CN102431967A - Method for preparing hydrogen and nitrogen gas with specific composition from multi-ingredient gas containing H2 and N2 - Google Patents

Method for preparing hydrogen and nitrogen gas with specific composition from multi-ingredient gas containing H2 and N2 Download PDF

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CN102431967A
CN102431967A CN2011102216276A CN201110221627A CN102431967A CN 102431967 A CN102431967 A CN 102431967A CN 2011102216276 A CN2011102216276 A CN 2011102216276A CN 201110221627 A CN201110221627 A CN 201110221627A CN 102431967 A CN102431967 A CN 102431967A
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何巨堂
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Abstract

The invention relates to a method for preparing hydrogen and nitrogen gas with specific composition from multi-ingredient gas containing H2 and N2, which comprises the steps that: in a flow division step 1000, raw material gas F100 is divided into a first path of raw material gas and a second path of raw material gas, and in addition, the flow rate ratio is controlled; in the step 2000, hydrogen and nitrogen gas PHN is prepared on the basis of the first path of raw material gas; in a pressure variation absorption and separation step 3000, the second path of raw material gas is used for preparing hydrogen gas PH and nitrogen-rich gas PN, and in addition, the PH or PN is selected to be used as regulation gas PT; and in the flow merging step 4000, the regulation gas PT and the PHN are mixed into hydrogen and nitrogen regulation gas P with the specific H2/N2 molecular proportion. Ring breaking gas produced in the inner heating coal dry distillation process is subjected to the integral treatment step to complete the steps of desulfuration, heavy hydrocarbon removal, deoxygenation, CO conversation nitrogen preparation and the like to obtain integrally treated gas used as the raw material gas F100, when the method is adopted, the synthesis ammonia raw material gas (hydrogen and nitrogen regulation gas P) and carbon-dioxide-rich gas can be simultaneously obtained, and the inner heat type coal dry distillation process for coproducing synthesis ammonia (or ammonium bicarbonate or urea) is formed.

Description

A kind of usefulness contains H 2, N 2Polycomponent gas prepares the method for specific composition hydrogen and nitrogen gas
Technical field
The present invention relates to a kind of usefulness and contain H 2, N 2Polycomponent gas prepares the method for specific composition hydrogen and nitrogen gas; Say especially and the present invention relates to a kind ofly produce the method that rich nitrogen raw gas is produced syngas for synthetic ammonia with the internally heated coal carbonization process; More particularly the present invention relates to a kind ofly produce the method that rich nitrogen raw gas is produced syngas for synthetic ammonia with the blue charcoal process of internal heat type coal system.
Background technology
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; Be 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.This technology has the general feature of the blue charcoal technology of internal heat type coal system: with the air is oxygen donator; The main body of combustion chamber temperature control component (non-flammable, non-oxidiser component that the combustion chambers burn process exists) is a nitrogen; The main body of coking chamber temperature control component (coking chamber gas-particle heat transfer process exist non-flammable, non-oxidiser component) is a nitrogen, the raw gas of generation be rich nitrogen 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.
With the air is the raw gas H of the blue charcoal process generation of coal system of oxygen donator 2/ N 2Molecular ratio KA changes and usually less than 3.0 with the variation of operation factors such as coal, pyrolysis temperature, destructive distillation time, between the KA coefficient is generally 0.3～1.2, be generally 0.5～1.0, certainly, possibly exceed above-mentioned scope under the few cases.
Raw gas (the CO+H that the blue charcoal process of coal system produces 2)/N 2Molecular ratio KB; Change and less than 3.0 with the variation of operation factors such as coal, pyrolysis temperature, destructive distillation time, between the KB coefficient is generally 0.6～1.6, be generally 0.8～1.4, certainly; Possibly exceed above-mentioned scope under the few cases, the present invention is primarily aimed at KB less than the blue charcoal process of 3 coal system.
Raw gas (the CO+H that the blue charcoal process of coal system produces 2+ hydro carbons steam reforming H 2)/N 2Molecular ratio KC; Change and less than 3.0 with the variation of operation factors such as coal, pyrolysis temperature, destructive distillation time; Between the KB coefficient is generally 0.9～2.6, be generally 1.2～2.2, certainly, possibly exceed above-mentioned scope under the few cases; The present invention is primarily aimed at KC less than the blue charcoal process of 3 coal system, but is equally applicable to KC greater than the blue charcoal process of 3 coal system.
Table 1 is that the blue charcoal process raw gas volume of oxygenant is formed with the air
Figure BSA00000550568300021
CO 2-CH 4-CO-N 2(being generally the main body component)-H 2For representing the system of component, be the raw material of a good preparation syngas for synthetic ammonia, but the raw gas (CO+H that the blue charcoal process of coal system produces 2)/N 2The desirable H that forms of molecular ratio and syngas for synthetic ammonia 2/ N 2Molecular ratio is 3.0 too wide in the gap, and nitrogen is excessive, and the nitrogen that needs excessive separation is separation of C H simultaneously 4, CO, CO 2Etc. component, promptly associated separation steps need be set, yet what occur the use pressure swing adsorption for many years can control product gas H always 2/ N 2The method of molecular ratio.Such as application number is that the denomination of invention of 201010220144.X is that the invention application of ammonia synthesis process discloses a kind of raw gas and prepares the synthetic ammonia feedstock gas method, yet proposes control product gas H 2/ N 2The concrete scheme of molecular ratio.
And the blue charcoal scale of CHINESE COAL system will reach 3000～4,000 ten thousand tons/year; The raw gas of its by-product; Even do not consider hydrocarbon components such as methane; Can produce 750～1,000 ten thousand tons of/year synthetic ammonia or 2250～3,000 ten thousand ton/year carbon ammonium or 2250～3,000 ten thousand ton/year urea in theory, can practice thrift～1,000 ten thousand tons of/year raw coal, so benefit be huge.
The present invention proposes and earlier raw gas is carried out comprehensive treating process,, be mixed into then and expect H then to General Office regulate the flow of vital energy controlledly processing and preparing high-purity hydrogen and High Purity Hydrogen nitrogen along separate routes 2/ N 2The method of the syngas for synthetic ammonia of molecular ratio has solved this technical barrier.
The raw gas of the blue charcoal process of coal system by-product, because hydrocarbon component volumetric concentration low (generally being lower than 10%) is directly produced raw gas to the blue charcoal process of coal system simply hydro carbons steam reforming process is set, its hydrogen production efficiency capacity usage ratio is lower, system scale is huge.Reasonably hydro carbons steam reforming method is to carry dense hydrocarbon component earlier, accomplish hydro carbons steam reforming, last combined recovery synthesis gas components CO, H then 2, the utilization ratio of nitrogen component in the raising raw gas.And the present invention possesses the function of separating and carrying dense hydrocarbon component just.
The used technology of the present invention is also uncomplicated, yet, consider in the time in 20～30 years, never to occur using the rich nitrogen raw gas of pressure swing absorption process utilization to prepare this technical scheme of syngas for synthetic ammonia, so technical scheme of the present invention is unusual.
As everyone knows, in the PSA technology, the separation factor of methane and nitrogen is less, but the blue charcoal process of the coal system of being based on is produced methane content lower (generally being lower than 7%) and (CO+H in the raw gas 2)/N 2Molecular ratio KB is far below 3 these two characteristics; In the shunt processing scheme; Put forward the hydrogen process and can isolate the almost whole methane in this road gas; Extract nitrogen hydrogen process and can isolate the most of methane in this road gas, owing to put forward the raw gas quantity that the raw gas quantity of hydrogen process processing is handled greater than extraction nitrogen hydrogen process usually, so the most of methane in the raw material raw gas can separated be gone out.The present invention mainly is based on this characteristics proposition.
The method of the invention is not appeared in the newspapers.，
Therefore, first purpose of the present invention is to propose a kind of usefulness and contains H 2, N 2Polycomponent gas prepares the method for specific composition hydrogen and nitrogen gas.
Second purpose of the present invention is to propose a kind ofly to produce the method that rich nitrogen raw gas is produced syngas for synthetic ammonia (or synthetic ammonia or carbon ammonium or urea) with the internally heated coal carbonization process.
The 3rd purpose of the present invention is to propose a kind ofly to produce the method that rich nitrogen raw gas is produced syngas for synthetic ammonia (or synthetic ammonia or carbon ammonium or urea) with the blue charcoal process of internal heat type coal system, is provided with and takes off CO 2The hydro carbons steam reforming hydrogen manufacturing process of high methane gas also reclaims this hydrogen, can at utmost increase production syngas for synthetic ammonia.
The 4th purpose of the present invention is to propose a kind of internally heated coal carbonization multi-production process of coproducing synthetic ammonia virgin gas, can coproduction high methane gas or natural gas liquids.
Summary of the invention
A kind of usefulness contains H 2, N 2Polycomponent gas prepares the method for specific composition hydrogen and nitrogen gas, it is characterized in that comprising following steps:
1. at minute flow step 1000, contain H 2, N 2Multi-component feedstock gas F100 splits into the second road virgin gas F102 that first via virgin gas F101 that flow rate is R101 and flow rate are R102, and the control flow rate guarantees 4. H among the hydrogen nitrogen blending gas P of step than R101/R102 2/ N 2Molecular ratio reaches desired value;
2. in step 2000, F101 obtains hydrogen and nitrogen gas PHN based on first via virgin gas;
3. at separating step 3000, separate the second road virgin gas F102 and obtain hydrogen PH and rich nitrogen PN, select hydrogen PH or rich nitrogen PN to get into step 4. as blending gas PT;
4. collaborating step 4000, hydrogen and nitrogen gas PHN and blending gas PT are mixed into hydrogen nitrogen blending gas P.
Virgin gas F100 of the present invention when encircling coal gas F0 from leaving of internally heated coal carbonization device, is characterized by:
2. step 2000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is generally 0.5～2.5MPa;
3. step 3000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.5～2.5MPa.
Virgin gas F100 of the present invention when regulating the flow of vital energy TF100 from the General Office from ring coal gas F0 of internally heated coal carbonization device, is characterized by:
1. in step 1000, virgin gas F100 is the TF100 that regulates the flow of vital energy from the General Office from ring coal gas F0 of internally heated coal carbonization device, and F0 contains H from ring coal gas 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in comprehensive treating process unit 1100, comprehensive treating process unit 1100 comprises CO transformation and hydrogen production step 1104;
2. step 2000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.8～1.5MPa;
3. step 3000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.8～1.5MPa; Select hydrogen PH to get into step 4. as blending gas PT;
4. in step 4000, hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is greater than the H of virgin gas F100 2/ N 2Molecular ratio.
