CN102061182B - Method for coal hydrogenation pyrolysis and gasification coupling - Google Patents

Method for coal hydrogenation pyrolysis and gasification coupling Download PDF

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Publication number
CN102061182B
CN102061182B CN 201110021674 CN201110021674A CN102061182B CN 102061182 B CN102061182 B CN 102061182B CN 201110021674 CN201110021674 CN 201110021674 CN 201110021674 A CN201110021674 A CN 201110021674A CN 102061182 B CN102061182 B CN 102061182B
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coal
gas
pyrolysis
gasification
rich
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CN 201110021674
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Chinese (zh)
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CN102061182A (en
Inventor
吴道洪
王五一
王其成
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北京华福工程有限公司
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONAGEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • C10B49/04Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated
    • C10B49/08Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form
    • C10B49/10Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form according to the "fluidised bed" technique
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONAGEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/463Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60Processes
    • C10J3/62Processes with separate withdrawal of the distillation products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/093Coal

Abstract

The invention discloses a method for coal hydrogenation pyrolysis and gasification coupling, comprising the steps of: drying and preheating raw material coal with granularity less than or equal to 2mm in a coal drying and preheating system; putting 60-80% of the dried and preheated raw material coal in a coal hydrogenation pyrolysis furnace to carry out coal hydrogenation pyrolysis; putting a pyrolyzed gas-phase product in a pyrolyzed gas purification and separation system to carry out separation; putting all the semicoke generated by the coal hydrogenation pyrolysis furnace in a coke hydrogenation gasification furnace to carry out hydrogenation gasification; putting a gasified gas-phase product in a gasified gas purification and separation system; and causing 20-40% of the dried and preheated raw material coal and high-temperature coke granules from the coke hydrogenation gasification furnace to enter a hydrogen-rich generator from upper and lower paths under the combined action of oxygen and a water vapor mixed gasification agent so as to carry out gasification reaction. The coal hydrogenation pyrolysis, semicoke hydrogenation gasification and coke granule hydrogen production are combined; therefore, the tar yield and the light component content are effectively improved and methane-rich pyrolyzed gas, gasified gas and coal chemical products such as naphthalene, benzene, phenol and the like with high added value can be obtained.

