CN117181306B - Preparation method of hydrolysis desulfurization bifunctional catalyst for blast furnace gas - Google Patents
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- 230000007062 hydrolysis Effects 0.000 title claims abstract description 52
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 51
- 230000023556 desulfurization Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 120
- -1 polyethylene Polymers 0.000 claims abstract description 66
- 239000004698 Polyethylene Substances 0.000 claims abstract description 64
- 229920000573 polyethylene Polymers 0.000 claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 63
- 239000005751 Copper oxide Substances 0.000 claims abstract description 34
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 88
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 60
- 238000001035 drying Methods 0.000 claims description 44
- 239000012074 organic phase Substances 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 23
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 claims description 20
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 229940125904 compound 1 Drugs 0.000 claims description 18
- 229940125782 compound 2 Drugs 0.000 claims description 18
- 229940126214 compound 3 Drugs 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- CLECMSNCZUMKLM-UHFFFAOYSA-N (4-ethenylphenyl)methanol Chemical compound OCC1=CC=C(C=C)C=C1 CLECMSNCZUMKLM-UHFFFAOYSA-N 0.000 claims description 10
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical compound CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 claims description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- NQIFXJSLCUJHBB-LBPRGKRZSA-N methyl (2s)-3-(4-hydroxyphenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoate Chemical compound CC(C)(C)OC(=O)N[C@H](C(=O)OC)CC1=CC=C(O)C=C1 NQIFXJSLCUJHBB-LBPRGKRZSA-N 0.000 claims description 10
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 10
- 239000012312 sodium hydride Substances 0.000 claims description 10
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000012778 molding material Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 229940116318 copper carbonate Drugs 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 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
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 abstract description 21
- 239000003795 chemical substances by application Substances 0.000 abstract description 19
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 15
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 15
- 230000003009 desulfurizing effect Effects 0.000 abstract description 13
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000009987 spinning Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a hydrolysis desulfurization bifunctional catalyst for blast furnace gas, which belongs to the technical field of desulfurization, and the preparation method organically combines hydrolysis active components with a desulfurizing agent to prepare the hydrolysis desulfurization bifunctional catalyst, meanwhile, a polyethylene derivative is loaded on copper oxide, and a polyethylene main chain is coated on the copper oxide, and because the end group of a side chain of the polyethylene derivative is amino and is provided with a pyridine ring, the reaction with hydrogen sulfide gas is easy, the adsorption of hydrogen sulfide is increased, and the sulfur capacity of the catalyst is increased; the catalyst can be used for hydrolyzing carbonyl sulfide in blast furnace gas, and simultaneously can remove hydrogen sulfide and associated hydrogen sulfide in the blast furnace gas, thereby saving the investment and the running cost of the catalyst.
Description
Technical Field
The invention belongs to the technical field of desulfurization, and particularly relates to a preparation method of a hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Background
Blast furnace gas is one of the main waste gases of the whole iron and steel department, and the main components are CO (carbon monoxide) and CO 2 (carbon dioxide), N 2 (Nitrogen) and also contains a small amount of O 2 (oxygen), COS (carbonyl sulfide), H 2 S (hydrogen sulfide), dust, etc.
The main current technology in the market is: pretreatment of blast furnace gas, front/rear hydrolysis of TRT (blast furnace gas residual pressure turbine generator) and rear desulfurization of TRT, and COS in the gas is firstly converted into H under the action of a hydrolytic agent 2 S, hydrolysis associated H 2 S and H existing in the raw material gas 2 S, simultaneously removing the desulfurizing agent to realize standard emission, and replacing the desulfurizing agent after adsorption saturation. Because chlorine in the coal gas is particularly easy to cause the inactivation of the hydrolytic agent, the traditional desulfurizing agent can only adsorb H 2 S, when COS in the gas enters dry desulfurization, the COS cannot be directly adsorbed by a desulfurizing agentAnd entering a back-end user, and failing to realize ultra-low emission.
The hydrolysis agent mainly depends on alkaline site to generate hydrolysis, and usually takes potassium or sodium alkali weak acid salt and potassium or sodium alkaline oxide as active components, and alumina balls as carriers, wherein the cost of the carriers is relatively high. After the active chlorine of the hydrolytic agent is poisoned and deactivated, the carrier also fails, and the service life of the hydrolytic agent is generally less than 3 months according to on-site operation data; the rear end desulfurization of blast furnace gas is usually carried out by adopting iron oxide desulfurizing agent with low price and wider temperature-resistant interval, and the production process is that ferrous salt and calcium hydroxide are oxidized after solid-solid mixing reaction, so as to better adsorb acid gas hydrogen sulfide, and the desulfurizing agent is alkaline. The replacement period of the dry iron-based desulfurizing agent is also generally 3 months, and the space velocity of the hydrolytic agent in the blast furnace gas desulfurization project is 3000h -1 The reaction time is 1.2s, and the space velocity of the desulfurizing agent is 500h -1 The reaction time is 7.2s, so that the reaction of hydrolysis into hydrogen sulfide is completed rapidly, and then the hydrogen sulfide is removed by reacting with a desulfurizing agent. However, the hydrolytic agent is easy to be poisoned by chlorine element in blast furnace gas, loses activity, has high operation cost and frequent replacement, so how to organically combine the hydrolytic active component with the desulfurizing agent to prepare the hydrolytic desulfurization dual-function catalyst has important research significance.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of a hydrolysis desulfurization bifunctional catalyst for blast furnace gas.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
the preparation method of the hydrolysis desulfurization bifunctional catalyst for the blast furnace gas comprises the following steps:
1) Adding solid ferrous salt and solid hydroxide into a kneader, mixing, stirring and reacting for 15-60 min, and then introducing oxidizing gas into the kneader for oxidizing reaction for 30-60 min to obtain a mixture;
2) Adding an alkaline compound aqueous solution with the mass concentration of 15-50% into the mixture prepared in the step 1), and carrying out solid-liquid mixing reaction for 30-60 min to obtain a mixed solution;
3) Adding a polyethylene derivative-copper oxide compound into the mixed solution obtained in the step 2), stirring and reacting for 15-60 min, extruding and molding materials in a kneader in a strip extruder after the reaction is completed, and finally naturally airing or drying the extruded and molded materials to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas;
the polyethylene derivative-copper oxide compound is prepared by the following steps:
(1) Dropwise adding an aqueous alkaline compound solution with a cation concentration of 0.4mol/L to Cu 2+ Heating copper salt aqueous solution with the concentration of 0.2mol/L to 40-80 ℃, stirring and reacting for 4-24 hours, and obtaining reaction liquid after the reaction is completed;
(2) Adding a polyethylene derivative into the reaction liquid obtained in the step (1), standing for 10-15 hours at 25-30 ℃, filtering, drying the obtained filter cake at 120 ℃ for 2-3 hours, and roasting at 250-300 ℃ for 3 hours to obtain a polyethylene derivative-copper oxide compound;
the structural formula of the polyethylene derivative is as follows:
。
the solid ferrous salt in the step 1) is one or two of ferrous sulfate, ferrous chloride and ferrous nitrate; the solid hydroxide is one or two of sodium hydroxide, calcium hydroxide and potassium hydroxide.
