CN116144404A - Coal hydro-gasification furnace system of liquid slag discharging moving bed and hydro-gasification method - Google Patents
Coal hydro-gasification furnace system of liquid slag discharging moving bed and hydro-gasification method Download PDFInfo
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Abstract
The invention belongs to the technical field of coal chemical processing, and discloses a coal hydro-gasification furnace system of a liquid slag removal moving bed and a hydro-gasification method. The gas outlet of the hydro-gasification furnace in the hydro-gasification system is communicated with the gas inlet of a hydrogen membrane separator through a decompression tank, a chilling water washing tower and a gas-liquid separator in sequence, the hydrogen membrane separator is provided with a hydrogen outlet and a methane-rich outlet, wherein the hydrogen outlet of the hydrogen membrane separator is communicated with a second gas inlet and a third gas inlet of the hydro-gasification furnace in two ways, and the liquid outlets of the decompression tank, the chilling water washing tower and the gas-liquid separator are all communicated with a tar collector. The hydro-gasification method can stabilize the product components to be regulated and controlled in the hydro-gasification process of coal, enhance the adaptability of raw materials and the multiple components of products, and has higher methane yield and high light aromatic hydrocarbon (BTX, PCXN) yield.
Description
Technical Field
The invention belongs to the technical field of coal chemical processing, and particularly relates to a coal hydro-gasification furnace system of a liquid slag removal moving bed and a hydro-gasification method.
Background
Energy is an important support for social and economic development. As the world energy production and consumption is large, the development of China will also need more energy sources and generate more emission in the future, and the faced resources and environmental pressure will be larger. In the energy structure of China, the production and consumption of coal are dominant all the time. Therefore, the efficient conversion of carbon and hydrogen elements rich in coal into chemical products with high added value is a core problem of low carbon utilization of modern coal chemical technologies including technologies such as coal-to-methane, coal-to-oil, coal-to-chemical products and the like.
However, the existing coal-to-methane and coal-to-oil technologies mainly convert coal into synthetic gas through a high-temperature high-pressure coal gasification technology and then carry out organic synthesis, so that the overall technology has high energy consumption, high investment and high water consumption. The coal hydro-gasification technology has single product component, can obtain high methane yield, high light aromatic hydrocarbon (BTX, PCXN) yield, high heat efficiency and the like under high temperature and high pressure, and is attracting more and more attention in the technical field of clean coal at home and abroad.
According to the discovery of related similar technologies, in the first and Chinese patent application CN102559310A, a method for preparing hydrocarbons such as natural gas by coal hydro-gasification by using industrial waste gas such as coke oven gas is disclosed, in the process, raw coal is heated to 300 ℃ to generate tar through pyrolysis, and blockage is easy to occur, so that the transportation is not facilitated; in addition, the process cannot obtain products with better quality and ensure the stable operation of the system because the input heat is insufficient to reach the temperature for exciting the hydro-gasification reaction. Secondly, chinese patent application CN108774549A discloses a method for preparing hydrocarbons such as natural gas by using entrained-flow pulverized coal hydro-gasification, the production process is relatively complex, coal is required to be ground to 125-180 um, the subsequent investment is large, the retention time of a coal sample is short, the hydro-gasification reaction is insufficient, meanwhile, the furnace structure is relatively complex, the scale is small, and the amplification characteristic is to be inspected.
Therefore, the development of a liquid slag-removing moving bed coal hydro-gasification furnace, a hydro-gasification system and a hydro-gasification method which have the advantages of high heat efficiency, simple gasification system, good stability, adjustable product composition and better quality is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to solve the technical problems of long process route, large investment, low thermal efficiency, complex gasification system, poor stability, poor product quality and the like of the coal hydro-gasification method in the prior art, and provides a liquid slag-removing moving bed coal hydro-gasification furnace, a hydro-gasification system and a hydro-gasification method, which have the advantages of high thermal efficiency, simple gasification system, good stability, adjustable product composition and better product quality. The liquid slag discharging moving bed coal hydro-gasification furnace, the hydro-gasification system and the hydro-gasification method can stably realize the hydro-gasification process of coal, the product components can be regulated and controlled, the adaptability of raw materials and the multiple properties of products are enhanced, and the yield of methane and the yield of high light aromatic hydrocarbons (BTX and PCXN) in the products are higher.
In order to achieve the above purpose, the invention adopts the following technical scheme: the utility model provides a coal hydro-gasification stove system of liquid sediment moving bed, the gas outlet of hydro-gasification stove is linked together through the air inlet of pipeline with the decompression jar, the gas outlet of decompression jar is linked together through the air inlet of pipeline with the chilling water scrubber, the gas outlet of chilling water scrubber is linked together through the air inlet of pipeline with the gas-liquid separator, decompression jar, chilling water scrubber and gas-liquid separator's liquid export all are linked together with the liquid inlet of tar collector, the gas outlet of gas-liquid separator is linked together through the air inlet of pipeline with the hydrogen membrane separator be provided with hydrogen outlet and rich methane export on the hydrogen membrane separator respectively, the hydrogen outlet of hydrogen membrane separator divide two ways through the pipeline with the second air inlet and the third air inlet of hydro-gasification stove are linked together.
