CN101613377B - Biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and method - Google Patents
Biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and method Download PDFInfo
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- CN101613377B CN101613377B CN2009100888958A CN200910088895A CN101613377B CN 101613377 B CN101613377 B CN 101613377B CN 2009100888958 A CN2009100888958 A CN 2009100888958A CN 200910088895 A CN200910088895 A CN 200910088895A CN 101613377 B CN101613377 B CN 101613377B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and a method. The equipment comprises a water storage tank, a material storage tank with a stirring device, a preheating system, a supercritical reaction system, a primary cooling system, a subcritical reaction system, a final cooling system, a product collection system and an electronic temperature controlling system. The method comprises the following processing steps: water reaching preheat temperature and biomass material paste are rapidly mixed and then injected into the supercritical reaction system to be pretreated under supercritical condition; the reaction product is cooled through the primary cooling system and depressurized through a pressure reducing valve and then enters into the subcritical reaction system to be hydrolyzed sequentially, therefore fermentable sugars are continuously generated and collected. The invention utilizes the advantages of the supercritical method that the reaction is rapid, activator is not required and product inhibition does not exit, realizes that the continuous hydrolysis conversion of wood fiber biomass can generate fermentable sugars, is the foundation of subsequent resource recovery technologies, such as ethanol production by fermentation and the like, and has wide application prospect.
Description
Technical field
The present invention relates to a kind of supercritical and subcritical combined continuous type pre-treatment and hydrolysis specific equipment and method of biomass as resources; Be particularly related to pre-treatment of a kind of wood fiber biomass supercritical and subcritical combined continuous type and hydrolysis device and method, belong to biomass energy and handle and utilize technical field.
Background technology
Agricultural crop straw is one of biomass energy of tool potentiality to be exploited, and particularly dealing with alcohol technology of its resource technology has received extensive concern.The bottleneck factor that stalk is produced alcohol fuel has two: the first, its hydrolysis difficulty of the structures shape of Mierocrystalline cellulose own.Mierocrystalline cellulose is the linear giant molecule that is formed by D-Glucopyranose acid anhydride keyed jointing, and intermolecular and molecular memory have highly crystalline and insoluble at a lot of hydrogen bonds, has reduced the contact area with catalyzer or enzyme, the hydrolysis difficulty.The second, the xylogen package action makes Mierocrystalline cellulose be difficult to hydrolysis.Xylogen is the difficult degradation superpolymer by phenylpropyl alcohol alkane cell link, and normal and semicellulose is filled between the cell walls fiber together, tightly is wrapped in Mierocrystalline cellulose, makes it more be difficult to be dissolved in hydrolysising solvent or contacts with enzyme, has strengthened the difficulty of its hydrolysis.
The method of stalk pre-treatment at present and hydrolysis mainly contains s.t., steam explosion and enzymic hydrolysis.The s.t. meeting causes equipment corrosion, environmental pollution; Steam explosion then can cause a large amount of wood sugar losses; Enzymic hydrolysis needs at least 3 kinds of main enzymes to exist simultaneously, and inhibitory substance must not be arranged, and strict to conditional request, enzyme consumption is big, cost is high, and the residence time needs more than 3 days.
Supercritical methanol technology is carried out pre-treatment and hydrolysis to stalk; Be to utilize water (374.2 ℃ increase (approximately than character such as high 3 one magnitude of normal temperature with the enhancing of the above solvating ability of 22.1MPa, degree of ionization under super critical condition; Make cellulose dissolution in the stalk; Realization separates with xylogen fully, and utilizes ionized H+ to be hydrolyzed as catalyzer.Utmost point short period of time inner cellulose can be accomplished hydrolysis and obtain products such as oligose, glucose, can solve technical problems such as s.t. etching apparatus, enzymic hydrolysis production efficiency be low.But glucose decomposition reaction speed in supercritical water is very big, promptly is decomposed into rapidly materials such as the erythrose that can not carry out ethanol fermentation, furfural.Therefore, existing supercritical process still can not obtain gratifying fermentable sugars transformation efficiency.
