CN1243025A - Process for reducing-absorbing treating tail gas from sulphur production without on-line furnace - Google Patents
Process for reducing-absorbing treating tail gas from sulphur production without on-line furnace Download PDFInfo
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- CN1243025A CN1243025A CN 98110371 CN98110371A CN1243025A CN 1243025 A CN1243025 A CN 1243025A CN 98110371 CN98110371 CN 98110371 CN 98110371 A CN98110371 A CN 98110371A CN 1243025 A CN1243025 A CN 1243025A
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- hydrogen
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Abstract
The present invention relates to a sulfur production tail-gas reduction and absorption treatment process without on-line furnace. It is characterized by that said invented process does not use on-line furnace to provide heat source and produce hydrogen, adds external hydrogen source and utilizes the fume heat produced after incineration of tail-gas in the tail-gas incinerator to heat tail-gas to required hydrogenation reduction reaction temp.. The hydrogen source can be pure hydrogen, waste hydrogen or cracking gas containing hydrogen. Said treatment process can meet the requirements for sulfur production tail-gas reduction absorption treatment equipment and technology of petrochemical plant and refinery, can reduce investment and operation cost, and can reduce the absolute discharge of pollutant being in the fume.
Description
The present invention relates to a kind of treatment process of making sulphur tail gas.
The raw material of system sulphur process mainly is the hydrogen sulfide containing sour gas that refining and petrochemical processing units produces, and produces sulphur through processes such as CLAUS reacting furnace and two-stage catalytic reactors.Still have a spot of H in the tail gas that system sulphur process produces
2S, SO
2, S
xCOS, CS
2Deng pollutant.In order to reduce pollution, need handle system sulphur tail gas to environment.
At present widely used is Holland technology, promptly tail gas is reduced to absorb the SCOT technology of handling, and absorbs treatment process through reduction, makes wherein pollutant be converted into hydrogen sulfide and returns system sulphur, and cleaned gas is through the tail gas burning furnace discharged in burning.It is temperature required that the reduction absorption technique needs tail gas to be heated to hydrogenation reduction, needs hydrogen source simultaneously.A key equipment of SCOT technology is exactly at line oven, in this stove, feed the combustible gas and an amount of air that contain lighter hydrocarbons, make it carry out time chemical equivalent burning, when taking place, heat produces a certain amount of hydrogen, high temperature gas flow enters the mixing chamber of burner hearth, mix with the sulfur recovery tail gas of low temperature, it is temperature required to make exhaust temperature rise to catalytic hydrogenation, and the hydrogen of generation is then as SO in the tail gas
2, S
xReduce required hydrogen source.It at first is under the effect of hydrogenation catalyst that reduction absorbs treatment process, carries out hydrogenation reaction, SO in hydrogenation reactor
2, S
xBe reduced to H
2S, cooling then absorbs H with pure ammonia solution or other lyosoption again
2S is purified tail gas, and clean-up effect is relevant with the kind and the performance of lyosoption.Be absorbed with H
2The solvent of S is through regeneration, and recycling, hydrogen sulfide returns system sulphur, and the tail gas after the purification is discharging atmosphere (with reference to the flow chart in Fig. 1 frame of broken lines) after tail gas burning furnace burns.
SCOT technology at line oven as using fuelled with natural gas, can obtain hydrogen manufacturing effect preferably because the main component of natural gas is a methane, the hydrogen content height, air distribution amount (blowing air) is more easy to control.When line oven is made fuel with the cracked gas of oil plant secondary operations device, because this gas componant complexity makes the control of air distribution become very difficult, the beds phenomenon that carbon distribution stops up hydrogenation reactor appears very easily.In addition, when the line oven fuel combustion, 79% be nitrogen in the air distribution amount, the addition of the High Temperature Gas after nitrogen and the burning accounts for 10% of tail gas amount, and under the prerequisite of identical clean-up effect, the amount that is equivalent to the pollutant in the discharged flue gas increases about 10%.
