CN103041679B - 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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- CN103041679B CN103041679B CN201310014582.4A CN201310014582A CN103041679B CN 103041679 B CN103041679 B CN 103041679B CN 201310014582 A CN201310014582 A CN 201310014582A CN 103041679 B CN103041679 B CN 103041679B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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 containing ammonia sour gas exhaust treatment system.
Background technology
In the production process such as petrochemical industry and Coal Chemical Industry, sulphur in raw material and nitrogen are finally formed containing ammonia, hydrogen sulfide containing sour gas through process, for the sour gas containing ammonia and hydrogen sulfide, current processing method mainly adopts Crouse's recovery technology of sulfur that the hydrogen sulfide in sour gas is changed into sulphur, and the ammonia simultaneously in sour gas at high temperature burns into N
2and nitrogen oxide.For the sour gas (general sulfur content is less than 5000 tons of sulphur/years) that sulfur content is less, also complex iron can be adopted to remove hydrogen sulfide, remove the ammonia-containing exhaust after hydrogen sulfide to enter combustion furnace again and at high temperature burn, make the ammonia in tail gas and nitrogen oxide rear discharge up to standard.
The general principle of Crouse's recovery technology of sulfur is containing H
2the sour gas of S carries out imperfect combustion with air in combustion furnace, strictly controls air capacity, makes H
2the SO generated after S burning
2amount meets H
2s/SO
2molecular proportion equals or close to 2, H
2s and SO
2generting element sulphur is reacted under high temperature, catalyst, by the restriction of thermodynamic condition, remaining H
2s and SO
2enter catalyst reaction section under the effect of catalyst, continue reaction generting element sulphur.The elementary sulfur generated 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, due to the difference of sulphur, nitrogen content in raw material, desulphurization technological process is different, in the sour gas produced, concentration of hydrogen sulfide height differs, according to the difference of hydrogen sulfide content in sour gas, claus process can adopt shunting and direct current method (partial combustion process), and shunting generally processes the sour gas containing comparatively low in hydrogen sulphide concentration (usual concentration of hydrogen sulfide 15 ~ 40%), be that the sour gas of about 1/3 tolerance is burnt in sulphur stove processed, make H wherein
2s all burns till SO
2, the sour gas of other 2/3 without burning, directly after sulphur stove processed with SO
2mixing, and under catalyst action subsequently, there is claus reaction generation sulphur.Shunting requires not containing the impurity such as ammonia and hydrocarbon in sour gas, if containing the impurity such as ammonia and hydrocarbon, should not adopt shunting.
For the sour gas (usual concentration of hydrogen sulfide is greater than 40%) contained compared with high hydrogen sulphide concentration, generally adopt direct current method, direct current method is that whole sour gas all enters sulphur stove processed, the oxygen amount needed for strict control combustion, makes the Oxidation of Hydrogen Sulfide of 1/3 become SO
2, then, SO
2with remaining hydrogen sulfide generation claus reaction, generate sulphur.Then can there is series reaction in the ammonia in sour gas, the key reaction relevant with ammonia is as follows in sulphur stove processed:
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, the decomposition temperature of ammonia more than at least 1250 DEG C.In addition, in direct current method technique, burner for producing sulfur runs under anoxic conditions, but ammonia will be made to burn completely and the NO generated
xminimum, then the oxygen that adopts micro-excessive more, and this requires it is contradiction with the air distribution of claus process, therefore, if ammonia content exceedes finite concentration in sour gas, understand because of anoxic and reaction temperature low and make ammonia incomplete combustion, cause NO
xexceed standard and the operational issue such as ammonium salt sedimentation.Further, because the burning of ammonia needs oxygen consumed, the N brought into oxygen
2, water etc. reduces the rate of recovery of sulphur.
In a word, for low in hydrogen sulphide concentration, the high sour gas containing ammonia, when adopting Claus unit sulfur recovery unit, sour gas burning furnace temperature is low, not only affects sulfur recovery rate, and ammonolysis craft is incomplete simultaneously; For making ammonolysis craft complete, needing to improve furnace temperature, fuel gas certainly will be added in raw material sour gas, increasing energy consumption so on the one hand, on the other hand in practical operation, often due to fuel gas incomplete combustion under anaerobic environment, easily causing black sulphur.Therefore, Claus unit sulfur recovery unit be not suitable for processing containing the higher sour gas of ammonia.
