CN102827620A

CN102827620A - Methane-rich gas production combined internal heat coal dry distillation poly-production technology

Info

Publication number: CN102827620A
Application number: CN2011101725692A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-06-17
Filing date: 2011-06-17
Publication date: 2012-12-19

Abstract

A methane-rich gas production combined internal heat coal dry distillation poly-production technology is characterized in that an oxygen-rich gas generated in an oxygen preparation unit 100 is adopted as an oxidant of the combustion chamber of a carbonization furnace of an oxygen-rich internal heat coal dry distillation unit 200, a ring removed coal gas generated in the unit 200 is adopted as a raw material of a comprehensive treatment unit 300, a comprehensive treatment gas generated in the unit 300 is adopted as a raw material of a purification unit 400, a sulfur and CO2 removed purified gas generated in the unit 400 is adopted as a raw material of a methanation unit 500, the unit 500 generates a methane-rich gas, and a CO2-rich gas generated in the unit 400 can enter the combustion chamber of the carbonization furnace of the unit 200 to provide the temperature control components for the combustion chamber. The technology is especially suitable for semi-coke, coal tar and substitute natural gas production combined internal coal dry distillation poly-production processes with coal and air as raw materials.

Description

A kind of internally heated coal carbonization multi-production process of coproduction high methane gas

Technical field

The present invention relates to a kind of internally heated coal carbonization multi-production process of coproduction high methane gas; Say the internally heated coal carbonization multi-production process that the present invention relates to a kind of coproduction substitute natural gas SNG especially; More particularly the present invention relates to the blue charcoal multi-production process of internally heated coal carbonization system of a kind of coproduction substitute natural gas SNG; Can produce hydrogen coal supply hydrogenation of tar upgrading process simultaneously and use, the high temperature heat conductive oil that the methanation unit produces is to coal tar hydrogenation modification process fractionation process input heat energy.

Background technology

The present invention is to be that 201110058345.9 invention application is " a kind of with CO to application number ₂Coal carbonization technology for combustion processes temperature control component " a kind of application extension.

As everyone knows; Anshan Thermal Energy Inst. of China Steel Group begins " is that raw material is at the special-purpose blue charcoal of internal thermal upright carbonization furnace refining iron alloy with non-caking coal or weakly caking coal lump coal " technology (hereinafter to be referred as middle steel gas making technology BT) of constantly research and development the early 1980s; Adopt suitable coal source (such as Chinese Datong District, the geographic coal in refreshing mansion); Refine blue charcoal and by-product raw gas and middle coalite tar; It is the mature industryization technology that a kind of blue charcoal good quality of product, production capacity are high, the coal tar productive rate is high, the active principle gas yield is big, lower, the supporting green technology of construction costs is perfect; Obtained already widely applying, its main weak point is that coal gas contains a large amount of nitrogen thereby active principle concentration is low, the low not convenient usefulness of unit volume calorific value.This technology has the general feature of the blue charcoal technology of internal heat type coal system: with the air is oxygen donator, and the main body of combustion chamber temperature control component (non-flammable, non-oxidiser component that combustion processes exists) is a nitrogen, and the raw gas of generation is with CO ₂-CH ₄-CO-N ₂(being generally the main body component)-H ₂For representing the system of component, typical raw gas volume composition is seen table 1.

The raw gas H that the blue charcoal process of coal system produces ₂/ CO molecular ratio K changes with the variation of operation factors such as coal, pyrolysis temperature, destructive distillation time, between k-factor is generally 1～3.5, be generally 1.2～2.5, certainly, possibly exceed above-mentioned scope under the few cases.

Table 1 is that the blue charcoal device of 600,000 tons/year of oxygenant effluxes the raw gas composition with the air

Application number is that 201110058345.9 invention application has proposed " a kind of with CO ₂Coal carbonization technology for combustion processes temperature control component " coal carbonization technology, can obtain poor nitrogenize raw gas, belong to CO ₂-CH ₄-CO-H ₂For representing the system of component, its classical group prejudice table 2.Because CO ₂Be easy to remove, poor nitrogenize raw gas is removed CO ₂Promptly obtain with CH ₄-CO-H ₂For representing the system gas of component, its classical group prejudice table 2.

CH ₄-CO-H ₂For representing the gas of component; It is the raw material of a good preparation substitute natural gas; And China is a country that lacks Sweet natural gas; Progressively rise in natural gas consumption market, and will become an emerging energy market, and Gas Prices presents the trend that progressively goes up in a following quite long period.When the raw gas of blue charcoal process generation at source formed surplus, this characteristic pointed out that can superfluous raw gas be converted into the cleaning substitute natural gas gas energy is input into into energy market outward.

Table 2 is that oxygenant, CO2 are combustion chamber temperature control component with the pure oxygen

600,000 tons of/year blue charcoal devices efflux raw gas and form

The method of the invention is not appeared in the newspapers.

Air separation technology, the blue charcoal technology of coal system, coke-oven gas system substitute natural gas or gasification system substitute natural gas are known technology, and the principle Technology of many steps of the present invention is identical with it, and special character of the present invention is:

1. oxygen enrichment or pure oxygen burning technology are adopted in the blue charcoal process of internal heat type coal system combustion chamber, and raw gas is poor nitrogen raw gas;

2. compare with conventional coke-oven gas system substitute natural gas technology, take off CO ₂Increase before the step and take off H ₂The S step is taken off H ₂The S step reduces takes off CO ₂Macromole hydrocarbon content in the step stripping gas creates conditions for obtaining high-pureness carbon dioxide; High-pureness carbon dioxide can be used for phenol sodium and decompose system crude phenols process or its usefulness;

3. compare with conventional coke-oven gas system substitute natural gas technology; Hotline heater is set; Utilize the high potential temperature heat energy heating of methanation reaction elute thermal oil, high temperature heat conductive oil is as reboiling heat source at the bottom of the coal tar hydrogenating process fractionation Tata, and the low temperature thermal oil returns hotline heater circulation heating.So can fuel saving consumption, for blue charcoal of majority system and coal tar hydrogenating associating processing factory, be coal tar hydrogenating process fractionating column heating furnace fuel because of it is common with raw coke oven gas, so can directly increase substitute natural gas output.

Therefore, first purpose of the present invention is to propose a kind of internally heated coal carbonization multi-production process of coproduction high methane gas.

Second purpose of the present invention is to propose a kind of internally heated coal carbonization multi-production process of coproduction high methane gas, comprehensive treating process qi exhaustion CO ₂Process is used two transformation fractionation by adsorption steps.

The 3rd purpose of the present invention is to propose a kind of internally heated coal carbonization multi-production process of coproduction high methane gas; Comprise the coal tar hydrogenating conversion process; At least a portion methanation reaction heat is used to heat thermal oil, and high potential temperature thermal oil is used as coal tar hydrogenating process fractionation process thermal source to reduce fuel consumption.

The 4th purpose of the present invention is to propose a kind of blue charcoal Poly-generation of internal heat type coal system combination process of coproduction high methane gas.

The 5th purpose of the present invention is to propose a kind of blue charcoal Poly-generation of internal heat type coal system combination process of coproduction substitute natural gas.

Summary of the invention

A kind of internally heated coal carbonization multi-production process of coproduction high methane gas is characterized in that comprising following steps:

1. make oxygen enrichment in system oxygen unit 100;

2. make in oxygen-enriched combusting internally heated coal carbonization unit 200 from encircling coal gas, charcoal, coal tar and containing coal tar sewage; Charring furnace combustion chamber oxygenant is the oxygen enrichment from unit 100; The charring furnace combustion chamber is a main combustion chamber temperature control component with carbonic acid gas, contains CH from ring coal gas ₄, H ₂, CO, CO ₂, H ₂S and organosulfur, 3. at least a portion gets into step from ring coal gas 200P;

3. in comprehensive treating process unit 300, become General Office from ring coal gas 200P through desulfurized step and regulate the flow of vital energy, 4. at least a portion General Office regulates the flow of vital energy 300P entering step;

4. at clean unit 400, the 300P that regulates the flow of vital energy of General Office is separated into desulfurization and takes off CO ₂Gas 400P is purified gas 400P and rich CO ₂Gas 400DG, 5. at least a portion purified gas 400PF gets into step;

5. in methanation unit 500, the sulphur content that gets into the methanation virgin gas of methanation reaction process is lower than the limits value of methanation catalyst to methanation virgin gas sulphur content, and the methanation virgin gas that comprises purified gas 400PF is converted into methane-rich gas.

Unit 300 of the present invention comprises CO transformation and hydrogen production step 304 usually.

When the oxygen components volumetric concentration was low in the oxygen enrichment of the present invention, each procedure condition was generally:

1. the oxygen components volumetric concentration is higher than 80% in the oxygen enrichment that makes of unit 100;

2. unit 200 is the blue charcoal of system unit, and argon gas and oxide gas volume concentrations sum are lower than 5% in ring coal gas, contain O from ring coal gas ₂

3. in the unit 300; Become and take off heavy hydrocarbon through the heavy hydrocarbon step 302 of taking off that pressure swing adsorption process takes off charcoal five and above hydrocarbon thereof from ring coal gas 200P from ring coal gas; Take off heavy hydrocarbon and become deoxidation from ring coal gas through impurity shortening step of converting 303 from ring coal gas; Deoxidation is accomplished the reaction of portion C O transformation and hydrogen production from ring coal gas through sulfur-resisting transformation step 304 and is obtained conversion gas, and the dehydration conversion gas that conversion air cooling obtains after but dewatering is regulated the flow of vital energy as General Office, the H that control General Office regulates the flow of vital energy ₂/ CO molecular ratio guarantees the H of methanation virgin gas ₂/ (CO+CO ₂) molecular ratio is 2.5～3.75;

4. in the unit 400, the CO of purified gas 400P ₂Volumetric concentration is lower than 5%, the H of control purified gas 400P ₂/ (CO+CO ₂) molecular ratio guarantees the H in the methanation virgin gas ₂/ (CO+CO ₂) molecular ratio is 2.5～3.75;

5. in the unit 500, the total sulfur volume content that gets into the methanation virgin gas of methanation reaction process is lower than 0.1PPm, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.85～1.15, the methane volumetric concentration is higher than 70% in the methane-rich gas.

1. in the unit 100, the oxygen components volumetric concentration is higher than 86% in the oxygen enrichment that makes,

2. in the unit 200, argon gas and oxide gas volume concentrations sum are lower than 3.2% in ring coal gas;

3. in the unit 300, the H that control General Office regulates the flow of vital energy ₂/ CO molecular ratio guarantees the H of methanation virgin gas ₂/ (CO+CO ₂) molecular ratio is 2.8～3.5;

4. in the unit 400, the CO of purified gas 400P ₂Volumetric concentration is lower than 2.5%, the H of control purified gas 400P ₂/ (CO+CO ₂) molecular ratio guarantees H in the methanation virgin gas ₂/ (CO+CO ₂) molecular ratio is 2.8～3.5;

5. in the unit 500, the methane volumetric concentration is higher than 75% in the methane-rich gas.

When the oxygen components volumetric concentration was higher in the oxygen enrichment of the present invention, each procedure condition was generally:

1. in the unit 100, the oxygen components volumetric concentration is higher than 98% in the oxygen enrichment that makes;

2. in the unit 200, argon gas and oxide gas volume concentrations sum are lower than 1.0% in ring coal gas;

3. in the unit 300, the H that control General Office regulates the flow of vital energy ₂/ CO molecular ratio guarantees the H of methanation virgin gas ₂/ (CO+CO ₂) molecular ratio is 2.95～3.25;

4. in the unit 400, the CO of purified gas 400P ₂Volumetric concentration is lower than 2%, the H of control purified gas 400P ₂/ (CO+CO ₂) molecular ratio guarantees the H of methanation virgin gas ₂/ (CO+CO ₂) molecular ratio is 2.95～3.25;

5. in the unit 500, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.94～1.06, the CO transformation efficiency is higher than 95%, CO ₂Transformation efficiency is higher than 85%, and the methane volumetric concentration is higher than 80% in the methane-rich gas, and methane and ethane volumetric concentration sum are higher than 90% in the methane-rich gas.

1. in the unit 100, the oxygen components volumetric concentration is higher than 99% in the oxygen enrichment that makes;

2. in the unit 200, argon gas and oxide gas volume concentrations sum are lower than 0.4% in ring coal gas;

3. in the unit 300, the H that control General Office regulates the flow of vital energy ₂/ CO molecular ratio guarantees the H of methanation virgin gas ₂/ (CO+CO ₂) molecular ratio is 3.00～3.15;

4. in the unit 400, the CO of purified gas 400P ₂Volumetric concentration is lower than 5.0%, the H of control purified gas 400P ₂/ (CO+CO ₂) molecular ratio guarantees the H of methanation virgin gas ₂/ (CO+CO ₂) molecular ratio is 3.00～3.15;

5. in the unit 500, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.98～1.02, the CO transformation efficiency is higher than 99%, CO ₂Transformation efficiency is higher than 90%, and the methane volumetric concentration is higher than 85% in the methane-rich gas, and methane and ethane volumetric concentration sum are higher than 93% in the methane-rich gas.

Unit of the present invention 300 flow processs are generally:

3. in the unit 300; Take off heavy hydrocarbon step 302 for using the pressure-swing adsorption process of acticarbon from ring coal gas 200P; Leaving the heavy hydrocarbon that takes off of step 302, to accomplish oxygen conversion from ring coal gas through impurity shortening step of converting 303 be that the reaction of water obtains deoxidation from ring coal gas, and deoxidation is accomplished CO preparing hydrogen by part changing process from ring coal gas through sulphur resisting and low temp conversing step 304.

Unit of the present invention 300 flow processs are generally:

3. in the unit 300, adopt wet desulphurizations that hydrogen sulfide volumetric concentration in the coal gas is reduced to 150～300PPm from the preparatory desulfurized step 301 of ring coal gas 200P and obtain preparatory desulfurization from ring coal gas; Desulfurization is to use the pressure-swing adsorption process of acticarbon from the heavy hydrocarbon step 302 of taking off of ring coal gas in advance; Take off heavy hydrocarbon and adopt low-temperature catalyzed hydrogenation deoxidation process and OTR near 100% from ring coal gas impurity shortening step of converting 303, deoxidation adopts low temperature sulfur-resisting transformation process to accomplish portion C O transformation and hydrogen production process from ring gas reforming step 304.

Unit 300 flow process preferablies of the present invention are:

3. in the unit 300, adopt " PDS+ tannin extract sulfur method " that hydrogen sulfide volumetric concentration in the coal gas is reduced to 150～300PPm from the preparatory desulfurized step 301 of ring coal gas 200P and obtain preparatory desulfurization from ring coal gas; Desulfurization is taken off heavy hydrocarbon step 302 for using the pressure-swing adsorption process of acticarbon from ring coal gas in advance; Taking off heavy hydrocarbon adopts low-temperature catalyzed deoxidation process to make OTR near 100% from ring coal gas impurity shortening step of converting 303; Deoxidation is adopted low temperature sulfur-resisting transformation process to accomplish the reaction of CO preparing hydrogen by part changing from ring gas reforming step 304 and is obtained conversion gas; Warm carbonyl sulfide hydrolysis method completion carbonyl sulfide hydrolysis was the poor organosulfur conversion gas of hydrogen sulfide reaction becoming during conversion gas carbonyl sulfide hydrolysis step 305 adopted; The conversion gas that obtains dewatering after poor organosulfur conversion air cooling is but dewatered, dehydration conversion gas is regulated the flow of vital energy as General Office.

When unit 400 of the present invention adopts the single-stage pressure swing adsorption process, it is characterized in that:

4. in the unit 400, adopt the single-stage pressure swing adsorption process, in the adsorbent bed adsorption process of transformation, the CO among the 300P that regulates the flow of vital energy of General Office ₂And the component that more is prone to be adsorbed such as water, hydrogen sulfide, carbon three hydrocarbon etc. are adsorbed agent absorption, H ₂, CH ₄, component such as CO passes the adsorbent bed purified gas 400P that becomes; In the adsorbent bed desorption process of transformation, the pressure when the control desorption procedure finishes, the component that is adsorbed is emitted from inlet end in reverse desorption procedure becomes stripping gas 400DG; The transformation adsorption step uses 2 or a plurality of adsorption tower, realizes the continous-stable operation.

