CN107233794B - Method for removing hydrogen sulfide in gas - Google Patents
Method for removing hydrogen sulfide in gas Download PDFInfo
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- CN107233794B CN107233794B CN201610185069.5A CN201610185069A CN107233794B CN 107233794 B CN107233794 B CN 107233794B CN 201610185069 A CN201610185069 A CN 201610185069A CN 107233794 B CN107233794 B CN 107233794B
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 93
- 239000007789 gas Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011593 sulfur Substances 0.000 claims abstract description 88
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 88
- 239000001257 hydrogen Substances 0.000 claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 238000001035 drying Methods 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 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
- 230000008569 process Effects 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005192 partition Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 238000005470 impregnation Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-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
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 22
- 238000011084 recovery Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000003197 catalytic effect Effects 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
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 reaction 1) Chemical compound 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 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
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Classifications
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- 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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- Oil, Petroleum & Natural Gas (AREA)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a method for removing hydrogen sulfide in gas, belonging to the field of industrial gas treatment. The method comprises the following steps: adding a catalyst for producing hydrogen by using sulfur into a high-temperature reactor, introducing gas containing hydrogen sulfide into the high-temperature reactor, introducing air or oxygen into the high-temperature reactor, wherein the volume ratio of the hydrogen sulfide to the oxygen is (4-1):1, and the reaction space velocity is 10000-50000 h‑1And reacting at the reaction temperature of 500-800 ℃ to obtain sulfur and hydrogen. The catalyst for preparing hydrogen from sulfur is prepared by the following method: adding water and an auxiliary agent into the carrier component, extruding the mixture into strips by using a strip extruding machine, and obtaining a catalyst carrier after primary drying and primary roasting; and preparing the active components into a solution with the mass concentration of 100-150 g/L, impregnating a catalyst carrier with the solution, and performing secondary drying and secondary roasting to obtain the sulfur-making and hydrogen-making catalyst. The method can adapt to the condition that the volume concentration of the hydrogen sulfide in the gas is 1.5-4%, and can effectively remove the hydrogen sulfide, and the operation is simple and convenient.
Description
Technical Field
The invention relates to the field of industrial gas treatment, in particular to a method for removing hydrogen sulfide in gas.
Background
Gases containing hydrogen sulfide are generated in the process of processing fossil fuels and the like, and the gases can cause bad influence on the environment if being directly discharged, so that the gases containing the hydrogen sulfide need to be treated to ensure the safe discharge of the gases. The claus process is one of the main processes for removing hydrogen sulfide from a gas, and removes hydrogen sulfide from a gas by conducting a claus reaction in a claus furnace, thereby incompletely combusting hydrogen sulfide, and reacting sulfur dioxide produced thereby with hydrogen sulfide to produce sulfur. In order to increase the sulfur recovery rate of the claus process, it is often necessary to increase the number of claus reactors and to subject the hydrogen sulfide to a multistage conversion, so that the final sulfur recovery rate reaches 94% to 97%, but the sulfur recovery rate of a single claus reactor is only 60% to 65%, and the sulfur recovery rate is relatively low. It is therefore desirable to provide a process for removing hydrogen sulfide that results in a higher sulfur recovery for a single claus reactor.
The prior art provides a super claus process, which adds a super claus reactor after the conventional claus reactor, and adds a selective oxidation catalyst therein to oxidize hydrogen sulfide in the tail gas into sulfur, thereby improving the conversion rate of the super claus reactor. On the basis of the super Claus method, the prior art also provides a super Claus method, wherein a hydrogenation reduction catalyst is added into a super Claus reactor, so that the sulfur recovery rate is further improved, the sulfur recovery rate of a single super Claus reactor reaches 89%, and the total sulfur recovery rate reaches 99.4%.
The inventor finds that the prior art has at least the following technical problems:
the superYokous method provided by the prior art can only be suitable for gas with smaller volume concentration of hydrogen sulfide, namely the volume concentration of the hydrogen sulfide in the gas is required to be less than 1.5%. Meanwhile, after the superYokous method is adopted, a small part of hydrogen sulfide exists in the discharged tail gas, so that the tail gas needs to be treated to further remove the hydrogen sulfide, and hydrogen is additionally introduced during the tail gas treatment, so that the whole hydrogen sulfide removal method is complicated.
