阅读说明：本技术 新型氧载体煤催化气化制氢反应装置及反应方法 (Novel oxygen carrier coal catalytic gasification hydrogen production reaction device and reaction method ) 是由 金渭龙 钟思青 徐俊 李勇征 于 2020-06-28 设计创作，主要内容包括：本发明提出了一种新型氧载体煤催化气化制氢反应装置及利用该装置的反应方法,该装置由气化还原炉、制氢炉和燃烧氧化炉组合,原料煤在气化还原炉内与气化剂和氧化载体进行催化热解、气化、氧化载体还原等反应,产生合成气、气化半焦和还原载体。其中还原载体再进入制氢炉中进行单一的制氢反应,生成富氢气体和亚氧化/氧化载体。亚氧化/氧化载体和未反应完全的还原载体再进入燃烧氧化炉中与含氧气体和气化半焦混合接触,进行燃烧、氧化反应,生成的氧化载体再循环回气化还原炉,实现了氧化载体的循环再生,平衡了热流和物流,提高了气化强度、碳转化率和氢气产率。(The invention provides a novel oxygen carrier coal catalytic gasification hydrogen production reaction device and a reaction method using the same. Wherein the reduction carrier enters the hydrogen production furnace to carry out single hydrogen production reaction to generate hydrogen-rich gas and a sub-oxidation/oxidation carrier. The sub-oxidation/oxidation carrier and the reduction carrier which is not completely reacted enter the combustion oxidation furnace to be mixed and contacted with the oxygen-containing gas and the gasified semicoke for combustion and oxidation reaction, and the generated oxidation carrier is recycled to the gasification reduction furnace, so that the cyclic regeneration of the oxidation carrier is realized, the heat flow and the material flow are balanced, and the gasification strength, the carbon conversion rate and the hydrogen yield are improved.)

1. A novel oxygen carrier coal catalytic gasification hydrogen production reaction device is characterized by comprising a gasification reduction furnace (1), a hydrogen production furnace (6) and a combustion oxidation furnace (9), the outlet of the gasification reduction furnace (1) is respectively connected with one end of a first cyclone separator (4) of the reduction furnace and one end of a second cyclone separator (7) of the reduction furnace, the other end of the first cyclone separator (4) of the reduction furnace is connected with the hydrogen production furnace (6), the other end of the second cyclone separator (7) of the reduction furnace is connected with the combustion oxidation furnace (9), the hydrogen making furnace (6) is connected with the combustion oxidation furnace (9), a first cyclone separator (16) of the oxidation furnace is arranged at the outlet of the combustion oxidation furnace (9), the first cyclone separator (16) of the oxidation furnace is connected with the gasification reduction furnace (1).

2. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device according to claim 1, wherein the gasification reduction furnace (1) comprises a reduction furnace lower layer space and a reduction furnace upper layer space, and the inner diameter of the reduction furnace lower layer space is larger than that of the reduction furnace upper layer space; the height of the upper layer space of the reducing furnace is more than or equal to that of the lower layer space of the reducing furnace.

3. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device according to claim 2, wherein the inner diameter of the lower layer space of the reduction furnace is 1.2 to 5.0 times of the inner diameter of the upper layer space of the reduction furnace; the height of the upper space of the reducing furnace is 1.0-3.0 times of the height of the lower space of the reducing furnace.

4. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device according to any one of claims 1 to 3, characterized in that the reaction device further comprises a reducing furnace gas distributor (3), the reducing furnace gas distributor (3) is horizontally arranged at the bottom of the gasification reduction furnace (1), the reducing furnace gas distributor (3) is provided with air caps uniformly arranged along the circumference, each air cap is provided with an axial channel (M1) and a radial channel (M2) or an axial channel (M1) and a short axial channel (M3), the upper end of the axial channel (M1) is closed, the lower end of the axial channel (M2) is communicated with the reducing furnace gas distributor (3), and the radial channels (M2) or the short axial channels (M3) are uniformly arranged along the circumference.

5. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device as claimed in claim 4, wherein the radial channel (M2) or the short axial channel (M3) has a rotation angle, and the rotation angle range is 0-45 °.

6. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device as claimed in any one of claims 1 to 3, wherein the hydrogen production furnace (6) comprises a hydrogen production furnace lower layer space and a hydrogen production furnace upper layer space, and the inner diameter of the hydrogen production furnace lower layer space is smaller than that of the hydrogen production furnace upper layer space; the height of the upper layer space of the hydrogen production furnace is more than or equal to that of the lower layer space of the hydrogen production furnace.

7. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device as claimed in claim 6, wherein the inner diameter of the lower space of the hydrogen production furnace is 1/3-2/3 of the inner diameter of the upper space of the hydrogen production furnace; the height of the upper space of the hydrogen production furnace is 1.0-2.0 times of the height of the lower space of the hydrogen production furnace.

8. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device as claimed in claim 6, wherein the hydrogen production furnace (6) is provided with a hydrogen production furnace upper layer gas distributor (12) and a hydrogen production furnace lower layer gas distributor (11), the hydrogen production furnace upper layer gas distributor (12) is positioned at the bottom of the hydrogen production furnace upper layer space and forms an included angle of less than or equal to 60 degrees with a horizontal axis, and the circular conical surface of the hydrogen production furnace upper layer gas distributor (12) is provided with gas holes which are uniformly distributed along the circumference; the lower-layer gas distributor (11) of the hydrogen production furnace is horizontally arranged at the bottom of the lower-layer space of the hydrogen production furnace, and gas holes are formed in the plane of the lower-layer gas distributor (11) of the hydrogen production furnace and are uniformly arranged along the circumference.

9. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device as claimed in claim 6, the reaction device also comprises a reduction carrier returning device (5), a gasification semicoke returning device (8), a sub-oxidation carrier returning device (14) and an oxidation carrier returning device (17), the other end of the first cyclone separator (4) of the reduction furnace is connected with the hydrogen production furnace (6) through the reduction carrier material returning device (5), the other end of the second cyclone separator (7) of the reduction furnace is connected with the combustion oxidation furnace (9) through the gasification semicoke returning device (8), the hydrogen production furnace (6) is connected with the combustion oxidation furnace (9) through the sub-oxidation carrier returning device (14), the first cyclone separator (16) of the oxidation furnace is connected with the gasification reduction furnace (1) through the oxidation carrier returning device (17).

10. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device as claimed in any one of claims 1 to 3, characterized in that the combustion oxidation furnace (9) adopts a fast fluidized bed, and the bottom of the combustion oxidation furnace (9) is provided with an oxidation furnace gas distributor (15) and an oxidation furnace slag hopper (20).

11. The novel oxygen carrier coal catalytic gasification hydrogen production reaction device as claimed in any one of claims 1 to 3, characterized in that an oxidation furnace second cyclone separator (18) is further arranged at the outlet of the combustion oxidation furnace (9).

12. A novel hydrogen production reaction method by catalytic gasification of oxygen carrier coal is characterized by comprising the following steps,

the method comprises the following steps of carrying out catalytic pyrolysis, gasification and oxidation carrier reduction reaction on raw material coal (A) with a gasifying agent (B) and an oxidation carrier in a gasification reduction furnace (1) to generate synthesis gas, gasified semicoke and a reduction carrier, enabling the reduction carrier to enter a hydrogen production furnace (6) and carry out reduction carrier and steam oxidation reaction with high-temperature steam (D) in the hydrogen production furnace (6) to generate hydrogen-rich gas and a sub-oxidation/oxidation carrier, enabling the sub-oxidation/oxidation carrier and the reduction carrier which is not completely reacted to enter a combustion oxidation furnace (9) to be in mixed contact with oxygen-containing gas and gasified semicoke for combustion and oxidation reaction, and recycling the generated oxidation carrier into the gasification reduction furnace (1).

13. The novel oxygen carrier coal catalytic gasification hydrogen production reaction method according to claim 12, characterized in that the reaction temperature of the gasification reduction furnace (1) is 600-1000 ℃, the gas phase line speed is 0.5-5.0 m/s, and the bed layer average density is 50-350 kg/m³(ii) a The reaction temperature of the hydrogen production furnace (6) is 500-900 ℃, the gas phase line speed is 0.1-1 m/s, and the average density of the bed layer is 250-600 kg/m³(ii) a The reaction temperature of the combustion oxidation furnace (9) is 800-1200 ℃, the gas phase line speed is 1.0-10 m/s, and the average density of the bed layer is 20-150 kg/m³The reaction pressure of the system is 0-2.0 MPa.

14. The novel oxygen carrier coal catalytic gasification hydrogen production reaction method according to claim 12 or 13, characterized in that a reducing furnace gas distributor (3) is further arranged at the bottom of the gasification reducing furnace (1), wind caps uniformly arranged along the circumference are arranged on the reducing furnace gas distributor (3), an axial channel (M1) and a radial channel (M2) or an axial channel (M1) and a short axial channel (M3) are arranged in each wind cap, and the outlet linear velocity of the wind cap radial channel (M2) or the short axial channel (M3) on the reducing furnace gas distributor (3) is 5-50M/s.

15. The novel oxygen carrier coal catalytic gasification hydrogen production reaction method according to claim 14, characterized in that the gasification agent (B) introduced into the gasification reduction furnace (1) comprises steam or CO₂Or the mixture of the raw materials and the gasifying agent, wherein the temperature of the gasifying agent is 200-800 ℃.

16. The novel oxygen carrier coal catalytic gasification hydrogen production reaction method according to claim 15, wherein the hydrogen production furnace (6) is provided with a hydrogen production furnace upper layer gas distributor (12) and a hydrogen production furnace lower layer gas distributor (11), the high-temperature water vapor (D) is introduced into the hydrogen production furnace lower layer gas distributor (11) and the hydrogen production furnace upper layer gas distributor (12), the temperature of the high-temperature water vapor (D) is 500-800 ℃, the proportion of the high-temperature water vapor (D) introduced into the hydrogen production furnace upper layer gas distributor (12) accounts for 10-50% of the sum of the high-temperature water vapor amount of the hydrogen production furnace upper layer gas distributor (12) and the hydrogen production furnace lower layer gas distributor (11), and the molar ratio of the high-temperature water vapor to the reduction carrier circulated back to the hydrogen production furnace (6) is 1.0-5.0 mol/mol.

17. The novel oxygen carrier coal catalytic gasification hydrogen production reaction method according to claim 16, wherein the oxygen-containing gas (G) introduced into the combustion oxidation furnace (9) comprises oxygen, air, oxygen-enriched air or a mixture thereof, wherein the molar ratio of the oxygen to carbon in the gasified semicoke is 1.5-3.0 mol/mol.

18. The novel oxygen carrier coal catalytic gasification hydrogen production reaction method according to claim 17, characterized in that the carrier exists in two states of oxidation state and reduction state or three states of oxidation state, sub-oxidation state and reduction state.

19. The novel oxygen carrier coal catalytic gasification hydrogen production reaction method as claimed in claim 18, characterized in that the carrier is Fe₂O₃One or more of pure iron powder, iron ore, waste iron slag or waste steel slag as main components; or a metal oxide having a reduced state; or a mixture of alkali metal, transition metal and the metal oxide with the reduction state, or a mixture of alkali metal, transition metal and alkaline earth metal Ca and the metal oxide with the reduction state, wherein the active component accounts for 0.1-30% of the mass of the catalyst, and is loaded on the carrier Al in any loading mode including an impregnation method, a dry mixing method or an ion exchange method₂O₃、ZrO₂、TiO₂Or SiO₂The above.

Technical Field

The invention relates to the field of coal hydrogen production, in particular to a gasification reduction furnace, a hydrogen production reaction device combining a hydrogen production furnace and a combustion oxidation furnace and a reaction method.

