CN110694695B - Catalyst loading method, catalyst loading unit and system - Google Patents
Catalyst loading method, catalyst loading unit and system Download PDFInfo
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- CN110694695B CN110694695B CN201911090125.7A CN201911090125A CN110694695B CN 110694695 B CN110694695 B CN 110694695B CN 201911090125 A CN201911090125 A CN 201911090125A CN 110694695 B CN110694695 B CN 110694695B
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Abstract
The invention provides a catalyst loading method, a catalyst loading unit and a system. The method comprises the following steps: s1, feeding the pretreated raw coal into a catalyst loading unit, and performing negative pressure pumping treatment on the catalyst loading unit; s2, introducing a catalyst into the catalyst loading unit, and then pressurizing the catalyst loading unit; and S3, finishing the catalyst loading, and outputting the raw coal loaded with the catalyst from the catalyst loading unit. The scheme provided by the invention effectively solves the problems that in the coal utilization process of the existing catalytic gasification process, the catalyst is not uniformly loaded and is not tightly combined with coal, the discrete catalyst is easy to react with mineral matters in ash to cause catalyst inactivation, and the discrete catalyst reacts with alkaline mineral matters in ash to form low-temperature eutectic substances in the gasification process to cause slag bonding in the gasification furnace. Effectively realizes the high-efficiency, uniform and dispersed loading of the catalyst.
Description
Technical Field
The invention relates to the field of coal use, in particular to a catalyst loading method, a catalyst loading unit and a catalyst loading system.
Background
Chinese coal resources are rich, and coal keeps a high proportion in energy consumption in China. The coal catalytic gasification process is an important way for realizing clean and efficient conversion of coal. The catalytic gasification process needs to firstly carry out catalyst loading and drying treatment on pulverized coal which is crushed and sieved and has a proper particle size, so as to obtain a qualified furnace coal raw material.
Most of the catalysts adopted in the catalytic gasification process are potassium carbonate, and the prior art is to dip the catalyst aqueous solution on the coal powder at normal temperature and normal pressure. The uneven distribution of coal quality and mineral substances on single coal dust particles and different particles leads to uneven distribution of the catalyst in the loading mode, the catalyst is difficult to enter the pore canal inside the coal quality, the contact between the catalyst and the coal quality is not tight, the catalyst is easy to separate from the coal particles after entering a gasification furnace, and the poor contact leads to great reduction of catalytic activity; in addition, the discrete catalyst is easy to react with the coal ash to generate salt without catalytic action in the gasification process, and is easy to react with minerals such as calcium, magnesium, iron, sodium and the like in the coal ash to generate low-temperature eutectic substances, so that slagging and stopping in the gasification furnace are caused.
Therefore, if a new catalyst loading method and a new catalyst loading system can be developed, the effective and uniform loading of the catalyst on the coal quality is enhanced, the content of the discrete catalyst which is inefficiently mixed with the coal particles is reduced, the inactivation probability of the catalyst in the raw material furnace entering the furnace is greatly reduced, the catalytic activity of the catalyst is improved, and the slagging risk of the gasification furnace caused by the large-amount combination reaction of the mineral substances is reduced.
Disclosure of Invention
The invention aims to provide a catalyst loading method, a catalyst loading unit and a catalyst loading system, which aim to solve the problem of uneven catalyst loading in the coal catalytic gasification process.
In order to achieve the above object, the present invention provides, in a first aspect, a method for supporting a catalyst, comprising the steps of:
s1, feeding the pretreated raw coal into a catalyst loading unit, and performing negative pressure pumping treatment on the catalyst loading unit;
s2, introducing a catalyst into the catalyst loading unit, and then pressurizing the catalyst loading unit;
and S3, finishing the catalyst loading, and outputting the raw coal loaded with the catalyst from the catalyst loading unit.
Optionally, the pressure range of the negative pressure pumping treatment is-150 KPa to-20 KPa.
Optionally, the pressure range of the negative pressure pumping treatment is-70 KPa to-50 KPa.
Alternatively, in S2, steam is introduced simultaneously with the introduction of the catalyst into the catalyst supporting unit.