Disclosure of Invention
The technical problem to be solved by the embodiment of the invention is to provide a method for removing hydrogen sulfide in gas, which can adapt to the condition that the volume concentration of hydrogen sulfide in gas is 1.5-4%, has high sulfur recovery rate, and can prepare hydrogen while recovering sulfur, and the specific technical scheme is as follows:
the embodiment of the invention provides a method for removing hydrogen sulfide in gas, which comprises the following steps:
adding a catalyst for producing hydrogen by using sulfur into a high-temperature reactor, introducing gas containing hydrogen sulfide into the high-temperature reactor, introducing air or oxygen into the high-temperature reactor, and controlling the reaction space velocity to be 10000～50000h-1Reacting at 500-800 ℃ to obtain sulfur and hydrogen; wherein the volume ratio of the hydrogen sulfide to the oxygen is (4-1): 1.
The catalyst for preparing hydrogen and sulfur is prepared by the following method:
adding water and an auxiliary agent into the carrier component, uniformly mixing, extruding into strips by using a strip extruding machine, and obtaining a catalyst carrier after primary drying and primary roasting; preparing the active components into a solution with the mass concentration of 100-150 g/L, impregnating the catalyst carrier with the solution at 50-60 ℃, and performing secondary drying and secondary roasting to obtain the sulfur-making and hydrogen-making catalyst after 2-3h of impregnation.
The auxiliary agent is cellulose and/or graphite, the carrier component is one of activated alumina, inert alumina or silicon dioxide, the mass of the water is 30-50% of that of the carrier component, and the mass of the auxiliary agent is 1-5% of that of the carrier component; the volume ratio of the catalyst carrier to the solution is 1 (1-1.2); the active component is at least one of nitrate or sulfite of iron, chromium or nickel.
Specifically, preferably, the catalyst support is in the shape of a circular bar having a length of 8 to 10mm and a diameter of 2 to 3 mm.
Specifically, the temperature of the primary drying and the temperature of the secondary drying are both 110-120 ℃, and the drying time is both 2-3 h; the temperature of the primary roasting is 600-800 ℃, the roasting time is 2-4h, the temperature of the secondary roasting is 700-800 ℃, and the roasting time is 1-3 h.
Particularly, the specific surface area of the catalyst for preparing hydrogen from sulfur is preferably 20-250m2(ii)/g, average crush strength of 100-.
Specifically, the mass fraction of the active component in the sulfur-production hydrogen production catalyst is preferably 3 to 5%.
In particular, as a preference, the high temperature reactor is a claus reactor comprising: the device comprises a reaction kettle, a Claus gas inlet arranged at the top of the reaction kettle, an air/oxygen inlet arranged at the upper part of the side wall of the reaction kettle, and a product outlet arranged at the bottom of the reaction kettle; a catalyst partition plate is horizontally arranged in the middle of the inner cavity of the reaction kettle and is heated by a temperature control electric furnace.
In particular, preferably, 2 to 3 of said claus reactors are used in series during use.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the method for removing hydrogen sulfide in gas provided by the embodiment of the invention can be suitable for the condition that the volume concentration of hydrogen sulfide in gas is 1.5-4%. The catalyst for preparing hydrogen and sulfur prepared by the method is added into a high-temperature reactor, so that hydrogen sulfide in gas reacts with oxygen in the high-temperature reactor to generate sulfur dioxide and water firstly, and then the sulfur dioxide reacts with the residual hydrogen sulfide to generate sulfur and water. Meanwhile, under the action of high temperature and a sulfur-producing hydrogen production catalyst, part of hydrogen sulfide is decomposed to generate sulfur and hydrogen, and the hydrogen can be directly used for tail gas treatment in the hydrogen sulfide removal process without introducing additional hydrogen, so that the tail gas treatment process is simplified, and resources are saved. Therefore, the method for removing hydrogen sulfide in gas provided by the embodiment of the invention can adapt to the condition that the volume concentration of hydrogen sulfide in gas is 1.5-4%, can effectively remove hydrogen sulfide, has a simple process, and is convenient for large-scale popularization and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
