CN101041120A - Device for the recovery and diffluence of sulfur dioxide and the system and method thereof - Google Patents
Device for the recovery and diffluence of sulfur dioxide and the system and method thereof Download PDFInfo
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- CN101041120A CN101041120A CNA2007100174164A CN200710017416A CN101041120A CN 101041120 A CN101041120 A CN 101041120A CN A2007100174164 A CNA2007100174164 A CN A2007100174164A CN 200710017416 A CN200710017416 A CN 200710017416A CN 101041120 A CN101041120 A CN 101041120A
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000011084 recovery Methods 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 57
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 269
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 227
- 239000011593 sulfur Substances 0.000 claims abstract description 227
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- 239000002253 acid Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 235000001508 sulfur Nutrition 0.000 claims description 222
- 239000007789 gas Substances 0.000 claims description 144
- 239000005864 Sulphur Substances 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 28
- 125000001741 organic sulfur group Chemical group 0.000 claims description 20
- 230000001413 cellular effect Effects 0.000 claims description 18
- 239000002918 waste heat Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003546 flue gas Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- 239000002737 fuel gas Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000002912 waste gas Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 229910002089 NOx Inorganic materials 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 22
- 238000002485 combustion reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a sulfur recovery equipment by sulfur dioxide recovery divided flow method and the sulfur recovery method. The acid material gas is divided into two channels. One channel is sent into the claus catalytic reactor with the sulfur dioxide from the sulfur dioxide recovery cell together to carry the catalytic conversion reaction out and the obtained tail gas is sent into the incinerator with the other channel together to burn in peroxy. All compounds with sulfur are translated into the sulfur dioxide to be sent into the sulfur dioxide recovery cell to carry sulfur dioxide recovery out so that after the sulfur dioxide in gas is coincidence with the discharge standard it is discharged in air and obtained sulfur dioxide is returned to the claus reactor again. It is provided with simple structure, low cost, on treatment for tail gas, simplified reaction process. Decreased invest, shrinkage cubage, little catalyzer dosage, no high-temperature heating reacting segment, no material acid air washing pretreatment process and no hydrolyzing catalyzer. It can treat poor H2S acid gas and solve environmental pollution. It can enlarge the sulfur recovery and the recovery invest can not be enlarged.
Description
Technical field
The present invention relates to chemical industry from containing H
2The system and device of Recovered sulphur and method in the S acid waste gas, particularly suitable sulfur dioxide recovery shunting sulfur recovery unit and system and device reclaim the method for sulphur.
Background technology
According to incompletely statistics, built up the sulfur recovery facility of cover more than 100 to China in 2003, by industry distribution petroleum refining 71 covers, natural gas purification 12 covers, metallurgical 7 covers of coking, coal gasification 21 covers, wherein, largest device is 100,000 t/a, and the device of scale minimum is 0.03 ten thousand t/a.Since 2004, oil plants such as China Petrochemical Industry Zhenghai, Fujian also will be invested to build the large-scale sulfur recovery facility of 3～4 cover 100,000 t/a levels, and total sulfur recovery ability has surpassed 1,000,000 t/a.In the covering device, the device that built up later in 2002 all has tail gas treating unit more than 100 for this, except the reduction absorption process technology of domestic SSR technology and domestic design voluntarily, is introduction technology, and big multipotency satisfies the environmental requirement of country.But as the process unit total sulfur conversion ratios of introducing in the past such as Sulfreen, Super Claus, MCRC and Clauspol discharge SO in the tail gas 98.5%～99.5%
2Basically at 1500～8000mg/Nm
3Do not establish exhaust gas processing device, SO in the discharging tail gas
2The overwhelming majority is higher than 15000mgN/m
3, all can not satisfy the new discharge standard requirement of country.Grow out of nothing and expand from small to large for China's sulfur recovery industrial production, under the cooperation of scientific research, design, production unit, for many years, all has greatly improved at aspects such as technological process, catalyst development, device structure, analysis and Control and develop, and constantly improve.The large and medium-sized device of part has been introduced foreign patent technology and key equipment, instrument and catalyst, and technical merit has reached external advanced level.Also there are a series of problems and gap at aspects such as sulfur recovery rate, vent gas treatment, automatic control level, production managements, remain further to improve and improve.
A, several Claus sulfur recovery technologies that exist at present
1), partial combustion process
H in the general sour gas
2The S volumetric concentration is higher than at 50% o'clock, recommends to adopt partial combustion process.This method is to allow most sour gas send into combustion furnace, and control air addition is burnt, and goes out the reacting gas of combustion furnace, enters converter after the cooling condensation sulphur removal.By on a small quantity not sending into the sour gas of combustion furnace and an amount of air in reheaters at different levels combustion reaction takes place, to provide and to keep the reaction temperature of converter.
The reaction mixture gas body after three grades of conversions and level Four refrigerated separation, H
2The S total conversion can reach more than 96%, its tail gas emptying, SO
2Concentration is at 15000mg/Nm
3More than.
2) shunting
H
2S concentration recommends to adopt shunting between 15%～50% the time.This method is sent into 1/3 sour gas in the combustion furnace, adds capacity air or oxygen-enriched air by H
2S completing combustion is converted into SO
2, mix with remaining 2/3 sour gas then, be made into H
2S/SO
2=2: 1 mist enters secondary formula converter again and transforms, and its total conversion can reach more than 90%.Characteristics such as this flow process has easy control of reaction conditions, and operation is simple.
3), direct oxidation method
H
2The S volumetric concentration recommends to adopt direct oxidation method during less than 15% (general 1%～20%).Because H in the feeding gas
2S content is low, is difficult to use combustion furnace, and with preheating furnace gas is heated to desired reaction temperature.Give in the feeding gas and allocate air into, directly enter catalytic reaction, H after the mixing
2S is converted into sulphur.Though this method is through two sections conversions, total conversion ratio only can reach 70%.Improve conversion ratio, can adopt three grades or level Four conversion, the sulfur recovery cost significantly improves.
