CN104674585B - Transcritical CO_2 response system hydrolyzes the method and device of slurrying - Google Patents

Transcritical CO_2 response system hydrolyzes the method and device of slurrying Download PDF

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CN104674585B
CN104674585B CN201510082886.3A CN201510082886A CN104674585B CN 104674585 B CN104674585 B CN 104674585B CN 201510082886 A CN201510082886 A CN 201510082886A CN 104674585 B CN104674585 B CN 104674585B
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gas
reactor
slurrying
response system
decompressor
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CN104674585A (en
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陈小鹏
梁杰珍
王琳琳
韦小杰
王华生
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Guangxi University
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Guangxi University
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C7/00—Digesters

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a kind of method that transcritical CO_2 response system hydrolyzes slurrying, comprises the following steps：(1) prepare raw material, by water and wood chip or blade in mass ratio 2:1～200:1 is mutually mixed, and then preheats；(2) hydrolysis, mixture obtained in step (1) is put in reactor, CO is filled with toward in reactor2, the temperature in reactor is 80～500 DEG C, and pressure is 3～50MPa；The temperature in device is answered to be 80～500 DEG C, reaction pressure is 0.5～50.0MPa, makes the CO being passed through2Gas is in a supercritical state or subcritical state；(3) reacted mixed gas in reactor are taken out；(4), after reacting 1～6h, Jing after decompression, material releases slurry and reducing sugar obtained in reaction from reactor.The present invention is with super/subcritical CO2Be dissolved in the water and chemical pulping is carried out as Bronsted acid replacement Caustic soda or sulfate or sulphite, reduce the discharge of heavily contaminated waste water, and the pulping process of the present invention is without black liquor also non-exhaust emission, is a kind of pulping process of environmental protection.

Description

Transcritical CO_2 response system hydrolyzes the method and device of slurrying
Technical field
The present invention relates to paper-making pulping field, the method for more particularly to a kind of transcritical CO_2 response system hydrolysis slurrying and Device.
Background technology
Paper and cardboard are caused based on paper pulp, and pulping process can be divided into：Chemical method and Mechanical Method and it is in two Chemical mechanical pulping, semichemical method between person.In whole world paper output, chemical pulp accounts for 72.4%, and mechanical pulp accounts for 16.6%, its It is remaining to account for 11.0%.Chemical pulping is divided into alkaline process and acid system, and alkaline process includes lime method and soda processes.Chemical pulping it is main Purpose is to make the intercellular lignin that fiber is bonded together make paper pulp in removing plant fiber material as much as possible, make Slurry process is mainly comprising operations such as steaming and decocting, washing and bleachings.Cooking process is plant material in Caustic soda or sulfate or sulfurous acid High temperature steaming in the presence of salt, so that the lignin degradation in plant fiber cells wall.Plant fiber material is obtained Jing after steaming and decocting About 50% paper pulp, forms a large amount of high-concentration waste liquids, to alkaline process system during 50% or so material is dissolved in cooking liquor in addition Slurry, this waste liquid is black liquor；To acid polishing, this waste liquid is referred to as red liquid.The Chinese paper mill of major part at present adopts alkaline process system Slurry, its black liquor for being discharged is pollutant levels highest in pulping process, the most deep waste water of colourity, wherein containing substantial amounts of wooden Catabolite, pigment, pentose class, residual alkali and other leachables such as element and hemicellulose, will discharge 10 every about 1 ton of paper pulp of production Ton black liquor, not only causes the waste of plant resourceses to also result in serious problem of environmental pollution, is the most thorny difficult problem of paper industry And study hotspot.
The information for being disclosed in the background section is merely intended to increase the understanding of the general background to the present invention, and should not When the prior art for being considered to recognize or imply the information structure in any form well known to persons skilled in the art.
The content of the invention
It is an object of the invention to provide a kind of method that transcritical CO_2 response system hydrolyzes slurrying, with super/subcritical CO2Be dissolved in the water and chemical pulping is carried out as Bronsted acid replacement Caustic soda or sulfate or sulphite, reduce heavily contaminated The discharge of waste water.
Another object of the present invention is to provide the device that a kind of transcritical CO_2 response system hydrolyzes slurrying.
