CN105295981A - Method for promoting quality of oil pyrolyzed from sludge - Google Patents

Method for promoting quality of oil pyrolyzed from sludge Download PDF

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Publication number
CN105295981A
CN105295981A CN201510662755.2A CN201510662755A CN105295981A CN 105295981 A CN105295981 A CN 105295981A CN 201510662755 A CN201510662755 A CN 201510662755A CN 105295981 A CN105295981 A CN 105295981A
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sludge
oil
pyrolyzed
mud
pyrolysis
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CN105295981B (en
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李宝霞
翁连进
于庆杰
卫文娟
酒帮帮
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Huaqiao University
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Huaqiao University
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    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

Abstract

The invention provides a method for promoting the quality of oil pyrolyzed from sludge. The method provided by the invention comprises the following steps: mixing sludge, waste biomass and a catalyst according to a weight ratio of 1: (1.0 to 1.5): (0.01 to 0.05); putting the mixture in a fixed bed reactor under a nitrogen atmosphere, segmentally pyrolyzing according to a certain temperature rise program, gradually raising the temperature to 550 DEG C, and condensing generated gas in a condensation device, wherein the yield and the quality of the obtained pyrolyzed oil, which are higher than those of oil pyrolyzed from pure sludge under the same conditions, are respectively: the oil productivity (no water base) is 35% to 45%, the lower calorific value is 30 to 35MJ/kg and the velocity is 15 to 18mm<2>/g. According to the method provided by the invention, the waste biomass and the sludge are co-pyrolyzed, the advantage that the waste biomass and the sludge are pyrolyzed separately is utilized sufficiently to supplement each other, the quality of the oil pyrolyzed from the sludge is promoted, the environmental pollution problem of the two wastes is solved, and clean and high-efficient resource utilization of the two wastes is realized.

