CN104399472A - Calcium-based compound catalyst and loading method thereof - Google Patents
Calcium-based compound catalyst and loading method thereof Download PDFInfo
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Abstract
The invention provides a calcium-based compound catalyst and a loading method thereof and relates to the technical field of catalytic coal gasification. The calcium-based compound catalyst has higher catalytic efficiency in both gasification reaction and methanation reaction, can realize gasification, conversion and methanation reaction coupling in a gasification furnace, and improves the content of methane in product gas. The calcium-based compound catalyst disclosed by the invention comprises a calcium-containing substance and a transition metal-containing substance. The calcium-based compound catalyst and the loading method thereof, disclosed by the invention, are applicable to the catalytic coal gasification process.
Description
Technical field
The present invention relates to catalytic coal gasifaction technical field, particularly a kind of calcium based composite catalysis agent and carrying method thereof.
Background technology
Catalytic coal gasifaction technology is a kind of important way of clean efficiency utilization coal.In catalytic coal gasifaction process, the reaction of potassium based catalysts catalytic gasification is usually adopted to generate object product.But because potassium based catalysts price is very expensive, and its alkalescence is perishable by force, often need reclaimed by operations such as washing, clear up and recycled, and removal process energy consumption, water consumption is all very large, that is: there is the shortcomings such as cost is higher, recovery process is complicated in potassium based catalysts.
In order to overcome this shortcoming of potassium based catalysts, in development subsequently, technical staff gathers sight to calcium based catalysts gradually.First, calcium based catalysts is cheap, environmental friendliness, and the lime-ash generated after gasification reaction can directly discharge or for construction material; Secondly, the interpolation of calcium based catalysts can consolidate sulphur, solid carbon, can effectively reduce pollution emissions.In addition, the interpolation of appropriate calcium based catalysts can also improve the ash fusion point of coal, effectively can reduce the risk of Slagging in Texaco Gasifier.But; however; existing calcium based catalysts still can not replace potassium based catalysts completely and be widely used in catalytic coal gasifaction process; this is because existing calcium based catalysts methanation reaction activity is low; this realizes gasification, conversion, methanation reaction coupling for requiring in gasification furnace; the catalysis gasification technique reaching heat balance is infeasible, and methane content in the gas product of coal gasification course usually can be caused very low.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of calcium based composite catalysis agent and carrying method thereof, gasification reaction catalytic efficiency and methanation reaction catalytic efficiency all higher, gasification in gasification furnace, conversion, methanation reaction coupling can be realized, improve the content of methane in gas product.
For achieving the above object, the technical solution used in the present invention is as follows:
The invention provides a kind of calcium based composite catalysis agent, comprise calcareous material and contain transition metal material.
Wherein, the described at least one comprised containing transition metal material in iron compound, nickeliferous material.
Preferably, describedly comprise iron compound containing transition metal material, the ferro element mass ratio in the calcium constituent in described calcareous material and described iron compound is 1-5:0.5-3; Or
Describedly comprise nickeliferous material containing transition metal material, the nickel element mass ratio in the calcium constituent in described calcareous material and described nickeliferous material is 1-5:0.1-2; Or
The described transition metal material that contains comprises iron compound and nickeliferous material, and the ferro element in the calcium constituent in described calcareous material, described iron compound, the nickel element mass ratio in nickeliferous material are 1-5:0.5-3:0.1-2.
The present invention also provides a kind of carrying method of calcium based composite catalysis agent, and described calcium based composite catalysis agent comprises calcareous material and contains transition metal material;
Described method comprises: described calcium based composite catalysis agent loaded on coal particle.
Particularly, described calcium based composite catalysis agent loaded on coal particle specifically comprise:
S1, judge described calcareous material and describedly whether there is precipitation reaction containing transition metal material;
If S2 does not exist precipitation reaction, then described calcareous material and the described transition metal material that contains are loaded on coal particle simultaneously; Or, first described calcareous material is loaded on coal particle, then containing transition metal material described in load;
If there is precipitation reaction, then first described calcareous material is loaded on coal particle, the more described solution containing transition metal material is joined load with set rate have on the coal particle of calcareous material.
In above-mentioned steps S2, if described calcareous material is solubility, described is solubility containing transition metal material, and described calcareous material does not exist precipitation reaction with the described transition metal material that contains, then:
Described by described calcareous material and describedly load on coal particle specifically comprise containing transition metal material simultaneously:
First described calcareous material, the described transition metal material that contains are mixed with described coal particle simultaneously, then add water and stir dipping, so that described calcareous material and the described transition metal material that contains are loaded on coal particle simultaneously; Or, first described calcareous material and the described transition metal material that contains are made into mixed solution, and then described mixed solution are mixed with coal particle, by dipping, described calcareous material and the described transition metal material that contains are loaded on coal particle simultaneously;
Describedly first described calcareous material to be loaded on coal particle, more specifically comprises containing transition metal material described in load:
First calcareous material is mixed with described coal particle, add water and stir dipping, so that described calcareous material is loaded on described coal particle, then the coal particle of described calcareous material is had to mix containing transition metal material with load, add water and stir dipping, to load to load by described have on the coal particle of described calcareous material containing transition metal material; Or; by calcareous material, be mixed with solution respectively containing transition metal material; first calcareous material solution is mixed with described coal particle; by dipping, described calcareous material is loaded on described coal particle; then the coal particle of described calcareous material will be had mix with load containing transition metal material solution, by flooding, the described transition metal material that contains is loaded to load and has on the coal particle of described calcareous material.
