CN103041679A - Waste gas treatment system of acid gas containing ammonia - Google Patents
Waste gas treatment system of acid gas containing ammonia Download PDFInfo
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- CN103041679A CN103041679A CN2013100145824A CN201310014582A CN103041679A CN 103041679 A CN103041679 A CN 103041679A CN 2013100145824 A CN2013100145824 A CN 2013100145824A CN 201310014582 A CN201310014582 A CN 201310014582A CN 103041679 A CN103041679 A CN 103041679A
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Abstract
The invention provides a waste gas treatment system of acid gas containing ammonia. The treatment system comprises an acid gas acid-washing ammonia removing unit, a deaminized acid gas thermal oxidation unit, a catalytic oxidation acid preparing system and a mother liquid vacuum evaporation unit, wherein sulfuric acid in the acid gas acid-washing ammonia removing unit contacts with the acid gas containing the ammonia so as to perform a deaminizing action and generate an ammonium sulfate solution and the deaminized acid gas containing hydrogen sulfide and water; the mother liquid vacuum evaporation unit is used for receiving and concentrating the ammonium sulfate solution generated by the acid gas acid-washing ammonia removing unit and pumping out the sulfuretted hydrogen dissolved in the ammonium sulfate solution to be sent into the deaminized acid gas thermal oxidation unit; the deaminized acid gas thermal oxidation unit is used for receiving the deaminized acid gas and the tail gas containing the sulfuretted hydrogen from the mother liquid vacuum evaporation unit, and carrying out a catalytic oxidation on the tail gas containing the sulfuretted hydrogen so as to generate the waste gas containing sulfur dioxide (SO2) and water vapor; the catalytic oxidation acid preparing system is used for receiving the waste gas and carrying out the catalytic oxidation on the waste gas so as to generate sulfur trioxide (SO3) and the sulfuric acid; and the sulfuric acid is supplied to the acid gas acid-washing ammonia removing unit.
Description
Technical field
The present invention relates to a kind of ammonia sour gas exhaust treatment system that contains.
Background technology
In the production processes such as petrochemical industry and Coal Chemical Industry, sulphur in the raw material and nitrogen contain ammonia, hydrogen sulfide containing sour gas through final formation of process, for the sour gas that contains ammonia and hydrogen sulfide, present processing method mainly is to adopt Crouse's recovery technology of sulfur that the hydrogen sulfide in the sour gas is changed into sulphur, and the ammonia in the sour gas at high temperature burns into N simultaneously
2And nitrogen oxide.For the less sour gas of sulfur content (general sulfur content is less than 5000 tons of sulphur/years), also can adopt complex iron to remove hydrogen sulfide, remove ammonia-containing exhaust behind the hydrogen sulfide and enter again combustion furnace and at high temperature burn, make ammonia and nitrogen oxide rear discharging up to standard in the tail gas.
The basic principle of Crouse's recovery technology of sulfur is to contain H
2The sour gas of S carries out imperfect combustion with air in combustion furnace, strictly control air capacity, makes H
2The SO that generates after the S burning
2Amount satisfies H
2S/SO
2Molecular proportion equals or near 2, H
2S and SO
2Reaction generting element sulphur is subjected to the restriction of thermodynamic condition, remaining H under high temperature, catalyst
2S and SO
2Enter catalyst reaction section under the effect of catalyst, continue reaction generting element sulphur.The elementary sulfur that generates is through condensation separation.
The chemical equation of reaction is as follows:
H
2S+3/2O
2---SO
2+H
2O
2H
2S+SO
2---3/2S
2+2H
2O
In petrochemical industry and Coal Chemical Industry actual production process, because the difference of sulphur, nitrogen content in the raw material, desulphurization technological process is different, concentration of hydrogen sulfide just differs in the sour gas that produces, according to the difference of hydrogen sulfide content in the sour gas, claus process can adopt shunting and direct current method (partial combustion process), the general sour gas that contains than low in hydrogen sulphide concentration (usually concentration of hydrogen sulfide 15 ~ 40%) of processing of shunting, be that sour gas with about 1/3 tolerance burns in sulphur stove processed, make H wherein
2S all burns till SO
2, other 2/3 sour gas is without burning, directly behind sulphur stove processed with SO
2Mix, and claus reaction generation sulphur occurs under catalyst action subsequently.Shunting requires not contain the impurity such as ammonia and hydrocarbon in the sour gas, if contain the impurity such as ammonia and hydrocarbon then should not adopt shunting.
For containing sour gas than high hydrogen sulfide concentration (concentration of hydrogen sulfide is greater than 40% usually), generally adopt direct current method, direct current method is that whole sour gas all enter sulphur stove processed, the oxygen amount that strict control combustion is required makes 1/3 Oxidation of Hydrogen Sulfide become SO
2, then, SO
2With remaining hydrogen sulfide generation claus reaction, generate sulphur.Series reaction then can occur in the ammonia in the sour gas in sulphur stove processed, the key reaction relevant with ammonia is as follows:
2NH
3+3/2
2---3H
2O+N
2
2NH
3---N
2+3H
2
2NH
3+SO
2---N
2+H
2S+2H
2O
2NH
3+5/2O
2---3H
2O+2NO
NO+1/2O
2---NO
2
NO
2+SO
2---NO+SO
3
In these reactions, the decomposition reaction of ammonia needs sufficiently high reaction temperature, and the decomposition temperature of ammonia is more than at least 1250 ℃.In addition, in the direct current method technique, burner for producing sulfur is to move under anoxia condition, but will make the NO of ammonia completing combustion and generation
xMinimum, then the oxygen that adopt little excessive more, and it is contradiction that this air distribution with claus process requires, and therefore, if ammonia content surpasses finite concentration in the sour gas, meeting cause NO because of anoxic and the low ammonia incomplete combustion that makes of reaction temperature
XExceed standard and the operational issue such as ammonium salt sedimentation.And, because the burning of ammonia needs oxygen consumed, the N that brings into oxygen
2, water etc. reduced the rate of recovery of sulphur.
