CN106701247A - Method for preparing tar residue solid fuel by pyrolyzing tar residue - Google Patents

Method for preparing tar residue solid fuel by pyrolyzing tar residue Download PDF

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Publication number
CN106701247A
CN106701247A CN201510810954.3A CN201510810954A CN106701247A CN 106701247 A CN106701247 A CN 106701247A CN 201510810954 A CN201510810954 A CN 201510810954A CN 106701247 A CN106701247 A CN 106701247A
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China
Prior art keywords
tar slag
tar
temperature
slag
pyrolysis
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Pending
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CN201510810954.3A
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Chinese (zh)
Inventor
孙承林
于杨
杨旭
卫皇瞾
荣欣
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CN201510810954.3A priority Critical patent/CN106701247A/en
Publication of CN106701247A publication Critical patent/CN106701247A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/48—Solid fuels essentially based on materials of non-mineral origin on industrial residues and waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • C10L5/447—Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/46—Solid fuels essentially based on materials of non-mineral origin on sewage, house, or town refuse
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/02—Combustion or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/08—Drying or removing water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

The invention relates to a method for preparing tar residue solid fuel by pyrolyzing tar residue. The method comprises the following steps: by adopting the waste tar residue produced by a tar factory as a raw material, removing moisture of the waste tar residue at 80 to 120 DEG C, adding a given amount of additives, uniformly mixing, and extruding to form strips; and carbonizing the mixture under a condition of insulating air at 300 to 800 DEG C to obtain the tar residue solid fuel. The tar residue solid fuel has the characteristics of high calorific value, solid form at normal temperature, convenience in transportation and storage and the like, so that the harmless utilization and recycling of the tar residue are facilitated.

