CN102753474A - Process for the recovery of sulphur from gaseous streams rich in ammonia, from acid gas and sulphur dioxide streams - Google Patents
Process for the recovery of sulphur from gaseous streams rich in ammonia, from acid gas and sulphur dioxide streams Download PDFInfo
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- CN102753474A CN102753474A CN2010800587951A CN201080058795A CN102753474A CN 102753474 A CN102753474 A CN 102753474A CN 2010800587951 A CN2010800587951 A CN 2010800587951A CN 201080058795 A CN201080058795 A CN 201080058795A CN 102753474 A CN102753474 A CN 102753474A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 87
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 74
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title claims abstract description 18
- 238000011084 recovery Methods 0.000 title claims abstract description 15
- 239000005864 Sulphur Substances 0.000 title abstract description 14
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000004291 sulphur dioxide Substances 0.000 title abstract description 4
- 235000010269 sulphur dioxide Nutrition 0.000 title abstract description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 claims description 56
- 230000003647 oxidation Effects 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 abstract description 32
- 239000003295 industrial effluent Substances 0.000 abstract description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 25
- 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
- 239000011819 refractory material Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture 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
- 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
- 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
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 230000002950 deficient Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- -1 nitrogen-containing organic compound Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory 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
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- 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
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- 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 invention relates to a process for the recovery of sulphur from gaseous streams rich in ammonia, optionally containing hydrogen sulphide, together with acid gas streams, having a NH3 /H2S volume ratio higher than 30, based on the overall stream of the two gaseous streams. The process allows also to convert the sulphur dioxide contained in industrial effluents into hydrogen sulphide and to recover sulphur together with the two above mentioned gaseous streams.
Description
Invention field
The objective of the invention is a kind of method of in the improvement thermal reactor of Claus process, carrying out; Said method is used for the optional rich ammoniated air-flow that comprises hydrogen sulfide and poor ammonia and comprises the recovery of the sulphur that the air-flow of hydrogen sulfide contains, and preferably ammonia/hydrogen sulfide volume ratio is higher than 30 based on total stream of two kinds of said air-flows.
Another object of the present invention is the method that allows in the presence of having two kinds of said flow of ammonia and sour gas, to make the Sulphur Dioxide that comprises in the industrial effluent become hydrogen sulfide and reclaim sulphur.
Summary of the invention
Known from the Claus method of the air flow recovery sulphur that comprises hydrogen sulfide in prior art.Said method is made up of the partially oxidation stage of in thermal reactor, carrying out, recovery of heat stage and one or more catalytic stages basically, and hydrogen sulfide in catalytic stages in the gas and the sulfurous gas reaction that produces in the said partially oxidation stage are to produce sulphur.
Method of the present invention is carried out in the suitable improvement thermal reactor of Claus method, and is made up of two further part oxidation stages; First oxidation is carried out the optional ammonia flow that comprises hydrogen sulfide, and second oxidation is carried out the air-flow that comprises hydrogen sulfide and poor ammonia, and the remaining content of ammonia is carried out, if having, the air-flow from first part's oxidation stage is carried out.
Oxidation element in two partially oxidations is present in airflow, or is present in the stream that is formed by air and pure oxygen (or enriched air (enriched air)).
Specifically, must be enough to guarantee that high amino originally changes into nitrogen and water, and wherein choose the temperature that the hydrogen sulfide that comprises partly transforms sulfurous gas wantonly, ammonia flows in the oxidation of oxygen lack lower section.
Under oxygen lack, the acid gas stream of poor ammonia is partially oxidation also, and hydrogen sulfide partly changes into sulfurous gas.
Ammonia decomposes with hydrogen sulfide and transforms essential oxidation element through not separating in the homogeneous turbulence at two, be contained in ammonia and sour gas respectively in ammonia and hydrogen sulfide stream short-term training ratio: the consistent thermal reactor of introducing of charging of other and two process flow of the said flow point of oxidation element.Specifically, divider is sent in the refractory materials manufacturing of the oxidation element in second oxidation stage through being different from the sour gas charging special.
The air-flow that obtains from the said partially oxidation stage gets into the Claus process catalysed partial that is used for the elementary sulfur recovery.