Optionally, the steam is introduced in an amount sufficient to maintain the gas-liquid two-phase equilibrium state in the catalyst loading unit all the time.
Optionally, in S1, the negative pressure pumping process is performed at ambient temperature;
in S2, the mass of the catalyst introduced into the catalyst supporting unit is 3-15% of the mass of the pretreated raw coal fed in S1.
Optionally, in S2, the set pressure range of the pressurization treatment is 0.1-0.5MPa, and the pressurization medium is CO2。
Optionally, in S2, after introducing the catalyst into the catalyst supporting unit, before the pressurizing the catalyst supporting unit, the method further includes: stirring the pretreated raw coal, and standing for 10-30min after stirring.
Optionally, before the S1, the method further includes: s0, performing deliming treatment on the pretreated raw coal;
the deashing treatment comprises the following steps: feeding the pretreated raw coal into a pretreatment unit, and continuously introducing water and CO into the pretreatment unit at a certain flow rate2Gas, make CO2And (3) performing solid-liquid separation treatment after the concentration of the coal in the aqueous solution reaches a supersaturated state and the coal is continuously stirred for a certain time to obtain the pre-treated raw coal after the ash removal treatment, wherein the pre-treated raw coal after the ash removal treatment is sent into the catalyst loading unit in the S1.
The invention provides a catalyst loading unit, which comprises negative pressure pumping equipment, a box body and a stirring device arranged in the box body, wherein the negative pressure pumping equipment is communicated with the box body and is used for pumping negative pressure to the box body; the box body is provided with a catalyst solution inlet, a raw coal outlet and a pressurizing inlet;
The catalyst solution inlet is used for inputting catalyst solution into the box body,
the raw coal inlet is used for inputting raw coal into the box body,
the raw coal outlet is used for discharging the raw coal in the box body,
the pressurizing inlet is used for inputting pressurizing media to the box body so as to pressurize the box body.
Optionally, the box body is further provided with a steam inlet, and the steam inlet is used for inputting steam into the box body;
the catalyst solution inlet and the raw coal inlet are positioned on the same side of the box body, and the steam inlet and the catalyst solution inlet are positioned on different sides of the box body.
The invention also provides a catalyst loading system, which comprises a crushing unit, a raw coal pretreatment unit, a filtering unit, the catalyst loading unit and a drying unit which are sequentially communicated;
the device comprises a crushing unit, a raw coal pretreatment unit, a filtering unit, a catalyst loading unit and a drying unit, wherein the crushing unit is used for crushing raw coal into raw coal meeting the requirement of particle size, the raw coal pretreatment unit is used for performing deliming treatment on the raw coal, the filtering unit is used for performing solid-liquid separation on solid and liquid after deliming, the catalyst loading unit is used for loading a catalyst on the pretreated raw coal, and the drying unit is used for drying the pretreated raw coal.
The scheme provided by the invention effectively solves the problems that in the coal utilization process of the existing catalytic gasification process, the catalyst is not uniformly loaded and is not tightly combined with coal, the discrete catalyst is easy to react with mineral matters in ash to cause catalyst inactivation, and the discrete catalyst reacts with alkaline mineral matters in ash to form low-temperature eutectic substances in the gasification process to cause slag bonding in the gasification furnace. Effectively realizes the high-efficiency, uniform and dispersed loading of the catalyst.
Drawings
FIG. 1 is a flow chart of a method of loading a catalyst in one embodiment of the present invention;
FIG. 2 is a flow chart of a method of loading a catalyst in another embodiment of the present invention;
FIG. 3 is a schematic diagram of a catalyst loading system in accordance with an embodiment of the present invention;
fig. 4 is a schematic diagram of a catalyst loading system in another embodiment of the present invention.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described in detail with reference to the accompanying drawings and examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. The specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
Referring to fig. 1, the present embodiment provides a catalyst supporting method including the steps of:
s1, feeding the pretreated raw coal into a catalyst loading unit, and performing negative pressure pumping treatment on the catalyst loading unit;
s2, introducing a catalyst into the catalyst loading unit, and then pressurizing the catalyst loading unit;
and S3, finishing the catalyst loading, and outputting the raw coal loaded with the catalyst from the catalyst loading unit.