In above-mentioned steps S2, if described calcareous material is solubility, described is slightly solubility containing transition metal material, and described calcareous material does not exist precipitation reaction with the described transition metal material that contains, then:
Described by described calcareous material and describedly load on coal particle specifically comprise containing transition metal material simultaneously:
Described calcareous material, the described transition metal material that contains being mixed with described coal particle, by being dry mixed mixing, described calcareous material and the described transition metal material that contains being loaded on coal particle simultaneously;
Describedly first described calcareous material to be loaded on coal particle, more specifically comprises containing transition metal material described in load:
First described calcareous material is mixed with described coal particle, add water and stir dipping, so that described calcareous material is loaded on described coal particle, or, first calcareous material is mixed with solution, calcareous material solution is mixed with described coal particle, by dipping, described calcareous material is loaded on described coal particle; Then be crushed to predetermined particle diameter by described containing transition metal material, then have the described coal particle of described calcareous material mix with load, by being dry mixed mixing, the described transition metal material that contains is loaded to load and has on the coal particle of described calcareous material.
Preferably, described predetermined particle diameter is below 0.1mm.
Particularly, described coal particle comprises low-order coal, or comprises the mixture of low-order coal and high-order coal; Described described calcium based composite catalysis agent being loaded on coal particle specifically comprises: described calcium based composite catalysis agent be dry mixed with coal particle and mix, described calcium based composite catalysis agent to be loaded on described coal particle.
Or described coal particle comprises high-order coal, or comprise the mixture of high-order coal and low-order coal; Described described calcium based composite catalysis agent is loaded on coal particle before, described method also comprises: carry out pre-oxidation to coal particle.
Preferably, the described at least one comprised containing transition metal material in iron compound, nickeliferous material.
Wherein, take coal particle as benchmark, in described calcareous material, the load capacity of calcium constituent is 1 ~ 5wt.%;
Described containing in transition metal material, the load capacity of described ferro element is 0.5 ~ 3wt.%, and/or the load capacity of nickel element is 0.1 ~ 2wt.%.
The invention provides a kind of calcium based composite catalysis agent and carrying method thereof, this calcium based composite catalysis agent comprises calcareous material and contains transition metal material, in catalytic coal gasifaction process, it is active that calcareous material improves catalysis coal gasification, methanation activity is improve containing transition metal material, namely this calcium based composite catalysis agent can on the basis of improving coal gasification reaction speed, promote the generation of methane in gaseous product, achieve gasification, synchronously carrying out of methanation reaction, ensure that the balance between gasification reaction stage and methanation reaction stage, gasification is achieved in gasification installation, conversion, the abundant coupling of methanation reaction, reach the catalysis gasification technique of heat balance, and then improve methane content in gas product.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below.
The flow chart of the carrying method of a kind of calcium based composite catalysis agent that Fig. 1 provides for the embodiment of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The embodiment of the present invention provides a kind of calcium based composite catalysis agent, comprises calcareous material and contains transition metal material.
In catalytic coal gasifaction process, usually can be divided into gasification reaction and two stages of methanation reaction, in the gasification reaction stage, coal particle and oxygen-containing gas react under catalyst action, generate and comprise CO, CO
2, H
2, H
2the coal gasification gaseous product of O, this stage is exothermic reaction; In the methanation reaction stage, above-mentioned gas product generates methane under catalyst action, and this stage is the endothermic reaction.The calcium based composite catalysis agent that the embodiment of the present invention provides comprises calcareous material and contains transition metal material, in catalytic coal gasifaction process, it is active that calcareous material improves catalysis coal gasification, methanation activity is improve containing transition metal material, namely this calcium based composite catalysis agent can on the basis of improving coal gasification reaction speed, promote the generation of methane in gaseous product, achieve gasification, synchronously carrying out of methanation reaction, ensure that the balance between gasification reaction stage and methanation reaction stage, gasification is achieved in gasification installation, conversion, the abundant coupling of methanation reaction, reach the catalysis gasification technique of heat balance, and then improve methane content in gas product.
In the embodiment of the present invention, calcareous material can comprise any material containing calcium constituent, can be such as at least one in calcium oxide, calcium hydroxide, calcium nitrate, calcium acetate, calcium sulfate.
At least one in iron compound, nickeliferous material can be comprised containing transition metal material.
Wherein, iron compound can be any material containing ferro element, it can be such as at least one in ferrous oxide, di-iron trioxide, tri-iron tetroxide, ferrous nitrate, ferrous acetate, ferrous carbonate, ferrous sulfate, in a word, as long as containing ferro element, the present invention is not construed as limiting this.
Nickeliferous material can be any material containing nickel element, can be such as at least one in nickel oxide, nickel nitrate, nickel acetate, nickelous carbonate, nickelous sulfate, as long as containing nickel element, the present invention is not construed as limiting this.
In the embodiment of the present invention, the calcium constituent in calcareous material has specific mass ratio with containing the transition metal in transition metal material.
Such as, when comprising iron compound containing transition metal material, calcium constituent in calcareous material and the ferro element mass ratio in iron compound can be 1-5:0.5-3, such as, can be 1:0.5,1:1,1:2,1:3,2:0.5,2:3,3:1,3:2,4:0.5,4:1.5,5:0.5,5:1,5:2.
Calcium constituent can affect with the mass ratio of ferro element gasify, convert, methanation reaction is coupled, if the mass ratio of calcium constituent and ferro element is too high, then cause gasification reaction speed higher than methanation reaction speed, if the mass ratio of calcium constituent and ferro element is too low, then cause gasification reaction speed lower than methanation reaction speed, this can cause between gasification reaction speed and methanation reaction speed unbalance, and gasification reaction stage and methanation reaction stage can not synchronously be carried out.The above-mentioned calcium constituent determined in the embodiment of the present invention and the mass ratio of ferro element can make the gasification reaction speed of calcium based composite catalysis agent and methanation reaction speed mutually balance, guarantee that gasification reaction stage and methanation reaction carry out simultaneously, adequately achieve gasification, conversion, methanation reaction coupling, reach heat balance.