For achieving the above object, the invention provides a kind of transcritical CO_2 response system hydrolyze slurrying method, including with Lower step：
(1) prepare raw material, by water and wood chip or blade in mass ratio 2:1～200:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, CO is filled with toward in reactor2, reaction Temperature in device is 80～500 DEG C, and pressure is 0.5～50MPa；The temperature in device is answered to be 80～500 DEG C, reaction pressure is 0.5 ～50.0MPa, makes the CO being passed through2Gas is in a supercritical state or subcritical state；
(3) reacted mixed gas in reactor are taken out；
(4), after reacting 1～6h, Jing after decompression, material releases slurry and reducing sugar obtained in reaction from reactor.
Preferably, in above-mentioned technical proposal, in step (3) mixed gas, contain CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～12000m3/ h, by gas by decompressor, expanded machine expands blood pressure lowering For 0～1.0MPa, lower the temperature as 5 DEG C～80 DEG C, decompressor is connected with turbocompressor, CO is supplemented toward in turbocompressor2Gas, Again mixed gas are passed through in reactor.When gas flow is 0, no gas flows out.
Preferably, in above-mentioned technical proposal, the gas flowed out in the step (3) divides into gas-liquid after decompressor Separated from device, remaining gas is CO2, by CO2Turbocompressor is passed through again.
Preferably, in above-mentioned technical proposal, the temperature of gas-liquid separator is 5～40 DEG C, and pressure is 0.0～1.0MPa, gas Liquid/gas separator fluid flow is 0～100m3/ h, gas flow are 0～10000m3/h.When liquid outflow amount and gas outflow are When 0, i.e., no liquid or gas flow out.
Preferably, in above-mentioned technical proposal, the step (2) point 1～10 stage toward in reactor is filled with CO2。
Preferably, in above-mentioned technical proposal, described wood chip or blade are in bagasse, Bambusa cerosissima McClure, Caulis et Folium Oryzae or Pinus massoniana Lamb It is a kind of.
A kind of device that slurrying is hydrolyzed for transcritical CO_2 response system, including：Reactor, which includes：Multiple heating Pipe, located inside reactor；And gas distributor, which includes air inlet and multiple shower nozzles for aerofluxuss；Decompressor, its with The reactor connection；And turbocompressor, which is connected with the decompressor, and drives the turbine by the decompressor Compressor operating, the gas outlet of the turbocompressor are connected with the reactor.
Preferably, in above-mentioned technical proposal, the gas distributor is L-shaped, and its bottom is annulus tubulose, in the annulus Multiple shower nozzles for aerofluxuss are uniformly provided with pipe, the shower nozzle is obliquely installed.
Preferably, in above-mentioned technical proposal, the heating tube is multiple, is distributed on the inside reactor in parallel；Institute Stating gas distributor has multiple, and the plurality of gas distributor is interconnected, and described each gas distributor is located at the heating Between pipe.
Preferably, in above-mentioned technical proposal, the device that slurrying is hydrolyzed for transcritical CO_2 response system also includes： Preprocessor, which is connected with the reactor, carries out pretreatment for the raw material needed for producing；Gas-liquid separator, its with it is described Decompressor connects；And jet discharging device, which connects in the reactor, for being blown off slurry and reducing sugar.
The mechanism of above-mentioned reaction is as follows：
CO is filled with toward in reactor2Mixed gas, CO2Gas is constantly circulated in reactor and bubbling flowing, in high temperature Under condition of high voltage, CO2In supercritical or subcritical state.Using super/subcritical CO2It is dissolved in the water to form Bronsted acid to planting Lignin, pentose class and half fiber in fibres etc. are hydrolyzed to degrade and generate reducing sugar, furfural and acetic acid etc., and generate Volatile products, the vapor such as furfural and acetic acid circulated CO2Entrainment is constantly flowed out from reactor and makes decompressor do work Turbocompressor 4 is driven, to reach expansion-compression self-loopa.