As a further supplementary explanation of the above technical scheme, two pipelines between the hydrogen outlet of the hydrogen membrane separator and the second air inlet and the third air inlet of the hydro-gasifier are respectively provided with a circulating gas compressor for providing conveying power.
As a further supplementary explanation of the above technical scheme, the hydro-gasifier comprises a pressure-resistant steel shell and a refractory material which are integrally cast into a furnace chamber, wherein the refractory material is cast into a furnace chamber, the top and the bottom of the hydro-gasifier are respectively provided with a solid inlet and a solid outlet, the side wall of the hydro-gasifier is respectively provided with a first air inlet, a second air inlet and a third air inlet from bottom to top, the air outlet is arranged on the side wall of the hydro-gasifier and above the third air inlet, the furnace chamber is divided into an oxidized slag layer, a reduction gasification layer, a hydro-gasification methanation layer, a hydro-pyrolysis layer and a drying layer from bottom to top, and the first air inlet, the second air inlet and the third air inlet are respectively arranged in the oxidized slag layer, the hydro-gasification methanation layer and the hydro-pyrolysis layer, and the reduction gasification layer is positioned between the first air inlet and the second air inlet.
As a further supplementary illustration of the above-described solution, an ash collection zone is provided in the furnace chamber below the oxidized slag layer and is in communication with a black water treatment system, wherein the black water treatment system provides circulating chilled water to the ash collection zone for cooling the molten ash.
As a further supplementary explanation of the above technical scheme, the aspect ratio of the hydro-gasification furnace is 10-50.
As a further supplementary explanation of the above technical solution, the ratio of the distance between the first air inlet and the second air inlet in the furnace chamber to the height of the hydro-gasifier is 1/5-1/3; the ratio of the distance between the second air inlet and the third air inlet in the furnace chamber to the height of the hydro-gasification furnace is 1/6-1/4; the distance between the third air inlet and the top of the furnace chamber in the furnace chamber is 1/5-1/3 of the height of the hydro-gasification furnace.
As a further supplementary explanation of the above technical scheme, the included angle between the first air inlet and the axis of the hydro-gasification furnace is 60-90 degrees, which is convenient for feeding the first strand of material into the oxidized slag layer along a specific angle direction.
The hydro-gasification method is carried out by adopting a coal hydro-gasification furnace system of a slag tapping moving bed in the technical scheme, and comprises the following steps:
step 1: adding pulverized coal with the grain diameter of 5-50mm and the water content of less than 5wt% into a furnace chamber from a solid inlet, sequentially and respectively feeding a first material containing high-pressure oxygen and water vapor, a second material containing hydrogen and water vapor and a third material containing hydrogen into an oxidized slag layer, a hydro-gasification methanation layer and a hydro-pyrolysis layer of a hydro-gasification furnace, wherein the operation pressure of the hydro-gasification furnace is 2MPa-10MPa, the relation between oxygen in the first material and the coal feeding amount is 0.2-1Nm < 3 >/kg, the relation between hydrogen in the second material and the coal feeding amount is 0.2-1Nm < 3 >/kg, and the mass flow ratio between hydrogen in the third material and the coal feeding amount is 0-1Nm < 3 >/kg;
step 2: oxygen in the first strand of material in the step 1 undergoes an oxygen-enriched combustion reaction in the oxidized slag layer and the gasified residues in the reduction gasification layer, and water vapor in the first strand of material is used for protecting a nozzle of the first air inlet, so that oxygen-enriched combustion gas products and molten ash are obtained, wherein the temperature of the oxidized slag reaction is 1400-1800 ℃;
step 3: the oxygen-enriched combustion gas product obtained in the step 2 contacts semicoke in the hydro-gasification methanation layer in the reduction gasification layer to carry out gasification reaction, so that the reduction gasification layer gas product and gasification residues are obtained;
step 4: the hydrogen in the second strand of material in the step 1 contacts with the reduced gasification layer gas product and the hydropyrolysis layer pyrolysis semicoke in the step 3 and performs hydro-gasification methanation reaction, so that the hydro-gasification methanation layer gas product and gasification residues are obtained, and the temperature of the hydro-gasification methanation reaction is 600-1200 ℃;
step 5: the hydrogen in the third strand of materials in the step 1 contacts with the coal in the drying layer in the step 4 and carries out a hydropyrolysis reaction to obtain a hydropyrolysis gas product and pyrolysis semicoke, the hydropyrolysis gas product and pyrolysis semicoke are conveyed into a decompression tank through an air outlet to be decompressed to obtain a liquid product and a purified gas, the purified gas is subjected to chilled water washing of a chilled water washing tower and gas-liquid separation of a gas-liquid separator in sequence, the gaseous product and the liquid product are separated through a hydrogen membrane separator to obtain a methane-rich gas and hydrogen, the hydrogen is conveyed into a hydrogasification furnace to be subjected to internal reaction through a second air inlet and a third air inlet under the action of a circulating gas compressor, the methane-rich gas is the obtained product gas, and the liquid product is the liquid oil and water which are uniformly recovered into a tar collector after layering;
wherein the temperature regulation product composition of the hydropyrolysis reaction in the step 5: at above 900 ℃, methane is mainly generated; the temperature is 800-900 ℃, and BTX and PCX can be enriched; the temperature is controlled at 400-600 ℃, and light oil products can be produced in a rich way.
