CN106753563B - Method for improving coal coke gasification reactivity - Google Patents

Method for improving coal coke gasification reactivity Download PDF

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CN106753563B
CN106753563B CN201611223268.7A CN201611223268A CN106753563B CN 106753563 B CN106753563 B CN 106753563B CN 201611223268 A CN201611223268 A CN 201611223268A CN 106753563 B CN106753563 B CN 106753563B
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CN106753563A (en
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闫伦靖
高美琪
吕鹏
杨志荣
李凡
白永辉
朱生华
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Taiyuan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime

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Abstract

The invention discloses a method for improving coal coke gasification reactivity in a coal catalytic gasification reaction process, which comprises the steps of adding calcium carbonate and sodium carbonate into raw coal, and loading the calcium carbonate and the sodium carbonate on the raw coal to prepare calcium-sodium-loaded coal containing 1.25-2.5% of calcium carbonate and 0.4-1% of sodium carbonate. Mixing the calcium-sodium-loaded coal with H2O/CO2The gasification reaction of the multi-element gasification agent shows far better than that of pure H2O or pure CO2The gasification reactivity of the multi-element gasification agent is improved, the gasification reactivity of the coal coke in the crushed coal pressure gasification process is improved, and the degree of the synergistic effect of the gasification reaction at higher temperature is promoted.

Description

Method for improving coal coke gasification reactivity
Technical Field
The invention belongs to the technical field of catalytic gasification of coal, relates to a multi-element gasification agent crushed coal pressure gasification process, and particularly relates to a method for improving the gasification reaction rate of the multi-element gasification agent and coal tar in the multi-element gasification agent crushed coal pressure gasification process.
Background
Coal gasification is a tap for clean conversion of coal and is one of important ways for developing modern coal chemical technology. At present, the synthetic natural gas made from coal becomes a new generation coal chemical engineering project preferentially developed in China, and the key of the natural gas made from coal is the selection of a coal gasification technology.
Compared with the entrained-flow bed gasification technology and the moving bed pressurized liquid-state slagging gasification technology, the moving bed pressurized solid-state ash discharge gasification technology has become the most competitive coal gasification technology for the coal-to-synthetic natural gas by virtue of the characteristics of low investment cost, low power consumption, mature technology, stable operation, inherent advantages in the aspect of synthetic natural gas and the like.
However, pressurized solid ash-discharging gas chemical industry in moving bedIn the process, excessive steam is needed to be introduced to reduce the furnace temperature in order to ensure dry ash discharge, so that a large amount of phenol-containing wastewater is generated. In addition, the coal gas is washed by low-temperature methanol to obtain CO2The concentration is high, carbon sources are wasted when the carbon source is directly discharged into the air, and the requirements of energy conservation and emission reduction are not met.
Introducing CO2The coal coke is returned to the furnace as a gasifying agent to replace partial steam, so that the coal coke and the multi-element gasifying agent (steam plus CO) are realized2) The gasification reaction of (3) can solve the above problems well. The method can utilize CO to the maximum extent2And the advantages of water saving, emission reduction and pollution-free high-efficiency crushed coal solid slag discharging and pressurizing gasification are realized.
Due to coal coke and CO2Reactivity of gasification comparing char with H2Low reactivity of O gasification, CO2The return to the furnace will affect the gasification reactivity of the char to some extent and even reduce the gasification reaction rate. Catalytic coal gasification has the advantage of increasing the rate of the gasification reaction while reducing the temperature of the gasification reaction.
The alkaline earth metal calcium has the characteristic of catalyzing the coal coke and the multi-element gasifying agent to generate a synergistic effect through gasification reaction, and the characteristic can improve the reaction rate of the coal coke and the multi-element gasifying agent to a certain extent. However, calcium is easy to sinter, and the catalytic ability of calcium is reduced along with the increase of the using times and the increase of the gasification temperature, so that the catalytic gasification reaction rate is reduced. Therefore, it is very important to find a substance that can inhibit the sintering phenomenon of calcium in the catalytic gasification reaction process, and to use it together with calcium as a composite catalyst to catalyze the gasification reaction of coal char and a multi-element gasification agent, so as to improve the stability of calcium and further improve the gasification reaction.
