CN1127369C - Method of treating waste gas containing sulfur and flammable component - Google Patents
Method of treating waste gas containing sulfur and flammable component Download PDFInfo
- Publication number
- CN1127369C CN1127369C CN 00110703 CN00110703A CN1127369C CN 1127369 C CN1127369 C CN 1127369C CN 00110703 CN00110703 CN 00110703 CN 00110703 A CN00110703 A CN 00110703A CN 1127369 C CN1127369 C CN 1127369C
- Authority
- CN
- China
- Prior art keywords
- waste gas
- concentration
- sulfur
- organic
- catalytic combustion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Abstract
The present invention relates to a method for purifying waste gas containing sulfur and flammable components, particularly to organic waste gas containing hydrogen sulfide and/or organic sulfur from a sewage treatment plant of a petrochemical enterprise. Firstly, a waste gas discharging source needs to be closed, so the waste gas enters a waste gas purification treatment system from a fixed waste gas discharging opening, and the waste gas purification treatment system is composed of a concentration homogenizer, a desulfurization treatment device and a catalytic combustor, wherein matter with strong absorbability is filled in the concentration homogenizer, an Fe2O3 type desulfurizing agent or a ZnO type desulfurizing agent is filled in the desulfurization treatment device, and a precious metal type catalyst is filled in the catalytic combustor. By a three-phase combined technique, the organic waste gas is combusted completely in catalytic combustion, so the waste gas is purified.
Description
The present invention relates to the purifying treatment method of a kind of sulfur-bearing and combustible components waste gas, more particularly, relate to the purifying treatment method of the organic exhaust gas that contains hydrogen sulfide and/or organic sulfur of a kind of petroleum chemical enterprise sewage-farm discharging.
Production by Catalytic Combustion Process is a kind of effective ways that purify flammable organic exhaust gas, and this method is particularly suitable for low concentration, multicomponent and does not have the improvement of the organic exhaust gas of recovery value.Catalytic combustion is owing to use catalyst, so combustion reaction carries out under the temperature more much lower than ordinary combustion, is CO making most of organic matter complete oxidation below 400 ℃ generally
2And H
2O, and can not produce NO
XAnd cause secondary pollution.Production by Catalytic Combustion Process has distinct advantages and therefore is widely used.
But, Production by Catalytic Combustion Process is applied to purifying sulfur-containing and combustible components waste gas, the organic exhaust gas of the complicated component of forming by multiple VOC (VOCs) that contains hydrogen sulfide and/or organic sulfur of petroleum chemical enterprise sewage-farm discharging particularly, but run into problem, promptly hydrogen sulfide in the waste gas and organic sulfur can cause catalyst at short notice because of the poisoning inactivation.Therefore must solve the problem that hydrogen sulfide and organic sulfur cause catalyst poisoning earlier with Production by Catalytic Combustion Process purified treatment sewage-farm organic exhaust gas; Another problem is, the composition that enters the waste water in sewage-farm can have greatly changed, and this concentration that can cause organic exhaust gas takes place than great fluctuation process.This fluctuation of concentration is disadvantageous to catalyst for catalytic combustion, and the unexpected increase of organic exhaust gas concentration can cause the temperature of catalytic bed to raise suddenly, thus make catalyst under high temperature thermal shocking because of surperficial sintering and the active component inactivation of reuniting.
