CN102844275A - Integrated process for treating refinery waste water, containing ammonia and hydrogen sulphide, and refinery exhaust acid gas containing hydrogen sulphide - Google Patents
Integrated process for treating refinery waste water, containing ammonia and hydrogen sulphide, and refinery exhaust acid gas containing hydrogen sulphide Download PDFInfo
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- CN102844275A CN102844275A CN2011800068615A CN201180006861A CN102844275A CN 102844275 A CN102844275 A CN 102844275A CN 2011800068615 A CN2011800068615 A CN 2011800068615A CN 201180006861 A CN201180006861 A CN 201180006861A CN 102844275 A CN102844275 A CN 102844275A
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- Prior art keywords
- logistics
- ammonia
- hydrogen sulfide
- stream
- stripping
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 138
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002351 wastewater Substances 0.000 title claims abstract description 15
- 239000007789 gas Substances 0.000 title abstract description 21
- 239000002253 acid Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 53
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 235000011089 carbon dioxide Nutrition 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 26
- 238000011084 recovery Methods 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 13
- 239000005864 Sulphur Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 241000610375 Sparisoma viride Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved 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
-
- 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
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/066—Overpressure, high pressure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a process for treating refinery waste water mainly containing hydrogen sulphide and ammonia in addition to acid gases effluent mainly containing hydrogen sulphide, comprising the following steps: a) stripping in the stripping tower (100) said waste water (1) at a pressure ranging from 8 to 20 bar g in order to produce a gaseous overhead stream (2) essentially containing hydrogen sulphide and water and a liquid bottom stream (4) essentially containing aqueous ammonia; b) stripping in a second stripping tower (110) the stream (4) at 1 to 3 bar g in order to produce a gaseous overhead stream (5-11) of ammonia essentially pure on dry basis and a liquid bottom stream (6) containing less than 1 ppm of hydrogen sulphide and less than 5 ppm of ammonia, said water composition having the requirements to be discharged into the sewer; c) using an oxidizer deficiency to nitrogen and water to oxidate the nitrogen contained in the stream (11) in the thermal oxidation unit (170), to produce an outlet stream (12) containing 50-150 ppm in volume of ammonia and 80-200 ppm in volume of nitrogen oxides; d) thermal oxidating the stream (12) in the thermal oxidiser unit (160).
Description
Invention is described
The invention discloses and be used to handle refinery's waste water of mainly comprising ammonia and hydrogen sulfide and handle usually the integration method that from refinery, mainly comprises the sour gas of hydrogen sulfide simultaneously; This method makes can remove ammonia and the hydrogen sulfide that is included in the above-mentioned logistics quantitatively; Thereby the content that obtains residual ammonia is equal to or less than the purified water that the content of 5ppm and residual hydrogen sulfide is equal to or less than 1ppm, and contains the SO less than the 1500ppm volume
2, less than 150 mg/Nm
3NO
xWith less than 1.3 mg/Nm
3The vent gas of ammonia.
Hydrogenating desulfurization and catalytic cracking process are the processes commonly used of refinery, and it is converted into hydrogen sulfide with organic compounds containing sulfur, and through with solvent wash hydrogen sulfide being separated from fuel, the regeneration of solvent obtains having the waste gas (acidity) of high hydrogen sulfide content subsequently.Before these elutes are discharged into atmosphere, hydrogen sulfide is converted into the elementary sulfur of mainly removing with liquid form.
In addition, except hydrogen sulfide transformed, hydrodesulfurization process had also produced ammonia by the organic compounds containing nitrogen that is comprised in the petroleum fractions.The ammonia that so produces is collected in the hydrocarbon washing water, removes from the hydrocarbon washing water through LP steam.According to present industrial practice, (being produced by the steam usually) logistics that is produced by above-mentioned stripping process is sent to the Claus complexes to carry out H simultaneously
2S and NH
3The partially oxidation of the two.