Description

A kind of method promoting pyrolyzing sludge oil quality
Technical field
The present invention relates to a kind of method of waste remediation and recycling, particularly relate to a kind of method utilizing abandoned biomass and mud copyrolysis to promote pyrolyzing sludge oil quality.
Background technology
Environmental pollution and energy dilemma have become the two large problems that society exists, and receive the extensive concern of various circles of society.How while meeting energy demand, the global environment mankind being protected to depend on for existence again becomes one of focus of scientific research instantly.And the mud of municipal wastewater treatment station (abbreviation mud) is as a kind of complicated component, quantity discharged is huge, the sewage purification by product that environmental toxicity is strong, carries out minimizing to it, stabilization, resource utilization, innoxious process receives common concern both domestic and external.With traditional burning, landfill, do and build compared with the treatment process such as filler, compost, pyrolytic technique lignin-sludge has obvious advantage.Pyrolyzing sludge not only can produce liquid oils and inflammable gas, simultaneously contained heavy metal passivation, and dioxin growing amount obviously reduces, and greatly reduces the secondary pollution of sludge handling process.There is much similar character to oil in sludge pyrolytic oil, can be used as fuel or other chemical, thus receive the concern of investigator in recent years.Because the change of properties of the different pyrolysis oil of the mode of production is very large, productive rate is low, acid number is comparatively large, water content is high, calorific value is low, viscosity is difficult to greatly the application that the features such as conveying affect sludge pyrolytic oil, also limit the development of pyrolyzing sludge technology.
Summary of the invention
The object of the invention is to overcome the problem that mud existing pyrolytic technique gained pyrolysis oil viscosity is higher, acid number is comparatively large, productive rate is low, a kind of method promoting pyrolyzing sludge oil quality is provided.
To achieve these goals, the present invention adopts following technical scheme:
A kind of method promoting pyrolyzing sludge oil quality; mud, abandoned biomass and catalyzer are pressed the weight ratio mixing of 1:1.0 ~ 1.5:0.01 ~ 0.05; be placed in the fixed-bed reactor under nitrogen protection; by certain heating schedule segmentation pyrolysis; progressively be warmed up to final temperature 550 DEG C; the gas condensation in condensing works generated, namely obtains the pyrolysis oil higher than pure pyrolyzing sludge oil quality.
Described heating schedule is: first with the heat-up rate of 20 DEG C/min from room temperature to 275 DEG C, constant temperature 10 minutes; Be warmed up to 450 DEG C with the heat-up rate of 20 DEG C/min from 275 DEG C again, constant temperature 10 minutes, then be warmed up to final temperature 550 DEG C with the heat-up rate of 20 DEG C/min from 450 DEG C, constant temperature 20 minutes.
Described mud is the filter sludge of municipal wastewater treatment station, its moisture content 10 ~ 15wt%, and granular size is for being less than 1mm; Described abandoned biomass is one or more in Pericarppium arachidis hypogaeae, Herba Eichhorniae, rice husk, rice straw, Folium Phragmitis and bagasse, and granular size is for being less than 1mm; Described catalyzer is oyster shells ash, and granular size is for being less than 0.1mm.
After adopting technique scheme, the inventive method adopts abandoned biomass and mud by suitable proportion blending and a small amount of catalyzer copyrolysis, utilizes the distinctive composition structure of biomass to improve pyrolyzing sludge process.The feature of biomass is that organic content is high, and the calorific value of pyrolysis product is high, but solid product density low, easily waft, be difficult to storing, and the moisture height of mud, calorific value are low, product liquid content is low, solid product density is large, and viscosity is difficult to greatly conveying simultaneously.By these two kinds of materials in the mixing of suitable ratio, then can learn from other's strong points to offset one's weaknesses.The distinctive fibrous texture of biomass can increase the porosity of pyrolyzing sludge process, reduces the reaction resistance of pyrolyzing sludge process; In biomass pyrolysis process, due to the quick generation of cracking process chain reaction process, create a large amount of hydroperoxyl radical, methyl free radicals etc., pyrolyzing sludge is had in high temperature environments more chain reaction initiating group, and depositing at hydroperoxyl radical makes the reductibility in inert atmosphere strengthen to some extent in case, more be conducive to alkane and ester compound generation, thus promote pyrolysis oil quality; In copyrolysis process, add catalyzer, optionally can control the distribution of pyrolysis product, increase the output of some certain expected target product, suppress some composition, especially the generation of acids, improve the quality of pyrolysis oil.
The invention has the advantages that, while promoting pyrolyzing sludge oil quality, achieve innoxious, the recycling of two kinds of wastes, reach the object of environmental protection, changing rejected material to useful resource, Sustainable development, significant to the economic construction of China.
Effect of the present invention is, the pyrolysis oil oil yield rate (moisture-free basis) 35% ~ 45%, Lower heat value 30 ~ 35MJ/kg, the viscosity 15 ~ 18mm that utilize technique scheme to obtain 2/ g.During GC-MS analysis pyrolysis oil main component known copyrolysis, the kind of the component that content is higher obviously reduces, and only has four large classes, illustrates that copyrolysis process is conducive to pyrolysis oil composition simplification more, facilitate follow-up deep processing and utilization.Contrast different sorts compound relative content can find, the copyrolysis gained pyrolysis oil of biomass and mud compares to the pyrolysis oil of the independent pyrolysis gained of mud, the content of ester class has obvious lifting, thus pyrolysis oil acid number and viscosity is significantly reduced, for the later use of pyrolysis oil is provided convenience.
