CN101735861B - Zinc oxide medium and high temperature coal gas fine desulfurizer and preparation method - Google Patents
Zinc oxide medium and high temperature coal gas fine desulfurizer and preparation method Download PDFInfo
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- CN101735861B CN101735861B CN 200910175382 CN200910175382A CN101735861B CN 101735861 B CN101735861 B CN 101735861B CN 200910175382 CN200910175382 CN 200910175382 CN 200910175382 A CN200910175382 A CN 200910175382A CN 101735861 B CN101735861 B CN 101735861B
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Abstract
The invention relates to a zinc oxide medium and high temperature coal gas fine desulfurizer and a preparation method, belonging to the technical field of the preparation and the application of desulfurizers, in particular to the preparation and the application of zinc oxide medium and high temperature coal gas fine desulfurizers. The zinc oxide medium and high temperature coal gas fine desulfurizer is characterized by having wide sources and high price and can finely remove sulfureted hydrogen at medium and high temperature (300-550 DEG C) in the strongly reducing atmosphere. The active ingredients of the desulfurizer are uniformly distributed on a carrier surface and have the particle diameter of 10-400 nm. In the preparation method, the two steps of semicoke carrier modification and the active ingredient dipping are combined into one step, the two functions for improving the carrier hole structure and loading the components can be synchronously finished in an autoclave. The semicoke has wide sources, high price and simple preparation technique; the prepared desulfurizer can finely remove sulfureted hydrogen at medium and high temperature in the strongly reducing atmosphere, has better thermal stability, and can be widely used in the field of desulfurizing and purifying the reducing chemical virgin gas which is prepared by using coal as materials.
Description
Technical field
Coal gas of high temperature desulfurizing agent and preparation method in the zinc oxide of the present invention; The technical field that belongs to the preparation and the application of sweetening agent; Relate in particular to the preparation and the application of coal gas of high temperature desulfurizing agent in the zinc oxide, technical scheme of the present invention can be applied in the middle high temperature coal gas purification in integrated gasification combined cycle for power generation technology, the polygenerations systeme and be in the preparation of desulfurizing decontaminating agent of reductibility material gas of feedstock production with the coal.
Background technology
It is the important energy source utilization technology that meets the human kind sustainable development target that the cleaning of coal transforms.In the coal gasification process, if can be removed to the cleaning transformation efficiency that lower level will improve coal at the sulphur in the following coal gas of middle hot conditions.Sulphur in the coal gas mainly exists with the form of hydrogen sulfide, so the technology that removes of hydrogen sulfide just becomes the focus of research.In integrated gasification combined cycle for power generation (IGCC) technology,, can make efficiency of energy utilization improve more than 2% if can raw gas be reduced to sulfurous gas wherein below the 20ppm under middle hot conditions.The coal gas conduct is synthesized when using raw material in the coal-based polygenerations systeme, for preventing that catalyst system therefor is poisoned in the subsequent technique, prolongs catalyst life, requires the H in the coal gas
2The S gas removal is to 0.05-10ppm, and the synthetic sensible heat waste that causes that after the technology coupling desulfurization of carrying out under the 300-550 ℃ of temperature can be avoided cooling, desulfurizing, heats up reaches effective target of improving utilising efficiency.In recent years; The middle high temperature desulfurizing of coal gas many researchs have been carried out both at home and abroad; But many researchs all focus on the research of thick sweetening agent, in 300-550 ℃ of warm area scope, under the strong reducing property atmosphere; The desulfurization precision of sweetening agent can only reach 40-100ppm, and this precision can't satisfy the desulfurization requirement such as the subsequent technique of IGCC technology and coal-based polygenerations systeme.Therefore also there is not sophisticated desulfurization technology to be widely used at present, in its industrialized process, problem such as it is poor still to exist such as the sweetening agent cycle thermal stability, and desulfurization precision is low.A kind of active carbocoal H that patent CN 100443161C announces
2The preparation method of S sweetening agent, semicoke is earlier to carry out modification through high pressure hydrothermal chemistry, incipient impregnation active component solution again, preparation process is complicated; And the sweetening agent of preparing can only remove H under as 40 ℃ in lower temperature
2S.