The embodiment of the invention provides a method for removing hydrogen sulfide in gas, which comprises the following steps:
adding a catalyst for producing hydrogen by using sulfur into a high-temperature reactor, then introducing gas containing hydrogen sulfide into the high-temperature reactor, introducing air or oxygen into the high-temperature reactor, and reacting at a space velocity of 10000-50000 h-1Reacting at 500-800 ℃ to obtain sulfur and hydrogen; wherein the volume ratio of the hydrogen sulfide to the oxygen is (4-1):1。
the catalyst for preparing hydrogen from sulfur is prepared by the following method:
adding water and an auxiliary agent into the carrier component, uniformly mixing, extruding into strips by using a strip extruding machine, and obtaining a catalyst carrier after primary drying and primary roasting; preparing the active components into a solution with the mass concentration of 100-150 g/L, impregnating a catalyst carrier with the solution at 50-60 ℃, impregnating for 2-3h, and performing secondary drying and secondary roasting to obtain a sulfur-making and hydrogen-making catalyst; wherein, the auxiliary agent is cellulose and/or graphite, the carrier component is one of activated alumina, inert alumina or silicon dioxide, the mass of water is 30-50% of the mass of the carrier component, and the mass of the auxiliary agent is 1-5% of the mass of the carrier component; the volume ratio of the catalyst carrier to the solution is 1 (1-1.2); the active component is at least one of nitrate or sulfite of iron, chromium or nickel.
The method for removing hydrogen sulfide in gas provided by the embodiment of the invention can be suitable for the condition that the volume concentration of hydrogen sulfide in gas is 1.5-4%. The catalyst for preparing hydrogen and sulfur prepared by the method is added into a high-temperature reactor, so that hydrogen sulfide in gas reacts with oxygen in the high-temperature reactor to generate sulfur dioxide and water firstly, and then the sulfur dioxide reacts with the residual hydrogen sulfide to generate sulfur and water. Meanwhile, under the action of high temperature and a sulfur-producing hydrogen production catalyst, part of hydrogen sulfide is decomposed to generate sulfur and hydrogen, and the hydrogen can be directly used for tail gas treatment in the hydrogen sulfide removal process without introducing additional hydrogen, so that the tail gas treatment process is simplified, and resources are saved. Therefore, the method for removing hydrogen sulfide in gas provided by the embodiment of the invention can adapt to the condition that the volume concentration of hydrogen sulfide in gas is 1.5-4%, can effectively remove hydrogen sulfide, has a simple process, and is convenient for large-scale popularization and application.
Specifically, after the gas containing hydrogen sulfide enters the high-temperature reactor, the hydrogen sulfide reacts with oxygen to generate sulfur dioxide and water (i.e. reaction 1), and the residual hydrogen sulfide continuously reacts with the sulfur dioxide to generate sulfur and water (i.e. reaction 2) due to the excess hydrogen sulfide. The above is the reaction which takes place in the conventional Claus process, but the conventional Claus processThe reaction conditions are harsh, and the ratio of hydrogen sulfide to oxygen must be strictly controlled to be 2:1, the sulfur recovery of the Claus process can reach a higher level. In the method provided in the embodiment of the invention, the reaction conditions are relatively mild, and the volume ratio of the hydrogen sulfide to the air or the oxygen is (4-1):1, such as 4:1, 3:1, 2:1, 1:1, preferably (4-3):1, so that the reaction is easier to control. Meanwhile, under the action of the catalyst for preparing hydrogen from sulfur, the residual hydrogen sulfide can be subjected to decomposition reaction to generate hydrogen and sulfur (namely reaction 3), so that the hydrogen is prepared while the sulfur is recovered, and the catalyst is convenient to use in tail gas treatment. And because the reaction 2 and the reaction 3 are reversible reactions, the composition of a reaction product in the high-temperature reactor is influenced by the composition of a reactant, the reaction temperature, the reaction space velocity and the catalyst for producing hydrogen by producing sulfur, and the reaction space velocity is controlled to 10000-50000 h-1For example, 10000h-1、20000h-1、30000h-1、40000h-1、50000h-1Preferably 20000--1The reaction temperature is controlled to be 500-800 ℃, for example, 500 ℃, 600 ℃, 700 ℃, 800 ℃, preferably 650-.