Description

A kind of method that tar slag pyrolysis prepares tar slag solid fuel
Technical field
The present invention relates to the method that a kind of pyrolysis of tar slag prepares tar slag solid fuel, it is adaptable to produce coke-oven plant Raw useless tar slag harmless treatment, belongs to solid waste resource recovery disposal field.
Background technology
Since 21 century, as economic develops rapidly, the steel industry of China enters fast-developing rank Section, China has turned into coke production, the first big country of consumption and outlet.During coke-oven plant's coking is produced, Under conditions of discharge or primary cooler cooling, high boiling organic compound is condensed shape high temperature coke oven coal gas Into coal tar, coal dust, the semicoke carried secretly in coal gas etc. is also mingled in coal tar, the group that formation is differed in size Block, these agglomerates are referred to as tar slag.The main component of tar slag is the carbon containing thing of polymerization with certain armaticity Matter.Wherein containing about 60% fixed carbon, the content of volatile matter is about 33%, and content of ashes is 4%, sulphur Content about 1.6%.Tar slag is the discarded object with pollution property produced during coking production, if Dealing with improperly can bring extremely serious environmental problem, such as contaminated land, water source.
Dependence is compared in utilization due to China to coal, and substantial amounts of Jiao can be produced in the evolution of coking industry The dregs of fat, nearly million tons of the tar slag that the annual coking industry in the whole nation is produced, in the middle of actual production and reclaiming, one As be that tar slag is carried out into stacking storage, tar slag overstocks for a long time, and storage capacity is not enough, the environment meeting of surrounding Had a strong impact on by tar slag bath, the utilization for how solving tar slag is one of bottleneck of following coking development. Carbon and coal tar and light components containing a large amount of uncombusteds in tar slag, combustion heat value are high, can be as combustion Material.Due to containing a certain amount of moisture in coal, can be escaped during coking, by can also be deposited after condensation It is that in tar slag, can improve tar slag mobility, is unfavorable for transport；The presence of moisture also results in Jiao The reduction of dregs of fat calorific value, therefore original tar slag is unfavorable for directly as fuel.
The tar slag pyrolytic process of present invention description is that tar slag is heated under conditions of air is completely cut off, The light components in tar slag are evaporated, then by condensation process withdrawal liquid fuel, the liquid of recovery Fuel can be processed into industrial fuel oil, and the tar slag solid fuel calorific value for being produced is high, by pyrolysis Tar slag moisture declines, it is easier to shipping storage.
The content of the invention
The present invention relates to the method that a kind of pyrolysis of tar slag prepares tar slag solid fuel, it is adaptable to produce coke-oven plant Raw useless tar slag harmless treatment, belongs to solid waste resource recovery disposal field, and the inventive method is solved Tar slag transport difficult, the relatively low technical problem of calorific value.
The method and step that the tar slag pyrolysis that the present invention is provided prepares tar slag solid fuel is as follows：
1) tar slag dried, crushed；
2) the tar slag extrusion for obtaining will be crushed, column tar slag is obtained；
Or, the tar slag for obtaining will be crushed and mixed with kaolin and/or activated carbon and/or sludge, extrusion, Obtain column tar slag；
3) under conditions of air is completely cut off, by step 2) the column tar slag that obtains is with 2~10 DEG C/min's After speed carries out 2~8h of pyrolysis at being warming up to 300~800 DEG C, normal temperature is cooled to, that is, obtains tar slag solid Fuel.
Step 1) in drying temperature be 80~120 DEG C, drying time be 10~72h, the tar slag after crushing Particle diameter is 2~10mm.
Step 1) described in dry, crush after tar slag in water content be less than 5%.
Step 2) in, in terms of 100 parts of weight content, tar slag is 80-100 parts to raw material, surplus stock choosing One or two or three kinds from kaolin, activated carbon, sludge, the kaolin are 0-20 part, active Charcoal is 0-20 parts, and sludge is 0-20 parts.
One kind in sludge, river bottom mud that the sludge is produced most preferably from city domestic sewage treatment plant or Two kinds.
Step 2) in extrusion when tar slag temperature be maintained between 20~60 DEG C.
Step 2) in a diameter of 4~10mm of column tar slag, length is 2mm-1cm.
Step 3) it is described isolation air pyrolytic reaction is carried out using nitrogen displacement air or in closed reactor.
Step 3) in preferably pyrolysis temperature be 550-650 DEG C, preferably pyrolysis time be 0.5-4h.
Step 3) under conditions of air is completely cut off, the temperature of reactor is gradually risen to pyrolysis temperature, purge out Temperature is reduced after the tar for coming is contacted with water, and insoluble with water, reclaims condensate liquid.
According to the tar slag solid fuel that the above method is prepared, calorific value is more than 25MJ/kg, substantially may be used To reach 30MJ/kg.
The advantages of the present invention are：
The inventive method causes that the moisture content of initial tar slag is reduced to 0~3%, initial tar slag by 10~30% Solid-state is changed into from liquid, calorific value improves 10~30%.
The present invention relates to a kind of method that tar slag pyrolysis prepares fuel, it is adaptable to the useless tar that coke-oven plant produces Slag harmlessness treatment, belongs to solid waste resource recovery disposal field.
Specific embodiment
The present invention is described in detail with reference to embodiment.