Description

The method of coal hydrogenation pyrolysis and gasification coupling
Technical field
The present invention relates to a kind of coal resources comprehensive utilization technique, relate in particular to the method for a kind of coal hydrogenation pyrolysis and gasification coupling.
Background technology
Enter 21 century, along with the rapid growth of economy, to the also sharply increase of demand of industrial chemicals, in the industrial chemicals structure, coal accounts for over half, and " Development of Coal chemical industry, exploitation and popularization clean coal technology " become the common recognition of industrial community and academia.For the classification that realizes coal resources efficiently utilizes, academia has proposed the process imagine of " coal pulls out head ", fully extracts gas, liquid fuel and fine chemicals in coal.
In the prior art, the tar yield of pyrolysis of coal technology is lower, and light constituent content is less; The quick hydropyrolysis technology of coal can improve tar yield, obtains simultaneously the high heating value gas of methane rich, but in the feed coal still some carbon exist with low value-added semicoke form, the total carbon utilisation rate of raw material is lower.Coal Gasification Technology can obtain the different synthetic gas of gaseous fraction by selecting different vaporized chemicals, but with regard to specific gasifying medium, its synthesis gas components is more single, also can't extract the more valuable Coal Chemical Industry products such as naphthalene, benzene, phenol simultaneously.
Summary of the invention
The method that the purpose of this invention is to provide a kind of coal hydrogenation pyrolysis and gasification coupling, the method combines coal hydrogenation pyrolysis, semicoke hydrogasification and the hydrogen manufacturing of burnt grain, fully in coal, extract gas, liquid fuel and fine chemicals, combine the advantage of pyrolysis of coal technology and Coal Gasification Technology, Effective Raise tar yield and light constituent content, can obtain simultaneously the Coal Chemical Industry products such as naphthalene, benzene, phenol of methane rich pyrolysis coal gas gentleization coal gas and high added value.
The objective of the invention is to be achieved through the following technical solutions:
The method of coal hydrogenation pyrolysis of the present invention and gasification coupling comprises the processing step of following order:
A, the feed coal that granularity is less than or equal to 2mm carry out drying and preheating in coal drying and preheating system, dry after total water be less than or equal to 8%, preheating temperature is 250-350 ℃;
Feed coal 60%-80% after drying and the preheating enters the coal hydrogenation pyrolysis stove, under pressure 1.0-3.0MPa and temperature 550-680 ℃ condition, carry out hydropyrolysis, the pyrolysis gas-phase product enters pyrolysis coal gas purification separation system to be separated, and the product after the separation comprises: methane rich pyrolysis coal gas, tar, naphthalene, benzene, phenol etc.;
The semicoke of B, the production of described coal hydrogenation pyrolysis stove all enters burnt hydrogasification stove, under pressure 1.0-3.0MPa and temperature 327-427 ℃ condition, carry out hydrogasification, the gasification gas-phase product enters gasification gas purification separation system, isolates the gasification gas that is rich in methane;
Feed coal 20%-40% after C, drying and the preheating with from the porous of described burnt hydrogasification stove, loose high-temperature coke grain the acting in conjunction of oxygen and water vapor mixture agent about in the of lower minute two-way enter rich hydrogen generator, under pressure 1.0-3.0MPa and temperature 900-1500 ℃ condition, carry out gasification reaction, the hydrogen-rich gas of producing uses as the fluidized reaction gas of described coal hydrogenation pyrolysis stove, and its lime-ash is processed and finished in slag removing system.
As seen from the above technical solution provided by the invention, the coal hydrogenation pyrolysis that the embodiment of the invention provides and the method for gasification coupling, because coal hydrogenation pyrolysis, semicoke hydrogasification and the hydrogen manufacturing of burnt grain are combined, can fully in coal, extract gas, liquid fuel and fine chemicals, the advantage of comprehensive pyrolysis of coal technology and Coal Gasification Technology, Effective Raise tar yield and light constituent content, can obtain simultaneously the Coal Chemical Industry products such as naphthalene, benzene, phenol of methane rich pyrolysis coal gas gentleization coal gas and high added value.
Description of drawings
In order to be illustrated more clearly in the technical scheme of the embodiment of the invention, the accompanying drawing of required use was done to introduce simply during the below will describe embodiment, apparently, accompanying drawing in the following describes only is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite of not paying creative work, can also obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is the process flow sheet of the method for coal hydrogenation pyrolysis of the present invention and gasification coupling.
Among the figure: 1, coal drying and preheating system, 2, the coal hydrogenation pyrolysis stove, 3, burnt hydrogasification stove, 4, rich hydrogen generator, 5, pyrolysis coal gas purification separation system, 6, the gasification gas purification system, 7, slag removing system.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on embodiments of the invention, those of ordinary skills belong to protection scope of the present invention not making the every other embodiment that obtains under the creative work prerequisite.
The method of coal hydrogenation pyrolysis of the present invention and gasification coupling, its better embodiment comprises the processing step of following order as shown in Figure 1:
A, the feed coal that granularity is less than or equal to 2mm carry out drying and preheating in coal drying and preheating system, dry after total water be less than or equal to 8%, preheating temperature is 250-350 ℃;