2H2S+3O2＝2SO2+2H2O (reaction 1)
4H2S+2SO2＝3S2+4H2O (reaction 2)
2H2S＝2H2+S2(reaction 3)
Specifically, the mass concentration of the solution prepared from the active component is 100-150 g/L, such as 100g/L, 120g/L, 140g/L and 150 g/L. The catalyst carrier is impregnated with the solution at 50-60 deg.C, such as 50 deg.C, 55 deg.C, 60 deg.C, the volume ratio of the catalyst carrier to the solution can be 1:1, 1:1.1, 1:1.2, and the impregnation time can be 2h, 2.5h, 3 h. In the catalyst carrier component, the mass of water is 30-50%, for example 30%, 40%, 50% of the mass of the carrier component, and the mass of the auxiliary agent is 1-5%, for example 1%, 3%, 5% of the mass of the carrier component. The catalyst support is in the form of a round bar having a length of 8 to 10mm, for example 8mm, 9mm, 10mm, and a diameter of 2 to 3mm, for example 2mm, 2.5mm, 3mm, so that the solution of the active component impregnates the catalyst support more thoroughly.
Specifically, the temperature of the primary drying and the secondary drying is 110-120 ℃, for example, 110 ℃, 115 ℃ and 120 ℃, and the drying time is 2-3h, for example, 2h, 2.5h and 3 h; the temperature of the first roasting is 600-800 ℃, such as 600 ℃, 700 ℃, 800 ℃, the roasting time is 2-4h, such as 2h, 3h, 4h, the temperature of the second roasting is 700-800 ℃, such as 700 ℃, 750 ℃, 800 ℃, and the roasting time is 1-3h, such as 1h, 2h, 3 h. The water and the auxiliary agent in the catalyst carrier for preparing hydrogen from sulfur are used for mixing and fixing the carrier components, so that the contribution to the catalytic action is small, and the water and the auxiliary agent in the catalyst carrier can be removed by drying and roasting, so that the catalyst can play a catalytic action in a high-temperature reactor conveniently.
Specifically, the specific surface area of the catalyst for preparing hydrogen from sulfur is 20-250m2G, e.g. 20m2/g、100m2/g、200m2/g、250m2The catalyst has an average crush strength of 100-150N/cm, such as 100N/cm, 125N/cm and 150N/cm, and a bulk density of 0.5 to 0.8g/ml, such as 0.5g/ml, 0.6g/ml and 0.8g/ml, so that the catalyst is sufficiently in contact with the hydrogen sulfide in the high-temperature reactor to catalyze the decomposition of the hydrogen sulfide.
Specifically, the mass fraction of the active component in the sulfur production hydrogen production catalyst is 3 to 5%, for example, 3%, 4%, 5%, preferably 4%. The carrier of the catalyst for preparing hydrogen from sulfur is preferably inert alumina, and the active component is preferably nickel oxide, so that the sulfur and hydrogen prepared by the method for removing hydrogen sulfide in gas provided by the embodiment of the invention reach optimal values.
In particular, the high temperature reactor is a claus reactor comprising: the reaction kettle, a gas inlet arranged at the top of the reaction kettle, an air/oxygen inlet arranged at the upper part of the side wall of the reaction kettle, and a product outlet arranged at the bottom of the reaction kettle. The gas containing hydrogen sulfide enters the reaction kettle from the gas inlet and reacts with the air or oxygen introduced from the air/oxygen inlet, and the obtained sulfur can be discharged from the product outlet. The inner diameter of the reaction kettle is 1300-1800mm, such as 1300mm, 1500mm and 1800mm, the height is 800-1000mm, such as 800mm, 900mm and 1000mm, the middle part of the inner cavity of the reaction kettle is horizontally provided with a catalyst partition plate, the catalyst partition plate is provided with a plurality of round through holes, the diameter is 1-2mm, and the filling height of the catalyst is 200-500mm, so that the sulfur-making and hydrogen-making catalyst is uniformly distributed on the catalyst partition plate. The reaction kettle is heated by the temperature control electric furnace, and the temperature in the reaction kettle is controlled, so that the gas in the reaction kettle reacts at a proper temperature.