When comprising nickeliferous material containing transition metal material, nickel element mass ratio in calcium constituent in calcareous material and nickeliferous material can be 1-5:0.1-2, such as, can be 1:0.1,1:0.5,1:1,1:2,2:0.1,2:0.5,2:1.5,3:0.5,3:1,3:2,4:1.5,5:1.5,5:2.As a same reason, this mass ratio of calcium constituent and nickel element makes gasification reaction speed and methanation reaction speed mutually balance, ensure that gasification reaction stage and methanation reaction carry out simultaneously, adequately achieve gasification, conversion, methanation reaction coupling, reach heat balance.
When comprising iron compound and nickeliferous material containing transition metal material, nickel element mass ratio in calcium constituent in calcareous material, the ferro element in iron compound, nickeliferous material can be 1-5:0.5-3:0.1-2, such as, can be 1:0.5:0.1,1:0.5:1,2:0.5:0.1,2:0.5:0.5,3:0.5:0.1,3:1:0.5,3:1:1.5,4:1.5:0.1,4:1.5:1,4:1:2,4:2.5:1,5:0.5:0.1,5:1.5:1,5:2:2,5:2.5:2,5:3:2.When the mass ratio of calcium constituent, ferro element, nickel element is within the scope of this, can guarantee to act synergistically between each composition, make calcium based composite catalysis agent have higher gasification reaction speed and methanation reaction speed simultaneously, guarantee to gasify, synchronously the carrying out of methanation reaction.
Correspondingly, the embodiment of the present invention additionally provides a kind of carrying method of calcium based composite catalysis agent, this calcium based composite catalysis agent any one calcium based composite catalysis agent for providing in the embodiment of the present invention, that is, this calcium based composite catalysis agent comprises calcareous material and contains transition metal material; Described method can comprise: calcium based composite catalysis agent loaded on coal particle.
The carrying method of the calcium based composite catalysis agent that the embodiment of the present invention provides, the calcium based composite catalysis agent used comprises calcareous material and contains transition metal material, in catalytic coal gasifaction process, it is active that calcareous material improves catalysis coal gasification, methanation activity is improve containing transition metal material, namely this calcium based composite catalysis agent can on the basis of improving coal gasification reaction speed, promote the generation of methane in gaseous product, achieve gasification, synchronously carrying out of methanation reaction, ensure that the balance between gasification reaction stage and methanation reaction stage, gasification is achieved in gasification installation, conversion, the abundant coupling of methanation reaction, reach the catalysis gasification technique of heat balance, and then improve methane content in gas product.
Preferably, in above-mentioned carrying method, at least one that can comprise containing transition metal material in iron compound, nickeliferous material in the calcium based composite catalysis agent used.
Be benchmark with coal particle, in loading process, in calcareous material, the load capacity of calcium constituent can be 1 ~ 5wt.%, such as, can be 1wt.%, 2wt.%, 2.5wt.%, 3wt.%, 4wt.%, 4.5wt.%, 5wt.%; Containing in transition metal material, the load capacity of ferro element can be 0.5 ~ 3wt.%, can be such as 0.5wt.%, 1wt.%, 2wt.%, 2.5wt.%, 3wt.%, and/or the load capacity of nickel element can be 0.1 ~ 2wt.%, such as, can be 0.1wt.%, 0.2wt.%, 0.5wt.%, 1wt.%, 2wt.%.
The load capacity of above-mentioned each element and the load percentage between them can be guaranteed to form synergy between each element, being conducive to calcium based composite catalysis agent impels gasification, methanation reaction synchronously to carry out, promote gasification, exchange, methanation reaction coupling, thus improve the content of methane in gas product; In addition, in above-mentioned calcium based composite catalysis agent, although the ash fusion point of coal particle can be reduced to a certain extent containing transition metal material, but the interpolation of calcareous material, can offset this effect effectively, and, compared to when not adding any catalyst, effectively can also improve the ash fusion point of coal particle, reduce the risk of gasification ash erosion.
In catalytic coal gasifaction, the carrying method of catalyst is comparatively large to the performance impact of catalyst, and especially for composite catalyst, the optimization of loading process is most important to catalyst activity.Whether the catalyst cupport method that the embodiment of the present invention provides, exist precipitation reaction according to calcareous material with containing between transition metal material in loading process, they can be loaded on coal particle simultaneously, or they be loaded to successively on coal particle.
Particularly, as shown in Figure 1, calcium based composite catalysis agent is loaded on coal particle specifically can comprise:
S1, judge calcareous material and whether there is precipitation reaction containing transition metal material;
If S2 does not exist precipitation reaction, then calcareous material is loaded on coal particle with containing transition metal material simultaneously; Or, can first calcareous material be loaded on coal particle, then load is containing transition metal material, or first will loads on coal particle containing transition metal material, then load calcareous material;
If there is precipitation reaction, then first calcareous material is loaded on coal particle, have on the coal particle of calcareous material by joining load containing transition metal material solution with set rate again, or, first will load on coal particle containing transition metal material, then calcareous material solution will be joined on the coal particle that load has containing transition metal material with set rate.
