CN104609368A - Method for converting desorbed waste gases from petroleum refinery to feed gases used in hydrogen production process - Google Patents
Method for converting desorbed waste gases from petroleum refinery to feed gases used in hydrogen production process Download PDFInfo
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Abstract
The invention provides a method for converting desorbed waste gases from a petroleum refinery to feed gases used in a hydrogen production process. The method comprises the steps that after being pretreated, the desorbed waste gases are divided into two parts, the first part is directly sent to a carbon dioxide reforming reactor of methane and the second part is sent to an autothermal reforming reactor; the carbon dioxide reforming reactor of methane adopts a form of fluidized bed and a cyclone separator is adopted at the top of the reactor to separate a catalyst in the reformed gases; the catalyst enters a combustion section of the autothermal reforming reactor; oxygen is pumped into the autothermal reforming reactor so as to carry out incomplete combustion on the combustion section to burn out carbon deposits on a carbon dioxide reforming catalyst of methane to regenerate a catalyst; the regenerated catalyst and the gases characterized by incomplete combustion enter the cyclone separator and then the catalyst is separated and returns to the carbon dioxide reforming reactor of methane to be used; the residual gases enter a conversion section of the autothermal reforming reactor to be reformed so as to convert methane to hydrogen.
Description
Technical field
The present invention relates to and a kind ofly petroleum refinery is resolved the method that exhaust gas conversion is process for making hydrogen unstripped gas.
Background technology
The parsing waste gas of petroleum refinery mainly comprises hydrogen, methane, carbon monoxide, carbonic acid gas and a small amount of Hydrocarbon Organic and sulphur.At present, about above-mentioned parsing waste gas recovery and comprehensive utilization mainly concentrate on the following aspects:
One, directly heat energy is provided as fuel using parsing waste gas, as the heating fuel as device for producing hydrogen.
Two, by pressure-variable adsorption separating high-purity hydrogen, carbonic acid gas, carbon monoxide and methane; Hydrogen obtains food grade and technical grade carbonic acid gas, methane and carbon monoxide as converter fuel or hydrogen feedstock as Hydrogen Source For Hydrotreating Unit, carbon dioxide purification;
Three, high-purity hydrogen or carbonic acid gas is obtained by membrane sepn.
For above first three plant recycle resolution gas scheme at present domestic more than 99% device be use as device for producing hydrogen fuel, advantage replaces other heating fuel, and the shortcoming of existence is that in component, carbon dioxide content is higher, causes transformation efficiency thermo-efficiency low.
And be technically ripe at present by stage variable pressure fractionation by adsorption four kinds of gases, but the pressure being limited by resolution gas is lower, and utilizing of carbonic acid gas market is bad, and price is lower.
Although carry out the separation of multistage PSA pressure-variable adsorption for described resolution gas can obtain the hydrogen of 99.9%, the carbonic acid gas of 97.5% and methane CO (carbon monoxide converter) gas, but under the background of full factory hydrogen source deficiency, be limited by the impact that plant investment is comparatively large, power consumption is higher, carbonic acid gas market value is lower, the investment repayment phase can be very long.
In addition, for the method being reclaimed the available gas in resolution gas by membrane separation process, the ultimate principle of membrane sepn is exactly that the dissolving rate of diffusion utilizing each gaseous fraction in high molecular polymer is different, and the speed thus causing it to penetrate through fiber membranous wall under the effect of film both sides partial pressure difference is different and be separated.Due to the control of discharge, while separation hydrogen, carbonic acid gas can not be discharged, also need the recovery carrying out carbonic acid gas, result also in the increase of process costs.