Because the raw coal is provided with the pores or the channels, water or other impurities can easily flow into the pores or the channels, and moisture or impurities remained in some blind holes (closed bottoms of the pores) or closed spaces in the raw coal are difficult to discharge under the normal stirring action, so that the load of the catalyst is influenced.
Therefore, the method effectively solves the problems that in the coal utilization process of the existing catalytic gasification process, the catalyst is not uniformly loaded and is not tightly combined with coal, the discrete catalyst is easy to react with mineral matters in ash to cause catalyst inactivation, and the discrete catalyst reacts with alkaline mineral matters in ash to form low-temperature eutectic substances in the gasification process to cause slag bonding in the gasification furnace. Effectively realizes the high-efficiency, uniform and dispersed loading of the catalyst and improves the catalytic activity of the catalyst.
In a specific embodiment, the pressure range of the negative pressure pumping treatment is-150 KPa to-20 KPa, and preferably, the pressure range of the negative pressure pumping treatment is-70 KPa to-50 KPa.
Further, in S2, steam is introduced into the catalyst-supporting means together with the catalyst, and the steam temperature is controlled to 103 to 150 ℃ such as 105 ℃, 106 ℃, 120 ℃, 130 ℃ and the like. Preferably, the steam is introduced in an amount which is sufficient to keep the inside of the catalyst loading unit in a gas-liquid two-phase equilibrium state all the time, so as to ensure that the pretreated raw coal is fully contacted with the catalyst in the solution in the gas-liquid two-phase state. Specifically, the temperature in the catalyst loading unit rises with the input of steam, the gas-liquid two-phase state is achieved in the catalyst loading unit, the steam input is stopped to avoid the condition that the temperature is too high to enable the inside of the catalyst loading unit to be in a complete gas-phase state, and when the temperature in the catalyst loading unit is reduced to the point that the gas-liquid two-phase balance is difficult to maintain, the steam is input into the catalyst loading unit again to enable the temperature in the catalyst loading unit to be always maintained in the gas-liquid two-phase balanced temperature range in order to avoid the inside of the catalyst loading unit to be in a complete liquid-phase state.
The catalyst and the steam are synchronously input, so that a catalyst solution can efficiently and quickly enter a raw coal particle pore channel, the adsorption capacity is increased, and particularly, catalyst solution inlets can be formed in the top and the side wall of the equipment to spray the catalyst solution on coal dust particles moving under the stirring of a central stirring device in the equipment; the steam is selectively entered from the steam inlets arranged at the bottom and the side wall of the device. And controlling the temperature of the catalyst loading unit to keep the internal part in a two-phase equilibrium state, wherein the temperature is the corresponding saturation temperature under the operation pressure of the device. The pretreated raw coal is fully contacted with the catalyst in the solution under the gas-liquid two-phase state, the surface areas of inner and outer pore passages of the pulverized coal particles are increased under the action of steam, and the number of oxygen-containing functional groups on the surface of the coal is increased, so that the K ions in the catalyst solution are favorably exchanged to the surface of the coal, and the high-efficiency, uniform and dispersed load of the catalyst is realized.
In this embodiment, before introducing the catalyst and the steam into the catalyst supporting unit, the catalyst supporting unit may be returned to the atmospheric pressure, and then the catalyst and the steam may be introduced into the catalyst supporting unit; the mode can ensure the stability of the input of the catalyst and steam and is beneficial to the formation of a gas-liquid two-phase state. Of course, the catalyst and the steam may be directly introduced into the catalyst supporting unit when the catalyst supporting unit is in a negative pressure state, and the pressure inside the catalyst supporting unit is gradually increased in the introduction process.
In a specific embodiment, in S1, the negative pressure pumping process is performed at ambient temperature; in S2, the mass of the catalyst introduced into the catalyst supporting unit is 3-15% of the mass of the pretreated raw coal fed in S1. At this ratio, it is possible to ensure that the catalyst is fully utilized.