In a word, contain the sour gas of ammonia for low in hydrogen sulphide concentration, height, when adopting Claus unit sulfur recovery unit, the sour gas burning furnace temperature is low, not only affects sulfur recovery rate, and ammonia decomposes not exclusively simultaneously; For ammonia is decomposed fully, need to improve furnace temperature, certainly will in the raw material sour gas, add fuel gas, increase so on the one hand energy consumption, on the other hand in practical operation, often because fuel gas incomplete combustion under anaerobic environment easily causes black sulphur.Therefore, Claus unit sulfur recovery unit and be not suitable for processing and contain the higher sour gas of ammonia.
The basic principle that complex iron removes hydrogen sulfide is: in liquid medium, adopt the iron ion complex compound as catalyst, hydrogen sulfide directly changes into elementary sulfur at normal temperatures, forms several microns to tens microns drusen.Simultaneously, iron ion catalyst is reduced into ferrous ion, and used catalyst recycles after regenerating with air oxidation.The solid sulfur that generates forms the sulphur cake of sulfur-bearing about 60% after sedimentation, filtration.
When adopting the complex iron processing to contain the ammonia sour gas, equally need to be to NH in the feeding gas
3Content control too high NH
3Content can cause drusen tiny, and effect of settling is poor, the filtering means dehydration difficulty.The sulphur that generates in the course of reaction can't be deviate from system, finally causes system normally to move, and tail gas also must adopt special combustion furnace to burn, and energy consumption is very high.Therefore, complex iron hydrogen sulfide stripping technique is not suitable for containing the higher Acidic Gas Treating of ammonia equally.
Summary of the invention
In view of the present the problems referred to above that exist in the propylhomoserin gas disposal technique that contain, the objective of the invention is to propose a kind of ammonia sour gas exhaust treatment system that contains, can effectively process and contain ammonia and sulfur-containing compound in the sour gas, make it all obtain the recycling of resource, simultaneously, satisfy strict discharge standard, operating flexibility is good.
The invention provides a kind of ammonia sour gas exhaust treatment system that contains, it comprises the sour gas pickling that connects in turn except ammonia unit, deamination sour gas thermal oxidation units, and catalytic oxidation relieving haperacidity unit; The described ammonia sour gas exhaust treatment system that contains also comprises mother liquor vacuum evaporation unit, and it is connected in described sour gas pickling except between ammonia unit and the described deamination sour gas thermal oxidation units; Described sour gas pickling contains the ammonia sour gas except the ammonia unit for receiving, and described sour gas pickling is used for contacting with deamination with containing the ammonia sour gas except the sulfuric acid in the ammonia unit, and generates ammonium sulfate and the deamination sour gas that contains hydrogen sulfide and water; Described mother liquor vacuum evaporation unit is used for reception and concentrated described sour gas pickling removes the ammonium sulfate that the ammonia unit produces, and described deamination sour gas thermal oxidation units is delivered in the hydrogen sulfide extraction that will be dissolved in the ammonium sulfate; The hydrogen sulfide-containing tail gas that described deamination sour gas thermal oxidation units be used for to receive the deamination sour gas and comes from mother liquor vacuum evaporation unit, and it is carried out thermal oxide generate and contain SO
2Waste gas with steam; Described catalytic oxidation relieving haperacidity unit is used for receiving described waste gas, it is carried out catalytic oxidation generate SO
3, and forming sulfuric acid, described sulfuric acid is supplied to described sour gas pickling except the ammonia unit, is used for deamination.
Wherein, the molten sulfur feeding unit of described deamination sour gas thermal oxidation units, described molten sulfur feeding unit are used to described deamination sour gas thermal oxidation units that molten sulfur is provided; The described ammonia sour gas exhaust treatment system that contains also comprises sulfuric acid cooling and the supply unit that is connected in described catalytic oxidation relieving haperacidity unit, and described sulfuric acid cooling and supply unit are used for the sulfuric acid cooling that described catalytic oxidation relieving haperacidity unit is produced and are transported to described sour gas pickling except the ammonia unit.
Wherein, described sour gas pickling comprises pickling tower, mother liquor tank, circulated sprinkling pump and cooler except the ammonia unit, described pickling tower gets off the ammonia stripping in the charging sour gas with sulfuric acid, and change into ammonium sulfate, described mother liquor tank is used for sulfuric acid and the ammonium sulfate mixed solution that collection is got off from the overhead streams of described pickling tower, described circulated sprinkling pump is used for the mixed solution in the described mother liquor tank is recycled to the distributor of described pickling top of tower, described cooler is used for cool cycles solution, takes out in the diluting concentrated sulfuric acid process and the heat in sulfuric acid and the ammonia react process.