In the method that the embodiment of the present invention provides, whether there is precipitation reaction according to calcareous material divide with containing transition metal material, optionally simultaneously or successively by calcareous material with load on coal particle containing transition metal material, effectively make use of the feature of different loads process, thus by corresponding loading process, calcareous material is loaded on coal particle effectively dispersedly with containing transition metal material.
In catalytic coal gasifaction process, in order to ensure that catalyst gives full play to catalytic action, need to make catalyst uniform load in coal particle surface.But, because the animal migration of calcium is poor, in order to ensure dispersed in coal particle surface of calcium constituent, preferably, can first calcareous material be loaded on coal particle, have an effect to make calcium constituent oxygen-containing functional group that is preferential and coal particle surface, thus improve calcareous material at the load capacity of coal particle surface and Load Balanced degree, and then will load on coal particle containing transition metal material, thus obtain the coal particle of all dispersed load of each component, to promote the synergy between each component.
In above-mentioned steps S2, if there is not precipitation reaction, can according to calcareous material with containing the dissolution properties of transition metal material, by dipping process or be dry mixed mixed process by them simultaneously or load to successively on coal particle.Particularly:
1) if calcareous material is solubility, be solubility containing transition metal material, and there is not precipitation reaction with containing transition metal material in calcareous material, then:
In above-mentioned steps S2, calcareous material is loaded on coal particle simultaneously specifically can comprise with containing transition metal material:
First by calcareous material, mix with coal particle containing transition metal material simultaneously, then add water and stir dipping, with by calcareous material with contain transition metal material and load on coal particle simultaneously;
Or, be first made into mixed solution by calcareous material with containing transition metal material, and then mixed solution mixed with coal particle, by dipping, calcareous material is loaded on coal particle with containing transition metal material simultaneously.
First calcareous material is loaded on coal particle, then load specifically can comprise containing transition metal material:
First calcareous material is mixed with coal particle, add water and stir dipping, to load on coal particle by calcareous material, then have the coal particle of calcareous material to mix containing transition metal material with load, add water and stir dipping, to have on the coal particle of calcareous material by loading to load containing transition metal material;
Or; by calcareous material, be mixed with solution respectively containing transition metal material; first calcareous material solution is mixed with coal particle; by dipping, calcareous material is loaded on coal particle; then there is the coal particle of calcareous material to mix with load the solution containing transition metal material, being had loading to load containing transition metal material on the coal particle of calcareous material by dipping.
Dipping process production cost is lower, and in dipping process, ion-exchange can be there is in the oxygen-containing functional group of coal particle surface with calcium ion, transition metal ion etc., thus reach uniform load effectively, and, each component can also be made by adsorption process uniform load on coal particle, improve the effective rate of utilization of each component.In dipping process, first calcareous material is loaded on coal particle, be conducive to calcium constituent functional group that is preferential and coal particle surface is had an effect, improve calcareous material at coal particle surface load capacity and Load Balanced, then have on the coal particle of calcareous material by loading to load containing transition metal material, like this, be conducive to catalyst components is loaded on coal particle all equably, promote the synergy between each component.
Such as, calcareous material is calcium nitrate, is the mixture of ferric nitrate and nickel nitrate containing transition metal material, then calcium nitrate and ferric nitrate, nickel nitrate are loaded on coal particle simultaneously and is specifically as follows:
Calcium nitrate, ferric nitrate, nickel nitrate are mixed with coal particle, load capacity according to the specific pore volume of coal particle, each component calculates water requirement, adds the corresponding water yield, stirs, reach dipping balance post-drying, so just obtain the coal particle that load simultaneously has calcium, iron, nickel element; Or, first calcium nitrate, ferric nitrate, nickel nitrate are made into mixed solution, and then by above-mentioned mixed solution and coal particle total immersion stain, reach balance post-drying, so just obtain the coal particle that load simultaneously has calcium, iron, nickel element.
Calcium nitrate and ferric nitrate, nickel nitrate are loaded to successively on coal particle and are specifically as follows:
First calcium nitrate can be mixed with coal particle; then add water stirring; dipping balance post-drying; the coal particle that load has calcium is obtained after oven dry; then the coal particle of calcium load is had to mix with ferric nitrate, nickel nitrate; add water stirring, and dipping balance post-drying, obtains the coal particle that load has calcium, iron, nickel.Certainly, also load can be had the coal particle of calcium first to mix with ferric nitrate, then add water stirring, dipping balance post-drying, load had the coal particle of calcium and iron to mix with nickel nitrate after oven dry, add water stirring, dipping balance post-drying, obtains the coal particle that load has calcium, iron, nickel; Or, first by calcium nitrate, ferric nitrate, nickel nitrate wiring solution-forming respectively, then mix total immersion stain with coal particle successively, each component loaded on coal particle successively; Certainly, ferric nitrate and nickel nitrate also can be made into mixed solution, first calcium nitrate solution are mixed total immersion stain with coal particle, and then ferric nitrate is mixed total immersion stain with the mixed solution of nickel nitrate with coal particle, thus obtain the coal particle that load has calcium, iron, nickel.
2) if calcareous material is solubility, be slightly solubility containing transition metal material, and there is not precipitation reaction with containing transition metal material in calcareous material, then:
Calcareous material is loaded on coal particle simultaneously specifically can comprise with containing transition metal material:
By calcareous material, mixing with coal particle containing transition metal material, by being dry mixed mixing, calcareous material being loaded on coal particle with containing transition metal material simultaneously;
First calcareous material is loaded on coal particle, then load specifically can comprise containing transition metal material:
First calcareous material is mixed with coal particle; add water and stir dipping; so that calcareous material is loaded on coal particle; or; first calcareous material is mixed with solution, calcareous material solution is mixed with coal particle, by dipping, calcareous material is loaded on coal particle; then there is the coal particle of calcareous material to mix containing transition metal material with load, having loading to load containing transition metal material on the coal particle of calcareous material by being dry mixed mixing.