1993, by crin Sa husband (Clinsulf) method of Linde AG company exploitation, its principle also was a claus reaction, but had technically absorbed polytechnic advantage, was applicable to H
2S content is 1%～20% acid gas, promptly can be used for Claus tail gases or directly handle other containing low dense H
2The gas of S.This law belongs to direct oxidation method.Catalyst system therefor is TiO
2Because reactor control temperature is low, so suppressed H
2The solubility of S in sulphur, the sulphur quality height of discharge, no H
2The S flavor has been avoided the refining step of general claus process to sulphur.Handling the acid gas ability is 500～50000m
3/ h, total sulfur recovery are 99.6%.The technological core of crin Sa Fufa is exactly the inner-cooled isothermal reactor that has Linde AG patented technology.This reactor is made up of adiabatic section, upper strata and lower floor's cooling section.Go into implication earlier in the adiabatic section reaction, temperature is promoted rapidly, carry out the hydrolysis of organic sulfur.Enter lower floor then and carry out isothermal reaction.Because temperature is low, so H
2S conversion ratio height than high about 5 percentage points of super Crouse, can be used for the technological process of inferior dew point (SDP) method.Because this technological development is later, rare at home achievement, after 2003, Linde AG company has stopped the transfer of this technology.
4), oxygen enrichment Sulfur Recovery Unit technology
In recent years, therefore the situation that need carry out plant modification replaces the oxygen enrichment sulfur recovery technology of air to cause generally with oxygen or oxygen-enriched air and payes attention to because many sulfur recovery units that built up face that acid tolerance increases considerably.
1985, the U.S. had two cover oil plant sulfur recovery units to adopt 55% oxygen-enriched air to replace air to operate first, and unit capacity has improved 85%, has obtained favorable economic benefit.At present, U.S.'s air products and chemical company (APCI), British Oxygen Co.Ltd (BOC), U.S.'s union carbide corporation and three big industrial gasses companies (BTIGI) etc. have all succeeded in developing the oxygen enrichment sulfur recovery technology of different process characteristics, as the Cope method of APCI company and the Sure method of BOC Co..
This technology and first three are planted unique difference and are used richness (pure) oxygen to substitute air exactly.Owing to adopt the technology (100vol.% pure oxygen, volume are air～1/5) of rich (pure) oxygen burning, the volume of device is dwindled greatly, not only saved floor space greatly, and can saving at double invest.But because oxygen generating plant will be arranged, the operating cost height, particularly the pure oxygen burning burner belongs to patented product, and price is higher.Relatively be suitable for having the enterprise of air separation unit.
Summary of the invention
The purpose of this invention is to provide a kind of simple in structurely, cost is low, and exhaust treatment system is not set, and course of reaction is simplified, and reduces investment, the volume-diminished of catalyzed conversion formula reactor, the sulfur dioxide recovery shunting sulfur recovery unit that catalyst amount reduces.
Another object of the present invention provides the method that system and device reclaims sulphur.
In order to overcome the deficiency that prior art exists, technical solution of the present invention is achieved in that sulfur dioxide recovery shunting sulfur recovery unit, mainly by first steam heater, second steam heater, first sulfur condenser, second sulfur condenser, the acid gas preheater, the sulfur dioxide preheater, waste heat boiler, incinerator, molten sulfur pond injector, high steam adds temperature-decreased pressure reducer, the incinerator air-blaster, the one section outlet air blast, liquid sulfur pump, first section claus reaction device, second section claus reaction device, the molten sulfur pond, the first molten sulfur lock hopper, the second molten sulfur lock hopper, on, following molten sulfur collecter ring, the sulfur dioxide recovery cellular system constitutes, its marked improvement of the present invention is to be connected by pipeline with the sulfur dioxide preheater from the sulfur dioxide pipeline of sulfur dioxide recovery cellular system, the acid gas line of raw material that gets the desulfurization unit system from front end is connected by pipeline with the acid gas preheater, the sulfur dioxide preheater, acid gas preheater and waste heat boiler are with being located in the heat exchange box, the acid gas preheater respectively with the incinerator bypass, the inlet of first steam heater connects by pipeline, the sulfur dioxide preheater is connected by pipeline with the inlet of first steam heater, establish a bypass in the porch of first steam heater, be connected with first steam heater through bypass, main road converges the back from the inlet of first steam heater and is connected by pipeline with first section claus reaction device, first section claus reaction device is connected by pipeline with first sulfur condenser, first sulfur condenser is connected with following molten sulfur collecter ring, following molten sulfur collecter ring is connected by pipeline with the first molten sulfur lock hopper with the one section outlet air blast respectively, the one section outlet air blast is connected by pipeline with second section claus reaction device, second section claus reaction device is connected by pipeline with second sulfur condenser, the molten sulfur collecter ring connects on second sulfur condenser, last molten sulfur collecter ring is connected by pipeline with the second molten sulfur lock hopper with incinerator respectively, the first molten sulfur lock hopper, the second molten sulfur lock hopper is connected with the molten sulfur pond by pipeline respectively, second sulfur condenser, first sulfur condenser and last, the shared housing of following molten sulfur collecter ring, second sulfur condenser, first sulfur condenser is in a tube bank, the incinerator air-blaster is connected with the incinerator inlet with the molten sulfur pond by pipeline respectively, hydrogen reclaims exhaust pipe and is connected with the incinerator inlet, molten sulfur pond injector is connected by pipeline with the incinerator inlet, the incinerator outlet connects the acid gas preheater of series connection, the sulfur dioxide preheater, waste heat boiler, behind waste heat boiler, be connected to the sulfur dioxide recovery cellular system by pipeline, high steam adds the temperature-decreased pressure reducer and first steam heater, second steam heater connects by pipeline, and the molten sulfur pond is connected by pipeline with liquid sulfur pump.
Several Claus sulfur recovery technologies from present existence will make the tail gas qualified discharge, all exhaust treatment system will be set basically.SO
2Reclaim the cyclic oxidation method exhaust treatment system is not set, system's total sulfur recovery reaches more than 99.9%.