In order to solve the above-mentioned trouble that refinery gas hydrogen manufacturing is occurred, Italian NIGI company invented a kind of need not to add in addition hydrogen source reduction absorption technique-H.C.R technology.The foundation of this technology is the hydrogen that the CLAUS reacting furnace will produce some in system sulphur process, and with the hydrogen source of this part hydrogen as conventional CLAUS reaction end gas hydrogenation, its amount is obviously not enough, if but the air distribution ratio of change CLAUS reaction makes H in the tail gas
2S/SO
2〉=10, then the amount of sulfur dioxide in the tail gas significantly reduces, and the amounts of hydrogen that produce in the CLAUS reacting furnace this moment just can satisfy in the tail gas hydrogenation reaction the demand of hydrogen, and unnecessary hydrogen sulfide returns system sulphur after solvent absorbs.
H.C.R process using sacrificial section CLAUS reaction conversion ratio reaches the purpose that need not add hydrogen source, and the problem of bringing thus is that excess hydrogen sulfide need use bigger absorption equipment and more solvent that it is reclaimed.In addition, for reaching suitable hydrogenation reaction inlet temperature, H.C.R technology is used online heating furnace (or electric heater).This technology has solved the difficult problem with refinery gas hydrogen manufacturing, but system sulphur conversion ratio reduction and absorption equipment and lyosoption amount new problem bigger than normal have occurred thereupon.
Present sulfur recovery unit major part both domestic and external concentrates on selexol process factory or petrochemical plant, oil plant, the sulfur recovery unit of selexol process factory, generally there is not hydrogen source, with fuelled with natural gas process for making hydrogen maturation, so vent gas treatment adopts SCOT or H.C.R technology to be fine.As petrochemical plant and oil plant, how to make fuel, because the problem of above-mentioned existence has its limitation with the cracking gas of secondary operations device.
The objective of the invention is to be fit to the system sulphur tail gas reduction absorption treating device and the technological requirement of petrochemical plant and oil plant to the treatment process of system sulphur tail gas, reducing investment outlay and reducing under the prerequisite of operating cost, reduce the absolute discharge capacity of the pollutant in the discharging flue gas better, can adopt the hydrogen source of various purity to satisfy the requirement that reduction absorbs treatment process.
Realize the process for reducing-absorbing treating tail gas from sulphur production of the object of the invention, be still tail gas and the hydrogen that to reach the hydrogenation reduction temperature and be mixed into reduction absorption treatment process that reduction absorbs the sour gas (H after handling
2S) recycle, the tail gas that is cleaned discharged in burning in tail gas burning furnace, its major technique characteristics are to utilize the flue gas heat after tail gas burning furnace burns to add hot exhaust gas to temperature required, hydrogen can be to sneak into before adding hot exhaust gas or after adding hot exhaust gas.
Technology of the present invention need not provide heat and hydrogen source by online reduction furnace, and hydrogen can be to be provided by hydrogen sources such as pure hydrogen, useless hydrogen or hydrogeneous cracking gases.
Illustrate below in conjunction with process flow diagram:
Fig. 1 is a process flow diagram of the present invention.
Among the figure in the frame of broken lines for reduction absorbs processing technological flow and device, with prior art with, as SCOT technology and H.C.R technology.
Tail gas burning furnace burns the temperature of back flue gas generally at 600～700 ℃, can be used as the intensification thermal source of tail gas in the hydrogenation reactor (130～170 ℃) hydrogenation reaction temperature required (300 ℃).The form of heater exhaust gas can be gas-gas heat exchanger, the heat transmission equipment of heat pipe heat exchanging equipment or other form.The front or rear of heater exhaust gas can add various forms of waste heat recovery apparatus, as the steam superheater among the figure.High-temperature flue gas has heated tail gas through heater exhaust gas, discharges atmosphere then.