Virgin gas F100 of the present invention when regulating the flow of vital energy TF100 from the General Office from ring coal gas F0 of the blue charcoal device of internal heat type coal system, contains H from encircling coal gas F0 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn; 1100 are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in the comprehensive treating process unit; First kind of comprehensive treating process flow process comprises following steps: become and take off heavy hydrocarbon from ring coal gas through the heavy hydrocarbon step 1102 of taking off that pressure swing adsorption process takes off charcoal five and above hydrocarbon thereof from ring coal gas F0; Take off heavy hydrocarbon and become deoxidation from ring coal gas through impurity shortening step of converting 1103 from ring coal gas; Deoxidation is accomplished the reaction of CO transformation and hydrogen production from ring coal gas through sulfur-resisting transformation step 1104 and is obtained conversion gas and CO interconversion rate greater than 85%, and the dehydration conversion gas that conversion air cooling obtains after but dewatering is as the TF100 that regulates the flow of vital energy of General Office.
Virgin gas F100 of the present invention when regulating the flow of vital energy TF100 from the General Office from ring coal gas F0 of the blue charcoal device of internal heat type coal system, contains H from encircling coal gas F0 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn; 1100 are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in the comprehensive treating process unit, and second kind of comprehensive treating process flow process comprises following steps: adopt wet desulphurizations that hydrogen sulfide volumetric concentration in the coal gas is reduced to 150～300PPm from the preparatory desulfurized step 1101 of ring coal gas F0 and obtain preparatory desulfurization from ring coal gas; Desulfurization is to use the pressure-swing adsorption process of acticarbon from the heavy hydrocarbon step 1102 of taking off of ring coal gas in advance; Taking off heavy hydrocarbon adopts low-temperature catalyzed hydrogenation deoxidation process and OTR near 100% from ring coal gas impurity shortening step of converting 1103; Deoxidation adopts low temperature sulfur-resisting transformation process to accomplish CO transformation and hydrogen production process and CO interconversion rate greater than 90% from ring gas reforming step 1104, and the dehydration conversion gas that conversion air cooling obtains after but dewatering is as the TF100 that regulates the flow of vital energy of General Office.
Virgin gas F100 of the present invention when regulating the flow of vital energy TF100 from the General Office from ring coal gas F0 of the blue charcoal device of internal heat type coal system, contains H from encircling coal gas F0 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn; 1100 are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in the comprehensive treating process unit, and the third comprehensive treating process flow process comprises following steps: 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 1101 of ring coal gas F0 and obtain preparatory desulfurization from ring coal gas; Desulfurization is taken off heavy hydrocarbon step 1102 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 1103; Deoxidation is adopted low temperature sulfur-resisting transformation process to accomplish the CO transformation and hydrogen production process from ring gas reforming step 1104 and is obtained conversion gas and CO interconversion rate greater than 95%; 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 1105 adopted; The conversion gas that obtains dewatering after poor organosulfur conversion air cooling is but dewatered, dehydration conversion gas is as the TF100 that regulates the flow of vital energy of General Office.
The H of hydrogen nitrogen blending gas P of the present invention 2/ N 2Molecular ratio: be generally 2.00～5.00, be generally 2.50～3.50, be 2.95～3.00 and especially finally as syngas for synthetic ammonia.
The present invention in step 1000, can regulate the flow of vital energy TF100 as virgin gas F100 with General Office.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and first kind of mode is: devulcanization hydrogen that TF100 obtains through the depriving hydrogen sulphide step is regulated the flow of vital energy as virgin gas F100 by General Office.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and the second way is: TF100 is regulated the flow of vital energy through taking off CO in General Office 2Step obtains takes off CO 2Gas is as virgin gas F100.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and the third mode is: the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through taking off CO 2Step obtains taking off CO 2Gas is as virgin gas F100.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and the 4th kind of mode is: with General Office regulate the flow of vital energy TF100 through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
The present invention; In step 1000; General Office's pre-separation step 1500 of regulating the flow of vital energy can be set, and the 5th kind of mode is: the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and the 6th kind of mode is: the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through taking off CO 2Step obtains taking off CO 2Gas will take off CO 2Gas through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
Step 2000 Action Target of the present invention is generally: 2. first via virgin gas F101 makes hydrogen and nitrogen gas PHN through transformation adsorption step 2100; In methanation unit 2200, hydrogen and nitrogen gas PHN accomplishes methanation reaction and obtains methanation reforming gas 2200P, and the CO volumetric concentration of reforming gas 2200P is lower than 20PPm, CO 2Volumetric concentration is lower than 20PPm, CH 4Volumetric concentration is lower than 2%, the argon gas volumetric concentration is lower than 2%.
Step 2000 Action Target of the present invention is generally: 2. in methanation unit 2200, and CO volumetric concentration and the CO of reforming gas 2200P 2The volumetric concentration sum is lower than 10PPm; The CH of while reforming gas 2200P 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.0%.
Step 4200 Action Target of the present invention is generally: 4. hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is 3.00～3.05; In methanation unit 4200, hydrogen nitrogen blending gas P accomplishes methanation reaction and obtains methanation reforming gas 4200P, and the CO volumetric concentration of reforming gas 4200P is lower than 15PPm, CO 2Volumetric concentration is lower than 15PPm, CH 4Volumetric concentration is lower than 2%, the argon gas volumetric concentration is lower than 2%.
Step 4200 Action Target of the present invention is generally: 4. CO volumetric concentration and the CO of reforming gas 4200P 2The volumetric concentration sum is lower than 10PPm; The CH of while reforming gas 4200P 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.0%.
When the present invention is provided with deep purifying step 5000, it is characterized in that:
5. in deep purifying step 5000, adopt pressure swing adsorption process, in the adsorbent bed adsorption process of transformation, non-hydrogen, non-nitrogen component such as CH among hydrogen nitrogen blending gas P or the methanation reforming gas 4200P 4, CO, CO 2Deng being adsorbed agent absorption, H 2, N 2Component is passed the adsorbent bed deep purifying gas 5000P 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 5000DG; The transformation adsorption step uses 2 or a plurality of adsorption tower, realizes the continous-stable operation.
When the present invention was provided with deep purifying step 5000, first kind of mode of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets into the methanation step and contacts the CO among the stripping gas 5000DG, CO with methanation catalyst as the methanation virgin gas 2Major part be converted into methane.
When the present invention was provided with deep purifying step 5000, the second way of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets into step 2000 as step 2000 virgin gas.
When the present invention was provided with deep purifying step 5000, the third mode of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets into transformation adsorption step 3000 as step 3000 virgin gas, the H among the stripping gas 5000DG 2Major part get among the hydrogen PH.
When the present invention was provided with deep purifying step 5000, the 4th kind of mode of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets among the step virgin gas F100 1..
When the present invention was provided with deep purifying step 5000, the 5th kind of mode of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets in the source of the gas gas of step virgin gas F100 1..
Deep purifying step 5000 operational condition of the present invention is generally: 5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 30～50 ℃, and working pressure is 0.8～5.0MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 20PPm, CH 4Volumetric concentration is lower than 1.5%, the argon gas volumetric concentration is lower than 2%.
Deep purifying step 5000 operational condition of the present invention is generally: 5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 35～45 ℃, and working pressure is 0.8～2.0MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 15PPm, CH 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.5%.
Deep purifying step 5000 operational condition of the present invention is preferably: 5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 37～43 ℃, and working pressure is 0.8～1.5MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 10PPm, CH 4Volumetric concentration is lower than 0.7%, the argon gas volumetric concentration is lower than 1.0%.
The present invention selects rich nitrogen PN to get into step 4. the time as blending gas PT in step 3000, and hydrogen PH and blending gas PT are mixed into hydrogen nitrogen blending gas P through mixing step 4001, the H of hydrogen nitrogen blending gas P 2/ N 2Molecular ratio is less than the H of virgin gas F100 2/ N 2Molecular ratio.
The sorbent material that step 2000 of the present invention and step 3000 are used is generally:
2. in step 2000, the sorbent material of use has activated alumina, silica gel, gac, molecular sieve;
3. in step 3000, the sorbent material of use has activated alumina, silica gel, gac, molecular sieve.
The sorbent material that step 2000 of the present invention and step 3000 are used is generally:
2. in step 2000, the sorbent material of use has silica gel, gac, molecular sieve;
3. in step 3000, the sorbent material of use has silica gel, gac, molecular sieve.
The sorbent material preferably that step 2000 of the present invention and step 3000 are used is:
2. in step 2000, the sorbent material of use has gac, molecular sieve;
3. in step 3000, the sorbent material of use has gac, molecular sieve.
The present invention is provided with General Office's pre-separation step 1500 of regulating the flow of vital energy in step 1000, separates the TF100 that regulates the flow of vital energy of General Office and can obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2High methane gas, rich CO 2Gas takes off CO this moment 2High methane gas can get into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtain the hydrogen manufacturing reforming gas; The step 1900 of going the hydrogen manufacturing reforming gas adopts pressure swing adsorption process to extract pure hydrogen APH as blending gas PT; Perhaps the hydrogen manufacturing reforming gas goes step 1900 to adopt pressure swing adsorption process to extract pure hydrogen and nitrogen gas APHN as blending gas PT; Perhaps the hydrogen manufacturing reforming gas is sneaked among the first via virgin gas F101; Perhaps the hydrogen manufacturing reforming gas is sneaked among the second road virgin gas F102, and perhaps the hydrogen manufacturing reforming gas is sneaked among the virgin gas F100, and perhaps the hydrogen manufacturing reforming gas is sneaked in the source of the gas gas of virgin gas F100.
The present invention is provided with General Office's pre-separation step 1500 of regulating the flow of vital energy in step 1000, separates the TF100 that regulates the flow of vital energy of General Office and can obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2High methane gas, rich CO 2Gas takes off CO this moment 2High methane gas can be as system liquefied methane gas virgin gas.
The present invention is provided with General Office's pre-separation step 1500 of regulating the flow of vital energy in step 1000, separates the TF100 that regulates the flow of vital energy of General Office and can obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2High methane gas, rich CO 2Gas at this moment, is handled rich CO 2Be so incensed that the rich CO of high purity 2Gas PCO2, PCO2 finally can also can be used as the plain virgin gas of antidiuresis as system carbon ammonium virgin gas.