Come from follow-up SO
2The SO of exhausting section
2Through heat exchanger and incinerator smoke heat exchange, from the acid material gas of front end through heat exchanger and incinerator smoke heat exchange, if temperature can reach activity of such catalysts temperature in the catalyzed conversion formula reactor, with regard to directly enter carry out in the catalyzed conversion formula reactor claus reaction (
H in the formula
2S is a hydrogen sulfide, SO
2Be sulfur dioxide, S
xBe S
6, S
8, wherein be mainly S
8, H
2O is a water, and+Q represents heat release), but when incinerator is undesired, can enters in first steam heater and heat, make it reach activity of such catalysts temperature in the catalyzed conversion formula reactor and send into again in the catalyzed conversion formula reactor and carry out claus reaction.The sulphur that generates arrives the sulphur storehouse through condensation, refining back.Two-stage catalytic transforms remaining SO
2With H
2S adds unconverted COS, CS
2Deng, add the H that puts forward from molten sulfur pond gas
2S, elemental sulfur and other sulfur-containing compounds are regulated by-pass at last, and a part of acid material gas is also joined into, send into incinerator, burn till SO in excess air and fuel gas burned flame
2Its molar flow is (with SO
2Or elementary sulfur S meter) should satisfy H in the catalyzed conversion formula that the enters reactor of prior setting
2S and SO
2The relation of mol ratio.Can regulate by regulating the by-pass flow.The high-temperature flue gas (～630 ℃) that comes out from incinerator is through with waste heat boiler, acid material gas with from SO
2The SO of exhausting section
2Through heat exchange, last water Quench, make temperature reduce to～enter SO after 60 ℃
2Recovery section, selectivity absorbs SO therein
2, make SO in the discharging tail gas
2Reach 35～350ppm.Rich solution after the absorption is regenerated, and makes it discharge SO
2(butt concentration 〉=99.9%), warp and the high-temperature flue gas heat exchange of coming out from incinerator are sent in the catalyzed conversion formula reactor as reactant.
System and device reclaims the method for sulphur, is undertaken by following step:
1), to wash the acid gas temperature from low first by pipeline is 25 ℃ and sends into heat exchange in the acid gas preheater, be divided into two-way then, one the tunnel sends into incinerator, the first steam heater front end is delivered on another road, being 35 ℃ from the sulfur dioxide temperature of sulfur dioxide recovery cellular system sends in the sulfur dioxide preheater after the heat exchange, also delivering to the first steam heater front end mixes with the raw material acid gas of sending here, the temperature of mist is not if reach 220～240 ℃, then be delivered in first steam heater and heat again by bypass, make its temperature reach 220～240 ℃, otherwise directly send in first section claus reaction device;
2), the gas after the last process heating is transported to by pipeline and carries out catalytic conversion reaction in first section claus reaction device (3):
Reaction equation:
(x=6 or 8, S
xMajor part is S
8S wherein
x, S
8Refer to the molecular formula of sulphur steam, S
xRepresent that this molecule forms S by x sulphur atom
8Represent that this molecule is made up of 8 sulphur atoms)+Q represents heat release, 270～350 ℃ of bed temperatures, air speed～470h-1, pressure are 5～10kPa (G);
3), the product behind the catalytic conversion reaction flows to first sulfur condenser by pipeline, make its temperature drop to 125～130 ℃, at this moment the part gaseous sulfur is condensed into droplet, through molten sulfur collecter ring separation down, molten sulfur after the separation flows to the first molten sulfur lock hopper by pipeline and sends into the molten sulfur pond then, isolated gas flows to the heating of second steam heater through the one section outlet air blast by pipeline, make its temperature reach about 210～220 ℃ and be conveyed into second section claus reaction device and carry out catalytic conversion reaction, its catalytic conversion reaction formula is:
H in the formula
2S is a hydrogen sulfide, SO
2Be sulfur dioxide, S
xBe S
6, S
8, wherein be mainly S
8, H
2O is a water, and+Q represents heat release, and 220～270 ℃ of bed temperatures, air speed～600h-1, pressure are 20～30kPa (G).Product is sent into second sulfur condenser, make its temperature drop to 125～130 ℃, at this moment the part gaseous sulfur is condensed into droplet, separate through last molten sulfur collecter ring, isolated molten sulfur flows to the second molten sulfur lock hopper by pipeline and sends into the molten sulfur pond then, and isolated gas is sent into incinerator through utilidor and burned;
4), the product collected through the first molten sulfur lock hopper, the second molten sulfur lock hopper sends into the molten sulfur pond, carries the H that is dissolved in wherein at the molten sulfur in molten sulfur pond by the part air gas that comes from the incinerator air-blaster
2Behind S and the Determination of Trace Sulfur steam, molten sulfur is transported to the assembly room by liquid sulfur pump, the H that gas exhaust gas and gas thereof propose
2S and Determination of Trace Sulfur steam mixture are sent into incinerator by molten sulfur pond injector and are burned; It is with air bubbling in molten sulfur, the H that is dissolved in the molten sulfur that said gas is carried
2S parses;
5), in incinerator, the hydrogen that reclaims exhaust pipe from hydrogen reclaims the tail gas gas that acts as a fuel, with burn in main burner from the part air of incinerator air-blaster inferior chemical equivalent with 80% fuel gas, the thermal-flame core that forms the reduction atmosphere is in case the NOx generation, x=1 or 2, (X-representative be numeral, work as x=1, NO represents nitric oxide; Work as x=2, NO
2Expression nitrogen dioxide,) from the in addition part air of incinerator air-blaster as cooperating wind to form the flame envelope of oxidizing atmosphere with 130% of fuel gas chemistry equivalent, always in the air of incinerator air-blaster, telling the part air again as secondary wind, be used for the burning of process gas (at the flame envelope of oxidizing atmosphere), for guaranteeing the H in the flue gas
2S content is no more than 10mg/Nm
3, require the O in the flue gas
2Content～10%, these process gas comprise: from the isolated gas of last molten sulfur collecter ring, wherein contain unreacted H completely
2S, does not capture clean elemental sulfur combustible, from the H in the acid gas preheater at organic sulfur
2S, the organic sulfur combustible is from the H of molten sulfur pond injector
2S, the Determination of Trace Sulfur combustible;
6), the gas of incinerator burning is successively through acid gas preheater, sulfur dioxide preheater, the waste heat boiler heat exchange of series connection, make its temperature reach～160 ℃ after, send into the sulfur dioxide recovery cellular system and reclaim wherein SO
2, and make SO in its discharge tail gas
2Content is at 35～350mg/Nm
3
The present invention compared with prior art has following characteristics:
1, compare with traditional Crouse's (comprising super Crouse), cancelled high temperature combustion furnace, that is, this technology no longer includes the elevated temperature heat conversion zone, thereby has avoided a series of NH
3With hydrocarbon, generate or consume COS, CS
2And generate and consumption CO, H
2Side reaction, process is simplified, investment reduces.