Wherein, described mother liquor vacuum evaporation unit comprises cold boiler and vavuum pump, described cold boiler is used for receiving the ammonium sulfate liquor from described mother liquor tank, in the described cold boiler agitator is set, skin arranges steam jacket, use low-pressure steam that ammonium sulfate liquor is carried out evaporation and concentration, described vavuum pump is used to described cold boiler that needed vacuum is provided, and described deamination sour gas thermal oxidation units is delivered in the hydrogen sulfide extraction that will be dissolved in the ammonium sulfate.Between described cold boiler and the described mother liquor tank connecting line and flow regulator are set, described flow regulator can be regulated the flow of the ammonium sulfate liquor that enters described cold boiler, the bottom of described cold boiler arranges flow regulator, and described flow regulator can be regulated the flow of the ammonium sulfate concentrate of discharging cold boiler.
Wherein, described deamination sour gas thermal oxidation units comprises combustion furnace, described combustion furnace comprises air inlet, and combustion chamber, and described deamination sour gas, the hydrogen sulfide containing tail gas from described cold boiler, described molten sulfur and combustion air enter in the described combustion chamber mixed combustion to generate SO from four air inlets respectively
2And steam.
Wherein, described catalytic oxidation relieving haperacidity unit comprises reactor and acid-producing apparatus, is provided with catalyst bed in the described reactor, in catalyst bed, and the SO in the burnt gas that described combustion furnace produces
2And O
2Reaction generates SO
3, having set gradually from bottom to up two-stage glass tube condenser, blower fan, demister and fume extractor in the described acid-producing apparatus, described acid-producing apparatus is used for receiving the SO that contains from described reactor
3With the waste gas of steam, described two-stage glass tube condenser is used for will be from the SO of the waste gas of described reactor
3Be combined into sulfuric acid with water condensation, described blower fan is used to the waste gas cooling of described acid-producing apparatus that cooling-air is provided, and described demister is used for removing the residue acid mist of described acid-producing apparatus, and residual gas is discharged by described fume extractor.
Wherein, described sulfuric acid cooling and supply unit comprise sulfuric acid storage tank, coolant circulation pump, sulfuric acid cooler and sulfuric acid delivery pump, store cold acid in the described sulfuric acid storage tank, by the sulfuric acid of input duct reception from described acid-producing apparatus, mix with cold acid, and mixed sulfuric acid is transported to described pickling tower by the fluid pipeline, described sulfuric acid cooler is used for the sulfuric acid cooling with described sulfuric acid storage tank, described coolant circulation pump provides power for the circulation of the sulfuric acid in the described sulfuric acid storage tank, between described sulfuric acid delivery pump and the described pickling tower flow regulator is set, described flow regulator can be regulated the flow that is transported to the sulfuric acid stream of described pickling tower from described sulfuric acid storage tank.
Wherein, described molten sulfur feeding unit comprises molten sulfur pond, liquid sulfur pump and heater, and described molten sulfur pond is used for storing molten sulfur, and described liquid sulfur pump is used for providing described molten sulfur to described combustion furnace, and described heater is used for the solid sulfur melting and remains on suitable temperature.
Wherein, described pickling tower, mother liquor tank, circulated sprinkling pump and cooler are the formations that one-level consists of or two-stage is above.
Wherein, described reactor and acid-producing apparatus are the formations that one-level consists of or two-stage is above.
According to the ammonia sour gas exhaust treatment system that contains of the present invention, because sour gas is taked in advance sulfuric acid scrubbing to remove the ammonia in the sour gas and is generated ammonium sulfate, then remaining sour gas is carried out thermal oxide and catalytic oxidation sulfuric acid processed, and the sulfuric acid of producing is used for the ammonia stripping of front end.Therefore, exhaust treatment system of the present invention has all carried out the recovery of resource to ammonia and the sulfide that contains in the ammonia sour gas, and the tail gas after the processing satisfies discharge standard, and does not have discharging of waste liquid in the system.
Mother liquor vacuum evaporation unit is extracted the hydrogen sulfide that dissolves in the ammonium sulfate out in Vacuum Evaporation Process, and enters combustion furnace with sour gas and burn and then to make sulfuric acid, has farthest controlled extra toxic emission; In addition, also the molten sulfur feeding unit can be set, when the sulfuric acid of producing by sour gas is not enough, adopt burning sulphur to replenish, improve treatment effeciency, make more balance of whole system.
Description of drawings
Fig. 1 is the schematic diagram that expression the present invention contains ammonia sour gas exhaust treatment system one embodiment.
The specific embodiment
Below, the present invention will be described in detail by reference to the accompanying drawings.
As shown in Figure 1, in one embodiment of the invention, contain ammonia sour gas exhaust treatment system and comprise that the sour gas pickling is except ammonia unit, deamination sour gas thermal oxidation units, catalytic oxidation relieving haperacidity unit, mother liquor vacuum evaporation unit, sulfuric acid cooling and supply unit and molten sulfur feeding unit.