The present invention is provided with General Office's pre-separation step 1500 of regulating the flow of vital energy in step 1000, separates the TF100 that regulates the flow of vital energy of General Office and obtains mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2Take off N 2High methane gas, rich CO 2Gas takes off CO 2Take off N 2High methane gas can be as system synthetic natural gas virgin gas.
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 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 intensity 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 separate raw materials gas.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 pressure-swing adsorption process according to the invention is used 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 force intensity and loading capacity.For the complicated virgin gas of composition, in practical application, use multiple sorbent material usually, press the absorption property compound adsorption bed of layering filling composition associating successively, also can design two-stage or multi stage process, single-stage is separated or the purpose of stage trapping to reach.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 target components ability, realizes the purification of the target components in the mixing raw material 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 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 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.
A kind of usefulness of the present invention contains H 2, N 2Polycomponent gas prepares the method for specific composition hydrogen and nitrogen gas, and its core technology scheme is:
1. at minute flow step 1000, contain H 2, N 2Multi-component feedstock gas F100 splits into the second road virgin gas F102 that first via virgin gas F101 that flow rate is R101 and flow rate are R102, and the control flow rate guarantees 4. H among the hydrogen nitrogen blending gas P of step than R101/R102 2/ N 2Molecular ratio reaches desired value;
2. in step 2000, F101 obtains hydrogen and nitrogen gas PHN based on first via virgin gas;
3. at separating step 3000, separate the second road virgin gas F102 and obtain hydrogen PH and rich nitrogen PN, select hydrogen PH or rich nitrogen PN to get into step 4. as blending gas PT;
4. collaborating step 4000, hydrogen and nitrogen gas PHN and blending gas PT are mixed into hydrogen nitrogen blending gas P.
The present invention is applied to the internally heated coal carbonization device and produces rich nitrogen when ring gas preparation hydrogen nitrogen blending gas P, and rich nitrogen need pass through the comprehensive treating process process usually from ring coal gas.
The present invention is applied to the internally heated coal carbonization device and produces rich nitrogen when the hydrogen nitrogen of ring gas preparation lower concentration oxycarbide is concocted gas P, and methanation need be set.
The present invention can be provided with deep purifying step 5000 and handle hydrogen nitrogen blending gas P, can further reduce the non-nitrogen component concentration of non-hydrogen in the finished product gas.
The present invention can be provided with high methane gas hydrogen production process raising the output hydrogen output, can further improve the nitrogen utilization ratio in ring coal gas.
Below describe internally heated coal carbonization according to the invention unit 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.
" 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: be oxygen donator with the air; The main body of combustion chamber temperature control component (non-flammable, non-oxidiser component that the combustion chambers burn process exists) is a nitrogen; The main body of coking chamber temperature control component (coking chamber gas-particle heat transfer process exist non-flammable, non-oxidiser component) is a nitrogen, the raw gas of generation be rich nitrogen with CO 2-CH 4-CO-N 2(being generally the main body component)-H 2For representing the system of component.
Internally heated coal carbonization according to the invention unit; Refer to any suitable internally heated coal carbonization process; Its charring furnace combustion chamber oxygenant is the internally heated coal carbonization process of rich nitrogen oxygen-containing gas; The gas mixtures that rich nitrogen oxygen-containing gas can be air or air and oxygen enrichment etc., rich nitrogen is (CO+H from the characteristics of ring coal gas 2)/N 2Molecular ratio KB is less than 3.The rich nitrogen of the blue charcoal process of coal system changes with the variation of operation factors such as coal, pyrolysis temperature, destructive distillation time and less than 3.0 from the KB value of ring coal gas; Between the KB coefficient is generally 0.6～1.4, be generally 0.8～1.2; Certainly, possibly exceed above-mentioned scope under the few cases.
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; Rich oxidation of nitrogen agent with combustion reactions formation high-temperature flue gas takes place in fuel gas gets into the charring furnace combustion chamber after entering coking chamber retort section 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 quenching step by coke extractor discharge coking chamber, 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.Usually 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; Usually can sneak into oxygenant (air) before the burnt cooling section of circulation heat-carrying gas entering charring furnace coking chamber and become mixing heat-carrying gas; The combination reaction heat release that oxygen and hydrogen promptly take place mixing heat-carrying gas (such as 570 ℃) after charring furnace coking chamber uphill process reaches certain temperature provides heat; This heat is mainly used in the heat supply of dry distillation of coal process in essence, and mixing heat-carrying gas continues upwards to flow and mixes with the high-temperature flue gas of charring furnace combustion chamber formation.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), there is little negative pressure sometimes.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.
Internally heated coal carbonization charring furnace operation scheme, what have does not establish the charring furnace combustion chamber, has so just lacked heating Regulation means, has also lost the risk prevention instruments of " control charing section temperature prevents that inflammable gas oxygen gathers blast accident in the stove ".
Internally heated coal carbonization process of the present invention can be provided with the charring furnace combustion chamber, also the charring furnace combustion chamber can be set.But recommend to be provided with the charring furnace combustion chamber usually.
Internally heated coal carbonization process of the present invention when possessing internally heated coal carbonization process characteristics, can make up the outside heating facility that uses the indirect heating means to use such as external-heat dry distillation of coal process.
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 describe a kind of specific form, but this is not to 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.Usually sneak into oxygenant (air) before the burnt cooling section of circulation heat-carrying gas entering charring furnace coking chamber and become mixing heat-carrying gas; The combination reaction heat release that oxygen and hydrogen promptly take place mixing heat-carrying gas (such as 570 ℃) after charring furnace coking chamber uphill process reaches certain temperature provides heat; This heat is mainly used in the heat supply of dry distillation of coal process in essence, and mixing heat-carrying gas continues upwards to flow and mixes with the high-temperature flue gas of charring furnace combustion chamber formation.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 rich oxidation of nitrogen agent of upright furnace combustion chamber is supplied with by gas blower pressurization back usually; Coal gas and oxygenant 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 H that contains according to the invention 2, N 2Multicomponent gas can be the H that contains from any technological process 2, N 2Multicomponent gas, can be gas from single process, also can be the gas mixture of multiple gases.
Rich nitrogen coal gas according to the invention can be that rich nitrogen coal gas is with CO from any technological process that produces rich nitrogen coal gas 2-CH 4-CO-N 2(being generally the main body component)-H 2For representing the gas of component, be characterized in (CO+H 2)/N 2Molecular ratio KB is usually less than 3.
Rich nitrogen coal gas according to the invention can be the single rich nitrogen coal gas from the internally heated coal carbonization process, also can be the gas mixture of multiple gases.
Rich nitrogen coal gas according to the invention can be the mixed gas of rich nitrogen coal gas and poor nitrogen coal gas, such as can being from the rich nitrogen coal gas of internally heated coal carbonization process with from the mixed gas of the poor nitrogen coal gas of external-heat dry distillation of coal process.
Describing below that the internally heated coal carbonization process produces from the ring gas reforming in detail is that the regulate the flow of vital energy process of TF100 of General Office is comprehensive treating process unit 1100.
Difference according to gas source contains H 2, N 2The composition of multicomponent gas is different.Producing rich nitrogen with the blue charcoal process of internally heated coal carbonization system is example from ring coal gas, and rich nitrogen coal gas contains H usually 2, Ar, O 2, N 2, CH 4, CO, C 2H 6, C 2H 4, CO 2, H 2S, organosulfur, charcoal three and above hydrocarbon thereof, H 2Components such as O are from encircling gas reforming for containing H 2, N 2The comprehensive treating process unit 1100 of multi-component feedstock gas F100 comprises preparatory desulfurized step 1101; Take off charcoal five and above hydrocarbon (comprises the tar that possibly exist; Naphthalene; Dirt) take off heavy hydrocarbon step 1102; Compression is boosted; Heat up; Increase the humidification step of water vapor concentration (satisfying the water charcoal molecular ratio of transformationreation needs); Impurity is (like oxygen; Alkene; Organosulfur) the shortening step of converting 1103; Low temperature sulfur-resisting transformation step 1104; Carbonylsulfide medium temperature hydrolyzation step 1105; In the steps such as cooled dehydrated step.Different sources of the gas is converted into and contains H 2, N 2The comprehensive treating process unit 1100 of multi-component feedstock gas F100 possibly comprise above-mentioned part steps or Overall Steps, but comprises impurity (like oxygen, alkene, organosulfur) shortening step of converting 1103 usually.
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 global transformation rate of CO is low in the coal gas according to the invention in addition can not have powerful COS transformation function with a large amount of CO depth conversion of production of raw-material gas for synthetic ammonia process and compare; Special-purpose organosulfur conversion process must be set usually, 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 1100; The source of the gas gas that refers to any suitable TF100 that General Office is regulated the flow of vital energy is such as the regulate the flow of vital energy process of TF100 of the General Office that forms for expection from the ring gas reforming; Flow process of the present invention comprises the CO conversion process usually; In order to produce hydrogen to greatest extent, the controlled target of CO conversion process normally guarantees the maximum conversion rate that CO is economic.
According to the invention from the preparatory desulfurized step 1101 of ring raw gas; 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 1101 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 preparatory desulfurized step 1101 according to the invention uses in detail.Known coal gas desulfurization hydrogen technology can be learnt from the listed publication of table 2.
The publication of table 2 record coal gas desulfurization hydrogen technology
Figure BSA00000550568300201
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 present invention will be controlled at a higher range from the hydrogen sulfide volumetric concentration of ring coal gas with desulfurization, make the necessary mass transfer theory level of the depriving hydrogen sulphide mass transfer workshop section of gas wet hydrogen sulfide removal process less, adopt the series connection of single tower or two towers to absorb usually and get final product.
Below describe in detail and according to the inventionly take off heavy hydrocarbon part 1102 from what ring gas reforming process possibly comprise.
As required; Setting of the present invention is taken off heavy hydrocarbon part 1102 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 1102 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 the said humidification step of taking off heavy hydrocarbon that unit 1100 of the present invention possibly comprise 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 shortening conversion process 1103 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 1103 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 3.
Table 3 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/m 3 700-800
6 Catalyst loading density, kg/m 3 700-800
7 Intensity, N/cm 2 ≥50.0
8 H 2The S maximum permissible concentration, mg/Nm 3 Do not limit
9 H 2The minimum safe level of S, mg/Nm 3 ≥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, normally 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.
Describe below that unit 1100 of the present invention comprises in detail from ring coal gas carbon monodixe conversion process 1104.
Said carbon monodixe conversion process 1104 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 4.
