CN100579896C - Method and system for preparing synthetic gas with appropriate hydrogen-carbon ratio from lurgi furnace outlet coal gas through non-catalytic partial oxidation by pure oxygen - Google Patents
Method and system for preparing synthetic gas with appropriate hydrogen-carbon ratio from lurgi furnace outlet coal gas through non-catalytic partial oxidation by pure oxygen Download PDFInfo
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- CN100579896C CN100579896C CN 200710037578 CN200710037578A CN100579896C CN 100579896 C CN100579896 C CN 100579896C CN 200710037578 CN200710037578 CN 200710037578 CN 200710037578 A CN200710037578 A CN 200710037578A CN 100579896 C CN100579896 C CN 100579896C
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Abstract
The invention discloses a making method and system of synthetic gas or hydrogen with fitful hydrogen carbon rate, which is characterized by the following: adding carbon monoxide combusting step before the rough gas from the Lurgi furnace into next procedure under 500-650 deg. c; producing high-temperature composite gas; cracking organics with organic sulfur such as thiofuran and organic hydrocarbon such as methane; hydrogenating; transmitting; cooling the high-temperature composite gas twice; purifying; stripping; refining; outputting the synthetic gas with hydrogen and carbon monoxide rate at 1. 2-1. 3 and less than 0. 1%V methane; satisfying the subsequent technical need of oil making through coal; ensuring the purifying quality of the synthetic gas.
Description
Technical field
The present invention relates to the coal is that raw material is produced the synthetic gas of hydrogen and carbon monoxide or hydrogen to make oil, synthetic ammonia and methyl alcohol technical field, and particularly lurgi gasifier outlet coal gas adds the method and system that pure oxygen non-catalytic partial oxidation is produced suitable hydrogen-carbon ratio synthetic gas.
Background technology
At present, be that having of the raw material technology comparative maturity of producing hydrogen and carbon monoxide synthetic gas or hydrogen is following several with the coal:
1, SHELL dry coal powder pure oxygen gasification technology, this technology is introduced software overhead height, operational condition harshness, vapourizing furnace device structure complexity (stove internals particularly, at present domestic still do not possess the processing and manufacturing ability, must introduce), facility investment is big, and domestic still do not have sophisticated technology and experience to use for reference.
2, TEXACO coal water slurry pure oxygen gasification technology.The operational condition harshness, the pure oxygen burner is changed frequent, the pulping process complexity, facility investment is big, limited by coal adaptability.
3, LURGI lump coal fixed bed pure oxygen gasification technology.Technology maturation, vapourizing furnace equipment is simple, and technology and equipment all can domesticize, and the technical software expense is low or do not have, the operational condition gentleness, facility investment is low.But gas liquor is handled complicated, and is seriously polluted; Raw gas purifying and methane recovery and utilize technical process long and complicated, investment is big, the energy consumption height.
4, atmosphere intermission air coal (Jiao) gas making fixed-bed process, throughput is low, and is seriously polluted, the energy consumption height.
5, continuous oxygen enrichment of normal pressure or pure oxygen coal (Jiao) gas making fixed-bed process, throughput is low, and is seriously polluted, the energy consumption height.
Adopt lurgi gas to produce the technological process of hydrogen and carbon monoxide synthetic gas at present, exist following problem:
1, the more and complicated component of organic content in the washing water in the raw gas, the recycling difficulty, environmental pollution is serious.
2, contain the about 8-10%V of a large amount of methane in the raw gas and do, reclaim and utilize difficulty, the long flow path investment is big; Waste raw material as not reclaiming then; Methane enters the efficient that the subsequent technique device will reduce coal system wet goods follow up device, and the available gas utilization ratio reduces.
3, hydrogen content height in the raw gas, carbon monoxide content is low, and hydrogen/carbon monoxide ratio is too high improper to coal system oil, must carry out dehydrogenation and adjust, carbon resource and hydrogen in the waste great amount of carbon dioxide.
4, raw gas need remove carbonic acid gas, also will waste carbon resource and hydrogen in the great amount of carbon dioxide.
5, contain organosulfur in the raw gas to raw gas purifying technology such as low-temperature rectisol or transformation adsorbing and removing difficulty, as thiophene, carbon oxysulfide, sulfurous gas etc., also contain the organism such as higher alkene or the higher alkane (light oil constituents) that pollute low temperature washing device for methanol, handle and reclaim difficulty.
6, lurgi gasifier export high temperature rough gas can only the by-product low-pressure steam, the steam grade is low, capacity usage ratio is low.
Summary of the invention
An object of the present invention is to provide a kind of lurgi gasifier outlet coal gas and add the method that pure oxygen non-catalytic partial oxidation is produced suitable hydrogen-carbon ratio synthetic gas, it is reasonable that this method is used for the process more economical of coal system wet goods device, give full play to the advantage that the lurgi gasifier coal Gasification Technology in Retrospect is ripe and domesticize, to solve the existing problem of present lurgi gasifier technology.
Another object of the present invention provides lurgi gasifier outlet coal gas and adds the system that method adopted that pure oxygen non-catalytic partial oxidation is produced suitable hydrogen-carbon ratio synthetic gas or hydrogen.