The sour gas pickling comprises except the ammonia unit: pickling tower 1, mother liquor tank 2, circulated sprinkling pump 3 and cooler 4.From the sour gas A that the outside is come, comprise certain density ammonia and hydrogen sulfide, enter pickling tower 1 from the bottom air inlet of pickling tower 1, sour gas A is in the 1 interior rising of pickling tower, with spray the sulfuric acid solution counter current contacting of getting off from tower distributor D, ammonia among the sour gas A and sulfuric acid generation chemical reaction also generate ammonium sulfate, removed the sour gas of ammonia, be called for short deamination sour gas 5 and enter follow-up deamination sour gas thermal oxidation units processing from the cat head outflow.The mother liquor of liquid containing ammonium sulfate flows under the influence of gravity into the mother liquor tank 2 of pickling tower bottom, circulated sprinkling pump 3 is extracted the distributor D that mother liquor turns back to the pickling column overhead out from mother liquor tank 2, and cool off by 4 pairs of circulation solutions of the cooler on the circulation line, to take out in the sulfuric acid dilution and the heat in ammonia and the sulfuric acid reaction process, keep the proper temperature of mother liquor.Distributor D makes circulating mother liquor in the 1 interior even distribution of pickling tower, comes from the fresh sulfuric acid 33 of sulfuric acid cooling and supply unit, and the pipeline that enters between cooler 4 and the distributor D adds to the sour gas pickling except the ammonia unit.The water that is used for dilute sulphuric acid replenishes from mother liquor tank 2.
Among Fig. 1, the sour gas pickling is adopted the one-level pickling except the ammonia unit, and namely described pickling tower 1, mother liquor tank 2, circulated sprinkling pump 3 and cooler 4 are that one-level consists of, but are not limited to these, can according to the ammonia content among the sour gas A, adopt the above pickling of secondary.When adopting the two-stage pickling, sour gas A is successively by firsts and seconds pickling tower, and the sulfuric acid that replenishes then at first enters secondary pickling tower, then the alternative fresh sulfuric acid of the mother liquor of part secondary pickling tower is added to one-level pickling tower.
Above-mentioned pickling tower, mother liquor tank, circulated sprinkling pump, cooler are not particularly limited, and can adopt same category of device well known in the art.The pickling tower can adopt packed tower, also can adopt empty spray tower, and pickling tower and mother liquor tank can manufacture one, also can separately build, and this is not particularly limited.
A part of mother liquor in the mother liquor tank enters mother liquor vacuum evaporation unit.Mother liquor vacuum evaporation unit comprises cold boiler 7 and vavuum pump 8, mother liquor enters cold boiler 7 under the effect of vacuum, cold boiler 7 is closed containers of an inner belt stirrer and external belt steam jacket, cold boiler 7 links to each other with vavuum pump 8 by pipeline, vavuum pump 8 provides necessary vacuum for cold boiler 7, stirring at agitator, under the acting in conjunction that Steam Heating and vavuum pump 8 vacuumize, a part of water in the mother liquor and a small amount of hydrogen sulfide that is dissolved in the mother liquor are evaporated from mother liquor, are delivered to deamination sour gas thermal oxidation units by vavuum pump 8.In mother liquor vacuum evaporation unit, mother liquor is purified and concentrates, and discharges from the bottom of cold boiler 7 with finite concentration as required, to sell with solid product after fluid sulphuric acid ammonium production marketing or the further crystallization.The mother liquid flow rate that enters mother liquor vacuum evaporation unit is regulated by flow regulator 6, discharges the flow of cold boiler 7 and is regulated by flow regulator 35, and flow regulator 6 and 35 is control valve in the present embodiment.
Enter deamination sour gas thermal oxidation units from the deamination sour gas 5 that contains hydrogen sulfide and water of pickling tower 1 cat head with from the tail gas that contains equally hydrogen sulfide and water vapour 9 of cold boiler 7.Deamination sour gas thermal oxidation units comprises combustion furnace 10.Combustion furnace 10 comprises air inlet and combustion chamber, as shown in Figure 1, from the deamination sour gas 5 of pickling tower 1 cat head, from the tail gas 9 of cold boiler 7, come the combustion air 12 of autocatalyzed oxidation relieving haperacidity unit and enter combustion chamber mixed combustion from four air inlets respectively from the molten sulfur 14 of molten sulfur feeding unit, carry out following reaction and generate SO
2:
H
2S+3/2O
2--SO
2+H
2O
Wherein, the molten sulfur feeding unit comprises molten sulfur pond 36, liquid sulfur pump 13 and heater 34, molten sulfur pond 36 is used for storing molten sulfur, liquid sulfur pump 13 is used for providing molten sulfur 14 to combustion furnace 10, the heater 34 general steam pipe coils that adopt, with the low-pressure steam heating, make the solid sulfur melting, and molten sulfur temperature in the molten sulfur pond is maintained at about 130～150 ℃.Above-mentioned molten sulfur pond, liquid sulfur pump and heater are not particularly limited, and can adopt same category of device well known in the art.Very few when the sulfuric acid amount of producing by sour gas, be not enough to charging sour gas A in the ammonia complete reaction time, the molten sulfur feeding unit replenishes molten sulfurs 14 to combustion furnace 10.Molten sulfur 14 carries out following reaction at combustion furnace 10 and generates SO
2:
S+O
2--SO
2
Therefore, the sulfide from the tail gas 11 that discharge the gas outlet of combustion furnace 10 mainly is SO
2Form, and contain O
2And water.Tail gas 11 enters catalytic oxidation relieving haperacidity unit subsequently.