Yet when temperature of reaction, when pressure reduces, the rate of decomposition of glucose also is index decreased, as (as 300 ℃, the rate of decomposition of glucose is than (reducing by 2 one magnitude as 400 ℃ in the supercritical water in the subcritical water.Because subcritical water density is bigger than supercritical water, its hydrolysis to high glycan and oligose is more favourable.Therefore; The supercritical and subcritical combined technical method can be proposed; At first stalk pre-treatment and hydrolysis in supercritical water makes Mierocrystalline cellulose thoroughly be hydrolyzed to oligose, further is hydrolyzed to glucose through undercritical conditions again; Both utilize supercritical methanol technology to be swift in response, to need not the advantage of catalyzer, the inhibition of no product, solved its unstable products, condition technical bottleneck rambunctious again.
Based on above-mentioned thinking; Crowd formula pre-treatment and the hydrolysis device and working method (the Zhao et al.Combined Supercritical and Subcritical Process for CelluloseHydrolysis to Fermentable Hexoses.Environ.Sci.Technol.2009 of the supercritical and subcritical combination of biomass have been developed both at home and abroad; 43 (5)), yet, formula pre-treatment and hydrolysis device criticized because batch operation does not have continuity; Equipment scale is difficult to amplify; Bigger to energy consumption, only limit to scientific experimentation and mechanism research at present, can not be applied to actual production.
Summary of the invention
The purpose of this invention is to provide a kind of biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis device and method; The operation that purport solves batch formula pre-treatment and hydrolysis does not have continuity; Equipment scale is difficult to amplify, and the technological deficiency bigger to energy consumption can realize that the supercritical and subcritical of lignocellulose raw material makes up continuous pre-treatment and hydrolysis; Novel and the resource utilization of a wood fiber biomass hydrolysis efficiently approach is provided, has broad application prospects.
The present invention adopts following technical scheme:
A kind of equipment that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis is characterized in that: said equipment comprises water storing tank 1, with the material-storage jar 2 of whipping appts; Preheat system 5; Supercritical reaction system 6, first cooling system 7, subcritical reaction system 8; Final cooling system 9, product collection system 10 and electron temperature-control system 11; Said water storing tank 1 through pipeline via high pressure intake pump 3 with preheat system 5 inlet and link to each other; Preheating system 5 outlet enters the mouth with supercritical reaction system 6 through threeway and links to each other; Said material-storage jar 2 with whipping appts links to each other with supercritical reaction system 6 inlets via high pressure charging pump 4 through pipeline, and 6 outlets of said supercritical reaction system enter the mouth with subcritical reaction system 8 with the first reducing valve 14a via first cooling system 7 through pipeline and link to each other; 8 outlets of said subcritical reaction system link to each other with product collection system 10 with final cooling system 9 via the second reducing valve 14b through pipeline; Described system, supercritical reaction system, first cooling system and the subcritical reaction system of preheating is connected with described electron temperature-control system 11 through temperature probe 13 and SW respectively.
Technical characterictic of the present invention also is: the described system 5 that preheats is by preheating pipeline and preheating apparatus is formed, and described preheating apparatus is made up of salt bath jar and the electrically heated rod that is arranged in this salt bath jar, and the described pipeline that preheats adopts spiral coil.Described supercritical reaction system 6 is made up of supercritical reaction pipeline and supercritical heated device, and described supercritical heated device is made up of salt bath jar and the electrically heated rod that is arranged in this salt bath jar, and described supercritical reaction pipeline adopts straight tube or bend pipe.Described subcritical reaction system 8 is made up of subcritical reaction pipeline and subcritical heating unit, and described subcritical heating unit is made up of porcelain bushing and the electrically heated rod that is arranged in this sleeve pipe, and described subcritical reaction pipeline adopts spiral coil.Described first cooling system 7 is made up of transfer conduit and cooling jacket with final cooling system 9, and described cooling jacket adopts reverse-flow water cooling sleeve pipe, and described transfer conduit adopts straight tube or spiral coil.