As a further explanation and limitation of the above technical solution, in step 2, the relationship between the oxygen and the coal throughput in the first stream of material must be able to undergo an oxycombustion reaction, and the heat generated by the oxycombustion reaction may enable the coal in the reduction gasification layer to undergo a gasification reaction, where the temperature of the oxidation slag layer reaction exceeds the ash flowing temperature, and mainly performs the following chemical reactions:
CO+O 2 ＝CO 2
as a further explanation and limitation of the above technical solution, in step 3, the reaction of the reduction gasification layer is a gasification reaction of coal, which is a water gas main generation layer, the temperature of the reduction layer is 1000-1300 ℃, and the following chemical reaction is mainly performed:
as further explanation and limitation of the above technical solution, in step 4, the relationship between the amount of hydrogen and water vapor in the second stream of material and the amount of coal treated is that the hydro-gasification methanation reaction can occur under the action of the gas product of the reduction gasification layer, and the mixed material is obtained at the moment that the hydrogen and water vapor in the second stream of material contacts the gas product of the reduction gasification layer and the pyrolysis semicoke of the hydro-pyrolysis layer, and mainly undergoes the following chemical reaction:
CO+3H 2 ＝CH 4 +H 2 O
CO+H 2 O＝CO 2 +H 2 ；
the light oil formation reaction is as follows:
nCO+(2n+1)H 2 ＝C n H 2n+2 +nH 2 O
2nCO+(n+1)H 2 ＝C n H 2n+2 +nCO 2 。
as further explanation and limitation of the above technical solution, in step 5, the hydrogen in the third stream of material is in contact with the gas product of the hydro-gasification methanation layer and the coal of the dry layer to obtain a mixture, and a hydro-pyrolysis reaction occurs, wherein the hydro-pyrolysis layer is a generation layer of pyrolysis tar and pyrolysis gas, and is also a key layer for producing gas-liquid fuel, and organic macromolecules in the coal are thermally decomposed to generate active small molecules, and the hydrocarbon compounds are generated by hydrogen reaction, and mainly undergo the following chemical reactions:
CH x O y +H 2 →C+CO+CH 4 +C m H n +BTX+PCX
CO+3H 2 ＝CH 4 +H 2 O
nCO+(2n+1)H 2 ＝C n H 2n+2 +nH 2 O
C m H n +H 2 ＝C m H n+2 。
compared with the existing technology for preparing methane and oil by coal, the invention has the following advantages:
1. the hydro-gasification system and the hydro-gasification method developed by the invention can stably realize the hydro-gasification process of coal, the product components can be regulated and controlled, the adaptability of raw materials and the multiple components of the product are enhanced, and the yield of methane and the yield of high light aromatic hydrocarbons (BTX and PCXN) in the product are higher.
2. The liquid slag discharging moving bed vaporization furnace designed by the invention has the advantages of high gasification efficiency and less sewage discharge, but the methane content in the coal gas is only 5-7%, and the economy of the process for co-producing methane and light hydrocarbon is to be improved.
3. The hydro-gasification system developed by the invention adopts a high-efficiency coal gasification theory combining moving bed slag-tap gasification and hydro-gasification, and efficiently converts carbon and hydrogen elements in coal into methane and light oil in situ, thereby improving the overall economy of the coal-to-oil and coal-to-methane system. According to measurement and calculation, for the indirect liquefaction coal-to-oil process, the synthesis scale can be reduced by about 1/3, and the energy efficiency of the system is improved by 10-20%.
4. The hydro-gasification system developed by the invention can realize complete non-synthetic methane production through hydrogen recycling in the coal methane production process, the overall energy efficiency is improved by 20-25%, and the investment is reduced by more than 20%. Meanwhile, in the fields of natural gas and oil production from coal, a technical route for efficiently producing the methane-rich light oil from the low-rank coal is created, and the method has the advantages of being simple in process and capable of reducing pollutant emission to the greatest extent, and can promote large-scale efficient conversion and utilization of the low-rank coal.
