CN103159595B - A kind of method that salix monogolica liquefaction prepares phenolic compound - Google Patents
A kind of method that salix monogolica liquefaction prepares phenolic compound Download PDFInfo
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- CN103159595B CN103159595B CN201310070141.6A CN201310070141A CN103159595B CN 103159595 B CN103159595 B CN 103159595B CN 201310070141 A CN201310070141 A CN 201310070141A CN 103159595 B CN103159595 B CN 103159595B
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- salix monogolica
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- 238000000034 method Methods 0.000 title claims abstract description 80
- 241000124033 Salix Species 0.000 title claims abstract description 34
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 150000002989 phenols Chemical class 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 230000008569 process Effects 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000007790 solid phase Substances 0.000 claims abstract description 11
- 239000012075 bio-oil Substances 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- 239000012074 organic phase Substances 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 238000000895 extractive distillation Methods 0.000 claims description 6
- 210000002966 serum Anatomy 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000000638 solvent extraction Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 15
- 239000000295 fuel oil Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- CHWNEIVBYREQRF-UHFFFAOYSA-N 4-Ethyl-2-methoxyphenol Chemical group CCC1=CC=C(O)C(OC)=C1 CHWNEIVBYREQRF-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- -1 Aliphatic acid Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to salix monogolica recycling field, and in particular to a kind of method that prepared by the process water direct reuse that salix monogolica hydrothermal liquefaction is produced into phenolic compound.Poured into autoclave after salix monogolica is crushed first, form the mixed liquor of certain solid-liquid mass ratio, to the inert gas that certain pressure is filled with reactor, 150 ~ 350 DEG C are stirred and be warming up to, 1 ~ 180min is kept, room temperature is rapidly cooled to, collect reactant mixture, it is solid, liquid two-phase that reactant mixture is separated by filtration, and liquid phase is process water, direct reuse as hydrothermal liquefaction next time liquefied medium；The organic compound in organic solvent extraction process water, remaining water can also be first used to be used as the liquefied medium of hydro-thermal reaction next time as backwater.Solid phase and process water are extracted and extracted with organic solvent, organic phase is separated and filtered, it is to obtain bio oil to remove organic solvent, and abundant phenolic compound is contained in bio oil.Hydrothermal liquefaction process water direct reuse can simplification of flowsheet, reduction wastewater treatment, while the generation of phenolic compound can be promoted.
Description
Technical field
The invention belongs to salix monogolica application technology as the second resource field, and in particular to a kind of that salix monogolica hydrothermal liquefaction process water is direct
Reuse liquefaction prepares phenolic compound（Mainly phenol, guaiacol, 4- ethyl -2- metoxyphenols and 2,6- dimethoxy
Phenol）Method.
Background technology
Salix monogolica is a strong class growth ability, adapts to the plant of drought environment.These features cause that they turn into and check winds and fix drifting sand
First-selection, planted large stretch of area in NW China arid area.These plants need stump at regular intervals, so every year
Substantial amounts of desert shrub branch can be produced, with wide Utilization prospects.
Hydrothermal liquefaction treatment biomass are a kind of new handling process, with raw material sources are wide, reaction condition and equipment
Simple and simple operation and other advantages.In recent years, start to cause the attention of people using biomass liquefying production of chemicals, patent is awarded
Notification number is weighed for the patent of invention of CN101245566 B is the side that phenol selectivity liquified cellulosic produces bio-based phenolic resin
Method.Number of patent application is a kind of by desert shrub preparing liquid fuel by hydrothermal liquification for the patent of invention of 201010291801.X
Salix monogolica is converted into liquid fuel by method, the method using hydrothermal liquefaction method.However, can be produced after hydrothermal liquefaction reaction a large amount of
Process water, this is a kind of waste water containing gas chromatography, and COD is high, and intractability is big, significantly limit water
The liquefied large-scale promotion of heat.If so the process water direct reuse that will be produced after hydrothermal liquefaction is used as hydrothermal liquefaction next time
The liquefied medium of reaction, then both simplified the flow process of hydrothermal liquefaction, decreases the cost of process water process.Together
When, small organic molecule such as acetic acid, phenol, alcohols etc. in hydrothermal liquefaction process water can promote hydrothermal liquefaction to react, and increase
The generation of strong phenolic compound.