Lurgi gasifier outlet coal gas as a first aspect of the present invention adds the method that pure oxygen non-catalytic partial oxidation is produced suitable hydrogen-carbon ratio synthetic gas, it is to increase by an oxidizing fire step before the raw gas that comes out from lurgi gasifier carries out next procedure, make the 500-600 ℃ of raw gas oxidizing fire that comes out from lurgi gasifier, forming hydrogen/carbon monoxide ratio is 1.2-1.3, and methane content is less than the raw gas of 0.1%V.In combustion processes, organism comprises organosulfur, as thiophene etc. and cracking at high temperature, hydrogenation and conversions such as organic hydrocarbon such as methane.
For the dust in the initial gross separation raw gas, before the oxidizing fire step, increase at least one and separate dust removal step.Can not add if do not need.
Above-mentioned next procedure comprises that twice step that cools, purifying step, essence take off purification step, the step that wherein once cools reclaims the heat of the high-temperature gas of oxidizing fire step formation, and the raw gas that pressure and/or low-pressure steam and formation temperature reduce in the by-product is also removed gas liquor; The secondary step that cools makes raw gas further reduce temperature and removes process condensate (gas liquor); Purifying step is sloughed the gas that hydrogen sulfide is rich in regeneration; Essence is taken off refining plant detrimental impurity is removed to satisfying the subsequent technique requirement.
Cool between the step at twice, a conversion and bypass regulating step can be set as required, the mode of regulating with conversion and bypass is regulated the ratio of hydrogen and carbon monoxide in the raw gas once more.
In conversion and bypass regulating step, adopt the sulfur-resisting transformation part that raw gas is carried out heat exchange and conversion.
Cool between the step at twice, can also increase at least one secondary separation dust removal step, the raw gas that reduces through the heat recuperation temperature is separated once more.Described secondary separation dust removal step can also once cool between step and conversion and the bypass regulating step.
Also connect a sulfur recovery step after purifying step, the gas of hydrogen sulfide is rich in the regeneration that the reception refining plant is sloughed, as producing sulphur or vitriolic unstripped gas.
The mode that adopts high temperature or have a cyclonic separation dedusting handplay person dust removal by filtration of certain temperature in above-mentioned flash liberation dust removal step is separated dedusting.
In the above-mentioned oxidizing fire step, adopt pure oxygen non-catalytic incendiary mode to carry out oxidizing fire.Can also be in the oxidizing fire process, raw gas is and carries out incendiary after the mixed gas of pure oxygen and safe steam mixes.
In above-mentioned oxidizing fire process, pure oxygen compresses earlier and preheating before entering oxidized still with the safety vapor mixing.
In the above-mentioned step that once cools, the mode of employing cold shock and/or waste heat boiler byproduct steam reclaims the heat of described high-temperature gas, and the gas liquor gas delivery water sepn and the treatment system of removing are handled; In the reducing temperature twice step, adopt spray refrigerative mode to lower the temperature.
In above-mentioned secondary separation dust removal step, adopt washing or/and the mode of cyclonic separation is separated dedusting.
In general above-mentioned purifying step is made up of desulfurization and decarburization two portions, and desulfurization mainly is the gas that hydrogen sulfide is rich in the regeneration of sloughing, as producing sulphur or vitriolic unstripped gas.Desulfurization and decarburization can adopt low-temperature rectisol or/and the transformation suction type carries out desulfurization and decarburization.For newly-built synthetic gas production equipment, generally adopt low-temperature rectisol or transformation suction type to carry out desulfurization and decarburization.And for the synthetic gas production equipment of transforming, consider that original low-temperature rectisol processing power is too small, generally will be on the low-temperature rectisol mode transformation suction type in parallel again or low-temperature rectisol mode, to improve the processing power of desulfurization and decarburization.
Take off in the purification step in above-mentioned essence and to adopt essence to take off refining plant to remove detrimental impurity to satisfying the subsequent technique requirement, making the ratio of hydrogen/carbon monoxide in the synthetic gas of its output is 1.2-1.3, and wherein methane content is less than 0.1%V.To satisfy the requirement of coal system oil.
Lurgi gasifier outlet coal gas as second aspect present invention adds the system that method adopted that pure oxygen non-catalytic partial oxidation is produced suitable hydrogen-carbon ratio synthetic gas, it is characterized in that, between the device of existing lurgi gasifier and next procedure, increase by an oxidized still, make the 500-600 ℃ of raw gas that comes out from lurgi gasifier oxidized still, carry out oxidizing fire, forming hydrogen/carbon monoxide ratio is 1.2-1.3, and methane content is less than the raw gas of 0.1%V.In combustion processes, organism comprises organosulfur such as thiophene etc. and cracking at high temperature, hydrogenation and conversions such as organic hydrocarbon such as methane.
In said system, oxidized still is the pure oxygen oxidized still.Described pure oxygen oxidized still is the pure oxygen non-catalytic partial oxidation stove.
Perhaps described oxidized still has the shower nozzle mixing tank and the combustion chamber of the mixed gas of inlet, outlet, input pure oxygen and safe steam, external pure oxygen of shower nozzle mixing tank and safe steam; Inlet pipe links to each other with the raw gas outlet of lurgi gasifier, export 500-600 ℃ of raw gas of output with the raw gas of accepting lurgi gasifier, the mixed gas of raw gas and pure oxygen and safe steam produces raw gas and outputs to next duct device by the air outlet in combustion chamber mixed firing.
