CN106748692B - A kind of method that selective catalysis wood vinegar is converted into ketone chemicals - Google Patents
A kind of method that selective catalysis wood vinegar is converted into ketone chemicals Download PDFInfo
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- CN106748692B CN106748692B CN201611127342.5A CN201611127342A CN106748692B CN 106748692 B CN106748692 B CN 106748692B CN 201611127342 A CN201611127342 A CN 201611127342A CN 106748692 B CN106748692 B CN 106748692B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
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- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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Abstract
The present invention provides a kind of methods that selective catalysis wood vinegar is converted into ketone chemicals, comprising the following steps: step 1, by Fe (NO3)3Aqueous solution and ZrO (NO3)2Ammonia spirit is added after aqueous solution mixing, generates sediment ZrO2·FeOx, sediment is obtained after filtering, sediment is calcined into powdering under certain condition, sediment is granulated after cooling, selects the particle of certain diameter as catalyst；Step 2 takes the wooden vinegar stoste of certain volume, and cation exchange resin is added and saves 12~36h at 1~8 DEG C, filters, obtains and the wood vinegar after ion exchange；Catalyst is put into fixed bed reactors by step 3, is heated to 200~450 DEG C and 1~2h of constant temperature with certain rate；Step 4, wood vinegar is mixed according to a certain percentage with deionized water, in certain rate injection fixed bed reactors, wood vinegar is reacted under the effect of the catalyst, the gas generated in reaction process is exported and condensed by carrier gas, the condensate liquid rich in ketone chemicals is obtained.
Description
Technical field
The present invention relates to a kind of methods that selective catalysis wood vinegar is converted into ketone chemicals.
Background technique
In recent years, with the rapid development of economy, demand of the people to fossil energy is increasing, coal accounts for non-renewable energy
In 30% share, for the whole world 40% or more power generation.Due to the large-scale use of fossil energy, it is subject to environment
Serious pollution, urgent need find a kind of renewable resource to substitute fossil energy production of chemicals.
Biomass is from a wealth of sources as a kind of sustainable development source, cheap.Most of researchs are not both at home and abroad
Do any processing and catalyst under the action of, by making biomass slow pyrolysis, the pyrolysis gas of generation obtains after condensing
The wooden vinegar stoste.The wooden vinegar stoste is harmless to people, animal, environmentally friendly, and the wooden vinegar stoste is further processed into green product as sterilized
Agent, plant growth promoter, foliar fertilizer, Insecticides (tech) & Herbicides (tech), preservative etc. can be widely used agricultural animal husbandry, chemical industry
The every field such as industry, food processing industry and medical and health industry, generate huge economic benefit.
People have found that the active chemical in the wooden vinegar stoste is relatively multiple when the further processing to the wooden vinegar stoste utilizes
It is miscellaneous and be not easy to separate, cause the utilization rate of the wooden vinegar stoste to reduce.The high value chemicals such as ketone contained in the wooden vinegar stoste simultaneously
The content of class chemicals is lower, and separating difficulty is big, is not easy to accomplish scale production.
Summary of the invention
The present invention is to carry out to solve the above-mentioned problems, and it is an object of the present invention to provide a kind of selective catalysis wood vinegar converts
For the method for ketone chemicals.
The present invention provides a kind of methods that selective catalysis wood vinegar is converted into ketone chemicals, have such spy
Sign, comprising: step 1, by Fe (NO3)3Aqueous solution and ZrO (NO3)2Ammonia spirit is added in aqueous solution after being mixed, it is heavy to generate
Starch ZrO2·FeOx, sediment is obtained after filtering, sediment is calcined into powdering under certain condition, by sediment after cooling
The granular sediment that diameter is 200~900 μm is granulated under without any binder, which is catalysis
Agent；Step 2 takes the wooden vinegar stoste of certain volume, and cation exchange resin is added and saves 12~36h at 1~8 DEG C, filters,
It obtains and the wood vinegar after ion exchange；Catalyst is put into fixed bed reactors by step 3, is heated with certain rate
To 200~450 DEG C and 1~2h of constant temperature；Step 4 mixes the ratio of wood vinegar and deionized water 1:1~10 in mass ratio, with
In the rate injection fixed bed reactors of 2~4mL/h, wood vinegar carries out catalysis reaction under the effect of the catalyst, will react
The gas generated in journey is by carrier gas with 10~20cm3The rate of/min exports, and derived gas is condensed, and obtains rich in ketone
The condensate liquid of chemicals.
It is converted into the method for ketone chemicals, can also have in this way in selective catalysis wood vinegar provided by the invention
Feature: where in step 1, time of mixing is 30~120s.