Yet, mixture NH in the whole logistics that produces by above-mentioned two kinds of logistics blending only
3/ H
2The mole composition of S is equal to or less than at 35/65 o'clock, and the sulfur recovery complexes just can be accepted acid gas stream and contain ammonia flow.
NH
3Content has the risk of the hot Claus reactor drum of excessive increase service temperature greater than the logistics of 35% mol, cause ammonium salt to be coated with or to be deposited on thus and make reactor drum damage on the cold relatively complexes parts, so complexes is stopped work or can not be produced again.
Have high-content and cause said NH based on the diffusion of the increase of the oil of nitrogen product
3/ H
2The inevitable increase of S ratio has surpassed Claus factory and has normally moved the receptible limit.
In addition, the day by day responsive local government that causes to environmental problem can formulate more harsh discharging qualification.Particularly for waste water, require usually ammonia content less than 5ppm weight and hydrogen sulfide content less than 1ppm weight.For gaseous emission, require SO
2Less than 1500ppm volume, NO
xLess than 150mg/Nm
3And ammonia is less than 1.3 mg/Nm
3Must be pointed out, in order to obtain this SO
2Value, the efficient in the sulfur recovery must be greater than 99.8%.
Have now found that, a kind ofly be used to handle the refinery's waste water that mainly comprises hydrogen sulfide and ammonia and mainly comprise hydrogen sulfide but the method for usually also wrapping ammoniated sour gas can overcome above-mentioned shortcoming.
The invention reside in a kind of integration method, said method makes:
(i) sulphur recovery efficiency is greater than 99.8%,
(ii) from refinery's acid waste water, quantitatively remove deammoniation and hydrogen sulfide and be not more than the purified water that 5ppm and hydrogen sulfide content are not more than 1ppm to obtain ammonia content,
The amount that (ii) can accept according to the Claus complexes is removed excess of ammonia gas through thermooxidizing in incinerator, can guarantee NO in the vent gas to be discharged into the atmosphere
xContent is lower than 150mg/Nm
3
In order to understand the present invention better, with reference to relating to Fig. 1 and the Fig. 2-4 that relates to the inventive method of art methods.Clear comparison between these two kinds of technology can be more directly and is in depth understood the present invention.
Fig. 1 and according to the description of the method involving of prior art
In Fig. 1:
200 is stripping tower;
210 for transferring hydrogen sulfide to the Claus complexes of sulphur;
220 is the TGCU unit, that is, be used for (being mainly S and SO through the catalytic reduction sulphur products
2) reclaim the unit of Claus complexes tail gas;
230 is thermal oxidation units;
240 chimneys for waste gas to be discharged into the atmosphere.
In the complexes that Fig. 1 describes, the waste water that mainly comprises ammonia and hydrogen sulfide (1) is introduced in 0.7-1.2 bar g (bar gauge pressure) bottom aqueous stream (3) and the air-flow (2) of stripping tower (200) to obtain purified water of operation down.Acid gas stream (4) and air-flow (2) are admitted to Claus complexes (210) with the tail gas recycle stream (5) from the unit (220) of the tail gas that is used to handle the Claus complexes.It is logistics (6) that the Claus complexes are converted into liquid sulfur with most hydrogen sulfide.
Logistics (8) from TGCU unit (220) mainly comprises N
2, CO
2, H
2O, SO
2Unconverted H with trace
2S.Said logistics is sent to thermal oxidation units (230), and thermal oxidation units (230) is converted into SO with the hydrogen sulfide of remnants
2Logistics (9) from thermal oxidation units (230) has similar identical composition with logistics (8), and difference is not exist H
2S.Said subsequently logistics is sent to unit (240) and is discharged into the air-flow (10) in the atmosphere with generation.
Have only when derived from mixture flow (2) and acid gas stream (3) and deliver to mol ratio NH in the final air-flow of Claus reactor drum (20)
3/ H
2S is equal to or less than at 35/65 o'clock, and these complexes are only the otherwise effective technique scheme.
