CN104312604A - Method for improving creosote content in biomass molding fuel tar - Google Patents

Method for improving creosote content in biomass molding fuel tar Download PDF

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Publication number
CN104312604A
CN104312604A CN201410605168.5A CN201410605168A CN104312604A CN 104312604 A CN104312604 A CN 104312604A CN 201410605168 A CN201410605168 A CN 201410605168A CN 104312604 A CN104312604 A CN 104312604A
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China
Prior art keywords
tar
biomass molding
molding fuel
creosote
pyrolysis
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CN201410605168.5A
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Chinese (zh)
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CN104312604B (en
Inventor
刘石彩
杨华
黄丽
邓先伦
蒋剑春
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Institute of Chemical Industry of Forest Products of CAF
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Institute of Chemical Industry of Forest Products of CAF
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/19—Working-up tar by thermal treatment not involving distillation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a method for improving creosote content in biomass molding fuel tar and is suitable for a production technology for preparing molding charcoal through the pyrolysis of a rodlike fuel briquetted by the raw materials of pine chips, fir chips and hard mixed wood chips under the condition of an oxygen containing environment. The biomass molding fuel is pyrolyzed under an alkaline air atmosphere (VNH3: V air = (1-3): 100), and ammonia gas is produced in a mode of heating ammonia water. The constituents of the tar pyrolyzed by the biomass molding fuel can be obviously changed by the pyrolysis method. The total creosote relative content can be improved from less than 80wt% to 85-92wt%, the substitution ratio of the tar byproduct in the reaction of substituting part of phenol and synthesizing a phenolic resin adhesive is increased from 25% to 30-50%, the pollution of the tar byproduct to the environment in the production process of the biomass molding fuel can be reduced, and the preparing cost of the phenolic resin adhesive is reduced.