Disclosure of Invention
The invention aims to provide a method for improving the coal coke gasification reactivity in a coal catalytic gasification reaction process, which is used for a multi-element gasification agent crushed coal pressurized gasification process by loading a low-content calcium-containing precursor and a low-content sodium-containing precursor on raw coal so as to improve the coal coke gasification reactivity and realize the high-efficiency utilization of coal resources.
The method for improving the coal coke gasification reactivity is to add calcium carbonate and sodium carbonate into raw coal, so that the calcium carbonate and the sodium carbonate are loaded on the raw coal to prepare the calcium-sodium-loaded coal.
Wherein the calcium and sodium loaded coal contains 1.25-2.5% of calcium carbonate and 0.4-1% of sodium carbonate by mass.
Preferably, the invention adopts an impregnation method to load the calcium carbonate and the sodium carbonate on raw coal.
Specifically, the calcium carbonate, the sodium carbonate and the raw coal are mixed, added with water, mixed and stirred uniformly, and dried to prepare the calcium-sodium-loaded coal.
Or mixing the calcium carbonate and the sodium carbonate to prepare a solution, adding the raw coal, uniformly mixing, and drying to obtain the calcium-sodium-loaded coal.
In consideration of the source and cost of the raw materials, the calcium carbonate added in the invention can be limestone, and the sodium carbonate can be soda powder.
At the gasification temperature of the coal catalytic gasification reaction, calcium carbonate is converted into calcium oxide catalytic active components, and sodium carbonate is converted into metal sodium or sodium oxide catalytic active components.
In the process of coke and multi-element gasifying agent (H)2O+CO2) When the generated gasification reaction is catalyzed, the calcium can play a strong catalytic role, so that a synergistic effect is generated, and the reaction rate of the coal coke and the gasification of the multi-element gasification agent is far higher than that of the coal coke and the single gasification agent (H)2O or CO2) The reaction rate of gasification. However, the activity of calcium-catalyzed gasification reaction decreases with the increase of the cycle number, and calcium is sintered at a higher temperature, so that the catalytic activity is reduced, and the degree of synergistic effect is reduced or even disappears. Due to the fluidity of sodium during the catalytic gasification reaction, the addition of sodium can improve the stability and anti-sintering capability of calcium to a certain extent, thereby further improving the degree of synergistic effect at higher temperature. Meanwhile, compared with a single gasifying agent, the gasification reactivity of the coal coke in the multi-element gasifying agent is improved most obviously by adding the sodium under the premise of the existence of the calcium.
In the prior art, the better catalytic effect is generally ensured by increasing the addition amount of the catalyst, and the addition amount of the catalyst is usually required to be 5% or even 10% (the metal in the catalyst accounts for the percentage of the coal sample). The amount of the supported catalyst is small, the mass fraction of calcium carbonate contained in the calcium-sodium-loaded coal is 1.25-2.5% (the mass fraction of calcium is 0.5-1%), the mass fraction of sodium carbonate is 0.4-1% (the mass fraction of sodium is 0.2-0.5%), and the addition amount of the catalyst is only about 1%, so that an ideal catalytic effect can be achieved. Therefore, the cost is saved, the method is economical and reliable, and meanwhile, the corrosion degree of the furnace wall of the gasification furnace caused by the lower loading amounts of alkali metal and alkaline earth metal is extremely small.
Therefore, the invention innovatively provides that limestone and soda ash are loaded on coal by adopting an impregnation method to prepare the calcium-sodium-loaded coal. The invention can improve the gasification reactivity of the multi-element gasification agent used for the coal coke in the crushed coal pressure gasification process and can further promote the degree of synergistic effect at higher temperature. The invention has certain promotion effect on the development and development of the fixed bed crushed coal pressurization dry ash discharge coal gasification technology by using the multi-element gasification agent, and has better application prospect and economic benefit.
Drawings
FIG. 1 is a carbon conversion curve for the catalytic coal gasification reaction of example 1 at 800 ℃.
FIG. 2 is a carbon conversion curve for the catalytic coal gasification reaction of example 1 at 900 ℃.
Fig. 3 is a carbon conversion curve for the catalytic coal gasification reaction of example 2.
Fig. 4 is a carbon conversion curve for the catalytic coal gasification reaction of example 3.
Fig. 5 is a carbon conversion curve for the catalytic coal gasification reaction of example 4.
Detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, which should not be construed as limiting the invention in any way. Any modification or change which can be easily made by a person skilled in the art without departing from the technical solution of the present invention will fall within the scope of the claims of the present invention.
Example 1: gasification experiment of delimed wucaiwan coal.
