CN104946700A - Preparation method for improving of sub-super-critical of hexose productive rate - Google Patents
Preparation method for improving of sub-super-critical of hexose productive rate Download PDFInfo
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Abstract
The invention relates to preparation method for improving of sub-super-critical of a hexose productive rate. A sub/supercritical fluid method of a salt bath heating system is adopted to pretreat straws, in order to make straw raw materials be in sufficient contact with supercritical water to carry out a reaction conveniently, before an experiment is conducted, mechanical smashing treatment is carried out on the straw raw materials, then the straw raw materials pass through a screen with 40 meshes, screened straw powder is taken to serve as a raw material for supercritical pretreatment and hydrolyzing to carry out follow-on experiment research, the solid-to-liquid ratio ranges from 1:41.7-1:125, the supercritical condition comprises that the temperature ranges from 270 DEG C to 290 DEG C, the operation pressure ranges from 10 MPa to 25 MPa, and the reaction time ranges from 12 seconds to 26 seconds; the subcritical reaction condition comprises that the temperature ranges from 180 DEG C to 260 DEG C, the operation pressure ranges from 10 MPa to 20 MPa, and the reaction time ranges from 10 seconds to 60 seconds; sub/supercritical water is adopted to serve as a reaction medium, the requirement for the equipment material performance is low, the reaction time is short, the conversion rate is high, and the maximum conversion rate is 20.7%.
Description
Technical field
The present invention relates to a kind of method that rice straw prepares hexose, belong to and utilize waste cellulose to prepare oligose, improve the novel method of oligose productive rate.
Background technology
Tradition chemical industry is smelted and is utilized non-renewable fossil resource, the mode of production concentrated with it, and efficient production efficiency, creates a large amount of material wealths, meets the material life needs of the mankind, greatly facilitates social development and progress; Meanwhile, the negative impacts such as environmental pollution, Global warming, fossil resource be day by day exhausted are also created.The world energy sources demand of world energy sources microstructure Prediction the year two thousand thirty will be more than 1.5 times of 2005; The year two thousand thirty Asia energy demand will be more than 2.1 times of 2005; CO2 emissions will be more than 1.5 times (the Energy Outlook 2030) of 2002 the year two thousand thirty.World's CO2 emissions in 2010 announced by international energy net is 331.6 hundred million tons, and wherein, China's CO2 emissions is 83.3 hundred million tons, accounts for 25.1% of world's share, ranks first in the world.On November 26th, 2009, it will be target the carbon dioxide discharge-reduction 40% ~ 45% of the year two thousand twenty per GDP that China has announced, includes national economy and social development medium-term and long-term plans in as the binding indicator.The field such as tool, household articles, fruit freshness preserving, purifying air, medical material has very wide application prospect.
Biomass are the world's fourth largest energy being only second to coal, oil, Sweet natural gas, in whole energy resource system, occupy critical role.Biomass resource substantial amounts in the world, form is various, has both comprised the biomass that timber, fuel wood, crop material, feces of livestock and poultry etc. are traditional, also comprises the modern biotechnology matter such as urban waste, biofuel, industrial foresty product, sugar industry product refuse.Agricultural crop straw, as a kind of a large amount of and cheap biomass energy, is converted into useful matter agricultural wastes straw, not only can reduce the dependence of the mankind to the petroleum base energy, can also environmental protect.Adopt supercritical and subcritical combination process, stalk first pre-treatment and hydrolysis in supercritical water, cellulose hydrolysis is wherein made to be oligose, hexose is hydrolyzed to further again through undercritical conditions, the technical bottleneck of the independent supercritical hydrolysis of lignocellulose and independent subcritical hydrolysis can be broken through, realize wood fibre refuse supercritical and subcritical combination pre-treatment and hydrolysis resource utilization, there is huge application market, and the technical concept of the innovation that it brings, more can drive the development of other related industrieies, bring larger economic and social benefit.