Above-mentioned combustion furnace is not had special restriction, can adopt combustion furnace well known in the art, the air inlet quantity of combustion furnace can be set as required.About 800～1000 ℃ of ignition temperature, simultaneously, combustion furnace should provide the sufficient time of staying, and the oxygen in the combustion air should be excessive, in order to can become SO to sulphur and sulphides burn
2, the incendivity thing other burns into CO such as hydrocarbon, hydrogen and CO
2And water, and can be with SO in follow-up catalytic oxidation relieving haperacidity unit
2All be oxidized to SO
3
Catalytic oxidation relieving haperacidity unit comprises reactor 15 and acid-producing apparatus 20, and 15 of reactors are as enclosed construction.Heat exchanger 16, catalyst bed 17 and cooler 18 have been set gradually from top to bottom in the reactor 15, heat exchanger 16 is used for the adjustment of the tail gas 11 of combustion furnace 10 generations is arrived the optimal reaction temperature of catalyst, under the catalytic action of catalyst bed 17, the SO in the combustion tail gas 11
2Generate SO with the oxygen reaction
3And release reaction heat, cooler 18 takes out reaction heat, and temperature is cooled to 260 ~ 280 ℃.
Catalyst in the above-mentioned catalyst bed is not particularly limited, as long as can be with SO
2Catalytic Oxygen changes into SO
3Get final product, for example can select Pt or V
2O
5Deng, but preferred honeycomb Pt coated catalysts, the Pt catalyst has lower initial reaction temperature, and its optimal reaction temperature interval is also than V
2O
5Low, therefore, for from SO
2To SO
3Exothermic reaction, the conversion ratio of Pt catalyst is higher, honeycomb is conducive to provide larger contact surface and the less pressure loss.When using the Pt coated catalysts, the temperature in the reactor is controlled at 350 ~ 400 ℃.Also without particular determination, can adopt heat exchanger well known in the art to above-mentioned heat exchanger.
The SO that contains from reactor 15 outflows
3Enter subsequently acid-producing apparatus 20 with the waste gas 19 of steam.Distribution apparatus G, two-stage glass tube condenser 21 and 22, blower fan 23 and 24, demister 25 and fume extractor 26 have been set gradually from bottom to up in the acid-producing apparatus 20.Waste gas 19 passes into from the below of acid-producing apparatus 20, enters distribution apparatus G, so that gas uniform disperses, temperature is down to about 80 ° of C the SO in the waste gas 19 after condenser 21 and 22 coolings
3The condensation of being combined with water becomes sulfuric acid 27, the cooling medium of waste gas 19 is the air that provided by blower fan 23 and 24 respectively, sulfuric acid 27 flows out acid-producing apparatus 20 afterwards under Action of Gravity Field under condensation on glass tube condenser 21 and 22, to enter follow-up sulfuric acid cooling and supply unit.Residue acid mist in the waste gas 19 is removed by electrostatic precipitator 25, then by fume extractor 26 dischargings.In the waste gas 19 of the air that blower fan 23 provides in cooling reactor, self temperature also is preheating to about 200 ℃, and it is combustion-supporting that the air that is preheated enters combustion furnace 10 as combustion air 12, and the preheating of combustion air can improve heat utilization ratio.
Among Fig. 1, be provided with first-class heat exchanger 16 and one deck catalyst bed 17 in the reactor 15, but be not limited to these, can according to the content of sulfur dioxide in the combustion tail gas 11, Multi-layer exchanging heat device and catalyst bed be set.Make combustion tail gas 11 through after which floor catalyst bed, SO
2To SO
3Conversion ratio enough high, after condensation from the tail gas of fume extractor 26 discharging SO
2Concentration can satisfy discharge standard.
Among Fig. 1, catalytic oxidation relieving haperacidity unit is first order reaction and condensation, and namely described reactor 15, acid-producing apparatus 20 are that one-level consists of, but are not limited to these, can according to the content of sulfur dioxide in the combustion tail gas 11, adopt the above reaction of secondary and condensation.
Sulfuric acid 27 enters sulfuric acid cooling and supply unit after flowing out acid-producing apparatus 20.Sulfuric acid cooling and supply unit comprise sulfuric acid storage tank 28, sulfuric acid circulating pump 29, sulfuric acid cooler 30 and sulfuric acid delivery pump 31.Store cold acid in the sulfuric acid storage tank 28, by the sulfuric acid 27 of input duct reception from acid-producing apparatus 20, mix with cold acid, and mixed sulfuric acid 33 is transported to pickling tower 1 by the fluid pipeline.Idiographic flow is: about 260 ~ 280 ℃ of the temperature of sulfuric acid 27, enter sulfuric acid storage tank 28 after, mix with cold acid in the tank.Sulfuric acid in the sulfuric acid storage tank 28 is through persulfuric acid circulating pump 29 pressurization, after sulfuric acid cooler 30 coolings, temperature by constant control at 40 ° below the C.Then use sulfuric acid delivery pump 31 that mixed sulfuric acid 33 is transported to pickling tower 1 from sulfuric acid storage tank 28, the flow that is transported to the sulfuric acid 33 of pickling tower 1 is regulated by flow regulator 32, and flow regulator 32 is control valve in the present embodiment.
Above-mentioned sulfuric acid storage tank, sulfuric acid circulating pump, sulfuric acid cooler, sulfuric acid delivery pump are not particularly limited, and can adopt same category of device well known in the art.
