CN102381686A - Treatment process of high-ammonia and low-sulfur gas - Google Patents
Treatment process of high-ammonia and low-sulfur gas Download PDFInfo
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- CN102381686A CN102381686A CN2011102157691A CN201110215769A CN102381686A CN 102381686 A CN102381686 A CN 102381686A CN 2011102157691 A CN2011102157691 A CN 2011102157691A CN 201110215769 A CN201110215769 A CN 201110215769A CN 102381686 A CN102381686 A CN 102381686A
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Abstract
The invention relates to the technical field of sulfur recovery and in particular relate to a treatment process of high-ammonia and low-sulfur gas, and the method is used for solving the technical problem of unsmooth Claus reaction resulting from low enthalpy value of the high-ammonia and low-sulfur gas. The treatment process comprises the following steps: (1) introducing fuel gas, acid gas, oxygen and air into the front part of a combustion furnace for combustion so as to generate high-temperature process gas; and (2) introducing acid gas containing no ammonia from the middle part of the combustion furnace so as to react with the high-temperature process gas generated in the step (1). By adopting the treatment process, the treatment amount of the whole device can be changed flexibly so that the device can stably run within a great load range, thus being of great social significance for reduction of environmental pollution.
Description
Technical field
The invention belongs to the sulphur recovery technical field, relate in particular to a kind of treatment process of high ammonia low sulfur gas.
Technical background
The hydrogen sulfide that contain ammonia of concentration of hydrogen sulfide scope about 5%～20%; Owing to itself can not satisfy the condition of claus reaction; Must make temperature of reaction meet and exceed the temperature that Ammonia decomposes through the mode that increases reaction heat or reduce the growing amount of combustion substance; Ammonia in the decomposing hydrogen sulfide concentrated gas is handled 2 S component wherein simultaneously smoothly, realizes the comprehensive treating process of hydrogen sulfide.
Energy industry all can produce the waste gas that contains nitrogen, sulphur, and wherein the nitrogen element mainly exists with the form of ammonia, and element sulphur exists with the form of hydrogen sulfide.The concentration of hydrogen sulfide is generally more than 50% in the virgin gas of Petrochemical Enterprises, and the amount that contains the ammonia sour gas is far smaller than the amount of cleaning sour gas (hydrogen sulfide that does not promptly contain ammonia); For some small-sized coal chemical industry enterprises, though the concentration of hydrogen sulfide is lower in the virgin gas, do not contain Ammonia, both of these case deals with all relatively easy.Difficulty is relatively just compared in processing for high ammonia low-sulfur sour gas, and reason is that the decomposition of Ammonia needs the high temperature more than 1250 ℃, and the heat that relies on the burning of hydrogen sulfide concentrated gas self to contribute does not reach the temperature requirement that decomposes Ammonia far away.The purity of system sulphur reaction in furnace temperature and hydrogen sulfide is relevant, and the purity of hydrogen sulfide is high more, and temperature of reaction is high more; Handle this kind situation, conventional treatment method is to adopt oxygen enrichment technology, thereby the amount that just reduces process gas promotes the temperature of whole roasting kiln; In a single day airborne oxygen level surpassed 29% when but oxygen enrichment technology was used; Need carry out large-scale redevelopment to roasting kiln, even need to adopt cold flow round-robin Technology, not only technological loaded down with trivial details; The control difficulty is big, exposes simultaneously the little drawback of device elasticity to occur.Can only in a certain narrow relatively sour gas compositing range, operate with this device that designs, bring great influence for the operation of device.
The principal element of high ammonia low-sulfur sour gas difficult treatment is that the enthalpy of itself is low, is not enough to support carrying out smoothly of claus reaction.
Summary of the invention
For solving the problems of the technologies described above, the invention provides the treatment process that a kind of apparatus structure is simple, burn the high high ammonia low sulfur gas of ammonia temperature.
Technical scheme of the present invention is: a kind of treatment process of high ammonia low sulfur gas comprises step:
(1) fuel gas, sour gas, oxygen and air are fed the roasting kiln front portion and burn, produce pyroprocess gas;
(2) feed the sour gas that does not contain ammonia from the roasting kiln middle part, with the pyroprocess gas hybrid reaction of step (1) generation.
Sour gas is to contain the sour gas of ammonia or do not contain in the sour gas of ammonia one or both in the said step (1).
Said pyroprocess temperature degree is 1250 ℃～1350 ℃, and main effect is the ammonia in the gas of reducing sourness.