Preferably, can by calcareous material, be crushed to predetermined particle diameter in advance containing transition metal material before being dry mixed mixing, such as, can be crushed to predetermined particle diameter is in advance below 0.1mm, such as, can be 0.09mm, 0.08mm, 0.06mm, 0.05mm, 0.03mm.The calcareous material of small particle diameter and be more conducive to load on coal particle being dry mixed in mixing containing transition metal material, thus improve the load factor of catalyst.
Such as, when calcareous material is calcium acetate, containing transition metal material be iron oxide, nickel oxide mixture time, in above-mentioned steps S2, calcium acetate and iron oxide, nickel oxide are loaded on coal particle simultaneously and are specifically as follows:
Calcium acetate is mixed with iron oxide, nickel oxide, and is crushed to particle diameter and is less than below 0.1mm, be then jointly placed in blender mechanical mixture with coal particle, by being dry mixed mixing to obtain the coal particle that load has calcium, iron, nickel;
Calcium acetate and iron oxide, nickel oxide are loaded to successively on coal particle and are specifically as follows:
First calcium acetate is mixed with coal particle; add water stirring; by dipping process, calcium is loaded on coal particle; again the mixture of iron oxide and nickel oxide is crushed to below 0.1mm; then there is the coal particle of calcium to be placed in blender with load, by being dry mixed mixing to obtain the coal particle that load has calcium, iron, nickel simultaneously.
3) if calcareous material is slightly solubility; be slightly solubility containing transition metal material; and when there is not precipitation reaction; then in above-mentioned steps S2; can directly by calcareous material, containing transition metal material and coal particle mechanical mixture, by be dry mixed mixing by calcareous material with load on coal particle containing transition metal material simultaneously.Similarly, before mixing with coal particle, can first by calcareous material, be crushed to particle diameter containing transition metal material and be less than 0.1mm.
4) if calcareous material is slightly solubility, be solubility containing transition metal material, and when there is not precipitation reaction, then, in above-mentioned steps S2, calcareous material specifically can be comprised with loading on coal particle containing transition metal material simultaneously:
By calcareous material, containing transition metal material and coal particle mechanical mixture, load on coal particle by being dry mixed mixed process simultaneously;
Calcareous material is loaded to successively on coal particle specifically can comprise with containing transition metal material:
First by calcareous material and coal particle mechanical mixture; calcareous material loaded to first will containing transition metal material load to coal particle on by dipping process by being dry mixed mixing on coal particle or first; load there is the coal particle containing transition metal material to mix with calcareous material again, being mixed to get by being dry mixed the coal particle that load has calcium, transition metal.
In above-mentioned steps S2, if there is precipitation reaction, preferably, first calcareous material can be loaded on coal particle, then have joining load containing the solution of transition metal material with set rate on the coal particle of calcareous material.Certainly, also first can will load on coal particle containing transition metal material, then the solution of calcareous material is joined on the coal particle that load has containing transition metal material with set rate.
Particularly, this set rate is usually less, be such as slowly drip, to ensure that calcareous material forms the very little sediment of particle diameter with containing transition metal material, occurrence those skilled in the art for set rate specifically can select according to the scale of operation, feed throughput in practical operation, the present invention is not construed as limiting this, can be such as 10ml/min.
Such as calcareous material is calcium hydroxide, and be the mixture of ferric acetate and nickel acetate containing transition metal material, then loading process specifically can comprise:
First by calcium hydroxide wiring solution-forming, by dipping process, calcium constituent is loaded on coal particle, then the mixed solution of ferric acetate and nickel acetate slowly being joined load has in the coal particle of calcium constituent, limit edged stirs, form the depositions settle of nominal particle size, thus iron, Ni are had on the coal particle of calcium constituent to load.
In precipitation deposition process, can guarantee to generate the even nano level tiny sediment of micron by controlling to add speed, stir speed (S.S.) etc., the sedimentary granularity of generation is more tiny, is more conducive to realizing the evenly effectively dispersion on coal particle of each component.
In embodiments of the present invention, the feed coal particle used can be low-order coal, or is the mixture of low-order coal and high-order coal.The oxygen-containing functional group that low-order coal is as a large amount of in brown coal contain and moisture.In catalysis gasification technique, low-order coal oxygen-containing functional group and the high feature of moisture can be utilized, directly catalyst is dry mixed with coal particle and mixes, reach the effect of effective spread loads, and do not need to add water retting, this not only can save low-order coal drying and upgrading operation energy consumption, can also reduce water consumption and drying process energy consumption in catalyst cupport process, can effectively reduce costs.
That is, calcium based composite catalysis agent is loaded on coal particle and specifically can comprise: calcium based composite catalysis agent is dry mixed with coal particle and mixes, so that calcium based composite catalysis agent is loaded on coal particle.
Or, in the embodiment of the present invention, when using the mixture of low-order coal or use low-order coal and high-order coal, also calcium based composite catalysis agent can be loaded on coal particle by several modes that the embodiment of the present invention is above-mentioned, when relating to dipping, the water yield of minimizing interpolation that can be suitable, also can reduce water consumption and drying process energy consumption to a certain extent.
In another embodiment, the feed coal particle used can be high-order coal.High-order coal is high because of degree of metamorphism, before catalyst cupport process, can be increased the number of oxygen-containing functional group on coal particle, namely increase the avtive spot of coal particle surface, to improve catalyst cupport efficiency and catalytic activity by pre-oxidation.