The general principle that complex iron removes hydrogen sulfide is: in liquid medium, and adopt iron ion complex compound as catalyst, hydrogen sulfide directly changes into elementary sulfur at normal temperatures, forms the drusen of several microns to tens microns.Meanwhile, iron ion catalyst is reduced into ferrous ion, and used catalyst air oxidation regeneration Posterior circle uses.The solid sulfur generated forms the sulphur cake of sulfur-bearing about 60% after sedimentation, filtration.
When adopting complex iron process containing ammonia sour gas, need equally NH in feeding gas
3content control, too high NH
3content can cause drusen tiny, and effect of settling is poor, filtering means dehydration difficulty.The sulphur generated in course of reaction cannot deviate from system, finally causes system normally to run, 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 equally containing the higher Acidic Gas Treating of ammonia.
Summary of the invention
In view of current contains the problems referred to above existed in ammonia Acidic Gas Treating technique, the object of the invention is to propose one containing ammonia sour gas exhaust treatment system, can effectively process in sour gas containing ammonia and sulfur-containing compound, it is made all to obtain the recycling of resource, simultaneously, meet strict discharge standard, operating flexibility is good.
The invention provides a kind of containing ammonia sour gas exhaust treatment system, it comprises the sour gas pickling connected in turn and removes 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 to described sour gas pickling except between ammonia unit and described deamination sour gas thermal oxidation units; Described sour gas pickling is used for receiving containing ammonia sour gas except ammonia unit, and described sour gas pickling is used for contact with containing ammonia sour gas with deamination except the sulfuric acid in ammonia unit, and generates ammonium sulfate and contain the deamination sour gas of hydrogen sulfide and water; The hydrogen sulfide be dissolved in ammonium sulfate extraction for the ammonium sulfate received and concentrated described sour gas pickling produces except ammonia unit, and is delivered to described deamination sour gas thermal oxidation units by described mother liquor vacuum evaporation unit; Described deamination sour gas thermal oxidation units for receiving deamination sour gas and coming from the hydrogen sulfide-containing tail gas of mother liquor vacuum evaporation unit, and carries out thermal oxide generation containing SO to it
2with the waste gas of steam; Described catalytic oxidation relieving haperacidity unit, for receiving described waste gas, carries out catalytic oxidation to it and generates SO
3, and forming sulfuric acid, described sulfuric acid is supplied to described sour gas pickling except ammonia unit, for deamination.
Wherein, the molten sulfur feeding unit of described deamination sour gas thermal oxidation units, described molten sulfur feeding unit is used for providing molten sulfur for described deamination sour gas thermal oxidation units; The described ammonia sour gas exhaust treatment system that contains also comprises the sulfuric acid cooling and supply unit that are connected to described catalytic oxidation relieving haperacidity unit, and described sulfuric acid cooling and supply unit are used for being cooled by the sulfuric acid that described catalytic oxidation relieving haperacidity unit produces and being transported to described sour gas pickling removing ammonia unit.
Wherein, described sour gas pickling removes ammonia unit and comprises pickling tower, mother liquor tank, circulated sprinkling pump and cooler, ammonia stripping in charging sour gas gets off by described pickling tower sulfuric acid, and change into ammonium sulfate, described mother liquor tank is for collecting the sulfuric acid that gets off from the overhead streams of described pickling tower and ammonium sulfate mixed solution, described circulated sprinkling pump is used for the distributor mixed solution in described mother liquor tank being recycled to described pickling top of tower, described cooler is used for cool cycles solution, takes out in diluting concentrated sulfuric acid process and heat in sulfuric acid and ammonia react process.
