CN102753474B - From rich in ammonia air-flow, from sour gas and sulfur dioxide flow back to receive sulfur method - Google Patents
From rich in ammonia air-flow, from sour gas and sulfur dioxide flow back to receive sulfur method Download PDFInfo
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- CN102753474B CN102753474B CN201080058795.1A CN201080058795A CN102753474B CN 102753474 B CN102753474 B CN 102753474B CN 201080058795 A CN201080058795 A CN 201080058795A CN 102753474 B CN102753474 B CN 102753474B
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- acid gas
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 101
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 79
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 67
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 57
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 27
- 239000011593 sulfur Substances 0.000 title claims abstract description 27
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- 230000003647 oxidation Effects 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 230000001590 oxidative effect Effects 0.000 claims description 17
- 238000011084 recovery Methods 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 235000010269 sulphur dioxide Nutrition 0.000 abstract description 20
- 239000003295 industrial effluent Substances 0.000 abstract description 4
- 239000004291 sulphur dioxide Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 239000011819 refractory material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- -1 nitrogen-containing organic compound Chemical class 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0456—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process the hydrogen sulfide-containing gas being a Claus process tail gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
- B01D53/523—Mixtures of hydrogen sulfide and sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0408—Pretreatment of the hydrogen sulfide containing gases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0413—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the combustion step
- C01B17/0421—Multistage combustion
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treating Waste Gases (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to and always flow the NH higher than 30 based on two kinds of air-flows from having3/H2The optional of S volume ratio wraps the method that the hydrogen sulfide containing air-flow rich in ammonia reclaims sulfur with acid gas stream. The Sulphur Dioxide that the method allows also to comprise in industrial effluent becomes hydrogen sulfide, and reclaims sulfur and two kinds of said flow.
Description
Invention field
It is an object of the invention to a kind of method carried out in the improvement thermal reactor of Claus process, described method is for optionally wrapping the hydrogen sulfide containing air-flow rich in ammonia and lean ammonia and the recovery wrapping the sulfur contained in hydrogen sulfide containing air-flow, it is preferable that ammonia/hydrogen sulfide volume ratio is higher than 30 based on total stream of two kinds of described air-flows.
Another object of the present invention allows for making the Sulphur Dioxide comprised in industrial effluent become hydrogen sulfide the method reclaiming sulfur under having ammonia and two kinds of said flow existence of sour gas.
Summary of the invention
Known in prior art from the Claus method wrapping hydrogen sulfide containing air flow recovery sulfur. Described method is substantially made up of the partial oxidation stage carried out in thermal reactor, recuperation of heat stage and one or more catalytic stages, and in catalytic stages, the hydrogen sulfide in gas reacts with the sulfur dioxide produced at described partial oxidation stage, to produce sulfur.
The method of the present invention is suitably modified in thermal reactor to carry out Claus method, and is made up of two further part oxidation stages; The hydrogen sulfide containing ammonia flow of optional bag is carried out by the first oxidation, and the air-flow comprising hydrogen sulfide and lean ammonia is carried out by the second oxidation, and ammonia remnants content is carried out, and if yes, the air-flow from Part I oxidation stage is carried out.
Oxidizing elemental in two partial oxidations is present in air stream, or is present in the stream formed by air and pure oxygen (or enriched air (enrichedair)).
Specifically, originally changing into nitrogen and water and the temperature of the hydrogen sulfide Partial Conversion sulfur dioxide wherein optionally comprised being sufficiently high to guarantee amino, ammonia stream aoxidizes in oxygen lack lower part.
Under oxygen lack, the acid gas stream of lean ammonia also partial oxidation, hydrogen sulfide is partially converted into sulfur dioxide.
Ammonolysis craft and hydrogen sulfide convert required oxidizing elemental through separating in two different stream, and the ammonia being contained in respectively in ammonia and sour gas and hydrogen sulfide stream short-term training ratio: the described stream of oxidizing elemental is consistent with the charging of two process streams respectively introduces thermal reactor. Specifically, the special interior allotter that the oxidizing elemental in the second oxidation stage manufactures by being different from the refractory material of sour gas charging is sent into.
The air-flow obtained from described partial oxidation stage enters the Claus process catalysed partial for recovery of elemental sulfur.