That is, before calcium based composite catalysis agent is loaded on coal particle, the method can also comprise: carry out pre-oxidation to coal particle, namely, this carrying method specifically can comprise: first carry out pre-oxidation to coal particle, more whether there is precipitation reaction simultaneously or load to successively on the coal particle of pre-oxidation treatment by calcareous material and containing transition metal material according to them.
Particularly, high-order coal can be at least one in bituminous coal, ub-bituminous coal or anthracite; In addition, the present invention is not construed as limiting method for pre-oxidizing, and method for pre-oxidizing well known by persons skilled in the art all can use in the present invention.
Like this, the embodiment of the present invention can use oxygen-containing functional group and the higher low-order coal of water content, active low high-order coal and low-order coal and high-order coal with certain proportion mixing coal blending, and the pretreatment modes such as pre-oxidation can be carried out according to actual conditions to high-order coal, on the basis ensureing reactivity, improve the catalytic gasification coal scope of application.
It should be noted that, it is the previous step of loading process to the pretreatment operation such as cooperation, pre-oxidation of the Coal rank of coal particle, other can increase coal particle functional group, improve water content etc. is also applicable to the pretreatment of coal particle the method that the embodiment of the present invention provides, be conducive to improving coal particle character thus make catalyst be easy to load on coal particle, improving the load factor of catalyst.
In the embodiment of the present invention, the calcareous material with gasification reactivity is carried out combination load with the transition metal material that contains with methanation activity, obtain calcium based composite catalysis agent, and produce synergy between each component, improve coal gasification activity and methanation activity simultaneously, promote gasification, exchange, methanation reaction coupling, improve the composition of methane in gas product.
In addition, the embodiment of the present invention optimizes the load process of calcium based composite catalysis agent, for different complex catalyst precursor volume propertys, adopt respective load method, impel calcium based composite catalysis agent such as to act synergistically between each component of Ca-Fe, Ca-Ni, Ca-Fe-Ni composite catalyst, play catalysis coal gasification and methanation difunctional.
Further, the calcium based composite catalysis agent used in the embodiment of the present invention, cheap, environmental friendliness, without the need to reclaiming, can directly to discharge or for construction material; In addition, calcareous material such as CaO or Ca (OH)
2have and consolidate carbon, sulfur fixation preferably, effectively can reduce toxic emission, economize energy.
Set forth the carrying method of the calcium based composite catalysis agent that the embodiment of the present invention provides below in conjunction with specific embodiments further.
Comparative example
(1) raw material: coal particle adopts brown coal, and is crushed to below 1mm, and calcareous material is CaO, Ca (OH)
2, CaSO
4, Ca (AC)
2, Ca (NO
3)
2in at least one, with coal particle quality for benchmark, in calcareous material, the load capacity of calcium constituent is 5%.
(2) carrying method: mixed with coal sample by calcareous material, add suitable quantity of water and stir, dipping, makes coal particle be dough, obtains the coal particle that load has calcium.
(3) catalytic coal gasification: the above-mentioned load prepared has the coal particle of calcium under the prerequisite of the smooth charging of energy, and drying is not directly delivered to gasification furnace, or is delivered to gasification furnace after drying process; Further, gasification furnace furnace temperature remains on 700-800 DEG C, thus carries out brown catalytic coal gasification.
(4) catalytic gasification product is analyzed: by analysis, in gasification furnace exit gas, methane content accounts for 8vol.%.
Embodiment 1
(1) raw material: coal particle adopts brown coal, and is crushed to below 1mm; Calcareous material is Ca (NO
3)
2, Ca (AC)
2in at least one, with coal particle quality for benchmark, in calcareous material, the load capacity of calcium constituent is 3%; Iron compound is Fe (NO
3)
2, Fe (AC)
2in at least one, in iron compound, the load capacity of ferro element is 1%; Nickeliferous material is Ni (NO
3)
2, Ni (AC)
2in at least one, in nickeliferous material, the load capacity of nickel element is 1%.
(2) carrying method: can adopt with the following method any one carry out the load of catalyst:
A) mixed with coal particle by calcareous material, add water stirring, dipping, then have the coal particle of calcareous material to mix with load iron compound or nickeliferous material, and add water stirring, dipping; Add water and stir in dipping process, for ensureing that coal particle mixes with between catalyst components, according to coal particle water content, suitable quantity of water should be added, making coal particle be dough, obtaining the coal particle that load has calcium, iron, nickel;
B) after being mixed with coal sample with iron compound or nickeliferous material by calcareous material, according to coal particle water content simultaneously, add suitable quantity of water and stir, total immersion stain, makes coal particle be dough, obtains the coal particle that load has calcium, iron, nickel.
(3) catalytic coal gasification: the above-mentioned load prepared has the coal particle of calcium, iron, nickel under the prerequisite of the smooth charging of energy, and drying is not directly delivered to gasification furnace, or is delivered to gasification furnace after drying process; Further, gasification furnace furnace temperature remains on 700-800 DEG C, thus carries out brown catalytic coal gasification.
(4) catalytic gasification product is analyzed: by analysis, in gasification furnace exit gas, methane content accounts for more than 25vol.%, can be directly used in fuel gas; The lime-ash that gasification furnace is discharged can directly discharge or for construction material.