It is converted into the method for ketone chemicals, can also have in this way in selective catalysis wood vinegar provided by the invention
Feature: where in step 1, the condition of calcining is calcined in air atmosphere, calcination temperature be 400~600 DEG C, calcining
Time is 1~3h.
It is converted into the method for ketone chemicals, can also have in this way in selective catalysis wood vinegar provided by the invention
Feature: where in step 2, it is described wood vinegar stoste be without by purification, purify the wooden vinegar stoste.
It is converted into the method for ketone chemicals, can also have in this way in selective catalysis wood vinegar provided by the invention
Feature: where in step 2, during preservation, every 30~60min shake 30~120s.
It is converted into the method for ketone chemicals, can also have in this way in selective catalysis wood vinegar provided by the invention
Feature: where in step 2, the volume of the wood vinegar stoste is 5~10mL, and the additional amount of cation exchange resin is 2
~4g.
It is converted into the method for ketone chemicals, can also have in this way in selective catalysis wood vinegar provided by the invention
Feature: where in step 3, the rate of heat addition of pyrolysis reactor is 5~10 DEG C/min.
It is converted into the method for ketone chemicals, can also have in this way in selective catalysis wood vinegar provided by the invention
Feature: where in step 4, be catalyzed reaction time be 2~4h, the carrier gas be inert gas or nitrogen.
The action and effect of invention
A kind of method that selective catalysis wood vinegar is converted into ketone chemicals involved according to the present invention, because using
ZrO2·FeOxIt is selective to convert aliphatic ketone for macromolecular substances in wood vinegar and part small-molecule substance as catalyst,
The content of high value chemicals in wood vinegar is improved, while not increasing additional greenhouse gases during conversion, it is right
It is environmental-friendly, there is huge Exploitative potential.
Detailed description of the invention
Fig. 1 is the schematic device that reaction is catalyzed in the embodiment of the present invention.
Specific embodiment
It is real below in order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention
The method that example combination attached drawing is converted into ketone chemicals to selective catalysis wood vinegar of the present invention is applied to be specifically addressed.
As shown in Figure 1, the device 10 for carrying out catalysis reaction includes fixed bed reactors 1, heater 2, syringe pump 3, carrier gas
Bottle 4, flow controller 5, ice water mixing channel 6, receiving flask 7 and gas bag 8.
The place of fixed bed reactors 1 offer wood vinegar and catalyst reaction.
Heater 2 heats fixed bed reactors 1.
Syringe pump 3 is connect with fixed bed reactors, control wood vinegar and deionized water charge velocity.
Carrier gas bottle 4 is connect by flow controller 5 with fixed bed reactors 1, and carrier gas is provided.
Ice water mixing channel 6 is connect with fixed reactor 1, provides low temperature environment, to derived gas in fixed reactor 1 into
Row condensation.
Receiving flask 7 is arranged in ice water mixing channel, collects the condensate liquid for being rich in ketone chemicals.
Gas bag 8 is connect with receiving flask 7, collects the incoagulable gas that fixed reactor 1 generates.
Embodiment one
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
2mm, holding time 12h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 4.5 DEG C/s, is sealed after being heated to 450 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 4.5g, pyrolysis time 60s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 30s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 400 DEG C,
Calcination time is 2h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 200 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 5mL, and the amount of cation exchange resin is 2g, saves temperature
Degree is 1 DEG C, holding time 12h, during preservation, shakes 30s every 30min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition be 12.5 DEG C/
Min is warming up to 200 DEG C of constant temperature 1.5h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:1, charge velocity
For 2mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 2h, and carrier gas is helium, and the rate for introducing gas is 10cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 18.8%, carboxylic acid content 8.3%, small molecule chemical combination
Object content is 10.5%, and the content of macromolecular compound is 7.8%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
4.3%, carboxylic acid content 8.6%, small molecule compound content is 16.0%, and macromolecular compound content is 45.1%.Aliphatic series
The content of ketone improves 4.37 times.
Embodiment two
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
3mm, holding time 10h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 6.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 9.75g, pyrolysis time 130s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 75s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 500 DEG C,
Calcination time is 1h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 550 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 7.5mL, and the amount of cation exchange resin is 3g, is saved
Temperature is 4.5 DEG C, and the holding time is for 24 hours, during preservation, to shake 75s every 45min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition be 12.5 DEG C/
Min is warming up to 325 DEG C of constant temperature 1h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:2, charge velocity
For 3mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 3h, and carrier gas is helium, and the rate for introducing gas is 15cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 23.4%, carboxylic acid content 12.5%, small molecule chemical combination
Object content is 8.6%, and the content of macromolecular compound is 12.2%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
3.6%, carboxylic acid content 9.4%, small molecule compound content is 14.6%, and macromolecular compound content is 56.1%.Aliphatic series
The content of ketone improves 6.50 times.