Summary of the invention
Coal gas of high temperature desulfurizing agent and preparing method's purpose is to mainly the sweetening agent cycle thermal stability of existence is poor in the at present middle coal gas of high temperature desulfurization technology in the zinc oxide of the present invention; Problems such as desulfurization precision is low, coal gas of high temperature desulfurizing agent and preparation method thereof in the zinc oxide that provide that a kind of step is simple, Heat stability is good and desulfurization precision is high.
Coal gas of high temperature desulfurizing agent in the zinc oxide of the present invention; It is characterized in that it being coal gas of high temperature desulfurizing agent in a kind of wide material sources, low-cost can be under middle high temperature (300-550 ℃) the strongly reducing atmosphere smart zinc oxide that removes hydrogen sulfide; This desulfurizer active component is evenly distributed at carrier surface; And particle diameter is 10-40nm, and this sweetening agent evaluation index is: when exporting concentration of hydrogen sulfide greater than 1ppm, think that promptly sweetening agent penetrates; Curing time equals time of break-through, and the accumulation Sulfur capacity in the time of break-through is the sweetening agent Sulfur capacity.
The preparation method of coal gas of high temperature desulfurizing agent in above-mentioned a kind of zinc oxide; It is characterized in that it being a kind of employing wide material sources; Low-cost semicoke and zinc oxide active ingredient make has thermostability preferably, can be widely used in the coal preparation method of coal gas of high temperature desulfurizing agent in the desulfurizing and purifying field of the reductibility material gas that is feedstock production, can be under the middle high temperature strongly reducing atmosphere smart zinc oxide that removes hydrogen sulfide; This method is with semicoke support modification and activity component impregnation two steps unification; When enlarging the carrier specific surface area, activity component impregnation is arrived carrier; The carrier hole structure is improved and two kinds of effects of component load can be accomplished in autoclave simultaneously, and its concrete process step is:
I, the raw material semi-coke powder is broken into the 4-8 order;
II, the semicoke that I is pulverized and mass concentration are that 5-24% zinc nitrate steeping fluid is to place autoclave at 0.7: 1 by volume, under 8-28atm impregnating by pressure 3-7 hour, naturally cool to room temperature;
III, the sample that the II impregnating by pressure is good take out in autoclave, place on the filter flask, and the zinc nitrate solution that will not be impregnated into above the carrier carries out solid-liquid separation through filter paper or filter membrane;
IV, with the solid sample after the III solid-liquid separation, in air drying cabinet at first 50-70 ℃ dry 3-10 hour down, and then 100-120 ℃ dry 3-10 hour down;
V, with the dry good sample of IV again in nitrogen atmosphere, 400-600 ℃ temperature lower calcination 3-7 hour, promptly make sweetening agent.
The preparation method of coal gas of high temperature desulfurizing agent in above-mentioned a kind of zinc oxide is characterized in that described semicoke is brown coal or bituminous coal semicoke, and its bulk density is 0.55-0.73g/ml, and specific surface area is 10.07-265.49m
2/ g, volatile content are 3-15%.
The preparation method of coal gas of high temperature desulfurizing agent in above-mentioned a kind of zinc oxide is characterized in that described nitrogen atmosphere is 99.99% pure nitrogen gas.