Fig. 2 (structure A) and description according to the operation of relevant complexes of the present invention
100 do not describe for prior art under high pressure the operation first stripping tower,
110 is second stripping tower of operation under low pressure like description of the Prior Art,
120 is the protection tower of also not describing in the prior art,
140 are equivalent to 210 among Fig. 1,
150 are equivalent to 220 among Fig. 1,
160 are equivalent to 230 among Fig. 1,
170 are not disclosed in the prior art unit, and this unit is by NH
3Thermal oxidation units form,
180 are equivalent to 240 among Fig. 1.
The present invention has considered other two kinds of structures (Fig. 3 constructs B and Fig. 4 constructs C).The said different embodiments that respectively is configured to the main structure of Fig. 2.
Hereinafter will be discussed all these structures.
The present invention relates to a kind of method that is used for except handling the sour gas refinery outflow thing (also containing ammonia sometimes) that mainly comprises hydrogen sulfide, also handling the refinery's waste water that mainly comprises hydrogen sulfide and ammonia, said method comprising the steps of:
A) 8-20 bar g scope, preferably under the pressure of 15 bar g in stripping tower (100) the said waste water of stripping (1) to produce gaseous overhead stream (2) that mainly comprises hydrogen sulfide and water and the liquid tower base stream (4) that mainly comprises ammoniacal liquor;
B) at 1-3 bar g, preferably in that stripping logistics (4) is with the gaseous overhead stream (5-11) that produces the pure basically ammonia of dry basis and comprise less than the hydrogen sulfide of 1ppm weight with less than the liquid tower base stream (6) of the ammonia of 5ppm weight in second stripping tower (110) under the 1 bar g, said current (6) satisfy the needs that enter water drain;
C) in thermal oxidation units (170), use with respect to contained ammonia in the poor oxygenant oxidation logistics (11) of nitrogen and water, contain the outlet logistics (12) of oxynitride of ammonia and the 80-200ppm volume of 50-150ppm volume with generation;
D) thermooxidizing logistics (12) in thermal oxidation units (160).
(Fig. 2, structure A) in a preferred embodiment of the invention, the air-flow of the ammonia that dry basis is pure (5) is delivered to protection tower (120), and the logistics (7) of alkaline water (pH 7.5-9) is circulated continuously slightly in protection tower (120).The purpose of this tower (120) is the hydrogen sulfide that possibly exist in the retentate stream (5), stops it to enter atmosphere through discharging gas (8) by this way.A spot of demineralization water is that logistics (9) is constant with the pH that keeps solution from the charging of protection column overhead, and a part of recycle stream is that logistics (10) is recycled to high-pressure tower so that guarantee the recovery fully of hydrogen sulfide simultaneously.Outlet at protection tower (120) obtains the air-flow (11) of the pure basically ammonia of dry basis, and this air-flow is delivered to ammonia thermal oxidation units (170) subsequently.
With regard to the composition in the logistics to be cleaned, said liquid aqueous logistics (1) has the ammonia concentration of 2.1%-4.22%mol and the H of 1.1-3.3 %mol usually
2S concentration, the surplus to 100 is mainly water.
Logistics (3) is known as " sour gas ".This term is used in reference to and possibly is mixed with CO
2, staple is H
2The air-flow of S.Yet sour gas also can comprise NH
3, the NH of 2% volume-15% volume particularly
3As an exception, sour gas can comprise its amount NH of 20% volume at the most
3, reason is that it possibly be recorded among the experimental embodiment based on True Data.Common logistics (3) comprises its amount of dry basis and is the H of 80%-95%mol
2Its amount of S and dry basis is the CO of 3%-18%mol
2Logistics (3) also can comprise the common hydrocarbon less than 2%mol of its amount.