The gas phase taken out from reactor by decompressor, the mixed gas of outflow include furfural, acetic acid, vapor and CO2.Decompressor is linked with turbocompressor, due to the CO in reactor2In supercritical or subcritical state, when gas phase is adopted Take out into after decompressor, CO2It is low-temp low-pressure normality from supercriticality or subcritical state transition, from super/subcritical shape State transition is that low-temp low-pressure normality is referred to as Trans-critical cycle state.Mixed gas gas expansion promote decompressor acting, decompressor with Turbocompressor connects, and decompressor drives compressor operating.Gaseous phase materials from decompressor flow through gas-liquid separator carry out condensation and Gas-liquid separation, gained liquid are furfural and second aqueous acid；Gas is primarily as the CO for recycling2, circulation CO2With The new CO for supplementing2Reactor is flowed back to Jing after turbocompressor pressurization.As the gas phase flowed out from reactor contains CO2, water vapour, Furfural and acetic acid etc., and the gas of pressurized circulation is only on-condensible gas CO2, this is because after expanded machine blood pressure lowering cooling, water, bran Aldehyde and acetic acid steam are condensed into liquid from gas-liquid separator separates out, and the gas for being used to circulate only is left on-condensible gas CO2 Reason, it is seen that drive decompressor gas flow more than turbocompressor pressurized recirculating gas flow, also i other words expansion The work(that machine is made is by heating coil supply water in reactor more than the energy increased needed for the work(needed for turbocompressor, system Evaporation heat energy, thus the system is capable of achieving expansion-compression self-loopa.
As Plant fiber hydrolyzes the furfural that generates and acetic acid is constantly wandered about as a refugee reactor, so as to eliminating product accumulation The feedback inhibition for causing, has broken the chemical equilibrium of lignin, pentose and hydrolysis of hemicellulose degraded in Plant fiber, has made Direction of the reaction constantly towards hydrolytic degradation is carried out, and so as to improve hydrolytic degradation response speed and equilibrium conversion, is realized Hydrolytic degradation reaction-detached coupling.Again due to CO2Constantly circulate in the reactor, enhance plant fiber material Bubbling stirring and Mass and heat transfer, and CO2Also produce " supercavity " effect, reduce to greatest extent material, water it is gentle it Between flow resistance, greatly increase the heat and mass effect of reactor.Moreover, CO2" same to molecule " effect can also be produced, Pulp fiber element degraded is suppressed to generate CO2Side reaction, improve the paper pulp yield of wood chip or blade slurrying.
Compared with prior art, the present invention has the advantages that：
(1) with super/subcritical CO2Be dissolved in the water Caustic soda or sulfate or sulphite are substituted as Bronsted acid Method slurrying, it is to adopt soda pulping process to reduce the discharge of heavily contaminated waste water, particularly most of China paper mill, often produces 1 Ton paper pulp will discharge 10 tons of black liquor, and the pulping process of the present invention is without black liquor also non-exhaust emission, is a kind of system of environmental protection Paste-making method.
(2) method that transcritical CO_2 response system of the present invention hydrolyzes slurrying, using Trans-critical cycle CO2Hydrolytic degradation reaction-point Slurrying is carried out from coupling, paper pulp also simultaneously by-product furfural, acetic acid and reducing sugar is not only produced, is taken full advantage of wood chip or blade The resources such as the lignin, pentose class and half fiber that contain in raw material produce large valuable chemical products, and eating dry bleeding can The effective ingredient of regenerated resources, realizes the zero-emission target of " atom economy ", greatly increases the utilization of biomass resource Rate.
(3) transcritical CO_2 response system of the present invention hydrolyzes the device of slurrying, using Trans-critical cycle CO2Expansion-compression self-loopa Mode, make from Trans-critical cycle reactor flow out high pressure CO2Turbocompressor is pushed directly on the expanded machine expansion of water vapour to add Pressure on-condensible gas CO2Circulating involuting system, reduces heat to power output process：The available energy of heat energy → mechanical energy → electric energy → mechanical energy Loss, improves the heat power efficiency of heat energy conversion, realizes the target of energy-saving and emission-reduction and zero-emission.
(4) using the CO of circulating involuting system2Spray from the gas distribution tube with many shower nozzles, promote Trans-critical cycle reactor Interior wood chip or the stirring of blade material directional-rotation and generation " supercavity " effect, enhance the heat and mass in reactor.By Mechanical stirring device is not needed in Trans-critical cycle reactor, manufacture, operation, maintenance and the leakproof of high pressure equipment is more beneficial for.
(5) with super/subcritical CO2The Bronsted acid for being dissolved in water generation substitutes Caustic soda or sulfate or sulphite Method slurrying, with low cost, no inflammable and explosive and strong corrosive material, has a safety feature.