The method of the present invention favorably carries out in by described distributor function reactor separately in two regions or vicinity and the room that connects therebetween: in first area at diverse location, sends into and optional wraps hydrogen sulfide containing ammonia flow and a part of oxidizing elemental; At second area at its initial part, what lean ammonia sour gas was manufactured by refractory material with remainder oxidizing elemental compare with ammonia feed is positioned at and ensures that the special allotter being enough to the distance of the time of staying at the quantitative ammonolysis craft of reactor second area is sent into.
If there is also the air-flow of the industrial effluent comprising sulfur dioxide, this also reactor second area start introduce.
State-of-art
Now, thick oil is commercially available with high-load nitrogen-containing organic compound more and more continually, and these nitrogen-containing compounds change into ammonia in oil, petrochemical industry and rendering industry process. In current industrial implementation, by ammonia streaming to sulfur recovery unit, and such as processed together with the general sour gas produced by amino washing liquid. But, same for the purpose of it, use Claus method to have the NH existed in the stream that mixing ammonia stream and lean ammonia sour gas obtain from burner3/H2S volume ratio limits. Actually, on the one hand, described restriction higher than increasing in Claus method the risk of ammonium salt precipitation in lightpenia territory, because the non-transformed ammonia of trace reacts with hydrogen sulfide, and with the SO of existence in process fluid2/SO3Reaction, thus equipment blocking.
On the other hand, due to kinetic reasons, ammonia converts needs to be not less than the operation temperature of 1250 DEG C, this temperature is because the strongly exothermic property of reaction increases with the increase of ammonia density in entire mixture, until becoming incompatible with the operation temperature to greatest extent that the refractory material forming thermal reactor liner is allowed, for comprising the refractory material of at least 90% corundum, operation temperature is equal to 1700-1750 DEG C to greatest extent.
For current Claus method, according to the H in sour gas2S concentration, allows NH to greatest extent3/H2S volume ratio is 25-30gap.
In the current situation, the partial oxidation reaction by carrying out at high temperature carries out ammonia stream process:
This reaction always splits into the reaction of its element with ammonia:
Reaction [1], heat release, limited by kinetics, and need commercial scale to use, operation temperature is higher than 1250 DEG C.
Order first two method can be used for the reaction [1] and [2] that carry out in Claus method:
1. aoxidized by high-strength combustor section;
2. partial oxidation in dual chamber.
First method is, sends in the burner with high pressure drop by ammonia and sour gas, to react the most probable Homogeneous phase mixing of agent and oxidizing elemental (general atmosphere pressure air oxygen), to ensure the high oxygenation efficiencies that flame temperature is corresponding to greatest extent.
According to Claus method stoichiometry, SO is changed into for ammonolysis craft and 1/3rd hydrogen sulfide sent into2Both required air overall flow rates are by forming the charging aperture feeding burner being suitable for shape to carry out sound response agent mixing.
Vulcanize H-H reactions according to following reaction (general Claus method, carry out in the temperature higher than 1,000 DEG C) is remaining with 2/3rds subsequently according to the sulfur dioxide that following reaction [3] produces, generate elementary sulfur and water:
The operation oxidation stage temperature that available the method obtains is such as diluting the temperature needed for sour gas can relatively low convert to complete ammonia, and only can ensure by heat before introducing reactor, generally use steam, three kinds of incoming flow ammonias, sour gas and oxidation air.
Except required preheater and associated steam consumption need, the method also has two defects, one is owing to the high pressure drop of dispensing burner has less motility in place capacity change, two is do not allow carefully to control oxide regions operation temperature, because this is based only on homogeneous reaction agent mixing. It practice, capacity reduces can endanger described Homogeneous phase mixing.
Second method, the partial oxidation in dual oxide region, is mixed with only partially acidic gas in the burner by ammonia, and remainder delivers to the second area of same reactor.Send into distribute to for required all air of ammonia oxidation and the reaction of Claus method and compare the burner reducing more pressure drops with the first method with high intensity.