Background

The hydrogen energy is used as a clean energy, the final product is water in the energy conversion process, zero emission of pollutants can be really realized, and the hydrogen energy can be widely applied to the aspects of space power, vehicle-mounted fuel, fuel cells, combustion power generation, chemical production and the like and plays an increasingly important role in energy structures. The main methods for preparing hydrogen energy at present comprise partial oxidation reforming hydrogen production of heavy oil, hydrogen production by water electrolysis, coal gasification hydrogen production and the like, wherein the coal gasification hydrogen production conforms to the energy structure characteristics and the basic national conditions of China and is a mainstream hydrogen production technology. The traditional coal hydrogen production mainly comprises the processes of coal gasification, coal gas purification, CO conversion, purification and the like, and has the defects of more related equipment, difficult temperature and pressure matching among the equipment, high energy consumption, long flow and low system energy conversion rate. The coal gasification device is key equipment for preparing hydrogen from coal, the coal gasification device in the prior art mainly adopts an entrained flow bed and a fluidized bed gasification furnace, the content of hydrogen in the synthesis gas at the outlet of the coal gasification device is generally low, and the load of subsequent purification, transformation and purification processes is increased.

Patent application with publication number CN102585911A proposes a coal gasification hydrogen production apparatus and method, in which a reactor couples three processes of coal gasification, carbon dioxide capture by calcium-based adsorbent and calcium carbonate calcination, and carbon dioxide in coal gasification synthesis gas is captured by calcium-based adsorbent to increase hydrogen content. The patent application with publication number CN101830432B discloses a method for preparing hydrogen and separating CO based on coal gasification₂Method and apparatus for gasification reaction and CO₂Absorption reactionIn a gasifier, CaCO₃And the coke enters a regeneration furnace again to be calcined and decomposed, and the CaO is obtained through regeneration. The method can directly improve the hydrogen content in the outlet synthesis gas and reduce the load of subsequent transformation and purification processes to a certain extent. But CO due to intensified shift effect₂The content is greatly increased, and the CO in the furnace₂The absorption reaction is influenced by the reaction process conditions and the performance of the absorbent, CO₂Low removing efficiency and content of CO and CH₄When the gas is mixed, the hydrogen content at the outlet of the reactor is still low, the high-purity grade cannot be achieved, and subsequent purification, transformation, separation and purification units cannot be omitted.

In the patent technology, the content of hydrogen in the outlet synthesis gas is greatly improved compared with the traditional gasification furnace, but the gasification, transformation and CO are improved₂A plurality of reactions such as absorption and the like are coupled in one reactor, the coupling difficulty of the reaction process is high, and the purity of hydrogen in the product gas is not high, so that the hydrogen can not be directly used as a clean hydrogen source.

Based on the consideration, the hydrogen production method can be used for performing single hydrogen production reaction in a single reactor, the product separation is simple, and the purity of hydrogen in product gas is high, so that a coal hydrogen production technology which is high in heat utilization rate, good in reaction performance, high in hydrogen yield, stable in operation and efficient is researched.

Disclosure of Invention

The invention mainly solves the technical problems of low carbon conversion rate, low hydrogen yield, high energy consumption and poor operation stability in the prior art, and provides a novel oxygen carrier coal catalytic gasification hydrogen production reaction device which is formed by combining a gasification reduction furnace, a hydrogen production furnace and a combustion oxidation furnace, wherein raw material coal, a gasification agent and an oxidation carrier are subjected to catalytic pyrolysis, gasification, oxidation carrier reduction and other reactions in the gasification reduction furnace to generate synthesis gas, gasification semicoke and a reduction carrier. Wherein the reduction carrier enters the hydrogen production furnace to carry out single hydrogen production reaction to generate hydrogen-rich gas and a sub-oxidation/oxidation carrier. The sub-oxidation/oxidation carrier and the reduction carrier which is not completely reacted enter the combustion oxidation furnace to be mixed and contacted with the oxygen-containing gas and the gasified semicoke for combustion and oxidation reaction, and the generated oxidation carrier is recycled to the gasification reduction furnace, so that the cyclic regeneration of the oxidation carrier is realized, the heat flow and the material flow are balanced, and the gasification strength, the carbon conversion rate and the hydrogen yield are improved.

The invention aims to solve the technical problem and provide a novel oxygen carrier coal catalytic gasification hydrogen production reaction method corresponding to the solution of one of the technical problems.

In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a novel oxygen carrier coal catalytic gasification hydrogen production reaction device mainly comprises: the device comprises a gasification reduction furnace, a hydrogen production furnace, a combustion oxidation furnace, a primary furnace first cyclone separator and a reduction furnace second cyclone separator, wherein one end of the reduction furnace first cyclone separator and one end of the reduction furnace second cyclone separator are respectively connected with an outlet of the gasification reduction furnace, the other end of the reduction furnace first cyclone separator is connected with the hydrogen production furnace, the other end of the reduction furnace second cyclone separator is connected with the combustion oxidation furnace, the hydrogen production furnace is connected with the combustion oxidation furnace, an oxidation furnace first cyclone separator is arranged at an outlet of the combustion oxidation furnace, and the oxidation furnace first cyclone separator is connected with the gasification reduction furnace.

In one embodiment, the gasification reduction furnace comprises a lower space of the reduction furnace and an upper space of the reduction furnace, wherein the inner diameter of the lower space of the reduction furnace is larger than that of the upper space of the reduction furnace and is between 1.2 times and 5.0 times of that of the upper space of the reduction furnace; the height of the upper layer space of the reducing furnace is more than or equal to that of the lower layer space of the reducing furnace and is between 1.0 and 3.0 times of that of the lower layer space of the reducing furnace.

In one embodiment, the raw material inlet is positioned in a lower space of a reduction furnace of the gasification reduction furnace, and is positioned at 1/3-2/3 of the height of the lower space of the gasification reduction furnace.

In one embodiment, the reaction device further comprises a reducing furnace gas distributor, the reducing furnace gas distributor is located at the bottom of the gasification reducing furnace and horizontally arranged, the reducing furnace gas distributor is provided with air caps, the air caps are evenly arranged along the circumference and are provided with 5-50 circles, each circle is provided with 10-100 air caps, each air cap is internally provided with 1 axial channel and 4-20 radial channels or short axial channels, the upper end of each axial channel is closed, the lower end of each axial channel is communicated with the reducing furnace gas distributor, the radial channels or the short axial channels are evenly arranged along the circumference, the inner diameter of an air outlet of each radial channel or the short axial channel is 0.1-2 mm, optional radial channels or short axial channels are provided with rotation angles, and the rotation angle ranges from 0-45 degrees.