Coal gas of high temperature desulfurizing agent and preparing method's advantage is in the zinc oxide of the present invention: semicoke and gac belong to carbon materials together, its physicochemical property and similar, and wide material sources, low price, preparation technology is simple.The sweetening agent that this method makes can essence remove hydrogen sulfide under middle high temperature strongly reducing atmosphere, and thermostability is preferably arranged.Can be widely used in the coal desulfurizing and purifying field of the reductibility material gas that is feedstock production.When the characteristics that the impregnating by pressure legal system is equipped with sweetening agent are to enlarge the carrier specific surface area with activity component impregnation to carrier, promptly the carrier hole structure improve with two kinds of effects of component load can completion simultaneously in autoclave.In the sweetening agent that makes, active ingredient is evenly distributed at carrier surface, and particle diameter less (10-40nm).The pressure of impregnating by pressure directly affects the specific surface area size of semicoke, and causes the uniform distribution degree of active ingredient on carrier.The sweetening agent evaluation index: when exporting concentration of hydrogen sulfide greater than 1ppm, think that promptly sweetening agent penetrates, sweetening agent no longer includes sweetening power, stops experiment.Curing time is time of break-through, and the accumulation Sulfur capacity in the time of break-through is the sweetening agent Sulfur capacity.
Description of drawings
Fig. 1 is the curability correlation curve of sweetening agent I and IV.
Label is among the figure: t-curing time (h);
C-exports H
2S concentration (ppm).
Fig. 2 is the scanning electron microscope image of sweetening agent I.
Fig. 3 is the scanning electron microscope image of sweetening agent IV.
Embodiment
Embodiment 1: with obtaining 4-8 order particle after the semicoke screening; With mass concentration is to put into autoclave after 20% zinc nitrate solution mixes by 0.7: 1 volume ratio, and impregnating by pressure is 5 hours under 28atm, naturally cools to room temperature afterwards; Take out the sample after-filtration; And 50 ℃ dry 5 hours down, again 100 ℃ dry 5 hours down, afterwards again at N
2Purge calcining down 5 hours, naturally cool to room temperature and make sweetening agent I.Under 500 ℃ temperature, vulcanize experiment, it is CO (33%) that reactant gases is formed (volume ratio), H
2(39%), H
2O (5%), H
2S (300ppm), N
2As balance gas, air speed 2000h
-1H
2The S exit concentration is during greater than 1ppm, and the Sulfur capacity that obtains this sweetening agent is the 4.46gS/100g sweetening agent, and time of break-through is 23h.The sweetening agent preparation method who adopts patent CN 100443161C to announce; Earlier semicoke is carried out high pressure hydrothermal chemistry and carry out modification; The sweetening agent IV of the zinc nitrate solution of incipient impregnation 20% preparation again, and it is carried out the curability test under the cure conditions identical with sweetening agent I, work as H
2The S exit concentration is during greater than 1ppm, and the Sulfur capacity and the time of break-through that obtain this sweetening agent are respectively 2.13gS/100g sweetening agent and 11h.
The sulfuration experimental result of table 1. sweetening agent I and IV relatively
Embodiment 2: with obtaining 4-8 order particle after the semicoke screening; With mass concentration be that 20% zinc nitrate solution is put into autoclave after by 0.7: 1 mixed; Impregnating by pressure naturally cooled to room temperature after 7 hours under 28atm, took out the sample after-filtration, and following dry 5 hours at 70 ℃; Descended dry 5 hours at 120 ℃ again, afterwards again at N
2Purge calcining down 5 hours, naturally cool to room temperature and make sweetening agent II.Under 500 ℃, vulcanize experiment, it is CO (33%) that reactant gases is formed (volume ratio), H
2(39%), H
2O (5%), H
2S (1000ppm), N
2As balance gas, air speed 2000h
-1H
2Sulfur capacity and the time of break-through of S exit concentration during greater than 1ppm is respectively 4.55gS/100g sweetening agent and 7.5h.
Embodiment 3: with obtaining 4-8 order particle after the semicoke screening; With mass concentration be that 20% zinc nitrate solution is put into autoclave after by 0.7: 1 mixed; Impregnating by pressure naturally cooled to room temperature after 5 hours under 20atm, took out the sample after-filtration, and following dry 5 hours at 50 ℃; Descended dry 5 hours at 100 ℃ again, afterwards again at N
2Purge calcining down 6 hours, naturally cool to room temperature and make sweetening agent III.Under 500 ℃, vulcanize experiment, it is CO (33%) that reactant gases is formed (volume ratio), H
2(39%), H
2O (5%), H
2S (1000ppm), N
2As balance gas, air speed 2000h
-1H
2Sulfur capacity and the time of break-through of S exit concentration during greater than 1ppm is respectively 6.57gS/100g sweetening agent and 16h.