Although the method for purifying sulfur-containing in the past and combustible components waste gas respectively has characteristics, but since these methods at the feature difference of the waste gas of the particularity of exhaust gas source and required processing, often meet difficulty when being used for the sulfur-bearing organic exhaust gas of other kinds of purified treatment.For example patent EP793996 has provided the method that a kind of purified treatment contains the organic exhaust gas of hydrogen sulfide, mercaptan.This process comprises desulfurization and two stages of catalytic combustion.The method of desulfurization is: air feeds in the organic exhaust gas behind the bubbling in akaline liquid, and under the effect of catalyst, hydrogen sulfide changes sulfide into, and mercaptan changes disulphide into.The organic exhaust gas that the process desulfurization is handled reaches the purpose that deodorization purifies again through catalytic combustion.This sulfur method can make odorants such as hydrogen sulfide and mercaptan change less sulfide of stink and disulphide into, but not it is not really removed and reaches the purpose that thoroughly removes, when catalyst for catalytic combustion with still might make catalyst poisoning after sulfide or disulphide contact.For reaching the desulfurization purpose, this sulfur method requires to feed the air of alkalization, this will inevitably dilute the organic exhaust gas of need handling, and this dilution is disadvantageous to the efficient of catalytic combustion when the concentration of organic waste gas own is not high, can make the energy consumption and the running cost increase of exhaust-gas treatment.In addition, this method will be used alkali lye, and the waste gas purification cost is improved, and also can cause the problem of secure context.
Purpose of the present invention just provides a kind of purifying sulfur-containing and combustible components waste gas, particularly the method for the organic exhaust gas of the complicated component of being made up of multiple VOC (VOCs) that contains hydrogen sulfide and/or organic sulfur of petroleum chemical enterprise sewage-farm discharging.
Sulfur-bearing organic exhaust gas among the present invention refers to contain the organic exhaust gas of hydrogen sulfide and/or organic sulfur, refer in particular to the organic exhaust gas that contains hydrogen sulfide and/or organic sulfur of petroleum chemical enterprise's sewage-farm discharging, this sulfur-bearing organic exhaust gas mainly is made up of VOC (VOCs), and contains a small amount of hydrogen sulfide and/or organic sulfur.Organic sulfur comprises all organic compounds containing sulfurs that may be produced by Sulfur-Containing Crude such as mercaptan, thioether, cos, organic disulfide compound (as DMDS), thiophene.
Purifying sulfur-containing of the present invention and combustible components waste gas is the method for the organic exhaust gas that contains hydrogen sulfide and/or organic sulfur of petroleum chemical enterprise sewage-farm discharging particularly, may further comprise the steps successively:
(A) collect waste gas, make waste gas enter the waste gas purification treatment system.
(B) waste gas is through the inner concentration homogenizer that is filled with concentration homogenizing material, so that exhaust gas concentration is steady.
(C) waste gas of concentration after steadily removes hydrogen sulfide and/or organic sulfur in the waste gas through the inner desulfurization processor that is filled with desulfurizing agent.
(D) enter catalytic combustion reactor through the waste gas of desulfurization, under the effect of catalyst by catalytic combustion fully, thereby reach the purpose of waste gas purification.
When the toxic emission source is uncovered,, must seal the toxic emission source earlier and derive waste gas from stationary exit, organic exhaust gas can be collected focus on.The organic exhaust gas that the petroleum chemical enterprise sewage-farm produces is generally open-air discharging, therefore needs to carry out airtight to the toxic emission source.Common sealing method has covered and enclosed, covering airtight etc., also can use additive method, as long as waste gas is closed.After the toxic emission source is sealed, reserve fixing outlet port, make waste gas import cleaning treatment system from this outlet by induced draught system.
