CN103074122A - Semi-coke coal gas wet desulfurization process comprising procedure of front detarring - Google Patents
Semi-coke coal gas wet desulfurization process comprising procedure of front detarring Download PDFInfo
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Abstract
The invention discloses a semi-coke coal gas wet desulfurization process comprising a procedure of front detarring. During the conventional wet desulfurization, coal gas is directly processed in a procedure of wet desulfurization after a procedure of electric tar trapping, such as a procedure of PDS aqueous solution desulfurization, production indicates that a desulfurization solvent deteriorates and generates a large amount of discharged waste liquor, the quality of foam sulfur generated during the regeneration of the desulfurization solvent is poor, and the quality of sulfur formed via hot melt is also poor, as a result, the sale price is low. Compared with the process of the conventional wet desulfurization, a procedure of deep detarring is increased between the produce of electric tar trapping and the procedure of wet desulfurization in the process disclosed by the invention, for example, the tar in the coal gas is removed by adopting a PSA technique, so that the content of the tar in the coal gas of the desulfurization raw material is reduced, the effect of the operation during the wet desulfurization is ameliorated, and the quality of the sulfur generated during the regeneration of the solvent is improved. The process is particularly suitable for the PDS wet desulfurization during preparing the semi-coke coal gas by adopting an internally heated coal dry distillation method.
Description
Technical field
The present invention relates to a kind of blue charcoal gas wet sulfur removal technology that uses preposition detar step, the present invention compares with conventional process of wet desulphurization between electrically trapped tar oil step and wet desulphurization step and to increase degree of depth detar step to use PSA or TSA technology to remove coal gas coal-tar middle oil, reduce the coal-tar middle oil content of desulfurization material coal gas, for gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed, the effect of the quality of the sulphur cream that have the desulfurization solvent quality of improving process of wet desulphurization, improves the generation of solvent reclamation process.
Background technology
In the high-temperature coking technique of metallurgy industry, usually behind the electrically trapped tar oil in the coal gas benzene content higher, coal gas enters process of wet desulphurization such as PDS aqueous solution sweetening process behind the electrically trapped tar oil after taking off the benzene operation, de-benzene process can be learnt from the listed publication of table 1, mention with active carbon adsorption and reclaim benzene.De-benzene process has the coal gas of purification function simultaneously.
The publication of table 1 record coal gas de-benzene process
The internal heat type of generation coal gas or external-heat retort process are such as the blue charcoal process of coal system at present, when benzene content in the coal gas behind the electrically trapped tar oil is low, usually directly enter " gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed " such as PDS aqueous solution sweetening process as the depriving hydrogen sulphide unstripped gas, production shows a large amount of discharging any waste liquors of the rotten generation of desulfurization solvent, the foam sulphur that the solvent reclamation process produces is of poor quality, sulfur melting kettle product sulphur is of poor quality, and selling price is low or be difficult to sell.The reason that this situation occurs is to contain a certain amount of tar component behind the electrically trapped tar oil in the coal gas, the part of these tar components enters into solution at process of wet desulphurization such as PDS aqueous solution sweetening process, and part has entered in the foam sulphur in the atmospheric oxidation process of PDS rich solvent, the long-term operation result of full scale plant is: on the one hand, the tar that accumulates in the solvent is more and more, in order to keep the desulfuration solution quality, have to efflux part solution and realize the impurity discharging; On the other hand, the foam sulphur sulfur melting kettle product sulphur that causes of poor quality is of poor quality.In order to address the above problem, the present invention proposes to adopt PSA or TSA technique to remove the method for tar purifying process of wet desulphurization unstripped gas, from high-temperature coking coal gas take off benzene take reclaim benzene as purpose different, the objective of the invention is to remove tar purifying process of wet desulphurization unstripped gas, improve the process of wet desulphurization operating effect.
The method of the invention has no report.
Therefore, the present invention first purpose is to propose a kind of blue charcoal gas wet sulfur removal technology that uses preposition detar step, reduces the coal-tar middle oil content of blue charcoal gas wet sweetening process raw material coal gas.