Wherein, described mother liquor vacuum evaporation unit comprises cold boiler and vavuum pump, described cold boiler is for receiving the ammonium sulfate liquor from described mother liquor tank, in described cold boiler, agitator is set, skin arranges steam jacket, use low-pressure steam to carry out evaporation and concentration to ammonium sulfate liquor, described vavuum pump is used for the vacuum for described cold boiler provides, and described deamination sour gas thermal oxidation units is delivered in the hydrogen sulfide be dissolved in ammonium sulfate extraction.Connecting line and flow regulator are set between described cold boiler and described mother liquor tank, described flow regulator can regulate the flow of the ammonium sulfate liquor entering described cold boiler, the bottom of described cold boiler arranges flow regulator, and described flow regulator can regulate the flow of the ammonium sulfate concentration liquid 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 to enter in 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 described reactor, in catalyst bed, and the SO in the burnt gas that described combustion furnace produces
2and O
2reaction generates SO
3, set gradually two-stage glass tube condenser, blower fan, demister and fume extractor in described acid-producing apparatus from bottom to up, described acid-producing apparatus for receive from described reactor containing SO
3with the waste gas of steam, described two-stage glass tube condenser is used for the SO in the waste gas from described reactor
3be combined into sulfuric acid with water condensation, described blower fan is used for for the waste gas cooling of described acid-producing apparatus provides cooling-air, and described demister is for removing the residue acid mist in 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, cold acid is stored in described sulfuric acid storage tank, the sulfuric acid from described acid-producing apparatus is received by input duct, mix with cold acid, and mixed sulfuric acid is transported to described pickling tower by fluid pipeline, described sulfuric acid cooler is used for the sulfuric acid cooling in described sulfuric acid storage tank, described coolant circulation pump provides power for the sulfuric acid in described sulfuric acid storage tank circulates, between described sulfuric acid delivery pump and described pickling tower, flow regulator is set, described flow regulator can regulate the flow of the sulfuric acid stream being transported to 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 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 solid sulfur melting and remains on suitable temperature.
Wherein, described pickling tower, mother liquor tank, circulated sprinkling pump and cooler be one-level form or two-stage more than formation.
Wherein, described reactor and acid-producing apparatus be one-level form or two-stage more than formation.
According to of the present invention containing ammonia sour gas exhaust treatment system, owing to taking sulfuric acid scrubbing be stripped of the ammonia in sour gas and generate ammonium sulfate in advance to sour gas, then thermal oxide and catalytic oxidation Sulphuric acid are carried out to remaining sour gas, and the sulfuric acid produced 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 containing the ammonia in ammonia sour gas and sulfide, and the tail gas after process meets discharge standard, and does not have discharging of waste liquid in system.
The hydrogen sulfide dissolved in ammonium sulfate is extracted out by mother liquor vacuum evaporation unit in Vacuum Evaporation Process, and enter together with sour gas combustion furnace burn then make sulfuric acid, farthest control extra toxic emission; In addition, also molten sulfur feeding unit can be set, when the sulfuric acid produced by sour gas is not enough, adopts burning sulphur to supplement, improve treatment effeciency, whole system is balanced more.
Accompanying drawing explanation
Fig. 1 represents that the present invention contains the schematic diagram of ammonia sour gas exhaust treatment system one embodiment.
Detailed description of the invention
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, comprise sour gas pickling 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 containing ammonia sour gas exhaust treatment system.
Sour gas pickling removes ammonia unit and comprises: pickling tower 1, mother liquor tank 2, circulated sprinkling pump 3 and cooler 4.Certain density ammonia and hydrogen sulfide is comprised from the sour gas A that outside is come, pickling tower 1 is entered from the bottom air inlet of pickling tower 1, sour gas A rises in pickling tower 1, with the sulfuric acid solution counter current contacting sprayed from tower distributor D, ammonia in sour gas A and sulfuric acid generation chemical reaction also generate ammonium sulfate, be stripped of the sour gas of ammonia, be called for short deamination sour gas 5 and enter follow-up deamination sour gas thermal oxidation units process from tower top 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 extracts from mother liquor tank 2 the distributor D that mother liquor turns back to pickling column overhead out, and cooled by the 4 pairs of circulation solutions of the cooler on circulation line, with the heat taking out in sulfuric acid dilution and in ammonia and sulfuric acid reaction process, maintain the proper temperature of mother liquor.Distributor D makes circulating mother liquor be uniformly distributed in pickling tower 1, comes from the fresh sulfuric acid 33 of sulfuric acid cooling and supply unit, and the pipeline entered between cooler 4 and distributor D adds to sour gas pickling except ammonia unit.Water for dilute sulphuric acid supplements from mother liquor tank 2.