Embodiment three
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
4mm, holding time 14h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 8.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 15g, pyrolysis time 200s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 120s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain materialization
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 600 DEG C,
Calcination time is 3h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 900 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 10mL, and the amount of cation exchange resin is 4g, is saved
Temperature is 8 DEG C, holding time 36h, during preservation, shakes 120s every 60min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition is 20 DEG C/min,
It is warming up to 450 DEG C of constant temperature 2h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:5, charge velocity
For 4mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 4h, and carrier gas is helium, and the rate for introducing gas is 20cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 32.8%, carboxylic acid content 6.6%, small molecule chemical combination
Object content is 7.2%, and the content of macromolecular compound is 15.6%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
4.5%, carboxylic acid content 7.2%, small molecule compound content is 12.1%, and macromolecular compound content is 60.5%.Aliphatic series
The content of ketone improves 7.29 times.
Example IV
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
5mm, holding time 12h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 6.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 9.5g, pyrolysis time 130s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 75s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 500 DEG C,
Calcination time is 2h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 550 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 7.5mL, and the amount of cation exchange resin is 3g, is saved
Temperature is 5 DEG C, and the holding time is for 24 hours, during preservation, to shake 75s every 45min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition is 13 DEG C/min,
It is warming up to 325 DEG C of constant temperature 1.5h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:5, charge velocity
For 3mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 3h, and carrier gas is helium, and the rate for introducing gas is 15cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 41.3%, carboxylic acid content 4.9%, small molecule chemical combination
Object content is 6.4%, and the content of macromolecular compound is 16.7%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
4.8%, carboxylic acid content 6.5%, small molecule compound content is 10.8%, and macromolecular compound content is 65.3%.Aliphatic series
The content of ketone improves 8.60 times.
Embodiment five
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
5mm, holding time 12h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 6.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 9.5g, pyrolysis time 130s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 75s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 500 DEG C,
Calcination time is 2h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 550 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 7.5mL, and the amount of cation exchange resin is 3g, is saved
Temperature is 5 DEG C, and the holding time is for 24 hours, during preservation, to shake 75s every 45min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition is 13 DEG C/min,
It is warming up to 325 DEG C of constant temperature 1.5h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:5, charge velocity
For 3mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 3h, and carrier gas is helium, and the rate for introducing gas is 15cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 49.3%, carboxylic acid content 5.5%, small molecule chemical combination
Object content is 5.5%, and the content of macromolecular compound is 18.1%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
5.3%, carboxylic acid content 5.1%, small molecule compound content is 9.3%, and macromolecular compound content is 65.3%.Aliphatic ketone
Content improve 9.30 times.
Embodiment six
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
7mm, holding time 12h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 6.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 9.5g, pyrolysis time 130s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 75s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 500 DEG C,
Calcination time is 2h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 550 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 7.5mL, and the amount of cation exchange resin is 3g, is saved
Temperature is 5 DEG C, and the holding time is for 24 hours, during preservation, to shake 75s every 45min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition is 13 DEG C/min,
It is warming up to 325 DEG C of constant temperature 1.5h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:5, charge velocity
For 3mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 3h, and carrier gas is helium, and the rate for introducing gas is 15cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 51.2%, carboxylic acid content 4.9%, small molecule chemical combination
Object content is 6.4%, and the content of macromolecular compound is 19.9%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
4.9%, carboxylic acid content 4.5%, small molecule compound content is 8.7%, and macromolecular compound content is 67.3%.Aliphatic ketone
Content improve 10.45 times.
Embodiment seven
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
8mm, holding time 12h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 6.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 9.5g, pyrolysis time 130s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 75s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 500 DEG C,
Calcination time is 2h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 550 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 7.5mL, and the amount of cation exchange resin is 3g, is saved
Temperature is 5 DEG C, and the holding time is for 24 hours, during preservation, to shake 75s every 45min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition is 13 DEG C/min,
It is warming up to 325 DEG C of constant temperature 1.5h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:5, charge velocity
For 3mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 3h, and carrier gas is helium, and the rate for introducing gas is 15cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 52.3%, carboxylic acid content 4.8%, small molecule chemical combination
Object content is 5.5%, and the content of macromolecular compound is 19.5%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
4.6%, carboxylic acid content 4.1%, small molecule compound content is 7.5%, and macromolecular compound content is 68.6%.Aliphatic ketone
Content improve 11.37 times.
