CN107233794A - A kind of method of hydrogen sulfide in removal gas - Google Patents
A kind of method of hydrogen sulfide in removal gas Download PDFInfo
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- CN107233794A CN107233794A CN201610185069.5A CN201610185069A CN107233794A CN 107233794 A CN107233794 A CN 107233794A CN 201610185069 A CN201610185069 A CN 201610185069A CN 107233794 A CN107233794 A CN 107233794A
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- catalyst
- hydrogen
- sulphur
- hydrogen sulfide
- reactor
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 85
- 239000007789 gas Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 73
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 239000001257 hydrogen Substances 0.000 claims abstract description 86
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 239000005864 Sulphur Substances 0.000 claims abstract description 74
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000004480 active ingredient Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 description 25
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 20
- 239000011593 sulfur Substances 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000470 constituent Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of method for removing hydrogen sulfide in gas, belong to industrial gasses process field.This method comprises the following steps：Sulphur catalyst for preparing hydrogen processed is added into high-temperature reactor, then, the gas containing hydrogen sulfide high-temperature reactor is introduced into, and is passed through into high-temperature reactor air or oxygen, the volume ratio of hydrogen sulfide and oxygen is (4 1):1, it is 10000~50000h in reaction velocity‑1, reaction temperature be 500~800 DEG C under conditions of reacted, obtain sulphur and hydrogen.Wherein, sulphur catalyst for preparing hydrogen processed is prepared via a method which to obtain：Water and auxiliary agent are added in carrier component, bar shaped is extruded into banded extruder, catalyst carrier is obtained through primary drying and once after roasting；By active ingredients into the solution that mass concentration is 100~150g/L, with solution impregnated catalyst carrier, sulphur catalyst for preparing hydrogen processed is obtained through redrying and after baking.This method adapts to hydrogen sulfide volumetric concentration in gas and is 1.5 4% situation, and effectively removes hydrogen sulfide, and easy to operate.
Description
Technical field
The present invention relates to industrial gasses process field, more particularly to a kind of method for removing hydrogen sulfide in gas.
Background technology
Hydrogen sulfide containing gas can be produced in the process such as fossil fuel, if the gas directly discharges meeting pair
Environment causes ill effect, it is therefore desirable to handle the gas containing hydrogen sulfide, to ensure gas
Safety dumping.Claus method is to remove one of main method of hydrogen sulfide in gas, and it passes through in Crouse
Claus reaction is carried out in combustion furnace, hydrogen sulfide is carried out imperfect combustion, and the sulfur dioxide for generating it
Sulphur is generated with hydrogen sulfide reaction, so as to remove the hydrogen sulfide in gas.In order to which the sulphur for improving Claus method is returned
Yield, often needs to increase the number of claus reaction device, hydrogen sulfide is carried out multi-stage conversion, so that finally
Sulfur recovery rate reach 94%-97%, but the sulfur recovery rate of single claus reaction device only has 60%-65%, sulphur
The rate of recovery is relatively low.Therefore it provides a kind of devulcanization for making single claus reaction utensil have higher sulfur recovery rate
Hydrogen methods are necessary.
Prior art provides a kind of super Claus method, and it is added after conventional Claus reactor
One super Claus reactor, and catalyst for selective oxidation is added wherein, by the vulcanization in tail gas
Hydrogen-oxygen turns to sulphur, improves the conversion ratio of super Claus reactor.On the basis of super Claus method
On, prior art additionally provides a kind of super excellent Crouse's method, and it is additionally added in super Claus reactor
Hydrogenating reduction catalyst, further increases sulfur recovery rate, makes single super excellent claus reaction device sulfur recovery
Rate reaches 89%, and total sulfur recovery reaches 99.4%.
Inventor has found that prior art at least has following technical problem：
Super excellent Crouse's method that prior art is provided may be only available for the less gas of hydrogen sulfide volumetric concentration,
Hydrogen sulfide volumetric concentration need to be less than 1.5% i.e. in gas.Simultaneously as after using super excellent Crouse's method, row
The presence of sub-fraction hydrogen sulfide is had in the tail gas put, so needing to carry out vent gas treatment further to remove
Hydrogen sulfide, and also need to extraly be passed through hydrogen during vent gas treatment so that whole depriving hydrogen sulphide method is more numerous
It is trivial.