Summary of the invention
The invention provides a kind of petroleum refinery and resolve the method that exhaust gas conversion is coal hydrogen feedstock gas, its main technological process the hydrogen in the methane in described parsing waste gas is converted into hydrogen and produces the process of carbon monoxide.The carbon dioxide content of resolving in waste gas due to petroleum refinery is higher, therefore the present invention mainly adopts methane reforming with carbon dioxide device, for methane reforming with carbon dioxide, and the mechanism more complicated of its reaction, still do not come to a conclusion at present, but main reaction mechanism is as follows:
CH4+CO2→2CO+2H2(△H°＝247kJ/mol)
What methane steam reforming and methane CO2 reformed has similar dynamic process and mechanism.This technique is not only significant for preparing synthetic gas, and the reduction of discharging for CO2 is also significant.But this reaction more easily produces carbon distribution compared with steam reforming.At catalyst activation, reaction mechanism and deactivation aspect, methane CO2 reforms and steam reforming has a lot of similarity, and in the synthesizer produced unlike this technique with steam reforming, the ratio of CO and H2 is 1:1, and the thermokinetics that the conversion of methane is reformed reaction limited.
Because methane reforming with carbon dioxide easily forms carbon distribution at catalyst surface, reduce reaction efficiency, and make catalyst deactivation, therefore, the present invention adopts methane reforming with carbon dioxide device to combine with autothermal reforming reaction device.The combustion heat of self-heating recapitalization carries out catalyst regeneration.Shunt small portion resolution gas simultaneously and carry out self-heating recapitalization, reduce oxygen depletion.Improve hydrogen generating quantity simultaneously.
Methane self-heating recapitalization technique (Autothermal reforming of methane) (ATR process) is the methane vapor reforming coupling by the Catalytic methane oxidation of heat release and heat absorption, the 1950's is developed by Haldor Topse, object is carried out in a reactor reformation, the first system of realization response itself from heat supply.In general, methane self-heating recapitalization technique is at high temperature carried out, and the temperature of combustion zone is higher than catalysis region temperature, can reduce the consumption of oxygen like this.The ratio of the H2/CO of reactor outlet accurately can be manipulated by the ratio adjusting H2O/CH4.This technique is also the more a kind of technique of current methane conversion hydrogen applications.
Technical scheme is specific as follows:
Petroleum refinery resolves the method that exhaust gas conversion is coal hydrogen feedstock gas, comprises following processing step:
(1) waste gas detar technique is resolved:
(1) the parsing waste gas sent here by refinery, first Hydrocarbon Organic washing tower is entered, cleaning solvent adopts the mineral oil based on dimethylbenzene, removes the Hydrocarbon Organic of resolving easily coking in waste gas, after washing, a cleaning solvent flash distillation part is reclaimed a part and is used for recirculation.
(2) will parsing waste gas out send into and resolve the voltage stabilizing of waste gas gas holder buffering from step (2), and resolve off-gas compressor and to bleed and after being pressurized to 0.2 ~ 1MPa from gas holder.
(3) the parsing waste gas through step (2) enters hydrodesulphurisatioreactors reactors, the upper strata of desulphurization reactor is Hydrobon catalyst layer, lower floor is adsorbent layer, and temperature of reaction is 300 DEG C ~ 400 DEG C, and the sulphur content of resolving in waste gas is reduced to 0.1ppm.
(4) by the parsing waste gas in step (2) again after gas holder voltage stabilizing, parsing waste gas is divided into two parts, first part directly sends into methane reforming with carbon dioxide device, and second section sends into autothermal reforming reaction device.
(5) methane reforming with carbon dioxide device adopts the pattern of fluidized-bed, and reactor head adopts the catalyzer in cyclonic separator separation reformed gas, and catalyzer enters the burning zone of autothermal reforming reaction device.
(6) pass into oxygen in autothermal reforming reaction device and carry out incomplete combustion at burning zone, burn the carbon distribution on methane carbon dioxide reformation catalyzer, carry out catalyst regeneration.Catalyzer after regeneration and unburnt gas carry out catalyst separating after entering cyclonic separator, and catalyzer returns methane reforming with carbon dioxide device and uses, and residual gas enters autothermal reforming reaction device conversion zone and reforms, and makes methane conversion be hydrogen.