Embodiment
A kind of method promoting pyrolyzing sludge oil quality of the present invention, is achieved by the following scheme:
Mud, abandoned biomass and catalyzer are pressed 1:(1.0 ~ 1.5): the weight ratio mixing of (0.01 ~ 0.05); be placed in the fixed-bed reactor under nitrogen protection; by certain heating schedule temperature-gradient method pyrolysis; finally be warmed up to 550 DEG C; the gas condensation in condensing works generated, namely obtains the pyrolysis oil higher than pure pyrolyzing sludge oil quality.
Wherein:
Fixed-bed reactor used are the temperature control fixed-bed reactor able to programme of φ 400 × 600mm, and said heating schedule is specific as follows: first with the heat-up rate of 20 DEG C/min from room temperature to 275 DEG C, constant temperature 10 minutes; Be warmed up to 450 DEG C with the heat-up rate of 20 DEG C/min from 275 DEG C again, constant temperature 10 minutes, then be warmed up to final temperature 550 DEG C with the heat-up rate of 20 DEG C/min from 450 DEG C, constant temperature 20 minutes.
Mud adopts the filter sludge of municipal wastewater treatment station, and its moisture content 10 ~ 15wt%, granular size is for being less than 1mm.
Abandoned biomass adopt in Pericarppium arachidis hypogaeae, Herba Eichhorniae, rice husk, rice straw, Folium Phragmitis and bagasse one or more, granular size is for being less than 1mm.
Catalyzer adopts oyster shells ash, and granular size is for being less than 0.1mm.
Embodiment 1:
Mud, Pericarppium arachidis hypogaeae and oyster shells ash presses the weight ratio mixing of 1:1.0:0.01; 60g is laid in quartzy Noah's ark altogether, and be placed in φ 400 × 600mm fixed-bed reactor, nitrogen protection airshed is 250mL/min; by aforementioned heating schedule segmentation pyrolysis, be progressively warming up to 550 DEG C.The pyrolysis oil productive rate (moisture-free basis) 36.23% that the gas generated obtains after condensation in condensing works, calorific value are 33.08MJ/kg, viscosity 18.06mm 2/ g;
Embodiment 2:
Mud, Herba Eichhorniae and oyster shells ash presses the weight ratio mixing of 1:1.2:0.03; 60g is laid in quartzy Noah's ark altogether, and be placed in φ 400 × 600mm fixed-bed reactor, nitrogen protection airshed is 250mL/min; by aforementioned heating schedule segmentation pyrolysis, be progressively warming up to 550 DEG C.The bio oil productive rate (moisture-free basis) 39.63% that the gas generated obtains after condensation in condensing works, calorific value 33.58MJ/kg, viscosity 17.34mm 2/ g;
Embodiment 3:
Mud, bagasse and oyster shells ash presses the weight ratio mixing of 1:1.0:0.01; 60g is laid in quartzy Noah's ark altogether, and be placed in φ 400 × 600mm fixed-bed reactor, nitrogen protection airshed is 250mL/min; by aforementioned heating schedule segmentation pyrolysis, be progressively warming up to 550 DEG C.The bio oil productive rate (moisture-free basis) 40.38% that the gas generated obtains after condensation in condensing works, calorific value 34.12MJ/kg, viscosity 16.17mm 2/ g;
Embodiment 4:
Mud, Folium Phragmitis and oyster shells ash presses the weight ratio mixing of 1:1.0:0.01; 60g is laid in quartzy Noah's ark altogether, and be placed in φ 400 × 600mm fixed-bed reactor, nitrogen protection airshed is 250mL/min; by aforementioned heating schedule segmentation pyrolysis, be progressively warming up to 550 DEG C.The pyrolysis oil productive rate (moisture-free basis) 35.13% that the gas generated obtains after condensation in condensing works, calorific value are 30.08MJ/kg, viscosity 17.03mm 2/ g;
Embodiment 5:
Mud, rice straw and oyster shells ash presses the weight ratio mixing of 1:1.0:0.01; 60g is laid in quartzy Noah's ark altogether, and be placed in φ 400 × 600mm fixed-bed reactor, nitrogen protection airshed is 250mL/min; by aforementioned heating schedule segmentation pyrolysis, be progressively warming up to 550 DEG C.The bio oil productive rate (moisture-free basis) 39.82% that the gas generated obtains after condensation in condensing works, calorific value 36.49MJ/kg, viscosity 16.85mm 2/ g;
Embodiment 6:
Mud, rice husk and oyster shells ash presses the weight ratio mixing of 1:1:0.03; 60g is laid in quartzy Noah's ark altogether, and be placed in φ 400 × 600mm fixed-bed reactor, nitrogen protection airshed is 250mL/min; by aforementioned heating schedule segmentation pyrolysis, be progressively warming up to 550 DEG C.The bio oil productive rate (moisture-free basis) 41.63% that the gas generated obtains after condensation in condensing works, calorific value 38.78MJ/kg, viscosity 15.48mm 2/ g;
Embodiment 7:
Mud, Herba Eichhorniae and oyster shells ash presses the weight ratio mixing of 1:1.5:0.03; 60g is laid in quartzy Noah's ark altogether, and be placed in φ 400 × 600mm fixed-bed reactor, nitrogen protection airshed is 250mL/min; by aforementioned heating schedule segmentation pyrolysis, be progressively warming up to 550 DEG C.The bio oil productive rate (moisture-free basis) 43.63% that the gas generated obtains after condensation in condensing works, calorific value 34.78MJ/kg, viscosity 16.88mm 2/ g;
Embodiment 8:
Mud, Pericarppium arachidis hypogaeae and oyster shells ash presses the weight ratio mixing of 1:1.5:0.05; 60g is laid in quartzy Noah's ark altogether, and be placed in φ 400 × 600mm fixed-bed reactor, nitrogen protection airshed is 250mL/min; by aforementioned heating schedule segmentation pyrolysis, be progressively warming up to 550 DEG C.The bio oil productive rate (moisture-free basis) 44.67% that the gas generated obtains after condensation in condensing works, calorific value 35.02MJ/kg, viscosity 15.29mm 2/ g.