At the function that operation temperature is the acid gas quantity delivering to the second oxidation reactor region that thermal reactor the first oxide regions produces: by increasing this amount, temperature in first reactor area rises and reaches peak 1,500-1,700 DEG C, consistent with air/ammonia and sour gas stoichiometric proportion in first area, reduce to increase with gas in second area, because air excess in the first region. Accompanying drawing 1 shows the dependency in sour gas percent and first area in the second area between temperature. Curve relates to the ammonia comprising about 66% volume ammonia and 34% volume of water, and sour gas essentially pure hydrogen sulfide.
By the sour gas flow of simple adjustment to second area, the temperature in first area is made to be controlled. Utilizing the method, incoming flow preheating is unnecessary, and can accurately control operation temperature in any place capacity condition.
In any case, for two kinds of methods, the ammonia amount (sour gas is equal) that available Claus method processes is by NH in total admixture of gas (two kinds of incoming flow total amounts)3/H2S volume ratio limits.
The present invention allows to overcome described restriction, therefore, it is possible to make Claus method process have any NH3/H2The ammonia of S ratio and hydrogen sulfide air-flow, therefore, more specifically allowing for that (especially to refinery) process can the thick oil with high nitrogen-containing that is commercially available of low cost.
Detailed Description Of The Invention
For the method being better understood from the present invention, with reference to accompanying drawing 2-4, accompanying drawing should not in any way limit the present invention.
Fig. 2 showed for the time of staying equal to 1 second, NH3/H2S molar ratio equal to 25 and air velocity be in stoichiometric ammonia inversion cuver (function for temperature);
Fig. 3 schematically shows the method that two kinds of air-flows (ammonia stream and acid gas stream) deposit the present invention in case;
Fig. 4 schematically shows the method too much depositing the present invention in case rich in the air-flow of sulfur dioxide.
By ammonia (2) (20 to 45% moles of ammonia, optionally comprise hydrogen sulfide, remainder is water) deliver to Part I oxidation stage (5), air or enriched air stream (8) the 50-90% volume relative to 33% stoichiometric air calculated to amino moiety oxidation reaction [1] (considering ammonia decomposition reaction [2]) and the partial oxidation reaction [3] also wrapping hydrogen sulfide in hydrogen sulfide containing situation at ammonia stream together with air or enriched air stream (8).
According to the empirical curve shown in the Fig. 2 obtained with above-mentioned parameter, ammonia is in the temperature Quantitative yield higher than 1350 DEG C. With upper curve by supposing NH in the time of staying, charging3/H2The function change of S molar ratio and oxidizing elemental shortage degree.
Therefore, in the Claus method that the method according to the invention regulates to process ammonia equally, operation temperature must be highest possible: namely, higher than 1,250 DEG C, but lower than 1,600 DEG C, in order to avoid damage forms the internally coated refractory material of device therefor.
Whole air-flow streams that the reaction [1], [2] and [3] occurred from the first oxidation stage (5) obtains are to the second stage (6) of the method for the present invention.
Sour gas (3) with make together with hydrogen sulfide is converted into the oxidizing elemental (4) needed for elementary sulfur according to Claus method, it is transported to the initial part of second stage (6) together with the ammonia (if yes) comprised in sour gas and the ammonia (if yes) that comprises in the stream flowed out from the stage (5), reacts according to following reaction [5] and [6]:
Overall result is that ammonia is fully converted into nitrogen.
Exporting (6) from second stage, the air-flow obtained (7) feeding Claus process catalysed partial, for sulfur recovery.
Oxidizing elemental and all sour gas section retards enter second stage (6), give the ammonia (2) from sour gas (3) and process independence, and this allows independent of the NH in the stream obtained from whole ammonias and sour gas3/H2S volume ratio processes the first stage.
Wherein in ammonia ammonia flow velocity not enough so that two kinds postpone in those situations of amount that charging (sour gas and corresponding air or enriched air (4)) reaches temperature needed for Claus method, i.e. at NH3/H2When S volume ratio is too low, such as 1-30, the method of the present invention can operate in second stage according to the method for partial oxidation, it is exactly, as mentioned above, making ammonia flow (2) mix in the ammonia burner inserting the first stage (5) with partially acidic gas (3), all the other sour gas parts deliver to second stage (6), because oxidizing elemental only delivers to the first stage (5).
