-Na
2sO
4-Ni (NO
3)
2-CaO, K/Na/Ni mol ratio is 3.5: 1.5: 5) and the most normally used in the art existing catalyst K
2cO
3impact on conversion ratio and methane production in coal gasification course.
Sample one: by 100 grams of incipient impregnations of the coal dust of described particle diameter 0.25-2.5mm in the K of 30mL
2cO
3in catalyst (Beijing Chemical Plant analyzes pure) solution, wherein M
1the mol ratio of (potassium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, puts into oven drying for subsequent use;
Sample two: according to the method for sample one, preparation M
1the sample that the mol ratio of (potassium atom)/C (carbon atom) is 0.025;
Sample three: according to the method for sample one, preparation M
1the sample that the mol ratio of (potassium atom)/C (carbon atom) is 0.050;
Sample four: by 100 grams of incipient impregnations of the coal dust of described particle diameter 0.25-2.5mm in the K of 30ml
2sO
4, Na
2sO
4and Ni (NO
3)
26H
2in O catalyst (Beijing Chemical Plant the analyzes pure) aqueous solution, wherein M
1the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) be 0.0125 and this aqueous solution in K/Na/Ni mol ratio be 3.5: 1.5: 5, leave standstill after 3 hours, put into the dry sample that makes of baking oven;
Sample five: CaO (Beijing Chemical Plant the analyzes pure) slurries that the sample (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) that sample four is made is put into 30mL carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample six: according to sample four, preparation M
1the sample that the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) is 0.025;
Sample seven: the sample that sample six is made, CaO (Beijing Chemical Plant the analyzes pure) slurries of putting into 30mL carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample eight: according to sample four, preparation M
1the sample that the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) is 0.050;
Sample nine: the sample that sample eight is made, CaO (Beijing Chemical Plant the analyzes pure) slurries of putting into 30mL carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Nine parts of samples producing are put into respectively to fixed bed (laboratory self-control, the structure of this fixed bed is as shown in Figure 1) in carry out pyrolysis, carry out gasification experiment with the semicoke after pyrolysis (semicoke is coal through pyrolysis, gets rid of the remainder of fugitive constituent and moisture).Pyrolytical condition: under nitrogen atmosphere (nitrogen flow rate is 150mL/min), with the firing rate to 700 ℃ of 10 ℃/min, stop after 90min at 700 ℃, close thermal source, nitrogen protection is down to normal temperature.
Char Gasification experiment: install as (the laboratory self-control of laboratory room small-sized fixed bed, the structure of this fixed bed is as shown in Figure 1) reactor, get 10g semicoke, pressure is 3.5MPa, initially entering steam/hydrocarbons ratio is 0.68mL/h/g, and nitrogen, using the flow velocity of 300mL/min as blowing gas, reacts six hours, take middle per half an hour airbag to collect gas, and carry out component analysis by gas-chromatography.
Experimental result: under the same terms, the ternary complex catalyst K of the present embodiment
2sO
4-Na
2sO
4-Ni (NO
3)
2with quaternary composite catalyst K
2sO
4-Na
2sO
4-Ni (NO
3)
2ternary complex catalyst K in-CaO and embodiment 1
2sO
4-Na
2sO
4-Ni (NO
3)
2with quaternary composite catalyst K
2cO
3-Na
2cO
3-Ni (NO
3)
2-Ca (OH)
2compare respectively, efficiency of carbon con version and methane production all decline to some extent, and especially, the in the situation that of low load capacity, this is mainly the impact of selected component in catalyst.Analyze from mechanism, the catalytic effect of catalyst depends on the ability of ion receiving and losing electrons (transmission electronics), is generally carbonate=hydroxide > sulfate > chloride for base metal catalysts.Transition metal and alkaline-earth metal are generally selected the common compound that solubility is higher, and therefore catalyst is selected above, potassium, the preferred carbonate of sodium catalyst, and Raney nickel is selected nitrate, calcium catalyst more options calcium hydroxide or calcium oxide.
Selecting coal is that (phosphorus content is about 65 quality % to Erdos bituminous coal, water absorption rate is 34g water/100g coal, total sulphur content is about 0.15 quality %), raw coal is through crushing and screening, make its particle diameter between 0.25-2.5mm, investigate different loads amount multiplex catalyst of the present invention and (select K
2cO
3-Na
2cO
3-Ni (NO
3)
2and K
2cO
3-Na
2cO
3-Ni (NO
3)
2-Ca (OH)
2, K/Na/Ni mol ratio is 3.5: 1.5: 5) and the existing catalyst K of this technology
2cO
3impact on conversion ratio and methane production in coal gasification course.