The content of the invention
Technical problem to be solved of the embodiment of the present invention is to adapt to hydrogen sulfide in gas there is provided one kind
Volumetric concentration is 1.5-4% situation, sulfur recovery rate is high and can prepare going for hydrogen while sulphur is reclaimed
Except the method for hydrogen sulfide in gas, concrete technical scheme is as follows：
The embodiments of the invention provide a kind of method for removing hydrogen sulfide in gas, this method comprises the following steps：
Sulphur catalyst for preparing hydrogen processed is added into high-temperature reactor, then, the gas containing hydrogen sulfide institute is introduced into
State high-temperature reactor, and air or oxygen be passed through into the high-temperature reactor, reaction velocity be 10000~
50000h-1, reaction temperature be 500~800 DEG C under conditions of reacted, obtain sulphur and hydrogen；Wherein,
The volume ratio of the hydrogen sulfide and the oxygen is (4-1):1.
The sulphur catalyst for preparing hydrogen processed is prepared via a method which to obtain：
Water and auxiliary agent are added in carrier component, is well mixed, bar shaped is extruded into banded extruder, through once doing
It is dry and once be calcined after obtain catalyst carrier；By active ingredients into mass concentration be 100~150g/L
Solution, at 50~60 DEG C, impregnated with the solution after the catalyst carrier, dipping 2-3h, through two
Secondary drying and after baking obtain the sulphur catalyst for preparing hydrogen processed.
The auxiliary agent be cellulose and/or graphite, the carrier component be activated alumina, inert alumina or
One kind in silica, the quality of the water is the 30%-50% of the carrier component quality, the auxiliary agent
Quality be the carrier component quality 1%-5%；The catalyst carrier and the volume ratio of the solution are
1:(1-1.2)；The active component is at least one of nitrate or sulphite of iron, chromium or nickel.
Specifically, preferably, the catalyst carrier is length 8-10mm, diameter 2-3mm circle bar
Shape.
Specifically, preferably, the temperature of the primary drying and the redrying is 110-120 DEG C,
Drying time is 2-3h；The temperature being once calcined is 600-800 DEG C, and roasting time is 2-4h, described
The temperature of after baking is 700-800 DEG C, and roasting time is 1-3h.
Specifically, preferably, the specific surface area of the sulphur catalyst for preparing hydrogen processed is 20-250m2/ g, it is average
Crushing strength is 100-150N/cm, and heap density is 0.5-0.8g/ml.
Specifically, preferably, mass fraction of the active component in the sulphur catalyst for preparing hydrogen processed is
3-5%.
Specifically, preferably, the high-temperature reactor is claus reaction device, the claus reaction device
Including：Reactor, the Crouse gas access being arranged at the top of the reactor, are arranged on the reactor
The air/oxygen entrance of side wall upper part, is arranged on the product exit of the reactor bottom；In the reactor
It is horizontally disposed in the middle part of chamber to have catalyst dividing plate, the reactor is heated by temperature control electric furnace.
Specifically, preferably, in use, the 2-3 claus reaction devices are used in series.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
The method of hydrogen sulfide, is applicable to hydrogen sulfide body in gas in removal gas provided in an embodiment of the present invention
The situation that product concentration is 1.5-4%.The sulphur catalyst for preparing hydrogen processed prepared by the above method is added into high temperature
In reactor, the hydrogen sulfide in gas is reacted with oxygen in high-temperature reactor, firstly generate sulfur dioxide
And water, then, sulfur dioxide generate sulphur and water with the reaction of remaining hydrogen sulfide again.Meanwhile, in high temperature and
In the presence of sulphur catalyst for preparing hydrogen processed, partial vulcanization hydrogen is set to decompose, generation sulphur and hydrogen, the hydrogen
It is used directly for removing the vent gas treatment of hydrogen sulfide process, without being additionally passed through hydrogen, simplifies tail gas
Processing procedure, has saved resource.It can be seen that, the method provided in an embodiment of the present invention for removing hydrogen sulfide in gas,
Adapt to hydrogen sulfide volumetric concentration in gas and be 1.5-4% situation, and effectively remove hydrogen sulfide, and flow letter
It is single, it is easy to large-scale promotion application.