In Fig. 1, sour gas pickling is except the pickling of ammonia unit employing one-level, and namely described pickling tower 1, mother liquor tank 2, circulated sprinkling pump 3 and cooler 4 are that one-level is formed, but are not limited to these, according to the ammonia content in sour gas A, can adopt the above pickling of secondary.When adopting two-stage pickling, sour gas A is successively by firsts and seconds pickling tower, and first the sulfuric acid supplemented then enter secondary pickling tower, then the mother liquor of part secondary pickling tower substituted fresh sulfuric acid and add 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.Pickling tower can adopt packed tower, and also can adopt empty spray tower, pickling tower and mother liquor tank can manufacture one, also separately can build, be not particularly limited this.
A part of mother liquor in 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 band agitator and external belt steam jacket, cold boiler 7 is connected with vavuum pump 8 by pipeline, vavuum pump 8 provides necessary vacuum for cold boiler 7, in the stirring of agitator, under the acting in conjunction that Steam Heating and vavuum pump 8 vacuumize, a part of water in mother liquor and a small amount of hydrogen sulfide be dissolved in mother liquor are evaporated from mother liquor, deamination sour gas thermal oxidation units is delivered to by vavuum pump 8.In mother liquor vacuum evaporation unit, mother liquor is purified and concentrates, and discharges as required with the bottom of finite concentration from cold boiler 7, to sell with solid product after fluid sulphuric acid ammonium production marketing or further crystallization.The mother liquid flow rate entering mother liquor vacuum evaporation unit is regulated by flow regulator 6, and the flow of discharging cold boiler 7 is regulated by flow regulator 35, and flow regulator 6 and 35 is control valve in the present embodiment.
The deamination sour gas 5 containing hydrogen sulfide and water from pickling tower 1 tower top and the same tail gas 9 containing hydrogen sulfide and water vapour from cold boiler 7 enter deamination sour gas thermal oxidation units.Deamination sour gas thermal oxidation units comprises combustion furnace 10.Combustion furnace 10 comprises air inlet and combustion chamber, as shown in Figure 1, deamination sour gas 5 from pickling tower 1 tower top, the tail gas 9 from cold boiler 7, come autocatalyzed oxidation relieving haperacidity unit combustion air 12 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, molten sulfur feeding unit comprises molten sulfur pond 36, liquid sulfur pump 13 and heater 34, molten sulfur pond 36 is for storing molten sulfur, liquid sulfur pump 13 is for providing molten sulfur 14 to combustion furnace 10, heater 34 generally adopts steam pipe coil, with low-pressure steam heating, make solid sulfur melting, and molten sulfur temperature in molten sulfur pond is maintained at about 130 ~ 150 DEG C.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.When the sulfuric acid amount produced by sour gas is very few, when being not enough to ammonia complete reaction in charging sour gas A, molten sulfur feeding unit supplements molten sulfur 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, from the sulfide mainly SO the tail gas 11 that the gas outlet of combustion furnace 10 is discharged
2form, and containing O
2and water.Tail gas 11 enters catalytic oxidation relieving haperacidity unit subsequently.
The restriction not special to above-mentioned combustion furnace, can adopt combustion furnace well known in the art, can arrange the air inlet quantity of combustion furnace as required.About 800 ~ 1000 DEG C of ignition temperature, meanwhile, combustion furnace should provide the sufficient time of staying, and the oxygen in combustion air should be excessive, sulphur and sulphides burn can be become SO
2, other incendivity thing, as hydrocarbon, hydrogen burn into CO with CO
2and water, and can by 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 reactor 15 is as enclosed construction.Heat exchanger 16, catalyst bed 17 and cooler 18 has been set gradually from top to bottom in reactor 15, heat exchanger 16 is adjusted to the optimal reaction temperature of catalyst for the temperature of the tail gas 11 produced by combustion furnace 10, under the catalytic action of catalyst bed 17, the SO in combustion tail gas 11
2react with oxygen and generate SO
3and release reaction is warm, reaction heat takes out by cooler 18, temperature is cooled to 260 ~ 280 DEG C.