The present invention second purpose is to propose a kind of blue charcoal gas wet sulfur removal technology that uses preposition detar step, and it is coal-tar middle oil to use PSA or TSA technology to remove coal gas.
Summary of the invention
A kind of blue charcoal gas wet sulfur removal technology that uses preposition detar step of the present invention is characterized in that comprising following steps:
1. the detar operation of coal gas behind the electrically trapped tar oil
Coal gas F100 behind the electrically trapped tar oil, by adsorbent bed, at least a portion tar component is adsorbed agent absorption, and the degree of depth detar coal gas P100 of adsorbent bed discharge uses as the process of wet desulphurization unstripped gas; In the regenerative process of sorbent material, the tar component in adsorbent bed is desorbed, and discharges adsorbent bed as stripping gas.
2. wet desulphurization operation
In the washer of desulfurization washing process, degree of depth detar coal gas P100 and desulfurization barren solution R200 counter current contact, hydrogen sulfide among the degree of depth detar coal gas P100 is desulfurized solution absorption, coal gas P200 discharges washing process after the desulfurization from washer top, and the rich desulfuration solution C200 of absorbing hydrogen sulphide discharges washing process from the washer bottom;
In rich desulfuration solution C200 regenerative process, rich desulfuration solution C200 contacts with oxygenant, is converted into desulfurization barren solution R200 and foam sulphur; Foam sulphur is converted into sulphur through sulfur melting kettle.
In order to improve the detar rate, feature of the present invention further is:
1. in the detar operation, the coal-tar middle oil content of degree of depth detar coal gas P100 usually≤20 milligrams/mark cubic meter, general≤10 milligrams/the mark cubic meter, best≤5 milligram/mark cubic meter.
In order to adapt to the subsequent technique requirement, feature of the present invention further is:
2. in the wet desulphurization operation, after the desulfurization among the coal gas P200 hydrogen sulfide content usually≤200 milligrams/mark cubic meter, general≤100 milligrams/the mark cubic meter, can≤30 milligrams/mark cubic meter.
Feature of the present invention further is:
2. wet desulphurization operation
Adopt gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed, described gas wet depriving hydrogen sulphide technique refers to: the depriving hydrogen sulphide solvent is the aqueous solution that contains solvent composition, and described solvent direct oxidation regeneration sulphur processed refers to: rich solvent and oxygen-containing gas (being generally air) directly contact finish solvent composition and regenerate in the rich solvent hydrogen sulfide be converted into sulphur (such as foam sulphur).Described gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed 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).
Working pressure scope of the present invention generally is:
1. the detar operation of coal gas behind the electrically trapped tar oil: working pressure is general≤0.3MPa (absolute pressure), usually≤0.15MPa (absolute pressure);
2. wet desulphurization operation: working pressure is general≤0.3MPa (absolute pressure), usually≤0.15MPa (absolute pressure).
Feature of the present invention further is: 1. in the detar operation, detar adsorbent reactivation mode can be any one suitable method, can select thermal regeneration, resurgent gases to be condensed and reclaim the TSA process of tar liquid, the gas that also can use coal gas following process process to produce washes regeneration, also can adopt and vacuumize parsing, stripping gas is regenerated by the mode that fluid or water liquid are captured, and can certainly be the combination of above form.
Feature of the present invention further is: blue charcoal coal gas can be the blue charcoal producer gas of internal heat type or the blue charcoal producer gas of external-heat.
Embodiment
Pressure of the present invention refers to absolute pressure.
Concentration of component of the present invention when not specializing, is weight concentration.
A kind of blue charcoal gas wet sulfur removal technology that uses preposition detar step of the present invention is characterized in that comprising following steps:
1. the detar operation of coal gas behind the electrically trapped tar oil
Coal gas F100 behind the electrically trapped tar oil, by adsorbent bed, at least a portion tar component is adsorbed agent absorption, and the degree of depth detar coal gas P100 of adsorbent bed discharge uses as the process of wet desulphurization unstripped gas; In the regenerative process of sorbent material, the tar component in adsorbent bed is desorbed, and discharges adsorbent bed as stripping gas.
