CN110801821B - Preparation method of composite adsorbent for removing hydrogen sulfide at high temperature - Google Patents
Preparation method of composite adsorbent for removing hydrogen sulfide at high temperature Download PDFInfo
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- CN110801821B CN110801821B CN201911037395.1A CN201911037395A CN110801821B CN 110801821 B CN110801821 B CN 110801821B CN 201911037395 A CN201911037395 A CN 201911037395A CN 110801821 B CN110801821 B CN 110801821B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 65
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 55
- 230000023556 desulfurization Effects 0.000 abstract description 55
- 239000007789 gas Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 16
- 238000011069 regeneration method Methods 0.000 abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 238000002474 experimental method Methods 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 238000002309 gasification Methods 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000003009 desulfurizing effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B01J20/3204—Inorganic carriers, supports or substrates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
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Abstract
本发明属于脱硫吸附剂技术领域，具体涉及一种高温脱除硫化氢复合吸附剂及其制备方法和应用。本发明所提供的脱除硫化氢复合吸附剂包括以下重量百分含量的各组分：10％‑50％的氧化锰，30％‑40％的氧化铝，2％‑15％的助剂，助剂选自氧化镧、氧化铈、氧化钡或氧化镍中至少任意两种的混合脱除硫化氢复合吸附剂，其可在800℃以上正常工作，并具有如下优点：1)新鲜吸附剂脱硫效果良好，在模拟还原气氛脱硫实验中，硫化氢的脱除率接近100％，尾气中硫化氢含量低于1mg/m3；2)在脱硫‑再生循环过程中吸附剂脱硫性能稳定，其突破硫容及脱硫效率均保持稳定，脱硫过程中尾气中硫化氢含量均低于3mg/m3；3)吸附剂为干态，使用时不需要水溶液，减少了水耗。
The invention belongs to the technical field of desulfurization adsorbents, and in particular relates to a high-temperature hydrogen sulfide removal composite adsorbent and a preparation method and application thereof. The composite adsorbent for removing hydrogen sulfide provided by the present invention includes the following components by weight: 10%-50% manganese oxide, 30%-40% alumina, 2%-15% auxiliary agent, The auxiliary agent is selected from lanthanum oxide, cerium oxide, barium oxide or nickel oxide. The mixed adsorbent for removing hydrogen sulfide can work normally above 800 °C and has the following advantages: 1) Fresh adsorbent desulfurization The effect is good. In the simulated reducing atmosphere desulfurization experiment, the removal rate of hydrogen sulfide is close to 100%, and the hydrogen sulfide content in the tail gas is lower than 1 mg/m 3 ; 2) The desulfurization performance of the adsorbent is stable during the desulfurization-regeneration cycle, and its breakthrough The sulfur capacity and desulfurization efficiency remain stable, and the hydrogen sulfide content in the exhaust gas during the desulfurization process is less than 3 mg/m 3 ; 3) The adsorbent is in a dry state, and does not require an aqueous solution during use, reducing water consumption.
Description
Technical Field
The invention belongs to the technical field of desulfurization adsorbents, and particularly relates to a high-temperature hydrogen sulfide removal composite adsorbent, and a preparation method and application thereof, which are suitable for integrated gasification combined cycle power generation (IGCC), fuel cells and Biomass Gasification Power Generation (BGPG).
Background
The integrated coal gasification combined cycle power generation technology is an advanced power system combining a coal gasification technology and an efficient combined cycle, can improve the energy conversion efficiency of the traditional power generation technology, and can reduce the pollution of gas pollutants to the environment; solid fuel cell technology; the biomass gasification power generation technology can not only solve the effective utilization of renewable energy sources, but also solve the environmental pollution of various organic wastes. However, gases generated in the three technical processes contain hydrogen sulfide with certain quality, which can corrode downstream equipment and pollute the environment, so that the removal of the hydrogen sulfide in the technical process is particularly important. At present, the most used desulfurization method is wet desulfurization, for example, low-temperature methanol washing. Wet desulfurization is generally carried out in a low temperature environment. Because the temperature of the gasified coal gas is generally over 800 ℃, the wet desulphurization needs to reduce the temperature to a low temperature through the heat exchanger before desulphurization, and then the temperature is raised to the gas temperature required by the subsequent process through the heat exchanger, the energy consumption of the process can be reduced by the temperature rise and fall, the energy waste is caused, and the water resource can be wasted by the wet desulphurization. The high-temperature desulfurization is generally carried out in a medium-high temperature environment, so that not only can heat exchange equipment be saved, but also the energy utilization rate of the process can be improved due to the fact that the link of temperature rise and drop is omitted.