Drawings
FIG. 1 is a process flow diagram of a hydro-gasification system according to the present invention;
FIG. 2 is a block diagram of a hydrogen adding gasification furnace according to an embodiment of the present invention.
In the figure: the hydrogenation gasification furnace is 10, the decompression tank is 20, the chilling water scrubber is 30, the gas-liquid separator is 40, the tar collector is 50, the hydrogen membrane separator is 60, and the recycle gas compressor is 70.
Wherein the hydro-gasifier structure comprises: the solid outlet is 104, the solid inlet is 105, the air outlet is 106, the furnace chamber is 107, the ash collecting area is 108, the oxidized slag layer is 109, the reduction gasification layer is 110, the hydro-gasification methanation layer is 111, the hydro-pyrolysis layer is 112, and the drying layer is 113.
Detailed Description
In order to further explain the technical scheme of the invention, the specific structure and the dimension of the hydro-gasifier according to the invention are further described through the best embodiment within the scope of protection disclosed in the technical scheme with reference to the accompanying drawings 1 to 2.
As shown in fig. 1 to 2, a liquid slag-discharging moving bed coal hydro-gasification furnace and a hydro-gasification system, wherein the hydro-gasification system mainly comprises a hydro-gasification furnace 10, a decompression tank 20, a chilled water scrubber 30, a gas-liquid separator 40, a tar collector 50 and a hydrogen membrane separator 60. The hydro-gasifier 10 comprises a pressure-resistant steel shell and refractory materials which are integrally cast into a furnace chamber 107, a solid inlet 105 and a solid outlet 104 are respectively arranged on the top and the bottom of the hydro-gasifier 10, a first air inlet 101, a second air inlet 102, a third air inlet 103 and an air outlet 106 are respectively arranged on the side wall of the hydro-gasifier 10 from top to bottom, wherein an included angle between the first air inlet 101 and the axis of the hydro-gasifier 10 is 60-90 degrees, the first air inlet 101 is convenient for feeding the first material into the oxidized slag layer 109 along a specific angle direction, the first air inlet 101 is used for feeding a first material containing oxygen and water vapor into the oxidized slag layer 109, the second air inlet 102 is used for feeding a second material containing hydrogen and water vapor into the hydro-gasifier layer 111, and the third air inlet 103 is used for feeding a third material containing hydrogen into the hydro-pyrolysis layer 112.
In the above embodiments, the internal design structure and the dimensional parameters of the hydro-gasifier are as follows:
we divide the furnace chamber 107 from bottom to top into an ash collection zone 108, an oxidized slag layer 109, a reduced gasification layer 110, a hydro-gasification methanation layer 111, a hydropyrolysis layer 112, a drying layer 113, wherein the ash collection zone 108 is in communication with a black water treatment system and recycled chilled water is provided to the ash collection zone 108 by the black water treatment system for cooling the molten ash. The first air inlet 101, the second air inlet 102 and the third air inlet 103 are respectively arranged in the oxidized slag layer 109, the hydro-gasification methanation layer 111 and the hydro-pyrolysis layer 112, the reduction gasification layer 110 is arranged between the first air inlet 101 and the second air inlet 102, and the drying layer 113 is arranged between the second air inlet 102 and the third air inlet 103.
(II) the height-diameter ratio of the hydro-gasification furnace is 10-50; the ratio of the distance between the first air inlet 101 and the second air inlet 102 in the furnace chamber to the height of the hydro-gasifier 10 is 1/5-1/3; the ratio of the distance between the second air inlet 102 and the third air inlet 103 in the furnace chamber to the height of the hydro-gasifier 10 is 1/6-1/4; the distance between the third air inlet 103 and the top of the furnace chamber in the furnace chamber is 1/5-1/3 of the height of the hydro-gasifier 10.
In the preferred embodiment, the ratio of the height to the diameter of the liquid slag discharging moving bed coal hydro-gasifier is 20, and the ratio of the distance between the first air inlet 101 and the second air inlet 102 in the furnace chamber to the height of the hydro-gasifier 10 is 1/4; the ratio of the distance between the second air inlet 102 and the third air inlet 103 in the furnace chamber to the height of the hydro-gasifier 10 is 1/5; the distance between the third air inlet 103 and the top of the furnace chamber in the furnace chamber is 1/4 of the height of the hydro-gasifier 10, and the included angle between the first air inlet 101 and the axis of the hydro-gasifier 10 is 85 degrees.