Embodiment 4: get the sweetening agent I that 20ml makes, in fixed-bed reactor, carry out activity rating.It is CO (33%) that reactant gases is formed (volume ratio), H
2(39%), H
2O (5%), H
2S (300ppm), N
2As balance gas, air speed 2000h
-1At 450 ℃, the temperature of 500 ℃ and 550 ℃ is vulcanized experiment, works as H
2The S exit concentration is during greater than 1ppm, obtains 4.32,4.46 respectively, the Sulfur capacity and 20,23 of 4.41gS/100g sweetening agent, the time of break-through of 21h.
Embodiment 5: the sweetening agent I that makes carries out three sulfurations and regeneration tests, and the sulfuration experimental temperature is 500 ℃, and it is CO (33%) that reactant gases is formed (volume ratio), H
2(39%), H
2O (5%), H
2S (300ppm), N
2As balance gas, air speed 2000h
-1Work as H
2The S exit concentration is during greater than 1ppm, and the Sulfur capacity of sweetening agent is respectively 4.46,4.03,3.95 and the 4.01gS/100g sweetening agent behind fresh sweetening agent that obtains and the tertiary recycling.Sulfur capacity after sweetening agent is regenerated the for the first time 0.43gS/100g sweetening agent that descended, but Sulfur capacity is constant basically in three times later sulfuration regeneration tests, and it is stable that sweetening effectiveness keeps, and has good cycle thermal stability.
Claims (4)
1. coal gas of high temperature desulfurizing agent in the zinc oxide is characterized in that it being the following process step of a kind of employing:
I, the raw material semi-coke powder is broken into the 4-8 order;
II, the semicoke that I is pulverized and mass concentration are that 5-24% zinc nitrate steeping fluid is to place autoclave at 0.7: 1 by volume, under 8-28atm impregnating by pressure 3-7 hour, naturally cool to room temperature;
III, the sample that the II impregnating by pressure is good take out in autoclave, place on the filter flask, and the zinc nitrate solution that will not be impregnated into above the carrier carries out solid-liquid separation through filter paper or filter membrane;
IV, with the solid sample after the III solid-liquid separation, in air drying cabinet at first 50-70 ℃ dry 3-10 hour down, and then 100-120 ℃ dry 3-10 hour down;
V, with the dry good sample of IV again in nitrogen atmosphere; 400-600 ℃ temperature lower calcination 3-7 hour, the sweetening agent that makes, this sweetening agent are coal gas of high temperature desulfurizing agents in a kind of wide material sources, low-cost can be under the middle high temperature 300-550 ℃ strongly reducing atmosphere smart zinc oxide that removes hydrogen sulfide; This desulfurizer active component is evenly distributed at carrier surface; And particle diameter is 10-40mm, and this sweetening agent evaluation index is: when exporting concentration of hydrogen sulfide greater than 1ppm, think that promptly sweetening agent penetrates; Curing time equals time of break-through, and the accumulation Sulfur capacity in the time of break-through is the sweetening agent Sulfur capacity.
2. the preparation method of coal gas of high temperature desulfurizing agent in the zinc oxide; It is characterized in that it being a kind of employing wide material sources; Low-cost semicoke and zinc oxide active ingredient make has thermostability preferably, can be widely used in the coal preparation method of coal gas of high temperature desulfurizing agent in the desulfurizing and purifying field of the reductibility material gas that is feedstock production, can be under the middle high temperature strongly reducing atmosphere smart zinc oxide that removes hydrogen sulfide; This method is with semicoke support modification and activity component impregnation two steps unification; When enlarging the carrier specific surface area, activity component impregnation is arrived carrier; The carrier hole structure is improved and two kinds of effects of component load can be accomplished in autoclave simultaneously, and its concrete process step is:
I, the raw material semi-coke powder is broken into the 4-8 order;
II, the semicoke that I is pulverized and mass concentration are that 5-24% zinc nitrate steeping fluid is to place autoclave at 0.7: 1 by volume, under 8-28atm impregnating by pressure 3-7 hour, naturally cool to room temperature;
III, the sample that the II impregnating by pressure is good take out in autoclave, place on the filter flask, and the zinc nitrate solution that will not be impregnated into above the carrier carries out solid-liquid separation through filter paper or filter membrane;
IV, with the solid sample after the III solid-liquid separation, in air drying cabinet at first 50-70 ℃ dry 3-10 hour down, and then 100-120 ℃ dry 3-10 hour down;
V, with the dry good sample of IV again in nitrogen atmosphere, 400-600 ℃ temperature lower calcination 3-7 hour, promptly make sweetening agent.