The Wucaiwan coal is a kind of long flame coal rich in inertinite from the Wucaiwan area of Xinjiang, and its ash component is characterized by high calcium, high sodium and low clay mineral matter. A quartering method is adopted to obtain a multicolored bay raw coal sample, the multicolored bay raw coal sample is crushed, ground and screened, and then the coal sample with the particle size smaller than 0.178mm is selected for experiment.
Raw coal from bay was acid washed with HCl and HF to remove minerals. Firstly, a coal sample and 6mol/L HCl are mixed in a beaker according to the proportion of 1g/10mL, the mixture is stirred for 12 hours at room temperature, the mixed solution of the coal sample and the HCl is filtered, and the filtered coal sample is washed by deionized water until the filtrate is neutral. Subsequently, the HCl-washed coal sample was mixed with 7.6mol/L HF at a ratio of 1g/10mL, and the above operation was repeated. The resulting demineralized coal was dried in an oven and designated as delimed confetti (WCWD).
Weighing 1g of delimed multicolored bay coal, 0.025g of calcium carbonate and 0.011g of sodium carbonate into a beaker, adding deionized water until the solid sample is completely immersed, stirring for 12 hours at room temperature, drying to prepare the delimed multicolored bay coal (1% Ca-0.5% Na-WCWD) loaded with calcium and sodium, and storing in a dryer.
The calcium-sodium-loaded deliming multicolored bay coal and the multi-element gasification agent (H) are mixed by using a multifunctional integrated thermal analyzer NETZSCH STA 449F 32O+CO2) The generated gasification reaction is subjected to a gasification reactivity test, and the calcium-sodium-loaded coal and H are respectively subjected to reaction2O or CO2The reactivity of the gasification of a single gasifying agent is used as a comparison.
The gasification experimental procedure was as follows: weighing 10mg of coal sample with the particle size of less than 0.178mm, uniformly spreading the coal sample on a flat-bottom crucible, respectively heating to 800 ℃ and 900 ℃ at the heating rate of 10 ℃/min under the condition of 40mL/min argon, introducing 200mL/min of multi-element gasifying agent for gasification reaction, wherein the component of the multi-element gasifying agent is 66.7% H2O+33.3%CO2. The sample mass was recorded every 2s during the reaction.
Under the same conditions, the temperature of the mixture is controlled,are respectively represented by H2O and CO2The gasification reaction was carried out for the gasifying agent and the mass of the sample during the reaction was recorded.
The calculation method of the carbon conversion rate in the coal gasification reaction process comprises the following steps:
Figure DEST_PATH_IMAGE001
。
wherein the content of the first and second substances,
Figure DEST_PATH_IMAGE002
refers to the mass of the coal sample before the gasification reaction begins,
Figure DEST_PATH_IMAGE003
refers to the mass of the sample at the reaction time t,
Figure DEST_PATH_IMAGE004
refers to the mass of ash after the reaction is completed.
The gasification reactivity of the coal sample is expressed by an average specific gasification reaction rate, and the calculation method is as follows:
Figure DEST_PATH_IMAGE005
。
wherein the content of the first and second substances,
Figure DEST_PATH_IMAGE006
represents the average specific gasification reaction rate (min)-1），
Figure DEST_PATH_IMAGE007
Which is indicative of the rate of the gasification reaction,
Figure DEST_PATH_IMAGE008
representing the carbon conversion at reaction time t.
The carbon conversion rate is selected from 20% to 80%, and the following formula is obtained by integrating the following formula:
Figure DEST_PATH_IMAGE009
。
wherein
Figure DEST_PATH_IMAGE010
Representing the time taken for carbon conversion to reach 80% from 20%.
At the same time, to compare the char with H2O+CO2The gasification reaction process of the multi-element gasifying agent and the difference between the gasification reaction process of the coal coke and the single gasifying agent
Figure DEST_PATH_IMAGE011
And
Figure DEST_PATH_IMAGE012
a comparison was made. Wherein
Figure 695614DEST_PATH_IMAGE011
The experimental value of the average specific gasification reaction rate in the gasification reaction process of the coal coke and the multi-element gasification agent,
Figure 675071DEST_PATH_IMAGE012
the calculation value of the average specific gasification reaction rate in the gasification reaction process of the coal coke and the multi-element gasifying agent is as follows:
Figure DEST_PATH_IMAGE013
。
in the formula of the calculation, the calculation formula,
Figure DEST_PATH_IMAGE014
which represents the average specific gasification reaction rate of the coal coke and steam gasification reaction process,
Figure DEST_PATH_IMAGE015
refers to coke and CO2Average specific gasification reaction rate of the gasification reaction process. When in use
Figure 205541DEST_PATH_IMAGE011
/
Figure 413800DEST_PATH_IMAGE012
>1, it meansThe coal coke and the multi-element gasifying agent have synergistic effect in the process of gasification reaction, and
Figure 290489DEST_PATH_IMAGE011
/
Figure 5895DEST_PATH_IMAGE012
the larger the value, the more pronounced the synergistic effect.