The high-temperature desulfurization generally uses metal oxide as a desulfurizing agent, and the requirements of the metal oxide desulfurizing agent are summarized as follows: 1) the vulcanization reaction equilibrium constant is high and the desulfurization rate is high; 2) the selectivity to hydrogen sulfide is high, and the side reaction is weak; 3) the reduction resistance is better; 4) the mechanical strength is high; 5) the regeneration performance is good. However, the single metal oxide desulfurizing agent has advantages and disadvantages, and cannot meet the requirements of the desulfurizing agent, so more and more researchers are dedicated to the research of the composite metal oxide desulfurizing adsorbent.
Disclosure of Invention
The invention aims to solve the problems of low desulfurization efficiency, poor desulfurization cycle stability, difficult regeneration and the like of a desulfurizer in high-temperature gasified gas, and provides a high-temperature desulfurizer which is high in desulfurization efficiency and good in cycle stability in a desulfurization-regeneration cycle process, and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
a preparation method of a composite adsorbent for removing hydrogen sulfide at high temperature comprises the following steps:
1) dissolving 60-70 parts by mass of aluminum nitrate in 100 parts by mass of water, then adding 10-50 parts by mass of polyvinyl alcohol, then adding 1-5 parts by mass of auxiliary nitrate, uniformly dissolving, adjusting the pH value of the mixed solution to 8-12 to prepare gel, washing the gel with water, drying at the temperature of 100-120 ℃, and calcining at the temperature of 500-900 ℃ for 4-8 hours to obtain a first calcined sample;
2) taking an auxiliary nitrate solution with the mass fraction of 5-20wt% as a first impregnation solution, impregnating the first calcined sample obtained in the step 1) in an equal volume manner, uniformly mixing, impregnating in a rotary mixer at 40-60 ℃ for 5-24 hours, and calcining at 700-900 ℃ for 4-8 hours to obtain a second calcined sample;
3) adding 2-10 parts by mass of auxiliary nitrate into 1-2mol/L of manganese nitrate solution to obtain a second impregnation solution;
4) soaking the second calcined sample obtained in the step 2) in the second soaking solution obtained in the step 3) in the same volume, uniformly mixing, soaking in a rotary mixer for 5-24 hours, and drying at 80-120 ℃ for 12 hours;
5) after repeating the step 4) for at least 4 times, calcining the dried sample at the temperature of 600-900 ℃ for 4-8 hours to obtain the high-temperature hydrogen sulfide removal composite adsorbent;
the nitrate of the auxiliary agent is selected from the mixture of at least any two of lanthanum nitrate, cerium nitrate, barium nitrate and nickel nitrate.
By adopting the technical scheme, the hydrogen sulfide removal composite adsorbent can be prepared, can normally work at the temperature of over 800 ℃, and has the following advantages:
1) the prepared fresh adsorbent has good desulfurization effect, the removal rate of the hydrogen sulfide is close to 100 percent in a simulated reducing atmosphere desulfurization experiment, and the content of the hydrogen sulfide in tail gas is lower than 1mg/m3；
2) The desulfurization performance of the adsorbent is stable in the desulfurization-regeneration cycle process, the breakthrough sulfur capacity and the desulfurization efficiency are stable, and the content of hydrogen sulfide in tail gas in the desulfurization process is lower than 3mg/m3；
3) The adsorbent is in a dry state, and does not need aqueous solution when in use, thereby reducing water consumption.
In the technical scheme, the polyvinyl alcohol is used as the pore-forming agent, so that the specific surface area of the prepared high-temperature hydrogen sulfide removal composite adsorbent can be increased.
Specifically, in the step 1), ammonia water is adopted to adjust the pH value.
Based on the technical scheme, impurities which are difficult to remove are not introduced.
Specifically, in the step 1), ultrasonic treatment is adopted to ensure uniform dissolution.
Based on the technical scheme, the components can be effectively and uniformly dissolved.
Specifically, in the step 2), ultrasonic treatment is adopted to uniformly mix.
Based on the technical scheme, the components can be effectively dissolved or dispersed uniformly.
Specifically, in the step 3), ultrasonic treatment is adopted to uniformly mix.
Based on the technical scheme, the components can be effectively dissolved or dispersed uniformly.
The invention also provides the high-temperature hydrogen sulfide removal composite adsorbent prepared by the preparation method.