The molar ratio of ferrous ions in the solid ferrous salt to hydroxyl ions in the solid hydroxide in step 1) is 1: 2-4.
The oxidizing gas in step 1) is oxygen or air.
The alkaline compound in the step 2) is one or two of sodium carbonate, potassium hydroxide and sodium hydroxide.
The mass of the alkaline compound in the step 2) is 0.1-0.3 times of the total mass of the solid ferrous salt and the solid hydroxide in the step 1).
The mass of the polyethylene derivative-copper oxide composite in the step 3) is 0.05-0.1 time of the total mass of the solid ferrous salt and the solid hydroxide in the step 1); wherein the drying temperature is 50-100 ℃ and the drying time is 0.5-24 h.
The copper salt in the step (1) is one or two of copper sulfate pentahydrate, copper chloride and copper carbonate; the molar ratio of the alkaline compound to the copper salt is 1: 2-4.
The mass volume ratio of the polyethylene derivative to the reaction liquid in the step (2) is 1g: 10-15 ml.
The polyethylene derivative is prepared by the following method:
(1) adding 3-hydroxypyridine, bromopropene and sodium hydride into tetrahydrofuran, stirring and dissolving, heating to 50-80 ℃ for reaction for 5-8 hours, adding water into the reaction solution after the reaction is finished, quenching the reaction, adding methylene dichloride, separating out an organic phase, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain a compound 1;
the mass ratio of the 3-hydroxypyridine to the bromopropene to the sodium hydride to the tetrahydrofuran to the water to the dichloromethane is 1: 1.2-1.5: 0.25-0.3: 5-10: 3-5: 5-10;
(2) adding (4-vinylphenyl) methanol and BOC-L-tyrosine methyl ester into tetrahydrofuran, adding triphenylphosphine and diisopropyl azodicarboxylate, reacting for 5-8 hours at 25-40 ℃, removing a solvent by reduced pressure distillation after the reaction is finished, adding dichloromethane into the obtained residue, performing suction filtration, adding water into the obtained filtrate for extraction for 3-5 times, and finally performing spin drying on an organic phase to obtain a compound 2;
the mass ratio of the (4-vinylphenyl) methanol to the BOC-L-tyrosine methyl ester to the tetrahydrofuran to the triphenylphosphine to the diisopropyl azodicarboxylate to the dichloromethane to the water is 1: 2.5-3: 10-15: 2.2-3: 1.7-2.5: 10-15: 10-15 parts;
(3) adding the compound 2 prepared in the step (2) and trifluoroacetic acid into tetrahydrofuran, reacting for 5-10 hours at 25-35 ℃, removing a solvent by reduced pressure distillation after the reaction is finished, adding the obtained residue into methanol, adding sodium hydroxide, reacting for 10-15 hours at 25-35 ℃, adding water after the reaction is finished, adding dichloromethane, extracting for 3-5 times, merging organic phases, spin-drying the organic phases, and drying to obtain a compound 3;
the mass ratio of the compound 2 to the trifluoroacetic acid to the tetrahydrofuran to the methanol to the sodium hydroxide to the water to the dichloromethane is 1:0.3 to 0.5: 5-10: 5-10: 0.15-0.25: 5-10: 5-10;
(4) adding the compound 1 obtained in the step (1), the compound 3 obtained in the step (3) and azodiisobutyronitrile into toluene, heating to 70-90 ℃ for reaction for 10-20 hours, removing a solvent by reduced pressure distillation after the reaction is finished, washing the obtained residue with acetone for 3-5 times, and drying to obtain a polyethylene derivative;
the mass ratio of the compound 1 to the compound 3 to the azodiisobutyronitrile to the toluene is 1-10: 2-20: 0.05-0.3: 5-40.
In the invention, firstly, ferrous hydroxide is generated by solid ferrous salt and solid hydroxide, then oxidizing gas is introduced to fully oxidize the ferrous hydroxide, the generated ferric hydroxide and hydrolysis active components are physically mixed and finally uniformly loaded on a polyethylene derivative-copper oxide compound, thus preparing the hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Compared with the prior art, the invention has the following advantages:
the hydrolysis desulfurization dual-function catalyst for the blast furnace gas is prepared by organically combining hydrolysis active components with a desulfurizing agent, and can be used for hydrolyzing carbonyl sulfide in the blast furnace gas and simultaneously removing hydrogen sulfide and associated hydrogen sulfide in the blast furnace gas; the catalyst uses desulfurizing agent as carrier for carrying hydrolytic active component, replaces alumina carrier with high price, and saves investment and running cost.