Embodiment
, below will be to embodiment of the present invention to make the object, technical solutions and advantages of the present invention clearer
It is described in further detail.
The embodiments of the invention provide a kind of method for removing hydrogen sulfide in gas, this method comprises the following steps：
Sulphur catalyst for preparing hydrogen processed is added into high-temperature reactor, then, the gas containing hydrogen sulfide is introduced high
Warm reactor, and air or oxygen is passed through into high-temperature reactor, it is 10000~50000h in reaction velocity-1、
Reaction temperature obtains sulphur and hydrogen to be reacted under conditions of 500~800 DEG C；Wherein, hydrogen sulfide with
The volume ratio of oxygen is (4-1):1.
Wherein, sulphur catalyst for preparing hydrogen processed is prepared via a method which to obtain：
Water and auxiliary agent are added in carrier component, is well mixed, bar shaped is extruded into banded extruder, through once doing
It is dry and once be calcined after obtain catalyst carrier；By active ingredients into mass concentration be 100~150g/L
Solution, at 50~60 DEG C, use the solution impregnated catalyst carrier, impregnate 2-3h, through redrying and
After baking obtains sulphur catalyst for preparing hydrogen processed；Wherein, auxiliary agent is cellulose and/or graphite, and carrier component is work
Property aluminum oxide, inert alumina or silica in one kind, the quality of water is carrier component quality
30%-50%, the quality of auxiliary agent is the 1%-5% of carrier component quality；The volume ratio of catalyst carrier and solution
For 1:(1-1.2)；Active component is at least one of nitrate or sulphite of iron, chromium or nickel.
The method of hydrogen sulfide, is applicable to hydrogen sulfide body in gas in removal gas provided in an embodiment of the present invention
The situation that product concentration is 1.5-4%.Sulphur catalyst for preparing hydrogen addition high temperature processed will be prepared by the above method anti-
Answer in device, hydrogen sulfide in gas react with oxygen in high-temperature reactor, firstly generate sulfur dioxide with
Water, then, sulfur dioxide generate sulphur and water with the reaction of remaining hydrogen sulfide again.Meanwhile, in high temperature and system
In the presence of sulphur catalyst for preparing hydrogen, partial vulcanization hydrogen is set to decompose, generation sulphur and hydrogen, the hydrogen can
To be directly used in the vent gas treatment of removing hydrogen sulfide process, without being additionally passed through hydrogen, simplify at tail gas
Reason process, has saved resource.It can be seen that, the method provided in an embodiment of the present invention for removing hydrogen sulfide in gas,
Adapt to hydrogen sulfide volumetric concentration in gas and be 1.5-4% situation, and effectively remove hydrogen sulfide, and flow letter
It is single, it is easy to large-scale promotion application.
Specifically, hydrogen sulfide containing gas enters after high-temperature reactor, hydrogen sulfide elder generation and oxygen reaction, generation
Sulfur dioxide and water (reacting 1), due to vulcanization excess hydrogen, so remaining hydrogen sulfide continues and titanium dioxide
Reaction of Salmon-Saxl, generation sulphur and water (reacting 2).The reaction as occurred above in conventional Claus method, but
The reaction condition of conventional Claus method is more harsh, and the ratio of hydrogen sulfide and oxygen must be strict controlled in 2：1,
Just the sulfur recovery rate of Claus method can be made to reach higher level.And the method provided in the embodiment of the present invention, instead
Answer condition relatively mild, the volume ratio of hydrogen sulfide and air or oxygen is (4-1):1, for example, 4:1、3:1、2:1、
1:1, be preferably (4-3):1, reaction is easier control.Meanwhile, in the presence of sulphur catalyst for preparing hydrogen processed,
Remaining hydrogen sulfide can decompose reaction, generation hydrogen and sulphur (reacting 3), so as to reclaim sulphur
Hydrogen is prepared while sulphur, is easy to use during vent gas treatment.And because reaction 2 and reaction 3 are all reversible
Reaction, in high-temperature reactor the composition of reaction product constituted by reactant, reaction temperature, reaction velocity and
The influence of sulphur catalyst for preparing hydrogen processed, is 10000~50000h by reaction velocity control-1, for example, 10000h-1、
20000h-1、30000h-1、40000h-1、50000h-1, preferably 20000-40000h-1, reaction temperature control
It is made as 500~800 DEG C, for example, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, preferably 650-800 DEG C,
Reaction time is 0.072-0.36s, and sulphur catalyst for preparing hydrogen processed is rationally prepared so that Recovery ratio and
Hydrogen yield is all optimal value.