In a specific embodiment, in S2, the pressurizingThe set pressure range of the treatment is 0.1-0.5MPa, and the pressurizing medium is CO2. In the pressurizing process, steam is converted into water, meanwhile, the solubility of the catalyst in the solution is increased, part of the catalyst which is not in full contact with coal particles is dissolved into water, and the catalyst solution is pressed into the pore canal of the raw coal powder to a certain extent under pressurization, so that the catalyst can reach the maximum adsorption quantity inside and outside the raw coal particles, and the efficient and uniform loading of the catalyst on the coal particles is enhanced.
Preferably, in S2, after introducing the catalyst into the catalyst supporting unit, before the pressurizing the catalyst supporting unit, the method further includes: stirring the pretreated raw coal, and standing for 10-30min after stirring. The stirring can promote the catalyst and the coal particles to be fully mixed, which is beneficial to the uniformity of the catalyst load, and during the standing period, the catalyst and the coal particles are also beneficial to be fully mixed according to the molecular dynamics theory.
Referring to fig. 2, in order to achieve better loading of the pulverized coal catalyst, before S1, the method further includes: and S0, performing deashing treatment on the pretreated raw coal.
Specifically, the deliming treatment comprises: feeding the pretreated raw coal into a pretreatment unit, and continuously introducing water and CO into the pretreatment unit at a certain flow rate2Gas, make CO2And (3) performing solid-liquid separation treatment after the concentration of the coal in the aqueous solution reaches a supersaturated state and the coal is continuously stirred for a certain time to obtain the pre-treated raw coal after the ash removal treatment, wherein the pre-treated raw coal after the ash removal treatment is sent into the catalyst loading unit in the S1.
In the pretreatment unit, water and CO are continuously introduced2And forming an acidic environment, dissolving and removing water-insoluble inorganic mineral substances such as calcium and magnesium carbonate and sulfate in the high-ash coal, and simultaneously replacing organic metal elements in the high-ash coal, which are combined with coal surface functional groups such as hydroxyl and carboxyl, by ion exchange with hydrogen ions in the acidic environment to dissolve in the solution and further remove the organic metal elements. The deashing treatment can remove impurities in the pretreated raw coal, increase pore passages of coal particles, reduce ash content and provide convenience for subsequent catalyst loading.
Based on the same inventive concept as the catalyst loading method, the embodiment also provides a catalyst loading unit, which comprises negative pressure pumping equipment, a box body and a stirring device arranged in the box body, wherein the negative pressure pumping equipment is communicated with the box body and used for pumping negative pressure to the box body; the box body is provided with a catalyst solution inlet, a raw coal outlet and a pressurizing inlet; the catalyst solution inlet is used for inputting a catalyst solution into the box body, the raw coal inlet is used for inputting raw coal into the box body, the raw coal outlet is used for discharging the raw coal in the box body, and the pressurizing inlet is used for inputting a pressurizing medium into the box body so as to pressurize the box body. The catalyst loading unit is provided with a negative pressure pumping device and a pressurizing inlet, and can realize negative pressure pumping operation and pressurizing operation on the box body, so that the uniformity of catalyst loading can be increased when the catalyst loading is carried out on raw coal.
Wherein the negative pressure pumping equipment can be vacuum pump, steam extractor, etc., and the pressurizing medium can be CO2。
Preferably, the box body is further provided with a steam inlet, and the steam inlet is used for inputting steam into the box body; therefore, the steam is introduced into the box body while the catalyst is input into the box body, and the box body is in a gas-liquid two-phase balanced state.
In a specific embodiment, the catalyst solution inlet and the raw coal inlet are located on the same side of the tank, and the steam inlet and the catalyst solution inlet are located on different sides of the tank. This spatial positioning enables the steam to be thoroughly mixed with the catalyst solution during the feed process.
Further, the present embodiment also provides a catalyst loading system, referring to fig. 3, the catalyst loading system includes a crushing unit, a raw coal pretreatment unit, a filtering unit, a catalyst loading unit, and a drying unit, which are sequentially communicated; the device comprises a crushing unit, a raw coal pretreatment unit, a filtering unit, a catalyst loading unit and a drying unit, wherein the crushing unit is used for crushing raw coal into raw coal meeting the requirement of particle size, the raw coal pretreatment unit is used for performing deliming treatment on the raw coal, the filtering unit is used for performing solid-liquid separation on solid and liquid after deliming, the catalyst loading unit is used for loading a catalyst on the pretreated raw coal, and the drying unit is used for drying the pretreated raw coal.