2, cancelled the elevated temperature heat conversion zone, as the oxidant of claus reaction (
H in the formula
2S is a hydrogen sulfide, SO
2Be sulfur dioxide, S
xBe S
6, S
8, wherein be mainly S
8, H
2O is a water, and+Q represents heat release) by from SO
2High-purity SO of exhausting section
2(SO
2〉=99.9%, butt) serve as 1 mole of SO
2To H
2The oxidation equivalent of S is equivalent to the oxidation equivalent of 5 mole air approximately, thereby makes the volume-diminished of catalyzed conversion formula reactor, and catalyst amount reduces, and has saved investment and expense.
3, need not wash preliminary treatment such as (need wash away methyl alcohol in the raw material acid gas etc. as super Crouse) to the raw material acid gas, a series of H of containing that reduced equipment investment and caused thus
2The troubles such as processing of S waste water have been saved investment and expense.
4, to the COS in the raw material acid gas, SC
2Deng organic sulfur, in catalyzed conversion formula reactor, can be counted as inert gas, need not consider in bed, to add hydrolyst, do not need these tempreture organic sulphur hydrolysis, thereby one section catalytic conversion reactor is maintained in the hope of making the high temperature of tempreture organic sulphur hydrolysis, can make one section catalytic conversion reactor maintain lower temperature, help claus reaction (
H in the formula
2S is a hydrogen sulfide, SO
2Be sulfur dioxide, S
xBe S
6, S
8, wherein be mainly S
8, H
2O is a water, and+Q represents heat release) chemical balance towards improving H
2The direction of S conversion ratio is carried out.
5, except that above characteristics, and different also being of traditional Sulfur Recovery Unit technology maximum:
1. need not be by improve H as far as possible
2The mode of S conversion ratio makes discharging tail gas up to standard.If the sulfur-bearing thing in the acid material gas only is H
2S, this technology only needs to keep catalyzed conversion formula reactor sulfur recovery rate～67% to get final product.If consider and contain other sulfur-containing compounds, can suitably improve this value, but can not require too high.
2. all organic sulfurs, the H in the acid material gas
2, CO, hydro carbons, NH
3, HCN etc. " combustible " all can by oxygen-excess combustion, be translated into SO in incinerator
2With the material of environmental sound, send SO to
2Exhausting section.Flow process and operation have been simplified.
3. needn't strictly control the H that enters gas in the catalyzed conversion formula reactor
2S and SO
2Be 2: 1 ratio, when the catalytic conversion stage sulfur recovery rate is 67%, H
2S and SO
2Ratio be 2: 1.In overall process, can regulate H according to activity of such catalysts and catalytic conversion stage sulfur recovery rate
2S and SO
2Ratio, generally can make it greater than 2: 1, (its restrictive condition is: { ε≤3/ η-1} and { ε≤V
0η/[V
0(1-η)-δ] } common factor, in the formula: ε-H
2S and SO
2Ratio; η-catalytic conversion stage sulfur recovery rate; Total COS, CS in the acid material gas of δ-from front end
2Deng sulfur-containing compound (in elementary sulfur S) molar flow; V
0-from H in the acid material gas of front end
2The S molar flow) helping guard catalyst is not subjected to the sulphation murder by poisoning or helps catalyst regeneration.
6, because SO
2Recovery has been adopted from third-party patented technology, and it is through reclaiming SO
2After incinerator smoke in SO
2Concentration can be controlled at 35～350mg/Nm
3, be significantly less than country and reach following now SO
2Discharge standard, need not to consider SO
2Discharge problem not up to standard.
7, owing to there not being the elevated temperature heat conversion zone, so need not consider the H in the acid material gas
2Whether the concentration of S is high to the degree that can burn, can handle poor H
2The S acid gas.Its H
2The concentration of S can be between 5%～100%.
8, SO
2Reclaim cyclic oxidation method sulfur recovery technology,, be more suitable for the acid waste gas that produces in handling the high-sulfur coal gasification in coal chemical technology.Because the H in the acid material gas
2The concentration of S is higher, and the economic benefit of this method sulfur recovery just significantly.Like this, not only use this method sulfur recovery process to have environment protection significance, but also have an economic benefit.
9, when normal the driving, heat from SO with incinerator smoke
2The SO of exhausting section
2And from the acid material gas of front end, it is temperature required and save steam consumption to make its temperature reach catalytic conversion reaction.
10, whole investment is low.Compare with super Crouse, can reduce by 1/3.Easy to operate, do not need to consider too high H
2The S conversion ratio.Operating cost is low, owing to can keep H for a long time
2S and SO
2Ratio greater than 2: 1, and do not have the possibility of leaking oxygen, do not need to use expensive TiO
2Anti-sulphation catalyst is only used common Al
2O
3Catalyst gets final product, and does not more need expensive patent import catalyst.
11, expansion is good.When there are enough investment capacitys in enterprise, can also be the SO in the boiler smoke
2Recovery can solve problem of environmental pollution in a wider context as the raw material of this technology, the sulfur recovery production capacity is enlarged and does not enlarge the sulfur recovery investment.
Description of drawings
Fig. 1 is a system and device structural representation of the present invention;
Fig. 2 is the flow chart that sulphur is reclaimed in the simplification of Fig. 1.
The specific embodiment
Accompanying drawing is embodiments of the invention.