What should stress is, sour gas (3) and liquid stream (1) the two all from same source, that is, and dehydrogenation sulfuration and/or catalytic cracking.The composition of above-mentioned logistics depends on the type and the operational condition thereof of different factors, particularly refinery.Yet important parameters is not the composition of single logistics (1) and (3), but the molar ratio NH of the mixture of logistics (2) and (3)
3/ H
2S, said mixture produces in Claus burner heap (burner stack).In fact, the Claus burner carried out blending to logistics (2) and (3) before the inlet that gets into Claus reactor drum device.As stated, the present invention has particularly solved molar ratio NH in the mixture of logistics (2) and logistics (3)
3/ H
2S was greater than 35/65 o'clock problem.Yet because the handiness of method of the present invention, method of the present invention also can be at molar ratio NH
3/ H
2S is less than 35/65 time operation.
Existing Fig. 2 constructs A, and method of the present invention is operated in the following manner:
The refinery's waste water that mainly comprises ammonia and hydrogen sulfide is delivered to first stripping tower of under about 15 bar g, operating under the pressure of 8-20 bar g, preferably (100) through pipeline (1), in first stripping tower (100), hydrogen sulfide is separated from the aqueous solution.
120 ℃-200 ℃, preferably under 140 ℃ temperature, take out air-flow (2) from the cat head of this stripping tower, said air-flow mainly comprises hydrogen sulfide and water.Above-mentioned logistics (2) is adapted at handling in the Claus complexes (140), and these Claus complexes (140) can be accepted also from the unitary sour gas of different refineries (3), for example from amine washing unit.The aqueous solution (4) that takes out from tower (100) bottom and almost contain whole ammonia is fed to second stripping tower (110) after reducing pressure through the lamination valve (lamination valve) that is fit to; Second stripping tower (110) is placed with first stripping tower in order, but operation under the pressure of 1-3 bar g, preferred about 1 bar g.
Ammonia is separated and takes out from the cat head of second tower, and temperature is delivered to above-mentioned protection tower (120) at 100 ℃-150 ℃, preferred about 120 ℃ logistics (5).Take out, contain the hydrogen sulfide amount at the bottom of the tower of tower (110) and be lower than the aqueous stream (6) that 1ppm weight and ammonia amount are lower than 5ppm weight.Therefore, said aqueous stream is fit to be discharged in the surface water.
The said low-down content of pollution products can obtain through the tower (100) of operation in the following manner:
-equal 50-100 kcal/kg feedstock solution, preferred 72 kcal/kg to the heat of reboiler;
Backflow among the-Ta is 5-20 kg/m
3Charging, preferred 11 kg/m
3
-at least 30 separating steps (separation steps).
The preferred operations condition of second tower (110) is following:
-equal 60-120 kcal/kg to the heat of reboiler to be fed to this unitary solution, preferred 90 kg/m
3
Backflow among the-Ta is 140-250 kg/m
3Charging, preferred 225 kg/m
3
-at least 35 separating steps.
Must be noted that; Under the low situation of the ammonia amount of treating from waste water, to remove; A plurality of steam stripping unit i.e. (100)+(110) can be used as single steam stripping unit operation, in the lamination valve downstream logistics (1) (being the logistics (19) that Fig. 3 constructs B) is transported to tower (110) thus got rid of the operation of tower (100) and (120).In this case, obtain single air-flow by steam stripping unit, said air-flow is made up of the wet mixture of hydrogen sulfide and ammonia, and this wet mixture can be fed directly into the Claus device.
Get back to Fig. 2 and construct A, comprise the ammonia of about 84% volume and the moisture and temperature of 16% volume is preferably 120 ℃ from the logistics (5) of the cat head of lower pressure column (110).In a preferred embodiment of the invention, protection tower (120) is delivered in said logistics (5), and the logistics (7) of alkaline water (pH 7.5-9) is circulated continuously slightly in protection tower (120).The purpose of this tower (120) is the hydrogen sulfide that possibly exist in the retentate stream (5), stops it to enter atmosphere through discharging gas (8) by this way.A spot of demineralization water is that logistics (9) is constant with the pH that keeps solution from the cat head charging of protection tower (120), and a part of recycle stream is that logistics (10) is recycled to high-pressure tower (100) so that guarantee the recovery fully of hydrogen sulfide simultaneously.