The content of the invention
Salix monogolica hydrothermal liquefaction process water direct reuse liquefaction is prepared into phenols chemical combination it is an object of the invention to provide one kind
The method of thing, specially makes salix monogolica branch be changed into the phenolic compound with market value high using hydrothermal liquefaction（Mainly
Phenol, guaiacol, 4- ethyl -2- metoxyphenols and 2,6- syringol etc.）, by the mistake for producing hydrothermal liquefaction
Cheng Shui direct reuses simplify the flow process of hydrothermal liquefaction and reduce process water as the liquefied medium after hydrothermal liquefaction next time
Processing cost, forms the hydrothermal liquefaction reaction system of complete set.
Thinking of the invention is, salix monogolica is checked winds and fixed drifting sand main plant as one kind, and substantial amounts of branch resource is produced every year, but
It is that cannot but effectively utilize.Hydrothermal liquefaction Wooden Biomass can obtain phenolic compound, and both are joined together, by sand
The maximization of economic benefit of willow.In addition, the process water direct reuse produced after hydrothermal liquefaction is reacted simplifies hydrothermal liquefaction
Flow process and reduction process cost of water treatment.
As shown in Figure 1, its key step is as follows for technology path of the invention：
（1）Salix monogolica branch is collected, after crushing, is poured into autoclave, it is 1 that the mixing that adds water makes to form solid-liquid mass ratio:
60~1:2 mixed liquor；
（2）To the N that 0 ~ 6MPa is filled with autoclave2, stir and be warming up to 150 ~ 350 DEG C and keep 1 ~ 180min,
Room temperature is rapidly cooled to, reactant mixture is collected；
（3）It is liquid phase and solid phase that reactant mixture is separated by filtration, and liquid phase is process water, process water direct reuse conduct
The liquefied medium of hydrothermal liquefaction next time；Also organic solvent extraction process water organic compound therein can be first used, this organises
Aliphatic acid and phenolic compound are rich in compound, remaining water is used as the liquefied medium of hydro-thermal reaction next time as backwater.
（4）Extractive distillation is carried out to solid phase with organic solvent, organic phase and solid residue, having in removing organic phase is obtained
Machine solvent 2 obtains bio oil, and phenolic compound is rich in bio oil（Mainly include phenol, guaiacol, 4- ethyl -2- first
Epoxide phenol, 2,6- syringol etc.）.Organic solvent can be reclaimed, recycled.
（5）Reuse step（3）In process water or backwater directly with salix monogolica crush branch configuration mixed serum continue
Above-mentioned hydro-thermal reaction step, isolated bio oil.
The described organic solvent for extractive distillation process water is ethyl acetate, dichloromethane or ether etc..
The described organic solvent for extractive distillation solid phase is tetrahydrofuran, ethyl acetate, dichloromethane or ether etc..
Hydrothermal liquefaction process water or backwater can infinitely be reused as the liquefied medium of salix monogolica, according to reaction solid-liquid quality
Than requiring, running water is suitably added.
Result of the invention is analyzed using gas-chromatography and GC-MS to the composition of bio oil, shows hydro-thermal liquid
The direct reuse of process water is feasible after change, and be greatly promoted biological oily yield increase and bio oil in phenols chemical combination
The content of thing.
Made full use of for salix monogolica branch, formd the double effectses checked winds and fixed drifting sand with economic benefit, greatly
Improve the economic worth and the ecological value of salix monogolica.Hydrothermal liquefaction technical operation is simple, low cost, it is easy to large-scale promotion.And
And, the process water direct reuse that hydrothermal liquefaction reaction is produced can be such that hydrothermal liquefaction technological process more simplifies, and cost is lower；
Simultaneously for sand ground arid area, process water direct reuse can effectively solve the problems, such as shortage of water and waste water handling problem.
Brief description of the drawings
Fig. 1 is experimental procedure figure.
Fig. 2 is the oil productivity change curve of the heavy oil that embodiment 1, example 2, example 3 and example 4 are produced and middle oil.
Specific embodiment
The invention is further illustrated by the following examples, but is not limitation of the invention.
Embodiment 1
Salix monogolica is crushed, 30g salix monogolica powder is taken and is poured into 250ml autoclaves and add 150ml distilled water, stirring is tuned into
Slurries, 2MPa N are filled with to reactor2, to 300 DEG C, holding 10min, logical running water makes to be cooled to room temperature for warming while stirring,
Reactant mixture is poured out, and kettle chamber is cleaned with tetrahydrofuran；Mixture filtering is divided into solid, liquid two-phase, liquid phase is process water.