When unit 400 of the present invention adopts the two-stage series connection pressure swing adsorption process, it is characterized in that:

4. in the unit 400, adopt the two-stage series connection pressure swing adsorption process, in adsorbent bed 401 adsorption processes of first step transformation, the regulate the flow of vital energy propane among the 300P and component such as water, hydrogen sulfide etc. that more are prone to be adsorbed thereof of General Office are adsorbed agent absorption, the CO in the virgin gas ₂And the more difficult component that is adsorbed is passed the adsorbent bed first step purified gas 401P that becomes; In adsorbent bed 401 desorption processes of first step transformation, the pressure when the control desorption procedure finishes, the component that is adsorbed is emitted from inlet end in reverse desorption procedure becomes first step stripping gas 401DG; In adsorbent bed 402 adsorption processes of second stage transformation, the H among the first step purified gas 401P ₂, CH ₄, component such as CO passes the adsorbent bed second stage purified gas 402P that becomes, CO ₂And the component such as hydrogen sulfide, carbon three hydrocarbon etc. that more are prone to be adsorbed are adsorbed the agent absorption; In adsorbent bed 402 desorption processes of second stage transformation, the pressure when the control desorption procedure finishes, the component that is adsorbed is emitted from inlet end in reverse desorption procedure becomes second stage stripping gas 402DG; Every grade of transformation adsorption step uses 2 or a plurality of adsorption tower, realizes the continous-stable operation; Second stage purified gas 402P is as purified gas 400P, and second stage stripping gas 402DG is as rich CO ₂Gas 400DG.

When unit 400 of the present invention adopts the low-temp methanol washing method, it is characterized in that:

4. in the unit 400, adopt the low-temp methanol washing method, separate the 300P that regulates the flow of vital energy of General Office and be purified gas 400P, high-purity CO ₂Gas, be rich in the CO of hydrogen sulfide ₂Gas, the gas that the hydrogen sulfide upgrading tower of Mathanol regenerating process uses is carried nitrogen from air-separating oxygen-making unit 100.

When unit 400 of the present invention adopts alcamines solvent absorbing method, it is characterized in that:

13, according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that:

4. in the unit 400, adopt the CO in the 300P counter current contact absorption gas that regulates the flow of vital energy of alcamines solvent and General Office in absorption step ₂, H ₂S is purified gas 400P and rich solvent, obtains the alcamines lean solvent and stripping gas is rich CO in the regenerative process of rich solvent ₂Gas 400DG, the alcamines lean solvent returns absorption step and recycles.

Unit of the present invention 501 Action Targets are generally:

5. in the unit 500, obtain the desulfurization methanation virgin gas that the total sulfur volumetric concentration is lower than 0.1PPm through desulphurization reaction step 501 from the purified gas 400PF of unit 400.

Unit of the present invention 500 Action Targets are generally:

5. in the unit 500; Purified gas 400PF from unit 400 obtains the desulfurization methanation virgin gas that the total sulfur volumetric concentration is lower than 0.1PPm through fixed bed catalyst desulphurization reaction step 501; Desulfurization methanation virgin gas gets into the methanation step 502 be provided with 3～8 methanators and makes methane-rich gas, and whole methanation step CO transformation efficiency is higher than 99%, CO ₂Transformation efficiency is higher than 90%, CH in the methane-rich gas ₄Volumetric concentration is higher than 80%, and methane and ethane volumetric concentration sum are higher than 90% in the methane-rich gas, and the high potential temperature heat of at least a portion methanator elute is used to heat thermal oil.

Unit of the present invention 200 operational conditions are generally:

2. in the unit 200, charring furnace combustion chamber carbonic acid gas temperature control component ratio is greater than 89%; The raw gas that leaves charring furnace is separated into cooled coal gas, coal tar and oily(waste)water through separating step; The part of cooled coal gas is returned the charring furnace coking chamber as circulation heat-carrying gas, and the carbonic acid gas temperature control component logistics of at least a portion charring furnace combustion chamber is the rich CO of unit 400 ₂Gas.

Unit of the present invention 200 operational conditions are generally:

2. in the unit 200, the carbonic acid gas temperature control component ratio of charring furnace combustion chamber is greater than 95%.

When unit 100 of the present invention adopted the separation by deep refrigeration separation of air, each procedure condition was generally:

1. unit 100 adopts the separation by deep refrigeration separation of air, and the oxygen components volumetric concentration is higher than 99% in the oxygen enrichment of production;

2. in the unit 200, the charring furnace working pressure is normal pressure～1.0MPa, and charring furnace combustion chamber carbonic acid gas temperature control component ratio is greater than 90%;

3. in the unit 300, adopt " PDS+ tannin extract sulfur method " that hydrogen sulfide volumetric concentration in the coal gas is reduced to 150～300PPm from the preparatory desulfurized step 301 of ring coal gas 200P, step 301 working pressure is normal pressure～1.0MPa; Desulfurization is taken off heavy hydrocarbon step 302 for using the pressure-swing adsorption process of acticarbon from ring coal gas in advance, and step 302 working pressure is 0.3～1.0MPa; Take off heavy hydrocarbon and from the reaction that catalytic hydrodeoxygenation generation water takes place ring coal gas impurity shortening step of converting 303 oxygen is transformed fully, step 303 working pressure is 0.3～3.0MPa; Deoxidation is adopted low temperature sulfur-resisting transformation process to accomplish the reaction of CO preparing hydrogen by part changing from ring gas reforming step 304 and is obtained conversion gas, and step 304 working pressure is 0.3～3.0MPa; Warm carbonyl sulfide hydrolysis method completion carbonyl sulfide hydrolysis was the poor organosulfur conversion gas of hydrogen sulfide reaction becoming during conversion gas carbonyl sulfide hydrolysis step 305 adopted; Step 305 working pressure is 0.3～3.0MPa; The conversion gas that obtains dewatering after poor organosulfur conversion air cooling is but dewatered, dehydration conversion gas is regulated the flow of vital energy as General Office;

4. in the unit 400, the regulate the flow of vital energy CO that takes off of 300P of General Office ₂Procedure pressure is 0.3～3.0MPa;

5. in the unit 500, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.85～1.15, the methanation virgin gas that comprises from the purified gas 400PF of unit 400 obtains the desulfurization methanation virgin gas that the total sulfur volumetric concentration is lower than 0.1PPm through desulphurization reaction step 501, and step 502 working pressure is 0.8～5.0MPa; Desulfurization methanation virgin gas gets into methanation step 502 and makes methane-rich gas, and step 502 working pressure is 0.8～5.0MPa, and whole methanation step CO transformation efficiency is higher than 90%, CO ₂Transformation efficiency is higher than 80%, CH in the methane-rich gas ₄Volumetric concentration is higher than 75%.

2. in the unit 200, the charring furnace working pressure is normal pressure～0.35MPa;

3. in the unit 300, be normal pressure～0.35MPa from preparatory desulfurized step 301 working pressures of ring coal gas; Taking off heavy hydrocarbon step 302 working pressure from ring coal gas is 0.3～0.8MPa; From ring coal gas deoxygenation step 303 working pressures is 0.5～1.5MPa; Deoxidation is 0.5～1.5MPa from ring gas reforming step 304 working pressure; Conversion gas carbonyl sulfide hydrolysis step 305 working pressure is 0.5～1.5MPa; H in the control dehydration conversion ₂/ CO molecular ratio guarantees the H of step methanation virgin gas 5. ₂/ (CO+CO ₂) molecular ratio is 2.8～3.3, whole gas reforming unit organosulfur transformation efficiency is higher than 90%;

4. in the unit 400, comprehensive treating process qi exhaustion CO ₂Procedure pressure is 0.5～1.5MPa;

5. in methanation unit 500, step 501 working pressure is 0.8～2.0MPa, and step 502 working pressure is 0.8～2.0MPa.

A kind of CO interconversion rate control method of unit 300 of the present invention is:

3. in the unit 300; Deoxidation is divided into two-way from ring coal gas; First via deoxidation is adopted low temperature sulfur-resisting transformation process to accomplish CO transformation and hydrogen production reaction through deoxidation from ring gas reforming step 304 from ring coal gas and is obtained first via conversion gas; It is that the reaction of hydrogen sulfide becomes poor organosulfur conversion gas that the gas mixture that the second tunnel deoxidation obtains after ring coal gas and at least a portion first via conversion gas mix carries out carbonyl sulfide hydrolysis through warm carbonyl sulfide hydrolysis method in the employing of carbonyl sulfide hydrolysis step 305; The conversion gas that obtains dewatering after poor organosulfur conversion air cooling is but dewatered, dehydration conversion gas is regulated the flow of vital energy as General Office.

When unit 100 of the present invention adopted transformation adsorption method of separation separation of air, each procedure condition was generally:

1. unit 100 adopts transformation adsorption method of separation separation of air, and the oxygen components volumetric concentration is higher than 80% in the oxygen enrichment of production;

3. in the unit 300, adopt " PDS+ tannin extract sulfur method " that hydrogen sulfide volumetric concentration in the coal gas is reduced to 150～300PPm from the preparatory desulfurized step 301 of ring coal gas 200P, step 301 working pressure is normal pressure～1.0MPa; Desulfurization is taken off heavy hydrocarbon step 302 for using the pressure-swing adsorption process of acticarbon from ring coal gas in advance, and step 302 working pressure is 0.3～1.0MPa; Take off heavy hydrocarbon and from the reaction of the low-temperature catalyzed hydrogenation deoxidation generation of the impurity shortening step of converting 303 generations water of ring coal gas oxygen is transformed fully, step 303 working pressure is 0.3～3.0MPa; Deoxidation is adopted low temperature sulfur-resisting transformation process to accomplish the reaction of CO preparing hydrogen by part changing from ring gas reforming step 304 and is obtained conversion gas, and step 304 working pressure is 0.3～3.0MPa; Warm carbonyl sulfide hydrolysis method completion carbonyl sulfide hydrolysis was the poor organosulfur conversion gas of hydrogen sulfide reaction becoming during conversion gas carbonyl sulfide hydrolysis step 305 adopted; Step 305 working pressure is 0.3～3.0MPa; Conversion gas obtains dewatering after poor organosulfur conversion air cooling is but dewatered; Dehydration conversion gas is regulated the flow of vital energy as General Office, the H in the control dehydration conversion ₂/ CO molecular ratio guarantees the H of step methanation virgin gas 5. ₂/ (CO+CO ₂) molecular ratio is 2.9～3.5, whole gas reforming unit organosulfur transformation efficiency is higher than 90%;

4. in the unit 400, the regulate the flow of vital energy CO that takes off of 300P of General Office ₂Procedure pressure is 0.3～3.0MPa, the CO of purified gas 400P ₂Volumetric concentration is lower than 5%;

5. in the unit 500, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.85～1.15; The purified gas 400PF that comprises from unit 400 obtains the desulfurization methanation virgin gas that the total sulfur volumetric concentration is lower than 0.1PPm through desulphurization reaction step 501; Desulfurization methanation virgin gas gets into methanation step 502 and makes methane-rich gas; Step 502 working pressure is 0.8～5.0MPa, and whole methanation step CO transformation efficiency is higher than 95%, CO ₂Transformation efficiency is higher than 80%, CH in the methane-rich gas ₄Volumetric concentration is higher than 75%.

3. in the unit 300, be normal pressure～0.35MPa from preparatory desulfurized step 301 working pressures of ring coal gas 200P; Taking off heavy hydrocarbon step 302 working pressure from ring coal gas is 0.3～0.8MPa; From ring coal gas deoxygenation step 303 working pressures is 0.5～1.5MPa; Deoxidation is 0.5～1.5MPa from ring gas reforming step 304 working pressure; Conversion gas carbonyl sulfide hydrolysis step 305 working pressure is 0.5～1.5MPa; H in the control dehydration conversion ₂/ CO molecular ratio guarantees the H of step methanation virgin gas 5. ₂/ (CO+CO ₂) molecular ratio is 3.0～3.15, whole gas reforming unit organosulfur transformation efficiency is higher than 90%;

4. in the unit 400, the regulate the flow of vital energy CO that takes off of 300P of General Office ₂Procedure pressure is 0.5～1.5MPa;

5. in methanation unit 500, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.94～1.06, step 502 working pressure is 0.8～2.0MPa, whole methanation step CO transformation efficiency is higher than 99%, CO ₂Transformation efficiency is higher than 90%, CH in the methane-rich gas ₄Volumetric concentration is higher than 80%.

When the present invention is provided with coal tar machining cell 600, it is characterized in that:

5. in the unit 500, the high potential temperature heat of at least a portion methanator elute is used to heat the low temperature thermal oil and forms high temperature heat conductive oil; The high temperature heat conductive oil temperature is 350～400 ℃, and lower temperature thermal oil temperature is high 30～50 ℃; The main ingredient of thermal oil is a biphenyl;

6. at coal tar machining cell 600; Be separated into coal-tar pitch and dead oil from step coal tar 2. through the separating step that includes separation column; Dead oil gets into dead oil hydro-upgrading unit and is converted into hydrogenated oil; Hydrogenated oil is separated into narrow fraction oil product such as diesel oil distillate, naphtha fraction etc. through the sepn process that includes separation column; At least a portion reboiling heat of at least one separation column of above-mentioned sepn process is by providing through the indirect heat exchange mode from step high temperature heat conductive oil 5., and the low temperature thermal oil that high temperature heat conductive oil heat release cooling back forms returns step and 5. recycles.

When the present invention is provided with conversion gas hydrogen manufacturing unit 700 with coal tar machining cell 600, it is characterized in that:

3. in conversion gas hydrogen manufacturing unit 700, a part of first via conversion gas cooling dehydration back entering transformation absorption decarbonation process 701 is separated into takes off CO ₂Purified gas 701P and rich CO ₂Stripping gas 701DG, at least a portion is taken off CO ₂Purified gas 701P entering transformation absorption hydrogen purification process 702 is separated into carries dense hydrogen 702P and methane rich stripping gas 702DG; At least a portion is carried dense hydrogen 702P and use raw hydrogen as the dead oil hydro-upgrading unit of step in 6., and at least a portion methane rich stripping gas 702DG gets into step and 5. is used as the methanation virgin gas; Put forward dense hydrogen 702P hydrogen volume concentration usually above 95%, generally be higher than 99%;

6. at coal tar machining cell 600, be separated into coal-tar pitch and dead oil from step coal tar 2. through the separating step that includes separation column, dead oil gets into dead oil hydro-upgrading unit and is converted into hydrogenated oil.

When the present invention is provided with conversion gas hydrogen manufacturing unit 800 with coal tar machining cell 600, it is characterized in that:

4. in purified gas hydrogen manufacturing unit 800; Part purified gas entering transformation absorption hydrogen purification process 800 is separated into carries dense hydrogen 800P and methane rich stripping gas 800DG; At least a portion is carried dense hydrogen 800P and use raw hydrogen as the dead oil hydro-upgrading unit of step in 6., and at least a portion methane rich stripping gas 800DG gets into step and 5. is used as the methanation virgin gas; Put forward dense hydrogen 800P hydrogen volume concentration usually above 95%, generally be higher than 99%;

Unit 300 of the present invention is provided with the preposition CO of taking off ₂During step 302K, it is characterized in that:

3. in the unit 300, take off heavy hydrocarbon from ring coal gas through the preposition CO of taking off ₂Step 302K takes off CO before being separated into conversion ₂Gas 302KP and rich CO ₂Gas 302KD takes off CO before the conversion ₂Gas 302KP gets into impurity shortening step of converting 303, the rich CO of at least a portion ₂Gas 302KD can get into the 2. said charring furnace of step combustion chamber provides the charring furnace combustion chamber with carbonic acid gas temperature control component.

