CN105903324A - Copper oxide loaded active carbon desulfurizing agent and preparation process thereof - Google Patents

Copper oxide loaded active carbon desulfurizing agent and preparation process thereof Download PDF

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Publication number
CN105903324A
CN105903324A CN201610332695.2A CN201610332695A CN105903324A CN 105903324 A CN105903324 A CN 105903324A CN 201610332695 A CN201610332695 A CN 201610332695A CN 105903324 A CN105903324 A CN 105903324A
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CN
China
Prior art keywords
active carbon
activated carbon
copper oxide
desulfurizing agent
oxide loaded
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Pending
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CN201610332695.2A
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Chinese (zh)
Inventor
张天喜
仝雪城
仝子禄
张福元
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Tianjin Puritech Materials Co Ltd
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Tianjin Puritech Materials Co Ltd
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Priority to CN201610332695.2A priority Critical patent/CN105903324A/en
Publication of CN105903324A publication Critical patent/CN105903324A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • 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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention provides a copper oxide loaded active carbon desulfurizing agent. The copper oxide loaded active carbon desulfurizing agent is prepared from the following raw materials according to the following weight proportion: 80-99 parts of an active carbon carrier and 3-42 parts of copper nitrate trihydrate Cu(NO3)2.3H2O. A preparation method comprises the following steps: (1) pre-treating active carbon, namely selecting the active carbon carrier with the granularity between 2-40 meshes; (2) immersing, namely weighing the screened active carbon carrier according to the ratio and weighing Cu(NO3)2.3H2O and completely dissolving Cu(NO3)2.3H2O into water; then pouring a copper nitrate trihydrate solution into a beaker filled with the active carbon and stirring; standing the immersed active carbon at the room temperature for 3h-5h; in the standing process, overturning and stirring for one time every one hour so as to sufficiently immerse the active carbon; (3) drying; (4) carrying out high-temperature calcining, namely after drying, transferring the active carbon into a heating furnace and heating; cooling to obtain the copper oxide loaded active carbon desulfurizing agent; and (5) discharging from the furnace and packaging. The copper oxide loaded active carbon desulfurizing agent has an efficient desulfurizing capability and long service life; and the preparation process is simple and efficient and is suitable for industrial production.