Method of the present invention is favourable carries out in two zones or chamber contiguous and that be communicated with therebetween in the reactor drum that is separated by said distributor function: at different positions, send into optional ammonia flow and a part of oxidation element that comprises hydrogen sulfide in the first area; At its initial portion, poor propylhomoserin property gas and rest part oxidation element relatively are positioned at the special divider that guarantees to be enough in the distance of the residence time that the quantitative ammonia of reactor drum second area decomposes with ammonia feed and send into through the refractory materials manufacturing at second area.
If also there is the air-flow of the industrial effluent comprise sulfurous gas, this also the reactor drum second area begin introduce.
State-of-art
Now, thick oil obtains on market with the high-content nitrogen-containing organic compound more and more continually, and these nitrogenous compounds change into ammonia in oil, petrochemical complex and rendering industry are handled.In present industrial implementation, ammonia stream is delivered to sulfur recovery unit, and for example handle with the sour gas of general generation through amino washing lotion.Yet,, use the Claus method to have and from burner, mix the NH that exists in the stream that ammonia flows and poor propylhomoserin property gas obtains equally for this purpose
3/ H
2The restriction of S volume ratio.In fact, on the one hand, said restriction increase in the Claus method the sedimentary risk of ammonium salt in the lightpenia territory than height ratio because micro-non-conversion ammonia reacts with hydrogen sulfide, and with process fluid in the SO that exists
2/ SO
3Reaction, thereby equipment stops up.
On the other hand; Owing to the kinetics reason; The ammonia conversion need be not less than 1250 ℃ service temperature, and this temperature is because the strong exothermicity of reaction increases with the increase of ammonia concentration in whole mixtures, up to becoming and to form the service temperature to greatest extent that the refractory materials of thermal reactor liner allows incompatible; For the refractory materials that comprises at least 90% corundum, service temperature equals 1700-1750 ℃ to greatest extent.
For present Claus method, according to the H in the sour gas
2S concentration is allowed NH to greatest extent
3/ H
2The S volume ratio is 25-30gap.
Under present case, carry out ammonia stream through the partial oxidation reaction that carries out at high temperature and handle:
This reaction always follows ammonia to split into the reaction of its element:
Reaction [1], heat release receives kinetic limitation, and needs technical scale to use, and service temperature is higher than 1250 ℃.
Present two kinds of methods can be used for carrying out reaction [1] and [2] in the Claus method:
1. through high-strength burner partially oxidation;
2. partially oxidation in two chambers.
First method is ammonia and sour gas to be sent in the burner with high pressure drop, to carry out the most probable uniform mixing of reagent and oxidation element (general atmosphere pressure atmospheric oxygen), to guarantee the corresponding high oxygenation efficiencies of flame temperature to greatest extent.
According to Claus method stoichiometry, the hydrogen sulfide of sending into for ammonia decomposition and 1/3rd changes into SO
2Both essential air overall flow rates are sent into burner through forming suitable shape to carry out sound response agent blended opening for feed.
The sulfurous gas that produces according to following reaction [3] vulcanizes H-H reactions, generting element sulphur and water according to following reaction (general Claus method is carried out in the temperature that is higher than 1,000 ℃) with 2/3rds remnants subsequently:
The operation oxidation stage temperature that available this method obtains for example can lowly transform required temperature to complete ammonia for the dilution sour gas; And can only guarantee, generally use steam, three kinds of incoming flow ammonias, sour gas and oxidation airs through heating before introducing reactor drum.
Except essential preheater with relevant steam consumption needs; This method also has two defectives; The one, because the high pressure drop of dispensing burner is having less handiness aspect the plant capacity variation; The 2nd, do not allow careful controlled oxidation region operation temperature, because this only mixes based on the homogeneous reaction agent.In fact, capacity reduces to endanger said uniform mixing.
Second method, the partially oxidation in the dioxygen zone is that ammonia is mixed with a part sour gas in burner, rest part is delivered to the second area of same reactor.All the essential air that are used for the reaction of ammonia oxidation and Claus method are sent into and are distributed to and have high-intensity first method and relatively reduce the burner that multiple pressure is more fallen.
The service temperature that produces in thermal reactor first oxide regions is to deliver to the function of the acid gas quantity in second oxidation reactor zone: through increasing this amount; Temperature in first reactor area rises and reaches peak 1; 500-1,700 ℃, consistent with air/ammonia and sour gas stoichiometric ratio in the first area; To reduce, because air is excessive in the first area with gas increase in the second area.Accompanying drawing 1 is presented in the second area dependency between the temperature in the sour gas percentage ratio and first area.Curve relates to the ammonia that comprises about 66% volume ammonia and 34% water by volume, and sour gas is pure hydrogen sulfide basically.