Solid phase is stripped with 150ml tetrahydrofurans, separating and extracting extract, with filtered on buchner funnel tetrahydrofuran phase, then depressurized
Distillation recovery tetrahydrofuran is to obtain heavy oil；Process water is extracted with ether, ether reclaims ether and is through vacuum distillation
Middle oil is obtained, water is mutually backwater, give over to experiment next time and use.Phenolic compound is rich in heavy oil and middle oil.
Embodiment 2
Salix monogolica is crushed, 30g salix monogolica powder is taken and is poured into 250ml autoclaves, the process water for adding embodiment 1 to obtain is made
It is medium, stirring is slurried, 2MPa N is filled with to reactor2, to 300 DEG C, holding 10min leads to originally for warming while stirring
Water makes to be cooled to room temperature, pours out reactant mixture, and kettle chamber is cleaned with tetrahydrofuran；Mixture filtering is divided into solid, liquid two-phase,
Liquid phase is process water.Solid phase is stripped with 150ml tetrahydrofurans, separating and extracting extract, with filtered on buchner funnel four
Hydrogen furans phase, then it is to obtain heavy oil that tetrahydrofuran is reclaimed in vacuum distillation.Process water is directly added into another reactor as next
The liquefied medium of secondary hydrothermal liquefaction reaction, repeats process above 1 time, obtain the heavy oil after the secondary response of process Water circulation 1 and
Process water.Process water is extracted with ether finally, then it is to obtain middle oil that ether is reclaimed in vacuum distillation.
Embodiment 3
Salix monogolica is crushed, 30g salix monogolica powder is taken and is poured into the process water of 250ml high pressures addition embodiment 12 as medium, stirring
It is slurried, 2MPa N is filled with to reactor2, to 300 DEG C, holding 10min, logical running water makes to be cooled to room for warming while stirring
Temperature, pours out reactant mixture, and kettle chamber is cleaned with tetrahydrofuran；Mixture filtering is divided into solid, liquid two-phase, liquid phase is process
Water.Solid phase is stripped with 150ml tetrahydrofurans, separating and extracting extract, with filtered on buchner funnel tetrahydrofuran phase, then subtracted
Pressure Distillation recovery tetrahydrofuran is to obtain heavy oil.Process water is directly added into another reactor to be reacted as hydrothermal liquefaction next time
Liquefied medium, repeat process above 2 times, obtain the heavy oil and process water after the secondary response of process Water circulation 2.Finally use ether
Process water is extracted, then it is to obtain middle oil that ether is reclaimed in vacuum distillation.
Embodiment 4
Salix monogolica is crushed, 30g salix monogolica powder is taken and is poured into the process water of 250ml high pressures addition embodiment 12 as medium, stirring
It is slurried, 2MPa N is filled with to reactor2, to 300 DEG C, holding 10min, logical running water makes to be cooled to room for warming while stirring
Temperature, pours out reactant mixture, and kettle chamber is cleaned with tetrahydrofuran；Mixture filtering is divided into solid, liquid two-phase, liquid phase is process
Water.Solid phase is stripped with 150ml tetrahydrofurans, separating and extracting extract, with filtered on buchner funnel tetrahydrofuran phase, then subtracted
Pressure Distillation recovery tetrahydrofuran is to obtain heavy oil.Process water is directly added into another reactor to be reacted as hydrothermal liquefaction next time
Liquefied medium, repeat process above 3 times, obtain the heavy oil and process water after the secondary response of process Water circulation 2.Finally use ether
Process water is extracted, then it is to obtain middle oil that ether is reclaimed in vacuum distillation.
As can be seen that the direct reuse number of times of process water is more from accompanying drawing 2, the oil productivity of heavy oil and middle oil is higher,
Oil productivity is obviously improved, and total oil productivity is up to 46%.Declarative procedure water direct reuse can not only simplify production technology and treatment
Cost, and promote the hydrothermal liquefaction reaction of salix monogolica.
As can be seen that the species change of phenolic compound is very small in heavy oil after the direct reuse of process water from subordinate list 1,
Main matter is phenol, guaiacol, 4- ethyl -2- metoxyphenols and 2,6- syringol；And total content has rising
Trend, so the direct reuse of process water does not change the quality of heavy oil, the content of phenolic compound is enhanced on the contrary.