(construct C) in another embodiment referring to Fig. 4; Specifically consider the reason relevant with flexibility of operation; Logistics (5) can be divided into two logistics, that is, and and logistics (19) and logistics (20); Logistics (19) is fed to protection tower (120), and logistics (20) is through combining to obtain waiting to deliver to the ammonia stream (21) of Claus unit (140) with ammonia stream (2).Control logistics (20) is so that deliver to the middle molar ratio NH of the final logistics (derived from all feed streams) of Claus unit (140)
3/ H
2S is lower than 35/65, and excess of ammonia is that logistics (19) is brought to thermal oxidation units (170) simultaneously.
Afterwards, Fig. 2 and Fig. 4 are equal to.Come the pure basically ammonia stream (11) of the dry basis of self-shield tower (120) to be removed, said logistics is through being converted into nitrogen according to following reaction (I) with ammonia and water is disposed:
Above-mentioned partial oxidation reaction (I) occurs in the relevant thermal oxidation apparatus (170), and air is an oxygenant.If desired, can use pure oxygen or oxygen-rich air.
In order to make the ammonia resistates from the logistics (12) that hot cell (170) comes out is that 50 ppm volume-150 ppm and amount of nitrogen oxides are 80-200 ppm volume, and said oxidizing reaction (I) is carried out (the molar ratio O that for example adopts subsequently under reductive condition under a little poorness of oxygenant (small oxidizer deficiency)
2/ NH
3Be 0.75/1 or be lower than this ratio slightly).Reaction (I) 1350 ℃-1500 ℃, preferably under 1500 ℃, carry out 1350 ℃ the temperature value minimum temperature that to be ammonia transform with acceptable speed.
Subsequently with logistics (12) be transported under 850 ℃-950 ℃ temperature, preferably under about 900 ℃, in the thermal oxidation units from the tail gas of sulfur recovery complexes (160) of oxygen excessive slightly down (that is to say under oxidizing condition) operation; So that guarantee the maximum conversion of denitrification reaction (II); This denitrification reaction (II) is used the nitrogen protoxide example, but all is effective for every kind of oxynitride.
Above-mentioned denitrification reaction (II) is widely used in SNCR process (SNCR, Selective Non Catalytic Reduction).This reaction makes residual ammonia and NO
xThe vent gas (logistics 8) of minimizing in being discharged into atmosphere comprises less than 150 mg/Nm
3NO
x, less than 1.3 mg/Nm
3Residual ammonia and less than 1500 ppm SO
2From the vent gas of unit (160) is that logistics (18) is delivered to chimney (180) and is disposed in the atmosphere as logistics (8) at last.
With refinery's sour gas (3), logistics (2) with from being fed to Claus unit (140) with logistics (15) that the relevant unit of recovery of Claus complexes tail gas (150) comes out.Above-mentioned logistics (15) is usually by N
2, H
2O and H
2S forms, wherein H
2S is 3% volume at the most.(Fig. 4 constructs C) in another embodiment under the divided situation of logistics (5), is fed to the Claus unit with refinery's sour gas (3), logistics (21) and recycle (15).The Claus complexes are operated under the well-known condition of those skilled in the art, and said process guarantees that hydrogen sulfide is converted into liquid sulfur.Sulphur recovery efficiency is about 95% under the situation about being made up of two tandem reactors in the Claus unit, or sulphur recovery efficiency is about 97.5% under the situation about being made up of three tandem reactors.Tail gas from Claus unit (140) is that logistics (16) is except comprising N subsequently
2, H
2O, H
2S, SO
2, COS, CS
2And H
2The outer hydrogen sulfide that also comprises obvious amount.In order sulphur recovery efficiency to be increased up to surpassing 99.5%, contained sulphur product (SO in the tail gas with unit (140) with high oxidation value
2And S) is reduced to hydrogen sulfide through the catalytic reduction process of in unit (150), carrying out.The hydrogen sulfide that so obtains is recycled to Claus complexes (140) further to transform as logistics (15).The outlet of (150) obtains logistics (17) in the unit, and said logistics is mainly by N
2, CO
2, H
2O, H
2S (being generally 200-350 ppm) and SO
2(being generally 20-50 ppm) formed.Thermal oxidation units (160) is delivered in above-mentioned subsequently logistics (17).