In said system,, can between lurgi gasifier and pure oxygen non-catalytic partial oxidation stove, increase at least one and separate cleaning apparatus according to the dedusting needs.Can not add if do not need.
Described flash liberation cleaning apparatus has inlet mouth and air outlet, inlet mouth links to each other with the raw gas outlet of lurgi gasifier, export 500-600 ℃ of raw gas of output with the raw gas of accepting lurgi gasifier, the raw gas that enters is carried out dedusting separate, the raw gas after dedusting separates is transported to oxidized still by the air outlet.
In said system, the device of described next procedure comprises twice cooling device, refining plant, essence and takes off refining plant, wherein a cooling device is connected with oxidized still, the secondary cooling device is connected with a cooling device, refining plant is connected with the secondary cooling device, essence is taken off refining plant and is connected with refining plant, and wherein cooling device is accepted high-temperature gas that oxidized still comes and to its cooling, cooling back separate discharge gas liquor; The raw gas that reduces through the heat recuperation temperature outputs to the secondary cooling device by the air outlet and cools off once more, and the cooled raw gas of secondary is transported to refining plant and purifies, the gas liquor discharging that cooling forms; Refining plant purifies raw gas, purifies raw gas later and is transported to essence and takes off refining plant and carry out essence and take off refining; Final formation hydrogen and the suitable synthetic gas of carbon monoxide ratio are transported to down the road synthesis procedure.
In said system, between twice cooling device, one conversion and bypass regulating device can be set as required, in the mode of regulating by conversion and bypass, ratio to raw gas carries out conversion and regulates hydrogen and carbon monoxide in the raw gas once more makes the synthetic gas of output reach processing requirement.
Described conversion and bypass regulating device comprise a sulfur-resisting transformation device.
Between twice cooling device, can also increase at least one secondary separation cleaning apparatus, the raw gas that reduces through the heat recuperation temperature is separated once more.Described secondary separation cleaning apparatus can also be once between cooling device and conversion and the bypass regulating device.
In said system, on refining plant, also connect a sulfur recovery unit, the gas of hydrogen sulfide is rich in the regeneration that the reception refining plant is sloughed, as producing sulphur or vitriolic unstripped gas.
In said system, also comprise an air separation facility, this air separation facility is connected with oxidized still with lurgi gasifier, provides pure oxygen to lurgi gasifier and oxidized still.
A described cooling device have one reclaim mouthful, air outlet and gas liquor discharge outlet, reclaim and mouthful link to each other, to accept raw gas that oxidized still comes and to its cooling, cooled gas liquor is discharged by the gas liquor discharge outlet with the air outlet of oxidized still; Export by the air outlet through the raw gas that the heat recuperation temperature reduces.
Described secondary separation cleaning apparatus has inlet mouth and air outlet, the air outlet of this inlet mouth and a last device, link to each other as the air outlet of oxidized still or the air outlet of a cooling device, wash once more and separate with the raw gas accepting raw gas or reduce through the heat recuperation temperature and to it, the air outlet links to each other with next device, link to each other as the mouth of conversion and bypass regulating device or the inlet mouth of secondary cooling device, be transported to conversion and bypass regulating device with the raw gas after will separating and carry out conversion and adjusting or secondary cooling device and cool off once more.
Described secondary cooling device has an inlet mouth, an air outlet and a gas liquor discharge outlet, its inlet mouth links to each other with the air outlet of a cooling device or another mouthful of conversion and bypass regulating device, to accept the suitable raw gas of hydrogen and carbon monoxide ratio and it cooled off once more, cooled raw gas is discharged by the air outlet, and the gas liquor that cooling forms is discharged by the gas liquor discharge outlet.
Described refining plant has an inlet mouth and two fens gas ports, its inlet mouth links to each other with the air outlet of secondary cooling device, to accept cooled hydrogen and the suitable raw gas of carbon monoxide ratio, the gas of hydrogen sulfide is rich in a branch gas port output regeneration, hydrogen and the suitable raw gas of carbon monoxide ratio that another minute gas port output is handled through desulfurization and decarburization.
Described essence is taken off refining plant and is had inlet mouth and air outlet, inlet mouth links to each other with another minute gas port of refining plant, to accept the suitable raw gas of the hydrogen handled through desulfurization and decarburization and carbon monoxide ratio and it to be carried out essence take off refiningly, essence is taken off hydrogen and the suitable synthetic gas of carbon monoxide ratio that refining back forms and is transported to down the road synthesis procedure by the air outlet.
Described sulfur recovery unit has one and reclaims a mouth and a discharge outlet, reclaiming mouth links to each other with a branch gas port of refining plant, be rich in the gas of hydrogen sulfide and it is reclaimed to accept regeneration, the gas that hydrogen sulfide is rich in the regeneration of recovery is produced sulphur or sulfuric acid by discharge outlet to sulphur or sulfuric acid device for making.
Described air separation facility has a gas inlet and pure oxygen delivery port, air is entered by gas inlet, the pure oxygen delivery port is divided into two-way, one the tunnel is connected with the import of lurgi gasifier pure oxygen, another road links to each other with the shower nozzle mixing tank of pure oxygen oxidized still, provides pure oxygen to lurgi gasifier and pure oxygen non-catalytic partial oxidation stove respectively.
In said system, described flash liberation cleaning apparatus is a cyclonic separator.