The present invention also provides a kind of method that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis, it is characterized in that this method comprises the steps:
1) each valve of equipment pipeline is all placed path; Unlocking electronic temperature controlling system 11 switches carry out preheating to preheating system 5, supercritical reaction system 6 and subcritical reaction system 8, are set at 350~370 ℃, 370~400 ℃ and 200~300 ℃ of assigned temperatures that scope is interior respectively;
2) biomass material and water are inserted in the material-storage jar 2 by 1: 40~1: 20 mixed of mass ratio, the whipping appts of opening material-storage jar 2 makes material be in evenly outstanding turbid state;
3) according to the suspension liquid volume in the material-storage jar, in water storing tank, add the water of 1~4 times of volume, the flow proportional of adjustable column high pressure intake pump and high pressure charging pump is 1: 1~4: 1;
4) when the temperature that preheats system 5, supercritical reaction system 6 and subcritical reaction system 8 during near the preheating assigned temperature; Open high pressure intake pump 3 and high pressure charging pump 4; Water in the water storing tank is injected the system that preheats; Reach after the preheating temperature with the biomass material slurries short mix of injecting through the high pressure charging pump by material-storage jar and inject the supercritical reaction system, reaction product through first cooling system and reducing valve cool off with step-down after entering subcritical reaction system;
5) regulate the first reducing valve 14a and the second reducing valve 14b, make supercritical reaction system 6 and subcritical reaction system 8 internal duct pressure be stabilized in 20~25MPa and 5~15MPa respectively;
6) cooling water flow of first cooling system 7 of adjusting and final cooling system 9, making separately, the export pipeline temperature is stabilized in 100~200 ℃ and 15~50 ℃ respectively;
7) treat flow in the said equipment, temperature and pressure all reach above-mentioned set(ting)value and stable after, utilize the final product of product collection system 10 continuous biomass collection pre-treatment and hydrolysis.
The present invention compared with prior art; Have the following advantages and the high-lighting effect: utilize supercritical methanol technology and subcritical method to be swift in response, to need not the advantage that catalyzer, no product suppress, can overcome that s.t. technology catalyst levels is big, difficult to be reclaimed and the reaction of enzymic hydrolysis technology is slow, product has deficiencies such as inhibition; And the control of the temperature and pressure through high pressure charging, sealing pipeline and each step of reaction; The operation that solves batch formula pre-treatment and hydrolysis is discontinuous, the difficult amplification of equipment, technological deficiency that energy consumption is big; The continous way pre-treatment and the hydrolysis that can realize wood fiber biomass transform and generate fermentable sugars; Be the basis of resource technologies such as follow-up fermentation producing and ethanol, have a extensive future.
Description of drawings
Accompanying drawing is supercritical and subcritical combined continuous type pre-treatment of the present invention and hydrolysis device and method flow synoptic diagram.
Among the figure: the 1-water storing tank; The 2-material-storage jar; 3-high pressure intake pump; 4-high pressure charging pump; 5-preheats system; 6-supercritical reaction system; The first cooling system of 7-; 8-subcritical reaction system; The final cooling system of 9-; 10-product collection jar; 11-electron temperature-control case; The 12-tensimeter; The 13-temperature probe; 14a-first reducing valve; 14b-second reducing valve; 15-pressure explosion trap.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is explained further details.
Fig. 1 is supercritical and subcritical combined continuous type pre-treatment of the present invention and hydrolysis device structural principle and method flow synoptic diagram.This equipment comprises water storing tank 1, and the material-storage jar 2 with stirring preheats system 5; Supercritical reaction system 6, first cooling system 7, subcritical reaction system 8; Final cooling system 9; Product collection system 10 and electron temperature-control system 11, said water storing tank 1 through pipeline via high pressure intake pump 3 with preheat system 5 inlet and link to each other, preheat system's 5 outlets and enter the mouth with supercritical reaction system 6 through threeway and link to each other; Saidly link to each other with supercritical reaction system 6 inlets via high pressure charging pump 4 and valve through pipeline with the material-storage jar that stirs 2,6 outlets of said supercritical reaction system are passed through pipeline and are entered the mouth with subcritical reaction system 8 with the first reducing valve 14a via first cooling system 7 and link to each other; 8 outlets of said subcritical reaction system link to each other with product collection system 10 with final cooling system 9 via the second reducing valve 14b through pipeline; Described system, supercritical reaction system, first cooling system and the subcritical reaction system of preheating is connected with described electron temperature-control system 11 through temperature probe 13 and SW respectively.