Exporting logistics in the method for the invention is:
* liquid sulfur (14)
* purified water (6)
The washed gas of * (8).
As for ammonia stream (11), said ammonia can separate from water and be retained in the refinery or be used for said refinery.Yet this always is not allowed to, and reason has multiple, can not storage of ammonia or can not use so a large amount of ammonia in inside such as this refinery.
Integration method of the present invention makes it possible to will be referred to from liquid state and/or gaseous stream, remove the deammoniation and the increasing strict demand of hydrogen sulfide and the needs of refinery operations handiness and combines; It comes from the bigger difference that crude oil exists usually on the one hand, comes from the other hand having the very demand of the increase of the diesel oil of low sulfur content.
As for the more details about operation well known in the prior art, it is following that the applicant has provided some reference:
Claus complexes+TGCU:I. Pasquon, G, Guerreri; Principi della Chimica Industriale, Vol. 3, Metodi di separazione e di purificazione e loro applicazione all ' industria chimica e petrolifera; Pag. 353 e seg.:Clup, 1895 A. Kohl, R. Nielsen; Gas purification, Gulf Publishing Company, 1997;
H.G. Paskall, J.A. Sames, Sulphur Recovery (sulfur recovery), Sulphur Experts (Western Research).This documents has also comprised the chapters and sections that relate to Claus complexes incinerator.
Incinerator: C.E. Baukal, The John Zink Combustion Handbook, CRC Press, 2001.
Provide following examples so that understand the present invention better.
Embodiment
A refinery must be handled 60m
3The water that is polluted by ammonia (1.20% weight) and hydrogen sulfide (1.70% weight) of/h.Because said water is excessive for the overall balance of this refinery, need be before being translated into surface water with its purifying so that the ammonia resistates is lower than 5 ppm weight and the hydrogen sulfide resistates is lower than 1 ppm weight.
In addition, also need remove and be included in about 1040 Nm
3/ h from contained sulphur in fluidized bed cracking unit and the unitary air-flow of hydrogenation cracking (sour gas), this air-flow comprises the hydrogen sulfide of about 62% volume and the ammonia of 20% volume.This total ammonia content (from the value of air-flow and from the value of sour gas add with) make and can not handle this two kinds of logistics according to conventional methods.
At last, in order to meet current regulation about airborne release, refinery must be with 99.8% the sulfur recovery in said liquid effluent and the said air-flow that is included in, and guarantees the NO in the chimney smoke
xContent is not higher than 100 mg/Nm
3
From this reason, must make the water after the processing reach high purity and dispose ammonia through the incinerator that specially provides.
In this case, the molar ratio of ammonia/hydrogen sulfide is about 87% mol in delivering to the unitary total logistics of Claus (global stream), and the complexes that then are used to reclaim sulphur in the prior art can not be accepted this logistics.
This problem is separated ammonia through two steps according to above-mentioned deployment (layerout) and through the two separates from refinery's water and solves with it with hydrogen sulfide; To be transported to the Claus complexes through the wet purifying hydrogen sulfide stream that step of high pressure obtains so that hydrogen sulfide is converted into the elementary sulfur of treating through concentrate collecting.And ammonia is delivered to two step thermal oxidation units (incinerator) so that be converted into nitrogen and water, in this way with NO
xFormation is reduced to 100 mg/Nm
3
Through the unit that carries out vent gas treatment based on the catalytic reduction of contained product based on sulphur wherein is installed in Claus complexes downstream 99.8% sulfur recovery is provided.