Sample one: by 100 grams of incipient impregnations of the coal dust of described particle diameter 0.25-2.5mm in the K of 34mL
2cO
3in catalyst (Beijing Chemical Plant analyzes pure) solution, wherein M
1the mol ratio of (potassium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, puts into oven drying for subsequent use;
Sample two: according to the method for sample one, preparation M
1the sample that the mol ratio of (potassium atom)/C (carbon atom) is 0.025;
Sample three: according to the method for sample one, preparation M
1the sample that the mol ratio of (potassium atom)/C (carbon atom) is 0.050;
Sample four: by 100 grams of incipient impregnations of the coal dust of described particle diameter 0.25-2.5mm in the K of 34mL
2cO
3, Na
2cO
3and Ni (NO
3)
26H
2in O catalyst (Beijing Chemical Plant analyzes pure) solution, wherein M
1the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) be 0.0125 and the aqueous solution in K/Na/Ni mol ratio be 3.5: 1.5: 5, leave standstill after 3 hours, put into the dry sample that makes of baking oven;
Sample five: the sample (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) that sample four is made is put into the Ca (OH) of 34mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample six: according to sample four, preparation M
1the sample that the mol ratio of (potassium atom, sodium atom and nickle atom)/C (carbon atom) is 0.025;
Sample seven: the sample that sample six is made, put into the Ca (OH) of 34mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample eight: according to sample four, preparation M
1the sample that the mol ratio of (potassium atom, sodium atom and nickle atom)/C (carbon atom) is 0.050;
Sample nine: the sample that sample eight is made, put into the Ca (OH) of 34mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Nine parts of samples producing are put into respectively to fixed bed (laboratory self-control, the structure of this fixed bed is as shown in Figure 1) in carry out pyrolysis, carry out gasification experiment with the semicoke after pyrolysis (semicoke is coal through pyrolysis, gets rid of the remainder of fugitive constituent and moisture).Pyrolytical condition: under nitrogen atmosphere (nitrogen flow rate is 150mL/min), with the firing rate to 700 ℃ of 10 ℃/min, stop after 90min at 700 ℃, close thermal source, nitrogen protection is down to normal temperature.
Char Gasification experiment: install as (the laboratory self-control of laboratory room small-sized fixed bed, the structure of this fixed bed is as shown in Figure 1) reactor, get 10g semicoke, pressure is 3.5MPa, initially entering steam/hydrocarbons ratio is 0.68mL/h/g, and nitrogen, using the flow velocity of 300mL/min as blowing gas, reacts six hours, take middle per half an hour airbag to collect gas, and carry out component analysis by gas-chromatography.
Experimental result: the Erdos bituminous coal king family tower coal facies ratio used with embodiment 1 that the present embodiment is used, carbon content is more or less the same, and sulfur content is lower.K of the present invention under the same terms
2cO
3-Na
2cO
3-Ni (NO
3)
2-Ca (OH)
2efficiency of carbon con version difference under the catalysis of quaternary composite catalyst is little, but methane production is significantly increased.Analyzing its main cause is that Erdos bituminous coal sulfur content is less, and the nickeliferous material in pyrolysis and gasification in quaternary composite catalyst is difficult for poisoning and deactivation, thereby promotes better the carrying out of methanation reaction.
Embodiment 5
Selecting coal is that (phosphorus content is about 70 quality % to king family's tower bituminous coal, water absorption rate is 30g water/100g coal, total sulphur content is about 0.60 quality %) and Erdos bituminous coal (phosphorus content is about 65 quality %, water absorption rate is 34g water/100g coal, total sulphur content is about 0.15 quality %), raw coal, through crushing and screening, makes its particle diameter between 0.25-2.5mm, investigates multiplex catalyst of the present invention and (selects K
2cO
3-Na
2cO
3-Ni (NO
3)
2-Ca (OH)
2, K/Na/Ni mol ratio is 3.5: 1.5: 5, M
1/ C=0.025) impact on conversion ratio in coal gasification course and methane production of the calcareous material of different loads amount.