Certainly, above-described embodiment only is used for exemplary illustration, can be out of shape said system, for example, can omit sulfuric acid cooling and supply unit and molten sulfur feeding unit, the sulfuric acid that catalytic oxidation relieving haperacidity unit is produced directly is supplied to the sour gas pickling and carries out deamination except the ammonia unit, can effectively process equally to contain ammonia and sulfur-containing compound in the sour gas, makes it all obtain the recycling of resource.
Exhaust treatment system of the present invention, because sour gas is taked in advance sulfuric acid scrubbing to remove the ammonia in the sour gas and is generated ammonium sulfate, then remaining sour gas is carried out thermal oxide and catalytic oxidation sulfuric acid processed, and the sulfuric acid produced is used for the ammonia stripping of front end, the hydrogen sulfide that dissolves in ammonium sulfate is evaporated in Vacuum Evaporation Process, and enter combustion furnace with sour gas and burn and then to make sulfuric acid, there is not extra toxic emission, when the sulfuric acid of producing by sour gas is not enough, adopt burning sulphur to replenish, therefore, exhaust treatment system of the present invention has all carried out the recovery of resource to ammonia and the sulfide that contains in the ammonia sour gas, tail gas after the processing satisfies discharge standard, and does not have discharging of waste liquid in the system.
Below, by embodiment, further describe the embodiment of one embodiment of the invention.This embodiment is to contain ammonia sour gas exhaust-gas treatment according to following step.
The component of a, raw material sour gas and character are: H
2S content 13.27%(V), CO
2Content 0.53% (V), NH
3Content 47.1% (V), H
2O content 39.1% (V), 80 ℃ of temperature, pressure 60KPa;
B, because the ammonia content in the sour gas is higher, the sour gas pickling is adopted two-stage except the ammonia unit, sour gas at first enters first order pickling tower, the pickling tower adopts packed tower, in-built structured packing, sulfuric acid solution counter current contacting under sour gas sprays in the pickling tower and from tower distributor, ammonia in the sour gas and sulfuric acid generation chemical reaction also generate ammonium sulfate, the acid solution of liquid containing ammonium sulfate flows under the influence of gravity into mother liquor tank, the circulated sprinkling pump is extracted the distributor that mother liquor turns back to the pickling column overhead out from mother liquor tank, and by the cooler on the circulation line circulation solution is cooled off, make the temperature of mother liquor maintain about 50 ℃, the cooling medium of cooler is recirculated cooling water.The sour gas that has removed ammonia flows out from first order pickling column overhead, enters second level pickling tower and continues to process.Be 3～4% in order to keep mother liquor acidity, the mother liquor in the mother liquor tank of the second level is added to first order mother liquor tank.
C, the sour gas that flows out from first order pickling cat head enters second level pickling tower, sulfuric acid solution counter current contacting under in the pickling tower and from tower distributor, spraying equally, ammonia in the sour gas and sulfuric acid generation chemical reaction also generate ammonium sulfate, the sour gas that has removed ammonia flows out from cat head and enters follow-up deamination sour gas thermal oxidation units processing, the mother liquor of liquid containing ammonium sulfate flows under the influence of gravity into the mother liquor tank of pickling tower bottom, the circulated sprinkling pump is extracted the distributor that mother liquor turns back to the pickling column overhead out from mother liquor tank, and by the cooler on the circulation line circulation solution is cooled off, about 50 ℃ of the temperature of mother liquor, the cooling medium of cooler is recirculated cooling water.Come from the pipeline that sulfuric acid cools off and the fresh sulfuric acid of supply unit enters between cooler and the distributor and add to second level pickling tower.Mother liquor acidity about 3 ~ 4%.Deliver to first order mother liquor tank from the mother liquor that second level mother liquor tank is discharged.
A part of mother liquor in d, the first order mother liquor tank is under the control under the effect of vacuum, at flow control valve, enter cold boiler, the inner belt stirrer of cold boiler and external belt steam jacket, cold boiler is vacuumized by vavuum pump, about 70 ℃ of the temperature in the cold boiler, the about 90KPa of vacuum, 80 rev/mins of mixing speeds, under the acting in conjunction of stirring, heating and vacuum, a part of water in the mother liquor and the hydrogen sulfide that is dissolved in the mother liquor are evaporated out, and deliver to combustion furnace; Ammonium sulfate concentrations is about 60 ~ 80%(W/V) in the solution after concentrated, under the control of flow control valve, discharges from the bottom of cold boiler, directly with fluid sulphuric acid ammonium production marketing.
E, the deamination sour gas that comes from second level pickling tower, from the hydrogen sulfide-containing tail gas of cold boiler, come from the molten sulfur of molten sulfur feeding unit and the combustion air that is preheating to about 200 ℃ in follow-up catalytic oxidation relieving haperacidity unit enters the combustion furnace of deamination sour gas thermal oxidation units together, in the combustion furnace internal combustion, 800～1000 ℃ of ignition temperatures, sulphur and sulfide in sour gas, cold boiler tail gas and the molten sulfur are oxidized to SO
2The tail gas of combustion furnace enters catalytic oxidation relieving haperacidity unit extracting sulfuric acid.
F, the tail gas that flows out from combustion furnace enter catalytic oxidation relieving haperacidity unit, in order to reach higher SO2 conversion ratio, catalytic oxidation relieving haperacidity unit also adopts two-stage, the tail gas of combustion furnace at first enters first order reactor, make temperature be reduced to 350～400 ℃ by finned heat exchanger, then successively through three layers of honeycomb Pt coated catalysts bed, with SO
2Change into SO
3, and by the heat exchanger that arranges behind every layer of beds reaction heat is taken out, keep the reaction temperature in the reactor.