Feed coal 60%-80% after drying and the preheating enters the coal hydrogenation pyrolysis stove, under pressure 1.0-3.0MPa and temperature 550-680 ℃ condition, carry out hydropyrolysis, the pyrolysis gas-phase product enters pyrolysis coal gas purification separation system to be separated, and the product after the separation comprises: methane rich pyrolysis coal gas, tar, naphthalene, benzene, phenol etc.;
The semicoke of B, the production of described coal hydrogenation pyrolysis stove all enters burnt hydrogasification stove, under pressure 1.0-3.0MPa and temperature 327-427 ℃ condition, carry out hydrogasification, the gasification gas-phase product enters gasification gas purification separation system, isolates the gasification gas that is rich in methane;
Feed coal 20%-40% after C, drying and the preheating with from the porous of described burnt hydrogasification stove, loose high-temperature coke grain the acting in conjunction of oxygen and water vapor mixture agent about in the of lower minute two-way enter rich hydrogen generator, under pressure 1.0-3.0MPa and temperature 900-1500 ℃ condition, carry out gasification reaction, the hydrogen-rich gas of producing uses as the fluidized reaction gas of described coal hydrogenation pyrolysis stove, and its lime-ash is processed and finished in slag removing system.
Described coal hydrogenation pyrolysis stove is fluidized-bed reactor, the pyrolysis coal gas after fluidized reaction gas is purified by a part and form from the hydrogen-rich gas of rich hydrogen generator;
Described burnt hydrogasification stove is fluidized-bed reactor, and fluidized reaction gas is the pyrolysis coal gas after a part purifies;
Described rich hydrogen generator is the cyclone bed reactor.
The present invention combines coal hydrogenation pyrolysis, semicoke hydrogasification and the hydrogen manufacturing of burnt grain, fully in coal, extract gas, liquid fuel and fine chemicals, combine the advantage of pyrolysis of coal technology and Coal Gasification Technology, Effective Raise tar yield and light constituent content, can obtain simultaneously the Coal Chemical Industry products such as naphthalene, benzene, phenol of methane rich pyrolysis coal gas gentleization coal gas and high added value.
Specific embodiment:
Take the industrial scale of coal treatment capacity 2t/h as example, the technical analysis before and after the upgrading of feed coal sees Table 1.The feed coal of mean particle size 0.6mm carries out drying and preheating in coal drying and preheating system (1) after, preheating temperature is 270 ℃, wherein 60% feed coal is introduced into coal hydrogenation pyrolysis stove (2), under pressure 1.0MPa and 600 ℃ of conditions of temperature, carry out hydropyrolysis, the pyrolysis gas-phase product enters pyrolysis coal gas purification separation system (5) and carries out purification separation, wherein the productive rates 4% such as pyrolysis gas yield 19.68% (methane-containing gas 52%), tar yield 14.63%, naphthalene, benzene, phenol; The solid product semicoke all enters burnt hydrogasification stove (3), carries out hydrogasification under pressure 1.0 and 327 ℃ of conditions of temperature, and the gasification gas-phase product enters gasification gas purification system (6), and the gasification gas component after the purification sees Table 2; After burnt hydrogasification stove (3) gasification remaining burnt grain and 40% feed coal the acting in conjunction of oxygen and water vapor mixture agent about in the of lower minute two-way enter rich hydrogen generator (4), further gasification reaction under pressure 1.0 and 1000 ℃ of conditions of temperature, the hydrogen-rich gas component of producing sees Table 3, and its lime-ash is processed and finished in slag removing system (7).
Technical analysis result (%) before and after the upgrading of table 1 feed coal
Sequence number Title Ratio/% before the dehydration Ratio/% after the dehydration
??1 Total water/M t ??17.9 ??2.5
??2 Air-dried moisture/M ad ??9.45
??3 As received basis ash content/A ar ??9.05 ??10.75
??4 As received basis fugitive constituent/V ar ??29.40 ??34.91
??5 As received basis fixed carbon/FC ar ??43.65 ??51.84
Lower heat value/Q net,ar ??21.35MJ/kg ??25.24MJ/kg
The gasification gas component that table 2 hydrogasification stove is produced
Sequence number Chemical name Content % (v/v)
??1 Hydrogen ??28.6
??2 Carbonic acid gas ??13.4
??3 Carbon monoxide ??32.0
??4 Methane ??26.0
The gaseous fraction that the rich hydrogen generator of table 3 is produced
Sequence number Chemical name Content % (v/v)
??1 Hydrogen ??35.0
??2 Carbonic acid gas ??15.0
??3 Carbon monoxide ??47.0
??4 Unsaturated olefin ??2.0
??5 Nitrogen ??1.0
The present invention compared with prior art has the following advantages:
The technical modules such as (1) the present invention is integrated coal hydrogenation pyrolysis, semicoke hydrogasification, the hydrogen manufacturing of burnt grain, realize effective extension of product chain and the comprehensive utilization of feed coal, also can coal hydrogenation pyrolysis, three technical modules of semicoke hydrogasification and burnt grain hydrogen manufacturing have been carried out different combinations according to the market requirement;
(2) the present invention can obtain the rich CH of high added value by the hydropyrolysis operation 4Pyrolysis coal gas simultaneously can Effective Raise tar yield and light constituent content;
(3) gasification gas of hydrogasification explained hereafter of the present invention is rich in CH 4Gas can be used as instead of natural gas and uses;
(4) rich hydrogen generator of the present invention utilizes the porous that forms after coal hydrogenation pyrolysis and the hydrogasification, loose high-temperature coke grain and the mixture of part material coal to prepare hydrogen-rich gas as solid material, and high, the total efficiency of carbon conversion of reaction efficiency is large.
The above; only for the better embodiment of the present invention, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.