Description

A kind of method improving creosote content in biomass molding fuel pyrolytic tar
Technical field
The present invention relates to a kind of method for pyrolysis of biomass molding fuel, especially relate to a kind of method utilizing pine sawdust, cedar sawdust and hardwood crumbs to improve for the coal-tar middle oil creosote content of production technique that forming charcoal is prepared in rod shape fuel pyrolysis under oxygenated environment condition that raw material is pressed into.
Background technology
China has abundant biomass resource, be that the solid molding fuel annual production of waste is at about 150,000 tons with wood chip, it can produce biomass molding charcoal through further pyrolysis deep processing, annual about 50,000 tons of the tar byproduct brought thus, tar is a kind of comparatively thick liquid of black, containing part creosote class, comprise phenol, 2-methylphenol, 4-methylphenol, 2-methoxyphenol, 3,4-xylenols, 2-ethylphenol etc.Phenols has harm to environment, and therefore, the tar byproduct developed in forming charcoal preparation process is the good thing of making a silk purse out of a sow's ear.Phenol aldehyde resin has excellent Joint strength, good water tolerance, thermotolerance and chemical stability, is the main glue of current indoor and outdoor wood-based plate.But its curing speed is slow, and solidification value is high, and cost is also higher.Current current research, with the higher phenol of the tar byproduct Some substitute price in formed of xylolite charcoal preparation process, carries out the synthesis of synvaren, has certain practicality, simultaneously also for the utilization of resources of tar provides a kind of new approach.
The total relative content of creosote that current forming charcoal prepares common process (only using warm air as pyrolysis medium) tar byproduct is less than 80%, cause the substitution ratio not high (lower than 25%) that tar byproduct is carried out in synvaren building-up reactions at Some substitute phenol, tar byproduct can not make full use of and form waste, and then causes environmental pollution.
Summary of the invention
The invention provides a kind of method improving creosote content in biomass molding fuel tar, the biomass molding fuel pyrolytic tar byproduct obtained by the present invention has the high advantage of the total relative content of creosote, carries out synvaren synthesis efficiency higher for Some substitute phenol.
The present invention adopts following technical scheme: a kind of method improving creosote content in biomass molding fuel pyrolytic tar, biomass moulding gac and tar byproduct is being obtained containing carrying out pyrolysis under oxygen condition with biomass molding fuel, pyrolysis is carried out containing under oxygen condition in alkalescence, and wherein the volume ratio of ammonia and air is V nH3: V air=(1-3): 100.
Described ammonia produces by the mode of ammoniacal liquor heating, and Heating temperature is 300-500 DEG C.
During pyrolysis, final pyrolysis temperature is 600-850 DEG C, and pyrolytic process temperature rise rate is 15-30 DEG C/h.
Described biomass molding fuel comprises the rod shape fuel be pressed into for raw material with pine sawdust, cedar sawdust or hardwood crumbs.
The tar that in described raising biomass molding fuel pyrolytic tar, the method for creosote content obtains, the total relative content of creosote is 85%wt ~ 92%wt.
The tar that in described raising biomass molding fuel pyrolytic tar, the method for creosote content obtains carries out the application in synvaren building-up reactions at alternative phenol, the substitution ratio of phenol is 30% ~ 50%.
Beneficial effect:
The present invention changes the biomass rodlike shaped fuel pyrolytic process that tradition take air as pyrolysis medium, alkaline air atmosphere is adopted to carry out the pyrolysis charring of shaped fuel as pyrolysis medium innovatively, with routine with air be pyrolysis medium biomass rodlike shaped fuel pyrolytic process compared with, make the composition of biomass molding fuel pyrolytic tar that significantly change occur, wherein the total relative content of creosote significantly improves, tar byproduct is made to carry out efficiency in synvaren building-up reactions at Some substitute phenol higher, specifically:
(1) the present invention adopts alkaline air atmosphere to carry out the pyrolysis charring of shaped fuel as pyrolysis medium first, make the composition of biomass molding fuel pyrolytic tar that significantly change occur, wherein the total relative content of creosote significantly improves, be conducive to improving the substitution ratio that tar byproduct is carried out at Some substitute phenol in synvaren building-up reactions, and improve the quality of sintetics.
(2) the present invention is adapted to prepare the production technique of forming charcoal with rod shape fuel pyrolysis under oxygenated environment condition that pine sawdust, cedar sawdust and hardwood crumbs are pressed into for raw material.Under alkaline atmosphere, pyrolysis can make the composition of biomass molding fuel pyrolytic tar that significantly change occurs, wherein the total relative content of creosote 80% can bring up to 85%-92% from being less than of common process (only using warm air as pyrolysis medium), and the substitution ratio that tar byproduct is carried out in synvaren building-up reactions at Some substitute phenol is increased to 30%-50% from 25%.
(3) invention increases the utilising efficiency of biomass coke tar, for the efficiency utilization promoting biomass resource, reduce the pollution that biomass molding fuel production process is brought to environment because of tar byproduct, reduce phenolic resin adhesive preparation cost and there is vital role.
Embodiment
Embodiment 1.
1, a method for pyrolysis for biomass molding fuel, is adapted to prepare the production technique of forming charcoal with rod shape fuel pyrolysis under oxygenated environment condition that pine sawdust, cedar sawdust and hardwood crumbs are pressed into for raw material.V under alkaline air atmosphere condition nH3: V air=(1-3): 100, make biomass molding fuel pyrolysis, final pyrolysis temperature is 600-850 DEG C, and pyrolytic process temperature rise rate is 15-30 DEG C/h, and wherein ammonia produces by the mode of ammoniacal liquor heating, and Heating temperature is 300-500 DEG C.This method for pyrolysis can make the composition of biomass molding fuel pyrolytic tar that significantly change occurs, wherein the total relative content of creosote 80% can bring up to 85%-92% from being less than of common process (only using warm air as pyrolysis medium), and the substitution ratio that tar byproduct is carried out in synvaren building-up reactions at Some substitute phenol is increased to 30%-50% from 25%.
Embodiment 2.
A method for pyrolysis for biomass molding fuel, V under alkaline air atmosphere condition nH3: V air=1:100, makes the pyrolysis of hardwood crumbs shaped fuel, and final pyrolysis temperature is 600 DEG C, and pyrolytic process temperature rise rate is 15 DEG C/h, and wherein ammonia produces by the mode of ammoniacal liquor heating, and Heating temperature is 300 DEG C.This method for pyrolysis can make the composition of biomass molding fuel pyrolytic tar that significantly change occurs, wherein the total relative content of creosote can bring up to 85%wt from the 80%wt that is less than of common process (only using warm air as pyrolysis medium), and the substitution ratio that tar byproduct is carried out in synvaren building-up reactions at Some substitute phenol is increased to 30%wt from 25%wt.
Embodiment 3.
A method for pyrolysis for biomass molding fuel, (V under alkaline air atmosphere condition nH3: V air=2:100), make the pyrolysis of pine sawdust shaped fuel, final pyrolysis temperature is 700 DEG C, and pyrolytic process temperature rise rate is 20 DEG C/h, and wherein ammonia produces by the mode of ammoniacal liquor heating, and Heating temperature is 400 DEG C.This method for pyrolysis can make the composition of biomass molding fuel pyrolytic tar that significantly change occurs, wherein the total relative content of creosote can bring up to 88%wt from the 80%wt that is less than of common process (only using warm air as pyrolysis medium), and the substitution ratio that tar byproduct is carried out in synvaren building-up reactions at Some substitute phenol is increased to 40%wt from 25%wt.
Embodiment 4.
A kind of method for pyrolysis of biomass molding fuel, VNH3:V air=3:100 under alkaline air atmosphere condition, make the pyrolysis of cedar sawdust shaped fuel, final pyrolysis temperature is 850 DEG C, pyrolytic process temperature rise rate is 30 DEG C/h, wherein ammonia produces by the mode of ammoniacal liquor heating, and Heating temperature is 500 DEG C.This method for pyrolysis can make the composition of biomass molding fuel pyrolytic tar that significantly change occurs, wherein the total relative content of creosote 80% can bring up to 92% from being less than of common process (only using warm air as pyrolysis medium), and the substitution ratio that tar byproduct is carried out in synvaren building-up reactions at Some substitute phenol is increased to 50% from 25%.