Embodiment 2
(1) raw material: coal particle adopts the coal blending of brown coal and the mixing of ub-bituminous coal, bituminous coal or anthracite, is crushed to below 1mm; Calcareous material is CaO, Ca (OH)
2, Ca (AC)
2, Ca (NO
3)
2in at least one, with coal particle quality for benchmark, in calcareous material, the load capacity of calcium constituent is 4.5%, and iron compound is FeO, Fe
2o
3, Fe
3o
4in at least one, in iron compound, the load capacity of ferro element is 0.5%; Or nickeliferous material is NiO, in nickeliferous material, the load capacity of nickel element is 0.5%, and iron compound and nickeliferous material are crushed to below 0.1mm in advance.
(2) carrying method: the catalyst and the Ca-Fe catalyst that comprise calcareous material and iron compound, and comprise the catalyst of calcareous material and nickeliferous material and Ca-Ni catalyst carries out load respectively by the following method:
A) mixed with coal particle by calcareous material, add water stirring, loads on coal particle by dipping process by calcium, then will being crushed to iron compound and the coal particle mechanical mixture of below 0.1mm, and being mixed to get by being dry mixed the coal particle that load has calcium, iron;
B) mixed with coal particle by calcareous material, add water stirring, loads on coal particle by dipping process by calcium constituent, then will being crushed to nickeliferous material and the coal particle mechanical mixture of below 0.1mm, and being mixed to get by being dry mixed the coal particle that load has calcium, nickel.
(3) catalytic coal gasification: reaction condition is with embodiment 1.
(4) catalytic gasification product is analyzed: by analysis, in gasification furnace exit gas, methane content accounts for more than 25vol.%, can be directly used in fuel gas; The lime-ash that gasification furnace is discharged can directly discharge or for construction material.
Embodiment 3
(1) raw material: coal particle adopts brown coal, is crushed to below 1mm; There is precipitation reaction and generate other product in calcareous material and iron compound or nickeliferous material, wherein, calcareous material can be selected from CaO, Ca (OH)
2, CaSO
4, Ca (AC)
2, Ca (NO
3)
2in at least one, with coal particle quality for benchmark, in calcareous material, the load capacity of calcium constituent is 3.5%; Iron compound can be selected from Fe (NO
3)
2, Fe (AC)
2, FeCO
3, FeSO
4in at least one, in iron compound, the load capacity of ferro element is 1.3%, and nickeliferous material can be selected from Ni (NO
3)
2, Ni (AC)
2, NiCO
3, NiSO
4in at least one, in nickeliferous material, the load capacity of nickel element is 0.2%.
(2) carrying method: first calcareous material is mixed with coal particle; add water stirring; dipping; so that calcareous material is loaded on coal particle; again iron compound and nickeliferous material are made into mixed solution, then the mixed solution of iron compound and nickeliferous material slowly being joined load has in the coal particle of calcium constituent, and limit edged stirs; the sediment that continuous generation granularity is tiny, obtains by depositions settle the coal particle that load has calcium, iron, nickel.
(3) catalytic gasification reaction: reaction condition is with embodiment 1.
(4) catalytic gasification product is analyzed: by analysis, in gasification furnace exit gas, methane content accounts for more than 25vol.%, can be directly used in fuel gas; The lime-ash that gasification furnace is discharged can directly discharge or for construction material.
Interpretation of result:
From the experimental result of comparative example and embodiment 1, the comparative example load Ca catalyst of 5wt.%, in the gas that catalytic gasification produces, methane content is 8vol.%, the embodiment 1 load Ca-Fe-Ni composite catalyst of 5wt.%, in the gas that catalytic gasification produces, methane content is more than 25vol.%.Visible, the calcium based composite catalysis agent that the embodiment of the present invention provides, fully can improve the difunctional of catalytic gasification and methanation, promotes gasification in gasification furnace, conversion, methanation reaction coupling, improves the composition of methane in gas product.
From embodiment 1-3, the carrying method of the calcium based composite catalysis agent that the embodiment of the present invention provides, whether precipitation reaction is there is with containing transition metal material according to calcareous material in composite catalyst, by adopting corresponding loading process, can load on coal particle by all dispersed for each component, promote the synergy between each component, promote gasification in gasification furnace, conversion, methanation reaction coupling, improve the composition of methane in gas product.
From embodiment 1, no matter by calcareous material and iron compound, nickeliferous material loads on coal particle simultaneously, still load to successively on coal particle, in gasification furnace exit gas, methane content all reaches more than 25vol.%, this shows when calcareous material is solubility with containing transition metal material, and when there is not precipitation reaction, calcareous material can not affect the Load Balanced of calcium based composite catalysis agent with the Mo-Co catalyst containing transition metal material, no matter which kind of Mo-Co catalyst, this calcium based composite catalysis agent can be made to have higher catalytic gasification and the double activity of methanation.
From embodiment 2, when iron compound or nickeliferous material are slightly solubility materials, can adopt and be dry mixed mixing by iron compound or nickeliferous material pay(useful) load on coal particle, thus obtain the calcium based composite catalysis agent of the double activity with higher catalytic gasification and methanation.
From embodiment 1 ~ 3, no matter composite catalyst is Ca-Fe composite catalyst, Ca-Ni composite catalyst or Ca-Fe-Ni composite catalyst, in gasification furnace exit gas after catalytic coal gasification, methane content all can reach more than 25vol.%, that is, these calcium based composite catalysis agent all can make to form good synergy between each component, thus have higher catalytic gasification and the double activity of methanation.
From embodiment 1 ~ 3, the carrying method of the calcium based composite catalysis agent that the embodiment of the present invention provides, feed coal particle can use low-order coal such as brown coal, also can use the coal blending of low-order coal and high-order coal, thus on the basis ensureing reactivity, improve the catalytic gasification coal scope of application.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of described claim.
Claims (12)
1. a calcium based composite catalysis agent, is characterized in that, comprises calcareous material and contains transition metal material.