In said system, the shower nozzle mixing tank in the described pure oxygen oxidized still can replace with burner.
In said system, a described cooling device is cold shock equipment and/or waste heat boiler.
In said system, described secondary separation device is for washing or/and cyclonic separator.
In said system, described secondary cooling device is air cooler or and water cooler equipment.
In said system, refining plant is made up of desulfurization and decarburization two portions.Low temperature washing device for methanol can be adopted or/and pressure-swing absorption apparatus.For newly-built synthetic gas production equipment, generally adopt low temperature washing device for methanol or pressure-swing absorption apparatus to carry out desulfurization and decarburization.And for the synthetic gas production equipment of transforming, consider that original low temperature washing device for methanol processing power is too small, generally will be on low temperature washing device for methanol a pressure-swing absorption apparatus in parallel again, to improve the processing power of desulfurization and decarburization.
The lurgi gasifier outlet coal gas that the present invention adopts adds the method and system that pure oxygen non-catalytic partial oxidation is produced hydrogen carbon synthetic gas, has solved the problem that present lurgi gasifier technology exists:
1, lurgi gasifier outlet raw gas is adopted high-temp combustion and reaction, the complicated organism of conversion or cracking is the simple molecules material substantially fully, and organism reduces greatly in the washing water, and gas liquor is handled simple, and environmental pollution improves.
2, contain the dried methane of 8-10%V in the raw gas and be converted into hydrogen and carbon monoxide substantially, the methane inert gas content is few, has improved the efficient of coal system wet goods subsequent technique process, has also eliminated the equipment that methane separation and steam reforming etc. are recycled.
3, the raw gas that goes out partial oxidation furnace is just met pressure and/or low-pressure saturated steam recovery heat in cold shock and/or the through exhaust gas boiler by-product.
4, the raw gas after heat recuperation further removes the dust and the organism of deentrainment again through washing and cyclonic separation.
5, raw gas can satisfy the subsequent technique requirement by the final hydrogen of sulfur-resisting transformation adjustment/carbon monoxide ratio.
6, raw gas adopts low-temperature rectisol or/and pressure swing adsorption purge device desulfurization and decarburization.
7, the synthetic gas through refining plant further purifies, and guarantees synthetic gas or hydrogen quality.
After adopting technical scheme of the present invention, make that producing the gas-making process that hydrogen and carbon monoxide be used for coal system wet goods process with the lurgi gasifier coal generating gas simplifies greatly, its advantage comprises that gas liquor separating treatment and simplification, raw gas purifying are reliable and stable, methane recovery and processing workshop section can cancel or the like.Another advantage is the requirement that oxidized still (POX) outlet proportion of composing satisfies follow-up coal system wet goods technological process substantially, can not adopt the part sulfur-resisting transformation, carries hydrogen through decarburization and regulates hydrogen/carbon monoxide ratio once more.The concrete advantage of the present invention is as follows:
1, handles the complicated organism that maybe can't handle owing to contain a large amount of subsequent techniques in the raw gas of lurgi gasifier production, adopt the high-temp combustion and the reaction of oxidized still of the present invention (POX), all be converted into useful component or be easy to remove easy-to-handle simple material, for example methane and light oil are converted into useful medium hydrogen and carbon monoxide; Thiophene is converted into hydrogen sulfide etc.
2, do not contain impurity such as naphthalene, thiophene and higher hydrocarbon in the raw gas, low-temperature rectisol or pressure swing adsorption purge device are reliable stable, do not cause the problem that impurity accumulation operation worsens in the methanol solution thereby do not exist, do not have the problem of polluting transformation absorption sorbent material because pollute methanol solution.
3, supporting necessary methane recovery and the processing workshop section of cancellation and former lurgi gasifier gas making, for example low temperature separation process methane (as liquid nitrogen washing) and steam reforming recycle section shorten flow process greatly, simplify the operation, save investment, cut down the consumption of energy.
4, oxygen in the raw gas of lurgi gasifier coal generating gas/carbon monoxide ratio is higher, and promptly the many carbon of hydrogen are few, and follow up device need remove unnecessary hydrogen and carbonic acid gas, thereby has wasted hydrogen and carbon source.Oxidized still of the present invention (POX) has in fact consumed unnecessary hydrogen, and carbonic acid gas is generated the carbon monoxide inverse transformation, produces the synthetic gas of the hydrogen/carbon monoxide ratio that meets the subsequent technique requirement; While also can be cancelled or reduce greatly to adjust once more the changing device of hydrogen/carbon monoxide ratio and put forward the scale of hydrogen production device.
5, after the employing technology of the present invention, the comparatively serious lurgi gasifier technology of traditional pollution will be replaced by technology of the present invention, and thoroughly the contaminated solution problem becomes friendly process (GLP), can compare favourably with Texaco's Coal Gasification Technology and shell Coal Gasification Technology.
Description of drawings
Further specify the present invention below in conjunction with the drawings and specific embodiments.
Fig. 1 is the schema of system of the present invention.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Following examples are to be example with coal system oil device, adopt lurgi gasifier to produce the synthetic gas of hydrogen and carbon monoxide.