In one embodiment, the hydrogen production furnace consists of a lower space of the hydrogen production furnace and an upper space of the hydrogen production furnace, wherein the inner diameter of the lower space of the hydrogen production furnace is smaller than that of the upper space of the hydrogen production furnace and is between 1/3 and 2/3 of the inner diameter of the upper space of the hydrogen production furnace; the height of the upper space of the hydrogen production furnace is more than or equal to that of the lower space of the hydrogen production furnace and is between 1.0 and 2.0 times of that of the lower space of the hydrogen production furnace.

In one embodiment, the hydrogen production furnace is provided with two layers of gas distributors, the lower layer of gas distributor of the hydrogen production furnace is positioned at the bottom of the lower layer of space of the hydrogen production furnace and is horizontally arranged, the plane of the lower layer of gas distributor of the hydrogen production furnace is provided with gas holes, the gas holes are uniformly arranged along the circumference and are totally arranged for 5-50 circles, each circle is provided with 10-100 gas holes, and the aperture ratio is 1-5%; the upper-layer gas distributor of the hydrogen production furnace is positioned at the bottom of the upper-layer space of the hydrogen production furnace and forms an included angle of less than or equal to 60 degrees with a horizontal axis, preferably 15-45 degrees, the annular conical surface of the upper-layer gas distributor of the gasification furnace is provided with gas holes, the gas holes are uniformly distributed along the circumference and are provided with 10-100 circles, each circle is provided with 10-100 gas holes, and the aperture ratio is 1-5%.

In one embodiment, the reaction device further includes a reduction carrier returning device, a gasification semicoke returning device, a sub-oxidation carrier returning device and an oxidation carrier returning device, the other end of the first cyclone separator of the reduction furnace is connected with the hydrogen production furnace through the reduction carrier returning device, the other end of the second cyclone separator of the reduction furnace is connected with the combustion oxidation furnace through the gasification semicoke returning device, the hydrogen production furnace is connected with the combustion oxidation furnace through the sub-oxidation carrier returning device, and the first cyclone separator of the oxidation furnace is connected with the gasification reduction furnace through the oxidation carrier returning device.

In one embodiment, the combustion oxidation furnace adopts a fast fluidized bed, and the bottom of the combustion oxidation furnace is provided with an oxidation furnace gas distributor and an oxidation furnace slag hopper.

In one embodiment, the outlet of the combustion oxidation furnace is further provided with an oxidation furnace second cyclone separator.

In order to solve the second problem, the invention provides a novel oxygen carrier coal catalytic gasification hydrogen production reaction method, which can be prepared by using the novel oxygen carrier coal catalytic gasification hydrogen production reaction device in any aspect, and the method comprises the following steps:

the raw material coal, a gasifying agent and an oxidation carrier are subjected to catalytic pyrolysis, gasification and oxidation carrier reduction reaction in a gasification reduction furnace to generate synthesis gas, gasification semicoke and a reduction carrier, the reduction carrier enters a hydrogen production furnace and is subjected to reduction carrier and steam oxidation reaction with high-temperature steam in the hydrogen production furnace to generate hydrogen-rich gas and a sub-oxidation/oxidation carrier, the sub-oxidation/oxidation carrier and the reduction carrier which is not completely reacted enter a combustion oxidation furnace to be mixed and contacted with oxygen-containing gas and gasification semicoke for combustion and oxidation reaction, and the generated oxidation carrier is recycled to the gasification reduction furnace.

Further, the reaction temperature of the gasification reduction furnace is 600-1000 ℃, the gas phase line speed is 0.5-5.0 m/s, and the average density of a bed layer is 50-350 kg/m³(ii) a The reaction temperature of the hydrogen production furnace is 500-900 ℃, the gas phase line speed is 0.1-1 m/s, and the average density of the bed layer is 250-600 kg/m³(ii) a The reaction temperature of the combustion oxidation furnace is 800-1200 ℃, the gas phase line speed is 1.0-10 m/s, and the average density of the bed layer is 20-150 kg/m³And the reaction pressure of the system is 0-2.0 MPa.

Further, a reducing furnace gas distributor is further arranged at the bottom of the gasification reducing furnace, blast caps uniformly distributed along the circumference are arranged on the reducing furnace gas distributor, an axial channel and a radial channel or an axial channel and a short axial channel are arranged in each blast cap, and the linear speed of the outlet of the blast cap radial channel or the short axial channel on the reducing furnace gas distributor is 5-50 m/s.

Further, theThe gasification reduction furnace is filled with gasification agent comprising water vapor and CO₂Or the mixture thereof, and the temperature of the gasifying agent is 200-800 ℃.

Further, the hydrogen production furnace is provided with a hydrogen production furnace upper layer gas distributor and a hydrogen production furnace lower layer gas distributor, high-temperature water vapor is introduced into the hydrogen production furnace lower layer gas distributor and the hydrogen production furnace upper layer gas distributor, the temperature of the high-temperature water vapor is 500-800 ℃, the proportion of the high-temperature water vapor introduced into the hydrogen production furnace upper layer gas distributor accounts for 10% -50% of the sum of the high-temperature water vapor amount of the hydrogen production furnace upper layer gas distributor and the hydrogen production furnace lower layer gas distributor, and the molar proportion of the high-temperature water vapor and a reduction carrier circulating back into the hydrogen production furnace, namely the water carrying ratio is 1.0-5.0 mol/mol.

Further, the oxygen-containing gas introduced into the combustion oxidation furnace comprises oxygen, air, oxygen-enriched air or a mixture of the oxygen and the air, wherein the molar ratio of the oxygen to carbon in the gasified semicoke, namely the oxygen-carbon ratio, is 1.5-3.0 mol/mol.