Catalyst in above-mentioned catalyst bed is not particularly limited, as long as can by SO
2catalytic Oxygen changes into SO
3, such as, can select Pt or V
2o
5deng, but preferred honeycomb Pt coated catalysts, 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, and honeycomb is conducive to provide larger contact surface and the less pressure loss.When using Pt coated catalysts, the temperature in reactor controls at 350 ~ 400 DEG C.To above-mentioned heat exchanger also without particular determination, heat exchanger well known in the art can be adopted.
What flow out from reactor 15 contains SO
3acid-producing apparatus 20 is entered subsequently 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 has been set gradually from bottom to up in acid-producing apparatus 20.Waste gas 19 passes into from the below of acid-producing apparatus 20, enters distribution apparatus G, and to make gas uniform disperse, after condenser 21 and 22 cools, temperature is down to 80 ° of about C, the SO in waste gas 19
3sulfuric acid 27 is become in conjunction with condensation with water, the cooling medium of waste gas 19 is the air provided by blower fan 23 and 24 respectively, sulfuric acid 27 under condensation, flows out acid-producing apparatus 20 under gravity afterwards on glass tube condenser 21 and 22, to enter follow-up sulfuric acid cooling and supply unit.Residue acid mist in waste gas 19 is removed by electrostatic precipitator 25, is then discharged by fume extractor 26.While the waste gas 19 of the air that blower fan 23 provides in cooling reactor, own temperature is also preheating to about 200 DEG C, and it is combustion-supporting that the air be preheated enters combustion furnace 10 as combustion air 12, and the preheating of combustion air can improve heat utilization ratio.
In Fig. 1, be provided with first-class heat exchanger 16 and one deck catalyst bed 17 in reactor 15, but be not limited to these, according to the content of sulfur dioxide in combustion tail gas 11, Multi-layer exchanging heat device and catalyst bed can be set.Make combustion tail gas 11 after which floor catalyst bed, SO
2to SO
3conversion ratio enough high, after condensation from fume extractor 26 discharge tail gas SO
2concentration can meet discharge standard.
In 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 is formed, but are not limited to these, according to the content of sulfur dioxide in combustion tail gas 11, can adopt the reaction of more than 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 sulfuric acid storage tank 28, receive the sulfuric acid 27 from acid-producing apparatus 20 by input duct, mix with cold acid, and mixed sulfuric acid 33 is transported to pickling tower 1 by fluid pipeline.Idiographic flow is: the temperature of sulfuric acid 27 about 260 ~ 280 DEG C, after entering sulfuric acid storage tank 28, mixes with the cold acid in tank.Sulfuric acid in sulfuric acid storage tank 28 pressurizes through persulfuric acid circulating pump 29, through sulfuric acid cooler 30 cool after, temperature by constant control at 40 ° of below 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 being 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 is only for exemplary illustration, can be out of shape said system, such as, sulfuric acid cooling and supply unit and molten sulfur feeding unit can be omitted, the sulfuric acid that catalytic oxidation relieving haperacidity unit produces directly being supplied to sour gas pickling except ammonia unit carries out deamination, can effectively process equally in sour gas containing ammonia and sulfur-containing compound, make it all obtain the recycling of resource.
Exhaust treatment system of the present invention, owing to taking sulfuric acid scrubbing be stripped of the ammonia in sour gas and generate ammonium sulfate in advance to sour gas, then thermal oxide and catalytic oxidation Sulphuric acid are carried out to remaining sour gas, and the sulfuric acid produced is used for the ammonia stripping of front end, the hydrogen sulfide dissolved in ammonium sulfate is evaporated in Vacuum Evaporation Process, and enter together with sour gas combustion furnace burn then make sulfuric acid, there is no extra toxic emission, when the sulfuric acid produced by sour gas is not enough, burning sulphur is adopted to supplement, therefore, exhaust treatment system of the present invention has all carried out the recovery of resource to containing the ammonia in ammonia sour gas and sulfide, tail gas after process meets discharge standard, and there is no discharging of waste liquid in system.
Below, by embodiment, further describe the embodiment of one embodiment of the invention.This embodiment carries out containing ammonia sour gas exhaust-gas treatment according to following step.