(6) Trans-critical cycle CO2Hydrolytic degradation pulping process is higher by 5%～10% than the paper pulp total yield of traditional pulping process, and And hardness is low, intensity is good, whiteness is high, bleachability good.
Description of the drawings
Fig. 1 is the process chart of hydrolysis slurrying of the invention.
Fig. 2 is the structural representation according to reactor of the present invention.
Fig. 3 is the structural representation according to single gas distributor in reactor of the present invention.
Fig. 4 is the top view according to single gas distributor in reactor of the present invention.
Specific embodiment
Below in conjunction with the accompanying drawings, the specific embodiment of the present invention is described in detail, it is to be understood that the guarantor of the present invention Shield scope is not limited by specific embodiment.
Explicitly indicate that unless otherwise other, otherwise in entire disclosure and claims, term " including " or its change Change such as "comprising" or " including " etc. and will be understood to comprise stated element or ingredient, and do not exclude other units Part or other ingredients.
Embodiment 1
As shown in Figures 1 to 4, the device of slurrying is hydrolyzed for transcritical CO_2 response system, including：It is preprocessor 1, anti- Answer device 2, decompressor 3, turbocompressor 4, gas-liquid separator 5, jet discharging device 6.
The discharging opening of preprocessor 1 is connected with the charging aperture of the reactor 2, preprocessor 1 for production needed for Raw material carries out heat pre-treatment.Reactor 2, in cylinder, the top of reactor is provided with charging aperture 21, gas outlet 22, and bottom sets There is discharging opening 23, reactor 2 includes heating tube 24, is heating coil, and which is located inside reactor；Gas distributor 25, its bag Include air inlet 251 and multiple shower nozzles 252 for aerofluxuss；Decompressor 3 is connected with the gas outlet of the reactor 2.Turbo compressor Machine 4 is connected with the decompressor 3, and drives the turbocompressor 4 to work by the decompressor 3, the turbocompressor 4 Gas outlet be connected with the reactor 2.Gas-liquid separator 4 is connected with the decompressor 3, mixed for what is produced after separating reaction Gas is closed, gas and liquid is isolated.Jet discharging device 6 is connected with reactor 2, for the slurry that is blown off in reactor 2 and reduction Sugar.
Preferably, the gas distributor 25 is L-shaped, and its bottom is annulus tubulose, is uniformly provided with the ring tube Multiple shower nozzles 252 for aerofluxuss, the shower nozzle are " L " type, are obliquely installed into same direction.It is evenly equipped with pipe annular in shape Multiple aerofluxuss shower nozzles, discharge gas and are more uniformly distributed so that be fully contacted as the material in reactor and gas, accelerate reaction Speed.The gas that the shower nozzle being inclined to set sprays is inclined toward same direction and sprays gas, makes bubble in contorted in reactor 2 Interior motion so that the material of reaction is fully contacted with gas, accelerates response speed.
Preferably, the heating tube 24 is multiple, is distributed on inside the reactor 2 in parallel；The gas distributor 25 have multiple, and the plurality of gas distributor 25 is interconnected, and the ring tube of each gas distributor 25 is located at described adding Between heat pipe 24.
By the use of above-mentioned device as reaction unit, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including with Lower step：
(1) prepare raw material, by water and bagasse in mass ratio 50:1 is mutually mixed, and then preheats.
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 160 DEG C, toward instead Answer2, keep the temperature in reactor to be 160 DEG C, pressure is 8MPa.
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 20 DEG C～30 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 10～20 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～50m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device.
(4), after reacting 2h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 62.5% that bagasse produces slurry total yield.
Embodiment 2
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and bagasse in mass ratio 200:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 300 DEG C, toward instead Answer2, the temperature in reactor is 300 DEG C, and pressure is 15MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 20 DEG C～30 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 10～20 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～50m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 2h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 61.07% that bagasse produces slurry total yield.
Embodiment 3
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and bagasse in mass ratio 70:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 500 DEG C, toward instead Answer2, the temperature in reactor is 500 DEG C, and pressure is 30MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 20 DEG C～30 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 10～20 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～50m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 3h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 55.10% that bagasse produces slurry total yield.
Embodiment 4
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Bambusa cerosissima McClure in mass ratio 50:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 150 DEG C, toward instead Answer2, the temperature in reactor is 150 DEG C, and pressure is 8MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 20 DEG C～30 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 10～20 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～50m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 3h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 52.40% that Bambusa cerosissima McClure produces slurry total yield.