The hydrogen source of hydrogenation reaction can be the high-purity hydrogen of device for producing hydrogen, also can be the useless hydrogen that reformer, hydrocracking unit are discharged, it can also be the hydrogeneous cracking gas of catalytic cracking unit, coking plant, hydrogen in the cracking gas is utilized, remainingly do not participate in reaction and enter tail gas burning furnace with subsequent handling such as reduction absorption etc., substitute part burning fuel gas, combustion decomposition is after the aiutage discharging.All the other components in the hydrogen-containing gas do not cause adverse effect to used lyosoption as long as high temperature polymerization, condensation, cracking do not take place in the hydrogenating reduction absorption process, all can be used as hydrogen source.The hydrogen concentration that contains that various hydrogen sources provide does not have special requirement, as long as the hydrogeneous total amount hydrogen more required than hydrogenation reaction is excessive a little, generally is that hydrogen accounts for 0.3～1.0% of cumulative volume after the hydrogenation reaction in the technology.
Advantage of the present invention:
1, sulfur recovery tail gas Reducing and absorption treatment process and the device of all kinds petrochemical plant and oil plant are had widely adaptability, available high-purity hydrogen, useless hydrogen or hydrogeneous cracking gas are made hydrogen source.
2, make thermal source with the tail gas burning furnace flue gas, it is temperature required to make tail gas reach hydrogenation reaction, and online reduction furnace or tail gas heating stove, avoided air distribution wayward, increase the drawback of pollutant discharge amount, reduce smoke discharge amount about 10%, the corresponding minimizing of discharge capacity of pollutant (sulfur dioxide), energy savings. The combustible of not participating in reaction in the used useless hydrogen of the present invention, the hydrogeneous cracking gas is used as part of fuel and is used in tail gas burning furnace.
3, saved in the SCOT technique control system loaded down with trivial details on line oven, it is about 10% that follow-up Reducing and absorption treatment process equipment volume can be dwindled, and H.C.R technique follow-up equipment is larger.
The present invention has saved investment cost and operating cost, is a kind of simple and direct treatment process that is fit to petrochemical plant and oil plant.
Below be the calculated data contrast table of treatment process of the present invention and SCOT technology:
Unstripped gas is system sulphur secondary and transforms CLAUS technology, and data are identical.
| Sequence number | The contrast project | The present invention | SCOT | SCOT/ the present invention |
| ??1 | System sulphur exhaust flow kmol/h | 103.723 | 104.211 | 1.005 |
| ??2 | System sulphur exhaust temperature ℃ | 130 | 130 | |
| ??3 | Sneak into the hydrogen amount or at line oven fuel quantity kmol/h (being all cracking gas) | 2.5 | 1.828 | 0.731 |
| ??4 | Use air capacity kmol/h before the hydrogenation reaction | 0 | 8.587 | |
| ??5 | Exhaust temperature ℃ after the hydrogenation reaction | 370.6 | 347.5 | |
| ??6 | Tail gas is formed kmol/h H after the hydrogenation reaction 2???????????????????????????????Ar ???????????????????????????????N 2???????????????????????????????CO ???????????????????????????????CO 2???????????????????????????????H 2S ???????????????????????????????COS ???????????????????????????????H 2O ???????????????????????????????C 1???????????????????????????????C 2???????????????????????????????C 3???????????????????????????????iC 4???????????????????????????????iC 5???????????????????????????????∑ | 0.584 0.611 51.419 0.027 24.61 1.989 0.004 25.272 0.475 0.523 0.013 0.003 0.011 105.54 | 0.915 0.695 58.369 0.04 25.775 2.002 0.004 26.717 114.517 | 1.085 |
| ??7 | Tail gas quench tower load KW | 465.567 | 490.121 | 1.053 |