According to the hydrolysis desulfurization bifunctional catalyst for blast furnace gas, polyethylene derivatives are loaded on copper oxide, and a main chain of polyethylene is coated on the copper oxide, and as the side chain end group of the polyethylene derivatives is amino and has a pyridine ring, the polyethylene derivatives can easily react with hydrogen sulfide gas, and active sites for reacting with hydrogen sulfide are increased, so that the sulfur capacity of the catalyst is increased.
The hydrolysis desulfurization dual-function catalyst for the blast furnace gas has larger sulfur capacity, is changed into a hydrolysis desulfurization integrated unit from a hydrolysis unit and a desulfurization unit, and is used for placing the hydrolysis and desulfurization of the blast furnace gas in the same process unit, so that the investment of equipment and civil engineering of the original independent hydrolysis tower is reduced, and the investment cost is saved; the daily process operation and management of the working section are omitted; meanwhile, the loading and unloading work of the alumina ball hydrolyzer is reduced, and the workload is saved; has good industrial prospect.
Detailed Description
The foregoing is further elaborated by the following description of embodiments of the present invention, which are given by way of example only, and should not be construed as limiting the scope of the present invention. All techniques implemented based on the above description of the invention are within the scope of the invention.
Example 1
Preparation of polyethylene derivatives:
(1) adding 1kg of 3-hydroxypyridine, 1.2kg of bromopropene and 0.25kg of sodium hydride into 5kg of tetrahydrofuran, stirring and dissolving, heating to 50 ℃ for reacting for 5 hours, adding 3kg of water into the reaction solution after the reaction is finished, quenching the reaction, adding 5kg of dichloromethane, separating out an organic phase, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain a compound 1; 1 H NMR (400 MHz, 298 K, DMSO-d 6 ): δ 7.55-7.72 (m, 1H), 7.15 (d, 1H), 6.32-6.66 (m, 2H), 5.75-6.13 (m, 1H), 5.25-5.57 (d, 2H), 4.87 (d, 2H)。
(2) adding 1kg of (4-vinylphenyl) methanol and 2.5kg of BOC-L-tyrosine methyl ester into 10kg of tetrahydrofuran, adding 2.2kg of triphenylphosphine and 1.7kg of diisopropyl azodicarboxylate, reacting for 5 hours at 25 ℃, distilling under reduced pressure after the reaction is finished to remove a solvent, adding 10kg of dichloromethane into the obtained residue, filtering, adding 10kg of water into the obtained filtrate, extracting for 3 times, and finally carrying out spin-drying on an organic phase to obtain a compound 2;
(3) adding 1kg of compound 2 and 0.3kg of trifluoroacetic acid into 5kg of tetrahydrofuran, reacting for 5 hours at 25 ℃, removing the solvent by reduced pressure distillation after the reaction is finished, adding the obtained residue into 5kg of methanol, adding 0.15kg of sodium hydroxide, reacting for 10 hours at 25 ℃, adding 5kg of water after the reaction is finished, adding 5kg of dichloromethane, extracting for 3 times, merging organic phases, spinning the organic phases, and drying to obtain the compoundTo compound 3; 1 H NMR (400 MHz, 298 K, DMSO-d 6 ): δ 12.65 (s, 1H), 8.55 (s, 2H), 7.63 (d, 2H), 7.25 (d, 2H), 6.95-7.16 (m, 4H), 6.65 (t, 1H), 5.25-5.88 (m, 2H), 5.09 (s, 2H), 4.22 (m, 1H), 3.45 (d, 1H), 3.05 (d, 1H)。
(4) 1kg of compound 1, 2kg of compound 3 and 0.05kg of azobisisobutyronitrile were added to 5kg of toluene, heated to 70 ℃ for reaction for 10 hours, and after the reaction was completed, the solvent was distilled off under reduced pressure, and the obtained residue was washed with acetone for 3 times and dried to obtain a polyethylene derivative.
Preparation of polyethylene derivative-copper oxide composite:
(1) 1L of 0.2mol/L sodium carbonate aqueous solution is dripped into 2L of 0.2mol/L copper chloride aqueous solution, the temperature is heated to 40 ℃, the reaction is stirred for 4 hours, and a reaction liquid is obtained after the reaction is completed;
(2) Adding 0.3kg of polyethylene derivative into the obtained reaction solution, standing at 25 ℃ for 10 hours, filtering, drying the obtained filter cake at 120 ℃ for 2 hours, and roasting at 250 ℃ for 3 hours to obtain the polyethylene derivative-copper oxide compound.