The oxidation carrier exists in oxidation state and reduction state or oxidation state, sub-oxidation state and reduction state, and can be selected from Fe₂O₃One or more of pure iron powder, iron ore, waste iron slag or waste steel slag as main components; or metal oxides having a reduced state and mixtures thereof, including but not limited to chemically synthesized Fe₂O₃，NiO，Mn₃O₄Etc.; or a mixture of alkali metal, transition metal and the metal oxide with the reduction state, or a mixture of alkali metal, transition metal and alkaline earth metal Ca and the metal oxide with the reduction state, wherein the active component accounts for 0.1-30% of the mass of the catalyst, and is loaded on Al in any mode including an impregnation method, a dry mixing method or an ion exchange method₂O₃，ZrO₂，TiO₂Or SiO₂And the like.

Compared with the prior art, the invention has the following advantages:

1) the oxygen carrier catalytic gasification hydrogen production device combining the gasification reduction furnace, the hydrogen production furnace and the combustion oxidation furnace is adopted to carry out catalytic pyrolysis, gasification, carrier reduction and other reactions in the gasification reduction furnace, only the reduction carrier enters the hydrogen production furnace to carry out single hydrogen production reaction with high-temperature steam, the product gas has high hydrogen purity and simple separation, and the gasified semicoke, the sub-oxidation carrier and the reduction carrier which is not completely reacted carry out combustion reaction in the combustion oxidation furnace. The gasification reduction furnace, the hydrogen production furnace and the combustion oxidation furnace are relatively independent, synthesis gas at the outlet of the gasification reduction furnace, hydrogen-rich gas at the outlet of the hydrogen production furnace and flue gas at the outlet of the combustion oxidation furnace are respectively discharged from respective pipelines, the content of hydrogen at the outlet of the hydrogen production furnace is up to more than 99%, the purity and the yield of hydrogen are improved, and the conversion rate of carbon is high.

2) Be provided with the hood on the reducing furnace gas distributor, a large amount of hoods are evenly arranged along the circumference, the axial passage of gasification agent in the hood flows from 4 ~ 20 radial passages or minor axis to the passageway, the gasification agent flows from the radial passage of different hoods or minor axis to the passageway after, the air current strikes each other, the shearing, transmission and mixing process have been strengthened, it is more even to make the gasification agent distribute in short time and short distance, and improved the mixing efficiency between its and the solid particle, the reaction effect in the gasification reducing furnace has been strengthened.

3) The heat required by the reactions such as catalytic pyrolysis, gasification and carrier reduction in the gasification reduction furnace is provided by the high-temperature oxidation carrier generated by the combustion oxidation furnace, the heat of the hydrogen production reaction in the hydrogen production furnace is also from the reduction heat carrier, and the low-temperature sub-oxidation/oxidation carrier performs the combustion reaction with the gasification semicoke in the combustion oxidation furnace and generates the high-temperature oxidation carrier, so that the heat balance is realized, and the process heat efficiency and the heat utilization rate are more efficient.

4) The hydrogen production furnace is divided into an upper layer space and a lower layer space, the upper layer space is additionally filled with steam, the contact between the reduction carrier and the steam in the furnace is strengthened, and the hydrogen production reaction process between the reduction carrier and the steam is enhanced.

5) The oxidation carrier used can be selected from inexpensive Fe₂O₃Is mainly composed ofOne or more of pure iron powder, iron ore, waste iron slag or waste steel slag; or metal oxides having a reduced state and mixtures thereof, including but not limited to chemically synthesized Fe₂O₃，NiO，Mn₃O₄Etc.; or a mixture of an alkali metal, a transition metal and the metal oxide with the reduction state, or a mixture of an alkali metal, a transition metal and an alkaline earth metal Ca and the metal oxide with the reduction state, wherein the active component accounts for 0.1-30% of the mass of the catalyst and is loaded on Al by an impregnation method, a dry mixing method or an ion exchange method₂O₃，ZrO₂，TiO₂Or SiO₂And the like. The difference of physical properties of the oxidation carrier, the gasified semicoke and the fine ash is large, the separation process can be completed by the oxidation carrier, the gasified semicoke, the oxidation carrier and the fine ash through simple separation equipment, and the problem of difficult separation is solved.

The technical features described above can be combined in various technically feasible ways to produce new embodiments, as long as the object of the invention is achieved.

Drawings

The invention will be described in more detail hereinafter on the basis of non-limiting examples only and with reference to the accompanying drawings. Wherein:

FIG. 1 shows a schematic flow diagram of a novel oxygen carrier coal catalytic gasification hydrogen production reaction device and a flow chart;

FIGS. 2 and 3 show a schematic illustration of the tuyere cap of the gas distributor of the reduction furnace of FIG. 1.

In the drawings, like components are denoted by like reference numerals. The figures are not drawn to scale.

Wherein the reference numerals are:

1. a gasification reduction furnace; 2. a raw material inlet; 3. a reducing furnace gas distributor; 4. a first cyclone separator of the reduction furnace; 5. a reduction carrier returning device; 6. a hydrogen production furnace; 7. a second cyclone separator of the reduction furnace; 8. a gasification semicoke returning device; 9. a combustion oxidation furnace; 10. a cooling and separating unit of the reducing furnace; 11. a lower layer gas distributor of the hydrogen production furnace; 12. an upper layer gas distributor of the hydrogen production furnace; 13. a hydrogen production furnace cooling separation unit; 14. a sub-oxidation carrier returning device; 15. an oxidizer gas distributor; 16. a first cyclone separator of the oxidation furnace; 17. an oxidation carrier returning device; 18. a second cyclone separator of the oxidation furnace; 19. an oxidation furnace cooling and purifying unit; 20. an oxidation slag hopper; m1, axial channel; m2, radial channel; m3, short axial channel; a is raw material coal; b is a gasifying agent; c is synthesis gas; d is high-temperature steam; e is condensed water; f is high-purity hydrogen; g is an oxygen-containing gas; h is fine ash; i is flue gas; j is coarse slag; k is a supplementary vector; l is the loosening air.

