CN114196449A - Pre-desulfurization process for blast furnace gas and application thereof - Google Patents
Pre-desulfurization process for blast furnace gas and application thereof Download PDFInfo
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- CN114196449A CN114196449A CN202111512394.5A CN202111512394A CN114196449A CN 114196449 A CN114196449 A CN 114196449A CN 202111512394 A CN202111512394 A CN 202111512394A CN 114196449 A CN114196449 A CN 114196449A
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 37
- 230000023556 desulfurization Effects 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 34
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims 1
- 238000006392 deoxygenation reaction Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 abstract description 3
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 39
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000009279 wet oxidation reaction Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013080 microcrystalline material Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Industrial Gases (AREA)
Abstract
The invention discloses a front desulfurization process of blast furnace gas and application thereof, comprising the following steps: (1) blast furnace gas is sent into a purification boundary area through an electric tar precipitator; (2) removing naphthalene and oil from the purified blast furnace gas by using active carbon, and then heating the blast furnace gas in a heat exchanger; (3) carrying out hydrogenation and hydrolysis reactions on organic sulfur in blast furnace gas by adopting a titanium-based fine desulfurization hydroconversion catalyst; (4) and recovering the sulfur. The method adopts titanium-based hydroconversion catalyst and titanium-based hydrolysis catalyst which have the functions of deoxidation, olefin saturation, organic sulfur hydrogenation, organic sulfur hydrolysis, HCN degradation and the like, and replaces four reactors of hydrogenation, iron-molybdenum hydrogenation, cobalt-molybdenum hydrogenation, hydrolysis and the like in the traditional blast furnace gas pre-desulfurization process; the reaction temperature is low, the airspeed is high, and the fixed cost of equipment and the daily operation cost are greatly saved. The pre-desulfurization process of the blast furnace gas is beneficial to energy conservation and emission reduction, improves the productivity, treats the environment, changes waste into valuable, and increases the economic benefit and the social benefit.
Description
Technical Field
The invention relates to the technical field of blast furnace gas treatment, in particular to a front desulfurization process of blast furnace gas and application thereof.
Background
China is a metallurgical industry, and the metallurgical industry generally has high energy consumption, large pollution and more wastes. Blast furnace gas is a byproduct combustible gas in the blast furnace ironmaking production process. The blast furnace gas is composed of a lot of combustible gases and has good utilization value; but it also contains some harmful organic and inorganic sulfur, which is harmful to the atmosphere and to human survival and health without being removed.
The blast furnace gas is used as fuel, and the treatment of dust, sulfur dioxide and nitrogen oxides brought by flue gas after combustion is commonly called 'post-desulfurization', namely dust removal, desulfurization and denitration. The treatment of the 'post-desulfurization' is more expensive, difficult and more waste than the former desulfurization. The front desulfurization technology of the blast furnace gas has many advantages that the process is simple, the waste is changed into valuable, and convenient conditions are provided for subsequent desulfurization and denitration; in particular, poisoning of sulfide can be effectively prevented in the denitration process. How to develop a technology and a process capable of effectively removing sulfur in blast furnace gas in the steel industry is necessary and has important practical significance.
Disclosure of Invention
In view of the defects and shortcomings in the prior art, the titanium-based fine desulfurization hydroconversion catalyst is adopted in the invention to replace four reactors of hydrogenation, iron-molybdenum hydrogenation, cobalt-molybdenum hydrogenation, hydrolysis and the like in the traditional blast furnace gas pre-desulfurization process; absorbing low-concentration arm spread hydrogen sulfide by using iron oxide and zinc oxide to generate iron sulfide and zinc sulfide (the iron oxide also has dechl)-Function) to remove the sulfide in the blast furnace gas and reach the emission standard.
In order to achieve the above object, the present invention provides a pre-desulfurization process for blast furnace gas, comprising the steps of:
(1) blast furnace gas is sent into a purification boundary area through an electric tar precipitator;
(2) removing naphthalene and oil from the purified blast furnace gas by using active carbon, and then heating the blast furnace gas in a heat exchanger;
(3) adopting a titanium-based hydrogenation conversion catalyst and a titanium-based hydrolysis catalyst to carry out hydrogenation and hydrolysis reactions on organic sulfur in blast furnace gas;
(4) and (3) absorbing the blast furnace gas obtained in the step (3) by using zinc oxide or ferric oxide, and recovering sulfur.
Preferably, the activated carbon in step (2) removes naphthalene and oil. To <1 ppm.
Preferably, the temperature after the temperature increase of the heat exchanger in the step (2) is determined by the organic sulfur component.
Preferably, the organic sulfur component in the blast furnace gas is single, namely only CS2COS, the heat exchange temperature can be only 90-120 ℃. However, if complex organic sulfur such as thiophene exists in the blast furnace gas, the temperature of the heat exchanger is increased to 180-200 ℃.