(7) from methane reforming with carbon dioxide device top through cyclonic separator top out gas and from autothermal reforming reaction device top gas out as the unstripped gas of coal gas hydrogen manufacturing, send into coal gas process for making hydrogen.
In the step (1) of technical scheme, because the organism usually containing hydro carbons in petroleum refinery's parsing waste gas is as polycyclic aromatic hydrocarbons naphthalene, pyrene, anthracene, acenaphthylene etc., easily coking in the process of these Hydrocarbon Organic gas cooling, and on pipeline, form clogged with deposits pipeline.Therefore washing tower is set in pre-treatment, the form of spray can be adopted, parsing waste gas is washed, cleaning solvent adopts the mineral oil of aromatics, be preferably the mineral oil based on dimethylbenzene, the name that such as French manufacturer Elf Atonchem supplies is called that Jaritherm AX 320 is specially the synthetic oil of single xylyl dimethylbenzene of 85%wt and two xylyl dimethylbenzene of 15wt%.Solvent after washing does not discharge, and after flash distillation, cleaning solvent reclaims, and is collected by Hydrocarbon Organic.
In the step (2) and step (4) of technical scheme, gas holder can adopt dry type or wet type high-pressure tank, and storage pressure reaches 5 ~ 10Mpa.
In the step (3) of technical scheme, hydrodesulphurisatioreactors reactors is adopted to carry out hydrogenating desulfurization, single desulphurization reactor can be adopted, also the reactor that two in parallel can be adopted, the upper strata of reactor is Hydrobon catalyst layer, and lower floor is adsorbent layer, and temperature of reaction is 300 DEG C ~ 400 DEG C, reaction pressure is 0.5 ~ 1Mpa, and air speed is 800 ~ 1000h
-1, the sulphur content of resolving in waste gas is reduced to 0.1ppm, and wherein Hydrobon catalyst adopts with Fe-Mo or Ni-Mo for active ingredient, with aluminum oxide Wei carrier, as JT-8 or JT-1.The high temperature desulfurizing sorbent material that it is activeconstituents with zinc titanate and zinc ferrite that desulfuration adsorbent adopts
In the step (5), (6) of technical scheme, the cyclonic separator at methane reforming with carbon dioxide device top adopts the cyclonic separator of high temperature material, methane reforming with carbon dioxide device adopts fluidized-bed reactor, temperature of reaction is 600 DEG C ~ 1000 DEG C, air speed is 8000 ~ 12000h-1, and reaction pressure is 1 ~ 3MPa.Autothermal reforming reaction device adopts fluidized-bed reactor, and temperature of reaction is 900 ~ 1500 DEG C, and reaction pressure is 0.8 ~ 2.5MP, and air speed is 9000 ~ 15000.The catalyzer that it be active ingredient is carrier with aluminum oxide or silicon-dioxide that the catalyzer of above-mentioned two reforming reactors can adopt with nickel.
Accompanying drawing illustrates: Fig. 1 is the process flow sheet that petroleum refinery of the present invention resolves that exhaust gas conversion is coal hydrogen feedstock gas.