The described system 5 that preheats preheats pipeline and adopts spiral coil by preheating pipeline and preheating apparatus is formed, and its caliber and pipe range can be adjusted according to equipment scale, flow and pre-heating temperature; Preheating apparatus is made up of salt bath jar and the electrically heated rod that is arranged in this salt bath jar, can make the fluid that preheats in the pipeline maintain the assigned temperature between 260~450 ℃.Supercritical reaction system 6 is made up of supercritical reaction pipeline and supercritical heated device, and the supercritical reaction pipeline can adopt straight tube or bend pipe, and its caliber and pipe range can be adjusted according to equipment scale, flow and supercritical reaction conditions; The supercritical heated device is made up of salt bath jar and the electrically heated rod that is arranged in this salt bath jar, can make the fluid in the supercritical reaction pipeline keep the assigned temperature between 260~450 ℃.Subcritical reaction system 8 is made up of subcritical reaction pipeline and subcritical heating unit, and the subcritical reaction pipeline adopts spiral coil, and its caliber and pipe range can be adjusted according to equipment scale, flow and subcritical reaction condition; Subcritical heating unit is made up of porcelain bushing and the electrically heated rod that is arranged in this sleeve pipe, can make the fluid in the subcritical reaction pipeline maintain the assigned temperature between 30~360 ℃.First cooling system 7 is made up of transfer conduit and cooling jacket with final cooling system 9; Cooling jacket adopts reverse-flow water cooling sleeve pipe; Transfer conduit adopts straight tube or spiral coil, and its caliber and pipe range can be adjusted according to the caliber and the pipe range of supercritical reaction system and subcritical reaction system respectively; Can make the transfer conduit inner fluid be quickly cooled to the lesser temps that 15~300 ℃ of assigned temperatures in the scope are beneficial in subcritical reaction and 15~100 ℃ of scopes respectively through controlled chilling discharge and be beneficial to product collection.
Pressure after supercritical reaction system 6, subcritical reaction system 8 and the subcritical reaction system can adopt tensimeter 12 to monitor respectively, and range can be 40MPa, and can regulate respectively through the first reducing valve 14a and the second reducing valve 14b; On the pipeline that preheats between system 5 and the supercritical reaction system 6, pressure explosion trap 15 is set, and is connected with water storing tank 1 through blow-down pipe.WP can be 40MPa, and must not be higher than the range of tensimeter 12 and the general design pressure of said device.
Principle of work of the present invention is following: make water after wood fiber biomass raw material and the preheating mix the back through high pressure charging pump 4 with high pressure intake pump 3 and inject supercritical reaction systems 6; Make wood fiber biomass under super critical condition, carry out pre-treatment and hydrolysis; Break the wood fibre structure, hydrolysis generates soluble oligosaccharide; Through the first cooling system 7 and the first reducing valve 14a, make the temperature and pressure of supercritical reaction product be reduced to undercritical conditions afterwards, and then in subcritical reaction system 8, continue hydrolysis, generate fermentable sugars; Collect the product of supercritical and subcritical combination pre-treatment and hydrolysis at last continuously in 10 product collection system through 9 final cooling systems.Its concrete operations step is following:
1) each valve of equipment pipeline is all placed path; Unlocking electronic temperature controlling system 11 switches carry out preheating to preheating system 5, supercritical reaction system 6 and subcritical reaction system 8, are set at 350~370 ℃, 370~400 ℃ and 200~300 ℃ of assigned temperatures that scope is interior respectively;
2) biomass material and water are inserted in the material-storage jar 2 by 1: 40~1: 20 mixed of mass ratio, the whipping appts of opening material-storage jar 2 makes material be in evenly outstanding turbid state;
3) according to the suspension liquid volume in the material-storage jar, in water storing tank, add the water of 1~4 times of volume, the flow proportional of adjustable column high pressure intake pump and high pressure charging pump is 1: 1~4: 1;