In addition, Δ K represents the difference between the reactivity of the Ca-Na-coal and the reactivity of the Ca-coal when gasification is performed under the same gasification agent ratio, and the calculation formula is as follows:
Figure DEST_PATH_IMAGE016
。
the larger Δ K indicates that the degree of improvement in gasification reactivity by the addition of sodium is larger in the presence of calcium.
The final experimental results are shown in fig. 1, fig. 2 and table 1.
Figure DEST_PATH_IMAGE017
As shown in FIG. 1 and FIG. 2, the coal of deliming color Bay loaded with 1% calcium and 0.5% sodium is mixed with H at the gasification temperature of 800 ℃ and 900 ℃2O and CO2The curves of carbon conversion rate in the reaction of the multi-element mixed gasification agent are all positioned between the curve and H2O or CO2Carbon conversion curve of gasification reaction alone, i.e. coke and H2In the gasification of O, CO2The introduction of (2) does not lead to the reduction of the gasification reaction rate, but greatly improves the gasification reaction rate, and shows a synergistic effect.
In Table 1, the average specific gasification reaction rates of 1% calcium-loaded deashed multicolored bay coal and 1% calcium +0.5% sodium-loaded deashed multicolored bay coal at different ratios of gasifying agents are compared
Figure DEST_PATH_IMAGE018
/
Figure DEST_PATH_IMAGE019
The magnitude of the value. As can be seen,the addition of sodium in the calcium-sodium-loaded deliming multicolored bay coal improves the gasification reactivity of the coal coke to a great extent, and the synergistic effect of the gasification reaction of the coal coke and the multi-element mixed gasification agent is further enhanced even if the addition of sodium is not at 800 ℃ ((
Figure 23661DEST_PATH_IMAGE018
/
Figure 35611DEST_PATH_IMAGE019
There is no major difference), but the addition of sodium leads to the most obvious improvement of the gasification reaction rate (expressed by delta K) when the coal coke and the multi-element gasification agent are gasified compared with the single gasification agent. In addition, the addition of Na reduces the sintering degree of Ca, so that the strong synergistic effect capability is still shown at a higher temperature (900 ℃).
Example 2: gasification experiment of deashing tin allied coal.
According to the method of example 1, a raw coal sample of the Nengguo (a lignite rich in vitrinite components and having an ash component characterized by a high clay mineral (> 50%)) was obtained by a quartering method, and after crushing, grinding and screening, a coal sample having a particle size of less than 0.178mm was selected for experiments. The deashed stannum allied coal (XMD) is prepared by acid washing and deashing, and then the deashed stannum allied coal (1 percent of Ca-0.5 percent of Na-XMD) loaded with calcium and sodium is prepared by adopting an impregnation method (the mass ratio of the deashed stannum allied coal to the calcium carbonate and the sodium carbonate is 100: 2.5: 1).
The gasification reactivity test of the deashed tin allied coal loaded with calcium and sodium is also carried out on a multifunctional comprehensive thermal analyzer NETZSCHRSTA 449F 3, the gasification experimental process and the selected gasification agent proportion are the same as those in example 1, and the selected gasification temperature is 800 ℃.
The carbon conversion rate is calculated by adopting the formula (1), the gasification reactivity of the coal coke is represented by the average specific gasification reaction rate calculated by the formula (3), and the strength of synergistic effect generated during the gasification reaction of the coal coke and the multi-element gasifying agent is used
Figure 766806DEST_PATH_IMAGE018
/
Figure 573219DEST_PATH_IMAGE019
Is shown as
Figure 327549DEST_PATH_IMAGE018
/
Figure 126878DEST_PATH_IMAGE019
>1, indicating that a synergistic effect is generated, wherein the larger the value of the synergistic effect is, the more obvious the synergistic effect is, wherein
Figure 463312DEST_PATH_IMAGE019
The calculation is performed by equation (4). In addition, Δ K represents the difference between the reactivity of 1% Ca-0.5% Na-XMD and 1% Ca-XMD when gasification is carried out under the same gasifying agent ratio, and the calculation formula adopts formula (5). The larger Δ K indicates that the degree of improvement in gasification reactivity by the addition of sodium is larger in the presence of calcium. The specific calculation results are shown in fig. 3 and table 2.