2. calcium based composite catalysis agent according to claim 1, is characterized in that, the described at least one comprised containing transition metal material in iron compound, nickeliferous material.
3. calcium based composite catalysis agent according to claim 2, is characterized in that, describedly comprises iron compound containing transition metal material, and the ferro element mass ratio in the calcium constituent in described calcareous material and described iron compound is 1-5:0.5-3; Or
Describedly comprise nickeliferous material containing transition metal material, the nickel element mass ratio in the calcium constituent in described calcareous material and described nickeliferous material is 1-5:0.1-2; Or
The described transition metal material that contains comprises iron compound and nickeliferous material, and the ferro element in the calcium constituent in described calcareous material, described iron compound, the nickel element mass ratio in nickeliferous material are 1-5:0.5-3:0.1-2.
4. a carrying method for calcium based composite catalysis agent, is characterized in that, described calcium based composite catalysis agent comprises calcareous material and contains transition metal material;
Described method comprises: described calcium based composite catalysis agent loaded on coal particle.
5. the carrying method of calcium based composite catalysis agent according to claim 4, is characterized in that, described described calcium based composite catalysis agent being loaded on coal particle specifically comprises:
S1, judge described calcareous material and describedly whether there is precipitation reaction containing transition metal material;
If S2 does not exist precipitation reaction, then described calcareous material and the described transition metal material that contains are loaded on coal particle simultaneously; Or, first described calcareous material is loaded on coal particle, then containing transition metal material described in load;
If there is precipitation reaction, then first described calcareous material is loaded on coal particle, the more described solution containing transition metal material is joined load with set rate have on the coal particle of described calcareous material.
6. the carrying method of calcium based composite catalysis agent according to claim 5, is characterized in that, in step S2, described calcareous material is solubility, described is solubility containing transition metal material, and described calcareous material does not exist precipitation reaction with the described transition metal material that contains, then:
Described by described calcareous material and describedly load on coal particle specifically comprise containing transition metal material simultaneously:
First described calcareous material, the described transition metal material that contains are mixed with described coal particle simultaneously, then add water and stir dipping, so that described calcareous material and the described transition metal material that contains are loaded on coal particle simultaneously; Or, first described calcareous material and the described transition metal material that contains are made into mixed solution, and then described mixed solution are mixed with coal particle, by dipping, described calcareous material and the described transition metal material that contains are loaded on coal particle simultaneously;
Describedly first described calcareous material to be loaded on coal particle, more specifically comprises containing transition metal material described in load:
First described calcareous material is mixed with coal particle, add water and stir dipping, so that described calcareous material is loaded on described coal particle, then the coal particle of described calcareous material is had to mix containing transition metal material with load, add water and stir dipping, to load to load by described have on the coal particle of described calcareous material containing transition metal material; Or; by calcareous material, be mixed with solution respectively containing transition metal material; first calcareous material solution is mixed with described coal particle; by dipping, described calcareous material is loaded on described coal particle; then the coal particle of described calcareous material will be had mix with load containing transition metal material solution, by flooding, the described transition metal material that contains is loaded to load and has on the coal particle of described calcareous material.
7. the carrying method of calcium based composite catalysis agent according to claim 5, is characterized in that, in step S2, described calcareous material is solubility, described is slightly solubility containing transition metal material, and described calcareous material does not exist precipitation reaction with the described transition metal material that contains, then:
Described by described calcareous material and describedly load on coal particle specifically comprise containing transition metal material simultaneously:
Described calcareous material, the described transition metal material that contains being mixed with described coal particle, by being dry mixed mixing, described calcareous material and the described transition metal material that contains being loaded on coal particle simultaneously;
Describedly first described calcareous material to be loaded on coal particle, more specifically comprises containing transition metal material described in load:
First described calcareous material is mixed with described coal particle, add water and stir dipping, so that described calcareous material is loaded on described coal particle, or, first calcareous material is mixed with solution, calcareous material solution is mixed with described coal particle, by dipping, described calcareous material is loaded on described coal particle; Then be crushed to predetermined particle diameter by described containing transition metal material, then have the described coal particle of described calcareous material mix with load, by being dry mixed mixing, the described transition metal material that contains is loaded to load and has on the coal particle of described calcareous material.
8. the carrying method of calcium based composite catalysis agent according to claim 7, is characterized in that, described predetermined particle diameter is below 0.1mm.
9. the carrying method of calcium based composite catalysis agent according to claim 4, is characterized in that, described coal particle comprises low-order coal, or comprises the mixture of low-order coal and high-order coal;
Described described calcium based composite catalysis agent being loaded on coal particle specifically comprises: described calcium based composite catalysis agent be dry mixed with coal particle and mix, described calcium based composite catalysis agent to be loaded on described coal particle.
10. the carrying method of calcium based composite catalysis agent according to claim 4, is characterized in that, described coal particle comprises high-order coal, or comprises the mixture of high-order coal and low-order coal;
Described described calcium based composite catalysis agent is loaded on coal particle before, described method also comprises: carry out pre-oxidation to coal particle.
The carrying method of 11. calcium based composite catalysis agent according to any one of claim 4 ~ 10, is characterized in that, the described at least one comprised containing transition metal material in iron compound, nickeliferous material.
The carrying method of 12. calcium based composite catalysis agent according to claim 11, is characterized in that,
Take coal particle as benchmark, in described calcareous material, the load capacity of calcium constituent is 1 ~ 5wt.%;
Described containing in transition metal material, the load capacity of described ferro element is 0.5 ~ 3wt.%, and/or the load capacity of nickel element is 0.1 ~ 2wt.%.
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