The tail gas of g, combustion furnace flows out from first order reactor, and temperature is controlled at about 260 ~ 280 ° of C, enters subsequently first order condenser; Behind the glass tube condenser, waste gas is cooled to 80 ℃, removes acid mist through the high-pressure electrostatic demister again, then enters second level reactor.The air of glass tube condenser cooling usefulness is supplied with by blower fan.Sulfuric acid under condensation on the glass tube condenser flows out from the condenser bottom.
After h, tail gas enter second level reactor, at first be heated to 350～400 ℃ by heat exchanger, then on honeycomb Pt coated catalysts bed, will remain SO
2Continue to be oxidized to SO
3, with heat exchanger temperature is controlled at about 260 ~ 280 ° of C again, enter subsequently second level condenser; Cool off and acid-mist-removing, sulfuric acid flows out exhaust emissions from the condenser bottom.Used catalyst, heat exchanger, condenser, blower fan, electrostatic precipitator etc. are identical with device type in first order reactor and the first order condenser in second level reactor and second level condenser.
I, the sulfuric acid that flows out from first order condenser and second level condenser enter sulfuric acid storage tank, mix with cold acid in the tank.Sulfuric acid in the sulfuric acid storage tank is through persulfuric acid circulating pump pressurization, after the sulfuric acid cooler cooling, temperature by constant control at 40 ° below the C.Then use the sulfuric acid delivery pump that sulfuric acid is transported to second level pickling tower from sulfuric acid storage tank.
J, solid sulfur is added in the molten sulfur pond, the steam pipe coil heating is set in the molten sulfur pond, with low-pressure steam solid sulfur is heated to 130～150 ℃, make sulfur melting, molten sulfur is transported to combustion furnace with liquid sulfur pump, is used for step e.
After testing, after the said system processing, the sulfuric acid concentration of discharging from condenser is 95 ~ 97%, satisfies standard GB/T/T534-2002, SO in the emission
2Concentration is 230mg/m
3, NO
xConcentration is 95mg/m
3, satisfy discharging standards.
Although described the present invention with reference to several exemplary embodiments, should be appreciated that used term is explanation and exemplary and nonrestrictive term.Because the present invention is implementation and do not break away from spirit of the present invention or essence in a variety of forms, so be to be understood that, above-described embodiment is not limited to any aforesaid details, and should be in the spirit and scope that claims limit explain widely, therefore fall into whole variations in claim or its equivalent scope and remodeling and all should be claims and contain.
Claims (10)
1. one kind contains ammonia sour gas exhaust treatment system, it is characterized in that, comprise that the sour gas pickling that connects in turn removes ammonia unit, deamination sour gas thermal oxidation units, reaches catalytic oxidation relieving haperacidity unit, the described ammonia sour gas exhaust treatment system that contains also comprises mother liquor vacuum evaporation unit, and it is connected in described sour gas pickling except between ammonia unit and the described deamination sour gas thermal oxidation units; Described sour gas pickling contains the ammonia sour gas except the ammonia unit for receiving, and described sour gas pickling is used for contacting with deamination with containing the ammonia sour gas except the sulfuric acid in the ammonia unit, and generates ammonium sulfate and the deamination sour gas (5) that contains hydrogen sulfide and water; Described mother liquor vacuum evaporation unit is used for reception and concentrated described sour gas pickling removes the ammonium sulfate that the ammonia unit produces, and described deamination sour gas thermal oxidation units is delivered in the hydrogen sulfide extraction that will be dissolved in the ammonium sulfate; Described deamination sour gas thermal oxidation units is used for the hydrogen sulfide containing tail gas (9) receive described deamination sour gas (5) and come from described mother liquor vacuum evaporation unit, and it is carried out thermal oxide generates and contain SO
2Waste gas (11) with steam; Described catalytic oxidation relieving haperacidity unit is used for receiving described waste gas (11), it is carried out catalytic oxidation generate SO
3, and forming sulfuric acid (27), described sulfuric acid (27) is supplied to described sour gas pickling except the ammonia unit, is used for deamination.
2. the ammonia sour gas exhaust treatment system that contains as claimed in claim 1, it is characterized in that, the described ammonia sour gas exhaust treatment system that contains also comprises the molten sulfur feeding unit that is connected in described deamination sour gas thermal oxidation units, and described molten sulfur feeding unit is used to described deamination sour gas thermal oxidation units that molten sulfur is provided; The described ammonia sour gas exhaust treatment system that contains also comprises sulfuric acid cooling and the supply unit that is connected in described catalytic oxidation relieving haperacidity unit, and described sulfuric acid cooling and supply unit are used for the sulfuric acid (27) that described catalytic oxidation relieving haperacidity unit produces being cooled off and being transported to described sour gas pickling except the ammonia unit.