Figure DEST_PATH_IMAGE020
In FIG. 3, the calcium and sodium-loaded deashed Sn-bearing coal also shows a remarkable synergistic effect when being gasified with the multi-element mixed gasification agent, and is specifically represented by that the deashed Sn-bearing coal loaded with 1% of calcium and 0.5% of sodium is gasified with H2O and CO2The curves of carbon conversion rate in the reaction of the multi-element mixed gasification agent are all positioned between the curve and H2O or CO2Carbon conversion curve of gasification reaction alone, i.e. coke and H2In the gasification of O, CO2The introduction of (2) does not lead to the reduction of the gasification reaction rate, but greatly improves the gasification reaction rate, and shows a synergistic effect. This can also be derived from the average specific gasification reaction rates of calcium-loaded and calcium-sodium loaded deashed tin coal in Table 2
Figure 768523DEST_PATH_IMAGE018
/
Figure 10148DEST_PATH_IMAGE019
Magnitude of valueTo obtain: for calcium sodium loaded deliming tin allied coal, it
Figure 92462DEST_PATH_IMAGE018
/
Figure 548982DEST_PATH_IMAGE019
The value is larger than that of deashed tin allied coal loaded with calcium, and the addition of sodium not only further enhances the synergistic effect of the coal coke and the multi-element gasifying agent during the gasification reaction, but also enhances the reaction rate (expressed by delta K) of the coal coke and the multi-element gasifying agent during the gasification reaction.
Example 3: and (3) carrying out gasification experiments on raw coal of the tin union.
The raw Sn Union coal having a particle size of less than 0.178mm in example 2 was subjected to no deliming treatment, and calcium-sodium-loaded Sn Union coal (1% Ca-0.5% Na-XM) was prepared by the impregnation method as it is (the mass ratio of Sn Union coal to calcium carbonate and sodium carbonate was 100: 2.5: 1). The gasification reactivity test is carried out on a multifunctional integrated thermal analyzer NETZSCH STA 449F 3, the gasification experimental process and the selected gasification agent proportion are the same as those in example 1, and the selected gasification temperature is 800 ℃.
The carbon conversion rate and the average specific gasification reaction rate were also calculated, and the strength of the synergistic effect generated by the gasification reaction of the coal char and the multi-element gasifying agent was compared, and the results are shown in fig. 4 and table 3.
Figure DEST_PATH_IMAGE021
The calcium and sodium loaded tin element raw coal also generates a synergistic effect when being gasified with a multi-element gasifying agent. In FIG. 4, coal char is compared with H2Gasification reaction of O, 1% calcium and 0.5% sodium-loaded raw coal of Sn union and H2O and CO2When multi-element mixed gasification agent reacts, CO2The introduction of (2) does not result in the reduction of the gasification reaction rate, but rather is improved to a certain extent, and a synergistic effect is shown.
And as can be seen from table 3, tin union raw coal loaded with 1% calcium +0.5% sodium is mixed with H2O and CO2When the multi-element mixed gasification agent is reacted,
Figure 946465DEST_PATH_IMAGE018
/
Figure 488436DEST_PATH_IMAGE019
>1, can also indicate that synergistic effects are apparent. In addition, as can be seen from the comparison of Δ K, the addition of sodium makes the gasification reaction rate of the calcium-sodium-loaded raw tin-allied coal when reacting with the multi-element mixed gasification agent be improved most obviously, and the calcium-sodium composite bimetallic catalyst makes the gasification reaction rate of the coal coke when reacting with the multi-element gasification agent be improved obviously.
Example 4: gasification experiments of delimed multicolored bay coal with different calcium and sodium loading.