(1). organism washing tower (2). condenser (3). gas holder 1 (4). compressor 1 (5). flash tank (6). desulphurization reactor A (7). desulphurization reactor B (8). gas holder 2 (9). compressor 2 (10). cyclonic separator (11). methane and carbon dioxide reactor (12). autothermal reforming reaction device
Embodiment:
1, the parsing waste gas sent here by refinery, first Hydrocarbon Organic washing tower (1) is entered, cleaning solvent adopts the synthetic oil of single xylyl dimethylbenzene of 85%wt and two xylyl dimethylbenzene of 15wt%, remove the Hydrocarbon Organic of resolving easily coking in waste gas, after washing by cleaning solvent through flash tank (5) flash distillation a part reclaim, another part after condenser (2) condensation for recirculation.To parsing waste gas out send into and resolve waste gas gas holder 1 (3) and cushion voltage stabilizing from Hydrocarbon Organic washing tower (1), and resolve off-gas compressor and to bleed and after compressor 1 (4) is pressurized to 0.5MPa from gas holder.Then resolve waste gas and enter hydrodesulphurisatioreactors reactors, desulphurization reactor adopts two fixed-bed reactor in parallel and desulphurization reactor A (6) and desulphurization reactor B (7), the upper strata of each desulphurization reactor is Hydrobon catalyst layer, lower floor is adsorbent layer, catalyzer is Ni-Mo is active ingredient, take aluminum oxide as carrier, lower floor is adsorbent layer, the sorbent material of sorbent material to be zinc titanate be activeconstituents, temperature of reaction is 305 DEG C, reaction pressure is 0.5MPa, and air speed is 800h
-1, the sulphur content of resolving in waste gas is reduced to 0.1ppm.Parsing waste gas after desulfurization is again after gas holder 2 (8) voltage stabilizing, through compressor 2 (9), parsing waste gas is being divided into two parts, first part directly sends into methane reforming with carbon dioxide device (11), and second section sends into autothermal reforming reaction device (5).Methane reforming with carbon dioxide device adopts the pattern of fluidized-bed, reactor head adopts the catalyzer in cyclonic separator (10) separation reformed gas, catalyzer enters the burning zone of autothermal reforming reaction device, pass into oxygen in autothermal reforming reaction device (12) and carry out incomplete combustion at burning zone, burn the carbon distribution on methane carbon dioxide reformation catalyzer, carry out catalyst regeneration.Catalyzer after regeneration and unburnt gas carry out catalyst separating after entering cyclonic separator (10), catalyzer returns methane reforming with carbon dioxide device (11) and uses, residual gas enters autothermal reforming reaction device (12) conversion zone and reforms, and makes methane conversion be hydrogen.Oxygen can come from air separation facility or other oxygen sources.From methane reforming with carbon dioxide device (11) top through cyclonic separator (10) top out gas and from autothermal reforming reaction device top gas out as the unstripped gas of coal gas hydrogen manufacturing, send into coal gas process for making hydrogen.Wherein for methane reforming with carbon dioxide device (11), temperature of reaction is 650 DEG C, and empty tower gas velocity is 8000h-1, and reaction pressure is 1.5MPa; For autothermal reforming reaction device (12), temperature of reaction is 900 DEG C, and reaction pressure is 1MP, and air speed is 9000h
-1.Catalyzer be nickel as catalyst activity component, aluminum oxide is carrier.
The table 1 composed as follows of the hydrogen feedstock gas after above-mentioned technique transforms:
| H2％ | CO％ | CH4％ | CO2％ | |
| Feed composition | 34.60％ | 3.30％ | 12.10％ | 50％ |
| Discharging forms | 42.4％ | 14.1％ | 3.30％ | 40.2％ |
Per-cent is wherein volume percent.