2. wet desulphurization operation
In the washer of desulfurization washing process, degree of depth detar coal gas P100 and desulfurization barren solution R200 counter current contact, hydrogen sulfide among the degree of depth detar coal gas P100 is desulfurized solution absorption, coal gas P200 discharges washing process after the desulfurization from washer top, and the rich desulfuration solution C200 of absorbing hydrogen sulphide discharges washing process from the washer bottom;
In rich desulfuration solution C200 regenerative process, rich desulfuration solution C200 contacts with oxygenant, is converted into desulfurization barren solution R200 and foam sulphur; Foam sulphur is converted into sulphur through sulfur melting kettle.
In order to improve the detar rate, feature of the present invention further is:
1. in the detar operation, the coal-tar middle oil content of degree of depth detar coal gas P100 usually≤20 milligrams/mark cubic meter, general≤10 milligrams/the mark cubic meter, best≤5 milligram/mark cubic meter.
In order to adapt to the subsequent technique requirement, feature of the present invention further is:
2. in the wet desulphurization operation, after the desulfurization among the coal gas P200 hydrogen sulfide content usually≤200 milligrams/mark cubic meter, general≤100 milligrams/the mark cubic meter, can≤30 milligrams/mark cubic meter.
Feature of the present invention further is:
2. wet desulphurization operation
Adopt gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed, described gas wet depriving hydrogen sulphide technique refers to: the depriving hydrogen sulphide solvent is the aqueous solution that contains solvent composition, and described solvent direct oxidation regeneration sulphur processed refers to: rich solvent and oxygen-containing gas (being generally air) directly contact finish solvent composition and regenerate in the rich solvent hydrogen sulfide be converted into sulphur (such as foam sulphur).Described gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed 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).
Working pressure scope of the present invention generally is:
1. the detar operation of coal gas behind the electrically trapped tar oil: working pressure is general≤0.3MPa (absolute pressure), usually≤0.15MPa (absolute pressure);
2. wet desulphurization operation: working pressure is general≤0.3MPa (absolute pressure), usually≤0.15MPa (absolute pressure).
Feature of the present invention further is: 1. in the detar operation, detar adsorbent reactivation mode can be any one suitable method, can select thermal regeneration, resurgent gases to be condensed and reclaim the TSA process of tar liquid, the gas that also can use coal gas following process process to produce washes regeneration, also can adopt and vacuumize parsing, stripping gas is regenerated by the mode that fluid or water liquid are captured, and can certainly be the combination of above form.
Feature of the present invention further is: blue charcoal coal gas can be the blue charcoal producer gas of internal heat type or the blue charcoal producer gas of external-heat.
Below describe the present invention in detail.
This paper is take the blue charcoal device technique of the large-scale upright furnace of Anshan Research Inst. of Heat Energy, China Iron ﹠ Steel Group and metallurgical furnace limited liability company of Huanggang Huaxing as example explanation the present invention.Yet this can not limit Application Areas of the present invention.
This section technical process that is used for description common process " carbonization process and charring furnace thermophore cyclic part " (or being referred to as the gas making part).The qualified shove charge coal that is shipped by standby coal workshop section is at first packed in the coal groove of furnace roof topmost, packs in the coking chamber through putting coal cock and auxiliary coal bin again.Continuously to the coking chamber coal.The lump coal that adds coking chamber is mobile 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 enters coking chamber middle part, and lump coal is heated to 680～820 ℃ by 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 thermophore circulating gas is cooled to 180～250 ℃ and becomes warm charcoal, the temperature charcoal enters and puts out charcoal section (quenching section) and be cooled to about 80 ℃ by coke quenching water, after discharging continuously with the scraper plate coke feeder, falls on the dryer by chute.The gas mixture (raw gas) of the coal gas that the coal gas that coal charge produces in carbonization process, combustion chamber produce when entering the high-temp waste gas of coking chamber and cooling coke, enter pneumatic trough through upcast, bridge tube, the gas mixture about 150～200 ℃ (raw gas) is cooled to about 80 ℃ through the cyclic ammonia water sprinkling in bridge tube and pneumatic trough.The ammonia water and tar oil that cooled coal gas gets off with condensation through air suction pipe enters 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 air of upright furnace heating usefulness is supplied with by the air-blaster pressurization is rear, coal gas and air mix through burner, in horizontal quirk internal combustion, and the high-temp waste gas that burning produces, enter coking chamber by equally distributed air inlet port on the coking chamber side wall, utilize the heat of high-temp waste gas that coal charge is carried out charing.From upright furnace raw gas out, effuser be recycled ammoniacal liquor spray be cooled to 80～90 ℃ after, enter washing tower along inhaling gas pipe through gas-liquid separator; Ammoniacal liquor is by washing tower top spray, and the bottom enters heat ring tank with the ammoniacal liquor of tar; Coal gas enters direct-cooled washing tower by the bottom, is discharged by direct-cooled washing tower top and enters inter cooler, is cooled to 40～45 ℃ at inter cooler coal gas by 60～65 ℃.Coal gas enters the Root's blower pressurization behind straight a, water cooler, through behind the electrical tar precipitator as electrically trapped tar oil after coal gas use.In common process, coal gas directly enters wet desulphurization hydrogen process behind the electrically trapped tar oil.