When unit 300 of the present invention was not provided with the CO shift step, each procedure condition was generally:

1. unit 100 is the raw material production oxygen enrichment with the air, and the oxygen components volumetric concentration is higher than 80% in the oxygen enrichment;

2. in the unit 200, the charring furnace working pressure is normal pressure～1.0MPa;

3. in the unit 300, adopt " PDS+ tannin extract sulfur method " that hydrogen sulfide volumetric concentration in the coal gas is reduced to 150～300PPm from the preparatory desulfurized step 301 of ring coal gas 200P, step 301 working pressure is normal pressure～1.0MPa; Desulfurization is taken off heavy hydrocarbon step 302 for using the pressure-swing adsorption process of acticarbon from ring coal gas in advance, and step 302 working pressure is 0.3～1.0MPa; Take off heavy hydrocarbon and from the reaction that low-temperature catalyzed hydrogenation deoxidation generation water takes place ring coal gas impurity shortening step of converting 303 oxygen is transformed fully, step 303 working pressure is 0.3～3.0MPa; It is that the poor organosulfur deoxidation of hydrogen sulfide reaction becoming is from encircling coal gas that deoxidation warm carbonyl sulfide hydrolysis method in ring coal gas entering carbonyl sulfide hydrolysis step 305 adopts is accomplished carbonyl sulfide hydrolysis; Step 305 working pressure is 0.3～3.0MPa, and poor organosulfur deoxidation obtains General Office and regulates the flow of vital energy after ring coal gas cooled dehydrated;

5. in the unit 500, the methanation virgin gas that comprises from the purified gas 400PF of unit 400 obtains the desulfurization methanation virgin gas that the total sulfur volumetric concentration is lower than 0.1PPm through desulphurization reaction step 501, and step 502 working pressure is 0.8～5.0MPa; Desulfurization methanation virgin gas gets into methanation step 502 and makes methane-rich gas, and step 502 working pressure is 0.8～5.0MPa, and whole methanation step CO transformation efficiency is higher than 90%, CO ₂Transformation efficiency is higher than 80%.

3. in the unit 300, be normal pressure～0.35MPa from preparatory desulfurized step 301 working pressures of ring coal gas; Taking off heavy hydrocarbon step 302 working pressure from ring coal gas is 0.3～0.8MPa; From ring coal gas impurity shortening step of converting 303 working pressures is 0.5～1.5MPa; Deoxidation is 0.5～1.5MPa from ring gas reforming step 304 working pressure; Conversion gas carbonyl sulfide hydrolysis step 305 working pressure is 0.5～1.5MPa; H during control General Office regulates the flow of vital energy ₂/ CO molecular ratio guarantees the H of step methanation virgin gas 5. ₂/ (CO+CO ₂) molecular ratio is 2.8～3.3, whole gas reforming unit organosulfur transformation efficiency is higher than 90%;

Embodiment

Below describe the present invention in detail.

Pressure of the present invention refers to absolute pressure.

Gas component concentrations of the present invention when not specializing, is volumetric concentration.

Because a plurality of steps of the present invention are used the transformation adsorption separation technology, so this paper at first describes the sorbent material of pressure-swing adsorption process of the present invention and use thereof in detail.

Absorption is meant: when the different materials contact of two kinds of phases, wherein the molecule of the low material of density at the higher material surface of density by the phenomenon of enrichment and process.Have adsorbing material (being generally the relatively large porosu solid of density) and be called as sorbent material, the material that is adsorbed (being generally less relatively gas of density or liquid) is called adsorbate.Absorption can be divided into four big types by the difference of its character, that is: chemisorption, activated adsorption, kapillary is condensing and physical adsorption.Absorption in transformation absorption (PSA) gas separation process is mainly physical adsorption.Physical adsorption is meant the absorption that relies on the molecular force (comprising Van der Waals force and electromagnetic force) between sorbent material and adsorption molecule to carry out.Be characterized in: do not have chemical reaction in the adsorption process, what adsorption process was carried out is exceedingly fast, and the running balance between each phase material of participating in adsorbing can be accomplished in moment, and this absorption is completely reversibility.Why the adsorption gas separating technology process is achieved is because two essential propertys that sorbent material is had in this physical adsorption: the one, and different to the adsorptive power of different components; The 2nd, the loading capacity of adsorbate on sorbent material rises with the dividing potential drop of adsorbate and increases, and descends with the rising of adsorption temp.Utilize first character of sorbent material, can realize making other component be able to purify the preferentially adsorbed of some component in the mixed gas; Utilize second attributes of sorbent material, can realize that sorbent material adsorbs under low temperature, high pressure and under high temperature, low pressure desorption and regeneration, thereby constitute the absorption and the reprocessing cycle of sorbent material, reach the purpose of continuous divided gas flow.The desorption method of transformation absorption sorbent material has depressurization desorption, heating desorption and flushing desorb and combination several different methods thereof.The sorbent material that the use of hydrogen process is proposed in said transformation absorption all is the solid particulate that has than bigger serface, mainly contains: activated alumina class, silica type, gac class and molecular sieve.The most important physical features of sorbent material comprises pore volume, pore size distribution, surface-area and surface properties etc.The different adsorption agent is owing to have different pore size distributions, different specific surface and different surface character, thereby each component in the mixed gas is had different adsorption ability and loading capacity.For the complicated virgin gas F of composition, in practical application, use multiple sorbent material usually, press the absorption property compound adsorption bed of layering filling composition successively, to reach the separation purpose.Transformation is adsorbed under the situation of stable operation, and the sorbent material life-span is quite long, generally can reach 8～10 years even longer.Ability based on this absorption impurity composition that sorbent material had far is better than the characteristic of adsorbing the hydrogen ability, realizes the hydrogen purification in the hydrogeneous virgin gas.Sorbent material is mainly estimated through the adsorption isothermal line of measuring the absorption property of gas, and good absorption property and bigger loading capacity are the pacing itemss of superior adsorbent.Simultaneously, in the industry during pressure-swing adsorption process selected adsorbent, must the Considering Adsorption agent should be big as far as possible to the separation factor of each component.So-called separation factor is meant: when reaching adsorption equilibrium, and the ratio of (weak absorbed component is the residual volume/total amount of weak absorbed component in adsorption bed in the adsorption bed dead space) and (strong absorbed component is the residual volume/strong total amount of absorbed component in adsorption bed in the adsorption bed dead space).Separation factor is big more, and it is easy more to separate.Generally speaking, the sorbent material separation factor in the transformation absorption hydrogen purification process should not be less than 3.In addition, the contradiction between the considered adsorption and desorption also in industrial pressure-swing adsorption process.Generally speaking, then desorb is more difficult more easily in absorption.As to strong adsorbates such as hydrogen sulfide, should select more weak relatively sorbent material of adsorptive power such as silica gel etc., desorb is easier to so that loading capacity is suitable; And to N ₂, O ₂, weak adsorbate such as CO, just should select stronger relatively sorbent material of adsorptive power such as molecular sieve, the special-purpose sorbent material of CO etc. so that loading capacity more greatly, separation factor is higher.In addition, in adsorption process, because the adsorption bed internal pressure is constantly to change, thereby sorbent material also should have enough intensity and resistance to abrasion.

In several kinds of sorbent materials that the transformation absorbed portion is used always, high-voidage activated alumina (Al ₂O ₃) belong to the solid that water is had strong avidity; General heat dehydration or the preparation of thermal activation method of adopting aluminum trihydrate or gibbsite, physical and chemical performance is extremely stable, resistance to wears, resists broken, nontoxic; Mainly be seated in the bottom of adsorption tower; Adsorb the moisture in the virgin gas, be used for the drying of gas, prevent that other sorbent material suction back adsorptive power from reducing.The silica type sorbent material; Be mainly used in and remove water, hydrogen sulfide, carbonic acid gas, heavy hydrocarbon etc.; Silica gel has high separation factor to the hydrogen sulfide in hydrogen sulfide, carbonic acid gas, methane, the nitrogen system, and silica gel particularly Kiselgel A has high separation factor to the carbonic acid gas in carbonic acid gas, methane, the nitrogen system.Gac class sorbent material is the flourishing especially special-purpose activated charcoal of hole that to be raw material with the coal obtain through special chemistry and thermal treatment; Belong to the nonpolarity sorbent material of water-resisting type; Be characterized in that oxide groups and inorganics impurity that the surface is had make surface properties show as low-pole or nonpolarity, add the king-sized internal surface area that gac has, make gac become a kind of superior adsorbent that can adsorb multiple low-pole and nonpolar organic molecule in a large number; Usually fill in the middle part of adsorption tower; Be mainly used in the carbonic acid gas and the part methane that remove with hydrogen coexistence, since cheap and loading capacity is bigger, be a kind of sorbent material commonly used of a large amount of uses.Zeolite molecular sieve class sorbent material is a kind of inclined to one side silico-aluminate of crystal form that has the cubes skeleton structure, contains alkaline earth element; Belong to strong polar adsorbent; Very consistent aperture structure and extremely strong adsorption selectivity are arranged; Usually fill in the top of adsorption tower, be mainly used in the nitrogen, carbon monoxide and the methane that remove with the hydrogen coexistence.

Transformation absorbed portion of the present invention, the number of every group of adsorption tower are 2～24 or more, and the tower number that is in adsorbed state simultaneously can be two or more.All transformation absorbed portions, every adsorption tower all moves by the programstep of its place group in proper order, just staggers each other on the time.The adsorption tower of each workshop section be in the tower number of adsorbed state can be identical also can be inequality.The increase and decrease of tower number all presses number of times to change, and what of isolation step can be confirmed according to the concrete operations needs.

The transformation adsorption separation process of coal gas described herein and conversion gas thereof belongs to CO ₂-CO-CH ₄-poor N ₂-H ₂The sepn process of system.Conversion qi exhaustion CO ₂The hydrogen process of carrying of the purified gas that forms belongs to CH ₄The poor N of-CO- ₂-H ₂The sepn process of system all has sophisticated technology to use for reference.For these reasons, this partial content of description is exceeded in the present invention.This paper mainly describes relevant special content of the present invention.

Overall procedure of the present invention is: the oxygen enrichment of making oxygen unit 100 by oneself gets into internal heat type oxygen-enriched combusting dry distillation of coal unit 200 and makes charcoal (like semicoke), leaves ring coal gas, coal tar and oily(waste)water; Get into from ring coal gas and after comprehensive treating processs are accomplished in ring coal gas comprehensive treating process unit 300, to be converted into General Office and to regulate the flow of vital energy, General Office regulates the flow of vital energy and gets into clean unit 400 and be separated into desulfurization and take off CO ₂Purified gas and rich CO ₂Gas, purified gas gets into methanation unit 500 and is converted into methane-rich gas.

When the present invention and coal tar hydrogenating conversion process were formed integrated technique, at least a portion methanation reaction heat of methanation unit 500 was used to heat thermal oil, and high potential temperature thermal oil is used as coal tar hydrogenating process fractionation process thermal source to reduce fuel consumption.

Below describe system oxygen according to the invention unit 100 in detail.

System oxygen described herein unit 100 refers to the process of any suitable preparation oxygen.

System oxygen described herein unit 100, being commonly referred to as with the air is the system oxygen process of raw material, make oxygen unit 100 and possibly also produce N this moment ₂Gas products or the liquid product of (nitrogen molecule) or Ar (argon molecule).Air-separating oxygen-making method commonly used has deep cooling process for separating, transformation adsorptive separation technology and the combined method of the two etc.Known air-separating oxygen-making technology can be learnt from the listed publication of table 3.

The publication of table 3 record separating air and making oxygen technology

Air low temperature separation process method for producing oxygen through can make volumetric concentration up to 99.6% high purity oxygen; Can make volumetric concentration simultaneously up to 99.99% high pure nitrogen and pure argon; But the investment of this method is higher, generally be suitable for the big occasion of oxygen output such as oxygen output greater than 30,000 SCMs/time occasion.

The transformation adsorptive separation technology can make volumetric concentration up to 85～90% oxygen enrichment; Be higher than 95.55% high purity oxygen gas but can not obtain the carrier of oxygen volume concentrations, this method generally be suitable for the not too high occasion of oxygen output middle and small scale, oxygen purity requirement such as oxygen output less than 10,000 SCMs/time system oxygen enrichment occasion.

Some special occasions possibly exist with oxygen be the course of processing of sub product such as the brine electrolysis process, if these oxygen components concentration are suitable, also can introduce the present invention " dry distillation of coal unit 200 " as charring furnace combustion chamber oxygenant.

Below describe oxygen-enriched combusting internally heated coal carbonization according to the invention unit 200 in detail.

Internally heated coal carbonization process described herein; Refer to any suitable internally heated coal carbonization process; Comprise the blue charcoal process of internal heat type coal system, such as the large-scale upright furnace internal heat type orchid charcoal process of Anshan Research Inst. of Heat Energy, China Iron & Steel Group and Huang gang, Hubei metallurgical furnace Ltd of Huaxing etc.This paper is the process modification of example explanation the present invention to the blue charcoal process of internal heat type with the blue charcoal process technology of the large-scale upright furnace of Anshan Research Inst. of Heat Energy, China Iron & Steel Group and Huang gang, Hubei metallurgical furnace Ltd of Huaxing.Yet this can not limit Application Areas of the present invention.The present invention is applicable to all internal heat type carbonization process.

Oxygen-enriched combusting internally heated coal carbonization according to the invention unit; The internally heated coal carbonization process that to refer to any its suitable charring furnace combustion chamber oxygenant be oxygen enrichment; Compare with the internally heated coal carbonization process of routine, main difference is to reduce the nitrogen quantity that charring furnace combustion chamber oxygenant carries.

" is that raw material is at the special-purpose blue charcoal of vertical retort refining iron alloy with non-caking coal or weakly caking coal lump coal " technology and equipment of Anshan Thermal Energy Inst. of China Steel Group; Employing is suitable coal source with geographic coal such as China Datong District, refreshing mansion; Adopt internal thermal upright formula charring furnace to refine blue charcoal and by-product raw gas and middle coalite tar, this technology has the general feature of similar blue charcoal technology: the charring furnace combustion chamber is the main heat-carrying component of combustion processes with nitrogen.In the representative data of these place row, the blue charcoal size of capacity of process is 600,000 tons/year, and year is 7920 hours/year (330 days date manufactured meter per year) when going into operation, and is raw material with Yulin city Shenmu County's coal, coal gas production capacity 1.03 * 10 ⁹Mark cubic meter/year, 60,000 tons/year of tar production capacities.

Typical feed coal character is following: the lump coal of 25～80mm, and the screening of feed coal with due regard to, daily requirement coal amount is 3000 tons/day, promptly 125 tons/time.

The blue charcoal of major product; Have excellent properties such as low ash, low-sulfur, low aluminium, hyperergy, high specific resistance; Can be widely used in industry such as iron alloy, calcium carbide, synthetic ammonia and blast furnace blowing, field such as civilian, can partly replace coking coal, gasification briquette and smokeless piece etc., realize resource rational utilization.

Blue charcoal according to the invention refers to the blue charcoal of discharging from blue charcoal oven carbonization chamber cooling section, and the hot charcoal character of typical blue charcoal process is seen table 6.

600,000 tons/year of blue carbon yields, wherein:

1. specification 1: granularity >=5mm, 520,000 tons/year, and blue charcoal＞5mm grade can supply domestic ferroalloy works, calcium carbide factory, fertilizer plant and outlet;

2. specification 2: granularity＜5mm, 80,000 tons/year, coke powder＜5mm, can supply Iron And Steel Plant's blast furnace blowing with or power plant for self-supply use.