| ??8 | Tail gas absorbs with quantity of solvent (30%MDEA) kg/h | 15581 | 15656 | 1.005 |
| ??9 | Return acid tolerance kmol/h after the absorption | 4.098 | 4.118 | 1.005 |
| ??10 | Purify tolerance kmol/h | 81.29 | 89.289 | 1.098 |
| ??11 | Vent gas treatment consumption fuel tolerance (comprising the 3rd) kmol/h | 5.009 | 6.719 | 1.341 |
| ??12 | Aiutage smoke discharge amount kmol/h | 123.44 | 136.27 | 1.104 |
| ??13 | SO in the aiutage flue gas 2Discharge capacity kg/hr | 1.92 | 2.048 | 1.067 |
| ??14 | Full device total sulfur yield % | 99.84 | 99.83 | |
| ??15 | Unit scale t/d | 14.43 | 14.43 |
Data as can be seen from table, (1) owing to SCOT/ the present invention=1.053～1.104 in the items such as tail gas quench tower thermic load, purification tolerance, aiutage smoke discharge amount, so the capital equipment scale of vent gas treatment is about 1.1 times of the present invention as hydrogenation reactor, steam generator, quench tower, absorption tower, tail gas burning furnace, aiutage etc.(2) SO from sequence number 13 visible aiutage flue gases
2One of discharge capacity, SCOT is 1.067 times of the present invention.(3) are 1.341 times of fuel gas consumption of the present invention from sequence number 11 visible SCOT fuel gas consumptions.
Claims (2)
1, a kind of nothing is at the line oven process for reducing-absorbing treating tail gas from sulphur production, be that the tail gas and the hydrogen that will reach the hydrogenation reduction temperature is mixed into reduction absorption treatment process, the sour gas that reduction absorbs after handling is recycled, the tail gas that is cleaned discharged in burning in tail gas burning furnace, it is characterized in that utilizing the flue gas heat after tail gas burning furnace burns to add hot exhaust gas to temperature required, hydrogen is sneaked into after can or adding hot exhaust gas before adding hot exhaust gas.
2, treatment process according to claim 1 is characterised in that hydrogen can be to be provided by hydrogen sources such as pure hydrogen, useless hydrogen or hydrogeneous cracking gases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98110371 CN1243025A (en) | 1998-07-28 | 1998-07-28 | Process for reducing-absorbing treating tail gas from sulphur production without on-line furnace |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98110371 CN1243025A (en) | 1998-07-28 | 1998-07-28 | Process for reducing-absorbing treating tail gas from sulphur production without on-line furnace |
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|---|---|
| CN1243025A true CN1243025A (en) | 2000-02-02 |
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|---|---|---|---|
| CN 98110371 Pending CN1243025A (en) | 1998-07-28 | 1998-07-28 | Process for reducing-absorbing treating tail gas from sulphur production without on-line furnace |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182926B (en) * | 2007-12-14 | 2011-01-26 | 镇海石化工程有限责任公司 | Stove-fuel flow online control device and method thereof |
| CN108163816A (en) * | 2017-12-29 | 2018-06-15 | 山东大学 | A kind of charcoal heat-also Primordial Qi coupling reduction SO2The device and method for preparing sulphur |
| US11795389B2 (en) | 2021-04-21 | 2023-10-24 | Shaanxi Lighte Optoelectronics Material Co., Ltd. | Nitrogen-containing compound, electronic component, and electronic device |
-
1998
- 1998-07-28 CN CN 98110371 patent/CN1243025A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182926B (en) * | 2007-12-14 | 2011-01-26 | 镇海石化工程有限责任公司 | Stove-fuel flow online control device and method thereof |
| CN108163816A (en) * | 2017-12-29 | 2018-06-15 | 山东大学 | A kind of charcoal heat-also Primordial Qi coupling reduction SO2The device and method for preparing sulphur |
| US11795389B2 (en) | 2021-04-21 | 2023-10-24 | Shaanxi Lighte Optoelectronics Material Co., Ltd. | Nitrogen-containing compound, electronic component, and electronic device |
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