The composite adsorbent for removing hydrogen sulfide provided by the invention can normally work at the temperature of more than 700 ℃, and has the following advantages:
1) the fresh adsorbent has good desulfurization effect, the removal rate of the hydrogen sulfide is close to 100 percent in a simulated reducing atmosphere desulfurization experiment, and the content of the hydrogen sulfide in tail gas is lower than 1mg/m3；
2) The desulfurization performance of the adsorbent is stable in the desulfurization-regeneration cycle process, the breakthrough sulfur capacity and the desulfurization efficiency are stable, and the content of hydrogen sulfide in tail gas in the desulfurization process is lower than 3mg/m3。
3) The adsorbent is in a dry state, and does not need aqueous solution when in use, thereby reducing water consumption.
Specifically, the high-temperature hydrogen sulfide removal composite adsorbent comprises the following components in percentage by weight: 10-50% of manganese oxide, 30-40% of aluminum oxide and 2-15% of auxiliary agent, wherein the auxiliary agent is selected from the mixture of at least any two of lanthanum oxide, cerium oxide, barium oxide and nickel oxide.
In the technical scheme, the lanthanum oxide, the barium oxide and the cerium oxide can improve the stable structure performance of the composite adsorbent in a high-temperature environment and inhibit sintering of the adsorbent in the high-temperature environment; cerium oxide, nickel oxide or barium oxide may stabilize the reactivity of the regenerated adsorbent. Further, at least one oxide is used in each of the two groups.
The invention also provides the application of the composite adsorbent for removing hydrogen sulfide at high temperature, which is used as the composite adsorbent for removing hydrogen sulfide at 700-900 ℃.
The composite adsorbent for removing hydrogen sulfide provided by the invention has good high-temperature stability, and can normally work at the temperature of over 700 ℃.
Specifically, the adsorbent is used as a hydrogen sulfide removal composite adsorbent in integrated gasification combined cycle power generation, as a hydrogen sulfide removal composite adsorbent in biomass gasification power generation or as a hydrogen sulfide removal composite adsorbent in fuel cell production.
The stability and the adsorption performance of the composite adsorbent for removing hydrogen sulfide provided by the invention meet the requirements of various working conditions, and the composite adsorbent has wide application.
Drawings
FIG. 1 is a desulfurization graph showing the desulfurization effect of the composite adsorbent for removing hydrogen sulfide 1 according to example 1 of the present invention.
Fig. 2 is a breakthrough sulfur capacity diagram in the cycle process of the desulfurization effect of the hydrogen sulfide removal composite adsorbent 1 provided in example 1 of the present invention, where CN is the cycle number.
FIG. 3 is a desulfurization graph showing the desulfurization effect of the composite adsorbent for removing hydrogen sulfide 2 according to example 2 of the present invention.
Fig. 4 is a breakthrough sulfur capacity diagram in the cycle process of the desulfurization effect of the composite adsorbent for removing hydrogen sulfide 2 provided in example 2 of the present invention, where CN is the cycle number.
FIG. 5 is a desulfurization graph showing the desulfurization effect of the composite adsorbent for removing hydrogen sulfide 3 according to example 3 of the present invention.
Fig. 6 is a breakthrough sulfur capacity diagram in the cycle process of the desulfurization effect of the composite adsorbent for removing hydrogen sulfide 3 provided in example 3 of the present invention, where CN is the cycle number.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
30 g of aluminum nitrate was dissolved in distilled water, 4.5 g of polyvinyl alcohol and 1 g of lanthanum nitrate were added, and ultrasonic treatment was performed for 6 hours to completely dissolve the aluminum nitrate. Then dilute ammonia was added dropwise to the solution, and stirred until the pH reached 9. An alumina gel was prepared and washed 3 times with distilled water. The sample was dried at 110 degrees and calcined at 600 degrees for 6 hours and cooled to room temperature to produce a modified alumina. 20 percent lanthanum nitrate solution with mass concentration is soaked in the modified alumina in equal volume, mixed evenly by ultrasonic dispersion, soaked in a rotary mixer for 12 hours and calcined at 800 ℃ for 6 hours. Soaking a mixed solution of manganese nitrate (2mol/L) and nickel nitrate (12%) in a sample generated by calcination in an equal volume, performing ultrasonic treatment for 10 minutes firstly in the soaking process, then soaking in a rotary mixer for 12 hours, then drying at 110 ℃ for 12 hours, repeating the above process for five times, and calcining the soaked sample at 900 ℃ for 6 hours to obtain the hydrogen sulfide removal composite adsorbent 1.