The typical upright furnace of table 4 is with Shenmu County's coal index of coal

Sequence number	Project	Unit	Data
				1	Moisture	％	≤7
2	Sulphur content	％	≤0.5
				3	Ash content	％	≤6.5
4	Volatile matter	％	29～36
				5	Thermostability		Well
6	Granularity	mm	25～80

One group of typical feed coal ature of coal survey report of table 5

Sequence number	Interventions Requested	Check data	The employing standard
				1	Total water (%)	10.8	GB/T211-1996
2	Analysis moisture (%)	3.74	GB/T212-2001
				3	Ash content (%)	4.92	GB/T212-2001
4	Volatile matter (%)	34.40	GB/T212-2001
				5	Characteristic of char residue (1-8)	2	GB/T212-2001
6	Fixed carbon (%)	60.04	GB/T212-2001
				7	Full sulphur (%)	0.21	GB/T214-1996
8	Hydrogen richness (%)	3.69	GB/T476-2001

The hot charcoal character of the typical blue charcoal process of table 6

Sequence number	Project	Unit	Data
				1	Fixed carbon	％	＞84
2	Ash content (Ad)	％	≯9
				3	Aluminum oxide (Al ₂Ox)	％	≯2
4	Phosphorus (P)	％	≯0.025
				5	Sulphur (S)	％	≯0.5
6	Moisture (H ₂O)	％	≯8
				7	Volatile matter (Vdaf)	％	≯4
8	Resistivity (ρ)	10 ^-5Ωm	≮3100
				9	Temperature	℃	180～250
10	Pressure

The technological process of production comprises coal workshop section, charing workshop section, the burnt workshop section of sieve fortune, the cold workshop section of drum and WWT workshop section fully.

Charing workshop section: vertical retort takes many grate furnaces body to arrange.The type of furnace can be selected ZNZL3082 type internal thermal upright carbonization furnace.Furnace binding and characteristics:

● this type of furnace has enlarged heat size than general upright carbonization furnace, and coking chamber length is increased to 3000～3500mm by 2100mm, and height is increased to 8200mm by 7000mm, thereby favourable condition is provided for the stable and high yields of upright carbonization furnace.

● increased the volume of combustion chamber and suitably increased air inlet port quantity, coal gas and air are fully burnt in the combustion chamber, hot waste gas evenly gets into coking chamber, thereby prevents to hang degrading of slag and inlet mouth effectively.

● coking chamber both sides, every hole are respectively equipped with two-layer totally 4 independently horizontal quirks (combustion chamber) up and down, and the temperature distribution that can regulate every hole coking chamber is neatly guaranteed whole stove uniform in quality, stable.

● the steam quenching is carried out in blue charcoal quenching earlier, carries out the water quenching then.Hydrogen richness makes blue carbonaceous amount increase simultaneously in the main raising coal gas.

● blue charcoal is discharged from upright furnace by the scraper plate machine, carries out classification on the sieve apparatus through being transported to behind the drying machine drying, and the blue charcoal after the classification is transported to storage Jiao Chang respectively by conveyor drive.

The technical process of gas purification workshop section: the coal gas → pneumatic trough → gas-liquid separator → direct-cooled one section tower → direct-cooled two sections tower → gas fans → electrical tar precipitator → part coal gas internal recycle that comes out from charring furnace returns outside charring furnace, the part coal gas and supplies the user.

WWT workshop section: industrial sewage adopts burning disposal, can accomplish the industrial sewage zero release.

According to the present invention; In internally heated coal carbonization charring furnace part; Coal charge gets into the blends preheating section on charring furnace coking chamber top; Oxygenant and fuel gas get into and combustion reactions takes place in the charring furnace combustion chamber form entering coking chamber retort section behind the high-temperature flue gas and contact with coal charge from the blends preheating section; The hot blue charcoal that leaves charring furnace coking chamber charcoal cooling section can be got into water by coke extractor discharge coking chamber and cease burnt step, and the raw gas that leaves charring furnace coking chamber charcoal preheating section gets into the coal gas separate part and obtains de-oiling, dehydration coal gas.At the coal gas separate part; Effectively accomplish gas-liquid separation under the operational condition certain; The product that obtains is discharged system, and wherein, the coal tar that obtains gets into following process program such as tar fractionation part; What obtain gets into following process program such as gas purification, conversion, puies forward procedure of processings such as hydrogen or methanation from ring coal gas, and the coal tar sewage that contains that obtains gets into Sewage treatment systems.At the coal gas separate part, part de-oiling, dehydration coal gas get into the burnt cooling section of charring furnace coking chamber as circulation heat-carrying gas.The WP of charring furnace each several part recommends to adopt lower WP, and this WP should be able to guarantee that usually gaseous stream dependence self pressure finally gets into subsequent handling certainly.The top WP of coking chamber is confirmed as required, can be for pressure-fired～1.0MPa (absolute pressure), be generally pressure-fired～0.35MPa (absolute pressure), be generally pressure-fired～0.16MPa (absolute pressure).

The working temperature of charring furnace each several part is confirmed according to feed coal character, burnt product quality indicator etc., is example with blue charcoal charring furnace; The top working temperature; Being generally 150～320 ℃, being generally 180～280 ℃, preferably is 200～250 ℃, retort section focus working temperature, and being generally 650～950 ℃, being generally 700～900 ℃, preferably is 750～850 ℃; Cooling section coke discharging temperature is generally 150～300 ℃, is generally 180～250 ℃.The service temperature of the blue charcoal charring furnace of various forms of internal heat types is identical substantially.

This section is used for specifically describing the technical process of " carbonization process and charring furnace perolene cyclic part " (or being referred to as the gas making part), only describes a kind of specific form, but does not limit its flow process form.At first pack in the coal groove of furnace roof topmost by being equipped with qualified shove charge coal that coal workshop section ships, again in putting coal cock and auxiliary coal bin (can the be coal lock system) coking chamber of packing into.Continuously to the coking chamber coal.The lump coal that adds coking chamber moves from top to bottom, sends into the high-temperature gas counter current contact of coking chamber with the combustion chamber.The top of coking chamber is preheating section, and lump coal is heated to about 350 ℃ in this section; Lump coal continues to move down the retort section that gets into the coking chamber middle part, and lump coal is heated to 780～820 ℃ through this section, and is blue charcoal by charing; When blue charcoal passes through the cooling section of coking chamber bottom; Being passed into this section perolene circulating gas is cooled to 180～250 ℃ and becomes warm charcoal; The temperature charcoal is through coke discharging system (coke extractor and can be employable burnt lock system) release coking chamber; The temperature charcoal gets into and to put out charcoal section (quenching section) and be cooled to about 80 ℃ by coke quenching water usually, after putting burnt machine and discharge continuously with scraper plate, falls on the dryer through chute.The gas mixture of the coal gas that produces when the high-temp waste gas of the coal gas that coal charge produces in carbonization process, combustion chamber entering coking chamber and cooling coke is discharged the every raw gas of coking chamber car; Get into pneumatic trough through upcast, bridge tube, the raw gas about 150～200 ℃ is cooled to about 80 ℃ through the cyclic ammonia water sprinkling in bridge tube and pneumatic trough.The ammonia water and tar oil that cooled coal gas gets off with condensation through air suction pipe gets into gas purification workshop section.The coal gas of upright furnace heating usefulness is through the further cooling of gas purification workshop section and the coal gas after purifying.The oxygen enrichment of upright furnace combustion chamber is supplied with by gas blower pressurization back by oxygen enrichment usually; Coal gas and oxygen enrichment mix through burner; In horizontal quirk internal combustion; The high-temp waste gas that burning produces gets into coking chamber through equally distributed air inlet port on the coking chamber side wall, utilizes the heat of high-temp waste gas that coal charge is carried out charing.The raw gas that comes out from upright furnace, effuser be recycled ammoniacal liquor spray be cooled to 80～90 ℃ after, get into washing tower along inhaling gas pipe through gas-liquid separator; Ammoniacal liquor is by washing tower top spray, and the ammoniacal liquor that the bottom has tar gets into heat ring tank; Coal gas is got into by direct-cooled washing tower bottom, and top is discharged and got into inter cooler; Coal gas is cooled to 40～45 ℃ by 80 ℃.Coal gas gets into the Root's blower pressurization behind straight a, water cooler, behind electrical tar precipitator, use as purifying coal gas.In common process, a large amount of raw gas are directly delivered to the upright furnace combustion chamber and are acted as a fuel.From the tar ammonia that gas-liquid separator and direct-cooled washing tower come out, flow into heat ring tank standing separation tar certainly, tar dewaters with being pumped to the tar storage tank, and thermal cycling ammoniacal liquor is with being pumped to the furnace roof effuser and direct-cooled washing tower recycles.From the tar ammonia that inter cooler comes out, flow into cold ring tank standing separation tar certainly, tar is with being pumped to the dehydration of tar storage tank, and cold cyclic ammonia water recycles with being pumped to inter cooler.Tar (moisture＜4%) after the dehydration of tar storage tank is delivered to tar job shop or entrucking outward transport.

The present invention uses following conceptual description internally heated coal carbonization technological process:

1. gas making part: with coal, water, oxygen donator, fuel body is raw material, obtains charcoal, tar, leaves ring coal gas, contains tar process sewage process, comprises that charring furnace ST and coal gas return stove part technological process;

2. gas making part internal recycle logistics: the recycle stream of gas making partial interior;

3. from ring coal gas processing part: the machining process that leaves the coal gas in coal gas internal recycle loop (promptly discharging the gas making part); Like gas preparation substitute natural gas process of the present invention;

4. gas making part outer circulation logistics: by leaving ring coal gas processing part to gas making part mobile recycle stream.

In order to describe coal carbonization process charring furnace combustion chamber technological process; The present invention divides the whole feed gas constituents in combustion chamber according to fuel, oxygenant, three kinds of functions of temperature control agent; And, define as follows by virtual oxygen donator and virtual combustion gas body conceptual analysis combustion processes heat effect:

1. virtual oxygen donator is made up of oxidant constituents and temperature control agent component; The oxygen components volumetric concentration can be controlled in the existing reliable rule of thumb data scope in the virtual oxygen donator: the ratio of first part's combustion chamber temperature control component volume amount and oxygen components volume amount is by 1.50～5.25 calculating (being that the oxygen components volumetric concentration is 16～40% in the virtual oxygen donator), and the present invention requires CO ₂The temperature control component ratio of component is greater than the 0.50 poor nitrogenize with the realization combustion processes; Virtual oxygen donator temperature control agent component source is unrestricted: can from outside the gas making process or within, can be from gas making part internal recycle or outer circulation;

2. virtual combustion gas body is made up of second section combustion chamber temperature control component and fuel element, and the calorific value of promptly virtual combustion gas body can be controlled in the existing reliable rule of thumb data scope: virtual combustion gas body volume calorific value is 1400～2600KCAL/NM ³, the component of virtual combustion gas body source is unrestricted: can from outside the gas making process or within, can be from gas making part internal recycle or outer circulation.

In order to describe coal carbonization process charring furnace coking chamber technological process, the present invention divides the whole feed gas constituents of coking chamber according to fuel, oxygenant, three kinds of functions of coking chamber heat-carrying component, and presses heat-carrying process and the combustion processes that this conceptual analysis coking chamber takes place.Why do not use temperature control agent one speech; Be to have much because of controlling factor in the coking chamber combustion processes; Comprise: the temperature of the hot charcoal of place space caloradiance, contact, a large amount of coking chamber heat-carrying component are to dissemination, the flame propagation velocity of " fuel and oxygenant ", exist many factors such as regional gas flow pattern at charcoal piece (or coal cinder), and " coking chamber fuel gas combustion processes " is the fuel gas combustion processes that there are significant difference in and " combustion chamber fuel gas combustion processes ".

So far, this paper gaseous constituent that will go out, go into charring furnace is divided by following function or attribute:

1. combustion components, its definition is outside from charring furnace, get into the component combustion chamber, that participate in combustion reactions, the fuel element (H that consumes like combustion processes ₂, CO, hydro carbons, H ₂S) and oxidant constituents O ₂After combustion processes finishes; Partly or entirely combustion components is converted into flue gas, and the residual combustion components that unburn transforms belongs to the superfluous combustion components of combustion processes, and promptly the combustion components amount comprises combustion components consumption and combustion components excess quantity; Superfluous combustion components can be fuel gas or oxygenant gas; When the combustion components of surplus was oxygenant gas, most of usually was flue gas in charring furnace charing section by reaction conversion, i.e. possibly there is corresponding oxygen consumption reaction (the charring furnace local space possibly form combustion reactions) in charring furnace charing section;

2. combustion chamber temperature control component; Its definition is outside from charring furnace, that in the combustion chambers burn process, exist, that possess control combustion product gases temperature function, but the non-combustibleconstituents of not participating in combustion reactions; Normally pass the combustion chamber and pass the non-combustibleconstituents that coking chamber contacts with coal or charcoal; Can be CO ₂, N ₂, Ar, H ₂O etc.; Can be the logistics of gas making part internal recycle, can be gas making part outer circulation logistics, also can be the N that the external non-combustibleconstituents of input coal carbonization process carries such as air ₂, external CO ₂Deng;

Combustion chamber according to the invention is a generalized concept: fuel gas gets into charring furnace and " charcoal or coal contact " with oxygenant generation combustion reactions gained flue gas, and its combustion space that " does not contact with charcoal or coal " promptly is combustion chamber according to the invention; Its form can be arbitrarily, but its flue-gas temperature must be by " combustion chamber temperature control component " control or major control;

3. coking chamber heat-carrying component (shift heat energy component), its definition is outside from charring furnace, pass component coking chamber, that all contact with coal with charcoal, that still do not participate in combustion reactions, is commonly referred to as whole components of charring furnace coking chamber heat-carrying gas;

Coking chamber heat-carrying component according to the invention; Flue gas composition (or its final products of combustion that does not comprise the charring furnace combustion chamber; If the flue gas composition of charring furnace combustion chamber reacts in coking chamber generation secondary combustion; Normally because combustion chamber oxygen surplus causes gas fume of combustion chamber to carry superfluous oxygen), do not comprise that the charcoal gaseous fraction of putting out that produces when water puts out charcoal does not belong to coking chamber heat-carrying component yet yet;

When the superfluous combustion components in combustion chamber is oxygenant when (promptly having superfluous oxygen), the part (normally small portion) of charring furnace coking chamber heat-carrying gas is reacted (the charring furnace local space possibly form combustion reactions) at charring furnace charing section and superfluous oxygen generation oxygen consumption; In fact in existing charring process, there is the heat release combustion reactions of some amount in the charring furnace local space;

Usually say that during ordinary production, the circulating gas through coking chamber of not participating in combustion reactions (not passing through the combustion chamber) belongs to coking chamber heat-carrying component (charring furnace heat-carrying component);

4. gasification component; Its definition be by go into that the charring furnace coal charge carries or produce in processes such as the desorb of coking chamber internal cause coal charge, conversion, evaporation, cracking, coal gas generations, get in the raw gas, but the component of not participating in combustion reactions comprises coal cracked gaseous things such as water component that coal charge carries, constituent of air, tar steam usually, puts out charcoal gas component;

5. other gaseous fraction comprises bleed sealing gland gas and other gas.The sealing gland of bleeding gas refer to when the charring furnace opening for feed with or discharge port etc. when using blanket gas, the part blanket gas gets into charring furnace and the final gas that bleeds that gets in the raw gas;

6. dust;

7. burning transforms component.

Can there be CO in dry distillation of coal gas making part coal gas internal recycle of the present invention in the path ₂Separate part PSA208 can contain certain CO owing to go into producer gas ₂Content so separate part PSA208 bypass A can be set as required, regulates producer gas CO ₂Content.CO in the raw gas internal recycle of the present invention path ₂Separate part PSA208 is owing to can contain CO from ring coal gas ₂, so separate part PSA208 bypass B can be set as required, regulate from ring coal gas CO ₂Content.

Can there be CO in the present invention ₂Outer circulation, this is because the combustion processes of charring furnace combustion chamber and the coal gas CO conversion process of existence certainly lead to CO ₂,, must carry out CO for its final discharge process ₂With separating of other component, owing to can not realize absolute the separation, and have a spot of CO of ratio in the coal gas usually ₂Combustion components that more is prone to be adsorbed such as hydrogen sulfide, carbon three hydrocarbon, ethene are so in order to separate and to recycle these components, utilize CO usually ₂Outer circulation is brought said components into the charring furnace combustion chamber.On this basis, look the particular case of process, consider whether to be provided with CO ₂Internal recycle, criterion is an economy certainly, mainly the factor of being limited by is CO ₂The internal recycle flow, CO ₂The internal recycle flow is uneconomical very little the time, does not set up independently internal recycle coal gas CO this moment usually ₂Separate part PSA208.