Through the sour gas flow of simple adjustment, make the temperature in the first area controlled to second area.Utilize this method, the incoming flow preheating is unnecessary, and can be in the accurate red-tape operati temperature of any plant capacity condition.
In any case, for two kinds of methods, the ammonia amount that available Claus method is handled (sour gas equates) receives NH in total gaseous mixture (two kinds of incoming flow total amounts)
3/ H
2The restriction of S volume ratio.
The present invention allows to overcome said restriction, therefore, the Claus method is handled had any NH
3/ H
2The ammonia of S ratio and hydrogen sulfide air-flow, therefore, the special thick oil that allows (especially to refinery) to handle and can low-cost on market, obtain with high nitrogen-containing.
Detailed Description Of The Invention
Method for a better understanding of the present invention, with reference to accompanying drawing 2-4, accompanying drawing should not limit the present invention by any way.
Fig. 2 demonstration equals 1 second, NH for the residence time
3/ H
2The S mol ratio equal 25 and air velocity be in stoichiometric ammonia conversion curve (for the function of temperature);
Fig. 3 illustrates to show method of the present invention under the situation that two kinds of air-flows (ammonia stream and acid gas stream) exist;
Fig. 4 illustrates to show method of the present invention under the situation that the air-flow that too much is rich in sulfurous gas exists.
With ammonia (2) (20 to 45% moles of ammonia; The optional hydrogen sulfide that comprises; Rest part is a water) deliver to first part's oxidation stage (5) with air or enriched air stream (8), air or enriched air stream (8) are with respect to the 50-90% volume of the stoichiometric air of 33% calculating of the partial oxidation reaction [3] of hydrogen sulfide under the situation that also comprises hydrogen sulfide to amino moiety oxidizing reaction [1] (considering ammonia decomposition reaction [2]) with at ammonia stream.
According to the empirical curve shown in the Fig. 2 that obtains with above-mentioned parameter, ammonia is in the temperature Quantitative yield that is higher than 1350 ℃.Press NH in the supposition residence time, the charging with upper curve
3/ H
2The function of S mol ratio and oxidation element shortage degree.
Therefore, in the Claus method of regulating according to the method for the invention with same processing ammonia, service temperature must be the highest possible: promptly, be higher than 1,250 ℃, but be lower than 1,600 ℃, in order to avoid damage forms the internally coated refractory materials of equipment used.
The reaction [1] that takes place from first oxidation stage (5), whole air-flows that [2] and [3] obtain flow to the subordinate phase (6) of method of the present invention.
Sour gas (3) is with make hydrogen sulfide be converted into the required oxidation element (4) of elementary sulfur according to the Claus method; Be transported to the initial portion of subordinate phase (6) together with the ammonia that comprises in the sour gas (if having words) with at the ammonia that from stage (5) effusive stream, comprises (if the words that have), react according to following reaction [5] and [6]:
Overall result is that ammonia changes into nitrogen fully.
From subordinate phase outlet (6), the air-flow that obtains (7) feeding Claus process catalysed partial is used for sulfur recovery.
Oxidation element and all sour gas partly postpone to enter subordinate phase (6), give to handle independence from the ammonia (2) of sour gas (3), and this allows to be independent of the NH from the stream that whole ammonias and sour gas obtain
3/ H
2The S volume ratio is handled the fs.
Therein in the ammonia ammonia flow velocity not enough so that two kinds postpone under those situation of amount that chargings (sour gas and corresponding air or enriched air (4)) reach the required temperature of Claus method, that is, and at NH
3/ H
2When the S volume ratio is too low; 1-30 for example, method of the present invention can be operated in subordinate phase according to the method for partially oxidation, is exactly; As stated; Ammonia flow (2) is mixed in the ammonia burner that inserts the fs (5) with part sour gas (3), and all the other sour gas are partly delivered to subordinate phase (6), because the oxidation element is only delivered to the fs (5).
Sometimes, have the industrial production facilities based on the equipment of Claus method be used for sulfur recovery therein, also produce the stream that is rich in sulfurous gas, for example, fluidized-bed in from refinery (FCC) is gone up in the treatment unit of elute of cracking process.