Be described further below in conjunction with the content of drawings and Examples invention:
With reference to shown in Figure 1, sulfur dioxide recovery shunting sulfur recovery system device, mainly by first steam heater 1, second steam heater 2, first sulfur condenser 7, second sulfur condenser 6, acid gas preheater 12, sulfur dioxide preheater 13, waste heat boiler 14, incinerator 11, molten sulfur pond injector 15, high steam adds temperature-decreased pressure reducer 20, incinerator air-blaster 17, one section outlet air blast 5, liquid sulfur pump 16, first section claus reaction device 3, second section claus reaction device 4, molten sulfur pond 18, the first molten sulfur lock hopper 9, the second molten sulfur lock hopper 10, on, following molten sulfur collecter ring 8, sulfur dioxide recovery cellular system 19 constitutes, be connected by pipeline from the sulfur dioxide pipeline of sulfur dioxide recovery cellular system 19 and sulfur dioxide preheater 13, the acid gas line of raw material that gets the desulfurization unit system from front end and acid gas preheater 12 are connected by pipeline, sulfur dioxide preheater 13, acid gas preheater 12 and waste heat boiler 14 are with being located in the heat exchange box, acid gas preheater 12 respectively with incinerator bypass 11, the inlet of first steam heater 1 connects by pipeline, sulfur dioxide preheater 13 is connected by pipeline with the inlet of first steam heater 1, establish a bypass in the porch of first steam heater 1, be connected with first steam heater 1 through bypass, main road converges back and first section claus reaction device 3 from the inlet of first steam heater 1 and is connected by pipeline, first section claus reaction device 3 is connected by pipeline with first sulfur condenser 7, first sulfur condenser 7 is connected with following molten sulfur collecter ring 8, following molten sulfur collecter ring 8 is connected by pipeline with the first molten sulfur lock hopper 9 with one section outlet air blast 5 respectively, one section outlet air blast 5 and second section claus reaction device 4 are connected by pipeline, second section claus reaction device 4 is connected by pipeline with second sulfur condenser 6, molten sulfur collecter ring 8 connects on second sulfur condenser 6, last molten sulfur collecter ring 8 is connected by pipeline with the second molten sulfur lock hopper 10 with incinerator 11 respectively, the first molten sulfur lock hopper 9, the second molten sulfur lock hopper 10 is connected with molten sulfur pond 18 by pipeline respectively, second sulfur condenser 6, first sulfur condenser 7 and last, following molten sulfur collecter ring 8 shared housings, second sulfur condenser 6, first sulfur condenser 7 is in a tube bank.Incinerator air-blaster 17 is connected with incinerator 11 inlets with molten sulfur pond 18 by pipeline respectively, hydrogen reclaims exhaust pipe and is connected with incinerator 11 inlets, molten sulfur pond injector 15 is connected by pipeline with incinerator 11 inlets, incinerator 11 outlets connect the acid gas preheater 12 of series connection, sulfur dioxide preheater 13, waste heat boiler 14, behind waste heat boiler 14, be connected to sulfur dioxide recovery cellular system 19 by pipeline, high steam adds the temperature-decreased pressure reducer 20 and first steam heater 1, second steam heater 2 connects molten sulfur pond 18 and liquid sulfur pump 16 by pipeline and is connected by pipeline, described sulfur dioxide recovery cellular system 19 is existing patent recovery system, this system comprises that heat exchange box is connected to the bottom on absorption tower by pipeline, the top on absorption tower is connected on poor amine cooler and the amine clarifier by pipeline, poor amine cooler is connected to diamine cold punching pond by pipeline, the amine clarifier is connected on the overhead condenser by pipeline, overhead condenser is connected on the regenerator by pipeline, be connected with heat exchanger by pipeline between poor amine cooler and the regenerator, the regenerator bottom connects a tower bottom reboiler.This device can insert outside the above-mentioned recovery system, can also mate with other sulfur dioxide recovery methods.
The method of the recovery sulphur of system and device, undertaken by following step:
1), will wash acid gas (～25 ℃) from low first by pipeline and send into heat exchange in the acid gas preheater 12, be divided into two-way then, the one tunnel sends into incinerator (being less than 1/3), first steam heater, 1 front end (more than 2/3) is delivered on another road.Send in the sulfur dioxide preheater 13 after the heat exchange from the sulfur dioxide (～35 ℃) of sulfur dioxide recovery cellular system 19, also deliver to first steam heater, 1 front end and mix with the raw material acid gas of sending here.The temperature of mist then is delivered in first steam heater 1 by bypass and heats if do not reach 220～240 ℃, makes its temperature reach 220～240 ℃, otherwise directly sends in first section claus reaction device 3;
2), the gas after the last process heating is transported to by pipeline in first section claus reaction device 3 and carries out catalytic conversion reaction
Reaction equation:
(x=6,8, S
xMajor part is S
8)
+ Q represents heat release, and 270～350 ℃ of bed temperatures, air speed～470h-1, pressure are 5～10kPa (G);
3), the product behind the catalytic conversion reaction flows to first sulfur condenser 7 by pipeline, make its temperature drop to 125～130 ℃, at this moment the part gaseous sulfur is condensed into droplet, through molten sulfur collecter ring 8 separation down, the molten sulfur after the separation flows to the first molten sulfur lock hopper 9 by pipeline and sends into molten sulfur pond 18 then.Gas flows to 2 heating of second steam heater through one section outlet air blast 5 by pipeline, makes its temperature reach about 210～220 ℃ and is conveyed into second section claus reaction device 4 and carries out catalytic conversion reaction, and its catalytic conversion reaction formula is:
H in the formula
2S is a hydrogen sulfide, SO
2Be sulfur dioxide, S
xBe S
6, S
8, wherein be mainly S
8, H
2O is a water, and+Q represents heat release, and 220～270 ℃ of bed temperatures, air speed～600h-1, pressure are 20～30kPa (G).Product is sent into second sulfur condenser 6, makes its temperature drop to 125～130 ℃, and at this moment the part gaseous sulfur is condensed into droplet, separates through last molten sulfur collecter ring 8, and isolated molten sulfur flows to the second molten sulfur lock hopper 10 by pipeline and sends into molten sulfur pond 18 then.Isolated gas is sent into incinerator 11 through utilidor and is burned;