Below describing in detail from the ring gas reforming is the process 300 that General Office regulates the flow of vital energy.

Difference according to conditions such as component composition, temperature, pressure; Possibly need to boost, heat up, increase part steps or Overall Steps in the steps such as the humidification step 303 of water vapor concentration (satisfying the water charcoal molecular ratio of transformationreation needs), hydrocracking impurity (like oxygen, alkene, organosulfur) step 304, low temperature sulfur-resisting transformation step 305, carbonylsulfide medium temperature hydrolyzation step 306, cooled dehydrated step 307 from ring coal gas, but comprise hydrocracking impurity (like oxygen, alkene, organosulfur) step 304 usually through depriving hydrogen sulphide step 301, take off the heavy hydrocarbon step 302, compression of taking off charcoal five and above hydrocarbon (comprising tar, naphthalene, the dirt that possibly exist) thereof.

The oxygen that in ring coal gas, contains some amount usually; Volumetric concentration is generally 0.1～0.8%; The situation that exceeds above-mentioned scope is also arranged certainly; Oxygen belongs to objectionable impurities, has constituted on the one hand the possibility of blast, in follow-up chemical reaction process such as methanation, CO transformation and hydrogen production process, organosulfur hydroconversion process, can form bigger hydrogenation exothermic effect on the other hand; In order to guarantee the safety of technological process, taking off heavy hydrocarbon usually is the oxygen hydroconversion process from first chemical conversion process of ring coal gas.

Usually contain alkene such as the ethene of some amount etc. in the coal gas from ring; Its volumetric concentration is generally 0.01～1.5%; The situation that exceeds above-mentioned scope is also arranged certainly; Alkene belongs to objectionable impurities; In follow-up chemical reaction process such as methanation, CO transformation and hydrogen production process, have on the one hand and analyse charcoal tendency thereby can the accelerator activator deactivation rate more greatly, in follow-up chemical reaction process such as methanation, CO transformation and hydrogen production process, can form bigger hydrogenation exothermic effect on the other hand, take off heavy hydrocarbon usually and comprise the hydrogenation of olefins saturation history from the hydrocracking impurity step of ring coal gas.

The organosulfur such as the CS that in ring coal gas, contain some amount usually ₂Or COS etc., volumetric concentration is generally 0.001～0.010%, and the situation that exceeds above-mentioned scope is also arranged certainly, and organosulfur can poison catalyzer shortening catalyst life fast at follow-up chemical reaction process such as methanation, so belong to objectionable impurities, must remove.On the other hand, organosulfur such as COS are difficult to be absorbed at process of wet desulphurization.Again on the one hand, organosulfur such as COS are difficult to oxidized zinc catalyst absorption.The low CO shift step that even is not provided with of CO interconversion rate of the present invention in addition; So can not have powerful COS transformation function with production of raw-material gas for synthetic ammonia CO depth conversion process compares; Special-purpose organosulfur conversion process must be set, therefore hope to take off heavy hydrocarbon and comprise the organosulfur hydroconversion process from the hydrocracking impurity step of ring coal gas.

Among the present invention, the conversion process of organosulfur occurs at a plurality of process steps in ring coal gas, its objective is in order to optimize technological process, to improve desulfuration efficiency and or the safety of raising sweetening process.

Described herein from ring coal gas comprehensive treating process unit 300; Refer to and anyly suitable will be converted into the process that General Office that expection forms regulates the flow of vital energy from the ring raw gas; Flow process of the present invention comprises the CO conversion process usually; In order to produce methane to greatest extent, the controlled target of CO conversion process normally guarantees the molecular ratio H of methanation virgin gas ₂/ (CO+CO ₂) greater than 3.

According to the invention from the preparatory depriving hydrogen sulphide of ring raw gas step 301; Can use any suitable leaving to encircle raw gas depriving hydrogen sulphide method; Consider that concentration of hydrogen sulfide in the coal gas is generally the high value of 150～2500 milligrams/mark cubic meter, step 301 is used the wet desulphurization hydrogen methods usually.Below describe gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration system sulphur combination process that depriving hydrogen sulphide step 301 according to the invention is used in detail.Known coal gas desulfurization hydrogen technology can be learnt from the listed publication of table 7.

The publication of table 7 record coal gas desulfurization hydrogen technology

The present invention possibly be used with gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration system sulphur combination process; Said gas wet depriving hydrogen sulphide technology refers to: the depriving hydrogen sulphide solvent is the aqueous solution that contains solvent composition, and said solvent direct oxidation regeneration system sulphur refers to: contact directly at rich solvent and oxygen-containing gas (being generally air) that hydrogen sulfide is converted into sulphur (such as foam sulphur) in the completion solvent composition regenerated while rich solvent.Said gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration system sulphur combination process have multiple; Such as improvement anthraquinone disulphonate method (ADA method), titanium cobalt phthalocyanine monosulfonate doctor treatment (PDS method), " PDS+ tannin extract method " (tannin extract method), generally absorb the hydrogen sulfide in the coal gas with alkaline carbonic acid sodium, ammonia soln etc., it is big to have processing power; Desulfurization all can be carried out with regeneration continuously; Advantages such as labour intensity is little simultaneously also can remove prussic acid removing hydrogen sulfide, are generally adopted by coke-oven plant both at home and abroad.At present, the most ripe with improvement anthraquinone disulphonate method (ADA method) and " PDS+ tannin extract method " (tannin extract method).

Improve anthraquinone disulphonate method (ADA method) sweetening soln by 2 of interpolation equal proportion in the dilute sodium carbonate solution, 6-and 2, the sodium salt solution of 7-anthraquinone disulfonic acid (ADA) and some other components are formulated.Have that desulfuration efficiency height (can reach more than 99.5%), coal gas flexibility are strong, the temperature, pressure wide accommodation, doctor solution is nontoxic, equipment corrosion is little, sub product quality of sulphur advantages of higher.Obtained widespread use in the coke-oven plant.But there are shortcomings such as easy blocking, ADA cost an arm and a leg in it.

The tannin extract method be on the basis of improvement ADA method, improve, a kind of more advanced coal gas desulfurization technology that researchdevelopment is got up, adopt tannin extract to replace ADA.The tannin extract method is an absorption liquid with ammoniacal liquor, is catalyzer with PDS and adds promotors such as tannin extract.PDS is a kind of polymkeric substance, and its staple is binuclear phthalocyanine cobalt six ammonium sulphonates, to H ₂The S liquid phase oxidation reaction has high catalytic performance, and composition combined action such as PDS and promotor tannin extract can provide higher catalytic activity.The effect of promotor mainly is: make oxygen more be prone to complexing, accelerate sulphur atom come off, have good clear tower effect.Tannin extract is to be the afforestation product of main raw material preparation with natural wild plant, and it is cheap, is 1/6 of ADA.Desulfurizing tanning extract is compared with improvement ADA method, on the key technical indexes such as gas purification degree, solution sulfur capacity, sulfur recovery rate, all can compare favourably.Tannin extract method typical commercial application flow process is following: be introduced into tubulent contact tower bottom and cat head from the raw gas (pressure-fired) of the cold bulging worker of preceding operation workshop section and spray the doctor solution counter current contact of getting off; Thereby the continuous turbulence of polypropylene pellets increases contact area in the tubulent contact tower; Improve desulfuration efficiency; Then series connection gets into two tassement polaire thionizer bottoms and sprays the doctor solution counter current contact of getting off with cat head and absorb afterwards (the complete adverse current of doctor solution and coal gas), H in the coal gas successively ₂S content can reach 0.02g/Nm ³Below, after removing droplet, mist workshop section delivers to follow-up worker workshop section through catching.From tubulent contact tower, absorbed H ₂The doctor solution of S and HCN flows into the solution circulated groove; After replenishing strong aqua and catalyst solution, be pumped to the pressurized air that regenerator column (A) bottom and compressed air station send here and flow into and regenerate with solution circulated; Regenerated liquid returns the tubulent contact tower top and sprays desulfurization from regenerator column top, so recycle; Go into thionizer (B) earlier from the desulfurization lean solution of regenerator column (B), absorbed H at this ₂The doctor solution of S and HCN is gone into thionizer (A) after flowing to additional equally strong aqua of semi lean solution groove and catalyst solution after the semi-leanpump pressurization, in thionizer (A), absorbed H ₂The doctor solution of S and HCN flow to the rich solution groove and pumps the pressurized air of sending here to regenerator column (B) and compressed air station and flow into the rich solution pump and regenerate, and the lean solution after the regeneration is returned thionizer (B) top and sprayed desulfurization from tower top, so recycle.The sulphur foam that produces in the regenerator column then flows into the sulphur foam chute by regenerator column top expansion section s certainly, by sending into sulfur melting kettle after the pressurization of sulphur foam pump, produces sulphur and sells outward again.Tannin extract method process characteristic is following:

1. according to the demands of different of coal gas desulfurization hydrogen precision, confirm the setting of depriving hydrogen sulphide mass transfer workshop section, can adopt Dan Ta, the series connection of two towers or three tower cascade connected absorption, but removal of organic sulfur from and inorganic sulfur and prussic acid, and desulfuration and decyanation efficient is high; Can the hydrogen sulfide content in the coal gas be taken off to≤20 milligrams/SCM;

2. tower carrying out adopted in regeneration, and pressurized air is advertised, and oxidation regeneration speed is fast, guaranteed that the sulphur foamy generates and flotation process has enough strokes;

3. " PDS+ tannin extract " composite catalyst, catalyst activity is high, and consumption is few, and is cheap in addition, can significantly reduce catalyst costs;

4. adopting the ammonia that self contains in the coal gas is alkali source, can reduce the outer alkali source quantity that supplies, and reduces production costs;

5. absorb with regeneration and all carry out at normal temperatures, technology is simple, and flow process is short, and equipment and materials is less demanding, and manufacturing expense is low;

6. sulfur recovery can directly be recovered as sulphur, and the sulphur foam separation is effective, is difficult for stopping up, and system is stable.

Because the tannin extract method possesses above-mentioned advantage, in the coal tar chemical industry journey project desulfurization process of design, majority adopts these technologies at present.Gas wet depriving hydrogen sulphide according to the invention and solvent direct oxidation regeneration system sulphur combination process are preferred method with the tannin extract method.

Based on the object of the invention; In order to guarantee the reactive behavior of sulfur-tolerant type carbon monoxide transformation catalyst, the hydrogen sulfide volumetric concentration in the carbon monodixe conversion reaction gas flow must maintain a reasonable high level (should not be lower than 100PPm, usually above 200PPm, be higher than 300PPm especially).

The hydrogen sulfide volumetric concentration that the present invention will purify raw gas is controlled at a higher range, makes the necessary mass transfer theory level of the depriving hydrogen sulphide mass transfer workshop section of gas wet hydrogen sulfide removal process less, adopts the series connection of single tower or two towers to absorb usually and gets final product.

Below describe in detail and according to the inventionly take off heavy hydrocarbon part 302 from what ring gas reforming process possibly comprise.

As required; Setting of the present invention is taken off heavy hydrocarbon part 302 from ring coal gas; Owing to contain carbon five and impurity such as macromole such as benzene, naphthalene, tar more thereof in the coal gas,, get into before the reactor drum of conversion process in order to prolong the transformation catalyst life-span, to improve purpose such as PSA transformation performance of the adsorbent from ring; Taking off heavy hydrocarbon part 302 from ring coal gas; To deviate to obtain to take off heavy hydrocarbon from ring coal gas from the impurity such as heavy hydrocarbon in the ring coal gas, can adopt variable-pressure adsorption separating method, use impurity such as acticarbon absorption heavy hydrocarbon usually; Desorption method is depressurization desorption, heating desorption and flushing desorb combined method, and what rinsing gas can come transformation into itself's gas transformation absorbed portion returns charring furnace stripping gas etc.

Get into branch flow container completion gas-liquid separation (liquid is oily(waste)water) such as boosting to 0.3MPa (absolute pressure) from ring coal gas through compressor, gas phase gets into pretreater (being at least two) and removes components such as tar, and pretreated raw gas goes subsequent handling.The detar part is minimum to be made up of 2 pretreaters, and wherein one is in absorption de-oiling state, and another is in reproduced state or stand-by state.Preprocessing part uses acticarbon.For the hydrogen sulfide sectional pressure that guarantees that carbon monoxide transformation catalyst needs, it is adsorbent bed that most of hydrogen sulfide has passed detar part adsorption tower in the raw gas.

Below describe said detar that unit 300 of the present invention possibly comprise humidification step in detail from ring coal gas.

Detar can be adopted any suitable operating method from the humidification step of ring coal gas, as long as can effectively increase humidity, therefore, can be to adopt conditioning tower mode, heat exchange and water spray associated form, conditioning tower and water spray associated form.

First kind of humidification mode is to adopt the conditioning tower mode: before ring coal gas entering humidification step is left in detar; Usually removing through grade one filter maybe entrained oil behind the foreign material such as dirt; Get into the conditioning tower bottom; In conditioning tower, accomplish the water evaporation and add an amount of steam, after secondary filter removes the impurity such as liquid water, greasy dirt of deentrainment, become humidification coal gas then with the circulating hot water counter current contact.According to the working pressure needs, detar possibly passed through compressor boost before ring coal gas gets into humidification step.

Second kind of humidification mode is to adopt the heat exchange and the associated form of spraying water: detar makes the follow-up liquid water vaporization completion humidification that sprays into become humidification coal gas from encircling after coal gas and high temperature logistics such as the heat exchange of transformationreation elute heat up.Need based on operating pressure, detar possibly need to remove steps such as foreign material through compressor boost, filter before ring coal gas gets into humidification step.

The third humidification mode is a conditioning tower and the water spray associated form: removing through grade one filter usually from ring coal gas in detar maybe the entrained oil dirt etc. behind the foreign material; Get into the conditioning tower bottom; In conditioning tower, accomplish the water evaporation and add an amount of steam, add water vapor liquid then and accomplish the humidification coal gas that humidification becomes expection humidity with the circulating hot water counter current contact.

Below describe the impurity hydroconversion process 303 from ring coal gas according to the invention in detail.

Owing in ring coal gas, contain certain density oxygen usually, coal gas through the hydrogenation deoxidation catalyst bed, all transformed oxygen fall before carrying out the carbon monodixe conversion hydrogen production process before getting into the transformation catalyst bed as far as possible usually.The method that adopts can be: low temperature hydrogenation dehydrogenation catalyst bed is set, accomplishes the hydrogenation reaction of oxygen.Usually the hydrogenation deoxidation catalyst of selecting also has prussiate hydrocon version functionality, the saturated function of alkene, certain organosulfur transformation function.Be generally from ring coal gas deoxidation gas process 303 operational conditions: oxygen almost all transforms, prussiate almost all transforms; Average reaction temperature generally is lower than 300 ℃, average reaction temperature is lower than 250 ℃ usually; Reaction pressure is 0.2～3.5MPa (absolute pressure), and typical dehydrogenation catalyst technical parameter is seen table 8.