Said fuel gas is a kind of in water-gas, Sweet natural gas, hydrogen or the coal mine gas, preferred hydrogen.
The staple of said water-gas is CO and H
2, the staple of Sweet natural gas is CH
4, the staple of hydrogen is H
2, the staple of coal mine gas is C
1, C
2And H
2, do not advise using the heavy hydrocarbon gas gas that acts as a fuel, mainly be for fear of occurring because incomplete combustion generation carbon black influences quality product.
Said fuel gas and sour gas, the known material of technician in the industry under being.
Thinking of the present invention is: in reducing products of combustion in the inert fraction amount (for example because a large amount of nitrogen that use air unavoidably to sneak into); Increase high ammonia low-sulfur sour gas burning liberated heat; Blending fuel gas just; Thereby improve the intensity of combustion of unit volume, reach the purpose of burning the ammonia temperature.
Aerating oxygen is in order to reduce the amount of inert fraction in the products of combustion in the step (1).Roasting kiln adopts the twin furnace design, and the front portion belongs to the oxygen-excess combustion chamber, and the rear portion belongs to the mixing and reaction chamber.Sour gas from roasting kiln anterior with oxygen, air and fuel gas in the mixed firing of oxygen-excess combustion chamber, produce and surpass 1250 ℃ pyroprocess gas, main purpose is the ammonia in the gas of reducing sourness.The sour gas that does not contain ammonia gets into from roasting kiln burner hearth middle part; The anterior oxygen-excess combustion of roasting kiln mixes with the pyroprocess gas that comes out in the oxygen-excess combustion chamber, owing to will produce more sulfurous gas; Further react with the hydrogen sulfide in the sour gas that does not contain ammonia that feeds, thereby reach molecular balance.The separation and the further low-temp reaction that comprise sulphur in the process again through follow-up processing are until reaching emission request.
It is dimerous that oxygen requirement in the whole process step is that the amount of oxygen, the hydrogen sulfide complete reaction in the sour gas that are needed by the fuel gas perfect combustion of blending generate the amount of oxygen that sulphur needs.All oxygen is all supplied with by anterior oxygen that feeds of roasting kiln and air; Because not containing the sour gas of ammonia, part do not get into from the roasting kiln middle part; Therefore caused roasting kiln forward amount of oxygen local superfluous; Help the decomposition of anterior Ammonia and the perfect combustion of hydro carbons, the hydrogen sulfide in the sour gas that does not contain ammonia that gets in the middle part of the sulfurous gas of oxygen-excess combustion production and the roasting kiln simultaneously is secondary response again, generates sulphur.Ratio through hydrogen sulfide and sulfurous gas in the process gas of monitoring secondary claus reaction device rear portion is controlled the oxygen feed rate.Get into the amount that the sour gas of ammonia is not contained at the roasting kiln middle part through control, can adjust roasting kiln forward peroxide degree flexibly.Need to prove; Said peroxide is not that the roasting kiln front portion has the residual of oxygen in this specification sheets; But generate the reaction of sulphur with respect to the hydrogen sulfide oxidation; Too much oxygen further reacts hydrogen sulfide and has generated sulfurous gas rather than sulphur, and crossing oxygen condition is a relative notion.
It is anterior that fuel gas, sour gas, oxygen and four kinds of gases of air get into roasting kiln through concentric tubes, and fuel gas is in the bosom of concentric tubes, the oxygen second layer, and the 3rd layer of sour gas, air gets in outermost tubes.The concentration of combustion gas blending amount and oxygen blending amount and sour gas has very big relation, and the final purpose of blending is to guarantee the temperature of oxygen-excess combustion chamber at 1250 ℃～1350 ℃, rather than a fixed value.At the burning initial stage, the concentration of sour gas is on the low side, and need provide more fuel gas and oxygen this moment, to guarantee roasting kiln forward temperature of combustion, the corresponding minimizing of supply meeting of air; After burning for some time, sour gas concentration is relatively stable, and the amount of fuel blend gas, oxygen is with relative fixed, and system will regulate and control the ration of air voluntarily, and furnace temperature is with fluctuating in 1250 ℃～1350 ℃ scopes simultaneously.