The bio-transformation of lignocellulose waste through pre-treatment, hydrolysis, fermentation and need be separated Four processes.In this technological process, pre-treatment, hydrolysis and fermentation are three topmost sport technique segments.The pretreated object of stalk removes xylogen to hemicellulose and cellulosic provide protection, destroys cellulosic crystalline texture, to increase reaction table area thus to improve subsequent fiber element hydrolysis of hemicellulose rate.Being hydrolyzed namely saccharifying, is make Mierocrystalline cellulose and hemicellulose be degraded to fermentable hexose (being mainly glucose) and five-carbon sugar (being mainly wood sugar) respectively.Fermenting process then mainly utilizes yeast or other microorganisms that glucose and xylose fermentation is produced ethanol.The pretreatment process of lignocellulose is in the majority with acid, alkali, hydrothermal method.By these methods while remove portion xylogen, can partial hydrolysis Mierocrystalline cellulose and hemicellulose, thus improve the efficiency of hydrolysis.The just severe reaction conditions of these methods, the problem such as there is etching apparatus, contaminate environment respectively, transformation efficiency is low, cost is high, efficiency is low, and can fermentation inhibitor be produced while destruction xylogen, affect follow-up fermentation efficiency, need technique is simple, efficiency is higher, cost is lower New Pre process and technology for hydrolyzing or technology and control badly.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of Asia/supercritical preparation process improving hexose productive rate.Adopt the combination pre-treatment of stalk supercritical and subcritical and hydrolysis process technology, first Mierocrystalline cellulose and stalk pre-treatment and hydrolysis in supercritical water, the winding of breaking xylogen is wrapped up and destroys cellulosic crystalline texture, cellulose hydrolysis is made to be oligose, again by controlling reaction conditions, in the elementary hydrolysis that undercritical conditions realizes avoiding glucose to produce as far as possible by controlling reaction conditions; Oligose generates the hexoses such as glucose through the subcritical water secondary hydrolysis that breakdown of glucose speed is relatively slow again, realize the maximization of full technological process fermentable sugars productive rate, be hydrolyzed to glucose further, both make use of supercritical methanol technology to be swift in response, without the need to catalyzer, advantage without Product inhibiton, solve again its unstable products, condition technical bottleneck rambunctious, thus realize stalk rapidly and efficiently be converted into fermentable sugars, to raising stalk produce the production efficiency of hexose and apply significant.
Improve Asia/supercritical preparation process of hexose productive rate, it is characterized in that, comprise the following steps:
(1) first maize straw complete feed and deionized water mixed that to add Asia/supercritical water be in the parallel reactor of two groups of medium and seal;
(2) two groups of parallel reactor levels inserted in postcritical salt bath apparatus and carry out supercritical reaction, horizontal oscillations is beneficial to mixing of materials and system heat transfer;
(3) adopt identical working method to be inserted by reactor in precritical salt bath apparatus and carry out subcritical reaction;
(4) be down to after normal pressure until still internal pressure and close water of condensation, agitator, open kettle cover, take out reaction product.
The quality of step (1) described maize straw is 20 ~ 60 grams, the solid-to-liquid ratio selected be solid-to-liquid ratio be 1:41.7 ~ 1:125.
Super critical condition described in step (2) is 270 ~ 290 DEG C, and working pressure is 10 ~ 25 MPa, and the reaction times is 12 ~ 26 seconds;
Subcritical reaction condition described in step (3) is 180 ~ 260 DEG C, and working pressure is 10 ~ 20 MPa, and the reaction times is 10 ~ 60 seconds.
Supercritical process, as a kind of emerging green chemistry process, is applied in the pre-treatment of lignocellulose, can reduce environmental pollution, makes product more easily separated, is a kind of promising pretreatment technology having modern environmental consciousness.The overcritical pretreatment process of lignocellulose is the special property utilizing supercutical fluid, pass through the action breaks down crystal structure of cellulose of water and properties-correcting agent at supercritical conditions, increased fiber element accessibility, break the connecting key between Mierocrystalline cellulose and hemicellulose, xylogen, thus reach the effect improving maize straw sugar yield.
The present invention adopts overcritical or subcritical abstraction reaction technology to carry out pre-treatment to maize straw, while raising stalk sugar yield, remove the inhibited xylogen of further fermenting process, produce for the clean and effective carrying out the products such as alcohol fuel further and provide an effective way.
Supercritical hydrolysis technology can make Mierocrystalline cellulose obtain fast hydrolyzing in the supercritical state of water, its distinguishing feature is: hydrolysis rate is fast, hydrolysis productive rate is high, can not need any catalyzer, environmentally safe, and directly can be hydrolyzed without pre-treatment when processing cellulose series biomass, simplifying production technique.
Accompanying drawing explanation
Fig. 1: overcritical/subcritical combination pre-treatment and hydrolysising reacting system schematic diagram.
1, reactor; 2, supercritical reaction thermopair; 3, subcritical reaction salt bath; 4, supercritical reaction salt bath; 5, subcritical reaction salt bath; 6, water-cooled pond; 7, electrical heating device; 8, temperature controlling system.
Embodiment
Below by embodiment, the present invention is further elaborated, and its object is only better to understand content of the present invention.Therefore, the cited case does not limit the scope of the invention.
embodiment 1:
With maize straw complete feed for raw material, get 20 g and put into reactor, solid-to-liquid ratio is 1:125.Operational condition is: super critical condition is 270 DEG C, and working pressure is 10 MPa, and the reaction times is 12 seconds; Subcritical reaction condition is 180 DEG C, and working pressure is 10 MPa, and the reaction times is 10 seconds.Solid materials saccharification is analyzed after pretreatment, and oligose productive rate is 14.8%.