The publication of table 4 record coal gas carbon monodixe conversion technology
Figure BSA00000550568300261
From ring coal gas carbon monodixe conversion hydrogen production process 1104 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 1104, 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 1104 operational conditions: the carbon monoxide transformation efficiency is greater than 80%; 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 1104 operational conditions: the carbon monoxide transformation efficiency is greater than 90%; 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 2.0～4.0 that average reaction temperature is lower than 300 ℃, pressure.
Be preferably from ring coal gas carbon monodixe conversion hydrogen production process 1104 operational conditions: the carbon monoxide transformation efficiency is greater than 95%; It is that 0.3～0.8MPa (absolute pressure), catalyzer are that sulfur-resistant transformation catalyst, catalyst volume air speed are 450～1650 SCMs virgin gas/cubic meter catalyzer, H that average reaction temperature is lower than 250 ℃, pressure 2The O/CO molecular ratio is 2.5～3.5.
About the carbon monodixe conversion process H that regulates the flow of vital energy of General Office 2The control method of O/CO molecular ratio can adopt the substep waterflood project: forwardly control H 2The O/CO molecular ratio is low such as being 1.5～2.5, with controls reaction speed, and control reaction heat; Forwardly control H 2The O/CO molecular ratio is higher such as being 2.5～3.5, with the control reaction conversion ratio.
General Office's carbon monodixe conversion process of regulating the flow of vital energy; 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 5.
Table 5CO transformation catalyst related data table
Figure BSA00000550568300281
Below describe conversion gas carbonyl sulfide hydrolysis process 1105 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 lower concentration CO conversion process is that the overall inversion quantity of carbon monoxide is less; Usually 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 separating step or the unitary zinc oxide desulfurization hydrogen of methanation process convenient remove it.Known carbonyl sulfide hydrolysis technology can be learnt from the listed publication of table 6.
The publication of table 6 record carbonyl sulfide hydrolysis technology
Figure BSA00000550568300282
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
Figure BSA00000550568300291
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 General Office's pre-separation step 1500 of regulating the flow of vital energy in detail.
The General Office described herein pre-separation step 1500 of regulating the flow of vital energy refers to the TF100 that regulates the flow of vital energy of any suitable separation General Office and obtains containing H 2, N 2The process of multi-component feedstock gas F100, pre-separation step 1500 are isolated a kind of component outside hydrogen and the nitrogen component at least, and its separation key component can be water or hydrogen sulfide or carbonic acid gas or methane or carbon monoxide.Therefore, the regulate the flow of vital energy flow process of pre-separation step 1500 of General Office can have multiplely, when adopting the transformation adsorption separation technology, 1 transformation adsorption step or 2 transformation adsorption steps or a plurality of transformation adsorption step can be arranged.Should combine other Action Target and decide, most economical reasonable method is exactly the best approach.Known gas sweetening decarbonation technology can be learnt from the listed publication of table 7.
The General Office described herein pre-separation step 1500 of regulating the flow of vital energy can be isolated the whole components that can separate outside hydrogen and the nitrogen component when special, and what obtain at this moment contains H 2, N 2Multi-component feedstock gas F100 can be mainly by H 2, N 2With the gas that a small amount of other component such as Ar etc. form, this moment, step 2000 can be with first via virgin gas F101 directly as hydrogen and nitrogen gas PHN.
The publication of table 7 record gas sweetening decarbonation technology
Figure BSA00000550568300301
In sum; General Office's pre-separation step 1500 of regulating the flow of vital energy can be 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 pre-separation step 1500 of regulating the flow of vital energy can be used 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 pre-separation step 1500 of regulating the flow of vital energy can be used 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 pre-separation step 1500 employing pressure swing absorption process is regulated the flow of vital energy by General Office; Can adopt the secondary pressure swing adsorption technique; In adsorbent bed 1501 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 1501P 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 1501 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 1502 adsorption processes of secondary transformation, the available gas among the first class purification gas 1501P passes adsorbent bed secondary purification gas 1502P, 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 1502 desorption processes of secondary transformation; Pressure when control vacuum desorption step finishes; The component that is adsorbed such as hydrogen sulfide, carbon three hydrocarbon, ethene etc. are emitted from inlet end in reverse vacuum desorption step, and this stripping gas 1502K can be used as high-purity CO 2Gas uses.
General Office's pre-separation step 1500 of regulating the flow of vital energy is taken 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 pre-separation step 1500 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 1502K 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.
When pre-separation step 1500 employing pressure swing absorption process is regulated the flow of vital energy by General Office; Can adopt three grades of pressure swing adsorption techniques; In adsorbent bed 1501 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 1501P 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 1501 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 1502 adsorption processes of secondary transformation, the available gas among the first class purification gas 1501P passes adsorbent bed secondary purification gas 1502P, 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 1502 desorption processes of secondary transformation; Pressure when control vacuum desorption step finishes; The component that is adsorbed such as hydrogen sulfide, carbon three hydrocarbon, ethene etc. are emitted from inlet end in reverse vacuum desorption step, and this stripping gas 1502K can be used as high-purity CO 2Gas uses.In three grades of adsorbent bed 1503 adsorption processes of transformation, the available gas H among the secondary purification gas 1502P 2, N 2Pass the adsorbent bed three grades of purified gas 1503P that become, the non-hydrogen that is prone to be adsorbed, non-nitrogen component such as CH 4, CO etc. is adsorbed agent and absorbs, and after absorption finishes, a unsaturation adsorption zone and or adsorption zone not arranged between absorb leading-edge and outlet.In three grades of adsorbent bed 1503 desorption processes of transformation, the pressure when the control desorption procedure finishes makes the component that is adsorbed emit from inlet end in reverse vacuum desorption step, and this stripping gas 1503K can use as high heat value gas.
CO is taken off in known desulfurization 2Technology can be learnt from the listed publication of table 8.
The publication of table 8 record sulfur removal technology
Below describe methanation 2200 or 4200 in detail.
Methanation described herein, 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 hydrogen nitrogen blending gas P end-use, hydrogen nitrogen blending gas P has different quality index.When hydrogen nitrogen blending gas P finally is used as syngas for synthetic ammonia, based on the CO volumetric concentration and the CO of syngas for synthetic ammonia 2The volumetric concentration sum is controlled at below the 10PPm usually, CO volumetric concentration and the CO of hydrogen nitrogen blending gas P 2The volumetric concentration sum also is controlled at below the 10PPm usually.As far as synthetic ammonia reaction process catalyzer, CO and CO 2Be unwanted component, CH 4Be inerts e, methanation is a process that unwanted component is converted into inerts e.
There are DAVY company, rope company of Denmark Top, German LURGI company in typical methanation technology supplier; Based on present methanation technology; Nearly all methanation catalyst is nickel-base catalyst; Technical process is then similar, and for the present invention, the CO in ring coal gas should be converted into H usually as far as possible 2Otherwise can become the synthesizing methane component; Methanation described herein, for the temperature rise of control catalyst bed, possibly 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 1 or 2.The operational condition of methanation is generally: service temperature is generally 250～680 ℃, is generally 250～500 ℃, and pressure is generally 1.0～8.5MPa, is generally 1.5～3.5MPa, and the CO transformation efficiency can reach more than 95%, CO 2Transformation efficiency can reach more than 85, and rare gas element such as methane and argon gas volumetric concentration receive raw material to form control.Methanation can comprise raw material preheating step, methanation protective reaction step, methanation reaction step, end reaction elute refrigerated separation water step etc.Methanation protective reaction step; 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 methanation protective reaction step 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 the relation between separating step 2000 hydrogen and nitrogen gas PHN purity, separating step 3000 hydrogen PH purity and rich nitrogen PN purity and the hydrogen nitrogen blending gas P purity in detail, its purpose is to propose to reduce the operating principle of running cost, optimization whole technological process.
P is an example as syngas for synthetic ammonia finally with hydrogen nitrogen blending gas, contains H 2, N 2H among the multi-component feedstock gas F100 2And N 2Be synthetic NH 3Active principle, the objective of the invention is to regulate the H of hydrogen nitrogen blending gas P 2/ N 2Molecular ratio also reduces invalid component such as Ar, CH simultaneously as far as possible 4Content, control unwanted component such as CO, CO 2Content, according to the present invention, unwanted component such as CO, CO 2The control of content can finally be accomplished through methanation and deep purifying step 5000, and the control of invalid component such as Ar content is then accomplished invalid component such as Ar and H through the control of Ar content among the separating step 3000 control hydrogen PH 2, N 2Be separated in separating step 2000 and can't realize invalid component such as CH 4The control of content is then mainly through CH among the separating step 2000 hydrogen and nitrogen gas PHN 4The control of content and through CH among the separating step 3000 hydrogen PH 4Completion is united in the control of content.Can know that based on above analysis Ar content can be controlled Ar content among the hydrogen nitrogen blending gas P among the separating step 3000 control hydrogen PH, yet Ar content is low more among the hydrogen PH, hydrogen PH is to H among the second road virgin gas F102 2The recovery of component is just low more; In order to obtain hydrogen PH to H among the second road virgin gas F102 2Component higher the recovery, just must improve the Ar yield of hydrogen PH.Yet improve the Ar recovery of hydrogen PH, cause the Ar content of syngas for synthetic ammonia (hydrogen nitrogen blending gas P) to improve, finally cause high pressure synthetic ammonia cycle gas system discharging high density hydrogen-containing gas.The present invention is the Ar content that performance constraint reduces hydrogen PH as far as possible with hydrogen recovery rate greater than 85% usually, the Ar content of hydrogen PH: be usually less than 0.5%, generally be lower than 0.25%, be preferably lower than 0.1%.Can know based on above analysis, can be through CH among the control separating step 2000 control hydrogen and nitrogen gas PHN 4, the CH among the CO content control hydrogen nitrogen blending gas P 4, CO content, CH among the PHN 4, CO content is low more, hydrogen and nitrogen gas PHN is to N among the first via virgin gas F101 2The recovery of component is just low more, and for rich nitrogen virgin gas, the existence of excessive nitrogen allows to reduce N 2The recovery of component and pursue and reduce CH among the PHN 4, CO content.The present invention, the CH of hydrogen and nitrogen gas PHN 4, CO content: be usually less than 5%, generally be lower than 3%, be preferably lower than 1%.Usually separating step 2000 uses excessive sorbent material, CH among the control hydrogen and nitrogen gas PHN 4, CO content.