4), the product collected through the first molten sulfur lock hopper 9, the second molten sulfur lock hopper 10 sends into molten sulfur pond 18, carries the H that is dissolved in wherein at the molten sulfur in molten sulfur pond 18 by the part air gas from incinerator air-blaster 17
2Behind S and the Determination of Trace Sulfur steam, molten sulfur is transported to the assembly room by liquid sulfur pump 16, the H that gas exhaust gas and gas thereof propose
2S and Determination of Trace Sulfur steam mixture are sent into incinerator 11 by molten sulfur pond injector 15 and are burned;
5), in incinerator 11, the hydrogen that reclaims exhaust pipe from hydrogen reclaims the tail gas gas that acts as a fuel, with burn in main burner from the part air of incinerator air-blaster 17 inferior chemical equivalent with 80% fuel gas, the thermal-flame core that forms the reduction atmosphere is (in case NOx generates, x=1,2), form the flame envelope of oxidizing atmosphere with 130% of fuel gas chemistry equivalent as cooperation wind from the part air in addition of incinerator air-blaster 17, always in the air of incinerator air-blaster 17, telling the part air again as secondary wind, be used for the burning of process gas (at the flame envelope of oxidizing atmosphere), for guaranteeing the H in the flue gas
2S content is no more than 10mg/Nm
3, require the O in the flue gas
2Content～10%.These process gas comprise: from last molten sulfur collecter ring 8 isolated gases, wherein contain unreacted H completely
2S, does not capture clean combustibles such as elemental sulfur, from the H in the acid gas preheater 12 at organic sulfur
2S, combustibles such as organic sulfur are from the H of molten sulfur pond injector 15
2S, combustibles such as Determination of Trace Sulfur;
6), the gas of incinerator 11 burning is successively through acid gas preheater 12, sulfur dioxide preheater 13, waste heat boiler 14 heat exchange of series connection, make its temperature reach～160 ℃ after, send into the SO that sulfur dioxide recovery cellular system 19 reclaims wherein
2, and make SO in its discharge tail gas
2Content is at 35～350mg/Nm
3
Enter first section H in the claus reaction device 3
2S and SO
2Mol ratio be not limited in 2: 1, its ratio can be in 2～3 scopes (H
2S/SO
2=2～3) can regulate according to the sulfur recovery rate in activity of such catalysts, first and second section claus reaction device 3,4.When the activity of such catalysts height, when sulfur recovery rate was higher, suitably the acid material gas ratio of incinerator 11 was directly sent in raising, thereby reduced H
2S and SO
2Mol ratio, otherwise suitably the acid material gas ratio of incinerator 11 is directly sent in reduction, thereby improve H
2S and SO
2Mol ratio, concrete control can be calculated according to formula 1-1.
Reaction in first and second section claus reaction device 3,4 is only considered
(x=6,8); COS, CS
2Be considered as inert gas Deng organic sulfur, do not consider in catalyzed conversion formula reactor reactions such as hydrolysis, hydrogenation to take place, these organic sulfurs are SO by excessive air oxidation in the incinerator 11 of back only
2
The H of first and second section claus reaction device 3,4 inlets
2S and SO
2Mol ratio can by adjusting make its greater than 2: 1 and do not have " leakage oxygen " may, do not need to install additional organic sulfur hydrolyst yet, so, only need the common Al of filling in first and second section claus reaction device 3,4
2O
3Catalyst, its loadings can be calculated acquisition according to catalyst parameter and user's acid gas amount to be processed that catalyst supply merchant provides, and suppose: the air speed of catalyst is Vsp (h
-1), the process gas flow that enters first section claus reaction device (3) is Q (m
3/ h), then loaded catalyst is Q/Vsp (m in first section claus reaction device 3
3), loaded catalyst can calculate with method in second section claus reaction device 4.
Part acid material gas is directly sent into from acid gas preheater 12 and is carried out the peroxide burning in the incinerator 11, and wherein sulfur-containing compound changes SO into
2, the flow of this part gas, can calculate by following formula:
This part molar flow of directly sending into the gas of incinerator (11) is---P, kmol/h
Then have:
H in in the formula-acid material gas
2The mole fraction of S
ε-enter H in first section claus reaction device 3
2S and SO
2Mol ratio
V
0The molar flow kmol/h of-acid material gas
The sulfur recovery rate of η-first and second section claus reaction device 3,4
COS, CS in δ-first acid material gas
2Molar flow kmol/h Deng organic sulfur
Also have other sulphur-containing exhaust gas desulfurization boiler flue gas desulfurization waste gas in addition in the factory, main component is SO
2, and wherein the maximum of sulphur is closed valency and is not higher than+4 valencys, and molar flow is δ
1(kmol/h is with elementary sulfur S
1Meter), can partly or entirely send into this device, close valency as if the maximum of sulphur to be lower than+4, send into incinerator 11 front ends, their are burned by peroxide in incinerator 11, the sulphur in the sulfur-containing compound is converted into SO
2, equal+4 as SO
2Then directly send into the SO that reclaims in the sulfur dioxide recovery cellular system 19 wherein
2, but the maximum of sending into this device is:
δ
1MAX＝V
0·[η(1+ε)-ε]/ε-δ
In the formula: H in -acid material gas
2The mole fraction of S
ε-enter H in first section claus reaction device 3
2S and SO
2Mol ratio
V
0The molar flow kmol/h of-acid material gas
The sulfur recovery rate of η-first and second section claus reaction device 3,4
COS, CS in δ-first acid material gas
2Molar flow kmol/h Deng organic sulfur.
Embodiment 1
Certain factory, the molar flow of acid material gas is---V
0=205.36kmol/h, H in the acid material gas
2The mole fraction of S is 25.16%, total COS, CS in the acid material gas
2Deng organic sulfur (with elementary sulfur S
1Meter) molar flow is---δ=1.00kmol/h enters first section H in the claus reaction device 3
2S and SO
2Mol ratio be---ε=2.2, the sulfur recovery rate of first and second section claus reaction device 3,4 is (with elementary sulfur S
1The meter)---η=90%, but then this system also the maximum of extra process sulphur-containing exhaust gas (with pure SO
2Meter) be:
δ
1MAX＝205.36×0.2516×[0.9×(1+2.2)-2.2]÷2.2-1＝14.97kmol/h。
At this moment, the sulphur amount of recovery has been brought up to 205.36 * 25.16 ÷, 100 * 32+14.97 * 32=2132 (kg/h) volume increase 29% from original 205.36 * 25.16 ÷, 100 * 32=1653 (kg/h).Handle the also corresponding raising of ability of waste gas, but the amplitude that improves to be determined according to the concentration of sulfide in the extra process waste gas.Suppose and want SO in the extra process waste gas
2Concentration be 20%, then disposal ability has improved (205.36+14.97 ÷ 0.2) ÷ 205.36 * 100-100=36%.