Detailed Description

The invention will be described in further detail below with reference to the drawings and specific examples. It should be noted that, as long as there is no conflict, the embodiments and the features of the embodiments of the present invention may be combined with each other, and the technical solutions formed are within the scope of the present invention.

Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The use of the terms "comprising" or "including" and the like in the present invention, means that the element or item presented before the term covers the element or item listed after the term and its equivalents, but does not exclude other elements or items. In the description of the present invention, the terms "upper", "lower" and "inner", "outer", etc. indicate orientations or positional relationships based on those shown in the drawings, only for convenience of description and simplification of description, but do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed and operated in a specific orientation, and when the absolute position of the described object is changed, the relative positional relationships may be changed accordingly, and thus, are not to be construed as limiting the present invention.

The technology not mentioned in the invention can be realized by reference to the prior art.

As shown in figure 1, the invention provides a novel oxygen carrier coal catalytic gasification hydrogen production reaction device, which comprises a gasification reduction furnace 1, a hydrogen production furnace 6, a combustion oxidation furnace 9, a reduction furnace gas distributor 3 and a reduction furnace first cyclone separator 4, wherein a raw material inlet 2 is connected with the gasification reduction furnace 1, an upper outlet of the gasification reduction furnace 1 is connected with the reduction furnace first cyclone separator 4 and a reduction furnace second cyclone separator 7, a lower part of the reduction furnace first cyclone separator 4 is connected with the hydrogen production furnace 6 through a reduction carrier returning device 5, a lower part of the reduction furnace second cyclone separator 7 is connected with the combustion oxidation furnace 9 through a gasification semicoke returning device 8, the hydrogen production furnace 6 is connected with the combustion oxidation furnace 9 through a sub-oxidation carrier returning device 14, an upper outlet of the combustion oxidation furnace 9 is connected with an oxidation furnace first cyclone separator 16 and an oxidation furnace second cyclone separator 18, the lower part of the first cyclone separator 16 of the oxidation furnace is connected with the gasification reduction furnace 1 through an oxidation carrier returning device 17. In other embodiments, the reducing carrier returning device 5, the gasified semicoke returning device 8, the sub-oxidation carrier returning device 14 and the oxidation carrier returning device 17 may be replaced by other structures capable of realizing the functions thereof, such as other types of non-mechanical valves, such as a J valve, an L valve and a V valve, a screw rod and the like.

The device adopts the oxygen carrier catalytic gasification hydrogen production device combining the gasification reduction furnace, the hydrogen production furnace and the combustion oxidation furnace, and carries out catalytic pyrolysis, gasification, carrier reduction and other reactions in the gasification reduction furnace, only the reduction carrier enters the hydrogen production furnace to carry out single hydrogen production reaction with high-temperature steam, the product gas has high hydrogen purity and simple separation, and the gasification semicoke, the sub-oxidation carrier and the reduction carrier which is not completely reacted carry out combustion reaction in the combustion oxidation furnace. The gasification reduction furnace, the hydrogen production furnace and the combustion oxidation furnace are relatively independent, synthesis gas at the outlet of the gasification reduction furnace, hydrogen-rich gas at the outlet of the hydrogen production furnace and flue gas at the outlet of the combustion oxidation furnace are respectively discharged from respective pipelines, the content of hydrogen at the outlet of the hydrogen production furnace is up to more than 99%, the purity and the yield of hydrogen are improved, and the conversion rate of carbon is high.

In an alternative embodiment, the gasification reduction furnace 1 is composed of a lower space of the reduction furnace and an upper space of the reduction furnace, wherein the inner diameter of the lower space of the reduction furnace is larger than that of the upper space of the reduction furnace, preferably 1.2 to 5.0 times of that of the upper space of the reduction furnace; the height of the upper space of the reducing furnace is more than or equal to that of the lower space of the reducing furnace, and preferably 1.0-3.0 times of that of the lower space of the reducing furnace.

In an alternative embodiment, the raw material inlet 2 is positioned in the lower layer space of the reduction furnace of the gasification reduction furnace 1, and is positioned at 1/3-2/3 of the height of the lower layer space of the gasification reduction furnace.

As shown in (a) and (b) of fig. 2, in an alternative embodiment, the reducing furnace gas distributor 3 is horizontally disposed at the bottom of the gasification reducing furnace 1, the reducing furnace gas distributor 3 is provided with hoods which are uniformly arranged along the circumference and have 5 to 50 turns, each turn is provided with 10 to 100 hoods, each hood is provided with 1 axial channel M1 and 4 to 20 radial channels M2, wherein the upper end of the axial channel M1 is closed, the lower end of the axial channel M1 is communicated with the reducing furnace gas distributor 3, the radial channels M2 are uniformly arranged along the circumference, the inner diameter of the air outlet of the radial channel M2 is 0.1 to 2mm, and in a preferred embodiment, the radial channel M2 has a rotation angle in the range of 0 to 45 °.

As shown in (a) and (b) of FIG. 3, the radial channel M2 can be replaced by a short axial channel M3, the short axial channels M3 are uniformly arranged along the circumference, the inner diameter of the air outlet of the short axial channel M3 is 0.1-2 mm, and preferably, the short axial channel M3 also has a rotation angle which is 0-45 degrees.

Be provided with the hood on the reducing furnace gas distributor, a large amount of hoods are evenly arranged along the circumference, the axial passage of gasification agent in the hood flows from 4 ~ 20 radial passages or minor axis to the passageway, the gasification agent flows from the radial passage of different hoods or minor axis to the passageway after, the air current strikes each other, the shearing, transmission and mixing process have been strengthened, it is more even to make the gasification agent distribute in short time and short distance, and improved the mixing efficiency between its and the solid particle, the reaction effect in the gasification reducing furnace has been strengthened.

In an alternative embodiment, the hydrogen production furnace 6 is composed of a lower space of the hydrogen production furnace and an upper space of the hydrogen production furnace, the inner diameter of the lower space of the hydrogen production furnace is smaller than that of the upper space of the hydrogen production furnace, and the height of the upper space of the hydrogen production furnace is larger than or equal to that of the lower space of the hydrogen production furnace.