Preferably, the temperature of the hydrogenation and hydrolysis reaction in the step (3) is 130-180 ℃.
Preferably, the space velocity of the hydrogenation and hydrolysis reaction in the step (3) is 3000-5000/h.
Preferably, the reaction formula for removing organic sulfur of the titanium-based fine desulfurization and hydroconversion catalyst in the step (3) is COS + H2＝H2S+CO。
Preferably, the reaction formula for removing organic sulfur of the titanium-based fine desulfurization and hydroconversion catalyst in the step (3) is CS2+4H2＝2H2S+CH4。
Preferably, the reaction formula for removing sulfur dioxide from the titanium-based fine desulfurization and hydroconversion catalyst in the step (3) is O2+2CO＝2CO2。
Preferably, the reaction formula of hydrolysis of the titanium-based fine desulfurization and hydroconversion catalyst in the step (3) is CS2+2H2O→CO2+2H2S、COS+H2O→H2S+CO2。
Preferably, the step (4) comprises the steps of absorbing the blast furnace gas by zinc oxide or ferric oxide, and then recovering H2S。
Preferably, said step (4) comprises first oxidizing H2S is oxidized into elemental S, and then sulfur is recovered by condensation.
Preferably, said step (4) is performed after burning S02＜35mg/m3。
Preferably, the amount of the titanium-based hydroconversion catalyst used in the step (3) is 1/3000 of the amount of the treated gas; the dosage of the titanium-based hydrolysis catalyst is 1/3000 of the treatment gas amount.
Another object of the present invention is to provide a use of a pre-desulfurization process for removing organic sulfur from blast furnace gas.
Compared with the prior art, the invention has the technical effects that:
the titanium-based fine desulfurization hydroconversion catalyst adopted by the invention has the functions of deoxidation, olefin saturation, organic sulfur hydrogenation, organic sulfur hydrolysis, HCN degradation and the like, and replaces four reactors of hydrogenation, iron-molybdenum hydrogenation, cobalt-molybdenum hydrogenation, hydrolysis and the like in the traditional blast furnace gas pre-desulfurization process; the titanium-based fine desulfurization hydroconversion catalyst has low reaction temperature (110-. The invention also adopts ferric oxide and zinc oxide to absorb the hydrogen sulfide of low concentration arm spread to generate ferric sulfide and zinc sulfide, which can be sent to sulfuric acid plant to bake sulfuric acid, thus being beneficial to the reclamation of wastes. The pre-desulfurization process of the blast furnace gas is beneficial to energy conservation and emission reduction, improves the productivity, treats the environment, changes waste into valuable, and increases the economic benefit and the social benefit.
Drawings
FIG. 1 is a flow diagram of a process for the pre-desulfurization of blast furnace gas.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which the specific conditions are not specified, were conducted under the conventional conditions or conditions recommended by the manufacturer.
The raw materials used in the examples of the present invention and the comparative examples were commercially available. The quantitative data in the following examples were set up in triplicate and the results averaged.
Example 1
Preparation of titanium-based fine desulfurization hydroconversion catalyst (T)205The method of A-1):
a hydrofining catalyst which takes titanium dioxide as a carrier and cobalt-molybdenum-nickel as an active component is provided by Zhejiang Sanlong catalyst Co of 1994 (patent number: ZL 201310229479.1). And the post-processing is improved on the basis. Rare earth elements CsO and La are added2O3The Ti-base fine desulfurizing and hydrogenating conversion catalyst has the functions of deoxidation, olefin saturation, organic sulfur hydrogenation, organic sulfur hydrolysis, HCN degradation, no methane alkylation, etc. The process parameters for these functions are based as follows:
1. pair CS at normal pressure2Hydrogenation of COS
2. To SO at normal pressure2By hydrogenation of
| SO2Concentration (%) | Space velocity (h)-1) | Temperature (. degree.C.) | Conversion (%) |
| 1.0 | 2000 | 180 | 100 |
| 1.0 | 3000 | 180 | 100 |
| 1.5 | 3000 | 180 | 100 |
| 2.0 | 3800 | 180 | 100 |
To C under 3.1.1 MPa4H4Hydrogenation of S
4. Industrialization data of deoxidation function
Principle of deoxidation O2+2CO→2CO2 △H＝-283.1kj/mol
5. COS and CS removal of titanium-based fine desulfurization hydroconversion catalyst2、SO2、O2Working principle and removal condition of HCN:
(1) and (3) removing the organic sulfur COS:
the operating principle of removing COS is COS + H2＝H2S+CO
The reaction condition is that the concentration of COS is 250mg/m3；
The reaction temperature is 130 ℃, and the space velocity is 2000-5000 h-1And the conversion rate is 100 percent.