Specifically, in the using process, 2-3 Claus reactors are connected in series for use, so that the total sulfur recovery rate can be further greatly improved, and the final sulfur recovery rate can reach 96.0% -98.0%. Meanwhile, a high-temperature reactor adopting the method for removing the hydrogen sulfide in the gas can be connected in series with a Claus reactor adopting a conventional Claus method, so that the final sulfur recovery rate is improved. When the high-temperature reactor adopted in the method is connected with the reduction hydrogenation Claus tail gas treatment device, because the product of the high-temperature reactor adopted in the method contains enough hydrogen, no additional hydrogen is needed to be introduced when the tail gas is treated, so that the process of removing hydrogen sulfide in the gas is simplified, and simultaneously, the hydrogen generated in the method can be recycled, thereby saving resources.
The following is illustrated in detail by specific examples:
example 1
The embodiment provides a method for removing hydrogen sulfide in gas, which comprises the following steps:
firstly, preparing a catalyst for preparing hydrogen from sulfur:
adding 30g of distilled water and 2g of hydroxyethyl cellulose into 100g of industrial grade active alumina powder, uniformly mixing, extruding into a round bar shape with the length of 10mm and the diameter of 2mm by using a bar extruding machine, drying for 2h at 110 ℃, and roasting for 3h at 750 ℃ to obtain the catalyst carrier. 74g of analytically pure Cr (NO)3)3·9H2The O crystal is prepared into 200ml of solution with the mass concentration of 100g/L,soaking a catalyst carrier in a solution at 50 ℃ for 2.5 hours at a volume ratio of the catalyst carrier to the solution of 1:1, drying at 110 ℃ for 2 hours, and roasting at 700 ℃ for 2 hours to obtain the sulfur-producing hydrogen-producing catalyst. The specific surface of the catalyst for preparing hydrogen and sulfur is 227m2The average crushing strength is 132N/cm, the bulk density is 0.68g/ml, and the mass fraction of the chromium oxide in the catalyst for preparing hydrogen from sulfur is 3.75%.
Secondly, removing hydrogen sulfide in the gas:
0.5ml of the catalyst for preparing hydrogen from sulfur prepared by the method is crushed into particles with the particle size of 0.5mm and evenly distributed on a catalyst partition plate of a Claus reactor, then gas containing 2.1 percent of hydrogen sulfide by volume concentration is introduced into the Claus reactor, air is introduced into the Claus reactor, the volume ratio of the hydrogen sulfide to oxygen in the air is 3.5:1, and the reaction space velocity is 15000h-1And reacting at 680 deg.C for 0.24s to obtain sulfur and hydrogen.
The respective components in the claus reactor before and after the reaction were measured, and the sulfur yield and the hydrogen yield were calculated, and the measurement and calculation results are shown in table 1.
TABLE 1 comparison table before and after reaction of hydrogen sulfide in gas
As can be seen from the data in table 1, after the method for removing hydrogen sulfide from gas provided by the embodiment of the present invention is adopted, hydrogen sulfide in gas is converted into sulfur, hydrogen and sulfur dioxide, the sulfur yield reaches 79.1%, the hydrogen yield is 11.6%, and the requirements for hydrogen amount in the processes of sulfur recovery and tail gas treatment can be met.
Example 2
The embodiment provides a method for removing hydrogen sulfide in gas, which comprises the following steps:
firstly, preparing a catalyst for preparing hydrogen from sulfur:
adding 40g of distilled water and 3.5g of hydroxyethyl cellulose into 100g of industrial-grade silicon dioxide powder, mixing uniformly, and usingExtruding into round bar shape with length of 8mm and diameter of 3mm by a bar extruder, drying at 115 deg.C for 2.5h, and calcining at 800 deg.C for 2h to obtain the catalyst carrier. 53g of analytically pure Fe2(SO4)3Preparing 240ml of solution with the mass concentration of 125g/L from the crystals, impregnating a catalyst carrier with the solution at 50 ℃, wherein the volume ratio of the catalyst carrier to the solution is 1:1.1, drying the impregnated catalyst carrier at 115 ℃ for 3 hours after impregnation, and roasting the impregnated catalyst carrier at 750 ℃ for 3 hours to obtain the sulfur-producing and hydrogen-producing catalyst. The specific surface of the catalyst for preparing hydrogen and sulfur is 49m2The chromium oxide catalyst has the advantages of high catalytic activity, low specific gravity, high.