Preferably, the inner diameter of the lower layer space of the hydrogen production furnace is 1/3-2/3 of the inner diameter of the upper layer space of the hydrogen production furnace; the height of the upper space of the hydrogen production furnace is 1.0-2.0 times of the height of the lower space of the hydrogen production furnace.

The hydrogen production furnace is divided into an upper layer space and a lower layer space, high-temperature steam is additionally introduced into the upper layer space, the contact between the reduction carrier and the steam in the furnace is strengthened, and the hydrogen production reaction process between the reduction carrier and the steam is enhanced.

In an optional embodiment, the hydrogen production furnace 6 is provided with two layers of gas distributors, the lower layer of gas distributor 11 is horizontally arranged at the bottom of the lower layer space of the hydrogen production furnace, the plane of the lower layer of gas distributor 11 of the hydrogen production furnace is provided with gas holes, the gas holes are uniformly arranged along the circumference, the number of the gas holes is preferably 5-50 circles, each circle is provided with 10-100 gas holes, and the aperture ratio is preferably 1-5%; the upper-layer gas distributor 12 of the hydrogen production furnace is positioned at the bottom of the upper-layer space of the hydrogen production bed furnace and forms an included angle of less than or equal to 60 degrees with the horizontal axis, preferably 15-45 degrees, the circular conical surface of the upper-layer gas distributor 12 of the hydrogen production furnace is provided with gas holes, the gas holes are uniformly distributed along the circumference, preferably 10-100 circles of gas holes are arranged, 10-100 gas holes are arranged in each circle, and the aperture ratio is preferably 1-5%.

In a preferred embodiment, the combustion oxidation furnace 9 is a fast fluidized bed, and is provided at the bottom with an oxidation furnace gas distributor 15 and an oxidation slag hopper 20.

The novel oxygen carrier coal catalytic gasification hydrogen production process adopted by the device comprises the following steps:

the raw material coal A enters the lower layer space of the reduction furnace of the gasification reduction furnace 1 from a raw material inlet 2, is mixed and contacted with an oxidation carrier from a combustion oxidation furnace 9 and a gasifying agent B of a reduction furnace gas distributor 3, and is subjected to reactions such as catalytic pyrolysis, gasification, reduction of the oxidation carrier and the like to generate H₂、CO、CO₂、CH₄After the synthesis gas, the gasified semicoke and the reducing carrier are discharged from the top, the synthesis gas, the gasified semicoke and the reducing carrier enter a first cyclone separator 4 of a reducing furnace and a second cyclone separator 7 of the reducing furnace, and the reducing carrier is discharged from the reducing furnaceSeparated in the first cyclone separator 4, enters the hydrogen production furnace 6 through the reduction carrier returning device 5, and performs hydrogen production reaction with high-temperature steam D in the hydrogen production furnace 6 to generate hydrogen-rich gas and a sub-oxidation/oxidation carrier. The hydrogen-rich gas passes through the hydrogen production furnace cooling separation unit 13 to obtain condensed water E and high-purity hydrogen F. The sub-oxidation/oxidation carriers and the reduction carriers which are not completely reacted are discharged from the upper space of the hydrogen production furnace 6 through a sub-oxidation carrier returning device 14 and enter the combustion oxidation furnace 9. The gasified semicoke L is separated from a second cyclone separator 7 of the reduction furnace, enters a combustion oxidation furnace 9 through a semicoke returning device 8, is mixed with oxygen-containing gas G, a sub-oxidation/oxidation carrier and a reduction carrier which does not completely react, and carries out semicoke combustion, oxidation reaction of the sub-oxidation carrier and the reduction carrier which does not completely react to generate CO₂And H₂Flue gas I of O, oxidation carriers and fine ash H. The flue gas I, the oxidation carrier and the fine ash H are discharged from an outlet at the top of the combustion oxidation furnace 9, the oxidation carrier is separated by a first cyclone separator 16 of the oxidation furnace and enters the gasification reduction furnace 1 through an oxidation carrier returning device 17, the fine ash H is separated by a second cyclone separator 18 of the oxidation furnace, the residual flue gas I is discharged after passing through a cooling and purifying unit 19 of the oxidation furnace, and the coarse slag J generated after combustion is discharged from the bottom of the combustion oxidation furnace 9 and enters an oxidation furnace slag hopper 20.

Further, the reaction temperature of the gasification reduction furnace 1 is 600-1000 ℃, the gas phase line speed is 0.5-5.0 m/s, and the average density of a bed layer is 50-350 kg/m³(ii) a The reaction temperature of the hydrogen production furnace 6 is 500-900 ℃, the gas phase line speed is 0.1-1 m/s, and the average density of the bed layer is 250-600 kg/m³(ii) a The reaction temperature of the combustion oxidation furnace 9 is 800-1200 ℃, the gas phase line speed is 1.0-10 m/s, and the average density of the bed layer is 20-150 kg/m³And the reaction pressure of the system is 0-2.0 MPa.

Furthermore, the outlet linear speed of the hood radial channel M2 or the short axial channel M3 on the gas distributor 3 of the reduction furnace is 5-50M/s.

Further, a gasifying agent B comprising water vapor and CO is introduced into the gasification reduction furnace 1₂Or the mixture of the raw materials and the gasifying agent B, wherein the temperature of the gasifying agent B is 200-800 ℃.

Further, in the method, high-temperature steam D is introduced into the hydrogen production furnace lower layer gas distributor 11 and the hydrogen production furnace upper layer gas distributor 12, the temperature of the high-temperature steam D is 500-800 ℃, the proportion of the high-temperature steam D introduced into the hydrogen production furnace upper layer gas distributor 12 accounts for 10-50% of the sum of the amounts of the high-temperature steam D in the hydrogen production furnace upper layer gas distributor 12 and the hydrogen production furnace lower layer gas distributor 11, and the molar proportion of the high-temperature steam and a reduction carrier circulated back to the hydrogen production furnace 6, namely the water carrying ratio is 1.0-5.0 mol/mol.