Embodiment 5
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Bambusa cerosissima McClure in mass ratio 200:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 300 DEG C, toward instead Answer2, the temperature in reactor is 300 DEG C, and pressure is 3MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 20 DEG C～30 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 10～20 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～50m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 3h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 48.70% that Bambusa cerosissima McClure produces slurry total yield.
Embodiment 6
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Caulis et Folium Oryzae in mass ratio 2:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 150 DEG C, toward instead Answer2, keep the temperature in reactor to be 150 DEG C, pressure is 8MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 20 DEG C～30 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 10～20 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～50m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 4h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 56.60% that Caulis et Folium Oryzae produces slurry total yield.
Embodiment 7
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Caulis et Folium Oryzae in mass ratio 200:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 300 DEG C, toward instead Answer2, keep the temperature in reactor to be 300 DEG C, pressure is 15MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 20 DEG C～30 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 10～20 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～50m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 1h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 55.42% that Caulis et Folium Oryzae produces slurry total yield.
Embodiment 8
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Pinus massoniana Lamb in mass ratio 20:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 300 DEG C, toward instead Answer2, keep the temperature in reactor to be 300 DEG C, pressure is 15MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 20 DEG C～30 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 10～20 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～50m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 5h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method, it is 61.20% that Pinus massoniana Lamb produces slurry total yield.
Embodiment 9
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Pinus massoniana Lamb in mass ratio 50:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 400 DEG C, toward instead Answer2, keep the temperature in reactor to be 400 DEG C, pressure is 15MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～12000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 60 DEG C～70 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 20～30 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～70m3/ H, gas flow are 0～9000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 5h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 60.70% that Pinus massoniana Lamb produces slurry total yield.
Embodiment 10
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Caulis et Folium Oryzae in mass ratio 100:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 200 DEG C, toward instead Answer2, keep the temperature in reactor to be 200 DEG C, pressure is 8MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 30 DEG C～40 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 20～30 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～20m3/ H, gas flow are 0～5000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 2h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 61.70% that Caulis et Folium Oryzae produces slurry total yield.
Embodiment 11
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Caulis et Folium Oryzae in mass ratio 150:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 250 DEG C, toward instead Answer2, keep the temperature in reactor to be 250 DEG C, pressure is 8MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～10000m3/ h, when gas flow is 0, no gas flows out.By gas By decompressor, the expansion blood pressure lowering of expanded machine is 0～1.0MPa, is lowered the temperature as 70 DEG C～80 DEG C, is carried out point into gas-liquid separator From the temperature of gas-liquid separator is 30～40 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～70m3/ H, gas flow are 0～8000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquids and gases flow out.It is surplus Under gas be CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2Reaction is passed through Jing after turbocompressor pressurization In device；
(4), after reacting 2h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 56.10% that Caulis et Folium Oryzae produces slurry total yield.
Embodiment 12
The reaction unit for using is same as Example 1, a kind of method that transcritical CO_2 response system hydrolyzes slurrying, including Following steps：
(1) prepare raw material, by water and Pinus massoniana Lamb in mass ratio 10:1 is mutually mixed, and then preheats；
(2) hydrolysis, mixture obtained in step (1) is put in reactor, after being heated to 350 DEG C, toward instead Answer2, keep the temperature in reactor to be 350 DEG C, pressure is 8MPa；
(3) reacted mixed gas in reactor are taken out, in mixed gas, contains CO2, water vapour, furfural and acetic acid, The flow that mixed gas are taken out from reactor is 0～8000m3/ h, when gas flow is 0, no gas flows out.Gas is led to Decompressor is crossed, expanded machine expansion blood pressure lowering is 0～1.0MPa, lowers the temperature as 20 DEG C～30 DEG C, is separated into gas-liquid separator, The temperature of gas-liquid separator is 5～15 DEG C, and pressure is 0.0～1.0MPa, and gas-liquid separator fluid flow is 0～100m3/ h, gas Body flow is 0～7000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquids and gases flow out.It is remaining Gas is CO2, by CO2Turbocompressor is passed through again, itself and the new CO for supplementing2It is passed through in reactor Jing after turbocompressor pressurization；
(4), after reacting 2h, reactor is decompressed to 1.0MPa, release from reactor slurry and reducing sugar obtained in reaction from Jet discharging device is put in reactor, using the quick blowing of direct total head material spray method.It is 60.20% that Pinus massoniana Lamb produces slurry total yield.