Embodiment eight
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
9mm, holding time 12h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 6.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 9.5g, pyrolysis time 130s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 75s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 500 DEG C,
Calcination time is 2h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 550 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 7.5mL, and the amount of cation exchange resin is 3g, is saved
Temperature is 5 DEG C, and the holding time is for 24 hours, during preservation, to shake 75s every 45min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition is 13 DEG C/min,
It is warming up to 325 DEG C of constant temperature 1.5h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:5, charge velocity
For 3mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 3h, and carrier gas is helium, and the rate for introducing gas is 15cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 53.3%, carboxylic acid content 4.8%, small molecule chemical combination
Object content is 4.3%, and the content of macromolecular compound is 18.7%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
4.4%, carboxylic acid content 3.8%, small molecule compound content is 6.6%, and macromolecular compound content is 65.5%.Aliphatic ketone
Content improve 12.11 times.
Embodiment nine
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
10mm, holding time 12h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 6.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 9.5g, pyrolysis time 130s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 75s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 500 DEG C,
Calcination time is 2h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 550 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 7.5mL, and the amount of cation exchange resin is 3g, is saved
Temperature is 5 DEG C, and the holding time is for 24 hours, during preservation, to shake 75s every 45min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition is 13 DEG C/min,
It is warming up to 325 DEG C of constant temperature 1.5h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:5, charge velocity
For 3mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 3h, and carrier gas is helium, and the rate for introducing gas is 15cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 54.1%, carboxylic acid content 3.5%, small molecule chemical combination
Object content is 3.1%, and the content of macromolecular compound is 16.9%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
4.3%, carboxylic acid content 4.8%, small molecule compound content is 7.5%, and macromolecular compound content is 58.3%.Aliphatic ketone
Content improve 12.58 times.
Embodiment ten
Step 1 will be pyrolyzed and generate the particle that the Wooden Biomass of wood vinegar is ground into partial size as 2~10mm, be put into dry
10~14h is saved in dry case at 100 DEG C.The Wooden Biomass used in the present embodiment is cedar sawdust, and powder particle diameter is
10mm, holding time 12h.
Step 2 seals after pyrolysis reactor is heated to 450~500 DEG C with the rate of heat addition of 4.5~8.5 DEG C/s.In
In the present embodiment, the rate of heat addition is 6.5 DEG C/s, is sealed after being heated to 475 DEG C.
Step 3 takes 4.5~15g of smashed cedar sawdust particle to be put into pyrolysis reactor, takes after being pyrolyzed 60~200s
Out, the gas produced in pyrolysis reactor export is condensed into liquid and collected, obtain the wooden vinegar stoste.In the present embodiment, China fir
The additional amount for considering particle to be worth doing is 9.5g, pyrolysis time 130s.
Step 4, by Fe (NO3)3·9H2O and ZrO (NO3)2·2H2O is made into after aqueous solution to be put into test tube respectively and mix
30~120s is stirred, ammonia spirit is added into mixed solution, generates sediment ZrO2·FeOx, in the present embodiment, mixing is stirred
Mixing the time is 75s, sediment ZrO2·FeOxThe value of middle X not can determine that may only determine it is iron oxide but uncertain specific chemistry
Formula.
Step 5, by sediment ZrO2·FeOxIt is placed in air atmosphere, 1~3h powdering is calcined at 400~600 DEG C,
After being cooled to room temperature, the sediment of powdery is granulated under without any binder.In the present embodiment, calcination temperature is 500 DEG C,
Calcination time is 2h.
Step 6, it is 200~900 μm of particle as catalyst that the sediment after granulation, which is crushed, and screens out diameter.
In the present embodiment, the catalyst particle diameter screened out is 550 μm.
Step 7, the 5~10mL of the wooden vinegar stoste for taking step 3 to obtain are put into reactor, and the cation that 2~4g is added is handed over
Resin is changed, 12~36h is saved at 1~8 DEG C, during preservation, shakes 30~120s every 30~60min.It filters later
Wood vinegar after being exchanged.In this embodiment, the amount of the wooden vinegar stoste is 7.5mL, and the amount of cation exchange resin is 3g, is saved
Temperature is 5 DEG C, and the holding time is for 24 hours, during preservation, to shake 75s every 45min.
Step 8, the catalyst that step 6 is obtained is put into fixed bed reactors, to fixed bed reactors with 5~20
DEG C/rate of heat addition of min is warming up to 200~450 DEG C, and 1~2h of constant temperature.In the present embodiment, the rate of heat addition is 13 DEG C/min,
It is warming up to 325 DEG C of constant temperature 1.5h.