The oxygen-containing gas G introduced into the gas distributor of the oxidation furnace comprises oxygen, air, oxygen-enriched air or a mixture of the oxygen and the air, wherein the molar ratio of the oxygen to carbon in the gasified semicoke, namely the oxygen-carbon ratio, is 1.5-3.0 mol/mol.

Further, the oxidation carrier exists in oxidation state, reduction state or oxidation state, sub-oxidation state and reduction state, and can be selected from Fe₂O₃One or more of pure iron powder, iron ore, waste iron slag or waste steel slag as main components; or metal oxides having a reduced state, including but not limited to chemically synthesized Fe₂O₃，NiO，Mn₃O₄Etc.; or a mixture of an alkali metal, a transition metal and the metal oxide with the reduction state, or a mixture of an alkali metal, a transition metal and an alkaline earth metal Ca and the metal oxide with the reduction state, wherein the active component accounts for 0.1-30% of the mass of the catalyst and is loaded on Al by an impregnation method, a dry mixing method or an ion exchange method₂O₃，ZrO₂，TiO₂，SiO₂And the like.

The heat required by the reactions such as catalytic pyrolysis, gasification and carrier reduction in the gasification reduction furnace is provided by the high-temperature oxidation carrier generated by the combustion oxidation furnace, the heat of the hydrogen production reaction in the hydrogen production furnace is also from the reduction heat carrier, and the low-temperature sub-oxidation/oxidation carrier performs the combustion reaction with the gasification semicoke in the combustion oxidation furnace and generates the high-temperature oxidation carrier, so that the heat balance is realized, and the process heat efficiency and the heat utilization rate are more efficient.

Due to the large difference of physical properties of the oxidation carrier, the gasified semicoke and the fine ash, the separation process can be completed by simple separation equipment, and the problem of difficult separation is solved.

The invention combines the gasification reduction furnace, the hydrogen production furnace and the combustion oxidation furnace, and carries out reactions such as catalytic pyrolysis, gasification, reduction of oxidation carriers and the like in the gasification reduction furnace, the reduction carriers enter the hydrogen production furnace to carry out hydrogen production reaction with high-temperature steam to produce hydrogen-rich gas, the gasified semicoke, the sub-oxidation carriers and the reduction carriers which are not completely reacted enter the combustion oxidation furnace to carry out high-temperature combustion reaction with oxygen-containing gas to produce oxidation carriers, fine ash and flue gas, wherein the oxidation carrier is circulated back to the gasification reduction furnace through the material returning device, thereby realizing the circulation of heat flow and material flow and achieving the purpose of full utilization, the carbon conversion rate at the outlet of the device can reach 99 percent, the hydrogen content at the outlet of the hydrogen production furnace reaches 99 percent, meanwhile, the method has the characteristics of high reaction strength, high energy utilization rate and high product gas yield, reduces equipment investment and production cost to a greater extent, and has good application prospect.

The following is a specific example illustrating the reaction method for producing hydrogen by catalytic gasification of coal with oxygen carrier using the apparatus of the present invention: :

[ example 1 ]

As shown in the following table, the novel oxygen carrier coal catalytic gasification hydrogen production reaction device comprises a gasification reduction furnace, wherein the inner diameter of the lower layer space of the gasification reduction furnace is 2.0m, the height of the lower layer space is 5m, the inner diameter of the upper layer space of the gasification reduction furnace is 1.0m, the height of the upper layer space is 10m, the diameter of the upper hood outlet of a gas distributor of the reduction furnace is 1mm, the height of a raw material inlet is 1/2 which is positioned at the height of the lower layer space of the gasification reduction furnace, the inner diameter of the lower layer space of the hydrogen production furnace is 1.5m, the height of the lower layer space is 6m, the inner diameter of the upper layer space of the hydrogen production furnace is 3m, the height of the upper layer space is 9m, the inner diameter of a combustion oxidation furnace is 3m, and the height is 25 m.

The method comprises the steps of selecting inner Mongolia lignite as a raw material, adding the inner Mongolia lignite into a gasification reduction furnace from a raw material inlet, introducing steam into a distributor of the reduction furnace, mixing and contacting the inner Mongolia lignite with an oxidation carrier, wherein the water-carbon ratio is 1.5mol/mol, carrying out catalytic pyrolysis, gasification, reduction of the oxidation carrier and other reactions, and generating gasification semicoke, synthesis gas and a reduction carrier at the operating temperature of 800 ℃ and the operating pressure of normal pressure of the gasification reduction furnace. The reduction carrier enters a hydrogen production furnace, high-temperature water vapor at 600 ℃ is introduced from a lower layer gas distributor and an upper layer gas distributor of the hydrogen production furnace, the water vapor introduced from the upper layer gas distributor of the hydrogen production furnace accounts for 30% of the sum of the water vapor amount of the upper layer gas distributor of the hydrogen production furnace and the lower layer gas distributor of the hydrogen production furnace, the water carrying ratio is 2.0mol/mol, the operating temperature of the hydrogen production furnace is 700 ℃, the operating pressure is normal pressure, hydrogen-rich synthetic gas and a sub-oxidation/oxidation carrier are generated, wherein the hydrogen content in the hydrogen-rich synthetic gas reaches 99%. The sub-oxidation/oxidation carrier and the reduction carrier which is not completely reacted enter a combustion oxidation furnace to be mixed and contacted with gasified semicoke and oxygen-containing gas, semicoke combustion and oxidation reaction of the sub-oxidation carrier and the reduction carrier are carried out, the operation temperature is 1000 ℃, the operation pressure is normal pressure, the oxygen-carbon ratio is 2.0mol/mol, smoke, oxidation carrier and fine ash are generated, the oxidation carrier enters the gasification reduction furnace through a first cyclone separator and an oxidation carrier returning device of the oxidation furnace, the fine ash is separated from a second cyclone separator of the oxidation furnace, coarse slag is discharged from the bottom of the combustion oxidation furnace, and the carbon conversion rate at the outlet of the combustion oxidation furnace reaches 99.5%.

Therefore, those skilled in the art should appreciate that although the embodiments of the present invention have been described above, the embodiments of the present invention are only used for understanding the present invention, and the present invention is not limited thereto. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.