The internal heat type of generation coal gas or external-heat retort process are such as the blue charcoal process of coal system at present, owing to benzene content in the coal gas behind the electrically trapped tar oil is lower, usually directly enter " gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed " such as PDS aqueous solution sweetening process as the depriving hydrogen sulphide unstripped gas, production shows a large amount of discharging any waste liquors of the rotten generation of desulfurization solvent, the foam sulphur that the solvent reclamation process produces is of poor quality, sulfur melting kettle product sulphur is of poor quality, and selling price is low.The reason that this situation occurs is to contain a certain amount of tar component behind the electrically trapped tar oil in the coal gas, the part of these tar components enters into solution at process of wet desulphurization such as PDS aqueous solution sweetening process, and part has entered in the foam sulphur in the atmospheric oxidation process of PDS rich solvent, the long-term operation result of full scale plant is: on the one hand, the tar that accumulates in the solvent is more and more, in order to keep the desulfuration solution quality, have to efflux part solution and realize the impurity discharging; On the other hand, the foam sulphur sulfur melting kettle product sulphur that causes of poor quality is of poor quality.
In order to address the above problem, according to the present invention, the detar operation of coal gas behind the electrically trapped tar oil is set, coal gas F100 behind the electrically trapped tar oil, by adsorbent bed, at least a portion tar component is adsorbed agent absorption, and the degree of depth detar coal gas P100 of adsorbent bed discharge uses as the process of wet desulphurization unstripped gas; In the regenerative process of sorbent material, the tar component in adsorbent bed is desorbed, and discharges adsorbent bed as stripping gas.
Below describe the sorbent material that detar operation of the present invention is used in detail.
Absorption refers to: 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 gas or the liquid of density less) is called adsorbate.Absorption can be divided into four large classes by the difference of its character, that is: chemisorption, activated adsorption, kapillary is condensing and physical adsorption.Absorption in pressure-variable adsorption (PSA) gas separation unit is mainly physical adsorption.The absorption that physical adsorption refers to rely on the molecular force (comprising Van der Waals force and electromagnetic force) between sorbent material and adsorption molecule CO2 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 the phase material that participates in adsorbing can be finished in moment, and this absorption is completely reversibility.The institute of adsorption gas separating technology process is realized it being because two essential propertys that sorbent material has in this physical adsorption: the one, and different to the adsorptive power of different components, the 2nd, the loading capacity of adsorbate on sorbent material rises with the dividing potential drop of adsorbate and increases, and descends with the rising of adsorption temp.Utilize first character of sorbent material, can realize the preferentially adsorbed of some component in the mixed gas and other component is purified; Utilize the second individual character matter of sorbent material, can realize that sorbent material adsorbs under low temperature, high pressure and under high temperature, low pressure desorption and regeneration, thereby consist of the absorption and regeneration circulation of sorbent material, reach the purpose of continuous divided gas flow.The desorption method of pressure-variable adsorption sorbent material has depressurization desorption, heating desorption and flushing desorb and combination several different methods thereof.The sorbent material that described pressure-variable adsorption is proposed the use of hydrogen process all is the solid particulate that has than bigger serface, mainly contains: activated alumina class, 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.Different sorbent materials is owing to have different pore size distributions, different specific surface area and different surface propertieies, thereby each component in the mixed gas is had different adsorptive poweies and loading capacity.For the complicated unstripped gas F of composition, usually use in actual applications multiple sorbent material, press successively layering filling composition composite adsorption bed of absorption property, to reach the separation purpose.Pressure-variable adsorption is in the situation of stable operation, and the sorbent material life-span is quite long, generally can reach 8～10 years even longer.The ability of this absorption impurity composition that has