Preparation of hydrolysis desulfurization bifunctional catalyst for blast furnace gas:
1) Adding 1.5kg of ferrous sulfate and 0.78kg of sodium hydroxide into a kneader, mixing, stirring and reacting for 15min, introducing air into the kneader, and oxidizing for 30min to obtain a mixture;
2) Adding 1.52kg of 15% sodium carbonate aqueous solution into the prepared mixture, and carrying out solid-liquid mixing reaction for 30min to obtain a mixed solution;
3) Adding 0.1kg of polyethylene derivative-copper oxide compound into the obtained mixed solution, stirring and reacting for 15min, extruding and molding materials in a kneader in a strip extruder after the reaction is completed, and finally naturally airing the extruded and molded materials to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Example 2
Preparation of polyethylene derivatives:
(1) adding 1kg of 3-hydroxypyridine, 1.3kg of bromopropene and 0.26kg of sodium hydride into 6kg of tetrahydrofuran, stirring and dissolving, heating to 60 ℃ for reaction for 6 hours, adding 3.5kg of water into the reaction solution after the reaction is finished, quenching the reaction, adding 6kg of dichloromethane, separating out an organic phase, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain a compound 1;
(2) adding 1kg of (4-vinylphenyl) methanol and 2.6kg of BOC-L-tyrosine methyl ester into 11kg of tetrahydrofuran, adding 2.3kg of triphenylphosphine and 1.9kg of diisopropyl azodicarboxylate, reacting for 6 hours at 30 ℃, distilling under reduced pressure after the reaction is finished to remove a solvent, adding 11kg of dichloromethane into the obtained residue, filtering, adding 11kg of water into the obtained filtrate, extracting for 4 times, and finally carrying out spin-drying on an organic phase to obtain a compound 2;
(3) adding 1kg of compound 2 and 0.35kg of trifluoroacetic acid into 6kg of tetrahydrofuran, reacting for 6 hours at 28 ℃, removing a solvent by reduced pressure distillation after the reaction is finished, adding the obtained residue into 6kg of methanol, adding 0.18kg of sodium hydroxide, reacting for 11 hours at 28 ℃, adding 6kg of water after the reaction is finished, adding 6kg of dichloromethane, extracting for 4 times, merging organic phases, spin-drying the organic phases, and drying to obtain a compound 3;
(4) 2kg of Compound 1, 4kg of Compound 3 and 0.1kg of azobisisobutyronitrile were added to 10kg of toluene, heated to 75℃for reaction for 12 hours, and after the completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained residue was washed with acetone for 4 times and dried to obtain a polyethylene derivative.
Preparation of polyethylene derivative-copper oxide composite:
(1) 1L of 0.2mol/L aqueous solution of potassium carbonate is dropwise added into 2.5L of 0.2mol/L aqueous solution of copper carbonate, the temperature is raised to 50 ℃, the reaction is stirred for 8 hours, and after the reaction is completed, a reaction solution is obtained;
(2) Adding 0.32kg of polyethylene derivative into the obtained reaction solution, standing at 26 ℃ for 11 hours, filtering, drying the obtained filter cake at 120 ℃ for 2.5 hours, and roasting at 260 ℃ for 3 hours to obtain the polyethylene derivative-copper oxide compound.
Preparation of hydrolysis desulfurization bifunctional catalyst for blast furnace gas:
1) Adding 1.27kg of ferrous chloride and 1.4kg of potassium hydroxide into a kneader, mixing, stirring and reacting for 25min, introducing air into the kneader, and oxidizing for 40min to obtain a mixture;
2) Adding 2kg of a 20% potassium carbonate aqueous solution into the prepared mixture, and carrying out solid-liquid mixing reaction for 35min to obtain a mixed solution;
3) Adding 0.16kg of polyethylene derivative-copper oxide compound into the obtained mixed solution, stirring and reacting for 25min, extruding and molding materials in a kneader in a strip extruder after the reaction is completed, and finally naturally airing the extruded and molded materials to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Example 3
Preparation of polyethylene derivatives:
(1) adding 1kg of 3-hydroxypyridine, 1.35kg of bromopropene and 0.27kg of sodium hydride into 8kg of tetrahydrofuran, stirring and dissolving, heating to 70 ℃ for reaction for 6.5 hours, adding 4kg of water into the reaction solution after the reaction is finished, quenching the reaction, adding 7kg of dichloromethane, separating out an organic phase, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain a compound 1;
(2) adding 1kg of (4-vinylphenyl) methanol and 2.7kg of BOC-L-tyrosine methyl ester into 12kg of tetrahydrofuran, adding 2.5kg of triphenylphosphine and 2.1kg of diisopropyl azodicarboxylate, reacting for 6.5 hours at 35 ℃, distilling under reduced pressure after the reaction is finished to remove a solvent, adding 12kg of dichloromethane into the obtained residue, filtering, adding 12kg of water into the obtained filtrate, extracting for 4 times, and finally spin-drying an organic phase to obtain a compound 2;
(3) adding 1kg of compound 2 and 0.4kg of trifluoroacetic acid into 7.5kg of tetrahydrofuran, reacting for 7 hours at 30 ℃, distilling under reduced pressure to remove a solvent after the reaction is finished, adding the obtained residue into 7kg of methanol, adding 0.2kg of sodium hydroxide, reacting for 12 hours at 30 ℃, adding 7kg of water after the reaction is finished, adding 7kg of dichloromethane, extracting for 4 times, merging organic phases, spin-drying the organic phases, and drying to obtain a compound 3;
(4) 4kg of compound 1, 8kg of compound 3 and 0.15kg of azobisisobutyronitrile were added to 20kg of toluene, heated to 80 ℃ for reaction for 15 hours, after the reaction was completed, the solvent was distilled off under reduced pressure, and the obtained residue was washed with acetone for 4 times and dried to obtain a polyethylene derivative.
Preparation of polyethylene derivative-copper oxide composite:
(1) 1L of 0.4mol/L potassium hydroxide aqueous solution is dripped into 6L of 0.2mol/L copper carbonate aqueous solution, the temperature is raised to 60 ℃, the reaction is stirred for 12 hours, and the reaction liquid is obtained after the reaction is completed;
(2) Adding 0.6kg of polyethylene derivative into the obtained reaction solution, standing at 27 ℃ for 12 hours, filtering, drying the obtained filter cake at 120 ℃ for 2.6 hours, and roasting at 275 ℃ for 3 hours to obtain the polyethylene derivative-copper oxide compound.