3. according to the preparation method of coal gas of high temperature desulfurizing agent in the described zinc oxide of claim 2, it is characterized in that described semicoke is brown coal or bituminous coal semicoke, its bulk density is 0.55-0.73g/ml, and specific surface area is 10.07-265.49m
2/ g, volatile content are 3-15%.
4. according to the preparation method of coal gas of high temperature desulfurizing agent in the described zinc oxide of claim 2, it is characterized in that described nitrogen atmosphere is 99.99% pure nitrogen gas.
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| CN102430383B (en) * | 2011-11-04 | 2013-08-28 | 太原理工大学 | Preparation method of adsorbing agent simultaneously removing H2S and Hg in middle temperature coal gas |
| CN104226248B (en) * | 2014-09-04 | 2016-03-02 | 太原理工大学 | A kind of preparation method of semicoke Supported Manganese copper adsorbent and the application of adsorbent thereof |
| CN104437072B (en) * | 2014-11-21 | 2016-03-16 | 太原理工大学 | A kind of preparation method of middle desulfurizing agent for high-temp gas |
| CN107903949B (en) * | 2017-11-15 | 2019-05-07 | 太原理工大学 | A kind of coke oven gas desulfurization denitrogenation takes off the deep-purifying method of benzene hydrocarbon |
| CN109526983B (en) * | 2018-12-29 | 2021-07-13 | 中国科学院兰州化学物理研究所 | Method for preparing hybrid antibacterial agent by using oil shale semicoke |
| CN112705163A (en) * | 2020-12-22 | 2021-04-27 | 长沙工研院环保有限公司 | Multi-metal in-situ doped desulfurizer based on low-coalification-degree inferior coal and preparation method thereof |
| CN117563556B (en) * | 2024-01-16 | 2024-04-02 | 北京北大先锋科技股份有限公司 | Renewable load-type desulfurizing agent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4233275A (en) * | 1977-12-02 | 1980-11-11 | Hitachi, Ltd. | Process and apparatus for purifying raw coal gas |
| CN1047219A (en) * | 1990-02-27 | 1990-11-28 | 黄家鹄 | Remove the low-temp desulfurization agent of organosulfur in the gas |
| CN1907544A (en) * | 2006-07-28 | 2007-02-07 | 哈尔滨工业大学 | Normal temperature nanometer desulfurizing agent and its preparation process |
| CN101053735A (en) * | 2007-04-27 | 2007-10-17 | 许庆华 | Montmorillonite as natural gas desulfurizing agent |
-
2009
- 2009-12-11 CN CN 200910175382 patent/CN101735861B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4233275A (en) * | 1977-12-02 | 1980-11-11 | Hitachi, Ltd. | Process and apparatus for purifying raw coal gas |
| CN1047219A (en) * | 1990-02-27 | 1990-11-28 | 黄家鹄 | Remove the low-temp desulfurization agent of organosulfur in the gas |
| CN1907544A (en) * | 2006-07-28 | 2007-02-07 | 哈尔滨工业大学 | Normal temperature nanometer desulfurizing agent and its preparation process |
| CN101053735A (en) * | 2007-04-27 | 2007-10-17 | 许庆华 | Montmorillonite as natural gas desulfurizing agent |
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