3. the ammonia sour gas exhaust treatment system that contains as claimed in claim 2, it is characterized in that, described sour gas pickling comprises pickling tower (1) except the ammonia unit, mother liquor tank (2), circulated sprinkling pump (3) and cooler (4), described pickling tower (1) gets off the ammonia stripping in the charging sour gas (A) with sulfuric acid, and change into ammonium sulfate, described mother liquor tank (2) is used for sulfuric acid and the ammonium sulfate mixed solution that collection is got off from the overhead streams of described pickling tower (1), described circulated sprinkling pump (3) is used for the mixed solution in the described mother liquor tank (2) is recycled to the distributor (D) at described pickling tower (1) top, described cooler (4) is used for cool cycles solution, takes out in the diluting concentrated sulfuric acid process and the heat in sulfuric acid and the ammonia react process.
4. the ammonia sour gas exhaust treatment system that contains as claimed in claim 2, it is characterized in that, described mother liquor vacuum evaporation unit comprises cold boiler (7) and vavuum pump (8), described cold boiler (7) is used for receiving the ammonium sulfate liquor from described mother liquor tank (2), described cold boiler arranges agitator in (7), skin arranges steam jacket, use low-pressure steam that ammonium sulfate liquor is carried out evaporation and concentration, described vavuum pump (8) is used to described cold boiler (7) that needed vacuum is provided, and described deamination sour gas thermal oxidation units is delivered in the hydrogen sulfide extraction that will be dissolved in the ammonium sulfate; Connecting line and flow regulator (6) are set between described cold boiler (7) and the described mother liquor tank (2), described flow regulator (6) can be regulated the flow of the ammonium sulfate liquor that enters described cold boiler (7), the bottom of described cold boiler (7) arranges flow regulator (35), and described flow regulator (35) can be regulated the flow of the ammonium sulfate concentrate of discharging cold boiler (7).
5. the ammonia sour gas exhaust treatment system that contains as claimed in claim 4, it is characterized in that, described deamination sour gas thermal oxidation units comprises combustion furnace (10), described combustion furnace (10) comprises air inlet and combustion chamber, described deamination sour gas (5), enters in the described combustion chamber mixed combustion to generate SO from four air inlets respectively from the tail gas (9) of described cold boiler (7), described molten sulfur (14) and combustion air (12)
2And steam.
6. the ammonia sour gas exhaust treatment system that contains as claimed in claim 5, it is characterized in that, described catalytic oxidation relieving haperacidity unit comprises reactor (15) and acid-producing apparatus (20), be provided with catalyst bed (17) in the described reactor (15), in described catalyst bed (17), the SO in the burnt gas (11) that described combustion furnace (10) produces
2And O
2Reaction changes into SO
3Set gradually from bottom to up two-stage glass tube condenser (21,22), blower fan (23,24), demister (25) and fume extractor (26) in the described acid-producing apparatus (20), described acid-producing apparatus (20) is used for receiving the SO that contains from described reactor (15)
3With the waste gas (19) of steam, described two-stage glass tube condenser (21,22) is used for will be from the SO of the waste gas (19) of described reactor (15)
3Be combined into sulfuric acid (27) with the water-cooled coalescence, described blower fan (23,24) is used to the waste gas (19) of described acid-producing apparatus (20) to cool off cooling-air is provided, described demister (25) is used for removing the residue acid mist of described acid-producing apparatus (20), and residual gas is discharged by described fume extractor (26).
7. sour gas exhaust treatment system as claimed in claim 6, it is characterized in that, described sulfuric acid cooling and supply unit comprise sulfuric acid storage tank (28), coolant circulation pump (29), sulfuric acid cooler (30) and sulfuric acid delivery pump (31), described sulfuric acid storage tank stores cold acid in (28), by the sulfuric acid (27) of input duct reception from described acid-producing apparatus (20), mix with cold acid, and mixed sulfuric acid (33) is transported to described pickling tower (1) by the fluid pipeline, described sulfuric acid cooler (30) is used for sulfuric acid (27) cooling with described sulfuric acid storage tank (28), described coolant circulation pump (29) provides power for the circulation of the sulfuric acid in the described sulfuric acid storage tank (28), between described sulfuric acid delivery pump (31) and the described pickling tower (1) flow regulator (32) is set, described flow regulator (32) can be regulated the flow that is transported to the sulfuric acid stream (33) of described pickling tower (1) from described sulfuric acid storage tank (28).
8. the ammonia sour gas exhaust treatment system that contains as claimed in claim 5, it is characterized in that, described molten sulfur feeding unit comprises molten sulfur pond (36), liquid sulfur pump (13) and heater (34), described molten sulfur pond (36) is used for storing molten sulfur (14), described liquid sulfur pump (13) is used for providing described molten sulfur (14) to described combustion furnace (10), and described heater (34) is used for the solid sulfur melting and remains on suitable temperature.
9. the ammonia sour gas exhaust treatment system that contains as claimed in claim 2, wherein, described pickling tower (1), mother liquor tank (2), circulated sprinkling pump (3) and cooler (4) are the formations that one-level consists of or two-stage is above.
10. the ammonia sour gas exhaust treatment system that contains as claimed in claim 6, wherein, described reactor (15) and acid-producing apparatus (20) are the formations that one-level consists of or two-stage is above.
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Effective date of registration: 20180712 Address after: 831300 East Industrial Park, the Xinjiang Uygur Autonomous Region economic and Technological Development Zone, No. 10077, No. 10077 Patentee after: Xinjiang Xinye Energy Chemical Co., Ltd. Address before: 100048 floor 10, 7 building, business center, 9 South Road, Haidian District, Beijing, 1001A Patentee before: Meijing (Beijing) Environmental Protection Tech. Co., Ltd. |