based on sorbent material far is better than the characteristic of absorption hydrogen ability, realizes the hydrogen purification among the unstripped gas F.Sorbent material is estimated the main adsorption isothermal line of measuring by experiment of the absorption property of gas, and good absorption property and larger loading capacity are the primary conditions of superior adsorbent.Simultaneously, during industrial pressure-swing absorption apparatus selected adsorbent, necessary consideration sorbent material should be large as far as possible to the separation factor of each component.So-called separation factor refers to: 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 larger, and it is easier to separate.Generally speaking, the sorbent material separation factor in the pressure-variable adsorption hydrogen purifying device should not be less than 3.In addition, in industrial pressure-swing adsorption process, also should consider contradiction between adsorption and desorption.Generally speaking, the easier then desorb of absorption is more difficult.As to strong adsorbates such as hydrogen sulfide, should select the relatively weak 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, the weak adsorbate such as CO, just should select the relatively strong sorbent material of adsorptive power such as molecular sieve, CO Special adsorbent etc., so that loading capacity is larger, 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.
The sorbent material that the detar operation is used can be any one suitable sorbent material, and commonly used is gac class sorbent material.Gac class sorbent material is the flourishing especially special-purpose activated charcoal of hole that obtains through chemical especially and thermal treatment take coal as raw material, belong to the nonpolarity sorbent material of water-resisting type, be characterized in the oxide-base that has of surface because of and inorganics impurity make surface properties show as low-pole or nonpolarity, add the king-sized internal surface area that gac has, so that gac becomes a kind of superior adsorbent that can adsorb in a large number multiple low-pole and nonpolar organic molecule, since cheap and loading capacity is larger, be a kind of sorbent material of a large amount of uses.
Below describe the programstep order of the adsorption tower that pressure-variable adsorption of the present invention partly uses in detail.
PSA of the present invention or TSA adsorption process, the number of every group of adsorption tower be 2～24 or etc. many, the tower number that is in simultaneously adsorbed state can be two or more.All pressure-variable adsorption parts, every adsorption tower all sequentially moves by the programstep of its place group, just mutually staggers on the time.The adsorption tower of each workshop section be in the tower number of adsorbed state can be identical can be not identical yet.The increase and decrease of tower number all presses number of times to change, and what of isolation step can be determined according to the concrete operations needs.
Detar operation adsorbent reactivation mode of the present invention can be any one mode, the TSA process that can select thermal regeneration, resurgent gases to be condensed into liquid and reclaim, the gas that also can use coal gas following process process to produce washes regeneration, also can adopt and vacuumize parsing, stripping gas is regenerated by the mode that fluid or water liquid are captured, and can certainly be the combination of above form.
Below describe gas wet depriving hydrogen sulphide of the present invention and solvent direct oxidation regeneration sulphur combination process processed in detail.
Wet desulphurization operation of the present invention, use gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed, stating gas wet depriving hydrogen sulphide technique refers to: the depriving hydrogen sulphide solvent is the aqueous solution that contains solvent composition, and described solvent direct oxidation regeneration sulphur processed refers to: rich solvent and oxygen-containing gas (being generally air) directly contact finish solvent composition and regenerate in the rich solvent hydrogen sulfide be converted into sulphur (such as foam sulphur).Described gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed 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 with the hydrogen sulfide in the absorption coal gas such as alkaline carbonic acid sodium, ammonia soln, it is large to have processing power, desulfurization and regeneration all can be carried out continuously, the advantages such as labour intensity is little, simultaneously also can remove prussic acid removing hydrogen sulfide, generally be adopted by domestic and international coke-oven plant.At present, the most ripe with improvement anthraquinone disulphonate method (ADA method) and " PDS+ tannin extract method " (tannin extract method).