The Sulphur Dioxide that method of the present invention allows in industrial effluent described in the Claus method, to comprise becomes hydrogen sulfide, reclaims sulphur then.
This conversion develops according to reduction reaction [7]:
Be reflected at high temperature and carry out, as shown in Figure 4 to overcome the kinetics limit of fixed, in the presence of the hydrogen that ammonia dissociation reaction [2] produces in its element, comprise of the beginning of the gas delivery of sulfurous gas to subordinate phase (6).
The air-flow of sulfurous gas is rich in reference number (9) expression, and it delivers to the beginning of second oxidation stage (6) of method of the present invention.
The total air flow in reference number (7) expression the inventive method downstream, total air flow is delivered to the catalysed partial of the Claus method that is used for sulfur recovery.Above-mentioned reference number is clearly represented the bioelement of method of the present invention; Promptly; Incoming flow (1), (2) and (3) (being respectively oxidation element, ammonia stream and acid gas stream), two partially oxidation stages (5) and (6) (being respectively ammonia and sour gas) and the optional air-flow that comprises sulfurous gas (9); At last, reference number (7) is illustrated in the total air flow that improves the inventive method downstream of obtaining in the Claus method reactor drum.
From ammonia flow and acid gas stream with high (promptly being higher than 30) and low when increase vent gas treatment process (be lower than 30, in Claus process downstream) NH
3/ H
2The S mol ratio produces the method for the present invention that can be used for the air-flow that elementary sulfur reclaims in the Claus process catalysed partial and can reclaim the sulphur that comprises greater than in 99.5% feed stream.
In addition, be rich in the presence of the 3rd air-flow of sulfurous gas equally, when increasing the vent gas treatment process, from ammonia flow and from acid gas stream with high NH
3/ H
2The said method that S mol ratio (promptly being higher than 30) reclaims sulphur can reclaim the sulphur that in three kinds of feed streams, comprises greater than 99.5%.
It is in order to estimate the present invention better, to the invention is not restricted to this that following examples are provided.
The equipment that is used to prepare mercaptobenzothiazole (a kind of vulcanizer) produces the 0.81 kmol/h gaseous effluent that comprises 89.59% volume hydrogen, 4.22% volumes carbon dioxide and 6.19% water by volume.
Recirculation water from equipment comprises significant quantity ammonia, and in order to meet the maximum allowable deviation that in waste water, equals 5ppm, these ammonia are removed through gas stripping process.
Extract 2.01 kmol/h ammonias from the stripping tower top, this ammonia comprises 39.6% volume hydrogen, 41% volume ammonia and 19.4% water by volume.
Two kinds of stream must be handled in the equipment based on the Claus process of sulfur recovery; But the amount between said two kinds of streams equals ammonia/hydrogen sulfide volume ratio of 54.3 than producing, and for operation need equal 30 value to greatest extent about said ratio the equipment of conventional Claus process, is excessive ratio.
Utilize method of the present invention, two kinds of all available Claus methods of stream are handled, and all ammonias are delivered to first conversion zone of improved thermal reactor according to the method for the invention with 2.94 kmol/h air.Under these conditions, reach 1,600 ℃ of temperature in said first area.In this temperature, ammonia oxidation Cheng Shui and nitrogen are quantitative.In the subordinate phase (6) of method, temperature is maintained at about 1450 ℃.
The stream that leaves subordinate phase (6) comprises nitrogen, water, unreacted hydrogen sulfide, sulfurous gas, elementary sulfur and hydrogen.Said sulphur is applicable in based on the catalysed partial of the equipment of conventional Claus process with aftertreatment.
In the up-to-dateness scope of its structure, refinery need handle from the amine regenerating unit and comprise 93.63% volume hydrogen and 25.9 kmol/h sour gas of 6.37% water by volume.
Refinery also produces and must handle ammonia stream, and this ammonia stream comprises 32% volume hydrogen, 50.6% volume ammonia and 17.4% water by volume.Under this particular case, the NH from total stream that all acid and ammonia obtain
3/ H
2The S volume ratio equals 42.1.
Further to these stream, refinery also need handle the stream that comprises 42.3 Kg/ sulfurous gas.
According to the method for the invention, ammonia is through being fit to burner and the 29.8 kmol/h air mixed of enrichment to 35% volume, and delivers to the fs (5), at this, reaches about 1,490 ℃ of temperature, the suitable temperature of this Quantitative yield of amino.