As the uncontrolled and CH of the argon content of final purpose product hydrogen nitrogen blending gas P 4, CO, CO 2Content is controlled tries one's best when hanging down, and contains H 2, N 2H among the multi-component feedstock gas F100 2, N 2, Ar can be regarded as active principle, the objective of the invention is to regulate the H of hydrogen nitrogen blending gas P 2/ N 2Molecular ratio also reduces controlled component such as CH simultaneously as far as possible 4, CO, CO 2Content, according to the present invention, unwanted component such as CO, CO 2The control of content can finally be accomplished through methanation and deep purifying step 5000, and separating step 3000 needn't be controlled Ar content among the hydrogen PH, also needn't strictness control N 2Content but need control CH 4, CO, CO 2Content, controlled component such as CH 4, CO, CO 2The control of content is then mainly united completion through the control of controlled component concentration among the separating step 2000 hydrogen and nitrogen gas PHN with through the control of controlled component concentration among the separating step 3000 hydrogen PH.Can know based on above analysis, be relative separation between the hydrogen PH of separating step 3000 and the rich nitrogen PN, reduces H among the hydrogen PH 2Purity can improve hydrogen PH to H among the second road virgin gas F102 2The recovery of component.
CO in the product gas of the present invention 2Control through methanation with the content of CO; There are two kinds of schemes the position of methanation in main-process stream; First kind of scheme is that whole hydrogen nitrogen mixed gas P are carried out methanation, and its advantage is to realize terminal control, and its shortcoming is that the methanation charging is large-minded thereby methanation step scale is big; Second kind of scheme is that hydrogen and nitrogen gas PHN is carried out methanation, and its shortcoming is to realize terminal control, and its advantage is the narrow-minded thereby methanation step small scale of methanation charging.Specifically select which kind of scheme for use, should look actual conditions and confirm.
Below describe deep purifying step 5000 in detail.
Deep purifying step 5000 described herein refers to any suitable hydrogen nitrogen that removes and concocts CO, CO among the gas P (or methanation reforming gas 4200P) 2, CH 4Deng the process of impurity composition, hydrogen nitrogen blending gas P is separated into removes CO, CO 2, CH 4Deng the purified gas 5000P of impurity composition with separate gas 5000DG, the purified gas 5000P of production is a high-purity hydrogen nitrogen blending gas, this high-purity hydrogen nitrogen blending gas 5000P can be used as syngas for synthetic ammonia.Therefore, on the one hand, purified gas 5000P component concentration must satisfy the requirement of subsequent user such as synthetic ammonia installation, satisfies the composition requirement of selected synthetic ammonia catalyst to virgin gas, guarantees the normal usefulness of synthetic ammonia unit catalyzer; Separate the active principle H among the gas 5000DG on the other hand 2, N 2Should recycle, finally recycle as syngas for synthetic ammonia such as returning in ring coal gas.
Deep purifying step 5000 of the present invention is used the one-level pressure swing adsorption technique usually, in the adsorption process, and the available gas H among the hydrogen nitrogen blending gas P 2, N 2Pass the adsorbent bed purified gas 5000P that becomes, CO, CO 2, CH 4Be adsorbed agent and absorb Deng impurity composition, after absorption finishes, a unsaturation adsorption zone and or adsorption zone are not arranged between absorb leading-edge and outlet.In desorption process; Pressure when the control desorption procedure finishes; The component that is adsorbed such as water, hydrogen sulfide, carbon three hydrocarbon, ethene etc. are emitted from inlet end in reverse desorption procedure; This stripping gas can return in the treating processes of ring coal gas and recycled (mainly being recover hydrogen), and the typically used scheme is that 5000DG circulation gets into step 2000 and produces hydrogen and nitrogen gas PHN as step 2000 virgin gas and remove methane simultaneously.
Clean unit 5000; Divide the absorption working condition operational condition to be: service temperature is generally 30～50 ℃, is generally 35～45 ℃; Pressure is generally 0.6～2.5MPa, is generally 0.8～2.0MPa; Adsorbent bed for a kind of in the activated alumina, gac, silica gel, molecular sieve 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, CO absorption and CH with the Kiselgel A 4Sorbent material serve as preferred with gac, molecular sieve.Usually the combination cot of forming with activated alumina bed, gac, molecular sieve.
Clean unit 5000, the CO of purified gas and CO 2The volumetric concentration sum usually less than 20PPm, be generally less than in 10PPm, especially less than 5PPm, the active principle recovery usually greater than 95%, generally greater than 98%, especially greater than 99%.
Below describe characteristic of the present invention in detail.
A kind of usefulness contains H 2, N 2Polycomponent gas prepares the method for specific composition hydrogen and nitrogen gas, it is characterized in that comprising following steps:
1. at minute flow step 1000, contain H 2, N 2Multi-component feedstock gas F100 splits into the second road virgin gas F102 that first via virgin gas F101 that flow rate is R101 and flow rate are R102, and the control flow rate guarantees 4. H among the hydrogen nitrogen blending gas P of step than R101/R102 2/ N 2Molecular ratio reaches desired value;
2. in step 2000, F101 obtains hydrogen and nitrogen gas PHN based on first via virgin gas;
3. at separating step 3000, separate the second road virgin gas F102 and obtain hydrogen PH and rich nitrogen PN, select hydrogen PH or rich nitrogen PN to get into step 4. as blending gas PT;
4. collaborating step 4000, hydrogen and nitrogen gas PHN and blending gas PT are mixed into hydrogen nitrogen blending gas P.
Virgin gas F100 of the present invention when encircling coal gas F0 from leaving of internally heated coal carbonization device, is characterized by:
2. step 2000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is generally 0.5～2.5MPa;
3. step 3000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.5～2.5MPa.
Virgin gas F100 of the present invention when regulating the flow of vital energy TF100 from the General Office from ring coal gas F0 of internally heated coal carbonization device, is characterized by:
1. in step 1000, virgin gas F100 is the TF100 that regulates the flow of vital energy from the General Office from ring coal gas F0 of internally heated coal carbonization device, and F0 contains H from ring coal gas 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in comprehensive treating process unit 1100, comprehensive treating process unit 1100 comprises CO transformation and hydrogen production step 1104;
2. step 2000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.8～1.5MPa;
3. step 3000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.8～1.5MPa; Select hydrogen PH to get into step 4. as blending gas PT;
4. in step 4000, hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is greater than the H of virgin gas F100 2/ N 2Molecular ratio.
Virgin gas F100 of the present invention when regulating the flow of vital energy TF100 from the General Office from ring coal gas F0 of the blue charcoal device of internal heat type coal system, contains H from encircling coal gas F0 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn; 1100 are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in the comprehensive treating process unit; First kind of comprehensive treating process flow process comprises following steps: become and take off heavy hydrocarbon from ring coal gas through the heavy hydrocarbon step 1102 of taking off that pressure swing adsorption process takes off charcoal five and above hydrocarbon thereof from ring coal gas F0; Take off heavy hydrocarbon and become deoxidation from ring coal gas through impurity shortening step of converting 1103 from ring coal gas; Deoxidation is accomplished the reaction of CO transformation and hydrogen production from ring coal gas through sulfur-resisting transformation step 1104 and is obtained conversion gas and CO interconversion rate greater than 85%, and the dehydration conversion gas that conversion air cooling obtains after but dewatering is as the TF100 that regulates the flow of vital energy of General Office.
Virgin gas F100 of the present invention when regulating the flow of vital energy TF100 from the General Office from ring coal gas F0 of the blue charcoal device of internal heat type coal system, contains H from encircling coal gas F0 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn; 1100 are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in the comprehensive treating process unit, and second kind of comprehensive treating process flow process comprises following steps: adopt wet desulphurizations that hydrogen sulfide volumetric concentration in the coal gas is reduced to 150～300PPm from the preparatory desulfurized step 1101 of ring coal gas F0 and obtain preparatory desulfurization from ring coal gas; Desulfurization is to use the pressure-swing adsorption process of acticarbon from the heavy hydrocarbon step 1102 of taking off of ring coal gas in advance; Taking off heavy hydrocarbon adopts low-temperature catalyzed hydrogenation deoxidation process and OTR near 100% from ring coal gas impurity shortening step of converting 1103; Deoxidation adopts low temperature sulfur-resisting transformation process to accomplish CO transformation and hydrogen production process and CO interconversion rate greater than 90% from ring gas reforming step 1104, and the dehydration conversion gas that conversion air cooling obtains after but dewatering is as the TF100 that regulates the flow of vital energy of General Office.
Virgin gas F100 of the present invention when regulating the flow of vital energy TF100 from the General Office from ring coal gas F0 of the blue charcoal device of internal heat type coal system, contains H from encircling coal gas F0 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn; 1100 are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in the comprehensive treating process unit, and the third comprehensive treating process flow process comprises following steps: 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 1101 of ring coal gas F0 and obtain preparatory desulfurization from ring coal gas; Desulfurization is taken off heavy hydrocarbon step 1102 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 1103; Deoxidation is adopted low temperature sulfur-resisting transformation process to accomplish the CO transformation and hydrogen production process from ring gas reforming step 1104 and is obtained conversion gas and CO interconversion rate greater than 95%; 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 1105 adopted; The conversion gas that obtains dewatering after poor organosulfur conversion air cooling is but dewatered, dehydration conversion gas is as the TF100 that regulates the flow of vital energy of General Office.
The H of hydrogen nitrogen blending gas P of the present invention 2/ N 2Molecular ratio: be generally 2.00～5.00, be generally 2.50～3.50, be 2.95～3.00 and especially finally as syngas for synthetic ammonia.
The present invention in step 1000, can regulate the flow of vital energy TF100 as virgin gas F100 with General Office.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and first kind of mode is: devulcanization hydrogen that TF100 obtains through the depriving hydrogen sulphide step is regulated the flow of vital energy as virgin gas F100 by General Office.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and the second way is: TF100 is regulated the flow of vital energy through taking off CO in General Office 2Step obtains takes off CO 2Gas is as virgin gas F100.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and the third mode is: the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through taking off CO 2Step obtains taking off CO 2Gas is as virgin gas F100.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and the 4th kind of mode is: with General Office regulate the flow of vital energy TF100 through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
The present invention; In step 1000; General Office's pre-separation step 1500 of regulating the flow of vital energy can be set, and the 5th kind of mode is: the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
The present invention in step 1000, can be provided with General Office's pre-separation step 1500 of regulating the flow of vital energy, and the 6th kind of mode is: the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through taking off CO 2Step obtains taking off CO 2Gas will take off CO 2Gas through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
Step 2000 Action Target of the present invention is generally: 2. first via virgin gas F101 makes hydrogen and nitrogen gas PHN through transformation adsorption step 2100; In methanation unit 2200, hydrogen and nitrogen gas PHN accomplishes methanation reaction and obtains methanation reforming gas 2200P, and the CO volumetric concentration of reforming gas 2200P is lower than 20PPm, CO 2Volumetric concentration is lower than 20PPm, CH 4Volumetric concentration is lower than 2%, the argon gas volumetric concentration is lower than 2%.