The present embodiment adopts the technological process shown in Fig. 1, and the step used water as overcritical or subcritical solvent pre-treatment maize straw is as follows:
(1) first 20 grams are mixed and add in two groups of parallel reactors through pulverizing air-dry maize straw and 2500 ml deionized waters and seal;
(2) two groups of parallel reactor levels are inserted that oneself reaches setting supercritical temperature (270 DEG C), pressure is in the salt bath apparatus of 10 MPa, horizontal oscillations is beneficial to mixing of materials and system heat transfer, is taken out by reactor and insert water-cooled pond fast to stop supercritical reaction after the reaction times (12 seconds) reaching setting;
(3) oneself reaches setting sub-critical temperature (180 DEG C), pressure is carry out subcritical reaction (reaction times is 10 seconds) in the salt bath apparatus of 10 MPa to adopt identical working method to be inserted by reactor.
(4) be down to after normal pressure until still internal pressure and close water of condensation, agitator, open kettle cover, take out reaction product and analyze.
embodiment 2:
With maize straw complete feed for raw material, get 30 g and put into reactor, solid-to-liquid ratio is 1:83.3.Operational condition is: super critical condition is 280 DEG C, and working pressure is 15 MPa, and the reaction times is 15 seconds; Subcritical reaction condition is 190 DEG C, and working pressure is 15 MPa, and the reaction times is 20 seconds.Solid materials saccharification is analyzed after pretreatment, and oligose productive rate is 16.1%.
The present embodiment adopts the technological process shown in Fig. 1, and the step used water as overcritical or subcritical solvent pre-treatment maize straw is as follows:
(1) first 30 grams are mixed and add in two groups of parallel reactors through pulverizing air-dry maize straw and 2500 ml deionized waters and seal;
(2) two groups of parallel reactor levels are inserted that oneself reaches setting supercritical temperature (280 DEG C), pressure is in the salt bath apparatus of 15 MPa, horizontal oscillations is beneficial to mixing of materials and system heat transfer, is taken out by reactor and insert water-cooled pond fast to stop supercritical reaction after the reaction times (15 seconds) reaching setting;
(3) oneself reaches setting sub-critical temperature (190 DEG C), pressure is carry out subcritical reaction in the salt bath apparatus of 15 MPa to adopt identical working method to be inserted by reactor, and the reaction times is 20 seconds.
(4) be down to after normal pressure until still internal pressure and close water of condensation, agitator, open kettle cover, take out reaction product and analyze.
embodiment 3:
With maize straw complete feed for raw material, get 40 g and put into reactor, solid-to-liquid ratio is 1:62.5.Operational condition is: super critical condition is 290 DEG C, and working pressure is 20 MPa, and the reaction times is 20 seconds; Subcritical reaction condition is 200 DEG C, and working pressure is 15 MPa, and the reaction times is 40 seconds.Solid materials saccharification is analyzed after pretreatment, and oligose productive rate is 16.7%.
The present embodiment adopts the technological process shown in Fig. 1, and the step used water as overcritical or subcritical solvent pre-treatment maize straw is as follows:
(1) first 30 grams are mixed and add in two groups of parallel reactors through pulverizing air-dry maize straw and 2500 ml deionized waters and seal;
(2) two groups of parallel reactor levels are inserted that oneself reaches setting supercritical temperature (290 DEG C), pressure is in the salt bath apparatus of 20 MPa, horizontal oscillations is beneficial to mixing of materials and system heat transfer, is taken out by reactor and insert water-cooled pond fast to stop supercritical reaction after the reaction times (20 seconds) reaching setting;
(3) oneself reaches setting sub-critical temperature (200 DEG C), pressure is carry out subcritical reaction in the salt bath apparatus of 15 MPa to adopt identical working method to be inserted by reactor, and the reaction times is 40 seconds.
(4) be down to after normal pressure until still internal pressure and close water of condensation, agitator, open kettle cover, take out reaction product and analyze.
embodiment 4:
With maize straw complete feed for raw material, get 50 g and put into reactor, solid-to-liquid ratio is 1:50.Operational condition is: super critical condition is 290 DEG C, and working pressure is 25 MPa, and the reaction times is 20 seconds; Subcritical reaction condition is 230 DEG C, and working pressure is 15 MPa, and the reaction times is 30 seconds.Solid materials saccharification is analyzed after pretreatment, and oligose productive rate is 20.7%.