Description

The activated carbon desulphurization agent of a kind of loaded copper oxide and preparation technology thereof
Technical field
The invention belongs to technical field of waste gas treatment, particularly to the activity of a kind of loaded copper oxide Charcoal desulfurizing agent and preparation technology thereof.
Background technology
China be coal production in the world and consumption the first big country, in coal gas sulphur the overwhelming majority with H2Presented in S, along with the burning of coal gas produces SO2, the SO of excess in environment2Can cause The formation of acid rain, the living environment of harm people.Along with mankind's airborne release to environmental pollutants The requirement of standard improves constantly, and in the combustion gas such as the natural gas used in industrial production, coal gas The restriction increasingly stringent of concentration of hydrogen sulfide, country the most gradually improves the various environment that hydrogen sulfide is relevant Standard and professional standard, China specifies its SO to burning producer gas stove2Maximum emission is dense Degree is 900mg/m3。
At present, the desulfurization technology of some maturations is widely used the most in the industrial production. According to desulfurization environment and mode of operation, sulfur method can be divided into 1, wet desulphurization: the method is Utilize specific solvent, be fully contacted reaction with waste gas and carry out desulfurization, apply in general to a large amount of The occasion that gas, sulfur content are high, its flow process is complicated, investment is higher.2, dry desulfurization: should Method is to utilize absorbent, adsorbent and catalyst etc., such as activated carbon, iron oxide, oxidation Zinc etc. carry out desulfurization, and efficiency is higher, apply in general to the fine desulfurization of the waste gas of relatively low sulfur content.
Activated carbon is a kind of porous material manually made, because of its have substantial amounts micropore, Mesoporous and higher specific surface area, is a kind of excellent absorption carrier, by bearing on the activated carbon Carry metal oxide catalyst, can significantly improve the desulphurizing ability of activated carbon, and have can be again Raw feature, is a kind of composite adsorbing material with extensive application potential and Development volue.
Summary of the invention
It is an object of the invention to provide the activated carbon desulphurization agent of a kind of loaded copper oxide, this desulfurizing agent There is high-efficiency desulfurization ability.
It is a further object of the present invention to provide the preparation technology of above-mentioned activated carbon desulphurization agent.
As above conceive, the technical scheme is that the active carbon desulfurization of a kind of loaded copper oxide Agent, it is characterised in that: it is made up according to following weight proportion of following raw materials according: absorbent charcoal carrier 80-99 part, nitrate trihydrate copper Cu (NO3)2·3H2O 3-42 part.
The preparation method of above-mentioned activated carbon desulphurization agent is as follows:
1. the pretreatment of activated carbon: select granule size absorbent charcoal carrier between 2-40 mesh；
2. dipping: weigh the absorbent charcoal carrier screened in proportion, then weigh Cu (NO3)2·3H2O, And it is dissolved completely in water, then pour nitrate trihydrate copper solution into burning equipped with activated carbon Stir in Bei, the activated carbon of dipping is stood 3-5h, every 1h during standing under normal temperature Need to stir once, make activated carbon be sufficiently impregnated with；
3. dry: be transferred in drying plant at 80-100 DEG C dry by the activated carbon after dipping 7-9h, notes stirring once every 1-2 hour needs；
4. high-temperature calcination: heat activated carbon being transferred in heating furnace after drying, and High-temperature heating 2-3h at 280-350 DEG C, slightly takes out after cooling, i.e. obtains the work of loaded copper oxide Property charcoal desulfurizing agent；
5. come out of the stove packaging.
Above-mentioned steps 2. under conditions of making nitrate trihydrate copper be completely dissolved keep water with activity The proportion of charcoal is 0.5-1.
The renovation process of the activated carbon desulphurization agent of above-mentioned loaded copper oxide is: at 250-400 DEG C of bar Under part, being passed through ammonia in the desulfurizing agent after using, flow velocity is 90-120ml/min, and ventilation is held Its regeneration can be realized after continuous 80-120min.
Advantages of the present invention and effect be:
1, after the micropore surface of activated carbon is loaded substantial amounts of cupric oxide by the present invention, defining can The composite catalyzing sorbing material of regeneration, has efficient desulphurizing ability and service life.
2, the present invention is with activated carbon as absorption carrier, and light weight, stability are strong and economical and practical.
3, the preparation technology that the present invention relates to is simple, efficient, is suitable for industrialized production.
Detailed description of the invention
By laboratory prepare 1kg containing cupric oxide be 12% activated carbon as a example by, comprise the steps:
1, the pretreatment of activated carbon:
Selecting the granular size after screening is that 4X10 mesh, iodine number are at the raw coal of more than 1000mg/g Briquetting charcoal is as activated carbon base charcoal.
2, dipping:
Weigh the activated carbon 900g screened in proportion, then weigh Cu (NO3)2·3H2O, (three The amount of water copper nitrate is obtained by the mass conversion of cupric oxide, and improves 0.5-2 according to proportioning target Part, the part to load the most completely in supplementary loading process) the present embodiment weighs Cu(NO3)2·3H2(ratio being equivalent to cupric oxide 135g, i.e. cupric oxide is 13% to O409g.) It is dissolved completely in 800ml water and (is kept under conditions of making nitrate trihydrate copper be completely dissolved The proportion of water-bath activated carbon is between 0.5-1), then copper nitrate solution is delayed in three times Slowly pour into equipped with in the beaker of activated carbon, be stirred continuously with glass bar simultaneously.Activity by dipping Charcoal stands 4h under normal temperature, need to stir once every 1h during standing, makes activated carbon obtain It is sufficiently impregnated with.
3, dry:
Activated carbon after dipping is transferred in pallet, place in constant temperature blast drying oven in Dry 8h at 90 DEG C, stir once every 2h.
4, high-temperature calcination:
Heat activated carbon being put in heater after drying, and high-temperature heating at 300 DEG C 2.5 hours, slightly take out after cooling, i.e. obtain the activated carbon of loaded copper oxide.
2Cu(NO3)2=2CuO+4NO2↑+O2↑
5, come out of the stove packaging:
Activated carbon after load is cooled to normal temperature after coming out of the stove, and checks other indexs, will meet the requirements Activated carbon load plastics valve bag, reinstall in 1L polyethylene bottle, seal also the most labelled.
The activated carbon desulphurization agent regeneration of the loaded copper oxide after 6, using:
Under the conditions of 300 DEG C, being passed through ammonia in the desulfurizing agent after using, flow velocity is 100ml/min, ventilation can realize its regeneration after continuing 100min.