Component and the character of a, raw material sour gas are: H
2s content 13.27%(V), CO
2content 0.53% (V), NH
3content 47.1% (V), H
2o content 39.1% (V), temperature 80 DEG C, pressure 60KPa;
B, because the ammonia content in sour gas is higher, sour gas pickling is except ammonia unit employing two-stage, first sour gas enters first order pickling tower, pickling tower adopts packed tower, in-built structured packing, the sulfuric acid solution counter current contacting that sour gas sprays in pickling tower and from tower distributor, ammonia in 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, circulated sprinkling pump extracts from mother liquor tank the distributor that mother liquor turns back to pickling column overhead out, and by the cooler on circulation line, circulation solution is cooled, the temperature of mother liquor is made to maintain about 50 DEG C, the cooling medium of cooler is recirculated cooling water.The sour gas being stripped of ammonia flows out from first order pickling column overhead, enters second level pickling tower and continues process.Be 3 ~ 4% to maintain 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 flowed out from first order pickling tower top enters second level pickling tower, same in pickling tower with the sulfuric acid solution counter current contacting sprayed from tower distributor, ammonia in sour gas and sulfuric acid generation chemical reaction also generate ammonium sulfate, the sour gas being stripped of ammonia flows out from tower top and enters follow-up deamination sour gas thermal oxidation units process, the mother liquor of liquid containing ammonium sulfate flows under the influence of gravity into the mother liquor tank of pickling tower bottom, circulated sprinkling pump extracts from mother liquor tank the distributor that mother liquor turns back to pickling column overhead out, and by the cooler on circulation line, circulation solution is cooled, the temperature of mother liquor about 50 DEG C, the cooling medium of cooler is recirculated cooling water.The fresh sulfuric acid pipeline entered between cooler and distributor coming from sulfuric acid cooling and supply unit adds to second level pickling tower.Mother liquor acidity about 3 ~ 4%.The mother liquor of discharging from second level mother liquor tank delivers to first order mother liquor tank.
A part of mother liquor in d, first order mother liquor tank is under the effect of vacuum, under the control of flow control valve, enter cold boiler, cold boiler inner band agitator and external belt steam jacket, cold boiler by vacuum pump evacuation, the temperature in cold boiler about 70 DEG C, vacuum is about 90KPa, mixing speed 80 revs/min, stirring, under the acting in conjunction of heating and vacuum, a part of water in mother liquor and the hydrogen sulfide be dissolved in mother liquor are evaporated, and deliver to combustion furnace; Ammonium sulfate concentrations about 60 ~ 80%(W/V in solution after concentrated), under the control of flow control valve, discharge from the bottom of cold boiler, directly with fluid sulphuric acid ammonium production marketing.
E, the deamination sour gas come from second level pickling tower, from cold boiler hydrogen sulfide-containing tail gas, come from the molten sulfur of molten sulfur feeding unit and enter the combustion furnace of deamination sour gas thermal oxidation units at the combustion air that subsequent catalyst producing acid by oxidation unit is preheating to about 200 DEG C together, in combustion furnace combustion, ignition temperature 800 ~ 1000 DEG C, the sulphur in sour gas, cold boiler tail gas and molten sulfur and sulfide are oxidized to SO
2.The tail gas of combustion furnace enters catalytic oxidation relieving haperacidity unit extracting sulfuric acid.
F, from combustion furnace flow out tail gas enter catalytic oxidation relieving haperacidity unit, in order to reach higher SO2 conversion ratio, catalytic oxidation relieving haperacidity unit also adopts two-stage, first the tail gas of combustion furnace enter first order reactor, temperature is made to be reduced to 350 ~ 400 DEG C by finned heat exchanger, then successively through three layers of honeycomb Pt coated catalysts bed, by SO
2change into SO
3, and by the heat exchanger arranged after every layer of beds, reaction heat is taken out, keep the reaction temperature in reactor.
The tail gas of g, combustion furnace flows out from first order reactor, and temperature controls, at about 260 ~ 280 ° of C, to enter first order condenser subsequently; After glass tube condenser, waste gas is cooled to 80 DEG C, then through high-pressure electrostatic demister removing acid mist, then enters second level reactor.The air of glass tube condenser cooling is supplied by blower fan.Sulfuric acid on glass tube condenser under condensation flows out bottom condenser.