Preparation of hydrolysis desulfurization bifunctional catalyst for blast furnace gas:
1) Adding 1.27kg of ferrous chloride and 1.2kg of sodium hydroxide into a kneader, mixing, stirring and reacting for 30min, introducing oxygen into the kneader, and oxidizing for 45min to obtain a mixture;
2) Adding 2kg of sodium hydroxide aqueous solution with mass concentration of 25% into the prepared mixture, and carrying out solid-liquid mixing reaction for 45min to obtain a mixed solution;
3) Adding 0.18kg of polyethylene derivative-copper oxide compound into the obtained mixed solution, stirring and reacting for 30min, extruding and molding materials in a kneader in a strip extruder after the reaction is completed, and finally drying the extruded and molded materials at 60 ℃ for 12h to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Example 4
Preparation of polyethylene derivatives:
(1) adding 1kg of 3-hydroxypyridine, 1.4kg of bromopropene and 0.27kg of sodium hydride into 9kg of tetrahydrofuran, stirring and dissolving, heating to 75 ℃ for reaction for 7 hours, adding 4.5kg of water into the reaction solution after the reaction is finished, quenching the reaction, adding 8kg of dichloromethane, separating out an organic phase, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain a compound 1;
(2) adding 1kg of (4-vinylphenyl) methanol and 2.9kg of BOC-L-tyrosine methyl ester into 14kg of tetrahydrofuran, adding 2.8kg of triphenylphosphine and 2.2kg of diisopropyl azodicarboxylate, reacting for 7 hours at 37 ℃, distilling under reduced pressure after the reaction is finished to remove a solvent, adding 13kg of dichloromethane into the obtained residue, filtering, adding 13kg of water into the obtained filtrate, extracting for 4 times, and finally carrying out spin-drying on an organic phase to obtain a compound 2;
(3) adding 1kg of compound 2 and 0.42kg of trifluoroacetic acid into 8kg of tetrahydrofuran, reacting for 8 hours at 30 ℃, removing a solvent by reduced pressure distillation after the reaction is finished, adding the obtained residue into 8kg of methanol, adding 0.22kg of sodium hydroxide, reacting for 13 hours at 32 ℃, adding 8kg of water after the reaction is finished, adding 8kg of dichloromethane, extracting for 4 times, merging organic phases, spin-drying the organic phases, and drying to obtain a compound 3;
(4) 6kg of compound 1, 12kg of compound 3 and 0.2kg of azobisisobutyronitrile were added to 25kg of toluene, heated to 85 ℃ for reaction for 17 hours, and after the reaction was completed, the solvent was distilled off under reduced pressure, and the obtained residue was washed with acetone for 4 times and dried to obtain a polyethylene derivative.
Preparation of polyethylene derivative-copper oxide composite:
(1) 1L of 0.4mol/L sodium hydroxide aqueous solution is dripped into 7L of 0.2mol/L copper sulfate pentahydrate aqueous solution, the temperature is raised to 70 ℃, the reaction is stirred for 18 hours, and the reaction liquid is obtained after the reaction is completed;
(2) Adding 0.62kg of polyethylene derivative into the obtained reaction solution, standing at 28 ℃ for 13 hours, filtering, drying the obtained filter cake at 120 ℃ for 2.8 hours, and roasting at 280 ℃ for 3 hours to obtain the polyethylene derivative-copper oxide compound.
Preparation of hydrolysis desulfurization bifunctional catalyst for blast furnace gas:
1) Adding 1.8kg of ferrous nitrate and 1.1kg of calcium hydroxide into a kneader, mixing, stirring and reacting for 50min, introducing oxygen into the kneader, and oxidizing for 50min to obtain a mixture;
2) Adding 2.4kg of 30% potassium hydroxide aqueous solution into the prepared mixture, and carrying out solid-liquid mixing reaction for 50min to obtain a mixed solution;
3) Adding 0.22kg of polyethylene derivative-copper oxide compound into the obtained mixed solution, stirring and reacting for 45min, extruding and molding materials in a kneader in a strip extruder after the reaction is completed, and finally drying the extruded and molded materials at 50 ℃ for 24h to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Example 5
Preparation of polyethylene derivatives:
(1) adding 1kg of 3-hydroxypyridine, 1.45kg of bromopropene and 0.29kg of sodium hydride into 9.5kg of tetrahydrofuran, stirring and dissolving, heating to 78 ℃ for reaction for 7.5 hours, adding 4.8kg of water into the reaction solution after the reaction is finished, quenching the reaction, adding 9kg of dichloromethane, separating out an organic phase, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain a compound 1;
(2) adding 1kg of (4-vinylphenyl) methanol and 2.9kg of BOC-L-tyrosine methyl ester into 14kg of tetrahydrofuran, adding 2.9kg of triphenylphosphine and 2.4kg of diisopropyl azodicarboxylate, reacting for 7.5 hours at 39 ℃, distilling under reduced pressure after the reaction is finished to remove a solvent, adding 14kg of dichloromethane into the obtained residue, filtering, adding 14kg of water into the obtained filtrate, extracting for 4 times, and finally spin-drying an organic phase to obtain a compound 2;
(3) adding 1kg of compound 2 and 0.48kg of trifluoroacetic acid into 9kg of tetrahydrofuran, reacting for 9 hours at 32 ℃, removing a solvent by reduced pressure distillation after the reaction is finished, adding the obtained residue into 9kg of methanol, adding 0.24kg of sodium hydroxide, reacting for 14 hours at 34 ℃, adding 9kg of water after the reaction is finished, adding 9kg of dichloromethane, extracting for 4 times, merging organic phases, spin-drying the organic phases, and drying to obtain a compound 3;
(4) 8kg of Compound 1, 18kg of Compound 3 and 0.25kg of azobisisobutyronitrile were added to 30kg of toluene, heated to 88℃for reaction for 19 hours, and after the completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained residue was washed with acetone for 4 times and dried to obtain a polyethylene derivative.