Step 2000 Action Target of the present invention is generally: 2. in methanation unit 2200, and CO volumetric concentration and the CO of reforming gas 2200P 2The volumetric concentration sum is lower than 10PPm; The CH of while reforming gas 2200P 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.0%.
Step 4200 Action Target of the present invention is generally: 4. hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is 3.00～3.05; In methanation unit 4200, hydrogen nitrogen blending gas P accomplishes methanation reaction and obtains methanation reforming gas 4200P, and the CO volumetric concentration of reforming gas 4200P is lower than 15PPm, CO 2Volumetric concentration is lower than 15PPm, CH 4Volumetric concentration is lower than 2%, the argon gas volumetric concentration is lower than 2%.
Step 4200 Action Target of the present invention is generally: 4. CO volumetric concentration and the CO of reforming gas 4200P 2The volumetric concentration sum is lower than 10PPm; The CH of while reforming gas 4200P 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.0%.
When the present invention is provided with deep purifying step 5000, it is characterized in that:
5. in deep purifying step 5000, adopt pressure swing adsorption process, in the adsorbent bed adsorption process of transformation, non-hydrogen, non-nitrogen component such as CH among hydrogen nitrogen blending gas P or the methanation reforming gas 4200P 4, CO, CO 2Deng being adsorbed agent absorption, H 2, N 2Component is passed the adsorbent bed deep purifying gas 5000P 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 5000DG; The transformation adsorption step uses 2 or a plurality of adsorption tower, realizes the continous-stable operation.
When the present invention was provided with deep purifying step 5000, first kind of mode of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets into the methanation step and contacts the CO among the stripping gas 5000DG, CO with methanation catalyst as the methanation virgin gas 2Major part be converted into methane.
When the present invention was provided with deep purifying step 5000, the second way of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets into step 2000 as step 2000 virgin gas.
When the present invention was provided with deep purifying step 5000, the third mode of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets into transformation adsorption step 3000 as step 3000 virgin gas, the H among the stripping gas 5000DG 2Major part get among the hydrogen PH.
When the present invention was provided with deep purifying step 5000, the 4th kind of mode of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets among the step virgin gas F100 1..
When the present invention was provided with deep purifying step 5000, the 5th kind of mode of recycle stripping gas 5000DG was: 5. stripping gas 5000DG circulation gets in the source of the gas gas of step virgin gas F100 1..
Deep purifying step 5000 operational condition of the present invention is generally: 5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 30～50 ℃, and working pressure is 0.8～5.0MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 20PPm, CH 4Volumetric concentration is lower than 1.5%, the argon gas volumetric concentration is lower than 2%.
Deep purifying step 5000 operational condition of the present invention is generally: 5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 35～45 ℃, and working pressure is 0.8～2.0MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 15PPm, CH 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.5%.
Deep purifying step 5000 operational condition of the present invention is preferably: 5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 37～43 ℃, and working pressure is 0.8～1.5MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 10PPm, CH 4Volumetric concentration is lower than 0.7%, the argon gas volumetric concentration is lower than 1.0%.
The present invention selects rich nitrogen PN to get into step 4. the time as blending gas PT in step 3000, and hydrogen PH and blending gas PT are mixed into hydrogen nitrogen blending gas P through mixing step 4001, the H of hydrogen nitrogen blending gas P 2/ N 2Molecular ratio is less than the H of virgin gas F100 2/ N 2Molecular ratio.
The sorbent material that step 2000 of the present invention and step 3000 are used is generally:
2. in step 2000, the sorbent material of use has activated alumina, silica gel, gac, molecular sieve;
3. in step 3000, the sorbent material of use has activated alumina, silica gel, gac, molecular sieve.
The sorbent material that step 2000 of the present invention and step 3000 are used is generally:
2. in step 2000, the sorbent material of use has silica gel, gac, molecular sieve;
3. in step 3000, the sorbent material of use has silica gel, gac, molecular sieve.
The sorbent material preferably that step 2000 of the present invention and step 3000 are used is:
2. in step 2000, the sorbent material of use has gac, molecular sieve;
3. in step 3000, the sorbent material of use has gac, molecular sieve.
The expansion of using as the present invention is provided with General Office's pre-separation step 1500 of regulating the flow of vital energy in step 1000, separates the TF100 that regulates the flow of vital energy of General Office and can obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2High methane gas, rich CO 2Gas takes off CO this moment 2High methane gas can get into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtain the hydrogen manufacturing reforming gas; The step 1900 of going the hydrogen manufacturing reforming gas adopts pressure swing adsorption process to extract pure hydrogen APH as blending gas PT; Perhaps the hydrogen manufacturing reforming gas goes step 1900 to adopt pressure swing adsorption process to extract pure hydrogen and nitrogen gas APHN as blending gas PT; Perhaps the hydrogen manufacturing reforming gas is sneaked among the first via virgin gas F101; Perhaps the hydrogen manufacturing reforming gas is sneaked among the second road virgin gas F102, and perhaps the hydrogen manufacturing reforming gas is sneaked among the virgin gas F100, and perhaps the hydrogen manufacturing reforming gas is sneaked in the source of the gas gas of virgin gas F100.
The present invention is provided with General Office's pre-separation step 1500 of regulating the flow of vital energy in step 1000, separates the TF100 that regulates the flow of vital energy of General Office and can obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2High methane gas, rich CO 2Gas takes off CO this moment 2High methane gas can be as system liquefied methane gas virgin gas.
The present invention is provided with General Office's pre-separation step 1500 of regulating the flow of vital energy in step 1000, separates the TF100 that regulates the flow of vital energy of General Office and can obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2High methane gas, rich CO 2Gas at this moment, is handled rich CO 2Be so incensed that the rich CO of high purity 2Gas PCO2, PCO2 finally can also can be used as the plain virgin gas of antidiuresis as system carbon ammonium virgin gas.
The present invention is provided with General Office's pre-separation step 1500 of regulating the flow of vital energy in step 1000, separates the TF100 that regulates the flow of vital energy of General Office and obtains mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2Take off N 2High methane gas, rich CO 2Gas takes off CO 2Take off N 2High methane gas can be as system synthetic natural gas virgin gas.
In the step 1800 that the present invention is provided with, take off CO 2High methane gas is accomplished hydro carbons steam reforming hydrogen manufacturing process and is obtained the hydrogen manufacturing reforming gas, and as required said step 1800 can comprise processes such as preparatory depriving hydrogen sulphide, deoxidation, alkene are saturated, deep desulfuration, hydro carbons steam reforming, middle temperature transformation hydrogen manufacturing.
The invention has the advantages that:
1. can realize with containing H 2, N 2Polycomponent gas prepares the purpose of specific composition hydrogen and nitrogen gas;
2. " separation of air and the gas making " dual-use function that utilizes the internally heated coal carbonization process to possess after the present invention's combination, has formed the internally heated coal carbonization multi-production process of coproducing synthetic ammonia virgin gas (or synthetic ammonia or carbon ammonium or urea), has prolonged industrial chain;
3. for the internally heated coal carbonization multi-production process of coproducing synthetic ammonia virgin gas, step 1800 completion is set takes off CO 2The hydro carbons steam reforming hydrogen manufacturing process of high methane gas also reclaims this hydrogen, can at utmost increase production syngas for synthetic ammonia, improves the nitrogen utilization ratio;
4. for the internally heated coal carbonization multi-production process of coproducing synthetic ammonia virgin gas, can coproduction high methane gas or natural gas liquids.
Embodiment one
Present embodiment is a kind of blue charcoal Poly-generation of internally heated coal carbonization system process of coproducing synthetic ammonia virgin gas, comprises following steps:
1. the charring furnace combustion chamber employing air of the blue charcoal process of internally heated coal carbonization system is an oxygenant, forms from ring coal gas and sees table 9-1, belongs to CO 2-CO-CH 4-Fu N 2-H 2System;
2. leave ring coal gas comprehensive treating process unit 300, accomplishing following task:
A accomplishes " wet desulphurization hydrogen process " 1101 from ring coal gas, with H 2The S volumetric concentration is reduced to～and 0.02%; 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 1102; 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 1103; 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 1104; Deoxidation coal gas is accomplished about 96% 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; 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 1105, conversion 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% with the overall percent hydrolysis of control carbonylsulfide, and process operation pressure is 0.8～1.2MPa;
G medium temperature hydrolyzation gas reduces temperature to 30～50 ℃, is under 0.8～1.2MPa condition at working pressure; Accomplish the dehydration hydrolysis gas that obtains dewatering;
3. adopt pressure swing adsorption process to obtain taking off CO in General Office's pre-separation step 1500 of regulating the flow of vital energy 2Gas: 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; Decarburization three hydrocarbon purified gass are pressure-swing adsorption process in the second stage, is raw material with decarburization three hydrocarbon purified gass, obtains taking off CO 2Purified 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; Take off CO 2Gas is as the H that contains according to the invention 2, N 2Multi-component feedstock gas F100; Rich CO 2Gas is after treatment as system carbon ammonium or urea virgin gas;
4. contain H 2, N 2Multi-component feedstock gas F100 production of raw-material gas for synthetic ammonia step:
A, at minute flow step 1000, virgin gas F100 splits into the second road virgin gas F102 that first via virgin gas F101 that flow rate is R101 and flow rate are R102, flow rate is than R101/R102=0.529/0.471=1.123, guarantees 4. H among the hydrogen nitrogen blending gas P of step 2/ N 2Molecular ratio reaches desired value 2.84;
B, at separating step 2000, separate first via virgin gas F101 and obtain hydrogen and nitrogen gas PHN;
C, at separating step 3000, separate the second road virgin gas F102 and obtain hydrogen PH and rich nitrogen PN, select hydrogen PH to get into step 4. as blending gas PT;
D, at the interflow step 4000, hydrogen and nitrogen gas PHN and blending gas PT are mixed into hydrogen nitrogen blending gas P.