The present embodiment adopts the technological process shown in Fig. 1, and the step used water as overcritical or subcritical solvent pre-treatment maize straw is as follows:
(1) first 50 grams are mixed and add in two groups of parallel reactors through pulverizing air-dry maize straw and 2500 ml deionized waters and seal;
(2) two groups of parallel reactor levels are inserted that oneself reaches setting supercritical temperature (290 DEG C), pressure is in the salt bath apparatus of 25 MPa, horizontal oscillations is beneficial to mixing of materials and system heat transfer, is taken out by reactor and insert water-cooled pond fast to stop supercritical reaction after the reaction times (20 seconds) reaching setting;
(3) oneself reaches setting sub-critical temperature (230 DEG C), pressure is carry out subcritical reaction in the salt bath apparatus of 15 MPa to adopt identical working method to be inserted by reactor, and the reaction times is 30 seconds.
(4) be down to after normal pressure until still internal pressure and close water of condensation, agitator, open kettle cover, take out reaction product and analyze.
embodiment 5:
With maize straw complete feed for raw material, get 60 g and put into reactor, solid-to-liquid ratio is 1:41.7.Operational condition is: super critical condition is 280 DEG C, and working pressure is 25 MPa, and the reaction times is 26 seconds; Subcritical reaction condition is 260 DEG C, and working pressure is 20 MPa, and the reaction times is 60 seconds.Solid materials saccharification is analyzed after pretreatment, and oligose productive rate is 18.2%.
The present embodiment adopts the technological process shown in Fig. 1, and the step used water as overcritical or subcritical solvent pre-treatment maize straw is as follows:
(1) first 30 grams are mixed and add in two groups of parallel reactors through pulverizing air-dry maize straw and 2500 ml deionized waters and seal;
(2) two groups of parallel reactor levels are inserted that oneself reaches setting supercritical temperature (280 DEG C), pressure is in the salt bath apparatus of 25 MPa, horizontal oscillations is beneficial to mixing of materials and system heat transfer, is taken out by reactor and insert water-cooled pond fast to stop supercritical reaction after the reaction times (26 seconds) reaching setting;
(3) oneself reaches setting sub-critical temperature (260 DEG C), pressure is carry out subcritical reaction in the salt bath apparatus of 20 MPa to adopt identical working method to be inserted by reactor, and the reaction times is 60 seconds.
(4) be down to after normal pressure until still internal pressure and close water of condensation, agitator, open kettle cover, take out reaction product and analyze.
Claims (4)
1. improve Asia/supercritical preparation process of hexose productive rate, it is characterized in that, comprise the following steps:
(1) first maize straw complete feed and deionized water mixed that to add Asia/supercritical water be in the parallel reactor of two groups of medium and seal;
(2) two groups of parallel reactor levels inserted in postcritical salt bath apparatus and carry out supercritical reaction, horizontal oscillations is beneficial to mixing of materials and system heat transfer;
(3) adopt identical working method to be inserted by reactor in precritical salt bath apparatus and carry out subcritical reaction;
(4) be down to after normal pressure until still internal pressure and close water of condensation, agitator, open kettle cover, take out reaction product.
2. a kind of Asia/supercritical preparation process improving hexose productive rate according to claim 1, is characterized in that, the quality of step (1) described maize straw is 20 ~ 60 grams, the solid-to-liquid ratio selected be solid-to-liquid ratio be 1:41.7 ~ 1:125.
3. a kind of Asia/supercritical preparation process improving hexose productive rate according to claim 1, it is characterized in that, the super critical condition described in step (2) is 270 ~ 290 DEG C, and working pressure is 10 ~ 25 MPa, and the reaction times is 12 ~ 26 seconds.
4. a kind of Asia/supercritical preparation process improving hexose productive rate according to claim 1, it is characterized in that, the subcritical reaction condition described in step (3) is 180 ~ 260 DEG C, and working pressure is 10 ~ 20 MPa, and the reaction times is 10 ~ 60 seconds.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497987A (en) * | 2016-11-07 | 2017-03-15 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of combined method for pre-processing microcrystalline cellulose of meto-super-critical |
| CN111979820A (en) * | 2020-08-28 | 2020-11-24 | 扬州交石新材料科技有限公司 | Method for preparing straw nano cellulose dispersion liquid by supercritical-high pressure homogenization technology |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492756A (en) * | 2011-12-13 | 2012-06-13 | 天津理工大学 | Method and device for converting straws into fermentable saccharides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492756A (en) * | 2011-12-13 | 2012-06-13 | 天津理工大学 | Method and device for converting straws into fermentable saccharides |
Non-Patent Citations (1)
| Title |
|---|
| 赵岩: "秸秆制乙醇的超临界亚临界组合预处理与水解研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497987A (en) * | 2016-11-07 | 2017-03-15 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of combined method for pre-processing microcrystalline cellulose of meto-super-critical |
| CN111979820A (en) * | 2020-08-28 | 2020-11-24 | 扬州交石新材料科技有限公司 | Method for preparing straw nano cellulose dispersion liquid by supercritical-high pressure homogenization technology |
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