Sometimes, exist wherein for, in the industrial production facilities of the equipment based on Claus method of sulfur recovery, also producing the stream rich in sulfur dioxide, for instance, in the process device of the effluent from the upper cracking process of fluid bed in refinery (FCC).
The method of the present invention allows the Sulphur Dioxide comprised in industrial effluent described in Claus method to become hydrogen sulfide, then reclaims sulfur.
This converts and develops according to reduction reaction [7]:
Reaction carries out at high temperature, and with the restriction overcoming kinetics to fix, as shown in Figure 4, under the hydrogen that ammonia dissociation reaction [2] produces in its element exists, the air-flow comprising sulfur dioxide is transported to the beginning of second stage (6).
Reference number (9) represents the air-flow rich in sulfur dioxide, and it delivers to the beginning of second oxidation stage (6) of the method for the present invention.
Reference number (7) represents the total air flow in the inventive method downstream, and total air flow delivers to the catalysed partial of the Claus method for sulfur recovery. Above-mentioned reference number clearly shows that the essential elements of the method for the present invention, namely, incoming flow (1), (2) and (3) (respectively oxidizing elemental, ammonia stream and acid gas stream), two partial oxidation stage (5) and (6) (respectively ammonia and sour gas) and the optional air-flow (9) comprising sulfur dioxide, finally, reference number (7) represents the total air flow in the inventive method downstream obtained in improving Claus method reactor.
From ammonia flow and acid gas stream with high (namely higher than 30) and low (lower than 30, when Claus process downstream increase vent gas treatment process) NH3/H2S molar ratio, produces to can be used for the method for the present invention of the air-flow of recovery of elemental sulfur in Claus process catalysed partial and can reclaim more than the sulfur comprised in 99.5% feed stream.
It addition, same under the 3rd air-flow rich in sulfur dioxide exists, when increasing vent gas treatment process, from ammonia flow and from acid gas stream with high NH3/H2S molar ratio (namely higher than 30) reclaims the described method of sulfur can reclaim the sulfur comprised in three kinds of feed streams more than 99.5%.
Thering is provided following example is to evaluate the present invention better, the invention is not restricted to this.
Embodiment 1
Equipment for preparing mercaptobenzothiazoler (a kind of vulcanizer) produces the 0.81kmol/h gaseous effluent comprising 89.59% volume hydrogen, 4.22% volumes carbon dioxide and 6.19% volume of water.
Recirculation water from equipment comprises significant quantity ammonia, and in order to meet the maximum allowable deviation being equal to 5ppm in waste water, these ammonia are removed by gas stripping process.
Extracting 2.01kmol/h ammonia from stripper top, this ammonia comprises 39.6% volume hydrogen, 41% volume ammonia and 19.4% volume of water.
Two kinds of streams must process in the equipment based on the Claus process of sulfur recovery, but the amount ratio between the two stream produces the ammonia/hydrogen sulfide volume ratio equal to 54.3, for excessive ratio for running the equipment needing to be equal to the conventional Claus process of the maximum limit angle value of 30 about described ratio.
The method utilizing the present invention, two kinds of all available Claus methods of stream process, and all ammonias are delivered to the first conversion zone of the thermal reactor that the method according to the invention is improved together with 2.94kmol/h air. Under these conditions, 1,600 DEG C of temperature is reached in described first area. In this temperature, ammoxidation Cheng Shui and nitrogen are quantitative. In the second stage (6) of method, temperature is maintained at about 1450 DEG C.
The stream leaving second stage (6) comprises nitrogen, water, unreacted hydrogen sulfide, sulfur dioxide, elementary sulfur and hydrogen. Described sulfur suitable in the catalysed partial at the equipment based on conventional Claus process with post processing.
Embodiment 2
Within the scope of the up-to-dateness of its structure, refinery's needs process from amine regenerating unit and the 25.9kmol/h sour gas comprising 93.63% volume hydrogen and 6.37% volume of water.
Refinery also produces to process ammonia stream, and this ammonia stream comprises 32% volume hydrogen, 50.6% volume ammonia and 17.4% volume of water. In this particular case, the NH from total stream that all acid and ammonia obtain3/H2S volume ratio is equal to 42.1.