Improvement anthraquinone disulphonate method (ADA method) desulfuration solution is by adding 2 of equal proportion in the dilute sodium carbonate solution, sodium salt solution and some other components of 6-and 2,7-anthraquinone disulfonic acid (ADA) are formulated.Have desulfuration efficiency height (can reach more than 99.5%), coal gas strong adaptability, temperature, pressure wide accommodation, doctor solution is nontoxic, equipment corrosion is little, byproduct sulphur quality advantages of higher.Be widely applied in the coke-oven plant.But the shortcomings such as its existence is stopped up easily, ADA is expensive.
The tannin extract method be improve on the basis of modified ADA method, 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 take ammoniacal liquor as absorption liquid, take PDS as catalyzer and add the promotors such as tannin extract.PDS is a kind of polymkeric substance, and its main component is binuclear phthalocyanine cobalt six ammonium sulphonates, and the H2S liquid phase oxidation reaction is had high catalytic performance, and the composition combined action such as PDS and promotor tannin extract can provide higher catalytic activity.The effect of promotor mainly is: make the easier complexing of oxygen, accelerate sulphur atom come off, have good clear tower effect.Tannin extract is the afforestation product of the preparation take the wild plant as main raw material, and it is cheap, is 1/6 of ADA.Desulfurizing tanning extract is compared with the modified ADA method, all can compare favourably on the key technical indexes such as gas purification degree, solution sulfur capacity, sulfur recovery rate.Tannin extract method typical commercial application flow process is as follows: be introduced into tubulent contact tower bottom and cat head from the raw gas (pressure-fired) of the cold bulging worker of front operation workshop section and spray the doctor solution counter current contact of getting off, thereby the continuous turbulence enlarge active surface of polypropylene pellets in the tubulent contact tower, improve desulfuration efficiency, then series connection enters two tassement polaire thionizer bottoms and cat head and sprays the doctor solution counter current contact of getting off and absorb afterwards (the complete adverse current of doctor solution and coal gas) successively, H2S content can reach below the 30 milligrams/mark cubic meter in the coal gas, delivers to follow-up worker workshop section after droplet is removed by mist 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 with solution circulated and flow to into regenerating, regenerated liquid returns the free and easy sulphur of tubulent contact tower top spray from regenerator column top, so recycle; Desulfurization lean solution from regenerator column (B) enters first thionizer (B), after this doctor solution that has absorbed H2S and HCN flow to the additional equally strong aqua of semi lean solution groove and catalyst solution, after the semi-leanpump pressurization, enter thionizer (A), 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 with the rich solution pump and flow to into regenerating, and the lean solution after the regeneration is returned the free and easy sulphur of thionizer (B) top spray from tower top, so recycle.The sulphur foam that produces in the regenerator column then flows into the sulphur foam chute certainly by regenerator column top expansion section s, 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 as follows:
1. according to the different requirements of coal gas desulfurization hydrogen precision, determine the setting of depriving hydrogen sulphide mass transfer workshop section, can adopt single tower, cascade 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; Hydrogen sulfide content in the coal gas can be taken off to≤30 milligrams/standard cubic meter;
2. tower carrying out adopted in regeneration, and pressurized air is advertised, and oxidation regeneration speed is fast, has guaranteed that the generation of sulphur foam and flotation process have enough strokes;
3. " PDS+ tannin extract " composite catalyst, catalyst activity is high, and consumption is few, and is in addition cheap, 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, technique 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 system run all right.
Because the tannin extract method possesses above-mentioned advantage, in the coal coking engineering projects project desulfurization process of design, majority adopts these techniques at present.
Gas wet depriving hydrogen sulphide of the present invention and solvent direct oxidation regeneration sulphur combination process processed are take the tannin extract method as preferred method.