2, the parsing waste gas sent here by refinery, first Hydrocarbon Organic washing tower (1) is entered, cleaning solvent adopts the synthetic oil of single xylyl dimethylbenzene of 85%wt and two xylyl dimethylbenzene of 15wt%, remove the Hydrocarbon Organic of resolving easily coking in waste gas, after washing by cleaning solvent through flash tank (5) flash distillation a part reclaim, another part after condenser (2) condensation for recirculation.To parsing waste gas out send into and resolve waste gas gas holder 1 (3) and cushion voltage stabilizing from Hydrocarbon Organic washing tower (1), and resolve off-gas compressor and to bleed and after compressor 1 (4) is pressurized to 0.8MPa from gas holder.Then resolve waste gas and enter hydrodesulphurisatioreactors reactors, desulphurization reactor adopts two fixed-bed reactor in parallel and desulphurization reactor A (6) and desulphurization reactor B (7), the upper strata of each desulphurization reactor is Hydrobon catalyst layer, lower floor is adsorbent layer, catalyzer is Ni-Mo is active ingredient, take aluminum oxide as carrier, lower floor is adsorbent layer, the sorbent material of sorbent material to be zinc titanate be activeconstituents, temperature of reaction is 360 DEG C, reaction pressure is 0.8MPa, and air speed is 1000h
-1, the sulphur content of resolving in waste gas is reduced to 0.1ppm.Parsing waste gas after desulfurization is again after gas holder 2 (8) voltage stabilizing, through compressor 2 (9), parsing waste gas is being divided into two parts, first part directly sends into methane reforming with carbon dioxide device (11), and second section sends into autothermal reforming reaction device (12).Methane reforming with carbon dioxide device (11) adopts the pattern of fluidized-bed, reactor head adopts the catalyzer in cyclonic separator (10) separation reformed gas, catalyzer enters the burning zone of autothermal reforming reaction device (12), pass into oxygen in autothermal reforming reaction device (12) and carry out incomplete combustion at burning zone, burn the carbon distribution on methane carbon dioxide reformation catalyzer, carry out catalyst regeneration.Catalyzer after regeneration and unburnt gas carry out catalyst separating after entering cyclonic separator (10), catalyzer returns methane reforming with carbon dioxide device (11) and uses, residual gas enters autothermal reforming reaction device (12) conversion zone and reforms, and makes methane conversion be hydrogen.Oxygen can come from air separation facility or other oxygen sources.From methane reforming with carbon dioxide device (11) top through cyclonic separator (10) top out gas and from the unstripped gas of autothermal reforming reaction device (12) top gas out as coal gas hydrogen manufacturing, send into coal gas process for making hydrogen.Wherein for methane reforming with carbon dioxide device (11), temperature of reaction is 800 DEG C, and empty tower gas velocity is 10000h-1, and reaction pressure is 1.5MPa; For autothermal reforming reaction device (12), temperature of reaction is 950 DEG C, and reaction pressure is 1.5MP, and air speed is 12000h
-1.Catalyzer be nickel as catalyst activity component, aluminum oxide is carrier.
The table 2 composed as follows of the hydrogen feedstock gas after above-mentioned technique transforms:
| H2％ | CO％ | CH4％ | CO2％ | |
| Feed composition | 34％ | 6％ | 11.50％ | 48.50％ |
| Discharging forms | 38％ | 14.5％ | 6％ | 41.5％ |
Per-cent is wherein volume percent.
3, the parsing waste gas sent here by refinery, first Hydrocarbon Organic washing tower (1) is entered, cleaning solvent adopts the synthetic oil of single xylyl dimethylbenzene of 85%wt and two xylyl dimethylbenzene of 15wt%, remove the Hydrocarbon Organic of resolving easily coking in waste gas, after washing by cleaning solvent through flash tank (5) flash distillation a part reclaim, another part after condenser (2) condensation for recirculation.To parsing waste gas out send into and resolve waste gas gas holder 1 (3) and cushion voltage stabilizing from Hydrocarbon Organic washing tower (1), and resolve off-gas compressor and to bleed from gas holder and after being pressurized to 1MPa by compressor 1 (4).Then resolve waste gas and enter hydrodesulphurisatioreactors reactors, desulphurization reactor adopts two fixed-bed reactor in parallel and desulphurization reactor A (6) and desulphurization reactor B (7), the upper strata of each desulphurization reactor is Hydrobon catalyst layer, lower floor is adsorbent layer, catalyzer is Ni-Mo is active ingredient, take aluminum oxide as carrier, lower floor is adsorbent layer, the sorbent material of sorbent material to be zinc titanate be activeconstituents, temperature of reaction is 390 DEG C, reaction pressure is 1MPa, and air speed is 1000h