2H2S+3O2=2SO2+2H2O (reaction 1)
4H2S+2SO2=3S2+4H2O (reaction 2)
2H2S=2H2+S2(reaction 3)
Specifically, with active ingredients into solution, its mass concentration be 100~150g/L solution, example
If concentration of polymer solution is 100g/L, 120g/L, 140g/L, 150g/L.At 50~60 DEG C, such as 50 DEG C,
At 55 DEG C, 60 DEG C, the solution impregnated catalyst carrier is used, the volume ratio of catalyst carrier and solution can be 1:1、
1:1.1、1:1.2, dip time can be 2h, 2.5h, 3h.In catalyst support component, the quality of water is load
The 30%-50% of body constituent mass, for example, 30%, 40%, 50%, the quality of auxiliary agent is vehicle group sub-prime
The 1%-5% of amount, for example, 1%, 3%, 5%.Catalyst carrier be length 8-10mm, for example, 8mm,
9mm, 10mm, diameter 2-3mm, for example, 2mm, 2.5mm, 3mm circle bar shaped, so that active
The solution of component is more abundant to the dipping of catalyst carrier.
Specifically, the temperature of primary drying and redrying is 110-120 DEG C, for example, 110 DEG C, 115 DEG C,
120 DEG C, drying time is 2-3h, for example, 2h, 2.5h, 3h；The temperature being once calcined is 600-800 DEG C,
For example, 600 DEG C, 700 DEG C, 800 DEG C, roasting time is 2-4h, for example, 2h, 3h, 4h, secondary roasting
The temperature of burning is 700-800 DEG C, and for example, 700 DEG C, 750 DEG C, 800 DEG C, roasting time is 1-3h, for example
For 1h, 2h, 3h.Because the effect of water and auxiliary agent in sulphur producing hydrogen, catalyzing agent carrier processed is to enter carrier component
Row mixing contributes little with fixing for catalytic action, and by drying and being calcined, can remove catalyst
Water and auxiliary agent in carrier, are easy to the catalyst to play catalytic action in high-temperature reactor.
Specifically, the specific surface area of sulphur catalyst for preparing hydrogen processed is 20-250m2/ g, for example, 20m2/g、100
m2/g、200m2/g、250m2/ g, average crush strength is 100-150N/cm, for example, 100N/cm,
125N/cm, 150N/cm, heap density are 0.5-0.8g/ml, for example, 0.5g/ml, 0.6g/ml, 0.8
G/ml, so that catalyst is fully in contact with the hydrogen sulfide in high-temperature reactor, the decomposition of catalysed curing hydrogen.
Specifically, mass fraction of the active component in sulphur catalyst for preparing hydrogen processed is 3-5%, for example, quality point
Number is 3%, 4%, 5%, preferably 4%.The carrier of sulphur catalyst for preparing hydrogen processed is preferably inert alumina, living
Property component be preferably nickel oxide so that it is provided in an embodiment of the present invention remove gas in hydrogen sulfide method, system
The sulphur and hydrogen obtained is all optimal value.