From subordinate list 2 as can be seen that in the primary product of oil be acetic acid and phenolic compound, and process water is directly returned
There is elevated trend with the acetic acid and the content of phenolic compound in rear middle oil.So, during the direct reuse of process water is enhanced
The quality of oil.
In sum, the direct reuse of process water is feasible after hydrothermal liquefaction, and is greatly promoted biological oily yield
Increase and bio oil in phenolic compound content.
The composition and content of the heavy oil that the embodiment 1 of table 1., example 2, example 3 and example 4 are produced
Note：RT.aIt is retention time, unit：Minute.
The composition and content of the middle oil that the embodiment 1 of table 2., example 2, example 3 and example 4 are produced
Note：RT.aIt is retention time, unit：Minute.
Claims (4)
1. a kind of method that salix monogolica hydrothermal liquefaction process water direct reuse liquefaction is prepared into phenols chemicals, it is characterised in that main
Step is as follows：
（1）Salix monogolica branch is collected, after crushing, is poured into autoclave, it is 1 that the mixing that adds water makes to form solid-liquid mass ratio:60~1:
2 mixed serum；
（2）To the N that 0 ~ 6MPa is filled with autoclave2, stir and be warming up to 150 ~ 350 DEG C and keep 1 ~ 180min, it is rapid cold
But to room temperature, reactant mixture is collected；
（3）It is liquid phase and solid phase that reactant mixture is separated by filtration, and liquid phase is process water, and process water direct reuse is used as next
The liquefied medium of secondary hydrothermal liquefaction；
（4）Extractive distillation is carried out to solid phase with organic solvent, organic phase and solid residue is obtained, it is organic molten in removing organic phase
Agent is to obtain the bio oil rich in phenolic compound, and organic solvent is reclaimed, recycled；
（5）Reuse step（3）In process water branch configuration mixed serum is directly crushed with salix monogolica to continue above-mentioned hydro-thermal anti-
Answer step, isolated bio oil.
2. the method for salix monogolica hydrothermal liquefaction process water direct reuse liquefaction being prepared into phenols chemicals as claimed in claim 1,
Characterized in that, described step（3）In for extractive distillation process water organic solvent be ethyl acetate, dichloromethane or second
Ether.
3. the method for salix monogolica hydrothermal liquefaction process water direct reuse liquefaction being prepared into phenols chemicals as claimed in claim 1,
Characterized in that, described step（4）In for extractive distillation solid phase organic solvent be tetrahydrofuran, ethyl acetate, dichloro
Methane or ether.
4. the method for salix monogolica hydrothermal liquefaction process water direct reuse liquefaction being prepared into phenols chemicals as claimed in claim 1,
It is characterized in that hydrothermal liquefaction process water is reused as the liquefied medium of salix monogolica infinitely, according to reaction solid-liquid mass ratio requirement,
Suitably add running water.
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| CN201310070141.6A CN103159595B (en) | 2013-03-06 | 2013-03-06 | A kind of method that salix monogolica liquefaction prepares phenolic compound |
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| CN105037111B (en) * | 2015-05-28 | 2017-03-01 | 复旦大学 | A kind of method of separating-purifying 2,6 syringol and acetosyringone from bio oil |
| CN108441248A (en) * | 2018-04-03 | 2018-08-24 | 北京林业大学 | A method of being prepared as raw material using discarded Poplar Powder has antioxidative bio oil |
| CN110373221B (en) * | 2019-08-20 | 2021-06-29 | 沈阳航空航天大学 | Extraction separation method for reducing water content of biomass hydrothermal liquefied oil |
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| CN101955787B (en) * | 2010-09-26 | 2013-07-10 | 复旦大学 | Method for preparing liquid fuel by performing hydrothermal liquefaction on sandy shrubs |
| CN102899069A (en) * | 2012-10-30 | 2013-01-30 | 复旦大学 | Separating and upgrading method of bio-oil by column chromatography |
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Effective date of registration: 20130809 Address after: 200433 Handan Road, Shanghai, No. 220, No. Applicant after: Fudan University Applicant after: Inner Mongolia Jinlvyuan Green Engineering Limited Liability Company Address before: 200433 Handan Road, Shanghai, No. 220, No. Applicant before: Fudan University |
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