Lurgi gasifier outlet coal gas of the present invention adds the method that pure oxygen non-catalytic partial oxidation is produced hydrogen carbon synthetic gas, comprises the steps:
1, utilization has the synthetic gas of the lurgi gasifier 1 production hydrogen/carbon monoxide of coal import 11, steam inlet 12, pure oxygen import 13, raw gas outlet 14, slag-drip opening 15; Lurgi gasifier 1 gas making technology adopts lump coal fixed bed pressurization gas-making process, with lump coal is raw material, pure oxygen and steam are oxygenant/vaporized chemical, come out from lurgi gasifier 1 the about 500-600 of raw gas temperature ℃, wherein the ratio of hydrogen/carbon monoxide about 1.7, be much higher than hydrogen/carbon monoxide ratio of the 1.2-1.3 of coal system oil matching requirements, and wherein contain the methane of 8-9%V.The steam inlet 12 steam-out (SO) sources of lurgi gasifier 1, pure oxygen import 13 is connected with the road output 41 that air separation facility 4 is come.
2, the 500-600 ℃ of raw gas that comes out from lurgi gasifier 1, export 14 from the flash liberation cleaning apparatus by raw gas, enter cyclonic separator 2 as cyclonic separator 2 with raw gas outlet 14 inlet mouths that link to each other 21 of lurgi gasifier 1, carrying out dedusting separates, remove most of dry dust, reduced the erosion corrosion influence of high-temperature dust, reduced dust content in the gas liquor, improved the gas liquor flowability follow-up equipment.The air outlet 22 of cyclonic separator 2 links to each other with the inlet mouth 31 of pure oxygen oxidized still 3, with the raw gas of carrying through the dedusting separating treatment to pure oxygen oxidized still 3.This step can need to select, and also the 500-600 ℃ of raw gas that comes out from lurgi gasifier 1 directly can be delivered to pure oxygen oxidized still 3 and carry out oxidizing fire.
3, the raw gas of process cyclonic separator 2 dust removal process enters into pure oxygen oxidized still 3 by the inlet mouth 31 of pure oxygen oxidized still 3, simultaneously another road output 42 pure oxygens of bringing of coming by air separation facility 4 separately or the safe steam of bringing with the steam-out (SO) source mixing and preheating, compression in burner/shower nozzle mixing tank form mixed gas and be sprayed onto the combustion chamber, with raw gas mixed firing, the raw gas of generation is by 32 outputs of the air outlet on the pure oxygen oxidized still 3.Through behind the high-temp combustion, organosulfur in the raw gas such as thiophene, carbon oxysulfide, sulfurous gas etc., or organism such as higher alkene or higher alkane etc., almost all be converted into inorganic sulfur such as hydrogen sulfide and simple molecules material, help the purification of low temperature washing device for methanol or pressure-swing absorption apparatus.Make simultaneously that organism reduces greatly in the washing water, gas liquor is handled simple, and environmental pollution improves.In combustion processes, methane 8-10%V is converted into hydrogen and carbon monoxide substantially in the raw gas, and the methane inert gas content is few, has improved the efficient of coal system wet goods subsequent technique process.At this moment hydrogen in the raw gas that comes out/carbon monoxide ratio is 1.2-1.3, meets the requirement of coal system oil device.
4, the raw gas by 32 outputs of the air outlet on the pure oxygen oxidized still 3 passes through a cooling device, recovery mouth 51 as cold shock equipment and/or waste heat boiler 5 enters into cold shock equipment and/or waste heat boiler 5, high-temperature gas is cooled off the recovery heat, and cooled gas liquor is by 52 dischargings of gas liquor discharge outlet; The raw gas that reduces through the heat recuperation temperature outputs to the secondary separation device by air outlet 53 and separates dedusting.
5, the raw gas process secondary separation cleaning apparatus through the reduction of heat recuperation temperature of coming by the recovery mouth 51 of cold shock equipment and/or waste heat boiler 5, or/and the inlet mouth 61 of cyclonic separator 6 enters washing or/and cyclonic separator 6 separates dedusting, further remove the dust and the organism of deentrainment as washing.Raw gas after the separation dedusting is transported to bypass regulating device 71 by air outlet 62.
Certainly, the secondary separation cleaning apparatus, as washing or/and cyclonic separator 6 also can be cancelled, to directly deliver to the secondary cooling device by the raw gas through the reduction of heat recuperation temperature that the recovery mouth 51 of cold shock equipment and/or waste heat boiler 5 is come cools off once more, perhaps deliver to bypass regulating device 71 and regulate hydrogen in the raw gas/carbon monoxide ratio once more, make it to reach the requirement of other synthesis technique, as synthetic ammonia etc.
6, by washing or/and the raw gas that the air outlet 62 of cyclonic separator 6 is brought by 71 1 mouths of bypass regulating device enter into bypass regulating device 71 and and connect the changing device of bypass regulating device 71, in sulfur-resisting transformation device 72, the raw gas of 72 pairs of parts of sulfur-resisting transformation device carries out conversion.The ratio that bypass regulating device 71 and sulfur-resisting transformation device 72 be final regulates hydrogen and carbon monoxide in the raw gas that the heat recuperation temperature reduces, to satisfy follow-up processing requirement such as synthetic, solved in the existing method hydrogen content height in the raw gas, the contradiction that carbon monoxide content is low.
Certainly, produce in the device of synthetic gas at some, in coal system oil device, also can not adopt bypass regulating device 71 and sulfur-resisting transformation device 72, because hydrogen/carbon monoxide ratio is 1.2-1.3 in the raw gas that is come out by pure oxygen oxidized still 3, meet the requirement of coal system oil device.