Beneficial effect of the present invention is: the temperature that the treatment process of high ammonia low sulfur gas provided by the invention can improve Crouse's roasting kiln smoothly reaches the burning ammonia temperature more than 1250 ℃; Solve the handling problem of high ammonia low sulfur gas, simultaneously the turndown ratio of expansion instrument.This technology is particularly suitable for the relatively low H 2 S-containing gas of concentration of hydrogen sulfide and handles.Owing to can change the amount of fuel gas and the degree of increase and decrease oxygen enrichment at any time according to the variation that sour gas is formed; Make the various materials composition variation of adaptive device voluntarily of this comprehensive processing technique; With common process to the requirement of rolling off the production line of device turndown ratio---30%, be reduced to about 10% smoothly.Like this; Adopt the device of this technology when the upstream device underrun, just can realize normally going into operation and steady running; This technology can change the treatment capacity of whole device flexibly, and implement device steady running in great load range has great social effect for reducing environmental pollution.
Embodiment
Below specify the present invention through embodiment.
Embodiment 1
A kind of treatment process of high ammonia low sulfur gas comprises step:
1, fuel gas, the sour gas that contains ammonia, oxygen and air are fed the roasting kiln front portion and burn, produce pyroprocess gas;
2, feed the sour gas that does not contain ammonia from the roasting kiln middle part, with the pyroprocess gas hybrid reaction of step 1 generation.
Receive the guide functions of its internal rotation blade when containing sour gas and the air admission roasting kiln of ammonia, produce rotation in the same way, intense mixing; Oxygen then gets into roasting kiln with spray regime.Because combustion gas and oxygen acutely burn, and produce huge heat.If merely with combustion gas and pure oxygen burning, furnace temperature can reach 2400 ℃ (not considering the theoretical value of calorific loss).And it is fewer to contain the combustiblesubstances such as hydrogen sulfide that contain in the sour gas of ammonia; Rare gas element for example carbonic acid gas ratio is big relatively; The sour gas that contain ammonia this moment has two effects, one of which: participate in reaction, contain in the sour gas of ammonia inflammable gas such as hydrogen sulfide and oxygen and react; Its two: contain a large amount of rare gas elementes that carry in the sour gas of ammonia and have cooling effect, can stabilize the huge heat that fuel gas and oxygen reaction generate, thereby be unlikely to burn roasting kiln when reaching suitable temperature of reaction.
Through the flow of adjustment fuel gas and oxygen, temperature steady running in 1250～1350 ℃ of scopes of control roasting kiln, under this TR, the ammonia that contains in the sour gas of ammonia can be decomposed generation nitrogen G&W fully; Hydro carbons decomposes generation carbonic acid gas and water fully.We can adjust the feeding amount of air through the hydrogen sulfide/sulfurous gas on-line analysis instrument at monitoring claus reaction device rear portion.
The parameter of this arts demand regulation and control many, for example: air capacity, amount of oxygen, fuel tolerance etc.The control thinking is explained as follows:
(1) fire box temperature of roasting kiln is controlled through the amount of fuel gas, and in a single day fire box temperature is lower than set(ting)value (generally setting 1280 ℃), and the amount that system will increase fuel gas automatically reaches set(ting)value until temperature.The amount of oxygen is the amount that fuel gas perfect combustion needs, and in production reality, controls the fire box temperature of roasting kiln through timely adjustment.This is one-level control, the decomposition temperature of principal security Ammonia.
(2) amount of bubbling air is to control through the hydrogen sulfide/sulfurous gas on-line analysis instrument at monitoring claus reaction device rear portion.This is secondary control, mainly is the molecular balance that guarantees Crouse.
The amount that feeds the sour gas that does not contain ammonia from the roasting kiln middle part can be adjusted according to practical situation.The fractional flow that does not contain the sour gas of ammonia is in theory healed big; The anterior temperature of roasting kiln is higher; But owing to receive the restriction of " claus reaction ratio "; The amount that contains hydrogen sulfide in the sour gas that does not contain ammonia that the middle part feeds must not surpass 66% of whole hydrogen sulfide in the sour gas that contains ammonia that feeds roasting kiln and the not ammoniated sour gas, otherwise will influence the transformation efficiency of whole claus reaction.
So-called " claus reaction ratio " is meant: claus reaction is exactly hydrogen sulfide and sulfurous gas water generation reaction and sulphur, and it is 2:1 that this reaction requires the ratio of hydrogen sulfide and sulfurous gas.
Said pyroprocess temperature degree is 1250 ℃～1350 ℃; Main effect is the ammonia in the gas of reducing sourness.
Said fuel gas is a kind of in water-gas, Sweet natural gas, hydrogen or the coal mine gas, preferred hydrogen.