The pipeline connection mode of each reaction device in the hydro-gasification system is as follows:
the gas outlet 106 of the hydro-gasifier 10 is communicated with the gas inlet of the decompression tank 20 through a pipeline, the gas outlet of the decompression tank 20 is communicated with the gas inlet of the chilling water scrubber 30 through a pipeline, the gas outlet of the chilling water scrubber 30 is communicated with the gas inlet of the gas-liquid separator 40 through a pipeline, the gas outlet of the gas-liquid separator 40 is communicated with the gas inlet of the hydrogen film separator 60 through a pipeline, the hydrogen film separator 60 is respectively provided with a hydrogen outlet and a methane-rich outlet, the hydrogen outlet of the hydrogen film separator 60 is communicated with the second gas inlet 102 and the third gas inlet 103 of the hydro-gasifier 10 through two paths through a pipeline, and the liquid outlets of the decompression tank 20, the chilling water scrubber 30 and the gas-liquid separator 40 are all communicated with the liquid inlet of the tar collector 50. A recycle gas compressor 70 is disposed on two pipelines between the hydrogen outlet of the hydrogen membrane separator 60 and the second and third air inlets 102 and 103 of the hydrogasification furnace 10, respectively, for providing conveying power.
The hydro-gasification method is carried out by adopting the coal hydro-gasification furnace system of the slag tapping moving bed in the embodiment, and comprises the following steps:
step 1: adding pulverized coal with the particle size of 5-50mm and the water content of less than 5wt% into a furnace chamber 107 from a solid inlet 105, sequentially and respectively feeding a first material containing high-pressure oxygen and water vapor, a second material containing hydrogen and water vapor and a third material containing hydrogen into an oxidized slag layer 109, a hydro-gasification methanation layer 111 and a hydro-pyrolysis layer 112 of the hydro-gasification furnace 10, wherein the operation pressure of the hydro-gasification furnace 10 is 2MPa-10MPa, the relation between oxygen and coal feeding amount in the first material is 0.2-1Nm3/kg, the relation between hydrogen and coal feeding amount in the second material is 0.2-1Nm3/kg, and the mass flow rate ratio between hydrogen and coal feeding amount in the third material is 0-1Nm3/kg;
step 2: oxygen in the first stream of material in the step 1 undergoes an oxygen-enriched combustion reaction in the oxidized slag layer 109 and the gasified residue in the reduction gasification layer 110, and water vapor in the first stream of material is used for protecting a nozzle of the first air inlet 101, so that oxygen-enriched combustion gas products and molten ash are obtained, wherein the temperature of the oxidized slag reaction is 1400-1800 ℃;
step 3: the oxygen-enriched combustion gas product obtained in the step 2 contacts semicoke in the reduction gasification layer 110 and the hydro-gasification methanation layer 111 to carry out gasification reaction, so as to obtain a reduction gasification layer gas product and gasification residues;
step 4: the hydrogen in the second strand of material in the step 1 contacts with the reduced gasification layer 110 gas product and the pyrolysis semicoke of the hydropyrolysis layer 112 in the step 3 and performs hydro-gasification methanation reaction, so that the hydro-gasification methanation layer 111 gas product and gasification residues are obtained, and the temperature of the hydro-gasification methanation reaction is 600-1200 ℃;
step 5: the hydrogen in the third strand of materials in the step 1 contacts with the coal in the drying layer 113 in the step 4 and carries out hydropyrolysis reaction to obtain hydropyrolysis gas products and pyrolysis semicoke, the hydropyrolysis gas products and pyrolysis semicoke are conveyed into a decompression tank 20 through an air outlet 106 to be decompressed to obtain liquid products and purified gas, wherein the purified gas is subjected to chilled water washing in a chilled water washing tower 30 and gas-liquid separation in a gas-liquid separator 40 in sequence, the gaseous products are separated by a hydrogen membrane separator 60 to obtain methane-rich gas and hydrogen, the hydrogen is conveyed into the hydrogasification furnace 10 to carry out internal reference reaction through a second air inlet 102 and a third air inlet 103 under the action of a circulating gas compressor 70, the methane-rich gas is the obtained product gas, and the liquid products are liquid oil products and water after layering and are uniformly recovered into a tar collector 50;
wherein the temperature regulation product composition of the hydropyrolysis reaction in the step 5: at above 900 ℃, methane is mainly generated; the temperature is 800-900 ℃, and BTX and PCX can be enriched; the temperature is controlled at 400-600 ℃, and light oil products can be produced in a rich way.