Claims (7)
1. one kind is used for flowing out the method for also handling the refinery's waste water that mainly comprises hydrogen sulfide and ammonia the thing except the sour gas of handling mainly to comprise hydrogen sulfide, said method comprising the steps of:
A) under the pressure of 8-20 bar g scope in stripping tower (100) the said waste water of stripping (1) to produce gaseous overhead stream (2) that mainly comprises hydrogen sulfide and water and the liquid tower base stream (4) that mainly comprises ammoniacal liquor;
B) in that stripping logistics (4) is with the gaseous overhead stream (5-11) that produces the pure basically ammonia of dry basis and comprise less than the hydrogen sulfide of 1ppm with less than the liquid tower base stream (6) of the ammonia of 5ppm in second stripping tower (110) under the 1-3 bar g, said water component satisfies the needs that enter water drain;
C) in thermal oxidation units (170), use with respect to contained ammonia in the poor oxygenant oxidation logistics (11) of nitrogen and water, contain the outlet logistics (12) of oxynitride of ammonia and the 80-200ppm volume of 50-150ppm volume with generation;
D) thermooxidizing logistics (12) in thermal oxidation units (160).
2. according to the process of claim 1 wherein that the stripping of step (a) operates under 15 bar g.
3. according to the process of claim 1 wherein that the stripping of step (b) operates under 1 bar g.
4. according to the process of claim 1 wherein that the temperature of ammonia thermal oxidation units (170) remains in 1350-1500 ℃ the scope, and oxygenant is poor slightly, and the ratio of preferred ammonia and hydrogen sulfide is 0.75/1, or is slightly smaller than this ratio.
5. according to the process of claim 1 wherein that logistics (1) has following composition: ammonia 2.1-4.22 % mol; Hydrogen sulfide 1.1-3.3% mol; Surplus is mainly water; And
Logistics (3) dry basis has following composition: hydrogen sulfide 80-95 % mol; Carbonic acid gas 3-18% mol; Hydrocarbon is less than 2 % mol; Ammonia 0 to 20% volume.
6. according to the process of claim 1 wherein that the overhead stream (5) of stripping tower (110) is drawn towards protection tower (120), delivers to ammonia thermal oxidation units (170) as logistics (11) subsequently.
7. according to the method for claim 6; Wherein logistics (5) is divided into two logistics; Logistics (19) and logistics (20), logistics (19) wait to be fed to protection tower (120), and logistics (20) treats to mix with logistics (2) logistics (21) that is fed to Claus unit (140) with generation; The flow velocity of controlling said logistics (20) is so that the molar ratio of ammonia and hydrogen sulfide is lower than 35/65 in the merging charging of Claus device, and excess of ammonia is that logistics (19) is drawn towards thermal oxidation units (170).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI2010A000080 | 2010-01-22 | ||
| ITMI2010A000080A IT1397745B1 (en) | 2010-01-22 | 2010-01-22 | INTEGRATED PROCESS OF PURIFICATION OF REFINERY WATERS, CONTAINING PRECISELY AMMONIA AND SULFIDRIC ACID, AND OF GAS ACIDS CONTAINING PREVIOUSLY SULFIDRIC ACID. |
| PCT/IT2011/000016 WO2011089635A1 (en) | 2010-01-22 | 2011-01-19 | Integrated process for treating refinery waste water, containing ammonia and hydrogen sulphide, and refinery exhaust acid gas containing hydrogen sulphide |
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| Publication Number | Publication Date |
|---|---|
| CN102844275A true CN102844275A (en) | 2012-12-26 |