The crushing unit comprises a primary crushing unit, a filtering unit and a secondary crushing unit, wherein pulverized coal with the particle size of less than 10mm from a coal mine is firstly subjected to primary crushing treatment in the primary crushing unit and is crushed into fine-particle pulverized coal by adopting a mechanical physical crushing mode;
and (2) screening the pulverized coal subjected to primary crushing in a filtering unit, directly feeding undersize materials with the particle size of less than 2mm into a subsequent raw coal pretreatment unit for raw coal pretreatment, discharging oversize materials with the particle size of more than 2mm through an outlet chute, conveying the oversize materials to a secondary crushing unit through a belt for secondary crushing treatment, crushing the oversize materials until the particle size is less than 2mm, and conveying the oversize materials to the raw coal pretreatment unit through a belt conveyor for pretreatment.
The raw coal pretreatment unit is a pressurized stirring axe, a stirrer is arranged in the middle of the raw coal pretreatment unit, and CO is arranged at the upper part of the device2An outlet and a pulverized coal inlet, wherein the bottom of the device is provided with a water inlet and CO2An inlet, a water overflow outlet arranged at the upper part of the side wall, and a solid solution outlet arranged at the lower part of the side wall. The raw coal pretreatment unit is operated intermittently, CO2And continuously introducing and discharging water, fully contacting the pulverized coal with the solution in the device, opening a valve on an outlet pipeline of the solid solution contained in the lower part of the side wall of the device after a certain retention time, and conveying the solid solution contained in the device to a subsequent filtering unit, wherein the filtering unit can be a vacuum filter, a filter press, a plate and frame filter and the like, and filtering to remove the water solution to obtain wastewater and pretreated raw coal.
Feeding the pretreated raw coal obtained by filtering into a subsequent catalyst loading unit, enabling the catalyst to be in contact with coal dust particles in a gas-liquid two-phase environment, keeping a preset temperature in the device, performing negative pressure pumping treatment, then recovering atmospheric pressure, performing pressurization treatment on the catalyst loading unit after a certain retention time, condensing steam in the catalyst loading unit into water, and then discharging wet coal powder loaded with the catalyst to a subsequent drying unit.
The drying unit is used for drying treatment and can adopt a direct heat exchange or indirect heat exchange mode, preferably a rotary dryer, and a plurality of steam heat exchanges are arranged in the rotary dryerA coil pipe, hot steam of a heat medium is introduced into the steam coil pipe, moisture in the coal powder is removed through heat exchange with the wet coal powder in the coil pipe, the removed moisture is taken out through hot carrier gas introduced from one side and is discharged through a hot flue gas outlet, and the hot carrier gas contains CO2The hot flue gas carrying the dust and the water vapor is directly sent to a raw coal pretreatment unit for use; and (3) discharging the furnace coal with the moisture content of less than 5% required by the catalytic gasification process after drying treatment from the bottom of the dryer, and sending the furnace coal into a gasification unit for catalytic gasification reaction.
In addition, the catalyst loading system provided in this embodiment may not be provided with a raw coal pretreatment unit and a filtration unit, that is, the system does not perform deliming treatment on raw coal, as shown in fig. 4.
In order to more fully illustrate the technical effects of the present embodiment, the following examples and comparative examples are further provided.
Selecting certain coal in inner Mongolia area for catalytic gasification process, wherein the coal quality analysis of raw coal is as follows:
the ash content of the coal is about 16 percent, belongs to high ash coal, and is rich in mineral substances such as calcium sulfate, calcium carbonate and iron. The traditional catalytic gasification coal preparation process is adopted for carrying out catalyst loading, namely, raw coal is crushed and screened to obtain coal powder with the particle size of less than 2mm, 10% of potassium carbonate catalyst solution is added at normal temperature and normal pressure, the mixture is stirred and mixed, and then the wet coal powder loaded with the catalyst is dried until the moisture content is less than 5%.