Embodiment 1
1. the tar slag for coke-oven plant being produced, 24h is dried at 105 DEG C, and carry out mechanical crushing, tar slag Middle water content is less than 5%；
2. the tar slag after crushing is mixed with kaolin, based on mass fraction 100, tar slag is 90 to raw material Part, kaolin is 10 parts, and column tar slag is obtained through extrusion, and during extrusion, it is 60 DEG C to keep tar slag temperature, Extrude a diameter of 5mm；
3. under conditions of air is completely cut off, the column tar slag that step (2) is obtained is with the speed of 3 DEG C/min After carrying out pyrolysis 3h at being warming up to 500 DEG C, normal temperature is cooled to, that is, obtains tar slag solid fuel, its calorific value It is 29.06MJ/kg.Temperature is reduced after pyrolysis tar out is contacted with water, and insoluble with water, reclaims condensation Liquid.
Embodiment 2
1. the tar slag for coke-oven plant being produced, 48h is dried at 80 DEG C, and carries out mechanical crushing, obtains tar Slag blocks of solid；
2. gained tar slag blocks of solid mixes with activated carbon, and based on mass fraction 100, tar slag is raw material 85 parts, activated carbon is 15 parts, and column tar slag is obtained through extrusion, and tar slag blocks of solid temperature is during extrusion 40 DEG C, extrude a diameter of 8mm；
3. under a nitrogen atmosphere, the column tar slag that step (2) is obtained is warming up to the speed of 10 DEG C/min After carrying out pyrolysis 2h at 600 DEG C, normal temperature is cooled to, that is, obtains tar slag solid fuel, its calorific value is 31.19 MJ/kg.Temperature is reduced after pyrolysis tar out is contacted with water, and insoluble with water, reclaims condensate liquid.
Embodiment 3
1. the tar slag for coke-oven plant being produced, 72h is dried at 120 DEG C, and carries out mechanical crushing, obtains Jiao Dregs of fat blocks of solid；
2. gained tar slag blocks of solid mixes with sludge, and based on mass fraction 100, tar slag is 92 to raw material Part, the sludge that city sewage plant is produced is 8 parts, obtains column tar slag through extrusion, tar during extrusion Clinker shape solid temperature is 50 DEG C, extrudes a diameter of 10mm；
3. under a nitrogen atmosphere, the column tar slag that step (2) is obtained is warming up to the speed of 8 DEG C/min After carrying out pyrolysis 4h at 800 DEG C, normal temperature is cooled to, that is, obtains tar slag solid fuel, its calorific value is 27.54 MJ/kg.Temperature is reduced after pyrolysis tar out is contacted with water, and insoluble with water, reclaims condensate liquid.
Embodiment 4
1. the tar slag for coke-oven plant being produced, 48h is dried at 120 DEG C, and carries out mechanical crushing, obtains Jiao Dregs of fat blocks of solid；
2. gained tar slag blocks of solid obtains column tar slag through extrusion, extrudes a diameter of 9mm；
3. under a nitrogen atmosphere, the column tar slag that step (2) is obtained is warming up to the speed of 3 DEG C/min After carrying out pyrolysis 2h at 500 DEG C, normal temperature is cooled to, that is, obtains tar slag solid fuel, its calorific value is 34.93 MJ/kg.Temperature is reduced after pyrolysis tar out is contacted with water, and insoluble with water, reclaims condensate liquid.
Embodiment 5
1. the tar slag for coke-oven plant being produced, 30h is dried at 100 DEG C, and carries out mechanical crushing, obtains Jiao Dregs of fat blocks of solid；
2. gained tar slag blocks of solid mixes with activated carbon, and based on mass fraction 100, tar slag is raw material 93 parts, activated carbon is 7 parts, and tar slag blocks of solid temperature is 45 when obtaining column tar slag extrusion through extrusion DEG C, extrude a diameter of 5mm；
3. under a nitrogen atmosphere, the column tar slag that step (2) is obtained is warming up to the speed of 5 DEG C/min After carrying out pyrolysis 5h at 400 DEG C, normal temperature is cooled to, that is, obtains tar slag solid fuel, its calorific value is 33.85 MJ/kg.Temperature is reduced after pyrolysis tar out is contacted with water, and insoluble with water, reclaims condensate liquid.
Embodiment 6
1. the tar slag for coke-oven plant being produced, 32h is dried at 105 DEG C, and carries out mechanical crushing, obtains Jiao Dregs of fat blocks of solid；
2. gained tar slag blocks of solid mix with activated carbon and kaolin, raw material based on mass fraction 100, Tar slag is 92 parts, and activated carbon is 4 parts, and kaolin is 4 parts, and column tar slag, extrusion are obtained through extrusion When tar slag blocks of solid temperature be 55 DEG C, extrude a diameter of 6mm；
3. under a nitrogen atmosphere, the column tar slag that step (2) is obtained is warming up to the speed of 4 DEG C/min After carrying out pyrolysis 4.5h at 450 DEG C, normal temperature is cooled to, that is, obtains tar slag solid fuel, its calorific value is 32.56 MJ/kg。
Embodiment 7
1. the tar slag for coke-oven plant being produced, 32h is dried at 105 DEG C, and carries out mechanical crushing, obtains Jiao Dregs of fat blocks of solid；
2. gained tar slag blocks of solid mixes with sludge, and based on mass fraction 100, tar slag is 96 to raw material Part, the sludge that city sewage plant is produced is 4 parts, obtains column tar slag through extrusion, tar during extrusion Clinker shape solid temperature is 50 DEG C, extrudes a diameter of 6mm；
3. under a nitrogen atmosphere, the column tar slag that step (2) is obtained is warming up to the speed of 3 DEG C/min After carrying out pyrolysis 4.5h at 450 DEG C, normal temperature is cooled to, that is, obtains tar slag solid fuel, its calorific value is 30.14 MJ/kg, and the common activated carbon calorific value of in the market is only 22~20MJ/kg, tar slag solid fuel calorific value is bright Aobvious is higher than normal activated carbon calorific value.Temperature is reduced after pyrolysis tar out is contacted with water, and insoluble with water, Reclaim condensate liquid.