In step 2, the relationship between the oxygen content and the coal content in the first stream of material must be able to perform an oxycombustion reaction, and the heat generated by the oxycombustion reaction may enable the coal in the reduction gasification layer to perform a gasification reaction, where the temperature of the reaction of the oxidized slag layer 109 exceeds the ash flowing temperature, and mainly performs the following chemical reactions:
CO+O 2 ＝CO 2
in step 3, the reaction of the reduction gasification layer 110 is a gasification reaction of coal, which is a water gas main generation layer, the temperature of the reduction layer is 1000-1300 ℃, and the following chemical reactions are mainly performed:
in step 4, the relationship between the hydrogen and the water vapor in the second stream of material and the coal throughput is that the hydro-gasification methanation reaction can occur under the action of the gas product of the reduction gasification layer 110, and the mixed material is obtained at the moment that the hydrogen and the water vapor in the second stream of material contact with the gas product of the reduction gasification layer 110 and the pyrolysis semicoke of the hydro-pyrolysis layer 112, and mainly undergoes the following chemical reactions:
CO+3H 2 ＝CH 4 +H 2 O
CO+H 2 O＝CO 2 +H 2 ；
the light oil formation reaction is as follows:
nCO+(2n+1)H 2 ＝C n H 2n+2 +nH 2 O
2nCO+(n+1)H 2 ＝C n H 2n+2 +nCO 2 。
in step 5, the hydrogen in the third stream of material is in contact with the gas product of the hydro-gasification methanation layer 111 and the coal of the drying layer 113 to obtain a mixed material instantly, and a hydro-pyrolysis reaction is performed, wherein the hydro-pyrolysis layer 112 is a generation layer of pyrolysis tar and pyrolysis gas, and is also a key layer for producing gas-liquid fuel, and organic matter macromolecules in the coal are thermally decomposed to generate active micromolecules, and the active micromolecules react with hydrogen to generate hydrocarbon compounds, and mainly perform the following chemical reactions:
CH x O y +H 2 →C+CO+CH 4 +C m H n +BTX+PCX
CO+3H 2 ＝CH 4 +H 2 O
nCO+(2n+1)H 2 ＝C n H 2n+2 +nH 2 O
C m H n +H 2 ＝C m H n+2 。
basic researches on coal pressurized pyrolysis and gasification are carried out on the liquid slag-discharging moving bed hydro-gasification process in the embodiment, and the pressurized pyrolysis characteristics of coal and the high-temperature high-pressure gasification reaction dynamics rules of the Shenmu coal are obtained; meanwhile, a liquid slag discharging moving bed gasification experimental device with the treatment capacity of 1t/d (6.0 MPa,1500 ℃) is established, and petroleum coke and supernatural wood bituminous coal are used as experimental raw materials for experimental research of a methane-rich and oil-rich gasification technology. The gasifier operating conditions were: the highest operating pressure is 5.3MPa, the O2 amount is 3-6 Nm3/h, the air amount is 2-6 Nm3/h, the water vapor amount is 0.1-0.3 kg/h, and the hydrogen amount is 3-6 Nm3/h. The content of CO in the gas at the outlet of the gasification furnace is 20-30%, the content of H2 is 35-50%, the content of CO2 is 6-12%, and the content of CH4 is 16-27%. The methane content in the raw gas is closely related to gasification raw materials and operation conditions, and the main conclusion is as follows:
(1) The methane content in the gas is closely related to the hydrogenation position of the gasification furnace. The methane content in the gas can reach more than 25% through hydrogen in the 900-1000 ℃ temperature section of the gasifier, which is about 2-3 times of the conventional liquid slag discharging gasification; and in the temperature section of the gasification furnace below 700 ℃, the methane content in the gas is greatly reduced.
(2) Increasing the system pressure can significantly increase the methane content in the gas. The increase of methane content in the crude gas is not obvious under the normal pressure hydrogenation condition, the pressure increase can obviously increase the yield of methane and micromolecular hydrocarbon, but when the system pressure is increased to more than 4.0MPa, the methane increase amplitude tends to be gentle. The operating pressure was increased from 4.0MPa to 5.0MPa, with only a-5% increase in methane content.
(3) The hydrogenation activity of gasification raw materials has a remarkable influence on the methane content in coal gas. The petroleum coke has weak hydrogenation activity, and the increase amplitude of the methane content in the coal gas is small after the gasification furnace is filled with hydrogen; the reactivity of the Shenmu bituminous coal is high, and after the gasification furnace is filled with hydrogen, the methane content is obviously and greatly increased, which is more than 5 times of that of petroleum coke under the same condition.
(4) The hydrogen gas is introduced into the gasification furnace, so that the content of small molecular hydrocarbon in the crude gas can be increased to a certain extent, but the increase amplitude is smaller compared with methane, and the small molecular hydrocarbon with the carbon number of less than 6 is increased by about 50-80%.
Experimental results show that the content of methane and micromolecular hydrocarbon in the coal gas can be greatly improved by introducing hydrogen into the proper position of the moving bed.
Table 1 industrial analysis and elemental analysis of coal
Table 2 ash melting point and ash composition of coal and particle size distribution of raw material charged into furnace
TABLE 3 composition of gas
As can be seen from Table 3, the CH4 content in the product gas can reach more than 23.93%, and the economic value is high.
The experimental result proves that the feasibility of improving the yield of methane and light hydrocarbon in coal gas by modifying the liquid slag-discharging gasifier based on the moving bed through a simple hydrogenation process.