The H of e, hydrogen nitrogen blending gas P 2/ N 2Molecular ratio is～2.84; In methanation unit 4200, hydrogen nitrogen blending gas P accomplishes methanation reaction and obtains methanation reforming gas 4200P, CO volumetric concentration and the CO of reforming gas 4200P 2The volumetric concentration sum is lower than 10PPm.
In methanation unit 4200, accomplish following task:
The first step: in the desulphurization reaction step, be 0.7～2.0MPa, be preferably under 0.7～1.1MPa condition that the methanation virgin gas is accomplished " deep desulfurization process " to satisfy the limits value of methanation catalyst, usually H at working pressure 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;
Second step in the methanation reaction step, was 0.8～2.0MPa at working pressure, is preferably 0.7～1.1MPa, and medial temperature is under 280～350 ℃ of conditions, and 1 or 2 methanators are set, control CO transformation efficiency greater than 95%, CO 2Transformation efficiency is greater than 90%;
F, in deep purifying step 5000, adopt pressure swing adsorption process, in the adsorbent bed adsorption process of transformation, the non-hydrogen among the methanation reforming gas 4200P, non-nitrogen component such as CH 4, CO, CO 2Deng being adsorbed agent absorption, H 2, N 2Component is passed the adsorbent bed deep purifying gas 5000P 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 5000DG; The transformation adsorption step uses 2 or a plurality of adsorption tower, realizes the continous-stable operation; Deep purifying gas 5000P is as syngas for synthetic ammonia; Stripping gas 5000DG returns in ring coal gas and recycles.
Present embodiment, deep purifying gas 5000P are finally as production of raw-material gas for synthetic ammonia, and the present invention and production of synthetic ammonia combination back form coproducing synthetic ammonia technology.
Each step logistics composition is seen table 9-1～table 9-13.
Table 9-1 embodiment 1 logistics data table 1
Figure BSA00000550568300481
Table 9-2 embodiment 1 logistics data table 2
Figure BSA00000550568300491
Table 9-3 embodiment 1 logistics data table 3
Figure BSA00000550568300492
Table 9-4 embodiment 1 logistics data table 4
Figure BSA00000550568300501
Table 9-5 embodiment 1 logistics data table 5
Figure BSA00000550568300502
Table 9-6 embodiment 1 logistics data table 6
Figure BSA00000550568300511
Table 9-7 embodiment 1 logistics data table 7
Table 9-8 embodiment 1 logistics data table 8
Table 9-9 embodiment 1 logistics data table 9
Figure BSA00000550568300522
Table 9-10 embodiment 1 logistics data table 10
Table 9-11 embodiment 1 logistics data table 11
Figure BSA00000550568300532
Table 9-12 embodiment 1 logistics data table 12
Figure BSA00000550568300541
Table 9-13 embodiment 1 logistics data table 13
Figure BSA00000550568300542
Table 9-14 embodiment 1 logistics data table 14
Figure BSA00000550568300551
Table 9-15 embodiment 1 logistics data table 15
Figure BSA00000550568300552
Table 9-16 embodiment 1 logistics data table 16
Figure BSA00000550568300561
Table 9-17 embodiment 1 logistics data table 17
Figure BSA00000550568300562
Table 9-18 embodiment 1 logistics data table 18
Figure BSA00000550568300571
Table 9-19 embodiment 1 logistics data table 19
Figure BSA00000550568300572
Table 9-20 embodiment 1 logistics data table 20
Figure BSA00000550568300581
Embodiment two
Based on embodiment one, in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, separate the TF100 that regulates the flow of vital energy of General Office and can obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2Take off N 2High methane gas, rich CO 2Gas is with the CO that takes off of step 1500 generation 2Take off N 2High methane gas uses as substitute natural gas, forms coproduction Sweet natural gas technology behind the present invention and the substitute natural gas process mix.
Embodiment three
Based on embodiment one, with the CO that takes off of step 1500 generation 2Take off N 2High methane gas is as system liquefied methane gas virgin gas, and the present invention and lng production process combination back form coproduction LNG technology.
Embodiment four
Based on embodiment one, with the CO that takes off of step 1500 generation 2Take off N 2High methane gas is handled rich CO as system liquefied methane gas virgin gas 2Be so incensed that the rich CO of high purity 2Gas PCO2, PCO2 finally as system carbon ammonium virgin gas, form coproduction carbon ammonium technology behind the present invention and the carbon ammonium process mix.
Embodiment five
Based on embodiment one, with the CO that takes off of step 1500 generation 2Take off N 2High methane gas is handled rich CO as system liquefied methane gas virgin gas 2Be so incensed that the rich CO of high purity 2Gas PCO2, PCO2 are finally as the plain virgin gas of antidiuresis, and the present invention and urea production process combination back form the coproduction urea technique.。
Embodiment six
Based on embodiment one, with the CO that takes off of step 1500 generation 2Take off N 2High methane gas takes off CO as system liquefied methane gas virgin gas 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas goes step 1900 to adopt pressure swing adsorption process to extract pure hydrogen APH as blending gas PT.
Embodiment seven
Based on embodiment one, with the CO that takes off of step 1500 generation 2Take off N 2High methane gas takes off CO as system liquefied methane gas virgin gas 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas goes step 1900 to adopt pressure swing adsorption process to extract pure hydrogen and nitrogen gas APHN as blending gas PT.
Embodiment eight
Based on embodiment one, with the CO that takes off of step 1500 generation 2Take off N 2High methane gas takes off CO as system liquefied methane gas virgin gas 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas is sneaked among the first via virgin gas F101.
Embodiment nine
Based on embodiment one, with the CO that takes off of step 1500 generation 2Take off N 2High methane gas takes off CO as system liquefied methane gas virgin gas 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas is sneaked among the second road virgin gas F102.
Embodiment ten
Based on embodiment one, with the CO that takes off of step 1500 generation 2Take off N 2High methane gas takes off CO as system liquefied methane gas virgin gas 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas is sneaked among the virgin gas F100.

Claims (47)

1. one kind with containing H 2, N 2Polycomponent gas prepares the method for specific composition hydrogen and nitrogen gas, it is characterized in that comprising following steps:
1. at minute flow step 1000, contain H 2, N 2Multi-component feedstock gas F100 splits into the second road virgin gas F102 that first via virgin gas F101 that flow rate is R101 and flow rate are R102, and the control flow rate guarantees 4. H among the hydrogen nitrogen blending gas P of step than R101/R102 2/ N 2Molecular ratio reaches desired value;
2. in step 2000, F101 obtains hydrogen and nitrogen gas PHN based on first via virgin gas;
3. at separating step 3000, separate the second road virgin gas F102 and obtain hydrogen PH and rich nitrogen PN, select hydrogen PH or rich nitrogen PN to get into step 4. as blending gas PT;
4. collaborating step 4000, hydrogen and nitrogen gas PHN and blending gas PT are mixed into hydrogen nitrogen blending gas P.
2. method according to claim 1 is characterized in that:
1. in step 1000, virgin gas F100 is from encircling coal gas F0 leaving of internally heated coal carbonization device;
2. step 2000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.5～2.5MPa;
3. step 3000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.5～2.5MPa.
3. method according to claim 1 is characterized in that:
1. in step 1000, virgin gas F100 is the TF100 that regulates the flow of vital energy from the General Office from ring coal gas F0 of internally heated coal carbonization device, and F0 contains H from ring coal gas 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in comprehensive treating process unit 1100, comprehensive treating process unit 1100 comprises CO transformation and hydrogen production step 1104;
2. step 2000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.8～1.5MPa;
3. step 3000 adopts the transformation adsorption method of separation, and the pressure-swing adsorption process working pressure is 0.8～1.5MPa; Select hydrogen PH to get into step 4. as blending gas PT;
4. in step 4000, hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is greater than the H of virgin gas F100 2/ N 2Molecular ratio.
4. method according to claim 3 is characterized in that:
1. in step 1000, virgin gas F100 is the TF100 that regulates the flow of vital energy from the General Office from ring coal gas F0 of the blue charcoal device of internal heat type coal system, and F0 contains H from ring coal gas 2, N 2, CH 4, CO, CO 2, H 2S, Ar, CmHn, O 21100 are converted into the TF100 that regulates the flow of vital energy of General Office from ring coal gas F0 in the comprehensive treating process unit; Comprehensive treating process unit 1100 comprises following steps: become and take off heavy hydrocarbon from ring coal gas through the heavy hydrocarbon step 1102 of taking off that pressure swing adsorption process takes off charcoal five and above hydrocarbon thereof from ring coal gas F0; Take off heavy hydrocarbon and become deoxidation from ring coal gas through impurity shortening step of converting 1103 from ring coal gas; Deoxidation is accomplished the reaction of CO transformation and hydrogen production from ring coal gas through sulfur-resisting transformation step 1104 and is obtained conversion gas and CO interconversion rate greater than 85%, and the dehydration conversion gas that conversion air cooling obtains after but dewatering is as the TF100 that regulates the flow of vital energy of General Office.
5. method according to claim 4 is characterized in that:
1. in step 1000, comprehensive treating process unit 1100 comprises following steps: adopt wet desulphurization that hydrogen sulfide volumetric concentration in the coal gas is reduced to 150～300PPm from the preparatory desulfurized step 1101 of ring coal gas F0 and obtain preparatory desulfurization from ring coal gas; Desulfurization is to use the pressure-swing adsorption process of acticarbon from the heavy hydrocarbon step 1102 of taking off of ring coal gas in advance; Taking off heavy hydrocarbon adopts low-temperature catalyzed hydrogenation deoxidation process and OTR near 100% from ring coal gas impurity shortening step of converting 1103; Deoxidation adopts low temperature sulfur-resisting transformation process to accomplish CO transformation and hydrogen production process and CO interconversion rate greater than 90% from ring gas reforming step 1104, and the dehydration conversion gas that conversion air cooling obtains after but dewatering is as the TF100 that regulates the flow of vital energy of General Office.
6. method according to claim 4 is characterized in that:
1. in step 1000, comprehensive treating process unit 1100 comprises following steps: 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 1101 of ring coal gas F0 and obtain preparatory desulfurization from ring coal gas; Desulfurization is taken off heavy hydrocarbon step 1102 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 1103; Deoxidation is adopted low temperature sulfur-resisting transformation process to accomplish the CO transformation and hydrogen production process from ring gas reforming step 1104 and is obtained conversion gas and CO interconversion rate greater than 95%; 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 1105 adopted; The conversion gas that obtains dewatering after poor organosulfur conversion air cooling is but dewatered, dehydration conversion gas is as the TF100 that regulates the flow of vital energy of General Office.