Example 2
30 g of aluminum nitrate was dissolved in distilled water, 4.5 g of polyvinyl alcohol and 1 g of cerium nitrate were added, and ultrasonic treatment was performed for 6 hours to completely dissolve the aluminum nitrate. Then dilute ammonia was added dropwise to the solution, and stirred until the pH reached 9. An alumina gel was prepared and washed 3 times with distilled water. The sample was dried at 110 degrees and calcined at 600 degrees for 6 hours, and cooled to room temperature to produce a modified alumina. 20 percent lanthanum nitrate solution with mass concentration is soaked in the modified alumina in equal volume, mixed evenly by ultrasonic dispersion, soaked in a rotary mixer for 12 hours and calcined at 800 ℃ for 6 hours. Soaking a mixed solution of manganese nitrate (2mol/L) and cerium nitrate (20%) in a calcined sample in an equal volume, performing ultrasonic treatment for 10 minutes firstly in the soaking process, soaking in a rotary mixer for 24 hours, then drying at 110 ℃ for 12 hours, repeating the above process for five times, and calcining the soaked sample at 900 ℃ for 6 hours to obtain the hydrogen sulfide removal composite adsorbent 2.
Example 3
30 g of aluminum nitrate was dissolved in distilled water, 5 g of polyvinyl alcohol and 2 g of lanthanum nitrate were added, and the mixture was subjected to ultrasonic treatment for 6 hours to completely dissolve the aluminum nitrate. Then dilute ammonia was added dropwise to the solution, and stirred until the pH reached 9. An alumina gel was prepared and washed 3 times with distilled water. The sample was dried at 110 degrees and calcined at 600 degrees for 6 hours and cooled to room temperature to produce a modified alumina. 20 percent lanthanum nitrate solution with mass concentration is soaked in the modified alumina in equal volume, mixed evenly by ultrasonic dispersion, soaked in a rotary mixer for 12 hours and calcined at 800 ℃ for 6 hours. Soaking a mixed solution of manganese nitrate (1mol/L) and barium nitrate (20%) in a calcined sample in equal volume, wherein the soaking process comprises the steps of firstly carrying out ultrasonic treatment for 10 minutes, then soaking in a rotary mixer for 24 hours, then drying at 110 ℃ for 12 hours, repeating the above process for five times, and calcining the soaked sample at 800 ℃ for 6 hours to obtain the hydrogen sulfide removal composite adsorbent 3.
Examples of effects
The small heating furnace in the laboratory comprises a nitrogen cylinder, a hydrogen sulfide cylinder, a hydrogen cylinder and an oxygen cylinder. Each gas bottle is communicated with a mixing cavity, the mixing cavity is communicated with a preheating cavity, the preheating cavity is communicated with a quartz reaction cavity, and the temperature in the quartz reaction cavity is detected by a temperature controller. The quartz reaction chamber is provided with a heating furnace, and the temperature in the heating furnace is detected and controlled by a temperature controller. The gas chromatograph is respectively communicated with the gas inlet end and the gas outlet end of the quartz reaction cavity and used for component detection.
And performing a laboratory small-scale heating furnace simulated gasified gas desulfurization-regeneration experiment by using the hydrogen sulfide removal composite adsorbent 1, the hydrogen sulfide removal composite adsorbent 2 and the hydrogen sulfide removal composite adsorbent 3. The experiment was carried out at atmospheric pressure, under the conditions of desulfurization: atmosphere conditions: 10% H2,2000mg/m3 H2S,N2For balance gas, desulfurization temperature 850 ℃, gas space velocity: 12L g-1·h-1(ii) a Regeneration conditions are as follows: 5% O2,N2The equilibrium gas, the regeneration temperature is 850 ℃, and the space velocity of the regeneration gas is as follows: 24L g-1·h-1. Evaluation indexes are as follows: when the tail gas is converged with H2The concentration of S is higher than 50mg/m3It is considered that the adsorbent penetrated and H adsorbed by the adsorbent during that time2S becomes a breakthrough Sulfur Capacity (SC).
As shown in fig. 1 and 2, the desulfurization effect of the composite adsorbent for removing hydrogen sulfide 1 is shown. As can be seen from fig. 1: the prepared fresh adsorbent for composite metal oxide has good desulfurization effect, the removal rate of hydrogen sulfide is close to 100 percent in a simulated reducing atmosphere desulfurization experiment, and the content of hydrogen sulfide in tail gas is lower than 1mg/m3(ii) a As can be seen from FIG. 2, the composite metal oxide adsorbent has stable desulfurization performance during the desulfurization-regeneration cycle, and both breakthrough sulfur capacity and desulfurization efficiency are maintainedStable and the content of hydrogen sulfide in tail gas in the desulfurization process is 3mg/m3Left and right.