While the principal features and advantages of the present invention have been shown and described, it will be apparent to those skilled in the art that the detailed description of the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other embodiments without departing from the spirit or essential characteristics of the invention, and the inventive concept and design concept of the invention shall be equally included in the scope of the invention disclosed in the appended claims. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (12)
1. A coal hydro-gasification furnace system of a slag tapping moving bed, which is characterized in that: the gas outlet (106) of the hydro-gasifier (10) is communicated with the gas inlet of the decompression tank (20) through a pipeline, the gas outlet of the decompression tank (20) is communicated with the gas inlet of the chilled water scrubber (30) through a pipeline, the gas outlet of the chilled water scrubber (30) is communicated with the gas inlet of the gas-liquid separator (40) through a pipeline, the liquid outlets of the decompression tank (20), the chilled water scrubber (30) and the gas-liquid separator (40) are all communicated with the liquid inlet of the tar collector (50), the gas outlet of the gas-liquid separator (40) is communicated with the gas inlet of the hydrogen film separator (60) through a pipeline, the hydrogen outlet of the hydrogen film separator (60) is respectively provided with a hydrogen outlet and a methane-rich outlet, and the hydrogen outlet of the hydrogen film separator (60) is communicated with the second gas inlet (102) and the third gas inlet (103) of the hydro-gasifier (10) through two paths.
2. A slag tapping moving bed coal hydro-gasifier system as defined in claim 1 wherein: and a circulating gas compressor (70) is respectively arranged on two pipelines between a hydrogen outlet of the hydrogen membrane separator (60) and a second air inlet (102) and a third air inlet (103) of the hydro-gasification furnace (10) and is used for providing conveying power.
3. A slag tapping moving bed coal hydro-gasifier system according to claim 1 or 2, characterized in that: the utility model provides a gasification furnace, including by withstand voltage steel shell and refractory material integrative pouring shaping, and cast into furnace chamber (107) by refractory material in it be provided with solid import (105) and solid export (104) respectively on the top and the bottom of gasification furnace (10) be provided with respectively on the lateral wall of gasification furnace (10) from down supreme first air inlet (101), second air inlet (102), third air inlet (103) that are provided with respectively, gas outlet (106) set up on the lateral wall of gasification furnace (10) and be located the top of third air inlet (103), and divide into oxidation slag layer (109), reduction gasification layer (110), hydro-gasification methanation layer (111), hydro-pyrolysis layer (112), dry layer (113), first air inlet (101), second air inlet (102), third air inlet (103) are provided with respectively in oxidation slag layer (109), hydro-pyrolysis layer (111), hydro-pyrolysis layer (112), reduction layer (110) are located between first air inlet (101) and second air inlet (102).
4. A slag tapping moving bed coal hydro-gasifier system according to claim 3, wherein: an ash collection zone (108) is disposed within the furnace chamber (107) below the oxidized slag layer (109) and is in communication with a black water treatment system, wherein the black water treatment system provides circulated chilled water to the ash collection zone (108) for cooling the molten ash.
5. A slag tapping moving bed coal hydro-gasifier system as defined by claim 4 wherein: the aspect ratio of the hydro-gasification furnace (10) is 10-50.
6. A slag tapping moving bed coal hydro-gasifier system as defined by claim 5 wherein: the ratio of the distance between the first air inlet (101) and the second air inlet (102) in the furnace chamber to the height of the hydro-gasifier (10) is 1/5-1/3; the ratio of the distance between the second air inlet (102) and the third air inlet (103) in the furnace chamber to the height of the hydro-gasifier (10) is 1/6-1/4; the distance from the third air inlet (103) to the top of the furnace chamber in the furnace chamber is 1/5-1/3 of the ratio of the height of the hydro-gasification furnace (10).
7. A slag tapping moving bed coal hydro-gasifier system as defined in claim 6 wherein: the included angle between the first air inlet (101) and the axis of the hydro-gasification furnace (10) is 60-90 degrees, so that a first strand of material is conveniently fed into the oxidized slag layer (109) along a specific angle direction.