7, the raw gas that reduces through the heat recuperation temperature of adjusting hydrogen of being brought by bypass regulating device 71 and sulfur-resisting transformation device 72 and carbon monoxide ratio is by the secondary cooling device, as the inlet mouth 81 that sprays wash-out equipment 8 enters in the spray wash-out equipment 8, it is carried out once more cooling, remove process condensate, promptly gas liquor is by 82 dischargings of gas liquor discharge outlet; The raw gas that cooled hydrogen and carbon monoxide ratio are suitable is transported to refining plant by air outlet 83 and purifies.Spray wash-out equipment 8 is that air cooler is or/and water cooler equipment.
8, carry the cooled hydrogen and the suitable raw gas of carbon monoxide ratio of coming by the air outlet 83 of spray wash-out equipment 8, enter into refining plant 9 by the inlet mouth on the refining plant 9 91 and carry out desulfurization and decarburization.Refining plant 9 is made up of desulfurization and decarburization two portions.Low temperature washing device for methanol can be adopted or/and pressure-swing absorption apparatus carries out desulfurization and decarburization.The gas that hydrogen sulfide is rich in the regeneration of handling through desulfurization and decarburization is transported to sulfur recovery unit 11a by a branch gas port 92 and reclaims.The suitable raw gas of hydrogen of handling through desulfurization and decarburization and carbon monoxide ratio by another minute gas port 93 be transported to essence and take off refining plant 10 and carry out essence and take off refining.The carbonic acid gas of deviating from discharges or is sent to treatment unit by evacuation port and handles.
Certainly for the synthetic gas production equipment of transforming, consider that original low temperature washing device for methanol processing power is too small, generally will be on low temperature washing device for methanol a low temperature washing device for methanol in parallel again or pressure-swing absorption apparatus, to improve the processing power of desulfurization and decarburization.
9, carry gas that the regeneration of coming the is rich in hydrogen sulfide recovery mouth 111a by sulfur recovery unit 11a to be sent to sulfur recovery unit 11a by the branch gas port 92 of refining plant 9 and reclaim, the gas that hydrogen sulfide is rich in the regeneration of recovery is produced sulphur or sulfuric acid by discharge outlet 112a to sulphur or sulfuric acid device for making;
10, the hydrogen and the suitable raw gas of carbon monoxide ratio of coming by another minute gas port 93 conveyings of refining plant 9, take off refining plant 10 inlet mouths 101 by essence and enter into essence and take off refining plant 10 and carry out essence and take off refiningly, essence is taken off hydrogen and the suitable synthetic gas of carbon monoxide ratio that refining back forms and is transported to down the road synthesis procedure by air outlet 102.Synthetic gas adopts smart sulphur refining plant further to purify, and removes detrimental impurity, and making the ratio of hydrogen/carbon monoxide in the synthetic gas of output is 1.2-1.3, and wherein methane content is less than 0.1%V.To satisfy the requirement of coal system oil, guaranteed the purified synthesis gas quality.
In the present embodiment, the cyclonic separator 2 that is adopted, pure oxygen oxidized still 3, cold shock equipment and/or waste heat boiler 5, washing are or/and the low temperature washing device for methanol of cyclonic separator 6, bypass regulating device 71, sulfur-resisting transformation device 72, spray wash-out equipment 8, refining plant 9 or pressure-swing absorption apparatus, sulfur recovery unit 11a, essence are taken off refining plant 10 and be equipment well-known to those skilled in the art, and this has not been described in detail again.
In the present embodiment, the selection of each apparatus and process parameter, this also is to realize than being easier to those skilled in the art, also is not described in detail at this.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (44)
1, lurgi gasifier outlet coal gas adds the method that pure oxygen non-catalytic partial oxidation is produced suitable hydrogen-carbon ratio synthetic gas, it is characterized in that before the raw gas that lurgi gasifier comes out carries out next procedure, increasing by an oxidizing fire step, make the raw gas oxidizing fire that comes out from lurgi gasifier, forming hydrogen/carbon monoxide ratio is 1.2-1.3, and methane content is less than the raw gas of 0.1%V.
2, method according to claim 1 is characterized in that, increased at least one and separate dust removal step before lurgi gasifier and pure zirconia combustion step.
3, method according to claim 1, it is characterized in that, described next procedure comprises that twice step that cools, purifying step, essence take off purification step, and the step that wherein once cools reclaims the raw gas that the heat formation temperature of the raw gas that the oxidizing fire step forms reduces and also removes out gas liquor; The secondary step that cools makes raw gas further reduce temperature and removes process condensate; Wherein purifying step is sloughed the gas that hydrogen sulfide is rich in regeneration.
4, method according to claim 3 is characterized in that, cools between the step at twice, and a conversion and bypass regulating step are set, and the mode of regulating with conversion and bypass is regulated the ratio of hydrogen and carbon monoxide in the raw gas once more.
5, method according to claim 3 is characterized in that, cools between the step at twice, also increases at least one secondary separation dust removal step, and the raw gas that reduces through the heat recuperation temperature is separated once more.
6, method according to claim 4 is characterized in that, is once cooling between step and conversion and the bypass regulating step, also increases at least one secondary separation dust removal step, and the raw gas that reduces through the heat recuperation temperature is separated once more.