As shown in fig. 3 and 4, the desulfurization effect of the composite adsorbent 2 for removing hydrogen sulfide is shown. As can be seen from fig. 3: the prepared fresh adsorbent for composite metal oxide has good desulfurization effect, the removal rate of hydrogen sulfide is close to 100 percent in a simulated reducing atmosphere desulfurization experiment, and the content of hydrogen sulfide in tail gas is lower than 1mg/m3(ii) a As can be seen from FIG. 4, the composite metal oxide adsorbent has stable desulfurization performance during the desulfurization-regeneration cycle, the breakthrough sulfur capacity and desulfurization efficiency are stable, and the hydrogen sulfide content in the tail gas during the desulfurization process is 2mg/m3Left and right.
As shown in fig. 5 and 6, the desulfurization effect of the composite adsorbent for removing hydrogen sulfide 3 is shown. As can be seen from fig. 5: the prepared fresh adsorbent for composite metal oxide has good desulfurization effect, the removal rate of hydrogen sulfide is close to 100 percent in a simulated reducing atmosphere desulfurization experiment, and the content of hydrogen sulfide in tail gas is lower than 1mg/m3(ii) a As can be seen from FIG. 6, the composite metal oxide adsorbent has stable desulfurization performance during the desulfurization-regeneration cycle, the breakthrough sulfur capacity and desulfurization efficiency are stable, and the content of hydrogen sulfide in the tail gas during the desulfurization process is 3mg/m3Left and right.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of a composite adsorbent for removing hydrogen sulfide at high temperature is characterized by comprising the following steps:
1) dissolving 60-70 parts by mass of aluminum nitrate in water, then adding 10-50 parts by mass of polyvinyl alcohol, then adding 1-5 parts by mass of auxiliary nitrate, uniformly dissolving, adjusting the pH value of the mixed solution to 8-12 to prepare gel, washing the gel with water, drying at the temperature of 100-120 ℃, and calcining at the temperature of 500-900 ℃ for 4-8 hours to obtain a first calcined sample;
2) taking an auxiliary nitrate solution with the mass fraction of 5-20wt% as a first impregnation solution, impregnating the first calcined sample obtained in the step 1) in an equal volume manner, uniformly mixing, impregnating in a rotary mixer at 40-60 ℃ for 5-24 hours, and calcining at 700-900 ℃ for 4-8 hours to obtain a second calcined sample;
3) adding 2-10 parts by mass of auxiliary nitrate into 1-2mol/L of manganese nitrate solution to obtain a second impregnation solution;
4) uniformly mixing the second calcined sample obtained in the step 2) with the second impregnation liquid obtained in the step 3) in an equal volume, impregnating in a rotary mixer for 5-24 hours, and drying at 80-120 ℃ for 12 hours;
5) after repeating the step 4) for at least 4 times, calcining the dried sample at the temperature of 600-900 ℃ for 4-8 hours to obtain the high-temperature hydrogen sulfide removal composite adsorbent;
wherein:
the nitrate of the auxiliary agent in the step 1) is selected from any one of lanthanum nitrate, barium nitrate or cerium nitrate, the nitrate of the auxiliary agent in the step 2) is selected from any one of lanthanum nitrate, barium nitrate or cerium nitrate, and the nitrate of the auxiliary agent in the step 1) and the nitrate of the auxiliary agent in the step 2) are the same or different;
the nitrate as the auxiliary agent in the step 3) is selected from any one of cerium nitrate, nickel nitrate or barium nitrate;
the obtained high-temperature hydrogen sulfide removal composite adsorbent comprises: 10-50% of manganese oxide, 30-40% of aluminum oxide and 2-15% of an auxiliary agent, wherein the auxiliary agent is selected from the mixture of at least any two of lanthanum oxide, cerium oxide, barium oxide or nickel oxide;
the high temperature is 700-900 ℃.
2. The preparation method of the composite adsorbent for removing hydrogen sulfide at high temperature according to claim 1, characterized in that: in the step 1), ammonia water is adopted to adjust the pH value.
3. The preparation method of the high-temperature hydrogen sulfide removal composite adsorbent according to claim 1 or 2, characterized in that: in the step 1), ultrasonic treatment is adopted to ensure that the solution is uniform; in the step 2), ultrasonic treatment is adopted to uniformly mix; in the step 4), ultrasonic treatment is adopted to uniformly mix.
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