Claims (13)
1. blue charcoal gas wet sulfur removal technology that uses preposition detar step is characterized in that comprising following steps:
1. the detar operation of coal gas behind electrically trapped tar oil, coal gas F100 behind the electrically trapped tar oil, by adsorbent bed, at least a portion tar component is adsorbed agent absorption, and the degree of depth detar coal gas P100 of adsorbent bed discharge uses as the process of wet desulphurization unstripped gas; In the regenerative process of sorbent material, the tar component in adsorbent bed is desorbed, and discharges adsorbent bed as stripping gas;
2. in the wet desulphurization operation, in the washer of desulfurization washing process, degree of depth detar coal gas P100 and desulfurization barren solution R200 counter current contact, hydrogen sulfide among the degree of depth detar coal gas P100 is desulfurized solution absorption, coal gas P200 discharges washing process after the desulfurization from washer top, and the rich desulfuration solution C200 of absorbing hydrogen sulphide discharges washing process from the washer bottom;
In rich desulfuration solution C200 regenerative process, rich desulfuration solution C200 contacts with oxygenant, is converted into desulfurization barren solution R200 and foam sulphur; Foam sulphur is converted into sulphur through sulfur melting kettle.
2. method according to claim 1 is characterized in that:
1. in the detar operation, the coal-tar middle oil content of degree of depth detar coal gas P100≤20 milligrams/mark cubic meter.
3. method according to claim 2 is characterized in that:
1. in the detar operation, the coal-tar middle oil content of degree of depth detar coal gas P100≤10 milligrams/mark cubic meter.
4. method according to claim 3 is characterized in that:
1. in the detar operation, the coal-tar middle oil content of degree of depth detar coal gas P100≤5 milligrams/mark cubic meter.
5. method according to claim 1 is characterized in that:
2. in the wet desulphurization operation, hydrogen sulfide content≤200 milligram among the coal gas P200/mark cubic meter after the desulfurization.
6. method according to claim 5 is characterized in that:
2. in the wet desulphurization operation, hydrogen sulfide content≤100 milligram among the coal gas P200/mark cubic meter after the desulfurization.
7. method according to claim 6 is characterized in that:
2. in the wet desulphurization operation, hydrogen sulfide content≤30 milligram among the coal gas P200/mark cubic meter after the desulfurization.
8. method according to claim 1 is characterized in that:
2. in the wet desulphurization operation, adopt gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed, described gas wet depriving hydrogen sulphide technique refers to: the depriving hydrogen sulphide solvent is the aqueous solution that contains solvent composition, and described solvent direct oxidation regeneration sulphur processed refers to: rich solvent and oxygen-containing gas (being generally air) directly contact finish solvent composition and regenerate in the rich solvent hydrogen sulfide be converted into sulphur (such as foam sulphur).
9. method according to claim 8 is characterized in that:
Described gas wet depriving hydrogen sulphide and solvent direct oxidation regeneration sulphur combination process processed are improvement anthraquinone disulphonate method (ADA method) or titanium cobalt phthalocyanine monosulfonate doctor treatment (PDS method) or " PDS+ tannin extract method " (tannin extract method).
10. method according to claim 1 is characterized in that:
1. the detar operation of coal gas: working pressure≤0.3MPa (absolute pressure) behind the electrically trapped tar oil; 2. wet desulphurization operation: working pressure≤0.3MPa (absolute pressure).
11. method according to claim 1 is characterized in that:
1. the detar operation of coal gas: working pressure≤0.15MPa (absolute pressure) behind the electrically trapped tar oil;
2. wet desulphurization operation: working pressure≤0.15MPa (absolute pressure).
12. method according to claim 1 is characterized in that:
1. in the detar operation, detar adsorbent reactivation mode is selected from following manner:
A, thermal regeneration, resurgent gases are condensed and reclaim the TSAA process of tar liquid;
B, the gas that uses coal gas following process process to produce wash regeneration;
C, employing vacuumizes parsing, stripping gas is regenerated by the mode that fluid or water liquid are captured;
The combination of d, above three kinds of reconstituted forms.
13. method according to claim 1 is characterized in that:
Blue charcoal coal gas of the present invention is the blue charcoal producer gas of internal heat type or the blue charcoal producer gas of external-heat.
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