Raw material sample one: by 300 grams of incipient impregnations of king family's tower coal dust of described particle diameter 0.25-2.5mm in the K of 90mL
2cO
3, Na
2cO
3and Ni (NO
3)
26H
2in the aqueous solution of O catalyst (Beijing Chemical Plant analyzes pure), wherein M
1the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) be 0.025 and the aqueous solution in K/Na/Ni mol ratio be 3.5: 1.5: 5, leave standstill 3 hours, put into the dry sample that makes of baking oven;
Raw material sample two: by 300 grams of incipient impregnations of the Erdos coal dust of described particle diameter 0.25-2.5mm in the K of 102mL
2cO
3, Na
2cO
3and Ni (NO
3)
26H
2in the aqueous solution of O catalyst (Beijing Chemical Plant analyzes pure), wherein M
1the mol ratio of (potassium atom, sodium atom and nickle atom sum)/C (carbon atom) be 0.025 and the aqueous solution in K/Na/Ni mol ratio be 3.5: 1.5: 5, leave standstill 3 hours, put into the dry sample that makes of baking oven;
Sample one: the Ca (OH) that evenly takes the sample 100g that raw material sample one makes (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) and put into 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample two: the Ca (OH) that evenly takes the sample 100g that raw material sample one makes (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) and put into 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.025, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample three: the Ca (OH) that evenly takes the sample 100g that raw material sample one makes (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) and put into 30mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.050, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample four: the Ca (OH) that evenly takes the sample 100g that raw material sample two makes (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) and put into 34mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.0125, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample five: the Ca (OH) that evenly takes the sample 100g that raw material sample two makes (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) and put into 34mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.025, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Sample six: the Ca (OH) that evenly takes the sample 100g that raw material sample two makes (moisture content is about 10%, and absorptivity is calculated by the water absorption rate of original coal) and put into 34mL
2in (Beijing Chemical Plant analyzes pure) slurries, carry out secondary incipient impregnation, wherein M
2the mol ratio of (calcium atom)/C (carbon atom) is 0.050, leaves standstill after 3 hours, and putting into oven drying, to make sample for subsequent use;
Six parts of samples producing are put into respectively to fixed bed (laboratory self-control, the structure of this fixed bed is as shown in Figure 1) in carry out pyrolysis, carry out gasification experiment with the semicoke after pyrolysis (semicoke is coal through pyrolysis, gets rid of the remainder of fugitive constituent and moisture).Pyrolytical condition: under nitrogen atmosphere (nitrogen flow rate is 150mL/min), with the firing rate to 700 ℃ of 10 ℃/min, stop after 90min at 700 ℃, close thermal source, nitrogen protection is down to normal temperature.
Char Gasification experiment: install as (the laboratory self-control of laboratory room small-sized fixed bed, the structure of this fixed bed is as shown in Figure 1) reactor, get 10g semicoke, pressure is 3.5MPa, initially entering steam/hydrocarbons ratio is 0.68mL/h/g, and nitrogen, using the flow velocity of 300mL/min as blowing gas, reacts six hours, take middle per half an hour airbag to collect gas, and carry out component analysis by gas-chromatography.
Experimental result: the present embodiment adopts two kinds of coal samples that sulfur content is different; can find by contrast table 5 data; improved after the load capacity of calcareous material, the conversion ratio of two kinds of coals is all improved to some extent, thereby has verified the catalytic activity protective effect to coal gasification catalyst.Improve for Erdos coal after the load capacity of calcareous material, methane production changes little, this is mainly that the catalyst effect of catalytic production of methane is not much affected because this coal sulfur content is lower, and the methane production of king family's tower coal that sulfur content is higher on the contrary improves obvious.
Industrial applicability
Comprise containing potassium material due to of the present invention, sodium-containing material, calcareous material, the one of nickeliferous material catalysis simultaneously coal gasification reaction, the quaternary composite catalyst of synthesis gas methanation reaction is except having better catalysis coal gasification effect and catalytic methane production, also there is cost advantage, the catalyst of load small amount can obtain higher catalytic effect, and in the situation that multiplex catalyst of the present invention contains calcareous material, especially for the higher coal of sulfur content, its methane production improves more obvious, thereby be very suitable for industrial sizable application.
Claims (10)
1. the multiplex catalyst for catalytic coal gasifaction, described multiplex catalyst contains containing potassium material, sodium-containing material and nickeliferous material, wherein the mol ratio of potassium atom/sodium atom/nickle atom is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and the ratio of the molal quantity of potassium atom, sodium atom and nickle atom molal quantity summation and carbon content in coal atom to be used is between 0.0125 and 0.05.
2. the multiplex catalyst for catalytic coal gasifaction according to claim 1, wherein said multiplex catalyst also contains calcareous material, and the ratio of the molal quantity of the calcium atom in described calcareous material and carbon content in coal atom to be used is between 0.0125 and 0.05, preferably between 0.0125 and 0.0375.
3. the multiplex catalyst for catalytic coal gasifaction according to claim 1 and 2, the described potassium material that contains is preferably sylvite or potassium hydroxide, and more preferably potassium hydroxide, potash, potassium acetate, potassium nitrate, potassium sulfate or potassium chloride, most preferably be potash.
4. the multiplex catalyst for catalytic coal gasifaction according to claim 1 and 2, described sodium-containing material is preferably sodium salt or NaOH, more preferably NaOH, sodium carbonate, sodium acetate, sodium nitrate, sodium sulphate or sodium chloride, most preferably be sodium carbonate.
5. the multiplex catalyst for catalytic coal gasifaction according to claim 1 and 2, described nickeliferous material is at least one of complex that is selected from nickel simple substance, nickel nitrate, nickel chloride and nickel, preferably nickel nitrate, nickel chloride, most preferably be nickel nitrate.