-1, the sulphur content of resolving in waste gas is reduced to 0.1ppm.Parsing waste gas after desulfurization is again after gas holder 2 (8) voltage stabilizing, through compressor 2 (9), parsing waste gas is divided into two parts, first part directly sends into methane reforming with carbon dioxide device (11), and second section sends into autothermal reforming reaction device (12).Methane reforming with carbon dioxide device (11) adopts the pattern of fluidized-bed, reactor head adopts the catalyzer in cyclonic separator (10) separation reformed gas, catalyzer enters the burning zone of autothermal reforming reaction device, pass into oxygen in autothermal reforming reaction device (12) and carry out incomplete combustion at burning zone, burn the carbon distribution on methane carbon dioxide reformation catalyzer, carry out catalyst regeneration.Catalyzer after regeneration and unburnt gas carry out catalyst separating after entering cyclonic separator (10), catalyzer returns methane reforming with carbon dioxide device (11) and uses, residual gas enters autothermal reforming reaction device (12) conversion zone and reforms, and makes methane conversion be hydrogen.Oxygen can come from air separation facility or other oxygen sources.From methane reforming with carbon dioxide device (11) top through cyclonic separator (10) top out gas and from the unstripped gas of autothermal reforming reaction device (12) top gas out as coal gas hydrogen manufacturing, send into coal gas process for making hydrogen.Wherein for methane reforming with carbon dioxide device (11), temperature of reaction is 950 DEG C, and empty tower gas velocity is 12000h-1, and reaction pressure is 3MPa; For autothermal reforming reaction device (12), temperature of reaction is 1500 DEG C, and reaction pressure is 2.5MP, and air speed is 15000h
-1.Catalyzer be nickel as catalyst activity component, aluminum oxide is carrier.
The table 3 composed as follows of the hydrogen feedstock gas after above-mentioned technique transforms:
| H2％ | CO％ | CH4％ | CO2％ | |
| Feed composition | 47.40％ | 9.60％ | 15.30％ | 27.70％ |
| Discharging forms | 56.2％ | 22.9％ | 5.00％ | 15.9％ |
Per-cent is wherein volume percent.
Comparative example:
The parsing waste gas sent here by refinery, first Hydrocarbon Organic washing tower (1) is entered, cleaning solvent adopts the synthetic oil of single xylyl dimethylbenzene of 85%wt and two xylyl dimethylbenzene of 15wt%, remove the Hydrocarbon Organic of resolving easily coking in waste gas, after washing by cleaning solvent through flash tank (5) flash distillation a part reclaim, another part after condenser (2) condensation for recirculation.To parsing waste gas out send into and resolve waste gas gas holder 1 (3) and cushion voltage stabilizing from Hydrocarbon Organic washing tower (1), and resolve off-gas compressor and to bleed from gas holder and after being pressurized to 1MPa by compressor 1 (4).Then resolve waste gas and enter hydrodesulphurisatioreactors reactors, desulphurization reactor adopts two fixed-bed reactor in parallel and desulphurization reactor A (6) and desulphurization reactor B (7), the upper strata of each desulphurization reactor is Hydrobon catalyst layer, lower floor is adsorbent layer, catalyzer is Ni-Mo is active ingredient, take aluminum oxide as carrier, lower floor is adsorbent layer, and the sulphur content of resolving in waste gas is reduced to 0.1ppm.Parsing waste gas after desulfurization is again after gas holder 2 (8) voltage stabilizing, through compressor 2 (9), parsing waste gas is divided into two parts, first part directly sends into methane reforming with carbon dioxide device (11), and second section sends into autothermal reforming reaction device (12).Methane reforming with carbon dioxide device (11) adopts the pattern of fluidized-bed, reactor head adopts the catalyzer in cyclonic separator (10) separation reformed gas, catalyzer enters the burning zone of autothermal reforming reaction device, pass into oxygen in autothermal reforming reaction device (12) and carry out incomplete combustion at burning zone, burn the carbon distribution on methane carbon dioxide reformation catalyzer, carry out catalyst regeneration.Catalyzer after regeneration and unburnt gas carry out catalyst separating after entering cyclonic separator (10), catalyzer returns methane reforming with carbon dioxide device (11) and uses, residual gas enters autothermal reforming reaction device (12) conversion zone and reforms, and makes methane conversion be hydrogen.Oxygen can come from air separation facility or other oxygen sources.From methane reforming with carbon dioxide device (11) top through cyclonic separator (10) top out gas and from the unstripped gas of autothermal reforming reaction device (12) top gas out as coal gas hydrogen manufacturing, send into coal gas process for making hydrogen.