The K loading amount of the coal dust particles with different particle size distributions is analyzed, and the following results are found: the content of K on the small particles is high, the specific surface area of the inner hole of the small particle is large, the content of moisture impurities in the pore channel is low, and functional groups on the surface of the small particle are relatively rich; the content of K on large particles is low, the number of inner holes is small, and the probability of catalyst entering the inner holes in the loading process is low due to high water and impurities in part of inner holes; in addition, discrete catalyst particles that are not sufficiently adsorbed and supported on the pulverized coal are also detected among the pulverized coal particles.
Comparative example:
the furnace coal prepared by the traditional process is introduced into a pressurized fluidized bed gasification furnace, the reaction temperature is controlled to be 750 ℃, the pressure is controlled to be 3.5MPa, the solid phase retention time is 1.5h, and the operation finds that: the temperature field in the furnace is unstable, the lower part of the fluidized bed is subjected to overtemperature slagging, the slag block is sampled and analyzed, the content of K is enriched due to uneven loading of the catalyst, silicates and aluminosilicates of K, Ca and Fe are enriched, and the added potassium carbonate catalyst, especially discrete catalyst particles which are not fully combined with coal, reacts with iron-calcium mineral substances in the coal ash to generate low-temperature eutectic substances, so that slagging of the gasification furnace is caused; . Analyzing the product gas at the outlet of the gasification furnace: the carbon conversion rate was 85% and the methane content was 16%.
Example 1:
the same coal types are adopted to be treated in the catalyst loading system provided by the embodiment, referring to fig. 4, firstly, the coal is crushed into coal powder with the particle size of less than 2mm, the coal powder is sent to a catalyst loading unit, and the micro negative pressure of-70 KPa to-50 KPa and the operation at the ambient temperature are controlled; and (2) spraying catalyst aqueous solution (the concentration of the potassium carbonate catalyst solution is 10 percent, and the catalyst is in a saturated state or a slightly over-saturated state in the catalyst solution) and steam, controlling the temperature of the catalyst loading unit to keep the internal state of a gas-liquid two-phase equilibrium state, wherein the temperature of the steam introduced into the catalyst loading unit is about 105 ℃, the introduction amount is adjusted according to the temperature to be kept by the catalyst loading unit, and the temperature is the corresponding saturation temperature under the operation pressure of the device. The coal powder is fully contacted with the catalyst in the solution in a gas-liquid two-phase state for 10-30min, and then the catalyst loading unit is pressurized at 0.1-0.5MPa, and the pressurizing medium adopts CO2The steam phase is converted into water, meanwhile, the solubility of the catalyst in the solution is increased, part of the catalyst which is not in full contact with the coal particles and is in an effective adsorption supersaturated state is dissolved into water, the catalyst solution is pressed into the pore canal of the coal dust under the pressurization, so that the catalyst can achieve the maximum adsorption capacity inside and outside the coal particles, the high-efficiency uniform loading of the catalyst on the coal particles is enhanced, and then the coal dust loaded with the catalyst wet solution is conveyed to a subsequent drying unit to be dried until the moisture content is less than 5%.
The K content of the coal particles with different particle sizes is detected, the loading amount of the K is relatively uniform, the catalyst is effectively loaded in the surface structure and the internal pore structure of the coal particles, and the discrete catalyst particles are not detected.
Introducing qualified coal loaded with the same amount of catalyst into a pressurized fluidized bed gasification furnace, controlling the reaction temperature at 750 ℃, the pressure at 3.5MPa and the solid-phase retention time at 1.5h, and finding out that: the temperature field in the furnace is even (which indicates that the catalyst is evenly distributed, the place with high catalyst content, the reaction is more sufficient and faster, the temperature can be higher), no local high temperature point exists, the slag discharge is smooth and stable, no slag bonding exists in the furnace, the bed materials in different time periods are sampled, and the K content is analyzed, and the temperature field is relatively stable and even. Analyzing the product gas at the outlet of the gasification furnace: the carbon conversion was 95% and the methane content was 20%.