7, method according to claim 3 is characterized in that, also connects a sulfur recovery step after described purifying step, and the gas of hydrogen sulfide is rich in the regeneration that the reception refining plant is sloughed, as producing sulphur or vitriolic unstripped gas.
8, method according to claim 2 is characterized in that, adopts the mode of cyclonic separation dedusting or dust removal by filtration to separate dedusting in the described separation dust removal step.
9, method according to claim 1 is characterized in that, in the described oxidizing fire step, adopts pure oxygen non-catalytic incendiary mode to carry out oxidizing fire.
10, method according to claim 3, it is characterized in that, in the described step that once cools, the mode of pressure and/or low-pressure steam reclaims the heat of described raw gas in employing cold shock and/or the waste heat boiler by-product, and the gas liquor gas delivery water sepn and the treatment system of removing are handled; Secondary cools in the step, adopts spray refrigerative mode to lower the temperature.
11, according to claim 5 or 6 described methods, it is characterized in that, in described secondary separation dust removal step, adopt washing or/and the mode of cyclonic separation is separated dedusting.
12, method according to claim 4 is characterized in that, adopts the sulfur-resisting transformation part that raw gas is carried out the part conversion in described conversion and bypass regulating step.
13, method according to claim 3 is characterized in that, described purifying step is made up of desulfurization and decarburization two portions, is rich in the gas of hydrogen sulfide with the regeneration of sloughing, as producing sulphur or vitriolic unstripped gas.
14, method according to claim 13 is characterized in that, described desulfurization and decarburization adopts low-temperature rectisol or/and the transformation suction type carries out desulfurization and decarburization.
15, method according to claim 13 is characterized in that, described desulfurization and decarburization adopts low-temperature rectisol and transformation absorption parallel way to carry out desulfurization and decarburization.
16, the employed lurgi gasifier outlet of a kind of the method for claim 1 coal gas adds the system that pure oxygen non-catalytic partial oxidation is produced suitable hydrogen-carbon ratio synthetic gas, it is characterized in that, between the device of existing lurgi gasifier and next procedure, increase by an oxidized still, make the raw gas that comes out from lurgi gasifier oxidized still, carry out oxidizing fire, forming hydrogen/carbon monoxide ratio is 1.2-1.3, and methane content is less than the raw gas of 0.1%V.
17, system according to claim 16 is characterized in that, described oxidized still is the pure oxygen oxidized still.
18, system according to claim 16 is characterized in that, also is provided with at least one and separates cleaning apparatus between lurgi gasifier and oxidized still.
19, system according to claim 18, it is characterized in that, described separation cleaning apparatus has inlet mouth and air outlet, inlet mouth links to each other with the raw gas outlet of lurgi gasifier, export the raw gas of output with the raw gas of accepting lurgi gasifier, the raw gas that enters is carried out dedusting separate, the raw gas after dedusting separates is transported to oxidized still by the air outlet.
20, system according to claim 16, it is characterized in that, the device of described next procedure comprises twice cooling device, refining plant, essence and takes off refining plant, wherein a cooling device is connected with oxidized still, the secondary cooling device is connected with a cooling device, refining plant is connected with the secondary cooling device, essence is taken off refining plant and is connected with refining plant, wherein cooling device is accepted raw gas that oxidized still comes and to its cooling, cooled gas liquor discharging; The raw gas that reduces through the heat recuperation temperature outputs to the secondary cooling device by the air outlet and cools off once more, and the cooled raw gas of secondary is transported to refining plant and purifies, the gas liquor discharging that cooling forms; Refining plant purifies raw gas, purifies raw gas later and is transported to essence and takes off refining plant and carry out essence and take off refining; Final formation hydrogen and the suitable synthetic gas of carbon monoxide ratio are transported to down the road synthesis procedure.
21, system according to claim 20 is characterized in that, between twice cooling device, a conversion and bypass regulating device is set.
22, system according to claim 21 is characterized in that, comprises a sulfur-resisting transformation device in described conversion and the bypass regulating device.
23, system according to claim 20 is characterized in that, between twice cooling device, also increases at least one secondary separation cleaning apparatus, and the raw gas that reduces through the heat recuperation temperature is separated once more.
24, system according to claim 21 is characterized in that, also increases at least one secondary separation cleaning apparatus between cooling device and conversion and bypass regulating device, and the raw gas that reduces through the heat recuperation temperature is separated once more.
25, system according to claim 20 is characterized in that, connects a sulfur recovery unit on described refining plant, and the gas of hydrogen sulfide is rich in the regeneration that the reception refining plant is sloughed, as producing sulphur or vitriolic unstripped gas.
26, system according to claim 19 is characterized in that, also comprises an air separation facility, and this air separation facility is connected with oxidized still with lurgi gasifier, provides pure oxygen to lurgi gasifier and oxidized still.
27, system according to claim 24, it is characterized in that, a described cooling device has one and reclaims mouth, air outlet and gas liquor discharge outlet, reclaiming mouth links to each other with the air outlet of oxidized still, to accept raw gas that oxidized still comes and to its cooling, cooled gas liquor is discharged by the gas liquor discharge outlet; Export by the air outlet through the raw gas that the heat recuperation temperature reduces.