Preparation of polyethylene derivative-copper oxide composite:
(1) 1L of 0.2mol/L sodium carbonate aqueous solution is dripped into 3.5L of 0.2mol/L copper chloride aqueous solution, the temperature is raised to 75 ℃, the reaction is stirred for 20 hours, and a reaction solution is obtained after the reaction is completed;
(2) Adding 0.32kg of polyethylene derivative into the obtained reaction solution, standing at 29 ℃ for 14h, filtering, drying the obtained filter cake at 120 ℃ for 2.5h, and roasting at 290 ℃ for 3h to obtain the polyethylene derivative-copper oxide compound.
Preparation of hydrolysis desulfurization bifunctional catalyst for blast furnace gas:
1) Adding 1.26kg of ferrous chloride and 1.4kg of sodium hydroxide into a kneader, mixing, stirring and reacting for 55min, introducing oxygen into the kneader, and oxidizing for 55min to obtain a mixture;
2) Adding 1.8kg of 40% potassium hydroxide aqueous solution into the prepared mixture, and carrying out solid-liquid mixing reaction for 55min to obtain a mixed solution;
3) Adding 0.24kg of polyethylene derivative-copper oxide compound into the obtained mixed solution, stirring and reacting for 50min, extruding and molding materials in a kneader in a strip extruder after the reaction is completed, and finally drying the extruded and molded materials at 90 ℃ for 20h to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Example 6
Preparation of polyethylene derivatives:
(1) adding 1kg of 3-hydroxypyridine, 1.5kg of bromopropene and 0.3kg of sodium hydride into 10kg of tetrahydrofuran, stirring and dissolving, heating to 80 ℃ for reaction for 8 hours, adding 5kg of water into the reaction solution after the reaction is finished, quenching the reaction, adding 10kg of dichloromethane, separating out an organic phase, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain a compound 1;
(2) adding 1kg of (4-vinylphenyl) methanol and 3kg of BOC-L-tyrosine methyl ester into 15kg of tetrahydrofuran, adding 3kg of triphenylphosphine and 2.5kg of diisopropyl azodicarboxylate, reacting for 8 hours at 40 ℃, distilling under reduced pressure after the reaction is finished to remove a solvent, adding 15kg of dichloromethane into the obtained residue, filtering, adding 15kg of water into the obtained filtrate, extracting for 5 times, and finally spin-drying an organic phase to obtain a compound 2;
(3) adding 1kg of compound 2 and 0.5kg of trifluoroacetic acid into 10kg of tetrahydrofuran, reacting for 10 hours at 35 ℃, removing the solvent by reduced pressure distillation after the reaction is finished, adding the obtained residue into 10kg of methanol, adding 0.25kg of sodium hydroxide, reacting for 15 hours at 35 ℃, adding 10kg of water after the reaction is finished, adding 10kg of dichloromethane, extracting for 5 times, merging organic phases, spin-drying the organic phases, and drying to obtain a compound 3;
(4) 10kg of compound 1, 20kg of compound 3 and 0.3kg of azobisisobutyronitrile were added to 40kg of toluene, heated to 90 ℃ for reaction for 20 hours, after the reaction was completed, the solvent was distilled off under reduced pressure, and the obtained residue was washed with acetone for 5 times and dried to obtain a polyethylene derivative.
Preparation of polyethylene derivative-copper oxide composite:
(1) 1L of 0.2mol/L potassium carbonate aqueous solution is dropwise added into 4L of 0.2mol/L copper chloride aqueous solution, the temperature is raised to 80 ℃, the reaction is stirred for 24 hours, and a reaction liquid is obtained after the reaction is completed;
(2) Adding 0.33kg of polyethylene derivative into the obtained reaction solution, standing at 30 ℃ for 15 hours, filtering, drying the obtained filter cake at 120 ℃ for 3 hours, and roasting at 300 ℃ for 3 hours to obtain the polyethylene derivative-copper oxide compound.
Preparation of hydrolysis desulfurization bifunctional catalyst for blast furnace gas:
1) Adding 1.26kg of ferrous chloride and 1.6kg of sodium hydroxide into a kneader, mixing, stirring and reacting for 60min, introducing oxygen into the kneader, and oxidizing for 60min to obtain a mixture;
2) Adding 1.7kg of 50% potassium hydroxide aqueous solution into the prepared mixture, and carrying out solid-liquid mixing reaction for 60min to obtain a mixed solution;
3) Adding 0.29kg of polyethylene derivative-copper oxide compound into the obtained mixed solution, stirring and reacting for 60min, extruding and molding materials in a kneader in a strip extruder after the reaction is completed, and finally drying the extruded and molded materials at 100 ℃ for 0.5h to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Comparative example
Preparation of copper oxide:
(1) 1L of 0.4mol/L potassium hydroxide aqueous solution is dripped into 6L of 0.2mol/L copper carbonate aqueous solution, the temperature is raised to 60 ℃, the reaction is stirred for 12 hours, and the reaction liquid is obtained after the reaction is completed;
(2) The obtained reaction solution is filtered, and the obtained filter cake is baked for 2.6 hours at 120 ℃ and then baked for 3 hours at 275 ℃ to obtain copper oxide.
Preparation of hydrolysis desulfurization bifunctional catalyst for blast furnace gas:
1) Adding 1.27kg of ferrous chloride and 1.2kg of sodium hydroxide into a kneader, mixing, stirring and reacting for 30min, introducing oxygen into the kneader, and oxidizing for 45min to obtain a mixture;
2) Adding 2kg of sodium hydroxide aqueous solution with mass concentration of 25% into the prepared mixture, and carrying out solid-liquid mixing reaction for 45min to obtain a mixed solution;
3) Adding 0.18kg of copper oxide into the obtained mixed solution, stirring and reacting for 30min, extruding and forming materials in a kneader in a strip extruder after the reaction is completed, and finally drying the extruded and formed materials at 60 ℃ for 12h to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas.