Specifically, high-temperature reactor is claus reaction device, and claus reaction device includes：Reactor, setting
Gas access at the top of reactor, is arranged on the air/oxygen entrance of reactor side wall upper part, is arranged on anti-
Answer the product exit in bottom portion.During gas containing hydrogen sulfide enters reactor from gas access, and with from sky
The air or oxygen that gas/oxygen intake is passed through is reacted, and obtained sulphur can be discharged from product exit.Instead
It is 1300-1800mm to answer kettle internal diameter, for example, 1300mm, 1500mm, 1800mm, is highly
It is horizontally disposed in the middle part of 800-1000mm, for example, 800mm, 900mm, 1000mm, reactor inner chamber
Having has multiple manholes on catalyst dividing plate, and catalyst dividing plate, a diameter of 1-2mm, Catalyst packing
It is highly 200-500mm, so that sulphur catalyst for preparing hydrogen processed is evenly distributed on catalyst dividing plate.Pass through temperature control
Electric furnace is heated to reactor, and the temperature in reactor is controlled, so that the gas in reactor
Reacted at a suitable temperature.
Specifically, in use, 2-3 claus reaction device is used in series, can further significantly
Total sulfur recovery is improved, final sulfur recovery rate is reached 96.0%-98.0%.At the same time it can also which this will be used
The high-temperature reactor of the method for hydrogen sulfide in gas is removed, with the claus reaction using conventional Claus method
Device is connected, to improve final sulfur recovery rate.When the high-temperature reactor used in this method and reduction hydrogenation class
When claus tail-gas clean-up device is connected, due in the product of the high-temperature reactor used in this method,
Hydrogen containing sufficient amount, so when carrying out vent gas treatment, without being additionally passed through hydrogen again, so as to simplify
The process of hydrogen sulfide in gas is removed, at the same time it can also be recycled to the hydrogen produced in this method,
Resource is saved.
It will be described in detail below by specific embodiment：
Embodiment 1
A kind of method for removing hydrogen sulfide in gas is present embodiments provided, this method comprises the following steps：
First, sulphur catalyst for preparing hydrogen processed is prepared：
30g distilled water and 2g hydroxyethyl celluloses are added in 100g technical grade active alumina powders,
It is well mixed, length 10mm is extruded into banded extruder, 2h is dried in diameter 2mm circle bar shaped at 110 DEG C,
Again through 750 DEG C of roasting 3h, catalyst carrier is obtained.74g is analyzed into pure Cr (NO3)3·9H2O crystal is prepared
Into the solution that 200ml mass concentrations are 100g/L, at 50 DEG C, with solution impregnated catalyst carrier, catalysis
The volume ratio of agent carrier and solution is 1:After 1, dipping 2.5h, 2h is dried at 110 DEG C, then through 700 DEG C of roastings
2h is burnt, sulphur catalyst for preparing hydrogen processed is obtained.The sulphur catalyst for preparing hydrogen processed than surface 227m2/ g, average crushing is strong
Spend for 132N/cm, heap density is 0.68g/ml, mass fraction of the chromium oxide in sulphur catalyst for preparing hydrogen processed is
3.75%.
Secondly, hydrogen sulfide in gas is removed：
The sulphur catalyst for preparing hydrogen processed for taking the 0.5ml above methods to prepare is broken into 0.5mm particulate, and makes
It is evenly distributed on the catalyst dividing plate of claus reaction device, then, will be containing hydrogen sulfide volumetric concentration
2.1% gas introduces claus reaction device, and is passed through air, the body of hydrogen sulfide and oxygen in air thereto
Product is than being 3.5:1, it is 15000h in reaction velocity-1, reaction temperature be 680 DEG C under conditions of reacted, instead
0.24s between seasonable, obtains sulphur and hydrogen.
Each constituent in claus reaction device before and after reaction is measured, and calculates Recovery ratio and hydrogen
Yield, is determined and result of calculation is as shown in table 1.
Contrast table before and after hydrogen sulfide reaction in the gas of table 1
It is can be seen that by the data in table 1 using hydrogen sulfide in removal gas provided in an embodiment of the present invention
Method after, hydrogen sulfide is converted into sulphur, hydrogen and sulfur dioxide in gas, and Recovery ratio reaches 79.1%, hydrogen
Gas yield 11.6%, disclosure satisfy that the demand to amounts of hydrogen during sulfur recovery and vent gas treatment.