It is aforementioned to the present invention specific illustrative embodiment description be in order to illustrate and illustration purpose.These descriptions It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, much can be changed And change.The purpose of selecting and describing the exemplary embodiment is that explaining that the certain principles and its reality of the present invention should With so that those skilled in the art can realize and using the present invention a variety of exemplaries and A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.

Claims (9)

1. a kind of method that transcritical CO_2 response system hydrolyzes slurrying, it is characterised in that comprise the following steps：
(1) prepare raw material, by water and wood chip or blade in mass ratio 2:1～200:1 is mutually mixed, and then preheats；
(2) Trans-critical cycle CO2Hydrolysis, mixture obtained in step (1) is put in reactor, CO is filled with toward in reactor2, Temperature in reactor is 80～500 DEG C, and pressure is 0.5～50MPa；
(3) Trans-critical cycle expansion compression process, in taking out reactor, continuously stream enters decompressor to reacted mixed gas, mixes Contain CO in closing gas2, water vapour, furfural and acetic acid, the flow of mixed gas is 0～12000m3/ h, by gas by expansion Machine, expanded machine expansion blood pressure lowering is 0～1.0MPa, is lowered the temperature as 5 DEG C～80 DEG C, realizes that Trans-critical cycle hydrolysis-separation coupling is made With；Decompressor is connected with turbocompressor, and CO is supplemented toward in turbocompressor2Gas, drives turbocompressor handle by decompressor Mixed gas circulating reflux is to reactor；
(4), after reacting 1～6h, Jing after decompression, material releases slurry and reducing sugar obtained in reaction from reactor.
2. Trans-critical cycle CO according to claim 12The method that response system hydrolyzes slurrying, it is characterised in that the step (3) gas flowed out in is separated into gas-liquid separator after decompressor, and remaining gas is CO2, by CO2It is passed through again Turbocompressor.
3. Trans-critical cycle CO according to claim 22The method that response system hydrolyzes slurrying, it is characterised in that gas-liquid separator Temperature be 5～40 DEG C, pressure be 0.0～1.0MPa, gas-liquid separator fluid flow be 0～100m3/ h, gas flow are 0 ～10000m3/ h, when liquid outflow amount and gas outflow are 0, i.e., no liquid or gas flow out.
4. Trans-critical cycle CO according to claim 12The method that response system hydrolyzes slurrying, it is characterised in that the step (2) toward in reactor, point 1～10 stage is filled with CO2。
5. Trans-critical cycle CO according to claim 12The method that response system hydrolyzes slurrying, it is characterised in that described wood chip Or blade is the one kind in bagasse, Bambusa cerosissima McClure, Caulis et Folium Oryzae or Pinus massoniana Lamb.
6. it is a kind of to be used for Trans-critical cycle CO2Response system hydrolyzes the device of slurrying, it is characterised in that include：
Reactor, which includes：Multiple heating tubes, located inside reactor；And gas distributor, which includes air inlet and multiple For the shower nozzle of aerofluxuss；
Decompressor, which is connected with the reactor；And
Turbocompressor, which is connected with the decompressor, and drives the turbocompressor work by the decompressor, described The gas outlet of turbocompressor is connected with the reactor.
7. according to claim 6 for Trans-critical cycle CO2Response system hydrolyzes the device of slurrying, it is characterised in that the gas Body distributor is L-shaped, and its bottom is annulus tubulose, and multiple shower nozzles for aerofluxuss are uniformly provided with the ring tube, described Shower nozzle is obliquely installed.
8. according to claim 6 for Trans-critical cycle CO2Response system hydrolyzes the device of slurrying, it is characterised in that described to add Heat pipe is multiple, is distributed on the inside reactor in parallel；The gas distributor has multiple, the plurality of gas distributor It is interconnected, described each gas distributor is located between the heating tube.
9. according to claim 6 for Trans-critical cycle CO2Response system hydrolyzes the device of slurrying, it is characterised in that also wrap Include：
Preprocessor, which is connected with the reactor, carries out pretreatment for the raw material needed for producing；
Gas-liquid separator, which is connected with the decompressor；And
Jet discharging device, which connects in the reactor, for being blown off slurry and reducing sugar.
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