After h, tail gas enter second level reactor, be first heated to 350 ~ 400 DEG C by heat exchanger, then will remain SO on honeycomb Pt coated catalysts bed
2continue to be oxidized to SO
3, then with heat exchanger, temperature is controlled, at about 260 ~ 280 ° of C, to enter second level condenser subsequently; Carry out cooling and acid-mist-removing, sulfuric acid flows out bottom condenser, exhaust emissions.Catalyst, heat exchanger, condenser, blower fan, electrostatic precipitator etc. used in second level reactor with second level condenser are identical with the device type in first order condenser with first order reactor.
I, the sulfuric acid flowed out from first order condenser and second level condenser enter sulfuric acid storage tank, mix with the cold acid in tank.Sulfuric acid in sulfuric acid storage tank through persulfuric acid circulating pump pressurization, through sulfuric acid cooler cooling after, temperature by constant control at 40 ° of below C.Then use sulfuric acid delivery pump that sulfuric acid is transported to second level pickling tower from sulfuric acid storage tank.
J, add in molten sulfur pond by solid sulfur, molten sulfur arranges steam-coil-heater in pond, with low-pressure steam, solid sulfur is heated to 130 ~ 150 DEG C, makes sulfur melting, and molten sulfur liquid sulfur pump is transported to combustion furnace, in step e.
After testing, after said system process, the sulfuric acid concentration of discharging from condenser is 95 ~ 97%, meets standard GB/T/T534-2002, SO in emission
2concentration is 230mg/m
3, NO
xconcentration is 95mg/m
3, meet discharging standards.
Although exemplary embodiment describe the present invention with reference to several, should be appreciated that term used illustrates and exemplary and nonrestrictive term.Spirit of the present invention or essence is not departed from because the present invention can specifically implement in a variety of forms, so be to be understood that, above-described embodiment is not limited to any aforesaid details, and should explain widely in the spirit and scope that claims limit, therefore fall into whole change in claim or its equivalent scope and remodeling and all should be claims and contained.
Claims (10)
1. one kind contains ammonia sour gas exhaust treatment system, it is characterized in that, comprise the sour gas pickling connected in turn and remove 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 to described sour gas pickling except between ammonia unit and described deamination sour gas thermal oxidation units; Described sour gas pickling is used for receiving containing ammonia sour gas except ammonia unit, and described sour gas pickling is used for contact with containing ammonia sour gas with deamination except the sulfuric acid in ammonia unit, and generates ammonium sulfate and contain the deamination sour gas (5) of hydrogen sulfide and water; The hydrogen sulfide be dissolved in ammonium sulfate extraction for the ammonium sulfate received and concentrated described sour gas pickling produces except ammonia unit, and is delivered to described deamination sour gas thermal oxidation units by described mother liquor vacuum evaporation unit; Described deamination sour gas thermal oxidation units for receiving described deamination sour gas (5) and coming from the hydrogen sulfide containing tail gas (9) of described mother liquor vacuum evaporation unit, and carries out thermal oxide generation containing SO to it
2with the waste gas (11) of steam; Described catalytic oxidation relieving haperacidity unit, for receiving described waste gas (11), carries out catalytic oxidation to it and generates SO
3, and forming sulfuric acid (27), described sulfuric acid (27) is supplied to described sour gas pickling except ammonia unit, for deamination.
2. as claimed in claim 1 containing ammonia sour gas exhaust treatment system, it is characterized in that, the described ammonia sour gas exhaust treatment system that contains also comprises the molten sulfur feeding unit being connected to described deamination sour gas thermal oxidation units, and described molten sulfur feeding unit is used for providing molten sulfur for described deamination sour gas thermal oxidation units; The described ammonia sour gas exhaust treatment system that contains also comprises the sulfuric acid cooling and supply unit that are connected to described catalytic oxidation relieving haperacidity unit, and described sulfuric acid cooling and supply unit are used for being cooled by the sulfuric acid (27) that described catalytic oxidation relieving haperacidity unit produces and being transported to described sour gas pickling removing ammonia unit.