4) when the temperature that preheats system 5, supercritical reaction system 6 and subcritical reaction system 8 during near the preheating assigned temperature; Open high pressure intake pump 3 and high pressure charging pump 4; Water in the water storing tank is injected the system that preheats; Reach after the preheating temperature with the biomass material slurries short mix of injecting through the high pressure charging pump by material-storage jar and inject the supercritical reaction system, reaction product through first cooling system and reducing valve cool off with step-down after entering subcritical reaction system;
5) regulate the first reducing valve 14a and the second reducing valve 14b, make supercritical reaction system 6 and subcritical reaction system 8 internal duct pressure be stabilized in 20~25MPa and 5~15MPa respectively;
6) cooling water flow of first cooling system 7 of adjusting and final cooling system 9, making separately, the export pipeline temperature is stabilized in 100~200 ℃ and 15~50 ℃ respectively;
7) treat flow in the said equipment, temperature and pressure all reach above-mentioned set(ting)value and stable after, utilize the final product of product collection system 10 continuous biomass collection pre-treatment and hydrolysis.
Claims (7)
1. equipment that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis, it is characterized in that: said equipment comprises water storing tank (1), with the material-storage jar (2) of whipping appts; Preheat system (5); Supercritical reaction system (6), first cooling system (7), subcritical reaction system (8); Final cooling system (9), product collection system (10) and electron temperature-control system (11); Said water storing tank (1) through pipeline via high pressure intake pump (3) with preheat system (5) inlet and link to each other; Preheating system (5) outlet enters the mouth with supercritical reaction system (6) through threeway and links to each other; The said material-storage jar (2) of having whipping appts enters the mouth with supercritical reaction system (6) via high pressure charging pump (4) through pipeline and links to each other, and said supercritical reaction system (6) outlet enters the mouth with subcritical reaction system (8) with first reducing valve (14a) via first cooling system (7) through pipeline and links to each other; Said subcritical reaction system (8) outlet links to each other with product collection system (10) with final cooling system (9) via second reducing valve (14b) through pipeline; Describedly preheat system, supercritical reaction system, first cooling system is connected with described electron temperature-control system (11) with SW through temperature probe (13) respectively with the subcritical reaction system.
2. according to the said equipment that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis of claim 1; It is characterized in that: the described system (5) that preheats is by preheating pipeline and preheating apparatus is formed; Described preheating apparatus is made up of salt bath jar and the electrically heated rod that is arranged in this salt bath jar, and the described pipeline that preheats adopts spiral coil.
3. according to the said equipment that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis of claim 1; It is characterized in that: described supercritical reaction system (6) is made up of supercritical reaction pipeline and supercritical heated device; Described supercritical heated device is made up of salt bath jar and the electrically heated rod that is arranged in this salt bath jar, and described supercritical reaction pipeline adopts straight tube or bend pipe.
4. according to the said equipment that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis of claim 1; It is characterized in that: described subcritical reaction system (8) is made up of subcritical reaction pipeline and subcritical heating unit; Described subcritical heating unit is made up of porcelain bushing and the electrically heated rod that is arranged in this sleeve pipe, and described subcritical reaction pipeline adopts spiral coil.
5. according to the said equipment that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis of claim 1; It is characterized in that: described first cooling system (7) and final cooling system (9) are made up of transfer conduit and cooling jacket; Described cooling jacket adopts reverse-flow water cooling sleeve pipe, and described transfer conduit adopts straight tube or spiral coil.
6. according to the said equipment that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis of claim 1; It is characterized in that: on the pipeline that preheats between system (5) and the supercritical reaction system (6), pressure explosion trap (15) is set, and is connected with water storing tank (1) through blow-down pipe.