7. according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that:
4. hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is 2.00～5.00.
8. according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that:
4. hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is 2.50～3.50.
9. according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that:
4. hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is 2.95～3.00, and hydrogen nitrogen blending gas P is finally as syngas for synthetic ammonia.
10. according to claim 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that:
1. in step 1000, TF100 is regulated the flow of vital energy as virgin gas F100 in General Office.
11., it is characterized in that according to claim 2 or 3 or 4 or 5 or 6 described methods:
1. in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, devulcanization hydrogen that TF100 obtains through the depriving hydrogen sulphide step is regulated the flow of vital energy as virgin gas F100 by General Office.
12., it is characterized in that according to claim 2 or 3 or 4 or 5 or 6 described methods:
1. in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, TF100 is regulated the flow of vital energy through taking off CO in General Office 2Step obtains takes off CO 2Gas is as virgin gas F100.
13., it is characterized in that according to claim 2 or 3 or 4 or 5 or 6 described methods:
1. in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through taking off CO 2Step obtains taking off CO 2Gas is as virgin gas F100.
14., it is characterized in that according to claim 2 or 3 or 4 or 5 or 6 described methods:
1. in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, with General Office regulate the flow of vital energy TF100 through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
15., it is characterized in that according to claim 2 or 3 or 4 or 5 or 6 described methods:
1. in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
16., it is characterized in that according to claim 2 or 3 or 4 or 5 or 6 described methods:
1. in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, the TF100 that regulates the flow of vital energy of General Office is obtained devulcanization hydrogen through the depriving hydrogen sulphide step, with devulcanization hydrogen through taking off CO 2Step obtains taking off CO 2Gas will take off CO 2Gas through the hydrogen and nitrogen gas that takes off non-hydrogen non-nitrogen composition step and obtain as virgin gas F100.
17., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:
2. first via virgin gas F101 makes hydrogen and nitrogen gas PHN through transformation adsorption step 2100; In methanation unit 2200, hydrogen and nitrogen gas PHN accomplishes methanation reaction and obtains methanation reforming gas 2200P, and the CO volumetric concentration of reforming gas 2200P is lower than 20PPm, CO 2Volumetric concentration is lower than 20PPm, CH 4Volumetric concentration is lower than 2%, the argon gas volumetric concentration is lower than 2%;
4. collaborating step 4000, reforming gas 2200P and blending gas PT are mixed into hydrogen nitrogen blending gas P.
18. method according to claim 17 is characterized in that:
2. in methanation unit 2200, CO volumetric concentration and the CO of reforming gas 2200P 2The volumetric concentration sum is lower than 10PPm.
19. method according to claim 18 is characterized in that:
2. in methanation unit 2200, the CH of reforming gas 2200P 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.0%.
20., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:
4. hydrogen nitrogen is concocted the H of gas P 2/ N 2Molecular ratio is 3.00～3.05; In methanation unit 4200, hydrogen nitrogen blending gas P accomplishes methanation reaction and obtains methanation reforming gas 4200P, and the CO volumetric concentration of reforming gas 4200P is lower than 15PPm, CO 2Volumetric concentration is lower than 15PPm, CH 4Volumetric concentration is lower than 2%, the argon gas volumetric concentration is lower than 2%.
21. method according to claim 20 is characterized in that:
4. CO volumetric concentration and the CO of reforming gas 4200P 2The volumetric concentration sum is lower than 10PPm.
22. method according to claim 21 is characterized in that:
4. the CH of reforming gas 4200P 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.0%.
23., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:
5. in deep purifying step 5000, adopt pressure swing adsorption process, in the adsorbent bed adsorption process of transformation, non-hydrogen, non-nitrogen component such as CH among the hydrogen nitrogen blending gas P 4, CO, CO 2Deng being adsorbed agent absorption, H 2, N 2Component is passed the adsorbent bed deep purifying gas 5000P 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 5000DG; The transformation adsorption step uses 2 or a plurality of adsorption tower, realizes the continous-stable operation.
24. method according to claim 23 is characterized in that:
5. stripping gas 5000DG circulation gets into the methanation step and contacts the CO among the stripping gas 5000DG, CO with methanation catalyst as the methanation virgin gas 2Major part be converted into methane.
25. method according to claim 23 is characterized in that:
5. stripping gas 5000DG circulation gets into step 2000 as step 2000 virgin gas.
26. method according to claim 23 is characterized in that:
5. stripping gas 5000DG circulation gets into transformation adsorption step 3000 as step 3000 virgin gas, the H among the stripping gas 5000DG 2Major part get among the hydrogen PH.
27. method according to claim 23 is characterized in that:
5. stripping gas 5000DG circulation gets among the step virgin gas F100 1..
28. method according to claim 23 is characterized in that:
5. stripping gas 5000DG circulation gets in the source of the gas gas of step virgin gas F100 1..
29. method according to claim 23 is characterized in that:
5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 30～50 ℃, and working pressure is 0.8～5.0MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 20PPm, CH 4Volumetric concentration is lower than 1.5%, the argon gas volumetric concentration is lower than 2%.
30. method according to claim 29 is characterized in that:
5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 35～45 ℃, and working pressure is 0.8～2.0MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 15PPm, CH 4Volumetric concentration is lower than 1.0%, the argon gas volumetric concentration is lower than 1.5%.
31. method according to claim 29 is characterized in that:
5. in deep purifying step 5000, the adsorbent bed sorbent material of transformation is gac, molecular sieve combination cot, and service temperature is 37～43 ℃, and working pressure is 0.8～1.5MPa; CO volumetric concentration and the CO of deep purifying gas 5000P 2The volumetric concentration sum is lower than 10PPm, CH 4Volumetric concentration is lower than 0.7%, the argon gas volumetric concentration is lower than 1.0%.
32. method according to claim 16 is characterized in that:
3. in step 3000, the second road virgin gas F102 makes hydrogen PH and rich nitrogen PN through transformation adsorption step 3001, selects rich nitrogen PN to get into step 4. as blending gas PT;
4. in step 4000, hydrogen PH and blending gas PT are mixed into hydrogen nitrogen blending gas P through mixing step 4001, the H of hydrogen nitrogen blending gas P 2/ N 2Molecular ratio is less than the H of virgin gas F100 2/ N 2Molecular ratio.
33., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:
2. in step 2000, the sorbent material of use has activated alumina, silica gel, gac, molecular sieve;
3. in step 3000, the sorbent material of use has activated alumina, silica gel, gac, molecular sieve.
34., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:
2. in step 2000, the sorbent material of use has silica gel, gac, molecular sieve;
3. in step 3000, the sorbent material of use has silica gel, gac, molecular sieve.
35., it is characterized in that according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods:
2. in step 2000, the sorbent material of use has gac, molecular sieve;
3. in step 3000, the sorbent material of use has gac, molecular sieve.
36., it is characterized in that according to claim 2 or 3 or 4 or 5 or 6 described methods:
1. in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, separates the TF100 that regulates the flow of vital energy of General Office and obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2High methane gas, rich CO 2Gas.
37. method according to claim 36 is characterized in that:
1. take off CO 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas goes step 1900 to adopt pressure swing adsorption process to extract pure hydrogen APH, as blending gas PT.
38. method according to claim 36 is characterized in that:
1. take off CO 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas goes step 1900 to adopt pressure swing adsorption process to extract pure hydrogen and nitrogen gas APHN, as blending gas PT.
39. method according to claim 36 is characterized in that:
1. take off CO 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas is sneaked among the first via virgin gas F101.
40. method according to claim 36 is characterized in that:
1. take off CO2 high methane gas entering step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtain the hydrogen manufacturing reforming gas, the hydrogen manufacturing reforming gas is sneaked among the second road virgin gas F102.
41. method according to claim 36 is characterized in that:
1. take off CO 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas is sneaked among the virgin gas F100.
42. method according to claim 36 is characterized in that:
1. take off CO 2High methane gas gets into step 1800 completion hydro carbons steam reforming hydrogen manufacturing process and obtains the hydrogen manufacturing reforming gas, and the hydrogen manufacturing reforming gas is sneaked in the source of the gas gas of virgin gas F100.
43. method according to claim 36 is characterized in that:
1. take off CO 2High methane gas is as system liquefied methane gas virgin gas.
44. method according to claim 36 is characterized in that:
1. handle rich CO 2Be so incensed that the rich CO of high purity 2Gas PCO2, PCO2 are finally as system carbon ammonium virgin gas.
45. method according to claim 10 is characterized in that:
1. handle rich CO 2Be so incensed that the rich CO of high purity 2Gas PCO2, PCO2 are finally as the plain virgin gas of antidiuresis.
46., it is characterized in that according to claim 2 or 3 or 4 or 5 or 6 described methods:
1. in step 1000 General Office's pre-separation step 1500 of regulating the flow of vital energy is set, separates the TF100 that regulates the flow of vital energy of General Office and obtain mainly by H 2And N 2The virgin gas F100 that forms, take off CO 2Take off N 2High methane gas, rich CO 2Gas takes off CO 2Take off N 2High methane gas is as system synthetic natural gas virgin gas.
47. method according to claim 20 is characterized in that:
5. in deep purifying step 5000, adopt pressure swing adsorption process, in the adsorbent bed adsorption process of transformation, the non-hydrogen among the methanation reforming gas 4200P, non-nitrogen component such as CH 4, CO, CO 2Deng being adsorbed agent absorption, H 2, N 2Component is passed the adsorbent bed deep purifying gas 5000P 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 5000DG; The transformation adsorption step uses 2 or a plurality of adsorption tower, realizes the continous-stable operation.
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WO2020067181A1 (en) * 2018-09-25 2020-04-02 積水化学工業株式会社 Gas treatment method and gas treatment device
CN110078076A (en) * 2019-04-21 2019-08-02 刘伟 A kind of process of tail of semi coke classification sub-prime comprehensive utilization Poly-generation chemicals
CN110652965A (en) * 2019-11-11 2020-01-07 中石化石油工程技术服务有限公司 Semicoke-based activated carbon adsorption material and preparation method and application thereof
CN112662437A (en) * 2020-12-30 2021-04-16 陕西东鑫垣化工有限责任公司 Grading and quality-based utilization process of raw coke oven gas
CN112758892A (en) * 2021-01-05 2021-05-07 西南化工研究设计院有限公司 Pressure swing adsorption hydrogen purification system and method thereof
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