Example 2:
the present example differs from example 1 in that: a deashing treatment step is added to the pretreated raw coal before it is fed to the catalyst loading unit. With reference to fig. 3, the following is provided:
the same coal types are adopted, firstly, the coal is crushed into coal powder with the particle size of less than 2mm, the coal powder is sent to a raw coal pretreatment unit, and deashing pretreatment is carried out under mild conditions. Continuously introducing water and CO into the raw coal pretreatment unit at a certain flow rate 2Gas, make CO2And when the concentration of the coal in the water solution reaches a supersaturated state, controlling the mass ratio of water to solid-phase pulverized coal in the device to be 5:1-50:1, controlling the pressure in the device to be 0.2-1MPa and the temperature to be 5-50 ℃, continuously stirring, discharging the solid-containing solution to a subsequent filtering unit for solid-liquid separation treatment after 1-3 hours, and obtaining wastewater and pretreated raw coal.
Sending the pretreated raw coal into a catalyst loading unit, and controlling the operation of micro negative pressure of-70 to-50 KPa and ambient temperature; and (3) spraying catalyst aqueous solution (the concentration of the potassium carbonate catalyst solution is 10 percent, and the catalyst is in a saturated state or a slightly over-saturated state in the catalyst solution) and steam, and controlling the temperature of the catalyst loading unit to keep the internal part in a gas-liquid two-phase equilibrium state. The temperature of the steam introduced into the catalyst loading unit is about 105 ℃, the introduction amount is adjusted according to the temperature to be kept by the catalyst loading unit, and the temperature is corresponding to the saturation temperature under the operating pressure of the deviceAnd a temperature. The coal powder is fully contacted with the catalyst in the solution in a gas-liquid two-phase state, the retention time is 10-30min, then the catalyst loading unit is pressurized, the pressure is 0.1-0.5MPa, and the pressurizing medium adopts CO2The steam phase is converted into water, meanwhile, the solubility of the catalyst in the solution is increased, part of the catalyst which is not in full contact with the coal particles and is in an effective adsorption supersaturated state is dissolved into water, the catalyst solution is pressed into the inside of a coal powder pore channel under pressure, so that the catalyst can achieve the maximum adsorption capacity inside and outside the coal particles, the high-efficiency uniform load of the catalyst on the coal particles is enhanced, and then the coal powder loaded with the catalyst wet solution is conveyed to a subsequent drying unit to be dried until the moisture content is less than 5%.
The K content of the coal particles with different particle sizes is detected, the loading capacity of the K is found to be more uniform, the catalyst is effectively loaded in the surface structure and the internal pore structure of the coal particles, and the discrete catalyst particles are not detected.
Introducing qualified coal loaded with the same amount of catalyst into a pressurized fluidized bed gasification furnace, controlling the reaction temperature at 750 ℃, the pressure at 3.5MPa and the solid-phase retention time at 1.5h, and finding out that: the temperature field in the stove is more even (explain that catalyst distributes evenly, and the place that catalyst content is high, reaction take place more abundant more fast, the temperature can be higher), does not have local high temperature point, arranges sediment smooth and easy stability, the stove is not slagging scorification, samples, analysis K content to the bed material of different periods of time, and it is more stable even. Analyzing the product gas at the outlet of the gasification furnace: the carbon conversion was 97% and the methane content was 23%.
From a comparison of the above examples it can be seen that: by adopting the catalyst loading method and the catalyst loading device provided by the embodiment, the problems that in the coal utilization process of the existing catalytic gasification process, the catalyst loading is uneven, the combination with coal quality is not tight, the discrete catalyst is easy to react with mineral matters in ash to cause catalyst inactivation, and the discrete catalyst is easy to slag in a gasification furnace due to the fact that the discrete catalyst reacts with alkaline mineral matters in ash to form low-temperature eutectic substances in the gasification process are solved. The high-efficiency, uniform and dispersed loading of the catalyst is realized, and the catalytic activity of the catalyst is improved.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. A method of loading a catalyst, comprising the steps of:
s1, feeding the pretreated raw coal into a catalyst loading unit, and performing negative pressure pumping treatment on the catalyst loading unit;
s2, introducing a catalyst and steam into the catalyst loading unit at the same time, wherein the introduction amount of the steam is in a state of keeping the gas-liquid two-phase equilibrium in the catalyst loading unit all the time; then pressurizing the catalyst loading unit; controlling the temperature of the steam to be 103-150 ℃; the set pressure range of the pressurization treatment is 0.1-0.5MPa, and the pressurizing medium is CO2；
And S3, finishing the catalyst loading, and outputting the raw coal loaded with the catalyst from the catalyst loading unit.