Claims (2)

1. the method for a coal hydrogenation pyrolysis and gasification coupling is characterized in that, comprises the processing step of following order:
A, the feed coal that granularity is less than or equal to 2mm carry out drying and preheating in coal drying and preheating system, dry after total water be less than or equal to 8%, preheating temperature is 250-350 ℃;
Feed coal 60%-80% after drying and the preheating enters the coal hydrogenation pyrolysis stove, under pressure 1.0-3.0MPa and temperature 550-680 ℃ condition, carry out hydropyrolysis, the pyrolysis gas-phase product enters pyrolysis coal gas purification separation system to be separated, and the product after the separation comprises: methane rich pyrolysis coal gas, tar, naphthalene, benzene, phenol;
The semicoke of B, the production of described coal hydrogenation pyrolysis stove all enters burnt hydrogasification stove, under pressure 1.0-3.0MPa and temperature 327-427 ℃ condition, carry out hydrogasification, the gasification gas-phase product enters gasification gas purification separation system, isolates the gasification gas that is rich in methane;
Feed coal 20%-40% after C, drying and the preheating with from the porous of described burnt hydrogasification stove, loose high-temperature coke grain the acting in conjunction of oxygen and water vapor mixture agent about in the of lower minute two-way enter rich hydrogen generator, under pressure 1.0-3.0MPa and temperature 900-1500 ℃ condition, carry out gasification reaction, the hydrogen-rich gas of producing uses as the fluidized reaction gas of described coal hydrogenation pyrolysis stove, and its lime-ash is processed and finished in slag removing system.
2. the method for coal hydrogenation pyrolysis according to claim 1 and gasification coupling is characterized in that:
Described coal hydrogenation pyrolysis stove is fluidized-bed reactor, the pyrolysis coal gas after fluidized reaction gas is purified by a part and form from the hydrogen-rich gas of rich hydrogen generator;
Described burnt hydrogasification stove is fluidized-bed reactor, and fluidized reaction gas is the pyrolysis coal gas after a part purifies;
Described rich hydrogen generator is the cyclone bed reactor.
CN 201110021674 2011-01-19 2011-01-19 Method for coal hydrogenation pyrolysis and gasification coupling CN102061182B (en)

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CN 201110021674 CN102061182B (en) 2011-01-19 2011-01-19 Method for coal hydrogenation pyrolysis and gasification coupling
PCT/CN2011/079252 WO2012097598A1 (en) 2011-01-19 2011-09-01 Preparation method of coal hydropyrolysis and gasification coupling and system thereof

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CN102226111A (en) * 2011-05-27 2011-10-26 吴道洪 Method for gasifying cyclone bed powder coal
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CN103911169B (en) * 2014-04-18 2015-10-14 上海交通大学 A kind of resinous shale supercharging hydrotorting liquefaction system and technique thereof
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