Secondly, removing hydrogen sulfide in the gas:
2.5ml of the catalyst for preparing hydrogen and sulfur prepared by the method is crushed into particles with the diameter of 0.8mm and evenly distributed on a catalyst partition plate of the Claus reactor. Then, gas containing 3.0% by volume of hydrogen sulfide was introduced into a Claus reactor, and oxygen was introduced thereinto at a volume ratio of 4:1 of hydrogen sulfide to oxygen and at a reaction space velocity of 35000h-1And reacting at 740 ℃ for 0.1s to obtain sulfur and hydrogen.
The respective components in the claus reactor before and after the reaction were measured, and the sulfur yield and the hydrogen yield were calculated, and the measurement and calculation results are shown in table 2.
TABLE 2 comparison table before and after reaction of hydrogen sulfide in gas
As can be seen from the data in table 2, after the method for removing hydrogen sulfide from gas provided by the embodiment of the present invention is adopted, hydrogen sulfide in gas is converted into sulfur, hydrogen and sulfur dioxide, the sulfur yield reaches 74%, the hydrogen yield is 24%, and the requirements for hydrogen amount in the processes of sulfur recovery and tail gas treatment can be met.
Example 3
The embodiment provides a method for removing hydrogen sulfide in gas, which comprises the following steps:
firstly, preparing a catalyst for preparing hydrogen from sulfur:
adding 50g of distilled water and 4.7g of graphite into 100g of industrial-grade inert alumina powder, uniformly mixing, extruding into a round bar shape with the length of 9mm and the diameter of 2mm by using a bar extruding machine, drying at 120 ℃ for 3h, and roasting at 680 ℃ for 2.5h to obtain the catalyst carrier. 95g of analytically pure Ni (NO)3)2·6H2Preparing 170ml of solution with the mass concentration of 150g/L from the O crystals, impregnating a catalyst carrier with the solution at 50 ℃, wherein the volume ratio of the catalyst carrier to the solution is 1:1.2, drying for 2.5h at 120 ℃ after impregnating for 2h, and roasting for 2.5h at 800 ℃ to obtain the sulfur-producing and hydrogen-producing catalyst. The specific surface of the catalyst for preparing hydrogen and sulfur is 25m2The average crushing strength is 147N/cm, the bulk density is 0.77g/ml, and the mass fraction of the chromium oxide in the catalyst for preparing hydrogen from sulfur is 4.83 percent.
Secondly, removing hydrogen sulfide in the gas:
4.0ml of the catalyst for preparing hydrogen and sulfur prepared by the method is crushed into particles with the diameter of 1.0mm and evenly distributed on a catalyst clapboard of a Claus reactor. Then, a gas containing 3.5% by volume of hydrogen sulfide was introduced into the Claus reactor, and air was introduced thereinto in a volume ratio of 3.5:1 of hydrogen sulfide to oxygen in the air at a reaction space velocity of 45000h-1And reacting at 800 ℃ for 0.08s to obtain sulfur and hydrogen.
The respective components in the claus reactor before and after the reaction were measured, and the sulfur yield and the hydrogen yield were calculated, and the measurement and calculation results are shown in table 3.
TABLE 3 comparison table before and after reaction of hydrogen sulfide in gas
As can be seen from the data in table 3, after the method for removing hydrogen sulfide from gas provided by the embodiment of the present invention is adopted, hydrogen sulfide in gas is converted into sulfur, hydrogen and sulfur dioxide, the sulfur yield reaches 54.3%, the hydrogen yield reaches 37.8%, and the requirements for hydrogen amount in the processes of sulfur recovery and tail gas treatment can be met.
Example 4
The embodiment provides a method for removing hydrogen sulfide in gas, which comprises the following steps:
firstly, preparing a catalyst for preparing hydrogen from sulfur:
the preparation method is the same as example 3.
Secondly, removing hydrogen sulfide in the gas:
two claus reactors are connected in series, i.e. the outlet of the first claus reactor is connected to the inlet of the second claus reactor. 8.0ml of the catalyst for preparing hydrogen and sulfur prepared by the method is crushed into particles with the diameter of 1.0mm, 4.0ml of the catalyst is respectively filled in the two Claus reactors and is evenly distributed on the catalyst partition plates of the Claus reactors. Then, a gas containing 3.5% by volume of hydrogen sulfide was introduced into the first Claus reactor, and air was introduced thereinto in a volume ratio of 3.5:1 of hydrogen sulfide to oxygen in the air, at airspeeds of 45000h in both the first reactor and the second reactor-1And the reaction is carried out at the reaction temperature of 800 ℃, and the reaction time of the two Claus reactors is 0.08s, so as to obtain sulfur and hydrogen.