Table 8 dehydrogenation catalyst related data and MSDS

Sequence number	Project	Numerical value or description
			1	The catalyzer title	Antitoxin protective material
2	Model and specification	W906
			3	Shape and size	φ3-5mm
4	Catalyst component	Co-Mo, rare earth/Al ₂O ₃
			5	Density of catalyst, kg/m3	700-800
6	Catalyst loading density, kg/m3	700-800
			7	Intensity, N/cm2	≥50.0
8	H ₂The S maximum permissible concentration, mg/Nm3	Do not limit
			9	H ₂The minimum safe level of S, mg/Nm3	≥50
10	Optimum working pressure, MPa (G)	Normal pressure～3.5
			11	Optimal working temp, ℃	150～250
12	Air speed h ^-1	Be not higher than 3000

Below describe the hydrogenation saturation history of the olefin component in the coal gas in detail.The volumetric concentration XP1 of alkene in the raw gas that the blue charcoal process of coal system produces changes with the variation of operation factors such as coal, pyrolysis temperature, destructive distillation time, and XP is generally less than 3%, usually less than 1.5%, certainly, possibly exceed above-mentioned scope under the few cases.According to the present invention, accomplish the hydrogenation of olefins saturated reaction synchronously at deoxidation process usually, alkene almost all transforms usually, and average reaction temperature generally is lower than 350 ℃, average reaction temperature is lower than 250 ℃ usually, and reaction pressure is 0.2～3.5MPa (absolute pressure).According to the present invention; Also can special-purpose hydrogenation of olefins saturated reaction process be set in the upper reaches or the downstream of deoxidation process; Usually alkene almost all transforms, and average reaction temperature generally is lower than 350 ℃, average reaction temperature is lower than 250 ℃ usually, and reaction pressure is 0.2～3.5MPa (absolute pressure).The hydrogenation of olefins saturation catalyst can be any one suitable hydrogenation of olefins saturation catalyst, preferably sulfur-tolerant type hydrogenation of olefins saturation catalyst.

Below describe the hydroconversion process of the dithiocarbonic anhydride component in the coal gas in detail.The volumetric concentration XP2 of dithiocarbonic anhydride component in the raw gas that the blue charcoal process of coal system produces; Variation with operation factors such as coal, pyrolysis temperature, destructive distillation times changes; XP is generally less than 200PPm, usually less than 50PPm, certainly, possibly exceed above-mentioned scope under the few cases.Because the dithiocarbonic anhydride component can hydrocracking under 175 ℃ of temperature be hydrogen sulfide, thus the dithiocarbonic anhydride component the coal gas deoxidation process with or the alkene saturation history can carry out hydrocracking synchronously.

What below detailed description unit 300 of the present invention comprised adjusts H from the carbon monodixe conversion of ring coal gas ₂/ CO molecular ratio process 304.

Said carbon monodixe conversion H ₂/ CO molecular ratio adjustment process 304 is used carbon monoxide transformation catalyst usually.Conversion process virgin gas (leaving ring coal gas behind the de-oiling humidification) is accomplished the end reaction elute that carbon monodixe conversion obtains; Usually be cooled to 35～45 ℃ through condensation and accomplish gas-liquid separation; Gained gas can be regulated the flow of vital energy as General Office; According to form from ring coal gas, the difference of carbon monodixe conversion rate, the composition that General Office regulates the flow of vital energy and changing within the specific limits.Known coal gas carbon monodixe conversion technology can be learnt from the listed publication of table 9.

The publication of table 9 record coal gas carbon monodixe conversion technology

From ring coal gas carbon monodixe conversion hydrogen production process 304 operational conditions, should decide according to concrete virgin gas composition, the catalyzer of selecting for use, concrete Action Target, its scope is very wide.

From ring coal gas carbon monodixe conversion hydrogen production process 304, can select high temperature shift, middle temperature transformation, low temperature shift or its array mode for use, but select the anti-hydrogen sulfide conversion of low temperature usually for use, to reduce temperature of reaction, to reduce investment and energy consumption.

Be generally from ring coal gas carbon monodixe conversion hydrogen production process 304 operational conditions: the carbon monoxide transformation efficiency satisfies H ₂/ CO molecular ratio adjustment requirement; Carbon monoxide transformation catalyst bed operational condition is generally: it is that 0.2～2.5MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that the molecular ratio of 50～15000 SCMs virgin gas/cubic meter catalyzer, water vapor/carbon monoxide is 1.3～6.0 that average reaction temperature is lower than 350 ℃, pressure.

Be generally from ring coal gas carbon monodixe conversion hydrogen production process 304 operational conditions: it is that 0.3～1.5MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 150～5000 SCMs virgin gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～3.0 that average reaction temperature is lower than 300 ℃, pressure.

Be preferably from ring coal gas carbon monodixe conversion hydrogen production process 304 operational conditions: it is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are that 450～1650 SCMs virgin gas/cubic meter catalyzer, water vapor/carbon monoxide molecule ratio are 1.5～2.5 that average reaction temperature is lower than 250 ℃, pressure.

About the regulate the flow of vital energy control method of carbon monodixe conversion rate of General Office, a kind of is to adopt the bypass control method, and a kind of is to adopt the control raw water to steam the method for quantity.

Regulate the flow of vital energy first kind of mode of carbon monodixe conversion rate of General Office is the bypass control method: deoxidation coal gas is divided into two-way; First via deoxidation coal gas goes the carbon monodixe conversion reaction process to obtain first via conversion gas; The first via conversion gas and the second tunnel deoxidation coal gas are mixed into General Office and regulate the flow of vital energy; At this moment, the carbon monodixe conversion reaction process is controlled higher interconversion rate usually.

Regulate the flow of vital energy second kind of mode of carbon monodixe conversion rate of General Office is water inspissation degree method in the control carbon monodixe conversion virgin gas: all the deoxidation coal gas get into the carbon monodixe conversion reaction process and obtain General Office and regulate the flow of vital energy; At this moment; Under the certain prerequisite of catalyst loading scheme; Usually water steams the interconversion rate that quantity controls each bed in each carbon monoxide transformation catalyst bed inlet virgin gas through controlling; The principle of carbon monoxide transformation catalyst bed number setting is: single beds temperature rise must not be greater than bed temperature rise control value such as 80 ℃, and the beds temperature out must not be greater than the service temperature controlling valu such as 300 ℃ simultaneously.

Typical C O transformation catalyst technical parameter is seen table 10.

Table 10 CO transformation catalyst related data table

Below describe conversion gas carbonyl sulfide hydrolysis process 305 according to the invention in detail.

Owing in ring coal gas, contain certain density carbonylsulfide (COS) usually; And conversion process of the present invention belongs to the part conversion process and the overall inversion quantity of carbon monoxide is less; Carbonylsulfide is difficult to whole conversions usually within the transformation catalyst bed; In order to prevent that COS from getting into the methanation step and poisoning methanation catalyst, according to changing coal gas carbonylsulfide content, after carrying out the carbon monodixe conversion hydrogen production process from ring; The step that cos conversion is a hydrogen sulfide possibly is set, can use the carbonyl sulfide hydrolysis catforming.After cos conversion is hydrogen sulfide, can follow-up General Office regulate the flow of vital energy clean unit 400 or methanation unit 500 zinc oxide desulfurization hydrogen process convenient remove it.Known carbonyl sulfide hydrolysis technology can be learnt from the listed publication of table 11.

The publication of table 11 record carbonyl sulfide hydrolysis technology

Arrange the carbonyl sulfide hydrolysis catalytic conversion step after the shift step, can essence take off carbonylsulfide and save energy consumption and investment, studied hydrolytic catalyst of carbonyl sulfur in recent years both at home and abroad, make it under mild conditions, be converted into H as far as possible ₂S, hydrolytic catalyst of carbonyl sulfur exist down, and the following formula reaction takes place:

COS+H ₂O＝H ₂S+CO ₂ ΔH ^Θ ₂₉₈＝-35.53kJ/M

This equilibrium constant of reaction reduces with temperature and increases, and the equilibrium constant is very big under the normal temperature, and it is favourable to the COS hydrolysis to reduce temperature.Once used Al in early days abroad ₂O ₃Carrying palladium and cobalt molybdenum is active ingredient, under 170～250 ℃ comparatively high temps, makes the COS hydrolysis, then uses the Al of dipping basic component in recent years instead ₂O ₃Be catalyzer, under the lesser temps of nearly room temperature, make the COS hydrolysis.

Conversion gas carbonyl sulfide hydrolysis process beds operational condition is confirmed according to the concrete catalyst performance of selecting, such as being that temperature is 100～200 ℃ a medium temperature hydrolyzation condition, also can is that temperature is 30～70 ℃ an ordinary-temp hydrolysis condition.

Conversion gas carbonyl sulfide hydrolysis process; In order to bring into play catalyst efficiency; Usually require service temperature to be higher than at least 30 ℃ of dew points, and, adopt ordinary-temp hydrolysis process need deep dehydration preprocessing process owing to contain a large amount of water vapors in the conversion gas; So adopt medium temperature hydrolyzation technology usually, solve in the protective reaction step of the halfway problem of carbonyl sulfide hydrolysis before methanator.

Below describe clean unit 400 in detail.

Clean unit 400 described herein, refer to any suitable remove General Office regulate the flow of vital energy in the process of hydrogen sulfide and carbonic acid gas, the purified gas 400P of production is used as methanation unit raw material gas.Therefore, on the one hand, purified gas 400P component concentration must satisfy the composition requirement of the selected catalyzer in methanation unit to virgin gas, guarantees the normal usefulness of methanation unit catalyzer; Non-active principle content among the purified gas 400P must satisfy the requirement of methanation unit product quality index limits value on the other hand, is satisfying under above-mentioned two condition prerequisites, and most economical reasonable method is exactly the best approach.Known gas sweetening decarbonation technology can be learnt from the listed publication of table 12.

The publication of table 12 record gas sweetening decarbonation technology

It is component composition, condensation product such as water-content, corrosive gases such as hydrogen sulfide content that methanation unit product quality index is mainly calorific value, and according to the requirement of different user, the occurrence of these indexs can change on a large scale.

Based on present methanation technology; Nearly all methanation catalyst is the nickel-base catalyst responsive to hydrogen sulfide; Usually catalyzer supply merchant limits that hydrogen sulfide content is lower than a very low numeric ratio such as 0.1PPm in the virgin gas; Therefore the regulate the flow of vital energy purified gas of clean unit 400 of General Office should satisfy this requirement as far as possible, that is to say that conversion gas clean unit 400 preferably also is a deep desulfuration hydrogen process.

On the other hand, based on present methanation technology, if great amount of carbon dioxide gets into methanation, CO ₂More hydrogen be can consume and methane production, CO promptly reduced ₂Be one can not provide heat, can only consumption of calorie component, this that is to say, there is a CO in General Office's clean unit 400 of regulating the flow of vital energy ₂And the competition between active principle separation accuracy, investment, the energy consumption, COMPREHENSIVE OPTIMAL person is only optimal selection, selects which kind of concrete scheme like this, just must combine the external conditions of concrete application scenario to consider as a whole.

In sum; General Office's clean unit 400 of regulating the flow of vital energy is removing carbonic acid gas and removing the process of hydrogen sulfide as far as possible of a strictness; The method that removes carbonic acid gas and hydrogen sulfide that can adopt has multiple, and the present invention can use low-temp methanol washing method, pressure swing absorption process, organic alkali lye washing method and transformation absorption integrated processes etc.

General Office's clean unit 400 of regulating the flow of vital energy can use the low-temp methanol washing method, and this method has been successfully applied to synthetic ammonia feedstock qi exhaustion CO ₂The process many decades; The nitrogen gas of Mathanol regenerating process is put forward step needs oxygen-free nitrogen, when this integrated technique is provided with the cryogenic air separation process and has a large amount of high-purity nitrogens to use, and in the unit when 400 virgin gas quantity are big; It is a kind of selection preferably; Can give full play to the following advantage of low-temperature rectisol: the rate that removes out the height of carbonic acid gas and hydrogen sulfide, active principle rate of loss are low, and CO2 removal goes out rate and can reach more than 99%, and the residual quantity of hydrogen sulfide can be reduced to below the 0.5PPm; The active principle rate of loss is low, is dissolved in active principle in the methanol absorbing agent and after flash separation, returns in the virgin gas and be recovered.As required, can obtain high-purity CO ₂Gas, be rich in the CO of hydrogen sulfide ₂Gas utilizes respectively.The weakness that but the working pressure that low-temp methanol washing process is had relatively high expectations usually, this point are them when comparing with pressure swing absorption process.

General Office's clean unit 400 of regulating the flow of vital energy can use the one-level pressure swing adsorption technique, and this method has been successfully applied to synthetic ammonia feedstock qi exhaustion CO ₂The process many decades, in the adsorption process, the available gas in the virgin gas passes the adsorbent bed purified gas that becomes, CO ₂And the component that more is prone to be adsorbed such as water, hydrogen sulfide, carbon three hydrocarbon, ethene etc. are adsorbed agent and absorb, after absorption finishes, and CO ₂Have between forward position and outlet a unsaturation adsorption zone with or adsorption zone not.In desorption process, the pressure when control vacuum desorption step finishes makes the component that is adsorbed such as water, hydrogen sulfide, carbon three hydrocarbon, ethene etc. emit from inlet end in reverse vacuum desorption step, and this stripping gas can be as the CO that returns the combustion chamber ₂Outer circulation gas.

When clean unit 400 employing pressure swing absorption process are regulated the flow of vital energy by General Office; Can adopt the secondary pressure swing adsorption technique; In adsorbent bed 401 adsorption processes of one-level transformation; Component that hydrogen sulfide and more being prone to is adsorbed such as water, hydrogen sulfide, carbon three hydrocarbon, ethene etc. are adsorbed agent and absorb available gas in the virgin gas and CO ₂, ethane component passes the adsorbent bed first class purification gas 401P that becomes, and after absorption finishes, a unsaturation adsorption zone and or adsorption zone not arranged between absorb leading-edge and outlet.In adsorbent bed 401 desorption processes of one-level transformation; Pressure when control vacuum desorption step finishes; The component that is adsorbed such as water, hydrogen sulfide, carbon three hydrocarbon, ethene etc. are emitted from inlet end in reverse vacuum desorption step, and this stripping gas can be as the CO that returns the combustion chamber ₂Outer circulation gas.In adsorbent bed 402 adsorption processes of secondary transformation, the available gas among the first class purification gas 401P passes adsorbent bed secondary purification gas 402P, the CO of becoming ₂And the component that more is prone to be adsorbed is adsorbed agent like, hydrogen sulfide, carbon three hydrocarbon, ethene etc. and absorbs, after absorption finishes, and CO ₂Have between forward position and outlet a unsaturation adsorption zone with or adsorption zone not.In adsorbent bed 402 desorption processes of secondary transformation, the pressure when control vacuum desorption step finishes makes the component that is adsorbed such as hydrogen sulfide, carbon three hydrocarbon, ethene etc. emit from inlet end in reverse vacuum desorption step, and this stripping gas 402K can be used as high-purity CO ₂Gas uses.

General Office's clean unit 400 of regulating the flow of vital energy takes off CO ₂Transformation fractionation by adsorption part absorption working condition operational condition is: service temperature is generally 30～50 ℃, is generally 35～45 ℃; Pressure is generally 0.6～2.5MPa, is generally 0.8～1.5MPa; Adsorbent bed for a kind of in the activated alumina, gac, silica gel or by wherein several kinds constitute the layering combination cot; The activated alumina bed is set grades CO absorption with planar water as the protection bed ₂Sorbent material be preferred with the Kiselgel A.

General Office's clean unit 400 of regulating the flow of vital energy, the hydrogen sulfide volumetric concentration of purified gas usually less than 50PPm, be generally less than 20PPm, especially less than 10PPm, the CO of purified gas ₂Volumetric concentration usually less than 5%, be generally less than in 2.5%, especially less than 1.5%, the active principle recovery usually greater than 90%, generally greater than 95%, especially greater than 98%.

Stripping gas 402K can mix with the flue gas of heating furnace of low sulfur content as the used CO of containing of phenol sodium carbonic acid gas decomposition method process ₂Gas.

CO is taken off in known desulfurization ₂Technology can be learnt from the listed publication of table 13.

The publication of table 13 record sulfur removal technology

Below describe methanation unit 500 in detail.

Methanation described herein unit 500, it is any suitable for CO and H in the methanation virgin gas to refer to ₂Be converted into CH ₄The process of (methane), according to the difference of the purposes of high methane gas, high methane gas has different quality index.Based on present methanation technology; There are DAVY company, rope company of Denmark Top, German LURGI company in typical methanation technology supplier; Nearly all methanation catalyst is nickel-base catalyst; Technical process is then similar, and the common characteristic is in order to control the single reactor reaction temperature rising, all adopt portioned product gas with or intermediates gas mix with virgin gas with the CO volumetric concentration in the inlet virgin gas of control catalyst bed; This concentration value controlling index is usually less than 3.5～7.0%, and the total number of reactor drum is generally three or four.Methanation is emitted a large amount of reaction heat, and how reclaiming and utilizing these heat energy is important engineering technology, and a few methanation technology suppliers' of family heat recuperation technology respectively has characteristics.