The explanation of this example, this technology not only can be used for handling traditional acid material gas, can also widen the sulphur-containing exhaust gas that other parts are come in the processing plant, and disposal ability is strengthened, and sulphur output is increased.
Claims (7)
1, a kind of sulfur dioxide recovery shunting sulfur recovery unit, mainly by first steam heater (1), second steam heater (2), first sulfur condenser (7), second sulfur condenser (6), acid gas preheater (12), sulfur dioxide preheater (13), waste heat boiler (14), incinerator (11), molten sulfur pond injector (15), high steam adds temperature-decreased pressure reducer (20), incinerator air-blaster (17), one section outlet air blast (5), liquid sulfur pump (16), first section claus reaction device (3), second section claus reaction device (4), molten sulfur pond (18), the first molten sulfur lock hopper (9), the second molten sulfur lock hopper (10), on, following molten sulfur collecter ring (8), sulfur dioxide recovery cellular system (19) constitutes, it is characterized in that being connected by pipeline with sulfur dioxide preheater (13) from the sulfur dioxide pipeline of sulfur dioxide recovery cellular system (19), the acid gas line of raw material that gets the desulfurization unit system from front end is connected by pipeline with acid gas preheater (12), sulfur dioxide preheater (13), acid gas preheater (12) and waste heat boiler (14) are with being located in the heat exchange box, acid gas preheater (12) respectively with incinerator bypass (11), the inlet of first steam heater (1) connects by pipeline, sulfur dioxide preheater (13) is connected by pipeline with the inlet of first steam heater (1), a bypass is established in porch at first steam heater (1), be connected with first steam heater (1) through bypass, main road converges the back from the inlet of first steam heater (1) and is connected by pipeline with first section claus reaction device (3), first section claus reaction device (3) is connected by pipeline with first sulfur condenser (7), first sulfur condenser (7) is connected with following molten sulfur collecter ring (8), following molten sulfur collecter ring (8) is connected by pipeline with the first molten sulfur lock hopper (9) with one section outlet air blast (5) respectively, one section outlet air blast (5) is connected by pipeline with second section claus reaction device (4), second section claus reaction device (4) is connected by pipeline with second sulfur condenser (6), second sulfur condenser (6) is gone up molten sulfur collecter ring (8) and is connected, last molten sulfur collecter ring (8) is connected by pipeline with the second molten sulfur lock hopper (10) with incinerator (11) respectively, the first molten sulfur lock hopper (9), the second molten sulfur lock hopper (10) is connected with molten sulfur pond (18) by pipeline respectively, second sulfur condenser (6), first sulfur condenser (7) and last, the shared housing of following molten sulfur collecter ring (8), second sulfur condenser (6), first sulfur condenser (7) is in a tube bank, incinerator air-blaster (17) is connected with incinerator (11) inlet with molten sulfur pond (18) by pipeline respectively, hydrogen reclaims exhaust pipe and is connected with incinerator (11) inlet, molten sulfur pond injector (15) is connected by pipeline with incinerator (11) inlet, incinerator (11) outlet connects the acid gas preheater (12) of series connection, sulfur dioxide preheater (13), waste heat boiler (14), behind waste heat boiler (14), be connected to sulfur dioxide recovery cellular system (19) by pipeline, high steam adds temperature-decreased pressure reducer (20) and first steam heater (1), second steam heater (2) connects by pipeline, and molten sulfur pond (18) are connected by pipeline with liquid sulfur pump (16).
2, a kind of method with claim 1 system and device recovery sulphur, undertaken by following step:
1), to wash the acid gas temperature from low first by pipeline is 25 ℃ and sends into heat exchange in the acid gas preheater (12), be divided into two-way then, one the tunnel sends into incinerator, first steam heater (1) front end is delivered on another road, being 35 ℃ from the sulfur dioxide temperature of sulfur dioxide recovery cellular system (19) sends in the sulfur dioxide preheater (13) after the heat exchange, also delivering to first steam heater (1) front end mixes with the raw material acid gas of sending here, the temperature of mist is not if reach 220～240 ℃, then be delivered in first steam heater (1) and heat again by bypass, make its temperature reach 220～240 ℃, otherwise directly send in first section claus reaction device 3;
2), the gas after the last process heating is transported to by pipeline and carries out catalytic conversion reaction in first section claus reaction device (3):
Reaction equation:
X=6 or 8, S
xMajor part is S
8S wherein
x, S
8Refer to the molecular formula of sulphur steam, S
xRepresent that this molecule forms S by x sulphur atom
8Represent that this molecule is made up of 8 sulphur atoms ,+Q represents heat release, 270～350 ℃ of bed temperatures, air speed～470h
-1, pressure is 5～10kPa (G;
3), product behind the catalytic conversion reaction flows to first sulfur condenser (7) by pipeline, make its temperature drop to 125～130 ℃, at this moment the part gaseous sulfur is condensed into droplet, through molten sulfur collecter ring (8) separation down, molten sulfur after the separation flows to the first molten sulfur lock hopper (9) by pipeline and sends into molten sulfur pond (18) then, isolated gas flows to second steam heater (2) heating through one section outlet air blast (5) by pipeline, make its temperature reach about 210～220 ℃ and be conveyed into second section claus reaction device (4) and carry out catalytic conversion reaction, its catalytic conversion reaction formula is:
H in the formula
2S is a hydrogen sulfide, SO
2Be sulfur dioxide, S
xBe S
6, S
8, wherein be mainly S
8, H
2O is a water, and+Q represents heat release, 220～270 ℃ of bed temperatures, air speed～600h
-1, pressure is 20～30kPa (G).Product is sent into second sulfur condenser (6), make its temperature drop to 125～130 ℃, at this moment the part gaseous sulfur is condensed into droplet, separate through last molten sulfur collecter ring (8), isolated molten sulfur flows to the second molten sulfur lock hopper (10) by pipeline and sends into molten sulfur pond (18) then, and isolated gas is sent into incinerator (11) through utilidor and burned;