The waste gas purification treatment system is made up of concentration homogenizer, desulfurization processor and catalytic burner three parts.After waste gas is imported into cleaning treatment system, at first will be through the over-richness homogenizer.The effect of concentration homogenizer is that to make concentration have concentration than the waste gas of great fluctuation process to be tending towards homogeneous steady, when avoiding combustible component concentration to increase suddenly catalyst for catalytic combustion is caused thermal shock, makes it because of moment high temperature inactivation.The concentration homogenizer is the tank container of a metal material, air inlet is arranged below it, and the gas outlet is arranged above, the material that inner filling has the concentration homogenization.Material with concentration homogenization is generally to be the stronger material of adsorptivity, comprise one or more combination of active carbon, molecular sieve, silica gel, aluminium oxide, diatomite etc., each material needs to become specific shape through forming processes mostly, as various suitable shapes such as sphere, strip, sheet, hollow cylindrical, gear-like, trilobals, also can be powder or graininess.The principle that the concentration homogenizer plays the concentration homogenization is: the bigger waste gas of fluctuation of concentration through adsorbability material absorption reach saturated after, promptly discharge its component with the concentration of homogeneous roughly because of desorption.Which kind of therefore need to decide use adsorbability material and determine its loadings according to the concentration of waste gas and the fluctuating range of concentration.Generally speaking, when the higher and fluctuation of concentration of organic exhaust gas concentration was big, the loadings of required adsorbability material was bigger.The operation air speed of concentration homogenizer is 2000～15000h
-1
Waste gas promptly enters the desulfurization processor after concentration homogenizer concentration of treatment is steady, remove hydrogen sulfide and organic sulfur in the waste gas, in order to avoid catalyst for catalytic combustion is poisoned.The desulfurization processor is made up of preheater and desulfurization reactor.But preheater is the electric heating system of A.T.C, and it is temperature required that waste gas was preheated to before entering desulfurization reactor.The inner filling of desulfurization reactor desulfurizing agent, desulfurizing agent is commercially available or homemade desulfurizer for refining gas, main component is Fe
2O
3Or ZnO, add a small amount of active A l
2O
3And adhesive after compressing tablet or extruded moulding.Desulfurizing agent bed inlet temperature is 50～400 ℃, and using the air speed scope is 2000～30000h
-1Need according to the tolerance of organic exhaust gas and service conditions such as the kind of hydrogen sulfide content and organic sulfur and use amount that concentration is determined desulfurizing agent and temperature, air speed wherein.In general, when organic waste gas concentration of sulfur is higher, need under less air speed and higher temperature, to use desulfurizing agent, but temperature can not be too high in order to avoid desulfurizing agent loses desulphurizing activated because of surperficial sintering.
Waste gas through desulfurization handle remove hydrogen sulfide and organic sulfur after, mix with air, be preheated to temperature requiredly again through preheater, enter catalytic combustion reactor then.Air is introduced by blower fan, can control its flow.When waste gas itself contains the air of q.s and waste gas and need not dilute, also can not introduce air in addition.Catalytic combustion reactor is a metal material, becomes cylindric or other any suitable shapes, its inner filling catalyst for catalytic combustion.Catalyst for catalytic combustion adopts the honeycomb type noble metal catalyst, and carrier is a honeycomb ceramic body, supports precious metals pt, Pd and CeO on it
2The isoreactivity component.The inlet bed temperature scope of catalytic combustion reactor is generally 100～450 ℃, and using the air speed scope is 5000～100000h
-1Adjust the serviceability temperature and the air speed of catalyst according to contained organic kind and concentration in the organic exhaust gas, on the one hand to make organic exhaust gas that clean-up effect is preferably arranged, avoid organic exhaust gas heat release when catalytic bed is reacted more and cause catalyst on the other hand again because of high temperature deactivation.
Use above-mentioned " concentration homogenizing-desulfurization-catalytic combustion " method purifying sulfur-containing and combustible components waste gas, the organic exhaust gas of the composition complexity that contains hydrogen sulfide and/or organic sulfur of petroleum chemical enterprise sewage-farm discharging particularly, can make the bigger organic exhaust gas concentration of fluctuation of concentration be tending towards homogeneous, avoid bigger fluctuation of concentration to cause that operating difficulties and catalyst are because of moment high temperature inactivation; Also can make hydrogen sulfide in the sulfur-bearing organic exhaust gas and the organic sulfur clearance greater than 90%, eliminate the stench that sulfur-containing compound causes and avoided the catalyst for catalytic combustion poisoning; Because concentration homogenizing and desulfurization measure are arranged, this method can keep the organic waste-gas purification rate greater than 90% under lower bed inlet temperature.The inventive method is at the special circumstances of exhaust gas source, solve the fluctuation of concentration problem of sewage-farm organic exhaust gas and catalyst that sulfur-containing compound causes problem, thereby make Production by Catalytic Combustion Process become the effective ways of administering the sewage-farm organic exhaust gas because of the poisoning inactivation.The inventive method flow process is short, and method is simple, and equipment investment, operating cost are all lower.The inventive method goes for the purified treatment of various sulfur-bearings and combustible components waste gas.