Further to these stream, refinery is also required to process the stream comprising 42.3Kg/ sulfur dioxide.
The method according to the invention, ammonia mixes with the 29.8kmol/h air being enriched to 35% volume by being suitable for burner, and delivers to the first stage (5), at this, reaches about 90 DEG C of temperature of Isosorbide-5-Nitrae, the temperature that this Quantitative yield of amino is suitable.
The applicable allotter of the overheated inside reactor that circulates comprising sulfur dioxide and sour gas is transported to second stage (6), wherein sends into 48.6kmol/h enriched air by the second allotter.
Gaseous effluent from second stage (6) is actual in ammonia, is certainly transported to the catalysed partial of the equipment based on conventional Claus processes. According to reduction reaction [7], for every mole of sulfur dioxide, produce 1 moles of hydrogen sulfide. Optimum condition for operating Claus process reaction needs the H in reactant mixture2S/SO2Volume ratio is equal to 2. In order to maintain this than and thereby ensure that best catalytic reactor efficiency, it is necessary to more air will be compared with stoichiometric number and deliver to second stage, compensate by introducing the compositions imbalance that sulfur dioxide causes to pass through to react [4].
Claims (8)
1. one kind obtains being applicable to that sulfur recovery processes has H between 2 and 2.5 from ammonia and acid gas stream and the optional air-flow that comprises sulfur dioxide2S/SO2The method of the air-flow of volume ratio, described acid gas stream comprises hydrogen sulfide and lean ammonia, the method is characterized in that and includes:
A) utilize substoichiometric oxidizing elemental, make ammonia stream through partial oxidation according to following reaction in the temperature higher than 1,250 DEG C:
B) according to following reaction temperature between 950 DEG C and 1,550 DEG C make acid gas stream with together with the admixture of gas of preceding oxidation through partial oxidation:
Carry out together with the optional air-flow comprising sulfur dioxide, described in comprise sulfur dioxide optional air-flow react according to following reaction:
��
2. the method for claim 1, from having the NH higher than 303/H2The ammonia of S volume ratio and acid gas stream and the air-flow comprising sulfur dioxide carry out, and the method is characterized in that and include:
A) utilize substoichiometric oxidizing elemental, make ammonia stream through partial oxidation according to following reaction in the temperature higher than 1,250 DEG C:
B) according to following reaction temperature between 950 DEG C and 1,550 DEG C make acid gas stream with together with the admixture of gas of preceding oxidation through partial oxidation:
Carry out together with the air-flow comprising sulfur dioxide, described in comprise sulfur dioxide air-flow react according to following reaction:
��
3. one kind obtains having H between 2 and 2.5 suitable in what sulfur recovery processed from ammonia and acid gas stream2S/SO2The method of the air-flow of volume ratio, described acid gas stream comprises hydrogen sulfide and lean ammonia, and described ammonia and acid gas stream have the NH higher than 303/H2S volume ratio, the method is characterized in that and include:
A) utilize substoichiometric oxidizing elemental, make ammonia stream through partial oxidation according to following reaction in the temperature higher than 1,250 DEG C:
;
B) according to following reaction temperature between 950 DEG C and 1,550 DEG C make acid gas stream with together with the admixture of gas of preceding oxidation through partial oxidation:
��
4. one kind obtains having H between 2 and 2.5 suitable in what sulfur recovery processed from ammonia and acid gas stream2S/SO2The method of the air-flow of volume ratio, described acid gas stream comprises hydrogen sulfide and lean ammonia, and described ammonia and acid gas stream have the NH between 1 and 303/H2S volume ratio, the method is characterized in that and include:
A) utilize substoichiometric oxidizing elemental, make ammonia stream and partially acidic gas passing portion divide oxidation in the temperature higher than 1,250 DEG C, ammonia stream is carried out according to following reaction:
And partially acidic gas stream is carried out according to following reaction:
;
B) according to above-mentioned reaction [3] and [4], the temperature between 950 DEG C and 1,550 DEG C so that it is remaining part divide acid gas stream with together with the air-flow of preceding oxidation through partial oxidation.
5. the method any one of aforementioned claim, the method is characterized in that oxidizing elemental is selected from air and enriched air.