Step 9, the ratio of the wood vinegar that step 7 is obtained and deionized water 1:1~10 in mass ratio, with 2~4mL/h
Rate is injected into fixed bed reactors.In the present embodiment, wood vinegar and the mass ratio of deionized water are 1:10, charge velocity
For 3mL/h.
Step 10, wood vinegar carry out catalysis 2~4h of reaction, the gas that will be generated in reaction process under the effect of the catalyst
By carrier gas with 10~20cm3The rate of/min is introduced into the collector in ice water mixing channel.In the present embodiment, catalysis is anti-
The time answered is 3h, and carrier gas is helium, and the rate for introducing gas is 15cm3/min。
Step 11 condenses the gas in collector, obtains the condensate liquid rich in ketone chemicals, incoagulability
Gas is collected by gas bag.
Obtained condensate liquid is measured, wherein aliphatic ketone content 55.0%, carboxylic acid content 1.2%, small molecule chemical combination
Object content is 2.7%, and the content of macromolecular compound is 14.2%.The content of aliphatic ketone is in the wooden vinegar stoste without catalysis
4.2%, carboxylic acid content 2.4%, small molecule compound content is 6.1%, and macromolecular compound content is 51.3%.Aliphatic ketone
Content improve 13.09 times.
The action and effect of embodiment
According to the above embodiments, because using ZrO2·FeOxCatalyst, the catalyst choice will be in wood vinegar
Macromolecular substances and part small-molecule substance are converted into aliphatic ketone, improve content of the ketone chemicals in wood vinegar.And
Greenhouse gases are not in addition generated in entire conversion process, it is environmentally friendly, there is huge Exploitative potential.This method simultaneously
Also provide a kind of method that substitution fossil energy produces useful chemicals.
Above embodiment is preferred case of the invention, the protection scope being not intended to limit the invention.
Claims (8)
1. a kind of method that selective catalysis wood vinegar is converted into ketone chemicals, which comprises the following steps:
Step 1, by Fe (NO3)3Aqueous solution and ZrO (NO3)2Ammonia spirit is added in aqueous solution after being mixed, generate sediment
ZrO2·FeOx, the sediment is obtained after filtering, the sediment is calcined into powdering under certain condition, by institute after cooling
It states sediment and is granulated into the granular sediment that diameter is 200~900 μm, the granular precipitating under without any binder
Object is catalyst；
Step 2 takes the wooden vinegar stoste of certain volume, and cation exchange resin is added and saves 12~36h at 1~8 DEG C, filters,
It obtains and the wood vinegar after ion exchange；
The catalyst is put into fixed bed reactors by step 3, is heated to 200~450 DEG C and perseverance with certain rate
1~2h of temperature；
Step 4 mixes the ratio of the wood vinegar and deionized water 1:1~10 in mass ratio, is infused with the rate of 2~4mL/h
Enter in the fixed bed reactors, the wood vinegar carries out catalysis reaction under the action of the catalyst, will be in reaction process
The gas of generation is by carrier gas with 10~20cm3The rate of/min exports, and derived gas is condensed, and obtains rich in the ketone
The condensate liquid of chemicals.
2. the method that selective catalysis wood vinegar according to claim 1 is converted into ketone chemicals, it is characterised in that:
Wherein, in step 1, the time of mixing is 30~120s.
3. the method that selective catalysis wood vinegar according to claim 1 is converted into ketone chemicals, it is characterised in that:
Wherein, in step 1, the condition of calcining is calcined in air atmosphere, and calcination temperature is 400~600 DEG C, when calcining
Between be 1~3h.
4. the method that selective catalysis wood vinegar according to claim 1 is converted into ketone chemicals, it is characterised in that:
Wherein, in step 2, the wood vinegar stoste is without the wooden vinegar stoste by purification, purification.
5. the method that selective catalysis wood vinegar according to claim 1 is converted into ketone chemicals, it is characterised in that:
Wherein, in step 2, during preservation, 30~120s is shaken every 30~60min.
6. the method that selective catalysis wood vinegar according to claim 1 is converted into ketone chemicals, it is characterised in that:
Wherein, in step 2, the volume of the wood vinegar stoste is 5~10mL, the additional amount of cation exchange resin is 2~
4g。
7. the method that selective catalysis wood vinegar according to claim 1 is converted into ketone chemicals, it is characterised in that:
Wherein, in step 3, the rate of heat addition of pyrolysis reactor is 5~10 DEG C/min.
8. the method that selective catalysis wood vinegar according to claim 1 is converted into ketone chemicals, it is characterised in that:
Wherein, in step 4, the time for being catalyzed reaction is 2~4h, and the carrier gas is inert gas or nitrogen.
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