The operational condition identical with above-mentioned 1-3 embodiment and feed composition is adopted to obtain comparative example 1-3 in comparative example as shown in table 4 below:
| H2％ | CO％ | CH4％ | CO2％ | |
| Feed composition | 34.60％ | 3.30％ | 12.10％ | 50％ |
| Embodiment 1 | 42.4％ | 14.1％ | 3.30％ | 40.2％ |
| Comparative example 1 | 38.5％ | 10.4％ | 8.1％ | 43％ |
| Feed composition | 34％ | 6％ | 11.50％ | 48.50％ |
| Embodiment 2 | 38％ | 14.5％ | 6％ | 41.5％ |
| Comparative example 2 | 36.5％ | 13.6％ | 9.6％ | 40.3％ |
| Feed composition | 47.40％ | 9.60％ | 15.30％ | 27.70％ |
| Embodiment 3 | 56.2％ | 22.9％ | 5.00％ | 15.9％ |
| Comparative example 3 | 50.8％ | 15.9％ | 12.4％ | 20.9％ |
As can be seen from above three embodiments and three comparative examples, conversion of the present invention is compared with methane conversion direct in employing prior art, effectively reduce the methane content in refinery's parsing waste gas, add the content of hydrogen simultaneously, therefore, meet the requirement of hydrogen feedstock gas, and the ratio of carbon monoxide obviously increases and also reflects effectively reduce carbon distribution in reaction process from composition.
Claims (6)
1. petroleum refinery resolves the method that exhaust gas conversion is coal hydrogen feedstock gas, it is characterized in that comprising following processing step:
(1) waste gas detar technique is resolved:
(1) the parsing waste gas sent here by refinery, first enters Hydrocarbon Organic washing tower, and cleaning solvent adopts the mineral oil based on dimethylbenzene, remove the Hydrocarbon Organic of resolving easily coking in waste gas, by organic solvent flash distillation after washing, a part reclaims, and another part is used for recirculation;
(2) will parsing waste gas out send into and resolve the voltage stabilizing of waste gas gas holder buffering from step (1), and resolve off-gas compressor and to bleed and after being pressurized to 0.2 ~ 1MPa from gas holder;
(3) the parsing waste gas through step (2) enters hydrodesulphurisatioreactors reactors, the upper strata of desulphurization reactor is Hydrobon catalyst layer, and lower floor is adsorbent layer, and temperature of reaction is 300 DEG C ~ 400 DEG C, reaction pressure is 0.5 ~ 1Mpa, and air speed is 800 ~ 1000h
-1, the degraded sulphur content analysed in waste gas is reduced to 0.1ppm;
(4) by the parsing waste gas in step (3) again after gas holder voltage stabilizing, parsing waste gas is divided into two parts, first part directly sends into methane reforming with carbon dioxide device, and second section sends into autothermal reforming reaction device;
(5) methane reforming with carbon dioxide device adopts the pattern of fluidized-bed, and reactor head adopts cyclonic separator, and be separated the catalyzer in reformed gas, catalyzer enters the burning zone of autothermal reforming reaction device;
(6) pass into oxygen in autothermal reforming reaction device and carry out incomplete combustion at burning zone, burn the carbon distribution on methane carbon dioxide reformation catalyzer, carry out catalyst regeneration.Catalyzer after regeneration and unburnt gas carry out catalyst separating after entering cyclonic separator, and catalyzer returns methane reforming with carbon dioxide device and uses, and residual gas enters autothermal reforming reaction device conversion zone and reforms, and makes methane conversion be hydrogen;
(7) from methane reforming with carbon dioxide device top through cyclonic separator top out gas and from autothermal reforming reaction device top gas out as the unstripped gas of coal gas hydrogen manufacturing, send into coal gas process for making hydrogen.