Claims (10)

1. a kind of method that tar slag pyrolysis prepares tar slag solid fuel, it is characterised in that：Including following step Suddenly：
1) tar slag dried, crushed；
2) the tar slag extrusion for obtaining will be crushed, column tar slag is obtained；
Or, the tar slag for obtaining will be crushed and mixed with kaolin and/or activated carbon and/or sludge, extrusion, Obtain column tar slag；
3) under conditions of air is completely cut off, by step 2) the column tar slag that obtains is with the speed of 2~10 DEG C/min After rate carries out 2~8h of pyrolysis at being warming up to 300~800 DEG C, normal temperature is cooled to, that is, obtains the combustion of tar slag solid Material.
2. in accordance with the method for claim 1, it is characterised in that：
Step 1) in drying temperature be 80~120 DEG C, drying time be 10~72h, the tar slag after crushing Particle diameter is 2~10mm.
3. in accordance with the method for claim 1, it is characterised in that：Step 1) described in dry, crush after Tar slag in water content be less than 5%.
4. in accordance with the method for claim 1, it is characterised in that：Step 2) in, raw material is with weight content 100 parts of meters, tar slag is 80-100 parts, and surplus stock is selected from the one kind in kaolin, activated carbon, sludge Or two or three, the kaolin is 0-20 parts, and activated carbon is 0-20 parts, and sludge is 0-20 parts.
5. according to the preparation method described in claim 1, it is characterised in that：Step 2) in extrusion when tar slag Temperature be maintained between 20~60 DEG C.
6. according to the preparation method described in claim 1, it is characterised in that：Step 2) in column tar slag it is straight Footpath is 4~10mm, and length is 2mm-1cm.
7. in accordance with the method for claim 1, it is characterised in that：Step 3) it is described isolation air use nitrogen Gas displaced air carries out pyrolytic reaction in closed reactor.
8. in accordance with the method for claim 1, it is characterised in that：Step 3) in preferably pyrolysis temperature be 550-650 DEG C, preferably pyrolysis time is 0.5-4h.
9. in accordance with the method for claim 1, it is characterised in that：Step 3) under conditions of air is completely cut off, The temperature of reactor is gradually risen to pyrolysis temperature, temperature is reduced after the tar for purging out is contacted with water, and It is insoluble with water, reclaim condensate liquid.
10. the tar slag solid fuel that a kind of any methods describeds of claim 1-9 are prepared.
CN201510810954.3A 2015-11-18 2015-11-18 Method for preparing tar residue solid fuel by pyrolyzing tar residue Pending CN106701247A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107903980A (en) * 2017-11-22 2018-04-13 云南大地绿坤环保科技有限公司 A kind of method that tar slag is modified
CN108504412A (en) * 2018-04-24 2018-09-07 佛山市尚柏科技有限公司 A kind of preparation method of sludge solid fuel
CN111961492A (en) * 2020-08-15 2020-11-20 新疆新业能源化工有限责任公司 Tar residue resource utilization process
CN112830489A (en) * 2021-01-20 2021-05-25 煤炭科学技术研究院有限公司 Resourceful treatment method for coal tar residues

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1693190A (en) * 2005-04-08 2005-11-09 中钢集团鞍山热能研究院 Method for mfg. particle active carbon and light coal tar by tar dregs

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1693190A (en) * 2005-04-08 2005-11-09 中钢集团鞍山热能研究院 Method for mfg. particle active carbon and light coal tar by tar dregs

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107903980A (en) * 2017-11-22 2018-04-13 云南大地绿坤环保科技有限公司 A kind of method that tar slag is modified
CN108504412A (en) * 2018-04-24 2018-09-07 佛山市尚柏科技有限公司 A kind of preparation method of sludge solid fuel
CN111961492A (en) * 2020-08-15 2020-11-20 新疆新业能源化工有限责任公司 Tar residue resource utilization process
CN112830489A (en) * 2021-01-20 2021-05-25 煤炭科学技术研究院有限公司 Resourceful treatment method for coal tar residues

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Application publication date: 20170524