Further illustrate the present invention below in conjunction with example, but do not limit protection scope of the present invention.
Embodiment 1-12
After the organic exhaust gas that contains hydrogen sulfide and/or organic sulfur of petroleum chemical enterprise sewage-farm discharging sealed, from outlet waste gas is introduced the concentration homogenizer with air-introduced machine, so that the concentration of waste gas is tending towards homogeneous; Waste gas removes hydrogen sulfide and organic sulfur through the desulfurization processor then; At last, the organic exhaust gas after the desulfurization mixes mutually with the air of introducing, is heated to enter catalytic combustion reactor after temperature required in preheater, is discharged behind the catalytic combustion fully therein.Waste gas purification treatment conditions among each embodiment are listed in table 1, and the purified treatment effect under each condition is listed in table 2.Wherein, consisting of of S1 desulfurizing agent: 80wt%Fe
2O
3, 10wt%Al
2O
3, 5wt%NaOH, 5wt% talcum powder, through compression molding; Consisting of of S2 desulfurizing agent: 80wt%ZnO
3, 10wt%Al
2O
3, 5wt%NaOH, 5wt% methylcellulose, add extruded moulding after the suitable quantity of water.The C1 catalyst supports 0.4wt%Pt, 0.2wt%Pd and 1.4wt%CeO by dipping on the honeycomb ceramic carrier
2Make, the C2 catalyst supports 0.6wt%Pt and 2wt%CeO by dipping on the honeycomb ceramic carrier
2Make.
Table 1 waste gas purification treatment conditions
| Embodiment | Exhausting waste gas amount (Nm 3/h) | Waste gas component and fluctuation of concentration | The concentration homogenizer | The desulfurization processor | Catalytic combustion reactor | ||||||
| Total hydrocarbon (mg/m 3) | Total sulfur (mg/m 3) | Fill | Loadings (L) | Desulfurizing agent | Inlet temperature (℃) | Catalyst | Inlet temperature (℃) | ||||
| Title | Loadings (L) | Title | Loadings (L) | ||||||||
| 1 | 10 | 3300～4200 | 21～33 | Activated carbon granule | 3 | S1 | 3 | 250 | C1 | 2 | 120 |
| 2 | 20 | 3400～5000 | 7～14 | Activated carbon granule+5A molecular sieve | 3+2 | S1 | 1 | 180 | C2 | 2 | 180 |
| 3 | 30 | 4400～8200 | 12～42 | Ф 2 active carbon ball+Ф 3 alumina balls | 10+5 | S1 | 15 | 200 | C1 | 0.75 | 380 |
| 4 | 30 | 2400～3800 | 12～18 | Ф 1 silica-gel sphere | 4 | S1 | 6 | 150 | C1 | 0.5 | 250 |
| 5 | 30 | 1300～1860 | 2～9 | Diatomite | 3 | S1 | 4 | 100 | C1 | 0.4 | 270 |
| 6 | 40 | 3500～4200 | 3～10 | Ф 3 * 3 active sketching charcoals | 8 | S2 | 6 | 190 | C2 | 0.8 | 330 |
| 7 | 50 | 2200～3600 | 4～10 | Ф 3 alumina balls | 6 | S2 | 5 | 50 | C1 | 2 | 350 |