Embodiment 2
A kind of method for removing hydrogen sulfide in gas is present embodiments provided, this method comprises the following steps：
First, sulphur catalyst for preparing hydrogen processed is prepared：
40g distilled water and 3.5g hydroxyethyl celluloses are added in 100g technical grade SiO 2 powders, mixed
Close uniform, length 8mm be extruded into banded extruder, 2.5h is dried in diameter 3mm circle bar shaped at 115 DEG C,
Again through 800 DEG C of roasting 2h, catalyst carrier is obtained.53g is analyzed into pure Fe2(SO4)3Crystal is configured to 240ml
Mass concentration is 125g/L solution, at 50 DEG C, with solution impregnated catalyst carrier, catalyst carrier with
The volume ratio of solution is 1:After 1.1, dipping 3h, 3h is dried at 115 DEG C, then through 750 DEG C of roasting 3h, obtain
To sulphur catalyst for preparing hydrogen processed.The sulphur catalyst for preparing hydrogen processed than surface 49m2/ g, average crush strength is
112N/cm, heap density is 0.53g/ml, and mass fraction of the chromium oxide in sulphur catalyst for preparing hydrogen processed is 4.14%.
Secondly, hydrogen sulfide in gas is removed：
The sulphur catalyst for preparing hydrogen processed for taking the 2.5ml above methods to prepare is broken into 0.8mm particulate, and makes
It is evenly distributed on the catalyst dividing plate of claus reaction device.Then, will be containing hydrogen sulfide volumetric concentration
3.0% gas introduces claus reaction device, and is passed through oxygen thereto, and the volume ratio of hydrogen sulfide and oxygen is
4:1, it is 35000h in reaction velocity-1, reaction temperature be 740 DEG C under conditions of reacted, the reaction time
0.1s, obtains sulphur and hydrogen.
Each constituent in claus reaction device before and after reaction is measured, and calculates Recovery ratio and hydrogen
Yield, is determined and result of calculation is as shown in table 2.
Contrast table before and after hydrogen sulfide reaction in the gas of table 2
It is can be seen that by the data in table 2 using hydrogen sulfide in removal gas provided in an embodiment of the present invention
Method after, hydrogen sulfide is converted into sulphur, hydrogen and sulfur dioxide in gas, and Recovery ratio reaches 74%, hydrogen
Gas yield 24%, disclosure satisfy that the demand to amounts of hydrogen during sulfur recovery and vent gas treatment.
Embodiment 3
A kind of method for removing hydrogen sulfide in gas is present embodiments provided, this method comprises the following steps：
First, sulphur catalyst for preparing hydrogen processed is prepared：
50g distilled water and 4.7g graphite are added in 100g technical grade inert alumina powder, are well mixed,
Length 9mm is extruded into banded extruder, 3h is dried in diameter 2mm circle bar shaped at 120 DEG C, then through 680 DEG C
2.5h is calcined, catalyst carrier is obtained.95g is analyzed into pure Ni (NO3)2·6H2O crystal is configured to 170ml
Mass concentration is 150g/L solution, at 50 DEG C, with solution impregnated catalyst carrier, catalyst carrier with
The volume ratio of solution is 1:After 1.2, dipping 2h, 2.5h is dried at 120 DEG C, then through 800 DEG C of roasting 2.5h,
Obtain sulphur catalyst for preparing hydrogen processed.The sulphur catalyst for preparing hydrogen processed than surface 25m2/ g, average crush strength is
147N/cm, heap density is 0.77g/ml, and mass fraction of the chromium oxide in sulphur catalyst for preparing hydrogen processed is 4.83%.
Secondly, hydrogen sulfide in gas is removed：
The sulphur catalyst for preparing hydrogen processed for taking the 4.0ml above methods to prepare is broken into 1.0mm particulate, and makes
It is evenly distributed on the catalyst dividing plate of claus reaction device.Then, will be containing hydrogen sulfide volumetric concentration
3.5% gas introduces claus reaction device, and is passed through air, the body of hydrogen sulfide and oxygen in air thereto
Product is than being 3.5:1, it is 45000h in reaction velocity-1, reaction temperature be 800 DEG C under conditions of reacted, instead
0.08s between seasonable, obtains sulphur and hydrogen.