The respective compositional components in the outlet gas of the second claus reactor were measured, and the sulfur yield and the hydrogen yield were calculated, and the measurement and calculation results are shown in table 4.
TABLE 4 comparison table before and after reaction of hydrogen sulfide in gas
As can be seen from the data in table 4, after the method for removing hydrogen sulfide from gas provided by the embodiment of the present invention is adopted, hydrogen sulfide in gas is converted into sulfur, hydrogen and sulfur dioxide, the sulfur yield reaches 62.2%, and the hydrogen yield is 35.8%. In this example, the reaction raw materials and the operation conditions are the same as those in example 3, but only one claus reactor is connected in series, so that it can be seen that, after two claus reactors connected in series are used, the sulfur yield is further improved, and is increased from 54.3% to 62.2%, the effect of producing hydrogen from sulfur is better, and the requirements of sulfur recovery and hydrogen amount in the tail gas treatment process can be better met.
The above description is only exemplary of the present invention and should not be taken as limiting the scope of the present invention, as any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A method for removing hydrogen sulfide from a gas, the method comprising the steps of:
adding a catalyst for producing hydrogen by using sulfur into a high-temperature reactor, then introducing gas containing hydrogen sulfide into the high-temperature reactor, introducing air or oxygen into the high-temperature reactor, and ensuring that the reaction space velocity is 10000-50000 h-1Reacting at 500-800 ℃ to obtain sulfur and hydrogen; wherein the volume ratio of the hydrogen sulfide to the oxygen is (4-1): 1;
the catalyst for preparing hydrogen and sulfur is prepared by the following method:
adding water and an auxiliary agent into the carrier component, uniformly mixing, extruding into strips by using a strip extruding machine, and obtaining a catalyst carrier after primary drying and primary roasting; preparing the active components into a solution with the mass concentration of 100-150 g/L, impregnating the catalyst carrier with the solution at 50-60 ℃, and obtaining the sulfur-making and hydrogen-making catalyst after secondary drying and secondary roasting after 2-3h of impregnation;
the auxiliary agent is cellulose and/or graphite, the carrier component is one of activated alumina, inert alumina or silicon dioxide, the mass of the water is 30-50% of that of the carrier component, and the mass of the auxiliary agent is 1-5% of that of the carrier component; the volume ratio of the catalyst carrier to the solution is 1 (1-1.2); the active component is at least one of nitrate or sulfite of iron, chromium or nickel;
the specific surface area of the catalyst for preparing hydrogen from sulfur is 20-250m2Per g, average crushThe strength is 100-150N/cm, and the bulk density is 0.5-0.8 g/ml;
the mass fraction of the active component in the catalyst for preparing hydrogen from sulfur is 3-5%;
the volume concentration of hydrogen sulfide in the gas is 1.5-4%.
2. The process according to claim 1, wherein the catalyst support has a shape of a circular bar having a length of 8 to 10mm and a diameter of 2 to 3 mm.
3. The method as claimed in claim 2, wherein the temperature of the primary drying and the secondary drying are both 110 ℃ and 120 ℃, and the drying time is 2-3 h; the temperature of the primary roasting is 600-800 ℃, the roasting time is 2-4h, the temperature of the secondary roasting is 700-800 ℃, and the roasting time is 1-3 h.
4. The process of claim 1, wherein the high temperature reactor is a Claus reactor comprising: the device comprises a reaction kettle, a Claus gas inlet arranged at the top of the reaction kettle, an air/oxygen inlet arranged at the upper part of the side wall of the reaction kettle, and a product outlet arranged at the bottom of the reaction kettle; a catalyst partition plate is horizontally arranged in the middle of the inner cavity of the reaction kettle and is heated by a temperature control electric furnace.
5. A process according to claim 4, wherein, in use, 2 to 3 of the Claus reactors are used in series.
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| 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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| 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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