4), the product collected through the first molten sulfur lock hopper (9), the second molten sulfur lock hopper (10) sends into molten sulfur pond (18), carries the H that is dissolved in wherein at the molten sulfur of molten sulfur pond (18) by the part air gas from incinerator air-blaster (17)
2Behind S and the Determination of Trace Sulfur steam, molten sulfur is transported to the assembly room by liquid sulfur pump (16), the H that gas exhaust gas and gas thereof propose
2S and Determination of Trace Sulfur steam mixture are sent into incinerator (11) by molten sulfur pond injector (15) and are burned;
5), in incinerator (11), the hydrogen that reclaims exhaust pipe from hydrogen reclaims the tail gas gas that acts as a fuel, with burn in main burner from the part air of incinerator air-blaster (17) inferior chemical equivalent with 80% fuel gas, the thermal-flame core that forms the reduction atmosphere is in case the NOx generation, x=1 or 2, what X-represented is numeral, works as x=1, and NO represents nitric oxide; Work as x=2, NO
2Expression nitrogen dioxide, form the flame envelope of oxidizing atmosphere with 130% of fuel gas chemistry equivalent as cooperation wind from the part air in addition of incinerator air-blaster (17), always in the air of incinerator air-blaster (17), telling the part air again as secondary wind, be used for the burning of process gas (at the flame envelope of oxidizing atmosphere), for guaranteeing the H in the flue gas
2S content is no more than 10mg/Nm
3, require the O in the flue gas
2Content～10%, these process gas comprise: from the isolated gas of last molten sulfur collecter ring (8), wherein contain unreacted H completely
2S, does not capture clean elemental sulfur combustible, from the H in the acid gas preheater (12) at organic sulfur
2S, the organic sulfur combustible is from the H of molten sulfur pond injector (15)
2S, the Determination of Trace Sulfur combustible;
6), the gas of incinerator (11) burning is successively through acid gas preheater (12), sulfur dioxide preheater (13), waste heat boiler (14) heat exchange of series connection, make its temperature reach～160 ℃ after, send into sulfur dioxide recovery cellular system (19) and reclaim wherein SO
2, and make SO in its discharge tail gas
2Content is at 35～350mg/Nm
3
3, reclaim the method for sulphur according to the described system and device of claim 2, it is characterized in that entering the H in first section claus reaction device (3)
2S and SO
2Mol ratio be not limited in 2: 1, its ratio can be in 2～3 scopes, i.e. H
2S/SO
2=2～3 can regulate according to the sulfur recovery rate in activity of such catalysts, first and second section claus reaction device (3,4).
4, reclaim the method for sulphur according to the described system and device of claim 2, it is characterized in that the reaction in first and second section claus reaction device (3,4) is only considered
COS, CS
2Be considered as inert gas Deng organic sulfur, do not consider in catalyzed conversion formula reactor reactions such as hydrolysis, hydrogenation to take place, these organic sulfurs are SO by excessive air oxidation in the incinerator (11) of back only
2
5, reclaim the method for sulphur according to the described system and device of claim 2, it is characterized in that the H of first and second section claus reaction device (3,4) inlet
2S and SO
2Mol ratio can by adjusting make its greater than 2: 1 and do not have " leakage oxygen " may, do not need to install additional organic sulfur hydrolyst yet, so, only need the common Al of filling in first and second section claus reaction device (3,4)
2O
3Catalyst, its loadings can be calculated acquisition according to catalyst parameter and user's acid gas amount to be processed that catalyst supply merchant provides, and suppose: the air speed of catalyst is Vsp (h
-1), the process gas flow that enters first section claus reaction device (3) is Q (m
3/ h), then loaded catalyst is Q/Vsp (m in first section claus reaction device (3)
3), loaded catalyst can calculate with method in second section claus reaction device (4).
6, reclaim the method for sulphur according to the described system and device of claim 2, it is characterized in that a part of acid material gas is directly sent into from acid gas preheater (12) carries out peroxide and burns in the incinerator (11), and wherein sulfur-containing compound changes SO into
2, the flow of this part gas, can calculate by following formula:
This part molar flow of directly sending into the gas of incinerator (11) is---P, kmol/h
Then have:
H in in the formula-acid material gas
2The mole fraction of S
ε-enter H in first section claus reaction device 3
2S and SO
2Mol ratio
V
0The molar flow kmol/h of-acid material gas
The sulfur recovery rate of η-first and second section claus reaction device (3,4)
COS, CS in δ-first acid material gas
2Molar flow kmol/h Deng organic sulfur.
7, reclaim the method for sulphur according to the described system and device of claim 2, it is characterized in that also having other sulphur-containing exhaust gas desulfurization boiler flue gas desulfurization waste gas in addition in the factory, main component is SO
2, and wherein the maximum of sulphur is closed valency and is not higher than+4 valencys, and molar flow is δ
1(kmol/h is with elementary sulfur S
1Meter), can partly or entirely send into this device, close valency as if the maximum of sulphur to be lower than+4, send into incinerator (11) front end, their are burned by peroxide in incinerator (11), the sulphur in the sulfur-containing compound is converted into SO
2, equal+4 as SO
2Then directly send into the SO that reclaims in the sulfur dioxide recovery cellular system (19) wherein
2, but the maximum of sending into this device is:
δ
1MAx＝V
0·[η(1+ε)-ε]/ε-δ
In the formula: H in -acid material gas
2The mole fraction of S
H in ε-enter first section claus reaction device (3)
2S and SO
2Mol ratio
V
0The molar flow kmol/h of-acid material gas
The sulfur recovery rate of η-first and second section claus reaction device (3,4)
COS, CS in δ-first acid material gas
2Molar flow kmol/h Deng organic sulfur.
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| CN102781823A (en) * | 2010-03-22 | 2012-11-14 | 蒂森克虏伯伍德公司 | Device and method for condensing, separating, and storing liquid sulfur in a claus plant |
| CN103505997A (en) * | 2013-09-29 | 2014-01-15 | 环境保护部华南环境科学研究所 | Smoke and multi-pollutant efficient synergistic purification method and application thereof |
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