(2) Removal of organic sulfur CS2:
Decs (dehydration of CS)2Working principle of (C)2+4H2＝2H2S+CH4
Reaction conditions CS2The concentration is 350mg/m3；
The reaction temperature is 130 ℃, and the space velocity is 2000-5000 h-1And the conversion rate is 100 percent.
(3) SO removal2:
SO removal2Working principle of (SO)2+3H2＝H2S+2H2O
Reaction conditions of SO2The concentration is 10000mg/m3；
The reaction temperature is 180 ℃, and the space velocity is 3000h-1And the conversion rate is 100 percent.
(4) The titanium-based fine desulfurization hydroconversion catalyst has hydrolysis function.
The working principle of hydrolysis is as follows:
CS2+H2O→COS+H2S
COS+H2O→H2S+CO2
(5) the titanium-based fine desulfurization hydroconversion catalyst has the function of superposition of hydrogenation and hydrolysis:
(6) the titanium-based fine desulfurization hydroconversion catalyst has the deoxidation function:
the operating principle of deoxidation is as follows: 2CO + O2＝2CO2Reaction conditions of-283.1 Kj/mol2The concentration is 0.5%, the CO concentration is 27.9%, the reaction temperature is 200-220 ℃, the air speed is 1000-3000/h, and the conversion rate is 100%.
(7) The titanium-based fine desulfurization hydroconversion catalyst has the function of degrading HCN:
the working principle of HCN degradation is as follows:
the HCN is particularly critical for the device valves and must be removed. The catalyst can be removed by hydrolysis, and the specific reaction principle is as follows:
HCN+H2O＝NH3+CO
the temperature is 210 ℃, the pressure is 1.3MPa, and the HCN at the inlet and the outlet of the hydrolytic agent is measured by adopting a spectrophotometry method, and the results are as follows:
| date | Inlet HCN | Outlet HCN | HCN conversion |
| 2 month and 21 days | 26.7ppm | 1.22ppm | 95.4％ |
| 3 month and 2 days | 70.2ppm | 1.56ppm | 97.8％ |
The test result shows that the catalyst has higher HCN hydrolysis activity under the working condition, and the conversion rate is still more than 95 percent after cumulative operation for 500 hours.
Example 2
H2S direct oxidation process for preparing sulfur
2H2S+O2＝2H2O+2S↓ △H＝-Kj/mol
Reaction conditions H2S concentration 1.5% (15000ppm), O2Excessive content;
the reaction temperature is 170-180 ℃, the space velocity is 700-1000/H, and H2The S oxidation rate is 100 percent.
Example 3
When H is contained in blast furnace gas2Low S and organic sulfur content (total sulfur)<100mg/m3) In the process, the blast furnace gas is sent into a purification area through an electric tar precipitator, and naphthalene and oil are removed by active carbon (shown in figure 1)<1ppm) enters a heat exchanger to raise the temperature. The temperature of the mixture entering the hydrogenation reactor is 130-180 ℃, and the space velocity is 3000-5000/h. Mainly converts organic sulfur into inorganic sulfur and degrades HCN into NH3And CO. Finally, the blast furnace gas is absorbed by zinc oxide or ferric oxide to ensure that the total sulfur is less than or equal to 0.1mg/m3. Post combustion S02＜35mg/m3。
Specific application evaluation data:
for H in blast furnace gas2S and organic sulfur concentration is low (total S is less than 100 mg/m)3) Blast furnace gas → organic sulfur hydrogenation, hydrolysis → zinc oxide (ferric oxide) absorption → sulfur recovery in sulfuric acid plant. The process route is economical and feasible. The process route has the advantages of low investment of fixed equipment and low normal operation cost; has obvious economic benefit and social benefit.
The coke oven gas of the steel mill can be desulfurized before being purified and discharged after reaching the standard according to the process.
Prior ArtThe process scheme of the front desulfurization of the blast furnace gas mainly comprises the following steps: 1) microcrystalline material adsorption method, 2) organic sulfur hydrolysis and NaOH absorption method, 3) organic sulfur hydrolysis and 888 wet oxidation method, 4) hydrogen peroxide oxidation and alkali liquor absorption method, 5) organic sulfur hydrolysis and complex iron dehydrogenation2S method, etc. These processes are difficult to use industrially. Because: 1) the adsorption method of the microcrystalline material only plays a role of organic sulfur and H2And (4) the concentration of S, and the concentrated gas is still sent back to the boiler for combustion. And organic sulfur and H2SO formed after combustion of S2Post-desulfurization is also required, increasing the difficulty and cost of desulfurization. 2) Organic sulfur hydrolysis + NaOH absorption method. The method belongs to wet treatment, and the subsequent waste water has secondary pollution. 3) Organic sulfur hydrolysis +888 wet oxidation. The quality of sulfur obtained by the treatment scheme is poor; moreover, 888 wet oxidation equipment is more, and the fixed investment cost is high. 4) The hydrogen peroxide oxidation and alkali liquor absorption method is stopped. 5) Organic sulfur hydrolysis and complex iron removal of H2The S method is not applied to blast furnace gas treatment. Disadvantages of the above methods include short service life, high operating costs, etc.