| CN102844275B CN102844275B (en) | 2014-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180006861.5A Expired - Fee Related CN102844275B (en) | 2010-01-22 | 2011-01-19 | Integrated process for treating refinery waste water, containing ammonia and hydrogen sulphide, and refinery exhaust acid gas containing hydrogen sulphide |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN102844275B (en) |
| EA (1) | EA022555B1 (en) |
| IT (1) | IT1397745B1 (en) |
| WO (1) | WO2011089635A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106457137A (en) * | 2014-03-05 | 2017-02-22 | 贝克特尔碳氢技术解决方案股份有限公司 | Systems and methods for enhanced separation of hydrogen sulfide and ammonia in hydrogen sulfide stripper |
| CN108794359A (en) * | 2017-04-28 | 2018-11-13 | 中国石油化工股份有限公司 | A method of dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide |
| CN108794362A (en) * | 2017-04-28 | 2018-11-13 | 中国石油化工股份有限公司 | A method of dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide |
| CN111072535A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfide by utilizing refinery acid gas |
| CN111252839A (en) * | 2020-01-18 | 2020-06-09 | 河北荣特化工股份有限公司 | Novel process for treating hydrogenation type waste water and waste gas |
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 |
| RU2620669C2 (en) * | 2016-05-30 | 2017-05-29 | Константин Владимирович Ладыгин | Method and installation for waste water burning |
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-
2010
- 2010-01-22 IT ITMI2010A000080A patent/IT1397745B1/en active
-
2011
- 2011-01-19 EA EA201290680A patent/EA022555B1/en unknown
- 2011-01-19 WO PCT/IT2011/000016 patent/WO2011089635A1/en active Application Filing
- 2011-01-19 CN CN201180006861.5A patent/CN102844275B/en not_active Expired - Fee Related
Patent Citations (5)
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|---|---|---|---|---|
| FR2263293A1 (en) * | 1974-03-05 | 1975-10-03 | Koppers Gmbh Heinrich | Ammonia removal from ammoniacal vapours - by partial combustion followed by total combustion to minimise nitrogen oxides |
| EP0492329A1 (en) * | 1990-12-22 | 1992-07-01 | Hoechst Aktiengesellschaft | Process for the treatment of hydrogen sulfide, hydrogen cyanide and ammonia containing aqueous solutions |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106457137A (en) * | 2014-03-05 | 2017-02-22 | 贝克特尔碳氢技术解决方案股份有限公司 | Systems and methods for enhanced separation of hydrogen sulfide and ammonia in hydrogen sulfide stripper |
| US10702799B2 (en) | 2014-03-05 | 2020-07-07 | Bechtel Hydrocarbon Technology Solutions, Inc. | Systems and methods for enhanced separation of hydrogen sulfide and ammonia in a hydrogen sulfide stripper |
| CN106457137B (en) * | 2014-03-05 | 2020-08-07 | 贝克特尔碳氢技术解决方案股份有限公司 | System and method for enhancing separation of hydrogen sulfide and ammonia in a hydrogen sulfide stripper |
| CN108794359A (en) * | 2017-04-28 | 2018-11-13 | 中国石油化工股份有限公司 | A method of dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide |
| CN108794362A (en) * | 2017-04-28 | 2018-11-13 | 中国石油化工股份有限公司 | A method of dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide |
| CN108794362B (en) * | 2017-04-28 | 2020-06-16 | 中国石油化工股份有限公司 | Method for producing dimethyl sulfoxide from hydrogen sulfide |
| CN111072535A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfide by utilizing refinery acid gas |
| CN111252839A (en) * | 2020-01-18 | 2020-06-09 | 河北荣特化工股份有限公司 | Novel process for treating hydrogenation type waste water and waste gas |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1397745B1 (en) | 2013-01-24 |
| CN102844275B (en) | 2014-11-26 |
| WO2011089635A1 (en) | 2011-07-28 |
| EA201290680A1 (en) | 2013-01-30 |
| EA022555B1 (en) | 2016-01-29 |
| ITMI20100080A1 (en) | 2011-07-23 |
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