Claims (4)

1. the activated carbon desulphurization agent of a loaded copper oxide, it is characterised in that: pressed by following raw materials according Make according to following weight proportion: absorbent charcoal carrier 80-99 part, nitrate trihydrate copper Cu(NO3)2·3H2O 3-42 part.
2. the system of the activated carbon desulphurization agent of a loaded copper oxide according to claim 1 Standby technique, it is characterised in that: comprise the steps:
1. the pretreatment of activated carbon: select granule size absorbent charcoal carrier between 2-40 mesh；
2. dipping: weigh the absorbent charcoal carrier screened in proportion, then weigh Cu (NO3)2·3H2O, And it is dissolved completely in water, then pour nitrate trihydrate copper solution into burning equipped with activated carbon Stir in Bei, the activated carbon of dipping is stood 3-5h, every 1h during standing under normal temperature Need to stir once, make activated carbon be sufficiently impregnated with；
3. dry: be transferred in drying plant at 80-100 DEG C dry by the activated carbon after dipping 7-9h, notes stirring once every 1-2 hour needs；
4. high-temperature calcination: heat activated carbon being transferred in heating furnace after drying, and High-temperature heating 2-3h at 280-350 DEG C, slightly takes out after cooling, i.e. obtains the work of loaded copper oxide Property charcoal desulfurizing agent；
5. come out of the stove packaging.
The preparation work of the activated carbon desulphurization agent of loaded copper oxide the most according to claim 2 Skill, it is characterised in that: above-mentioned steps 2. under conditions of making nitrate trihydrate copper be completely dissolved protect Water holding is 0.5-1 with the proportion of activated carbon.
The preparation work of the activated carbon desulphurization agent of loaded copper oxide the most according to claim 2 Skill, it is characterised in that: under the conditions of 250-400 DEG C, the work of the loaded copper oxide after using Property charcoal desulfurizing agent in be passed through ammonia, flow velocity is 90-120ml/min, ventilation continue 80-120min After can realize its regeneration.
CN201610332695.2A 2016-05-18 2016-05-18 Copper oxide loaded active carbon desulfurizing agent and preparation process thereof Pending CN105903324A (en)

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Application Number Priority Date Filing Date Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107583636A (en) * 2017-10-17 2018-01-16 天津普瑞特净化技术有限公司 A kind of activated carbon desulphurization agent of supported magnesium oxide and preparation method thereof
CN113522234A (en) * 2021-06-28 2021-10-22 中国兵器工业第五九研究所 Sulfur dioxide adsorption material and preparation method thereof
CN115010238A (en) * 2022-06-23 2022-09-06 天津市创嘉生物技术有限公司 Water purifying agent and preparation method thereof
CN117563556A (en) * 2024-01-16 2024-02-20 北京北大先锋科技股份有限公司 Renewable load-type desulfurizing agent and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1876232A (en) * 2006-07-04 2006-12-13 北京交通大学 Activated charcoal carried copper oxide catalyst and process for preparing same
CN101804289A (en) * 2010-03-31 2010-08-18 淮阴工学院 Preparation of flue gas desulfurizer and use and regeneration method thereof
CN101879435A (en) * 2010-06-08 2010-11-10 华东理工大学 High-adsorption-capacity room-temperature nitrogen oxide adsorbent and preparation method thereof
CN102500362A (en) * 2011-12-02 2012-06-20 中国科学院山西煤炭化学研究所 Catalyst for removing H2S from gas by catalytic oxidation, preparation method and application
CN102512941A (en) * 2011-12-08 2012-06-27 西安瑞金源能源科技有限责任公司 Preparation method of desulfurizer
CN102580525A (en) * 2012-03-21 2012-07-18 河北工业大学 Method for using activated carbon load copper oxide composite catalyst to absorb nitrogenous oxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1876232A (en) * 2006-07-04 2006-12-13 北京交通大学 Activated charcoal carried copper oxide catalyst and process for preparing same
CN101804289A (en) * 2010-03-31 2010-08-18 淮阴工学院 Preparation of flue gas desulfurizer and use and regeneration method thereof
CN101879435A (en) * 2010-06-08 2010-11-10 华东理工大学 High-adsorption-capacity room-temperature nitrogen oxide adsorbent and preparation method thereof
CN102500362A (en) * 2011-12-02 2012-06-20 中国科学院山西煤炭化学研究所 Catalyst for removing H2S from gas by catalytic oxidation, preparation method and application
CN102512941A (en) * 2011-12-08 2012-06-27 西安瑞金源能源科技有限责任公司 Preparation method of desulfurizer
CN102580525A (en) * 2012-03-21 2012-07-18 河北工业大学 Method for using activated carbon load copper oxide composite catalyst to absorb nitrogenous oxide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107583636A (en) * 2017-10-17 2018-01-16 天津普瑞特净化技术有限公司 A kind of activated carbon desulphurization agent of supported magnesium oxide and preparation method thereof
CN113522234A (en) * 2021-06-28 2021-10-22 中国兵器工业第五九研究所 Sulfur dioxide adsorption material and preparation method thereof
CN115010238A (en) * 2022-06-23 2022-09-06 天津市创嘉生物技术有限公司 Water purifying agent and preparation method thereof
CN117563556A (en) * 2024-01-16 2024-02-20 北京北大先锋科技股份有限公司 Renewable load-type desulfurizing agent 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

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Application publication date: 20160831