The invention develops a catalyst for hydrogenation conversion and hydrolysis of organic sulfur and deoxidation in the presence of sulfide by utilizing the advantages of a titanium carrier, thereby achieving the new process for treating blast furnace gas with low temperature (110-130 ℃), high space velocity (3000-5000 h < -1 >), strong poisoning resistance (chlorine resistance, oxidation resistance and sulfur resistance), long service life (more than 1 year) and high cost performance.
Comparative example 1
60000m for certain blast furnace gas3The existing process adopts a medium-temperature hydrolysis catalyst, and the loading amount is 200m3About 300/h of airspeed and 180-186 ℃, the catalyst needs to be replaced after 2-3 months of use, otherwise the total S of the outlet is not qualified. After the novel process is adopted, a titanium-based hydroconversion catalyst (T205A-1 type) is adopted for 20m3About 3000/h, a temperature of 110-120 ℃ and a service life of > 12 months. Using titanium-based hydrolysis catalyst (SL-T-0)3) 20m3(approximate airspeed 3000/h), temperature of 120-130 ℃, and service life of more than 12 months. Adopting fine desulfurizer 60m3(approximate airspeed 1500/h), temperature 120-130 ℃, service life > 12And (4) month. The total sulfur at the gas outlet is less than 0.1 ppm.
Compared with the existing process, the new process saves the running cost, fixed investment and low-temperature running energy-saving cost each year.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, so that the variations of the features of the raw materials, the features of the steps, the formula and the like, which are described in the scope of the present invention, are all included in the scope of the present invention.
Claims (10)
1. The front desulfurization process of blast furnace gas is characterized by comprising the following steps of:
(1) blast furnace gas is sent into a purification boundary area through an electric tar precipitator;
(2) removing naphthalene and oil from the purified blast furnace gas by using active carbon, and then heating the blast furnace gas in a heat exchanger;
(3) adopting a titanium-based hydrogenation conversion catalyst and a titanium-based hydrolysis catalyst to carry out hydrogenation and hydrolysis reactions on organic sulfur in blast furnace gas;
(4) and (3) absorbing the blast furnace gas obtained in the step (3) by using zinc oxide or ferric oxide, and recovering sulfur.
2. The front desulfurization process for blast furnace gas according to claim 1, characterized in that the temperature of the hydrogenation and hydrolysis reaction in step (3) is 110-130 ℃.
3. The front desulfurization process of blast furnace gas according to claim 1, characterized in that the space velocity of the hydrogenation and hydrolysis reaction in the step (3) is 3000-5000/h.
4. The pre-desulfurization process for blast furnace gas according to claim 1, wherein the reaction formula for removing organic sulfur of the titanium-based fine desulfurization hydroconversion catalyst in the step (3) is COS + H2＝H2S+CO。
5. The pre-desulfurization process for blast furnace gas according to claim 1, characterized in that the titanium-based concentrate of step (3)The reaction formula for removing organic sulfur by using desulfurization and hydrogenation conversion catalyst is CS2+4H2＝2H2S+CH4。
6. The pre-desulfurization process for blast furnace gas according to claim 1, characterized in that the titanium-based fine desulfurization hydroconversion catalyst of step (3) is subjected to a deoxygenation reaction. Reaction formula is O2+2CO＝2CO2。
7. The process of pre-desulfurization of blast furnace gas according to claim 1, characterized in that the step (4) comprises the blast furnace gas being first absorbed by zinc oxide or iron oxide and then recovering H2S。
8. The process of pre-desulfurization of blast furnace gas according to claim 1, characterized in that the post-combustion S0 of the step (4)2＜35mg/m3。
9. The process for the pre-desulfurization of blast furnace gas according to claim 1, wherein the titanium-based hydroconversion catalyst used in the step (3) is 1/3000 of the amount of the treated gas; the dosage of the titanium-based hydrolysis catalyst is 1/3000 of the treatment gas amount.
10. Use of the pre-desulfurization process according to any one of claims 1 to 9 for removing organic sulfur from blast furnace gas.
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| CN116588938A (en) * | 2023-06-21 | 2023-08-15 | 上海汉兴化工科技有限公司 | Process for pretreating coal gas and purifying carbon monoxide |
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