Claims (3)

1. one kind promotes the method for pyrolyzing sludge oil quality; it is characterized in that: mud, abandoned biomass and the catalyzer weight ratio by 1:1.0 ~ 1.5:0.01 ~ 0.05 is mixed; be placed in the fixed-bed reactor under nitrogen protection; by certain heating schedule segmentation pyrolysis; progressively be warmed up to final temperature 550 DEG C; the gas condensation in condensing works generated, namely obtains the pyrolysis oil higher than pure pyrolyzing sludge oil quality.
2. a kind of method promoting pyrolyzing sludge oil quality according to claim 1, is characterized in that: described heating schedule is: first with the heat-up rate of 20 DEG C/min from room temperature to 275 DEG C, constant temperature 10 minutes; Be warmed up to 450 DEG C with the heat-up rate of 20 DEG C/min from 275 DEG C again, constant temperature 10 minutes, then be warmed up to final temperature 550 DEG C with the heat-up rate of 20 DEG C/min from 450 DEG C, constant temperature 20 minutes.
3. a kind of method promoting pyrolyzing sludge oil quality according to claim 1 and 2, it is characterized in that: described mud is the filter sludge of municipal wastewater treatment station, its moisture content 10 ~ 15wt%, granular size is for being less than 1mm; Described abandoned biomass is one or more in Pericarppium arachidis hypogaeae, Herba Eichhorniae, rice husk, rice straw, Folium Phragmitis and bagasse, and granular size is for being less than 1mm; Described catalyzer is oyster shells ash, and granular size is for being less than 0.1mm.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106433713A (en) * 2016-11-01 2017-02-22 新疆大学 Sludge pyrolysis method adopting biomass adding
CN106977068A (en) * 2017-04-14 2017-07-25 中国科学院广州能源研究所 A kind of method for improving sludge carbon yield
CN107663002A (en) * 2016-07-28 2018-02-06 华云新能源科技（深圳）有限公司 A kind of sludge method for cracking treatment and equipment
CN108587669A (en) * 2018-05-18 2018-09-28 武汉理工大学 A kind of shale gas oil-based drill cuttings resource utilization method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643687A (en) * 2009-08-24 2010-02-10 中国矿业大学 Oil producing technology for co-pyrolysis of municipal sewage sludge and agricultural waste
CN102936087A (en) * 2012-11-06 2013-02-20 大连海事大学 Method for preparing pyrolysis oil and synthesis gases by pyrolysis of sludge
CN103396820A (en) * 2013-07-04 2013-11-20 北京林业大学 Method for preparing bio-oil through biomass pyrolysis
US20150166899A1 (en) * 2013-12-14 2015-06-18 Anellotech, Inc. Catalysts and Processes for Producing p-xylene from Biomass

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643687A (en) * 2009-08-24 2010-02-10 中国矿业大学 Oil producing technology for co-pyrolysis of municipal sewage sludge and agricultural waste
CN102936087A (en) * 2012-11-06 2013-02-20 大连海事大学 Method for preparing pyrolysis oil and synthesis gases by pyrolysis of sludge
CN103396820A (en) * 2013-07-04 2013-11-20 北京林业大学 Method for preparing bio-oil through biomass pyrolysis
US20150166899A1 (en) * 2013-12-14 2015-06-18 Anellotech, Inc. Catalysts and Processes for Producing p-xylene from Biomass

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107663002A (en) * 2016-07-28 2018-02-06 华云新能源科技（深圳）有限公司 A kind of sludge method for cracking treatment and equipment
CN106433713A (en) * 2016-11-01 2017-02-22 新疆大学 Sludge pyrolysis method adopting biomass adding
CN106977068A (en) * 2017-04-14 2017-07-25 中国科学院广州能源研究所 A kind of method for improving sludge carbon yield
CN108587669A (en) * 2018-05-18 2018-09-28 武汉理工大学 A kind of shale gas oil-based drill cuttings resource utilization method

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