2. The catalyst loading method according to claim 1, wherein the pressure range of the negative pressure extraction process is-150 KPa to-20 KPa.
3. The catalyst loading method according to claim 2, wherein the pressure range of the negative pressure extraction treatment is-70 KPa to-50 KPa.
4. The catalyst supporting method according to claim 1, wherein in S1, the negative pressure suction treatment is performed at ambient temperature;
in S2, the mass of the catalyst introduced into the catalyst supporting unit is 3-15% of the mass of the pretreated raw coal fed in S1.
5. The method of claim 1, wherein the step of pressurizing the catalyst-supporting member after the step of introducing the catalyst into the catalyst-supporting member in S2 further comprises: stirring the pretreated raw coal, and standing for 10-30min after stirring.
6. The catalyst loading method according to claim 1, further comprising, before the S1: s0, performing deliming treatment on the pretreated raw coal;
the deliming treatment comprises the following steps: feeding the pretreated raw coal into a pretreatment unit, and continuously introducing water and CO into the pretreatment unit at a certain flow rate 2Gas, make CO2And (3) performing solid-liquid separation treatment after the concentration of the coal in the aqueous solution reaches a supersaturated state and the coal is continuously stirred for a certain time to obtain the pre-treated raw coal after the ash removal treatment, wherein the pre-treated raw coal after the ash removal treatment is sent into the catalyst loading unit in the S1.
7. A catalyst supporting unit for performing the catalyst supporting method according to any one of claims 1 to 6, comprising a negative pressure suction apparatus, a tank, and an agitation device provided in the tank, the negative pressure suction apparatus communicating with the tank for sucking a negative pressure to the tank; the box body is provided with a catalyst solution inlet, a raw coal outlet and a pressurizing inlet; the box body is also provided with a steam inlet, and the steam inlet is used for inputting steam into the box body; controlling the temperature of the steam to be 103-150 ℃;
the catalyst solution inlet is used for inputting catalyst solution into the box body,
the raw coal inlet is used for inputting raw coal into the box body,
the raw coal outlet is used for discharging the raw coal in the box body,
the pressurizing inlet is used for inputting a pressurizing medium to the box body so as to pressurize the box body; the pressurizing pressure is 0.1-0.5MPa, and the pressurizing medium is CO 2。
8. The catalyst support unit of claim 7,
the catalyst solution inlet and the raw coal inlet are positioned on the same side of the box body, and the steam inlet and the catalyst solution inlet are positioned on different sides of the box body.
9. A catalyst loading system is characterized by comprising a crushing unit, a raw coal pretreatment unit, a filtering unit, the catalyst loading unit of claim 7 or 8 and a drying unit which are communicated in sequence;
the crushing unit is used for crushing raw coal into raw coal meeting the requirement of particle size, the raw coal pretreatment unit is used for performing deliming treatment on the raw coal, the filtering unit is used for performing solid-liquid separation on solid and liquid after deliming, the catalyst loading unit is used for loading a catalyst on the pretreated raw coal, and the drying unit is used for drying the pretreated raw coal.
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| JPS5727164A (en) * | 1980-07-24 | 1982-02-13 | Janome Sewing Mach Co Ltd | Method and apparatus for vacuum impregnation |
| CN105396574A (en) * | 2015-11-25 | 2016-03-16 | 杨秋良 | Method for recycling composite coal gasification catalyst |
| CN110075931A (en) * | 2019-04-26 | 2019-08-02 | 新奥科技发展有限公司 | A kind of catalyst carrying method of coal gasification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5727164A (en) * | 1980-07-24 | 1982-02-13 | Janome Sewing Mach Co Ltd | Method and apparatus for vacuum impregnation |
| CN105396574A (en) * | 2015-11-25 | 2016-03-16 | 杨秋良 | Method for recycling composite coal gasification catalyst |
| CN110075931A (en) * | 2019-04-26 | 2019-08-02 | 新奥科技发展有限公司 | A kind of catalyst carrying method of coal gasification |
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