Each constituent in claus reaction device before and after reaction is measured, and calculates Recovery ratio and hydrogen
Yield, is determined and result of calculation is as shown in table 3.
Contrast table before and after hydrogen sulfide reaction in the gas of table 3
It is can be seen that by the data in table 3 using hydrogen sulfide in removal gas provided in an embodiment of the present invention
Method after, hydrogen sulfide is converted into sulphur, hydrogen and sulfur dioxide in gas, and Recovery ratio reaches 54.3%, hydrogen
Gas yield 37.8%, disclosure satisfy that the demand to amounts of hydrogen during sulfur recovery and vent gas treatment.
Embodiment 4
A kind of method for removing hydrogen sulfide in gas is present embodiments provided, this method comprises the following steps：
First, sulphur catalyst for preparing hydrogen processed is prepared：
Preparation method be the same as Example 3.
Secondly, hydrogen sulfide in gas is removed：
Two claus reaction devices are connected, i.e., first claus reaction device outlet connection, second Crouse
Reactor inlet.The sulphur catalyst for preparing hydrogen processed for taking the 8.0ml above methods to prepare is broken into the micro- of 1.0mm
Grain, loads 4.0ml catalyst in two claus reaction devices respectively, and it is anti-it is evenly distributed on Crouse
Answer on the catalyst dividing plate of device.Then, first will be introduced for 3.5% gas containing hydrogen sulfide volumetric concentration
Claus reaction device, and it is 3.5 to be passed through the volume ratio of oxygen in air, hydrogen sulfide and air thereto:1,
First reactor and second reactor air speed are 45000h-1, reaction temperature be under conditions of 800 DEG C
Reacted, the reaction time is 0.08s in two claus reaction devices, obtains sulphur and hydrogen.
Each constituent in second claus reaction device exit gas is measured, and calculates Recovery ratio
And hydrogen yield, determine and result of calculation is as shown in table 4.
Contrast table before and after hydrogen sulfide reaction in the gas of table 4
It is can be seen that by the data in table 4 using hydrogen sulfide in removal gas provided in an embodiment of the present invention
Method after, hydrogen sulfide is converted into sulphur, hydrogen and sulfur dioxide in gas, and Recovery ratio reaches 62.2%, hydrogen
Gas yield 35.8%.In the present embodiment, reaction raw materials and operating condition are all with unanimously, being many in embodiment 3
Connect a claus reaction device, it can be seen that after the claus reaction devices using two series connection, sulphur is received
Rate has further raising, has risen to 62.2% from 54.3%, the effect of sulphur hydrogen manufacturing processed is more preferable, Neng Gougeng
The demand to amounts of hydrogen during sulfur recovery and vent gas treatment is met well.
Presently preferred embodiments of the present invention is the foregoing is only, the protection domain being not intended to limit the invention is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements made etc., all should be included
Within protection scope of the present invention.
Claims (7)
1. a kind of method for removing hydrogen sulfide in gas, it is characterised in that methods described comprises the following steps：
Sulphur catalyst for preparing hydrogen processed is added into high-temperature reactor, then, the gas containing hydrogen sulfide institute is introduced into
State high-temperature reactor, and air or oxygen be passed through into the high-temperature reactor, reaction velocity be 10000~
50000h-1, reaction temperature be 500~800 DEG C under conditions of reacted, obtain sulphur and hydrogen；Wherein,
The volume ratio of the hydrogen sulfide and the oxygen is (4-1):1；
The sulphur catalyst for preparing hydrogen processed is prepared via a method which to obtain：
Water and auxiliary agent are added in carrier component, is well mixed, bar shaped is extruded into banded extruder, through once doing
It is dry and once be calcined after obtain catalyst carrier；By active ingredients into mass concentration be 100~150g/L
Solution, at 50~60 DEG C, impregnated with the solution after the catalyst carrier, dipping 2-3h, through two
Secondary drying and after baking obtain the sulphur catalyst for preparing hydrogen processed；
The auxiliary agent be cellulose and/or graphite, the carrier component be activated alumina, inert alumina or
One kind in silica, the quality of the water is the 30%-50% of the carrier component quality, the auxiliary agent
Quality be the carrier component quality 1%-5%；The catalyst carrier and the volume ratio of the solution are
1:(1-1.2)；The active component is at least one of nitrate or sulphite of iron, chromium or nickel.