6. the multiplex catalyst for catalytic coal gasifaction according to claim 2, described calcareous material is at least one being selected from quick lime, white lime, calcium oxalate, calcium phosphate and organic calcium salt, is preferably at least one in quick lime and white lime.
7. the multiplex catalyst for catalytic coal gasifaction according to claim 1 and 2, potassium atom/sodium atom/nickle atom mol ratio is between 2.1: 0.9: 7 to 4.9: 2.1: 3.
8. the multiplex catalyst for catalytic coal gasifaction according to claim 1 and 2, the ratio of potassium atom, sodium atom and nickle atom molal quantity summation and coal carbon content in coal atomic molar number to be used is between 0.0125 and 0.0375.
9. a method of preparing the multiplex catalyst for catalytic coal gasifaction described in aforementioned any one, described method comprises the steps:
The first step, according to the water absorption rate of used coal, determines catalyst solution volume according to the method for incipient impregnation supported catalyst;
Second step, by certain load capacity containing potassium material, sodium-containing material and nickeliferous material are according to the liquor capacity obtained aqueous solution of catalyst definite in first step, and flood described coal by incipient impregnation method, after stirring, leave standstill, then dry, obtain the products A that moisture content is 10 % by weight-20 % by weight, wherein in described products A, the mol ratio of potassium atom/sodium atom/nickle atom is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and potassium atom, the ratio of sodium atom and nickle atom molal quantity summation and carbon content in coal atomic molar number is between 0.0125 and 0.05,
Optionally, the 3rd step, calculate the aqueous solution volume of calcareous material according to the method for the water absorption rate of original coal and incipient impregnation supported catalyst, and make the aqueous solution of corresponding certain load capacity calcareous material, be further used for being immersed in the products A obtaining in second step, after stirring, leave standstill, then dry, obtaining moisture content is the final products below 2 % by weight, wherein potassium atom/sodium atom/nickle atom mol ratio is between 0.63: 0.27: 9 and 6.3: 2.7: 1, and potassium atom, the ratio of sodium atom and nickle atom molal quantity summation and carbon content in coal atomic molar number is between 0.0125 and 0.05, the ratio of the calcium atom in described calcareous material and carbon content in coal atomic molar number is between 0.0125 and 0.05.
10. a multiplex catalyst of preparing according to the multiplex catalyst described in any one in claim 1 to 8 or by the method described in any one in claim 9 is applied in catalysis coal gasification reaction and synthesis gas methanation reaction at the same time.
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| CN104399472A (en) * | 2014-11-26 | 2015-03-11 | 新奥科技发展有限公司 | Calcium-based compound catalyst and loading method thereof |
| CN106622394A (en) * | 2016-09-27 | 2017-05-10 | 新奥科技发展有限公司 | Loading method of composite catalyst |
| CN106753563A (en) * | 2016-12-27 | 2017-05-31 | 太原理工大学 | A kind of method for improving char gasification reactivity |
| CN111203240A (en) * | 2020-01-21 | 2020-05-29 | 新奥科技发展有限公司 | Catalyst loading method and system, coal powder adding method and coal catalytic gasification system |
| CN114042464A (en) * | 2021-11-03 | 2022-02-15 | 新奥科技发展有限公司 | Salt-containing wastewater catalyst and method for catalyzing coal gasification reaction by using same |
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| CN104399472A (en) * | 2014-11-26 | 2015-03-11 | 新奥科技发展有限公司 | Calcium-based compound catalyst and loading method thereof |
| CN106622394A (en) * | 2016-09-27 | 2017-05-10 | 新奥科技发展有限公司 | Loading method of composite catalyst |
| CN106622394B (en) * | 2016-09-27 | 2019-07-23 | 新奥科技发展有限公司 | A kind of carrying method of composite catalyst |
| CN106753563A (en) * | 2016-12-27 | 2017-05-31 | 太原理工大学 | A kind of method for improving char gasification reactivity |
| CN106753563B (en) * | 2016-12-27 | 2020-05-01 | 太原理工大学 | Method for improving coal coke gasification reactivity |
| CN111203240A (en) * | 2020-01-21 | 2020-05-29 | 新奥科技发展有限公司 | Catalyst loading method and system, coal powder adding method and coal catalytic gasification system |
| CN111203240B (en) * | 2020-01-21 | 2023-04-21 | 新奥科技发展有限公司 | Catalyst loading method and system, pulverized coal adding method and coal catalytic gasification system |
| CN114042464A (en) * | 2021-11-03 | 2022-02-15 | 新奥科技发展有限公司 | Salt-containing wastewater catalyst and method for catalyzing coal gasification reaction by using same |
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