2. petroleum refinery resolves the method that exhaust gas conversion is coal hydrogen feedstock gas according to claim 1, it is characterized in that: cleaning solvent described in step (1) is the synthetic oil of single xylyl dimethylbenzene of 85%wt and two xylyl dimethylbenzene of 15wt%.
3. petroleum refinery resolves exhaust gas conversion is according to claim 1 the method for coal hydrogen feedstock gas, it is characterized in that: the hydrodesulphurisatioreactors reactors described in step (2) is single reactor or two reactors in parallel.
4. petroleum refinery resolves the method that exhaust gas conversion is coal hydrogen feedstock gas according to claim 1, it is characterized in that: step (5) and (6) middle methane reforming with carbon dioxide device adopt fluidized-bed reactor, temperature of reaction is 600 DEG C ~ 1000 DEG C, air speed is 8000 ~ 12000h-1, and reaction pressure is 1 ~ 3MPa.
5. petroleum refinery resolves the method that exhaust gas conversion is coal hydrogen feedstock gas according to claim 1, it is characterized in that: step (5) and (6) middle autothermal reforming reaction device adopt fluidized-bed reactor, temperature of reaction is 900 ~ 1500 DEG C, reaction pressure is 0.8 ~ 2.5MP, and air speed is 9000 ~ 15000.
6. petroleum refinery resolves the method that exhaust gas conversion is coal hydrogen feedstock gas according to claim 1, it is characterized in that: in step (5) and (6), the catalyzer that it be active ingredient is carrier with aluminum oxide or silicon-dioxide that the catalyzer of methane reforming with carbon dioxide device and autothermal reforming reaction device all adopts with nickel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114991740A (en) * | 2022-06-21 | 2022-09-02 | 西安石油大学 | Method and system for cooling and saving energy of coal underground gasification produced gas |
| CN116332130A (en) * | 2021-12-24 | 2023-06-27 | 中国石油天然气集团有限公司 | Method and system for producing hydrogen by using organic waste gas and related application |
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| US20090298957A1 (en) * | 2004-11-16 | 2009-12-03 | Pierre-Robert Gauthier | Method and installation for combined production of hydrogen and carbon dioxide |
| CN101111452A (en) * | 2005-01-28 | 2008-01-23 | 爱沃特株式会社 | Apparatus and method for hydrogen generation |
| CN101274746A (en) * | 2007-01-03 | 2008-10-01 | 通用电气公司 | Reforming system for combined cycle plant with partial CO2 capture |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116332130A (en) * | 2021-12-24 | 2023-06-27 | 中国石油天然气集团有限公司 | Method and system for producing hydrogen by using organic waste gas and related application |
| CN114991740A (en) * | 2022-06-21 | 2022-09-02 | 西安石油大学 | Method and system for cooling and saving energy of coal underground gasification produced gas |
| CN114991740B (en) * | 2022-06-21 | 2023-08-25 | 西安石油大学 | Method and system for cooling and energy saving of produced gas from underground coal gasification |
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Effective date of registration: 20180122 Address after: 256500 Boxing, Shandong Province Economic Development Zone, Beijing Bo Industrial Park Patentee after: Shandong Bozhongcheng Clean Energy Co., Ltd. Address before: 256500 Boxing, Shandong Province Economic Development Zone, Beijing Bo Industrial Park Patentee before: Shandong Efirm Biochemistry and Environmental Protection Co., Ltd. |