The staple of said water-gas is CO and H
2, the staple of Sweet natural gas is CH
4, the staple of hydrogen is H
2, the staple of coal mine gas is C
1, C
2And H
2, do not advise using the heavy hydrocarbon gas that acts as a fuel, mainly be for fear of occurring because incomplete combustion generation carbon black influences quality product.
Embodiment 2
A kind of treatment process of high ammonia low sulfur gas comprises step:
1, the sour gas that fuel gas, the sour gas that contains ammonia, oxygen, air and part is not contained ammonia feeds the roasting kiln front portion and burns, and produces pyroprocess gas;
2, feed the sour gas that part does not contain ammonia from the roasting kiln middle part, with the pyroprocess gas hybrid reaction of step 1 generation.
Receive the guide functions of its internal rotation blade when containing the sour gas of ammonia, sour gas and air admission roasting kiln that part does not contain ammonia, produce rotation in the same way, intense mixing; Oxygen then gets into roasting kiln with spray regime.Because combustion gas and oxygen acutely burn, and produce huge heat.If merely with combustion gas and pure oxygen burning, furnace temperature can reach 2400 ℃ (not considering the theoretical value of calorific loss).And it is fewer to contain the combustiblesubstances such as hydrogen sulfide that contain in the sour gas of ammonia; Rare gas element for example carbonic acid gas ratio is big relatively; The sour gas that contain ammonia this moment has two effects, one of which: participate in reaction, contain in the sour gas of ammonia inflammable gas such as hydrogen sulfide and oxygen and react; Its two: contain a large amount of rare gas elementes that carry in the sour gas of ammonia and have cooling effect, can stabilize the huge heat that fuel gas and oxygen reaction generate, thereby be unlikely to burn roasting kiln when reaching suitable temperature of reaction.
All the other are with embodiment 1.
Claims (5)
1. the treatment process of a high ammonia low sulfur gas is characterized in that, comprises step:
(1) fuel gas, sour gas, oxygen and air are fed the roasting kiln front portion and burn, produce pyroprocess gas;
(2) feed the sour gas that does not contain ammonia from the roasting kiln middle part, with the pyroprocess gas hybrid reaction of step (1) generation.
2. according to the treatment process of the said high ammonia low sulfur gas of claim 1, it is characterized in that sour gas is to contain the sour gas of ammonia or do not contain in the sour gas of ammonia one or both in the said step (1).
3. according to the treatment process of claim 1 or 2 said high ammonia low sulfur gas, it is characterized in that said pyroprocess temperature degree is 1250 ℃～1350 ℃.
4. according to the treatment process of claim 1 or 2 said high ammonia low sulfur gas, it is characterized in that said fuel gas is a kind of in water-gas, Sweet natural gas, hydrogen or the coal mine gas.
5. according to the treatment process of the said high ammonia low sulfur gas of claim 4, it is characterized in that said fuel gas is hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2011102157691A CN102381686A (en) | 2011-07-29 | 2011-07-29 | Treatment process of high-ammonia and low-sulfur gas |
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| CN2011102157691A CN102381686A (en) | 2011-07-29 | 2011-07-29 | Treatment process of high-ammonia and low-sulfur gas |
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| CN102381686A true CN102381686A (en) | 2012-03-21 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9370745B2 (en) | 2013-04-24 | 2016-06-21 | Jiangsu New Century Jiangnan Environmental Protection Co., Ltd | Flue gas-treating method and apparatus for treating acidic tail gas by using ammonia process |
| US10016721B1 (en) | 2017-05-25 | 2018-07-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desufurization process and apparatus |
| US10092877B1 (en) | 2017-05-25 | 2018-10-09 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10099170B1 (en) | 2017-06-14 | 2018-10-16 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US10112145B1 (en) | 2017-09-07 | 2018-10-30 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US20190001267A1 (en) | 2017-07-03 | 2019-01-03 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10207220B2 (en) | 2017-03-15 | 2019-02-19 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
| US10953365B2 (en) | 2018-07-20 | 2021-03-23 | Jiangnan Environmental Protection Group Inc. | Acid gas treatment |
| US11027234B2 (en) | 2018-04-13 | 2021-06-08 | Jiangnan Environmental Protection Group Inc. | Oxidization of ammonia desulfurization solution |
| CN113432131A (en) * | 2021-06-24 | 2021-09-24 | 中石化南京化工研究院有限公司 | Combined treatment method for high-ammonia-content acidic gas and liquid sulfur |