The suitable divider that comprises the overheated inside reactor of circulation of sulfurous gas and sour gas is transported to subordinate phase (6), wherein sends into 48.6 kmol/h enriched airs through second divider.
Gaseous effluent reality from subordinate phase (6) does not contain ammonia, is transported to the catalysed partial based on the equipment of conventional Claus method certainly.According to reduction reaction [7],, produce 1 moles of hydrogen sulfide for every mole of sulfurous gas.The top condition that is used for operating the Claus process reaction needs the H of reaction mixture
2S/SO
2Volume ratio equals 2.In order to keep this, be necessary with delivering to subordinate phase, with uneven by the compsn that introducing sulfurous gas causes through reaction [4] compensation with many some air of stoichiometric number than also therefore guaranteeing best catalyticreactor efficient.
Claims (8)
- One kind from ammonia and acid gas stream and the possible air-flow that comprises sulfurous gas obtain being applicable to sulfur recovery handles have 2 and 2.5 between H 2S/SO 2The method of the air-flow of volume ratio is characterized in that comprising:A) utilize substoichiometric oxidation element, make ammonia stream process partially oxidation according to the following temperature that is higher than 1,250 ℃ that is reflected at:
B) temperature that is reflected between 950 ℃ and 1,550 ℃ below the basis makes acid gas stream pass through partially oxidation with the gaseous mixture from the front oxidation:
Possible air-flow with comprising sulfurous gas reacts according to following reaction:。
- 2. the method for claim 1 is higher than 30 NH from having 3/ H 2The ammonia of S volume ratio and acid gas stream and the air-flow that comprises sulfurous gas is characterized in that comprising:A) utilize substoichiometric oxidation element, make ammonia stream process partially oxidation according to the following temperature that is higher than 1,250 ℃ that is reflected at:
B) temperature that is reflected between 950 ℃ and 1,550 ℃ below the basis makes acid gas stream pass through partially oxidation with the gaseous mixture from the front oxidation:React according to following reaction with the air-flow that comprises sulfurous gas:。
- 3. the method for claim 1 is higher than 30 NH from having 3/ H 2The ammonia of S volume ratio and acid gas stream is characterized in that comprising:A) utilize substoichiometric oxidation element, make ammonia stream process partially oxidation according to the following temperature that is higher than 1,250 ℃ that is reflected at:；
B) temperature that is reflected between 950 ℃ and 1,550 ℃ below the basis makes acid gas stream pass through partially oxidation with the gaseous mixture from the front oxidation:。
- 4. the method for claim 1 is from having the NH between 1 and 30 3/ H 2The ammonia of S volume ratio and acid gas stream is characterized in that comprising:A) utilize substoichiometric oxidation element, make ammonia stream and be fit to part sour gas process partially oxidation for being reflected at the temperature that is higher than 1,250 ℃ below the ammonia stream basis:
And for the part acid gas stream, the following reaction of process:；
B) according to above-mentioned reaction [3] and [4], the temperature between 950 ℃ and 1,550 ℃ makes the rest part acid gas stream pass through partially oxidation with the air-flow from the front oxidation. - 5. each method in the aforementioned claim is characterized in that the oxidation element is selected from air and enriched air.
- 6. the method for claim 2 is used for being higher than with the Claus process in the combination of vent gas treatment equipment used the purposes of 99.5% feed sulfur recovery.
- 7. the method for claim 3 is used for being higher than with the Claus process in the combination of vent gas treatment equipment used the purposes of 99.5% feed sulfur recovery.
- 8. the method for claim 4 is used for being higher than with the Claus process in the combination of vent gas treatment equipment used the purposes of 99.5% feed sulfur recovery.
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 true CN102753474A (en) | 2012-10-24 |
| CN102753474B 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) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 WO PCT/IB2010/002650 patent/WO2011048461A1/en active Application Filing
- 2010-10-18 CN CN201080058795.1A patent/CN102753474B/en not_active Expired - Fee Related
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 |
|---|---|
| ITMI20091849A1 (en) | 2011-04-24 |
| CN102753474B (en) | 2016-06-08 |
| EA201270588A1 (en) | 2012-12-28 |
| EA022453B1 (en) | 2016-01-29 |
| IT1396917B1 (en) | 2012-12-20 |
| WO2011048461A1 (en) | 2011-04-28 |
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