| 8 | 60 | 2700～4200 | 5～18 | The 5A molecular sieve spheres of Ф 2 | 4 | S2 | 4 | 80 | C1 | 3 | 300 |
| 9 | 60 | 3700～6900 | 12～18 | 5A molecular sieve+Ф 4 silica-gel spheres | 3+2 | S1 | 2 | 220 | C2 | 0.6 | 450 |
| 10 | 60 | 2600～3800 | 30～42 | The 5A molecular sieve spheres of Ф 3 alumina balls+Ф 2 | 2+4 | S1 | 3 | 300 | C2 | 3 | 400 |
| 11 | 60 | 3100～4500 | 42～58 | Ф 2 active carbon ball+Ф 1 silica-gel sphere | 8+2 | S2 | 2 | 350 | C2 | 4 | 360 |
| 12 | 60 | 2400～5200 | 40～70 | Ф 3 * 3 active sketching charcoal+Ф 3 alumina balls | 10+2 | S1 | 3 | 400 | C1 | 5 | 240 |
Table 2 waste gas purification treatment effect
| Embodiment | Concentration range after the homogenizing | Total sulfur removal rate (%) | Total hydrocarbon conversion rate (%) | |
| Total hydrocarbon (mg/m 3) | Total sulfur (mg/m 3) | |||
| 1 | 3600～3950 | 26～29 | 95 | 91 |
| 2 | 4000～4400 | 10～12 | 92 | 93 |
| 3 | 6150～6400 | 24～29 | 97 | 95 |
| 4 | 3000～3400 | 15～16 | 96 | 98 |
| 5 | 1420～1750 | 5～7 | 98 | 96 |
| 6 | 3700～4000 | 5～9 | 100 | 94 |
| 7 | 2800～3000 | 6～8 | 98 | 99 |
| 8 | 3200～3650 | 10～14 | 94 | 95 |
| 9 | 5100～5550 | 14～16 | 96 | 96 |
| 10 | 3100～3300 | 34～38 | 93 | 97 |
| 11 | 3700～3950 | 49～51 | 96 | 98 |
| 12 | 3600～4000 | 52～57 | 95 | 96 |
Claims (5)
1, the purifying treatment method of a kind of sulfur-bearing and combustible components waste gas may further comprise the steps successively:
(A) collect waste gas, make waste gas enter cleaning treatment system;
(B) waste gas is through the inner concentration homogenizer that is filled with concentration homogenizing material;
(C) waste gas of concentration after steadily is through the inner desulfurization processor that is filled with desulfurizing agent;
(D) waste gas through desulfurization enters catalytic combustion reactor;
Wherein concentration homogenizing material is active carbon, molecular sieve, silica gel, aluminium oxide, diatomaceous one or more combination; Desulfurizing agent can remove hydrogen sulfide and the organic sulfur in the waste gas, and its main component is Fe
2O
3Or ZnO, add a small amount of active A l
2O
3And adhesive after compressing tablet or extruded moulding.
2,, it is characterized in that described catalyst for catalytic combustion is the honeycomb type noble metal catalyst according to the method for claim 1.
3, according to the method for claim 1, the operation air speed that it is characterized in that described concentration homogenizer is 2000～15000h
-1
4, according to the method for claim 1, the operation air speed that it is characterized in that described devulcanizer is 2000～30000h
-1, layer bed inlet temperature is 50～400 ℃.