Experimental example
The hydrolysis desulfurization bifunctional catalysts for blast furnace gas prepared in examples 1 to 6 and comparative example of the present invention were analyzed for specific surface area and pore volume by an automatic adsorption apparatus, and the detection results are shown in table 1.
Table 1 physical parameter tables for catalysts prepared in examples 1 to 6 and comparative example
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | Comparative example |
| Specific surface area (m) 2 /g） | 73 | 79 | 83 | 81 | 82 | 76 | 89 |
| Pore volume (cm) 3 /g） | 0.53 | 0.57 | 0.62 | 0.60 | 0.60 | 0.55 | 0.66 |
As can be seen from the results in Table 1, the hydrolysis desulfurization bifunctional catalyst for blast furnace gas prepared by the invention has higher specific surface area and pore volume, and compared with the comparative example, the catalyst occupies part of pore channels on a carrier due to the load of polyethylene derivatives, resulting in reduction of the specific surface area and pore volume.
The two-functional catalysts for hydrolysis and desulfurization of blast furnace gas prepared in examples 1-6 and comparative example are arranged in a fixed bed micro-reactor for performance test, the size of the reactor is phi 10mm x 12mm x 300mm, the loading capacity of the catalyst is 5mL, quartz sand is filled at the upper end and the lower end of the reactor, 20mg/L of carbonyl sulfide standard gas is adopted as an inlet, nitrogen is adopted as a background gas, and the airspeed is 300h -1 Intermittently detecting the total sulfur content of the outlet, wherein the total sulfur concentration of the outlet exceeds 1mg/L, stopping the experiment, and detecting the contents of carbonyl sulfide and hydrogen sulfide in the inlet and outlet raw materials by adopting a gas chromatograph; the sulfur capacity test method was performed according to the method provided in HG/T2513-2014, and the test results are shown in Table 2.
Table 2 table of evaluation of the performance of the catalysts prepared in examples 1 to 6 and comparative example
| Outlet carbonyl Sulfur concentration (mg/L) | Outlet hydrogen sulfide concentration (mg/L) | Sulfur capacity (%) | Penetration time (h) | |
| Example 1 | 0.02 | 0.03 | 17 | 23.5 |
| Example 2 | 0.01 | 0 | 18 | 25 |
| Example 3 | 0.01 | 0 | 21 | 29 |
| Example 4 | 0.01 | 0 | 20 | 27.7 |
| Example 5 | 0.01 | 0 | 16 | 22.1 |
| Example 6 | 0.01 | 0.02 | 18 | 25 |
| Comparative example | 0.15 | 0.12 | 12 | 16.6 |
As can be seen from the results in Table 2, the hydrolysis desulfurization bifunctional catalyst for blast furnace gas prepared by the invention has the advantages that the adsorption and removal of hydrogen sulfide are increased due to the load of polyethylene derivatives, compared with the comparative example, the catalyst has larger sulfur capacity, longer penetration time, stronger conversion adsorption capacity of carbonyl sulfide and good desulfurization effect.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (9)
1. A preparation method of a hydrolysis desulfurization bifunctional catalyst for blast furnace gas is characterized by comprising the following steps: the method comprises the following steps:
1) Adding solid ferrous salt and solid hydroxide into a kneader, mixing, stirring and reacting for 15-60 min, and then introducing oxidizing gas into the kneader for oxidizing reaction for 30-60 min to obtain a mixture;
2) Adding an alkaline compound aqueous solution with the mass concentration of 15-50% into the mixture prepared in the step 1), and carrying out solid-liquid mixing reaction for 30-60 min to obtain a mixed solution;
3) Adding a polyethylene derivative-copper oxide compound into the mixed solution obtained in the step 2), stirring and reacting for 15-60 min, extruding and molding materials in a kneader in a strip extruder after the reaction is completed, and finally naturally airing or drying the extruded and molded materials to obtain the hydrolysis desulfurization dual-function catalyst for blast furnace gas;
the polyethylene derivative-copper oxide compound is prepared by the following steps:
(1) Dropwise adding an aqueous alkaline compound solution with a cation concentration of 0.4mol/L to Cu 2+ Heating copper salt aqueous solution with the concentration of 0.2mol/L to 40-80 ℃, stirring and reacting for 4-24 hours, and obtaining reaction liquid after the reaction is completed;
(2) Adding a polyethylene derivative into the reaction liquid obtained in the step (1), standing for 10-15 hours at 25-30 ℃, filtering, drying the obtained filter cake at 120 ℃ for 2-3 hours, and roasting at 250-300 ℃ for 3 hours to obtain a polyethylene derivative-copper oxide compound;
the structural formula of the polyethylene derivative is as follows:
；
the polyethylene derivative is prepared by the following method:
(1) adding 3-hydroxypyridine, bromopropene and sodium hydride into tetrahydrofuran, stirring and dissolving, heating to 50-80 ℃ for reaction for 5-8 hours, adding water into the reaction solution after the reaction is finished, quenching the reaction, adding methylene dichloride, separating out an organic phase, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain a compound 1;
the mass ratio of the 3-hydroxypyridine to the bromopropene to the sodium hydride to the tetrahydrofuran to the water to the dichloromethane is 1: 1.2-1.5: 0.25-0.3: 5-10: 3-5: 5-10;