Claims (6)

1. one kind is improved the method for creosote content in biomass molding fuel pyrolytic tar, biomass moulding gac and tar byproduct is being obtained containing carrying out pyrolysis under oxygen condition with biomass molding fuel, it is characterized in that, pyrolysis is carried out containing under oxygen condition in alkalescence, and wherein the volume ratio of ammonia and air is V nH3: V air=(1-3): 100.
2. the method improving creosote content in biomass molding fuel pyrolytic tar as claimed in claim 1, is characterized in that, described ammonia produces by the mode of ammoniacal liquor heating, and Heating temperature is 300-500 DEG C.
3. the method improving creosote content in biomass molding fuel pyrolytic tar as claimed in claim 1, it is characterized in that, during pyrolysis, final pyrolysis temperature is 600-850 DEG C, and pyrolytic process temperature rise rate is 15-30 DEG C/h.
4. the method improving creosote content in biomass molding fuel pyrolytic tar as claimed in claim 1, it is characterized in that, described biomass molding fuel comprises the rod shape fuel be pressed into for raw material with pine sawdust, cedar sawdust or hardwood crumbs.
5. the tar that in the arbitrary described raising biomass molding fuel pyrolytic tar of Claims 1 to 4, the method for creosote content obtains, it is characterized in that, the total relative content of creosote is 85%wt ~ 92%wt.
6. the tar that in the arbitrary described raising biomass molding fuel pyrolytic tar of Claims 1 to 4, the method for creosote content obtains carries out the application in synvaren building-up reactions at alternative phenol, it is characterized in that, the substitution ratio of phenol is 30% ~ 50%.
CN201410605168.5A 2014-10-30 2014-10-30 A kind of improve the method for creosote content in biomass molding fuel pyrolytic tar Expired - Fee Related CN104312604B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105861100A (en) * 2016-06-20 2016-08-17 中国林业科学研究院林产化学工业研究所 Method for reducing acid value of biomass briquette pyrolysis tar
CN106367150A (en) * 2016-09-22 2017-02-01 浙江农林大学 Molding charcoal prepared from wood tar-based adhesive and gasified charcoal
CN107337587A (en) * 2017-07-13 2017-11-10 华中科技大学 A kind of method that rich phenol liquid oil is prepared using biomass
CN112441885A (en) * 2020-12-04 2021-03-05 华中科技大学 Method for preparing 4-vinylphenol by using lignin at high yield

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US20120116135A1 (en) * 2010-11-09 2012-05-10 Conocophillips Company Heat integrated process for producing high quality pyrolysis oil from biomass
CN104031671A (en) * 2014-06-30 2014-09-10 厦门大学 Method for preparing bio-oil through biomass pyrolysis
CN104073278A (en) * 2014-07-15 2014-10-01 厦门大学 Method for converting lignin into liquid fuel through adopting two-step method

Patent Citations (3)

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US20120116135A1 (en) * 2010-11-09 2012-05-10 Conocophillips Company Heat integrated process for producing high quality pyrolysis oil from biomass
CN104031671A (en) * 2014-06-30 2014-09-10 厦门大学 Method for preparing bio-oil through biomass pyrolysis
CN104073278A (en) * 2014-07-15 2014-10-01 厦门大学 Method for converting lignin into liquid fuel through adopting two-step method

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朱锡锋等: "生物质热解液化与美拉德反应", 《燃料化学学报》 *
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105861100A (en) * 2016-06-20 2016-08-17 中国林业科学研究院林产化学工业研究所 Method for reducing acid value of biomass briquette pyrolysis tar
CN105861100B (en) * 2016-06-20 2018-12-14 中国林业科学研究院林产化学工业研究所 A method of reducing biomass molding fuel pyrolytic tar acid value
CN106367150A (en) * 2016-09-22 2017-02-01 浙江农林大学 Molding charcoal prepared from wood tar-based adhesive and gasified charcoal
CN107337587A (en) * 2017-07-13 2017-11-10 华中科技大学 A kind of method that rich phenol liquid oil is prepared using biomass
CN112441885A (en) * 2020-12-04 2021-03-05 华中科技大学 Method for preparing 4-vinylphenol by using lignin at high yield

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