| US11224838B2 (en) | 2019-12-26 | 2022-01-18 | Jiangnan Environmental Protection Group Inc. | Controlling aerosol production during absorption in ammonia-based desulfurization |
| CN114132900A (en) * | 2021-12-07 | 2022-03-04 | 北京航化节能环保技术有限公司 | Sulfur recovery device switched by oxygen-enriched/air method in coking industry |
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Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9370745B2 (en) | 2013-04-24 | 2016-06-21 | Jiangsu New Century Jiangnan Environmental Protection Co., Ltd | Flue gas-treating method and apparatus for treating acidic tail gas by using ammonia process |
| US10207220B2 (en) | 2017-03-15 | 2019-02-19 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
| US10675584B2 (en) | 2017-03-15 | 2020-06-09 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
| US10413864B2 (en) | 2017-03-15 | 2019-09-17 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
| US10406477B2 (en) | 2017-03-15 | 2019-09-10 | Jiangnan Environmental Protection Group Inc. | Method and apparatus for removing sulfur oxides from gas |
| US10213739B2 (en) | 2017-05-25 | 2019-02-26 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10471383B2 (en) | 2017-05-25 | 2019-11-12 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10016721B1 (en) | 2017-05-25 | 2018-07-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desufurization process and apparatus |
| US10561982B2 (en) | 2017-05-25 | 2020-02-18 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desulfurization process and apparatus |
| US10343110B2 (en) | 2017-05-25 | 2019-07-09 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10092877B1 (en) | 2017-05-25 | 2018-10-09 | Jiangnan Environmental Protection Group Inc. | Dust removal and desulfurization of FCC exhaust gas |
| US10413865B2 (en) | 2017-05-25 | 2019-09-17 | Jiangnan Enviromental Protection Group Inc. | Ammonia-based desulfurization process and apparatus |
| US10399033B2 (en) | 2017-05-25 | 2019-09-03 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desulfurization process and apparatus |
| US10406478B2 (en) | 2017-05-25 | 2019-09-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-based desulfurization process and apparatus |
| US10583386B2 (en) | 2017-06-14 | 2020-03-10 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US10159929B1 (en) | 2017-06-14 | 2018-12-25 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US10099170B1 (en) | 2017-06-14 | 2018-10-16 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US10589212B2 (en) | 2017-06-14 | 2020-03-17 | Jiangnan Environmental Protection Group Inc. | Ammonia-adding system for ammonia-based desulfurization device |
| US10618001B2 (en) | 2017-07-03 | 2020-04-14 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10421040B2 (en) | 2017-07-03 | 2019-09-24 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10427097B2 (en) | 2017-07-03 | 2019-10-01 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US20190001267A1 (en) | 2017-07-03 | 2019-01-03 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10556205B2 (en) | 2017-07-03 | 2020-02-11 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10561984B2 (en) | 2017-07-03 | 2020-02-18 | Jiangnan Environmental Protection Group Inc. | Desulfurization absorption tower |
| US10449488B2 (en) | 2017-09-07 | 2019-10-22 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US10112145B1 (en) | 2017-09-07 | 2018-10-30 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US10357741B2 (en) | 2017-09-07 | 2019-07-23 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US10369517B2 (en) | 2017-09-07 | 2019-08-06 | Jiangnan Environmental Protection Group Inc. | Method for controlling aerosol production during absorption in ammonia desulfurization |
| US11027234B2 (en) | 2018-04-13 | 2021-06-08 | Jiangnan Environmental Protection Group Inc. | Oxidization of ammonia desulfurization solution |
| US10953365B2 (en) | 2018-07-20 | 2021-03-23 | Jiangnan Environmental Protection Group Inc. | Acid gas treatment |
| US11529584B2 (en) | 2018-07-20 | 2022-12-20 | Jiangnan Environmental Protection Group Inc. | Acid gas treatment |
| US11224838B2 (en) | 2019-12-26 | 2022-01-18 | Jiangnan Environmental Protection Group Inc. | Controlling aerosol production during absorption in ammonia-based desulfurization |
| CN113432131A (en) * | 2021-06-24 | 2021-09-24 | 中石化南京化工研究院有限公司 | Combined treatment method for high-ammonia-content acidic gas and liquid sulfur |
| CN114132900A (en) * | 2021-12-07 | 2022-03-04 | 北京航化节能环保技术有限公司 | Sulfur recovery device switched by oxygen-enriched/air method in coking industry |
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Application publication date: 20120321 |