5, according to the method for claim 1, the operation air speed that it is characterized in that described catalytic combustion reactor is 5000～100000h
-1, layer bed inlet temperature is 100～450 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110703 CN1127369C (en) | 2000-07-24 | 2000-07-24 | Method of treating waste gas containing sulfur and flammable component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110703 CN1127369C (en) | 2000-07-24 | 2000-07-24 | Method of treating waste gas containing sulfur and flammable component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1335198A CN1335198A (en) | 2002-02-13 |
| CN1127369C true CN1127369C (en) | 2003-11-12 |
Family
ID=4580682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00110703 Expired - Lifetime CN1127369C (en) | 2000-07-24 | 2000-07-24 | Method of treating waste gas containing sulfur and flammable component |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1127369C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7727507B2 (en) * | 2005-03-30 | 2010-06-01 | Shell Oil Company | Process for producing a gas stream depleted of hydrogen sulphide |
| CN101347684B (en) * | 2007-07-18 | 2010-05-19 | 中国石油化工股份有限公司 | Method for treating tail gas during production processes of polyalcohol |
| CN101721893B (en) * | 2009-12-30 | 2011-11-02 | 湖北华邦化学有限公司 | Storage tank breathing waste-gas desulfurization deodorizing technique |
| CN106215878B (en) * | 2016-08-30 | 2018-12-25 | 西南化工研究设计院有限公司 | A kind of extraordinary desulfurizing agent and deodorization process of food waste deodorization process |
| CN108926974A (en) * | 2017-05-24 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of security protection technique for VOCs Treatment process |
| CN110368814A (en) * | 2019-08-23 | 2019-10-25 | 四川省达科特能源科技股份有限公司 | A kind of method of catalytic oxidation treatment pressure-changeable adsorption decarbonization device discharge gas |
| CN113209816A (en) * | 2020-01-21 | 2021-08-06 | 中国石油化工股份有限公司 | Catalyst grading method for catalytic oxidation of sulfur-containing VOCs and method for catalytic oxidation of sulfur-containing VOCs |
| CN113432135A (en) * | 2020-03-23 | 2021-09-24 | 大连佳纯气体净化技术开发有限公司 | Removing CO from gasified and transported pulverized coal2Method and device for producing methanol in gas |
| CN113295601A (en) * | 2021-05-13 | 2021-08-24 | 上海长肯试验设备有限公司 | Corrosion testing machine for chimney pipeline |
-
2000
- 2000-07-24 CN CN 00110703 patent/CN1127369C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1335198A (en) | 2002-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100496678C (en) | Combined purification method for effluvial exhaust air | |
| CN101362101B (en) | Semi-coke forming SO2and NO adsorptive catalyst and preparation method thereof | |
| CN101391177B (en) | Gas purification method of low concentration organic compound | |
| RU2177361C2 (en) | Method of lowering total sulfur level in gases including hydrogen sulfide and other sulfur-containing components | |
| CN102049181A (en) | Purification method of sulfur-containing organic waste gas | |
| CN1127369C (en) | Method of treating waste gas containing sulfur and flammable component | |
| CN102500323B (en) | Modified active carbon desulfurizer and preparation method thereof and treatment method of hydrogen sulfide waste gas | |
| CN110711485A (en) | Waste gas purification device for sewage treatment station of sterile raw material medicine production line | |
| CN1242838C (en) | Process for cleaning waste gas containing combustible components | |
| CN101462063B (en) | Desulfurizing agent for removing carbonyl sulfur, thiol and hydrogen sulphide by catalytic oxidation as well as preparation and application | |
| CN102039077A (en) | Method for treating malodorous waste gas containing hydrocarbon | |
| CN1255205C (en) | Method for purifying organic waste gas with high concentration | |
| CN112892484B (en) | VOCs adsorbent and preparation method thereof | |
| CN113426289A (en) | Hydrolysis adsorbent, blast furnace gas desulfurization method and desulfurization equipment | |
| CN1768924A (en) | Absorbent for purifying sulfur-containing foul waste gas and preparation method thereof | |
| CN102908849B (en) | The processing method of discharged exhaust gas in sewage disposal field | |
| CN1253848A (en) | Method for treating industrial waste gas containing sulphur oxide | |
| CN108211779B (en) | Deodorant and preparation method thereof | |
| CN113877405B (en) | Waste lubricating oil hydrogenation gas treatment and discharge process | |
| CN109289466A (en) | The smog environment-friendly disposal system and processing method in post-cure workshop | |
| CN114432870B (en) | FCC regenerated flue gas treatment method and device | |
| CN214020058U (en) | Organic waste gas's purification unit | |
| JPS6153104B2 (en) | ||
| CN211800030U (en) | Waste gas purification device for sewage treatment station of sterile raw material medicine production line | |
| CN211328916U (en) | Molecular trapping catalytic oxidation exhaust gas purification system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20031112 |
|
| CX01 | Expiry of patent term |