(2) adding (4-vinylphenyl) methanol and BOC-L-tyrosine methyl ester into tetrahydrofuran, adding triphenylphosphine and diisopropyl azodicarboxylate, reacting for 5-8 hours at 25-40 ℃, removing a solvent by reduced pressure distillation after the reaction is finished, adding dichloromethane into the obtained residue, performing suction filtration, adding water into the obtained filtrate for extraction for 3-5 times, and finally performing spin drying on an organic phase to obtain a compound 2;
the mass ratio of the (4-vinylphenyl) methanol to the BOC-L-tyrosine methyl ester to the tetrahydrofuran to the triphenylphosphine to the diisopropyl azodicarboxylate to the dichloromethane to the water is 1: 2.5-3: 10-15: 2.2-3: 1.7-2.5: 10-15: 10-15 parts;
(3) adding the compound 2 prepared in the step (2) and trifluoroacetic acid into tetrahydrofuran, reacting for 5-10 hours at 25-35 ℃, removing a solvent by reduced pressure distillation after the reaction is finished, adding the obtained residue into methanol, adding sodium hydroxide, reacting for 10-15 hours at 25-35 ℃, adding water after the reaction is finished, adding dichloromethane, extracting for 3-5 times, merging organic phases, spin-drying the organic phases, and drying to obtain a compound 3;
the mass ratio of the compound 2 to the trifluoroacetic acid to the tetrahydrofuran to the methanol to the sodium hydroxide to the water to the dichloromethane is 1:0.3 to 0.5: 5-10: 5-10: 0.15-0.25: 5-10: 5-10;
(4) adding the compound 1 obtained in the step (1), the compound 3 obtained in the step (3) and azodiisobutyronitrile into toluene, heating to 70-90 ℃ for reaction for 10-20 hours, removing a solvent by reduced pressure distillation after the reaction is finished, washing the obtained residue with acetone for 3-5 times, and drying to obtain a polyethylene derivative;
the mass ratio of the compound 1 to the compound 3 to the azodiisobutyronitrile to the toluene is 1-10: 2-20: 0.05-0.3: 5-40.
2. The method for preparing the hydrolysis desulfurization bifunctional catalyst for blast furnace gas according to claim 1, wherein: the solid ferrous salt in the step 1) is one or two of ferrous sulfate, ferrous chloride and ferrous nitrate; the solid hydroxide is one or two of sodium hydroxide, calcium hydroxide and potassium hydroxide.
3. The method for preparing the hydrolysis desulfurization bifunctional catalyst for blast furnace gas according to claim 1, wherein: the molar ratio of ferrous ions in the solid ferrous salt to hydroxyl ions in the solid hydroxide in step 1) is 1: 2-4.
4. The method for preparing the hydrolysis desulfurization bifunctional catalyst for blast furnace gas according to claim 1, wherein: the oxidizing gas in step 1) is oxygen or air.
5. The method for preparing the hydrolysis desulfurization bifunctional catalyst for blast furnace gas according to claim 1, wherein: the alkaline compound in the step 2) is one or two of sodium carbonate, potassium hydroxide and sodium hydroxide.
6. The method for preparing the hydrolysis desulfurization bifunctional catalyst for blast furnace gas according to claim 1, wherein: the mass of the alkaline compound in the step 2) is 0.1-0.3 times of the total mass of the solid ferrous salt and the solid hydroxide in the step 1).
7. The method for preparing the hydrolysis desulfurization bifunctional catalyst for blast furnace gas according to claim 1, wherein: the mass of the polyethylene derivative-copper oxide composite in the step 3) is 0.05-0.1 time of the total mass of the solid ferrous salt and the solid hydroxide in the step 1); wherein the drying temperature is 50-100 ℃ and the drying time is 0.5-24 h.
8. The method for preparing the hydrolysis desulfurization bifunctional catalyst for blast furnace gas according to claim 1, wherein: the copper salt in the step (1) is one or two of copper sulfate pentahydrate, copper chloride and copper carbonate; the molar ratio of the alkaline compound to the copper salt is 1: 2-4.
9. The method for preparing the hydrolysis desulfurization bifunctional catalyst for blast furnace gas according to claim 1, wherein: the mass volume ratio of the polyethylene derivative to the reaction liquid in the step (2) is 1g: 10-15 ml.
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| CN104058491A (en) * | 2014-07-04 | 2014-09-24 | 岳阳海达环保科技有限公司 | Ferric oxide desulfurizer and preparation method thereof |
| CN109999626A (en) * | 2019-04-30 | 2019-07-12 | 太原理工大学 | A method of preparing copper oxide/carbon nano-fiber flexible compound gas desulfurizer |
| CN111763539A (en) * | 2020-06-08 | 2020-10-13 | 太原理工大学 | Preparation method of iron oxide gas desulfurizer |
| CN113289583A (en) * | 2021-07-01 | 2021-08-24 | 浙江工业大学 | Active carbon desulfurizer loaded with metal oxide as well as preparation method and application thereof |
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| CN110404578A (en) * | 2019-02-01 | 2019-11-05 | 中国石油大学(北京) | The bifunctional catalyst and its preparation method and application of hydrodesulfurization coupling isomerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058491A (en) * | 2014-07-04 | 2014-09-24 | 岳阳海达环保科技有限公司 | Ferric oxide desulfurizer and preparation method thereof |
| CN109999626A (en) * | 2019-04-30 | 2019-07-12 | 太原理工大学 | A method of preparing copper oxide/carbon nano-fiber flexible compound gas desulfurizer |
| CN111763539A (en) * | 2020-06-08 | 2020-10-13 | 太原理工大学 | Preparation method of iron oxide gas desulfurizer |
| CN113289583A (en) * | 2021-07-01 | 2021-08-24 | 浙江工业大学 | Active carbon desulfurizer loaded with metal oxide as well as preparation method and application thereof |
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