28, according to claim 23 or 24 described systems, it is characterized in that, described secondary separation cleaning apparatus has inlet mouth and air outlet, this inlet mouth links to each other with the air outlet of a last device, wash once more and separate with the raw gas accepting raw gas or reduce through the heat recuperation temperature and to it, the air outlet links to each other with next device, is transported to conversion and bypass regulating device with the raw gas after will separating and carries out conversion and adjusting or secondary cooling device and cool off once more.
29, system according to claim 28 is characterized in that, a described last device is oxidized still or a cooling device.
30, system according to claim 28 is characterized in that, described next device is conversion and bypass regulating device or secondary cooling device.
31, system according to claim 20, it is characterized in that, described secondary cooling device has an inlet mouth, an air outlet and a gas liquor discharge outlet, its inlet mouth links to each other with a last device, to accept the suitable raw gas of hydrogen and carbon monoxide ratio and it cooled off once more, cooled raw gas is discharged by the air outlet, and the gas liquor that cooling forms is discharged by the gas liquor discharge outlet.
32, system according to claim 31 is characterized in that, a described last device is cooling device or conversion and bypass regulating device.
33, system according to claim 20, it is characterized in that, described refining plant has an inlet mouth and two fens gas ports, its inlet mouth links to each other with the air outlet of secondary cooling device, to accept cooled hydrogen and the suitable raw gas of carbon monoxide ratio, the gas of hydrogen sulfide is rich in a branch gas port output regeneration, hydrogen and the suitable raw gas of carbon monoxide ratio that another minute gas port output is handled through desulfurization and decarburization.
34, system according to claim 20, it is characterized in that, described essence is taken off refining plant and is had inlet mouth and air outlet, inlet mouth links to each other with another minute gas port of refining plant, to accept the suitable raw gas of the hydrogen handled through desulfurization and decarburization and carbon monoxide ratio and it to be carried out essence take off refiningly, essence is taken off hydrogen and the suitable synthetic gas of carbon monoxide ratio that refining back forms and is transported to down the road synthesis procedure by the air outlet.
35, system according to claim 25, it is characterized in that, described sulfur recovery unit has one and reclaims a mouth and a discharge outlet, reclaiming mouth links to each other with a branch gas port of refining plant, be rich in the gas of hydrogen sulfide and it is reclaimed to accept regeneration, the gas that hydrogen sulfide is rich in the regeneration of recovery is produced sulphur or sulfuric acid by discharge outlet to sulphur or sulfuric acid device for making.
36, system according to claim 26, it is characterized in that, described air separation facility has a gas inlet and pure oxygen delivery port, air is entered by gas inlet, the pure oxygen delivery port is divided into two-way, one the tunnel is connected with the import of lurgi gasifier pure oxygen, and another road links to each other with the shower nozzle mixing tank of oxidized still, provides pure oxygen to lurgi gasifier and oxidized still respectively.
37, system according to claim 18 is characterized in that, described flash liberation cleaning apparatus is a cyclonic separator.
38, system according to claim 17 is characterized in that, the shower nozzle mixing tank in the described oxidized still replaces with burner.
39, system according to claim 21 is characterized in that, a described cooling device is cold shock equipment and/or waste heat boiler.
40, system according to claim 23 is characterized in that, described secondary separation cleaning apparatus is for washing or/and cyclonic separator.
41, system according to claim 21 is characterized in that, described secondary cooling device is that air cooler is or/and water cooler equipment.
42, system according to claim 21 is characterized in that, described refining plant is made up of desulfurization and decarburization two portions.
According to the described system of claim 42, it is characterized in that 43, described refining plant is that low temperature washing device for methanol is or/and pressure-swing absorption apparatus.
44, according to the described system of claim 43, it is characterized in that a pressure-swing absorption apparatus in parallel on the low temperature washing device for methanol of described refining plant.
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| CN102443440A (en) * | 2010-10-15 | 2012-05-09 | 中国石油化工股份有限公司 | Stationary bed pressurizing and gasifying device for preparing synthesis gas |
| CN102443439A (en) * | 2010-10-15 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing synthetic gas by gasifying on fixed bed under increased pressure |
| CN102320568A (en) * | 2011-08-25 | 2012-01-18 | 上海泽玛克敏达机械设备有限公司 | Method and device for preparing synthetic gas or hydrogen with BGL pressuring slag gasification and pure oxygen non-catalytic partial oxidation |
| CN103031154A (en) * | 2011-09-30 | 2013-04-10 | 上海国际化建工程咨询公司 | Method and device for preparing synthesis gas or hydrogen by direct connection of non-catalytic partial oxidation furnace with BGL gasifier or crushed coal pressurized slag gasifier |
| EP3018094A1 (en) | 2014-11-06 | 2016-05-11 | Casale SA | Process for producing a synthesis gas |
| FR3041336B1 (en) * | 2015-09-18 | 2017-09-01 | Air Liquide | PROCESS AND APPARATUS FOR PRODUCING A MIXTURE OF CARBON MONOXIDE AND HYDROGEN |
| CN113526465B (en) * | 2021-08-06 | 2022-11-08 | 西南大学 | Method for preparing synthesis gas by combining non-catalytic partial oxidation of natural gas with reforming of carbon dioxide |
| CN114110424B (en) * | 2021-11-26 | 2023-09-01 | 鲁西化工集团股份有限公司煤化工二分公司 | Optimizing resource to prepare synthetic gas (CO: H) 2 =1:1) system and process |
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