3. as claimed in claim 2 containing ammonia sour gas exhaust treatment system, it is characterized in that, described sour gas pickling removes ammonia unit and comprises pickling tower (1), mother liquor tank (2), circulated sprinkling pump (3) and cooler (4), ammonia stripping in charging sour gas (A) gets off with sulfuric acid by described pickling tower (1), and change into ammonium sulfate, described mother liquor tank (2) is for collecting the sulfuric acid that gets off from the overhead streams of described pickling tower (1) and ammonium sulfate mixed solution, described circulated sprinkling pump (3) is for being recycled to the distributor (D) at described pickling tower (1) top by the mixed solution in described mother liquor tank (2), described cooler (4) is for cool cycles solution, take out in diluting concentrated sulfuric acid process and heat in sulfuric acid and ammonia react process.
4. as claimed in claim 2 containing ammonia sour gas exhaust treatment system, it is characterized in that, described mother liquor vacuum evaporation unit comprises cold boiler (7) and vavuum pump (8), described cold boiler (7) is for receiving the ammonium sulfate liquor from described mother liquor tank (2), described cold boiler arranges agitator in (7), skin arranges steam jacket, low-pressure steam is used to carry out evaporation and concentration to ammonium sulfate liquor, the vacuum of described vavuum pump (8) for providing for described cold boiler (7), and described deamination sour gas thermal oxidation units is delivered in the hydrogen sulfide be dissolved in ammonium sulfate extraction, connecting line and flow regulator (6) are set between described cold boiler (7) and described mother liquor tank (2), described flow regulator (6) can regulate the flow of the ammonium sulfate liquor entering described cold boiler (7), the bottom of described cold boiler (7) arranges flow regulator (35), and described flow regulator (35) can regulate the flow of the ammonium sulfate concentration liquid of discharging cold boiler (7).
5. as claimed in claim 4 containing ammonia sour gas exhaust treatment system, 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), to enter in 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. as claimed in claim 5 containing ammonia sour gas exhaust treatment system, it is characterized in that, described catalytic oxidation relieving haperacidity unit comprises reactor (15) and acid-producing apparatus (20), catalyst bed (17) is provided with in 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 two-stage glass tube condenser (21,22), blower fan (23,24), demister (25) and fume extractor (26) in described acid-producing apparatus (20) from bottom to up, described acid-producing apparatus (20) for receive from described reactor (15) containing SO
3with the waste gas (19) of steam, described two-stage glass tube condenser (21,22) is for will from the SO in the waste gas of described reactor (15) (19)
3sulfuric acid (27) is combined into water-cooled coalescence, described blower fan (23,24) is for providing cooling-air for the waste gas (19) of described acid-producing apparatus (20) carries out cooling, described demister (25) is for removing the residue acid mist in 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), the sulfuric acid (27) from described acid-producing apparatus (20) is received by input duct, mix with cold acid, and mixed sulfuric acid (33) is transported to described pickling tower (1) by fluid pipeline, described sulfuric acid cooler (30) is for cooling the sulfuric acid (27) in described sulfuric acid storage tank (28), described coolant circulation pump (29) provides power for the sulfuric acid in described sulfuric acid storage tank (28) circulates, between described sulfuric acid delivery pump (31) and described pickling tower (1), flow regulator (32) is set, described flow regulator (32) can regulate the flow of the sulfuric acid (33) being transported to described pickling tower (1) from described sulfuric acid storage tank (28).
8. as claimed in claim 5 containing ammonia sour gas exhaust treatment system, 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 for storing molten sulfur (14), described liquid sulfur pump (13) is for providing described molten sulfur (14) to described combustion furnace (10), and described heater (34) is for remaining on suitable temperature by solid sulfur melting.
9. as claimed in claim 3 containing ammonia sour gas exhaust treatment system, wherein, described pickling tower (1), mother liquor tank (2), circulated sprinkling pump (3) and cooler (4) be one-level form or two-stage more than formation.
10. as claimed in claim 6 containing ammonia sour gas exhaust treatment system, wherein, described reactor (15) and acid-producing apparatus (20) are formations more than one-level formation or two-stage.
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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. |
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