8. A hydro-gasification process using a slag tapping moving bed coal hydro-gasification furnace system according to claim 7, comprising the steps of:
step 1: adding pulverized coal with the grain diameter of 5-50mm and the water content of less than 5wt% into a furnace chamber (107) from a solid inlet (105), sequentially and respectively feeding a first material containing high-pressure oxygen and water vapor, a second material containing hydrogen and water vapor and a third material containing hydrogen into an oxidized slag layer (109), a hydro-gasification methanation layer (111) and a hydro-pyrolysis layer (112) of a hydro-gasification furnace (10), wherein the operation pressure of the hydro-gasification furnace (10) is 2MPa-10MPa, the relation between oxygen in the first material and the coal feeding amount is 0.2-1Nm < 3 >/kg, the relation between hydrogen in the second material and the coal feeding amount is 0.2-1Nm < 3 >/kg, and the mass flow ratio between hydrogen in the third material and the coal feeding amount is 0-1Nm < 3 >/kg;
step 2: oxygen in the first strand of material in the step 1 undergoes an oxygen-enriched combustion reaction in the oxidized slag layer (109) and the reduction gasification layer (110), and water vapor in the first strand of material is used for protecting a nozzle of the first air inlet (101) to obtain oxygen-enriched combustion gas products and molten slag, wherein the temperature of the oxidized slag reaction is 1400-1800 ℃;
step 3: the oxygen-enriched combustion gas product obtained in the step 2 contacts semicoke in the reduction gasification layer (110) and the hydro-gasification methanation layer (111) to carry out gasification reaction, so as to obtain a reduction gasification layer gas product and gasification residues;
step 4: the hydrogen in the second strand of material in the step 1 contacts with the reduced gasification layer (110) gas product and the hydropyrolysis layer (112) pyrolysis semicoke in the step 3 and carries out hydro-gasification methanation reaction, so that the hydro-gasification methanation layer (111) gas product and gasification residues are obtained, and the temperature of the hydro-gasification methanation reaction is 600-1200 ℃;
step 5: the hydrogen in the third strand of material in the step 1 contacts with the coal in the drying layer (113) in the step 4 and carries out a hydropyrolysis reaction to obtain a hydropyrolysis gas product and pyrolysis semicoke, the hydropyrolysis gas product and pyrolysis semicoke are conveyed into a decompression tank (20) through an air outlet (106) to be decompressed to obtain a liquid product and purified gas, wherein the purified gas is subjected to gas-liquid separation sequentially through a chilled water washing tower (30) and a gas-liquid separator (40), the gaseous product and the liquid product are separated through a hydrogen membrane separator (60) to obtain methane-rich gas and hydrogen, the hydrogen is conveyed into a hydro-gasifier (10) through a second air inlet (102) and a third air inlet (103) to be reacted under the action of a circulating gas compressor (70), the methane-rich gas is the obtained product gas, and the liquid product is the liquid oil product and water after layering and is uniformly recovered into a tar collector (50);
wherein the temperature regulation product composition of the hydropyrolysis reaction in the step 5: at above 900 ℃, methane is mainly generated; the temperature is 800-900 ℃, and BTX and PCX can be enriched; the temperature is controlled at 400-600 ℃, and light oil products can be produced in a rich way.
9. A hydro-gasification process according to claim 8 wherein: in step 2, the relationship between the oxygen and the coal throughput in the first stream of material must be able to undergo an oxycombustion reaction and the heat generated by the oxycombustion reaction is able to cause the coal in the reduction gasification layer to undergo a gasification reaction, and the temperature of the reaction of the oxidized slag layer (109) exceeds the ash flowing temperature, and mainly the following chemical reactions are performed:
CO+O 2 ＝CO 2
10. a hydro-gasification process according to claim 9 wherein: in the step 3, the reaction of the reduction gasification layer (110) is a gasification reaction of coal, is a water gas main generation layer, has the temperature of 1000-1300 ℃, and mainly carries out the following chemical reaction:
11. a hydro-gasification process according to claim 10 wherein: in step 4, the relation between the hydrogen and the water vapor in the second stream of material and the coal throughput can be obtained through hydro-gasification methanation reaction under the action of the gas product of the reduction gasification layer (110), and the mixed material is obtained at the moment that the hydrogen and the water vapor in the second stream of material are in contact with the gas product of the reduction gasification layer (110) and the pyrolysis semicoke of the hydro-pyrolysis layer (112), and mainly carries out the following chemical reaction:
CO+3H 2 ＝CH 4 +H 2 O
CO+H 2 O＝CO 2 +H 2 ；
the light oil formation reaction is as follows:
nCO+(2n+1)H 2 ＝C n H 2n+2 +nH 2 O
2nCO+(n+1)H 2 ＝C n H 2n+2 +nCO 2 。
12. a hydro-gasification process according to claim 11 wherein: in the step (5), the hydrogen in the third strand of material is in contact with the gas product of the hydro-gasification methanation layer (111) and the coal of the drying layer (113) to obtain a mixed material instantly, and a hydro-pyrolysis reaction is carried out, wherein the hydro-pyrolysis layer (112) is a generation layer of pyrolysis tar and pyrolysis gas and is also a key layer for producing gas-liquid fuel, and organic matter macromolecules in the coal are thermally decomposed to generate active micromolecules, and the hydrocarbon compounds are generated by the hydrogen reaction, and mainly carry out the following chemical reactions:
CH x O y +H 2 →C+CO+CH 4 +C m H n +BTX+PCX
CO+3H 2 ＝CH 4 +H 2 O
nCO+(2n+1)H 2 ＝C n H 2n+2 +nH 2 O
C m H n +H 2 ＝C m H n+2 。
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