6. the method for claim 2 is used for and the purposes reclaimed higher than 99.5% feed sulfur in the Claus process that vent gas treatment device therefor combines.
7. the method for claim 3 is used for and the purposes reclaimed higher than 99.5% feed sulfur in the Claus process that vent gas treatment device therefor combines.
8. the method for claim 4 is used for and the purposes reclaimed higher than 99.5% feed sulfur in the Claus process that vent gas treatment device therefor combines.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI2009A001849A IT1396917B1 (en) | 2009-10-23 | 2009-10-23 | PROCESS FOR RECOVERY OF SULFUR FROM GAS CURRENCIES RICH IN AMMONIA, FROM CURRENTS OF GAS ACIDS AND SULFUR DIOXIDE |
| ITMI2009A001849 | 2009-10-23 | ||
| PCT/IB2010/002650 WO2011048461A1 (en) | 2009-10-23 | 2010-10-18 | Process for the recovery of sulphur from gaseous streams rich in ammonia, from acid gas and sulphur dioxide streams |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102753474A CN102753474A (en) | 2012-10-24 |
| CN102753474B true CN102753474B (en) | 2016-06-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201080058795.1A Expired - Fee Related CN102753474B (en) | 2009-10-23 | 2010-10-18 | From rich in ammonia air-flow, from sour gas and sulfur dioxide flow back to receive sulfur method |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN102753474B (en) |
| EA (1) | EA022453B1 (en) |
| IT (1) | IT1396917B1 (en) |
| WO (1) | WO2011048461A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20130268A1 (en) | 2013-02-25 | 2014-08-26 | Saipem Spa | METHOD AND SYSTEM FOR THE KILLING OF AMMONIA FROM A GASEOUS FLOW OF DISCHARGE OF A UREA PLANT |
| BE1025690B1 (en) * | 2017-11-08 | 2019-06-11 | Europem Technologies Nv | Method and system for the incineration of waste comprising nitrogen-bound components |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2116531A (en) * | 1982-03-11 | 1983-09-28 | Shell Int Research | Process and apparatus for the combustion of ammonia-containing waste gases |
| US5508013A (en) * | 1991-04-25 | 1996-04-16 | Elf Aquitaine Production | Process for the production of sulphur from at least one sour gas containing hydrogen sulphide and a fuel effluent and thermal reactor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1926629C3 (en) * | 1969-05-24 | 1979-04-26 | Guenter Dr. 4250 Bottrop Wunderlich | Process for removing ammonia separated from coke oven gases and their condensates |
| US3970743A (en) * | 1974-09-16 | 1976-07-20 | Ralph M. Parsons Company | Process for the production of sulfur from mixtures of hydrogen sulfide and fixed nitrogen compounds |
| DE3335931C2 (en) * | 1983-10-04 | 1986-06-12 | Davy McKee AG, 6000 Frankfurt | Process for the production of sulfur from an NH? 3? -Containing and an NH-? 3? -Free acid gas |
| JP3924150B2 (en) * | 2001-10-26 | 2007-06-06 | 三菱重工業株式会社 | Gas combustion treatment method and apparatus |
-
2009
- 2009-10-23 IT ITMI2009A001849A patent/IT1396917B1/en active
-
2010
- 2010-10-18 EA EA201270588A patent/EA022453B1/en unknown
- 2010-10-18 CN CN201080058795.1A patent/CN102753474B/en not_active Expired - Fee Related
- 2010-10-18 WO PCT/IB2010/002650 patent/WO2011048461A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2116531A (en) * | 1982-03-11 | 1983-09-28 | Shell Int Research | Process and apparatus for the combustion of ammonia-containing waste gases |
| US5508013A (en) * | 1991-04-25 | 1996-04-16 | Elf Aquitaine Production | Process for the production of sulphur from at least one sour gas containing hydrogen sulphide and a fuel effluent and thermal reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| EA022453B1 (en) | 2016-01-29 |
| EA201270588A1 (en) | 2012-12-28 |
| WO2011048461A1 (en) | 2011-04-28 |
| CN102753474A (en) | 2012-10-24 |
| IT1396917B1 (en) | 2012-12-20 |
| ITMI20091849A1 (en) | 2011-04-24 |
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