The operational condition of methanation unit 500 is generally: service temperature is generally 250～680 ℃, is generally 300～615 ℃, and pressure is generally 1.0～8.5MPa, is generally 1.5～3.5MPa, and the CO transformation efficiency can reach more than 99%, CO ₂Transformation efficiency can reach more than 90, and the available gas residual volume receives raw material to form control, and rare gas element such as nitrogen and argon gas volumetric concentration receive raw material to form control.

Methanation unit 500 can comprise raw material preheating step, methanation protective reaction step 501, methanation reaction step 502, end reaction elute refrigerated separation water step etc.

The methanator temperature out of using based on methanation of the present invention is generally 400～650 ℃ of these current conditions; The present invention is provided with the flow process of heat-conducting oil system; The high potential temperature heat energy of at least a portion methanation reaction elute is used to heat thermal oil such as biphenyl with high-temperature stability and produces high potential temperature thermal oil, and high potential temperature thermal oil is realized the direct utilization of energy as the thermal source of endothermic process such as coal tar hydrogenating process.The present invention proposes the scheme of utilizing of above-mentioned novelty, to improve the utilising efficiency of methanation reaction heat.

According to the present invention; Can produce the low high heating value substitute natural gas of nitrogen and argon concentration; Concrete scheme of the present invention can be: the charring furnace combustion chamber uses high-purity oxygen to make the nitrogen of oxygenant minimizing charring furnace combustion chamber and the inlet of argon gas, rationally controls the H of methanation virgin gas ₂/ CO molecular ratio and CO ₂Content; Improve methanation reaction process CO transformation efficiency and CO as far as possible ₂Transformation efficiency, non-combustion components concentration is low as far as possible in the control high methane gas.

Below describing step 501 according to the invention in detail can employable method.

Methanation protective reaction step 501; Its main purpose is in order to guarantee that the methanation catalyst LP efficiently moves; Its major function is that the poisonous substance in the virgin gas is removed, the method for employing normally absorb with or transform absorption technique, one of them main purpose is to reduce sulphur content.Because the sulphur in the methanation virgin gas can present variform such as H ₂S, COS, CS ₂Deng, therefore need to combine particular case to confirm that concrete sulfur removal technology is selecting catalyst or sorbent material, selection operation temperature and working pressure, selection flow process.As required; Can select hydroconversion process, carbonyl sulfide hydrolysis catforming, transform absorption process, absorption process a kind of method or the combination of two kinds of methods or the combination of several different methods wherein, put in the last position of 501 steps usually and zinc oxide desulfurization hydrogen catalyst bed is set with final control total sulfur content.In order to reduce the sulphur content in the methanation virgin gas as far as possible; When COS content is higher; When selecting inversion absorption type catalyzer (being generally the gac that internal surface adheres to active ingredient) for use; Can in the methanation virgin gas, inject oxygen enrichment or pure oxygen and keep the carrier of oxygen volume concentrations and reach 0.03～0.10%, can add water vapour simultaneously and keep the water vapour volumetric concentration and reach 0.03～1.0%, improve desulfurization degree; Can before methanation reaction, arrange low-temperature catalyzed hydrogenation deoxidation step that the excess oxygen cyclostrophic is turned to water.In order to reduce the sulphur content in the methanation virgin gas as far as possible, when COS content is higher when selecting hydrolyst for use, can adds entry or water vapour and keep the water vapour volumetric concentration and reach 0.03～1.0%, improve desulfurization degree.

Below describe deoxidation in detail from the CO interconversion rate of ring gas reforming process 305, the CO of clean unit 400 ₂Decreasing ratio (takes off CO in other words ₂The CO of purified gas ₂Volumetric concentration), the CO of methanation 500 ₂Relation between the transformation efficiency, its purpose are to propose to reduce the running cost of clean unit 400, the operating principle of optimization whole technological process.

As far as final purpose product methane, the H in ring coal gas ₂With CO is to synthesize CH ₄Effective raw material, the present invention under the prerequisite of consume water steam, regulates H through the CO transformationreation ₂/ CO molecular ratio makes H in the methanation reaction process ₂All be converted into CH with CO according to 3: 1 molecular ratios ₄It is idealized situation.As H from ring coal gas ₂/ CO≤3 o'clock, the CO of the enormous amount that in ring coal gas, exists ₂Component is an invalid component as far as methanation, and CO ₂Component gets into the methanation reaction process can increase the hydrogen consumption, reduces methane production, so the present invention is provided with clean unit 400 and removes CO ₂Yet any pressure swing adsorption technique of unit 400 all can not be realized CO ₂With active principle (be C ₂H ₆, CO, CH ₄, H ₂) absolute sharp separation, CO ₂The rate of loss of the high more then active principle of decreasing ratio component is high more, the low more then CO of the rate of loss of active principle component ₂Decreasing ratio is low more.When unit 400 adopts pressure swing adsorption technique, too high for fear of the rate of loss of active principle, must control CO ₂Decreasing ratio can not be too high such as generally not being higher than 95%, just takes off CO ₂The CO of purified gas ₂Retention rate can not be crossed low such as being not less than 5%.But take off CO ₂The CO of purified gas ₂Concentration Gao Ze causes CO in the methanation product high methane gas when amount of hydrogen is not enough ₂Excessive concentration, for fear of this situation, the present invention controls CO transformationreation process interconversion rate, regulates H ₂/ CO molecular ratio greater than 3: 1 such as reaching 3.15: 1 even higher, cause H ₂/ CO molecular ratio is called as excessive transformationreation greater than 3: 1 transformationreation.Exist the excessive transformationreation of some amount can allow to take off CO ₂Separating unit 400 possesses the handiness of wide region in operation, can reduce investment and energy consumption.In fact, CO and H ₂The H that the excessive transformationreation of O generates ₂And CO ₂Be converted into CO gas and H again in the methanation overwhelming majority ₂O gas, final H ₂The liquid water of O condensation of gas can return CO and H ₂The excessive transformationreation process of O recycles.Above-mentioned analysis explanation; Recycling with water component is condition; Can form and regulate flexibly the virgin gas utilization ratio and totally control scheme and since the liquid water that the water component working cycle comprises be vaporizated into steam process can with take off heavy hydrocarbon and under the condition that ring coal gas contact, accomplish, so utilize the effect of its reduction steam dividing potential drop; Can utilize the heat energy of lower temperature position to accomplish the liquid water vaporization, so energy cost is not high.Certainly, say that CO transformationreation process liberated heat is the low temperature potential energy from the energy transformation angle, and H ₂And CO ₂Be converted into CO gas and H at methanation ₂The heat that the O gas absorbs is the high temperature potential energy, and the two is compared, and has an energy level difference, has formed the energy level loss.

The general value of technology controlling and process target of the present invention, hydrogen efficient (3 * CO+3 * CO ₂)/(3 * CO+4 * CO ₂)>=0.85, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.85～1.15.

The general value of technology controlling and process target of the present invention, hydrogen efficient (3 * CO+3 * CO ₂)/(3 * CO+4 * CO ₂)>=0.90, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.94～1.06.

The preferred values of technology controlling and process target of the present invention, hydrogen efficient (3 * CO+3 * CO ₂)/(3 * CO+4 * CO ₂)>=0.94, the molecular ratio H of methanation virgin gas ₂/ (3 * CO+4 * CO ₂) be 0.98～1.02.

Below describing in detail exists the energy utilization to unite the dead oil hydrogenation process 600 of relation.

Dead oil hydrogenation process 600 described herein; Refer to any course of processing that comprises dead oil hydro-upgrading process; Its coal tar raw material can be the distillate from the coal tar of step 200; Also can be from the coal tar beyond the step 200; Also can be the distillate from the coal tar beyond the step 200, the hot procedure that can certainly be coal tar can also be two or more oily mixing oils in the above-mentioned oil product such as the oil product that is suitable for hydro-upgrading that coking or visbreaking process obtain.

Typical full cut coal tar hydrogenation modification process 600 comprises fractionating step 601, dead oil hydro-upgrading step 602, the hydrogenated oil fractionating step 603 of coal tar usually; Usually use separation column in step 601 and step 603; Usually the part separation column is provided with reboiler furnace or charging process furnace at the bottom of the tower, common consume fuel oil of these process furnace or fuel gas at least.The factory that is provided with simultaneously for blue charcoal process of coal system and coal tar hydrogenating process, based on the price of fuel oil height and factory's this reality of raw gas surplus, in most cases process furnace fuel is exactly raw gas, also can be described as the unitary virgin gas of methanation.Utilize the energy replacing fuel gas heat supply of suitable high potential temperature thermal source, can realize " high " of energy level, obtain remarkable economic efficiency with low generation.The present invention points out; For said process; Employing is provided with the flow process of heat-conducting oil system; At least a portion methanation reaction heat is used to heat thermal oil, and high potential temperature thermal oil is used as the thermal source of endothermic process such as coal tar hydrogenating process with reduction fuel gas consumption, thereby increases the output of high methane gas or substitute natural gas.

Thermal oil CH medium can be a biphenyl; Biphenyl has high thermostability and low-vapor pressure; Mix the back as perolene separately or with phenyl ether; Use in the industry that wider to form mass ratio by biphenyl and phenyl ether be 26.5: 73.5 eutectic mixture, the use temperature scope can for 250～400 ℃, be generally 250～380 ℃, in order to keep the quality of thermal oil CH in the life-time service process; Can the used thermal oil of discharge unit, replenish fresh thermal oil simultaneously, the thermal oil of discharging can use as coal tar hydrogenation modification process raw material.

Thermal oil CH medium can be the high boiling point oil product that hydrogenated oil fractionating step 603 obtains; In order to keep the quality of thermal oil CH in the life-time service process; Can the used thermal oil of discharge unit, replenish fresh thermal oil simultaneously, the raw oil of the hydrogenation process that the thermal oil of discharging can comprise as the coal tar hydrogenating process uses.

Below describe co-producing hydrogen process 700 in detail.

Co-producing hydrogen process 700 according to the invention, virgin gas can be taken from any source of the gas position such as can being first via conversion gas, but are based on the flow process optimization criteria usually to take off CO ₂Purified gas is a hydrogen feedstock gas.

The present invention takes off CO ₂Conversion gas belongs to CO-CH ₄-H ₂System in co-producing hydrogen process 700 according to the invention, is separated into the hydrogen product and the CO-CH of expection purity through transformation adsorption separation process 701 ₄-poor H ₂The system stripping gas, stripping gas can be done the virgin gas use or be used as factory's high performance fuel gas as required in the demethanization unit.

Transformation adsorption separation process 701 absorption working condition operational conditions of the present invention are: service temperature is generally 30～50 ℃, is generally 35～45 ℃; Pressure is generally 0.6～2.5MPa, is generally 0.8～1.5MPa; Adsorbent bed for a kind of in the gac, silica gel, zeolite molecular sieve or by wherein several kinds constitute the layering combination cot; The activated alumina bed can be set simultaneously adsorb possible moisture etc. as the protection bed; Hydrogen recovery rate usually greater than 85%, generally greater than 90%, especially greater than 95%, hydrogen product concentration usually greater than 95%, generally greater than 99%, especially greater than 99.9%.

Below describe characteristic of the present invention in detail.

1. make oxygen enrichment in system oxygen unit 100;

Unit of the present invention 300 flow processs are generally:

Unit 300 flow process preferablies of the present invention are:

Unit of the present invention 501 Action Targets are generally:

Unit of the present invention 500 Action Targets are generally:

Unit of the present invention 200 operational conditions are generally:

Compare with already known processes, the invention has the advantages that:

1. compare with the blue charcoal technology of the conventional coal system that with the air is charring furnace combustion chamber oxygenant, oxygen enrichment or pure oxygen burning technology are adopted in the blue charcoal process of internal heat type coal system of the present invention combustion chamber, and raw gas is poor nitrogen raw gas;

3. compare with conventional coke-oven gas system substitute natural gas technology; Hotline heater is set; Utilize the high potential temperature heat energy heating of methanation reaction elute thermal oil, high temperature heat conductive oil is as reboiling heat source at the bottom of the coal tar hydrogenating process fractionation Tata, and the low temperature thermal oil returns hotline heater circulation heating.So can fuel saving consumption, for blue charcoal of majority system and coal tar hydrogenating associating processing factory, be coal tar hydrogenating process fractionating column heating furnace fuel because of it is common with raw coke oven gas, so can directly increase substitute natural gas output;

4. compare with the raw gas electricity generating plan, capacity usage ratio of the present invention is high, and construction investment is low, and major cause is that a considerable amount of methane in the product high methane gas are not sintetics but existing methane component in ring coal gas;

5. strong to raw material fluctuation of load adaptive faculty, be easy to control and adjusting.

Reference examples

" is that raw material is at the special-purpose blue charcoal of vertical retort refining iron alloy with non-caking coal or weakly caking coal lump coal " technology and equipment of Anshan Thermal Energy Inst. of China Steel Group; Employing is suitable coal source with China Datong District, the geographic coal in refreshing mansion; Be employed in the blue charcoal of the interior refining of vertical retort and refine blue charcoal and by-product raw gas and middle coalite tar, this technology has the general feature of similar blue charcoal technology: be the main heat-carrying component of combustion processes with nitrogen.In the representative data of this reference examples, the process scale is 600,000 tons/year of blue charcoal production capacities, and year is 7920 hours/year (330 days date manufactured meter per year) when going into operation, and is raw material with Yulin city Shenmu County's coal, coal gas production capacity 1.03 * 10 ⁹Mark cubic meter/year, 60,000 tons/year of tar production capacities.

1. typical feed coal character is following:

With the report of Shenmu County's coal analysis, design requires as follows the ature of coal of upright furnace with coal:

It is the lump coal of 25～80mm that the used feed coal of the blue charcoal of internal thermal upright carbonization furnace production requires, and project is the screening of feed coal with due regard to, and daily requirement coal amount is 3000t/d, i.e. 125t/h.

One group of typical feed coal ature of coal survey report of table 14

2. the blue charcoal of major product; Have excellent properties such as low ash, low-sulfur, low aluminium, hyperergy, high specific resistance; Can be widely used in industries such as iron alloy, calcium carbide, synthetic ammonia and blast furnace blowing, field such as civilian; Can partly replace coking coal, gasification briquette and smokeless piece etc., realize resource rational utilization;

Blue carbon yield 600,000 t/a

Wherein: specification 1: >=5mm, 520000t/a, specification 2:＜5mm, 80000t/a

Blue charcoal＞5mm grade can supply domestic ferroalloy works, calcium carbide factory, fertilizer plant and outlet;

Coke powder＜5mm can supply Iron And Steel Plant's blast furnace blowing to use or power plant for self-supply uses.

3. coalite tar in one of sub product is the coal process macromolecular organic compound that Pintsch process produced.Because of the cracking temperature of coal in the upright furnace relatively low; In coalite tar character better and be rich in lower boiling phenol; It is the petroleum products surrogate that non-phenol distillate is easy to hydrocracking, and residual oil (or claiming coal-tar pitch) can coking hot-work be coke and coking distillate (making hydrogenating materials);

Coal tar output 60000t/a, its main character is seen table 15.

The main character of table 15 coal tar

	Density g/cm ³	Ash content %	Moisture %	Viscosity E ₈₀
					Coal tar	～1.05	0.02～0.2	≤4	2～10

Coal tar belongs to semi coking tar, contains cuts such as light oil, Wood creosote and pitch, is mainly used in to produce oil fuel, linkrusta, carbon black and general carbon product.