The delimed pentacolous bay coal with the particle size of less than 0.178mm obtained in example 1 was taken and subjected to impregnation method to obtain delimed pentacolous bay coal (0.5% Ca-0.2% Na-WCWD) loaded with calcium and sodium (the mass ratio of the delimed pentacolous bay coal to the calcium carbonate and the sodium carbonate is 100: 1.25: 0.4). The gasification reactivity test is carried out on a multifunctional comprehensive thermal analyzer NETZSCH STA 449F 3, the gasification experiment process and the selected gasification agent proportion are the same as those in example 1, and the selected gasification temperature is 900 ℃.
The carbon conversion rate is calculated by the formula (1), the gasification reactivity of the coal coke is represented by the average specific gasification reaction rate calculated by the formula (3), and the strength of synergistic effect generated when the coal coke and the multi-element gasifying agent are subjected to gasification reaction is used
Figure 629567DEST_PATH_IMAGE018
/
Figure 940594DEST_PATH_IMAGE019
Is shown as
Figure 712241DEST_PATH_IMAGE018
/
Figure 725196DEST_PATH_IMAGE019
>1, indicating that a synergistic effect is generated, wherein the larger the value of the synergistic effect is, the more obvious the synergistic effect is, wherein
Figure 420751DEST_PATH_IMAGE019
The calculation is performed by equation (4). Similarly, the difference between the reactivity of 0.5% Ca-0.2% Na-WCWD and 0.5% Ca-WCWD when gasification is carried out under the same gasification agent ratio is expressed by delta K, and the calculation formula adopts the formula (5). The larger Δ K indicates that the degree of improvement in gasification reactivity by the addition of sodium is larger in the presence of calcium. The results are shown in FIG. 5 and Table 4.
Figure DEST_PATH_IMAGE022
FIG. 5 is a graph showing the carbon conversion rate of the gasification reaction of 0.5% calcium and 0.2% sodium-loaded delimed colored Bay coal at 900 deg.C, which shows that the delimed colored Bay coal loaded with 0.5% calcium and 0.2% sodium is reacted with H2O and CO2The curves of carbon conversion rate in the reaction of the multi-element mixed gasification agent are all positioned between the curve and H2O or CO2Carbon conversion curve of gasification reaction alone, i.e. coke and H2In the gasification of O, CO2The introduction of (2) does not lead to the reduction of the gasification reaction rate, but greatly improves the gasification reaction rate, and shows a synergistic effect. Therefore, the addition of the calcium and the sodium with lower content can also catalyze the coal coke and the multi-element gasifying agent to generate synergistic effect when gasification reaction is carried out at higher temperature. And as can also be seen from table 4, the addition of sodium makes the gasification reaction rate of the deashed pentacolor bay coal loaded with 0.5% of calcium +0.2% of sodium be improved most obviously when reacting with the multi-component mixed gasification agent, and fig. 5 and table 4 show that the calcium-sodium composite bimetallic catalyst makes the gasification reaction rate (expressed by Δ K) of the coal coke be improved obviously when reacting with the multi-component gasification agent.

Claims (5)

1. For H2O+CO2The method for improving coal coke gasification reactivity by using the multi-element gasification agent crushed coal pressure gasification process comprises the steps of simultaneously adding calcium carbonate and sodium carbonate into raw coal, and loading the calcium carbonate and the sodium carbonate on the raw coal by adopting an impregnation method to form calcium-sodium-loaded coal, wherein the calcium carbonate contained in the calcium-sodium-loaded coal accounts for 1.25-2.5% by mass, and the sodium carbonate accounts for 0.4-1% by mass.
2. For H according to claim 12O+CO2The method for improving the coal coke gasification reactivity by the multi-element gasification agent crushed coal pressure gasification process is characterized in that calcium carbonate, sodium carbonate and raw coal are mixed, added with water, mixed and stirred uniformly, and dried to prepare the calcium-sodium-loaded coal.
3. For H according to claim 12O+CO2The method for improving the coal coke gasification reactivity by the multi-element gasification agent crushed coal pressure gasification process is characterized in that calcium carbonate and sodium carbonate are mixed to prepare a solution, raw coal is added to be uniformly mixed, and the calcium-sodium-loaded coal is obtained by drying.
4. For H according to claim 12O+CO2The method for improving the coal coke gasification reactivity by the multi-element gasification agent crushed coal pressure gasification process is characterized in that the calcium carbonate uses limestone.
5. For H according to claim 12O+CO2The method for improving the coal coke gasification reactivity by the multi-element gasification agent crushed coal pressure gasification process is characterized in that soda powder is used as the sodium carbonate.
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