2. according to the method described in claim 1, it is characterised in that the catalyst carrier is length
8-10mm, diameter 2-3mm circle bar shaped.
3. method according to claim 2, it is characterised in that the primary drying and described secondary dry
Dry temperature is 110-120 DEG C, and drying time is 2-3h；The temperature being once calcined is 600-800 DEG C,
Roasting time is 2-4h, and the temperature of the after baking is 700-800 DEG C, and roasting time is 1-3h.
4. method according to claim 3, it is characterised in that the ratio table of the sulphur catalyst for preparing hydrogen processed
Area is 20-250m2/ g, average crush strength is 100-150N/cm, and heap density is 0.5-0.8g/ml.
5. method according to claim 4, it is characterised in that the active component is in the sulphur system processed
Mass fraction in hydrogen catalyst is 3-5%.
6. method according to claim 5, it is characterised in that the high-temperature reactor is that Crouse is anti-
Device is answered, the claus reaction device includes：Reactor, the Crouse's gas being arranged at the top of the reactor
Entrance, is arranged on the air/oxygen entrance of the reactor side wall upper part, is arranged on the reactor bottom
Product exit；It is horizontally disposed in the middle part of the reactor inner chamber to have catalyst dividing plate, by temperature control electric furnace to described
Reactor is heated.
7. method according to claim 6, it is characterised in that in use, by 2-3 institute
Claus reaction device is stated to be used in series.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233930A (en) * | 2018-10-26 | 2019-01-18 | 常州工程职业技术学院 | It is a kind of for removing the device and removal methods of hydrogen sulfide in methane |
| CN111151240A (en) * | 2020-01-07 | 2020-05-15 | 中国石油大学(华东) | Preparation method of catalyst for converting hydrogen sulfide in Claus tail gas |
| CN111689464A (en) * | 2020-06-18 | 2020-09-22 | 中国科学院大学 | Method for preparing hydrogen and elemental sulfur by oxidizing, catalytically decomposing and hydrogen sulfide under trace oxygen atmosphere |
| CN114471528A (en) * | 2022-03-21 | 2022-05-13 | 西南石油大学 | High-sulfur natural gas direct conversion material and large-scale preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105178A (en) * | 1993-03-16 | 1995-07-12 | 埃尔夫·阿奎坦生产公司 | Method for removing hydrogen sulphide from a gas and recovering in the form of sulphur |
| CN103282118A (en) * | 2010-09-01 | 2013-09-04 | 中国石油化工股份有限公司 | Method for treating sulfur-ontaining gas and hydrogenation catalyst used in the method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105178A (en) * | 1993-03-16 | 1995-07-12 | 埃尔夫·阿奎坦生产公司 | Method for removing hydrogen sulphide from a gas and recovering in the form of sulphur |
| CN103282118A (en) * | 2010-09-01 | 2013-09-04 | 中国石油化工股份有限公司 | Method for treating sulfur-ontaining gas and hydrogenation catalyst used in the method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233930A (en) * | 2018-10-26 | 2019-01-18 | 常州工程职业技术学院 | It is a kind of for removing the device and removal methods of hydrogen sulfide in methane |
| CN111151240A (en) * | 2020-01-07 | 2020-05-15 | 中国石油大学(华东) | Preparation method of catalyst for converting hydrogen sulfide in Claus tail gas |
| CN111689464A (en) * | 2020-06-18 | 2020-09-22 | 中国科学院大学 | Method for preparing hydrogen and elemental sulfur by oxidizing, catalytically decomposing and hydrogen sulfide under trace oxygen atmosphere |
| CN114471528A (en) * | 2022-03-21 | 2022-05-13 | 西南石油大学 | High-sulfur natural gas direct conversion material and large-scale preparation method and application thereof |
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