7. one kind is adopted the method that is used for biomass supercritical and subcritical combined continuous type pre-treatment and hydrolysis of equipment according to claim 1, it is characterized in that this method comprises the steps:
1) each valve of equipment pipeline is all placed path; Unlocking electronic temperature controlling system (11) switch carries out preheating to preheating system (5), supercritical reaction system (6) and subcritical reaction system (8), is set at 350~370 ℃, 370~400 ℃ and 200~300 ℃ of assigned temperatures that scope is interior respectively;
2) biomass material and water are inserted in the material-storage jar (2) by 1: 40~1: 20 mixed of mass ratio, the whipping appts of opening material-storage jar (2) makes material be in evenly outstanding turbid state;
3) according to the suspension liquid volume in the material-storage jar, in water storing tank, add the water of 1~4 times of volume, the flow proportional of regulating high pressure intake pump and high pressure charging pump is 1: 1~4: 1;
4) when the temperature that preheats system (5), supercritical reaction system (6) and subcritical reaction system (8) during near the preheating assigned temperature; Open high pressure intake pump (3) and high pressure charging pump (4); Water in the water storing tank is injected the system that preheats; Reach after the preheating temperature with the biomass material slurries short mix of injecting through the high pressure charging pump by material-storage jar and inject the supercritical reaction system, reaction product through first cooling system and reducing valve cool off with step-down after entering subcritical reaction system;
5) regulate first reducing valve (14a) and second reducing valve (14b), make supercritical reaction system (6) and subcritical reaction system (8) internal duct pressure be stabilized in 20~25MPa and 5~15MPa respectively;
6) regulate the cooling water flow of first cooling system (7) and final cooling system (9), making separately, the export pipeline temperature is stabilized in 100~200 ℃ and 15~50 ℃ respectively;
7) treat flow in the said equipment, temperature and pressure all reach above-mentioned set(ting)value and stable after, utilize product collection system (10) final product of biomass collection pre-treatment and hydrolysis continuously.
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CN2009100888958A CN101613377B (en) | 2009-07-21 | 2009-07-21 | Biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and method |
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CA2769746C (en) * | 2010-01-19 | 2013-10-15 | Renmatix, Inc. | Production of fermentable sugars and lignin from biomass using supercritical fluids |
CN101886143B (en) * | 2010-07-13 | 2012-12-26 | 大连理工大学 | Method for preparing reducing sugar by hydrolyzing biomass with super-critical/sub-critical water in two steps |
EP2635713A4 (en) * | 2010-11-01 | 2017-07-05 | Renmatix, Inc. | Process for controlled liquefaction of a biomass feedstock by treatment in hot compressed water |
CA2854291A1 (en) | 2011-11-08 | 2013-05-16 | Reac Fuel Ab | Liquefaction of biomass at low ph |
US8759498B2 (en) | 2011-12-30 | 2014-06-24 | Renmatix, Inc. | Compositions comprising lignin |
BR102013006389A2 (en) | 2012-08-01 | 2015-03-17 | Cnpem Ct Nac De Pesquisa Em En E Materiais | Process for simultaneous conversion of sugarcane bagasse using uhtst reactors |
NZ629052A (en) | 2013-03-15 | 2017-04-28 | Renmatix Inc | High purity lignin, lignin compositions, and higher structured lignin |
CN103570526A (en) * | 2013-11-21 | 2014-02-12 | 青岛科技大学 | Novel biomass supercritical/subcritical hydrolysis reactor |
FI3186286T3 (en) | 2014-09-26 | 2024-07-10 | Renmatix Inc | Cellulose-containing compositions and methods of making same |
CN108339496A (en) * | 2017-01-23 | 2018-07-31 | 赖泽民 | A kind of biomass is subcritical or supercritical hydrolysis device and method |
JP6836046B1 (en) * | 2019-11-20 | 2021-02-24 | 清水 幹治 | Subcritical or supercritical continuous processing equipment and methods for organic substances |
CN114247170B (en) * | 2022-01-11 | 2023-06-30 | 深圳市九然生物科技有限公司 | Continuous SPE-SFF production equipment |
CN117209037B (en) * | 2023-09-27 | 2024-05-28 | 北京新风航天装备有限公司 | Horizontal supercritical water oxidation reactor and reaction method |
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