The results of elemental analyses (%) of table 16 shenfu coal upright furnace coking gained coal tar

Sample	C	H	N	0	S	The H/C atomic ratio	Remarks
								Shenfu coal tar 1#	86.28	8.31	1.11	3.86	0.36	1.16
Shenfu coal tar 2#	86.03	8.45	1.14	3.93	0.45	1.18

The main character of table 17 shenfu coal upright furnace coking gained coal tar

Table 18 reference examples raw gas purposes

Table 19 reference examples is formed data from ring coal gas

The component sequence number	Component	Nm ³/h	v/v
				1	?H ₂	17858.66	27.47％
2	?CO ₂	5952.89	9.16％
				3	?CO	8750.74	13.46％
4	?O ₂	416.70	0.64％
				5	?N ₂	21549.44	33.15％
6	?CH ₄	4643.25	7.14％
				7	?C ₂H ₄	59.53	0.09％
8	?C ₂H ₆	297.64	0.46％
				9	?H ₂S	71.97	0.11％
10	?H ₂O	4875.00	7.50％
				11	Organosulfur (COS)	0.00	0.00％
12	?C _mH _n	0.86	0.00％
				13	Argon gas	523.32	0.81％
14	Other	0.00	0.00％
				Add up to		65000.00	100.00％

4. a large amount of coal gas of by-product; A part is used as coking chamber heat-carrying component; A part is as the combustion chamber fuel of charring furnace; Have part not through the combustion chamber but burn in coking chamber charing section through the coal gas of coking chamber cold charcoal section, the present invention supposes that for the simplification problem combustion reactions does not partly take place the charring furnace coking chamber.

The coal gas that charring furnace produces, a part supply charring furnace to make fuel, and a part of coked waste water that supplies burns usefulness, and residual gas is defeated outward with being used as fuel and hydrogen feedstock.

5. project content: the type of furnace is selected ZNZL3082 type internal thermal upright stove for use, and stove group scale is 8 * 8 holes, and corresponding auxiliary facility has fully coal, sieve storage Jiao, charing, bulging cold, WWT and public utility etc.

6. production workshop section

Charing workshop section: vertical retort takes many grate furnaces body to arrange.The type of furnace is chosen as ZNZL3082 type internal thermal upright carbonization furnace.Furnace binding and characteristics:

Embodiment one

Present embodiment is a kind of blue charcoal Poly-generation of internally heated coal carbonization system process of coproduction high methane gas, and high methane gas can be used as substitute natural gas SNG, and present embodiment comprises following steps:

1. in system oxygen unit 100, be raw material with the air, adopt separation by deep refrigeration to prepare oxygen enrichment, the oxygen components volume content is 99.5% in the oxygen enrichment, the argon component volume content is 0.5% oxygen, and system oxygen unit 100 produces high-purity nitrogen and argon gas simultaneously;

2. in the blue charcoal of internally heated coal carbonization system unit 200, it is the burning process of oxygenant that pure oxygen is adopted in the charring furnace combustion chamber of the blue charcoal process of coal system, and combustion chamber temperature control component all is CO ₂, pure oxygen from step 1..Based on reference examples, according to " wait heat-capacity flowrate replacement " notion with combustion chamber temperature control component N ₂All use CO ₂Replace, the carrier of oxygen volume concentrations is 30% in the virtual oxygen donator, supposes that dry distillation of coal effect is constant in the charring furnace, then forms from ring coal gas component and sees table 21-1.Raw gas belongs to CO before transforming ₂-CO-CH ₄-Fu N ₂-H ₂System is transformed the back raw gas and is belonged to CO ₂-CO-CH ₄-H ₂System, a part that goes out the raw gas of charring furnace is returned charring furnace use (part is as internal recycle coking chamber heat-carrying component, and a part is as internal recycle fuel gas), and all the other efflux raw gas (superfluous raw gas) conduct and use from ring coal gas; This process operation pressure is normal pressure～0.35MPa;

3. leave ring coal gas comprehensive treating process unit 300, accomplishing following task:

A accomplishes " wet desulphurization hydrogen process " 301 from ring coal gas, and target is with H ₂The S volumetric concentration is reduced to 0.025%; Coal gas is divided into two portions in the technical process; First part's coal gas becomes desulfurization coal gas through the solvent absorbing process of using 1 or 2 solvent absorbing tower; Also flow regeneration after rich solvent and the air mixed and produce foam sulphur simultaneously; Foam sulphur produces sulphur through sulfur melting kettle, and " PDS+ tannin extract " lean solvent to solvent absorbing process after the regeneration recycles.Desulfurization coal gas and second section coal gas are mixed into desulfurization coal gas, to control overall desulfurization degree, H in the desulfurization coal gas ₂The S volumetric concentration is controlled to be 0.015～0.035%, and the absorption process working pressure is normal pressure～0.35MPa, and the absorption process service temperature is 35～45 ℃;

B desulfurized coal qi exhaustion heavy hydrocarbon process 302; At working pressure is 0.4～0.6MPa, and temperature is under 35～45 ℃ of conditions, adopts temperature swing adsorption process; Adsorb heavy hydrocarbon with acticarbon; The adsorbent reactivation process adopts and improves the temperature desorption technique, and the sorbent material temperature-rise period uses 250 ℃ of steam heating, uses two adsorption towers;

C takes off heavy hydrocarbon coal gas humidification process, takes off the compression of heavy hydrocarbon coal gas and is pressurized to 0.9～1.3MPa, contacts with hot water through conditioning tower and accomplishes humidification process;

Coal gas deoxidation of d humidification and hydrogenation of olefins saturation history 303; Humidification coal gas and hot logistics heat exchange to 190 ℃; Get into hydrogenation deoxidation and hydrogenation of olefins saturation catalyst bed then; Accomplish full the conversion, in the deoxidation reforming gas, spray into de-oxygenised water then and reduce temperature to 200 ℃ as deoxidation coal gas, the water that sprays into all gasification to increase the H of conversion gas ₂The O/CO molecular ratio; Working pressure is 0.9～1.3MPa;

E gas reforming process 304; Deoxidation coal gas is divided into two portions; First part accomplishes about 95% CO as conversion virgin gas series connection through the sulfur and carbon monoxide resistant conversion process that comprises 3 or 4 beds and is for conversion into conversion gas, and conversion gas and second section deoxidation coal gas are mixed into mixing transformation gas, are 38.6% to control the global transformation rate; Transformationreation process operation pressure is normal pressure 0.9～1.3MPa, and carbon monodixe conversion reaction process medial temperature is 240～290 ℃;

F carbonyl sulfide hydrolysis process 305, mixing transformation gas reduce temperature to 140～160 and ℃ accomplish the medium temperature hydrolyzation process through the hydrolytic catalyst of carbonyl sulfur bed, are higher than 90% to control overall percent hydrolysis, and process operation pressure is 0.8～1.2MPa; Medium temperature hydrolyzation gas reduces temperature to 30～50 and ℃ accomplishes the dehydration hydrolysis gas that obtains dewatering, and working pressure is 0.8～1.2MPa;

4. at comprehensive treating process qi exhaustion CO ₂Unit 400 adopts pressure swing adsorption process to obtain taking off CO ₂Conversion gas namely for methane virgin gas.Adopt the two-stage pressure swing adsorption process, obtain rich carbon three hydrocarbon stripping gass and decarburization three hydrocarbon purified gass in first step pressure-swing adsorption process, first step pressure-swing adsorption process working pressure is 0.8～1.2MPa; Pressure-swing adsorption process obtains taking off CO in the second stage ₂Conversion gas, rich CO ₂Gas comprises CO ₂, H ₂The rich CO of rich carbon three hydrocarbon stripping gas parts of S ₂Gas circulation usually returns charring furnace combustion chamber formation " combustion chamber temperature control component CO ₂" outer circulation, the rich CO of at least a portion ₂Gas discharge system is used to discharge the CO that combustion processes produces ₂Gas, the rich CO of this high purity ₂Gas can be used as phenol sodium CO ₂Decompose legal system crude phenols branch and vent one's spleen, second stage pressure-swing adsorption process working pressure is 0.75～1.15MPa.The rich CO of outer circulation ₂A spot of hydrogen sulfide in the gas, carbon three hydrocarbon, ethane etc. are brought the combustion chambers burn heat release into and are accomplished separation and utilization; Reduction reaction takes place in charring furnace the oxide compound of hydrogen sulfide becomes hydrogen sulfide, finally is absorbed and can be exchanged into sulphur at the ammonia scrubbing that goes out the charring furnace raw gas and from the process of wet desulphurization that encircles coal gas;

5. in methanation unit 500, accomplish following task:

A is in desulphurization reaction step 501, is 0.7～2.0MPa at working pressure, is preferably under 0.7～1.1MPa condition, and the methanation virgin gas is accomplished " deep desulfurization process " to satisfy the limits value of methanation catalyst, usually H ₂The S volumetric concentration is reduced to 0.1PPm or lower; Process operation pressure is a little more than methanation pressure, and temperature is 180 a ℃～methanation reaction starting temperature; Deep desulfurization catalyst is the combination of medium temperature hydrolyzation organosulfur COS catalyzer and Zinc oxide catalytic; Technical process for to be warming up to～140 ℃ methanation feed gas stream adds entry makes volume of water concentration reach 0.1～0.2%; Pass then organosulfur COS medium temperature hydrolyzation beds control work off one's feeling vent one's spleen in organosulfur COS volumetric concentration be lower than 0.05 milligram/SCM; Be that the total sulfur volumetric concentration is lower than 0.1 milligram/SCM during control is worked off one's feeling vent one's spleen under 180～280 ℃ the condition through the Zinc oxide catalytic bed in temperature then, this gas is used as the methanation reaction virgin gas;

B is in methanation step 502, is 0.8～2.0MPa at working pressure, is preferably 0.7～1.1MPa, and temperature is under 280～650 ℃ of conditions, and 3 or 4 methanators are set, control CO transformation efficiency greater than 99%, the CO2 transformation efficiency is greater than 90%;

The dehydration of c high methane gas; High methane gas is cooled to about 40 ℃; Accomplish one-level gas, water sepn, to 5.0MPa, one-level dehydration high methane gas is cooled to about 40 ℃ to one-level dehydration high methane gas then through compressor boost; Accomplish secondary gas, water sepn, it is defeated outward to get into gas distributing system after the secondary dehydration high methane gas process deep dehydration tower dehydration reduction humidity.The deep dehydration tower can load sorbing material such as silica gel, activated alumina, molecular sieve of suction etc.The dehydration degree of depth of the deep dehydration process of secondary dehydration high methane gas adopts the bypass regulative mode usually: secondary dehydration high methane gas splits into two-way gas; First via secondary dehydration high methane gas becomes the deep dehydration high methane gas through the deep dehydration tower, becomes the defeated product of high methane gas of expection humidity after deep dehydration high methane gas and the second road secondary dehydration high methane gas mix outward.

Each step logistics composition is seen table 21-1～table 21-13.

Table 20 embodiment 1 internally heated coal carbonization charring furnace gas stream is formed

Table 21-1 embodiment 1 logistics data table 1

Table 21-2 embodiment 1 logistics data table 2

Table 21-3 embodiment 1 logistics data table 3

Table 21-4 embodiment 1 logistics data table 4

Table 21-5 embodiment 1 logistics data table 5

Table 21-6 embodiment 1 logistics data table 6

Table 21-7 embodiment 1 logistics data table 7

Table 21-8 embodiment 1 logistics data table 8

Table 21-9 embodiment 1 logistics data table 9

Table 21-10 embodiment 1 logistics data table 10

Table 21-11 embodiment 1 logistics data table 11

Table 21-12 embodiment 1 logistics data table 12

Table 21-13 embodiment 1 logistics data table 13

Table 22 embodiment 1 methanation virgin gas leading indicator is analyzed

There is fluctuation in present embodiment owing to produce, as H in ring coal gas ₂When/CO molecular ratio increases, the CO interconversion rate is promptly done the adjustment that descends; As H in ring coal gas ₂When/CO molecular ratio reduces, the CO interconversion rate is promptly done to increase adjustment, as the production control target, control hydrogen efficient>=0.92, control molecular ratio H ₂/ (3 * CO+4 * CO ₂)>=0.96.

During concrete engineering design, each process function all considers to produce the demand of fluctuation.

Lift 1 embodiment although this paper just lists, the effect that it shows is present in equally and anyly is suitable for adopting in the process of the present invention.

Claims

1. the internally heated coal carbonization multi-production process of a coproduction high methane gas is characterized in that comprising following steps:

1. make oxygen enrichment in system oxygen unit 100;

2. method according to claim 1 is characterized in that:

1. in the unit 100, be that raw material makes oxygen enrichment with the air;

3. in the unit 300, become the process that General Office regulates the flow of vital energy from ring coal gas and comprise CO transformation and hydrogen production step 304.

3. method according to claim 2 is characterized in that:

4. method according to claim 3 is characterized in that:

1. in the unit 100, the oxygen components volumetric concentration is higher than 86% in the oxygen enrichment that makes;

5. method according to claim 4 is characterized in that:

6. method according to claim 3 is characterized in that:

7. according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that:

8. according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that:

9. according to claim 1 or 2 or 3 or 4 or 5 or 6 methods of stating, it is characterized in that:

10. according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that:

11., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

12., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

13., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

14., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

15., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

16., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

17. method according to claim 16 is characterized in that:

18., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

19. method according to claim 18 is characterized in that:

20., it is characterized in that according to claim 3 or 4 or 5 or 6 described methods:

21., it is characterized in that according to claim 1 or 2 or 3 described methods:

22. method according to claim 21 is characterized in that:

23., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

5. in the unit 500, the high potential temperature heat of at least a portion methanator elute is used to heat the low temperature thermal oil and forms high temperature heat conductive oil;

24. method according to claim 23 is characterized in that:

6. the high temperature heat conductive oil temperature is 350～400 ℃, and lower temperature thermal oil temperature is high 30～50 ℃.

25. method according to claim 24 is characterized in that:

6. the main ingredient of thermal oil is a biphenyl.

26. method according to claim 20 is characterized in that:

3. in conversion gas hydrogen manufacturing unit 700, a part of first via conversion gas cooling dehydration back entering transformation absorption decarbonation process 701 is separated into takes off CO ₂Purified gas 701P and rich CO ₂Stripping gas 701DG, at least a portion is taken off CO ₂Purified gas 701P entering transformation absorption hydrogen purification process 702 is separated into carries dense hydrogen 702P and methane rich stripping gas 702DG; At least a portion is carried dense hydrogen 702P and use raw hydrogen as the dead oil hydro-upgrading unit of step in 6., and at least a portion methane rich stripping gas 702DG gets into step and 5. is used as the methanation virgin gas;

27. method according to claim 26 is characterized in that:

3. in the unit 700, put forward dense hydrogen 702P hydrogen volume concentration and be higher than 95%.

28. method according to claim 27 is characterized in that:

3. in the unit 700, put forward dense hydrogen 702P hydrogen volume concentration and be higher than 99%.

29., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:

4. in purified gas hydrogen manufacturing unit 800; Part purified gas entering transformation absorption hydrogen purification process 800 is separated into carries dense hydrogen 800P and methane rich stripping gas 800DG; At least a portion is carried dense hydrogen 800P and use raw hydrogen as the dead oil hydro-upgrading unit of step in 6., and at least a portion methane rich stripping gas 800DG gets into step and 5. is used as the methanation virgin gas;

30. method according to claim 29 is characterized in that:

4. in the unit 800, put forward dense hydrogen 800P hydrogen volume concentration and be higher than 95%.

31. method according to claim 30 is characterized in that:

4. in the unit 800, put forward dense hydrogen 800P hydrogen volume concentration and be higher than 99%.

32. method according to claim 7 is characterized in that:

3. take off heavy hydrocarbon from encircling coal gas through the preposition CO of taking off ₂Step 302K takes off CO before being separated into conversion ₂Gas 302KP and rich CO ₂Gas 302KD takes off CO before the conversion ₂Gas 302KP gets into impurity shortening step of converting 303.

33. method according to claim 32 is characterized in that:

3. the rich CO of at least a portion ₂Gas 302KD gets into the 2. said charring furnace of step combustion chamber provides the charring furnace combustion chamber with carbonic acid gas temperature control component.

34. method according to claim 1 is characterized in that:

35. method according to claim 34 is characterized in that: