CN106987259A - A kind of method that reclaims stalk preparation biological carbon of utilization wicker products - Google Patents
A kind of method that reclaims stalk preparation biological carbon of utilization wicker products Download PDFInfo
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- CN106987259A CN106987259A CN201710253831.3A CN201710253831A CN106987259A CN 106987259 A CN106987259 A CN 106987259A CN 201710253831 A CN201710253831 A CN 201710253831A CN 106987259 A CN106987259 A CN 106987259A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a kind of method that stalk prepares biological carbon that reclaims of utilization wicker products, belong to stalk material processing technique field, comprise the following steps:(1)Cleaning treatment,(2)Steam treatment,(3)Modifier treatment,(4)Heat carbonization treatment.The present invention has carried out targetedly improvement processing for the deficiency of existing carbonization treatment technique, the internal organizational structure of stalk is reclaimed by adjusting, adjust inner material content and ratio, control the technological parameter of carbonization treatment, finally effectively improve overall carbonation rate and carbonization quality, the carbonation rate of wherein stalk is up to more than 99.0%, and the specific surface area of obtained biological carbon is not less than 3200m2/ gram, improving micropore ratio in more than 20%, and biological carbon produced by the present invention compared with prior art more than 95.2%, there is very strong adsorption capacity, and use value is higher.
Description
Technical field
The invention belongs to stalk material processing technique field, and in particular to prepared by a kind of recovery stalk of utilization wicker products
The method of biological carbon.
Background technology
Funan County, is under the jurisdiction of Anhui Province's Fuyang City, area earlier is developed in category inland, on the Anhui Province northwestward, Huaihe River
Middle reaches joint portion north bank.Funan County have " famous-brand and high-quality special product county ", the title of " Natural resources reservoir ", be national grain-production great Xian, in
The unique agricultural in township, the whole nation of state's wicker plaiting article(Forestry)Recycling economy demonstration pilot project county, Funan is the township of national wicker plaiting article, wicker products
It is sold abroad.
Wicker products is container, handicraft common during current people live etc., but it is respectively provided with as most commodity
Certain service life, it uses functional lesion or forfeiture after destructurized, is finally abandoned by people.Most wicker productses
Formed by the braiding such as purple willow branch, agricultural crop straw, although in can be degraded under natural conditions, but required time is longer, people
Burning destruction is generally carried out, and this measure can bring larger destruction to environment, while will also result in the waste of raw material.
Biological carbon can not only greatly improve soil fertility, and fertile high carbon storehouse soil is cultivated on dead soil,
Most direct effect is exactly to significantly improve crop yield and quality, and the chemicals such as chemical fertilizer, agricultural chemicals can also be reduced indirectly
Amount of application.Most critical is that effectively absorption solidification in the middle of biological carbon, reduces the discharge of greenhouse gases carbon, and to stone
The dependence of oil product.It there is now and carry out the method that carbonization processing prepares biological carbon, but most carbonation rates using raw materials such as stalks
It is not high, typically not greater than 80%, and obtained biological carbon poor, the streaking etc. that there are the performance parameters such as specific surface area, voidage
Problem, limits the recycling of stalk etc..
The content of the invention
The purpose of the present invention is to prepare biology there is provided a kind of recovery stalk of utilization wicker products the problem of being directed to existing
The method of carbon.
The present invention is achieved by the following technical solutions:
A kind of method for reclaiming stalk preparation biological carbon of utilization wicker products, comprises the following steps:
(1)Cleaning treatment:
By the stalk reclaimed from wicker products classification code it is good after, be rinsed with clear water, wash away sand, the soil on its surface etc. miscellaneous
It is standby after matter;
(2)Steam treatment:
By step(1)Stalk after processing is put into vapor tight tank, and temperature is then passed through into vapor tight tank and is contained for 100 ~ 105 DEG C
The water vapour of zinc chloride, and increase the pressure in vapor tight tank to 2.4 ~ 2.8MPa, heat-insulation pressure keeping is handled after 1 ~ 1.5h, then is quickly unloaded
Pressure is cooled to normal temperature and pressure, and stalk finally is taken out into standby;
(3)Modifier treatment:
By step(2)The stalk handled well is put into pond, then to the soy oligosaccharides that its gross mass 15 ~ 20% is sprayed on stalk
Sugar aqueous solution, takes out standby after stalk is fully absorbed;
(4)Heat carbonization treatment:
By step(3)Stalk after processing, which is put into carbide furnace, carries out carbonization treatment, first control heating speed for 20 ~ 23 DEG C/
Min, 400 DEG C are risen to by the temperature in carbide furnace by normal temperature, and the speed for then adjusting heating is 8 ~ 13 DEG C/min, by carbide furnace
Temperature rise to 550 DEG C by 400 DEG C, after the completion of carbonization stalk is taken out.
Further, step(2)Described in water vapour in zinc chloride mass percent be 12 ~ 17%.
Further, step(2)Described in release be cooled to used in the whole process of normal temperature and pressure duration control for 10 ~
15min。
Further, step(3)Described in soy oligosaccharides sugar aqueous solution in soyabean oligosaccharides mass percent for 2 ~
5%。
Further, step(4)Described in carbonization treatment whole process in maintain the pressure in carbide furnace for 0.3 ~
0.5MPa。
The mode of existing straw-carbonized handling process is although various, but to there is carbonation rate low, to utilization rate of raw materials
Not high, the problem of biological carbon processed is of poor quality, the present invention has found carbon to improve this problem by substantial amounts of practice summary
The breath such as improvement, the ratio of inner material content, the controls of carbonization technique parameter of raw material institutional framework such as rate etc. and stalk
Manner of breathing is closed, and has been carried out rational adjustment and improvement to processing technology based on this, wherein first having carried out steam treatment to stalk, has been used
The recovery stalk usual water content of wicker products after long period is relatively low, and overall fibre structure is after drying shrinkage is used for a long time
It is comparatively dense, it is unfavorable for the carbonization treatment in later stage, the steam treatment of HTHP is then carried out to it, can effectively loose it be fine
Dimensional tissue structure, promotes the space between the separation activation of cellulose, lignin etc., increase string, can strengthen later stage carbonization
Rate and carbonization quality, wherein with the addition of zinc chloride in steam, zinc chloride can be more conducive in stalk by steam treatment operation
Scattered and absorption of the stalk to zinc chloride, effectively enhance the using effect of zinc chloride, further improve later stage carbonization
Quality, and modifier treatment has been carried out to stalk, it is specifically that the aqueous solution containing soyabean oligosaccharides is with the addition of into stalk, this
Lift and effectively improve oligosaccharide content in stalk, and this oligosaccharide can effectively and stalk during the carbonization treatment in later stage
In aromatic hydrocarbons structure lignocellulosic combine generation biomass carbon material, and then improve utilization rate and the carbonization of stalk material
Rate, finally rises to 400 DEG C in heating carbonization treatment first with higher programming rate, and programming rate is then reduced again and continues to rise
To 550 DEG C, this fit system can ensure the flash carbonization of stalk main body in early stage, can ensure the complete carbon of stalk surplus afterwards
Change, the carbonizing degree of more traditional single heating mode is higher, be carbonized more complete.
The present invention has advantages below compared with prior art:
The present invention has carried out targetedly improvement processing for the deficiency of existing carbonization treatment technique, and stalk is reclaimed by adjusting
Internal organizational structure, adjustment inner material content and ratio, control the technological parameter of carbonization treatment, finally effectively improve entirety
Carbonation rate and carbonization quality, the carbonation rate of wherein stalk is up to more than 99.0%, and the specific surface area of obtained biological carbon is not less than
3200m2/ gram, micropore ratio is improved in more than 20%, and biological carbon produced by the present invention more than 95.2% compared with prior art,
There is very strong adsorption capacity, use value is higher.
Embodiment
Embodiment 1
A kind of method for reclaiming stalk preparation biological carbon of utilization wicker products, comprises the following steps:
(1)Cleaning treatment:
By the stalk reclaimed from wicker products classification code it is good after, be rinsed with clear water, wash away sand, the soil on its surface etc. miscellaneous
It is standby after matter;
(2)Steam treatment:
By step(1)Stalk after processing is put into vapor tight tank, and temperature is then passed through into vapor tight tank and is contained for 100 ~ 102 DEG C
The water vapour of zinc chloride, and increase the pressure in vapor tight tank to 2.4MPa, heat-insulation pressure keeping is handled after 1h, then fast pressure relief is cooled to
Normal temperature and pressure, finally takes out standby by stalk;
(3)Modifier treatment:
By step(2)The stalk handled well is put into pond, then to the soy oligosaccharides syrup that its gross mass 15% is sprayed on stalk
Solution, takes out standby after stalk is fully absorbed;
(4)Heat carbonization treatment:
By step(3)Stalk after processing, which is put into carbide furnace, carries out carbonization treatment, and the speed for first controlling heating is 20 DEG C/min,
Temperature in carbide furnace is risen to 400 DEG C by normal temperature, the speed for then adjusting heating is 8 DEG C/min, by the temperature in carbide furnace
Rise to 550 DEG C by 400 DEG C, after the completion of carbonization stalk is taken out.
Further, step(2)Described in water vapour in zinc chloride mass percent be 12%.
Further, step(2)Described in release be cooled to used in the whole process of normal temperature and pressure duration control and be
10min。
Further, step(3)Described in soy oligosaccharides sugar aqueous solution in soyabean oligosaccharides mass percent be 2%.
Further, step(4)Described in carbonization treatment whole process in maintain carbide furnace in pressure be 0.3MPa.
Embodiment 2
A kind of method for reclaiming stalk preparation biological carbon of utilization wicker products, comprises the following steps:
(1)Cleaning treatment:
By the stalk reclaimed from wicker products classification code it is good after, be rinsed with clear water, wash away sand, the soil on its surface etc. miscellaneous
It is standby after matter;
(2)Steam treatment:
By step(1)Stalk after processing is put into vapor tight tank, and temperature is then passed through into vapor tight tank and is contained for 102 ~ 104 DEG C
The water vapour of zinc chloride, and increase the pressure in vapor tight tank to 2.6MPa, heat-insulation pressure keeping is handled after 1.2h, then fast pressure relief cooling
To normal temperature and pressure, stalk is finally taken out standby;
(3)Modifier treatment:
By step(2)The stalk handled well is put into pond, then to the soy oligosaccharides syrup that its gross mass 18% is sprayed on stalk
Solution, takes out standby after stalk is fully absorbed;
(4)Heat carbonization treatment:
By step(3)Stalk after processing, which is put into carbide furnace, carries out carbonization treatment, and the speed for first controlling heating is 22 DEG C/min,
Temperature in carbide furnace is risen to 400 DEG C by normal temperature, the speed for then adjusting heating is 11 DEG C/min, by the temperature in carbide furnace
Rise to 550 DEG C by 400 DEG C, after the completion of carbonization stalk is taken out.
Further, step(2)Described in water vapour in zinc chloride mass percent be 15%.
Further, step(2)Described in release be cooled to used in the whole process of normal temperature and pressure duration control and be
12min。
Further, step(3)Described in soy oligosaccharides sugar aqueous solution in the mass percents of soyabean oligosaccharides be
3.5%。
Further, step(4)Described in carbonization treatment whole process in maintain carbide furnace in pressure be 0.4MPa.
Embodiment 3
A kind of method for reclaiming stalk preparation biological carbon of utilization wicker products, comprises the following steps:
(1)Cleaning treatment:
By the stalk reclaimed from wicker products classification code it is good after, be rinsed with clear water, wash away sand, the soil on its surface etc. miscellaneous
It is standby after matter;
(2)Steam treatment:
By step(1)Stalk after processing is put into vapor tight tank, and temperature is then passed through into vapor tight tank and is contained for 104 ~ 105 DEG C
The water vapour of zinc chloride, and increase the pressure in vapor tight tank to 2.8MPa, heat-insulation pressure keeping is handled after 1.5h, then fast pressure relief cooling
To normal temperature and pressure, stalk is finally taken out standby;
(3)Modifier treatment:
By step(2)The stalk handled well is put into pond, then to the soy oligosaccharides syrup that its gross mass 20% is sprayed on stalk
Solution, takes out standby after stalk is fully absorbed;
(4)Heat carbonization treatment:
By step(3)Stalk after processing, which is put into carbide furnace, carries out carbonization treatment, and the speed for first controlling heating is 23 DEG C/min,
Temperature in carbide furnace is risen to 400 DEG C by normal temperature, the speed for then adjusting heating is 13 DEG C/min, by the temperature in carbide furnace
Rise to 550 DEG C by 400 DEG C, after the completion of carbonization stalk is taken out.
Further, step(2)Described in water vapour in zinc chloride mass percent be 17%.
Further, step(2)Described in release be cooled to used in the whole process of normal temperature and pressure duration control and be
15min。
Further, step(3)Described in soy oligosaccharides sugar aqueous solution in soyabean oligosaccharides mass percent be 5%.
Further, step(4)Described in carbonization treatment whole process in maintain carbide furnace in pressure be 0.5MPa.
Comparative example 1
This comparative example 1 compared with Example 2, changes step(2)The method of steam treatment, is specifically to be put into chlorination with stalk
Immersion treatment is replaced in the zinc aqueous solution, and the mass percent of Chlorine in Solution zinc used is 17% during immersion, and immersion duration is set to 18
~ 24h, method and step all same in addition.
Comparative example 2
This comparative example 2 compared with Example 2, saves step(3)Modifier treatment, method and step all same in addition.
Comparative example 3
This comparative example 3 compared with Example 2, changes step(4)The method for heating carbonization treatment, specifically will entirely be heated
The speed of heating controls as 22 DEG C/min, method and step all same in addition all the time.
Control group
Existing conventional straw-carbonized processing method.
In order to contrast effect of the present invention, experimental subjects, general are used as from the cotton stalk of the wicker products with a collection of recovery
It is randomly divided into five groups, respectively with above-described embodiment 2, comparative example 1, comparative example 2, comparative example 3, control group institute
The method stated is processed, and carries out attribute test, specific correction data such as table 1 below institute to the biological carbon being processed into
Show:
Table 1
Cotton stalk carbonation rate(%) | Biological carbon average specific surface area(m2/ gram) | Micropore ratio in biological carbon(%) | |
Embodiment 2 | 99.5 | 3320 | 95.9 |
Comparative example 1 | 85.7 | 2480 | 86.2 |
Comparative example 2 | 94.2 | 3260 | 93.8 |
Comparative example 3 | 92.1 | 3150 | 91.4 |
Control group | 78.8 | 2100 | 80.6 |
The carbonation rate of the more existing carbonization treatment method of the present invention, carbonization quality have good lifting it can be seen from upper table 1,
Obtained biological carbon adsorptivity, performance more preferably, effectively improve the economic benefit of processing, with good progressive meaning.
Claims (5)
1. a kind of method for reclaiming stalk preparation biological carbon of utilization wicker products, it is characterised in that comprise the following steps:
(1)Cleaning treatment:
By the stalk reclaimed from wicker products classification code it is good after, be rinsed with clear water, wash away sand, the soil on its surface etc. miscellaneous
It is standby after matter;
(2)Steam treatment:
By step(1)Stalk after processing is put into vapor tight tank, and temperature is then passed through into vapor tight tank and is contained for 100 ~ 105 DEG C
The water vapour of zinc chloride, and increase the pressure in vapor tight tank to 2.4 ~ 2.8MPa, heat-insulation pressure keeping is handled after 1 ~ 1.5h, then is quickly unloaded
Pressure is cooled to normal temperature and pressure, and stalk finally is taken out into standby;
(3)Modifier treatment:
By step(2)The stalk handled well is put into pond, then to the soy oligosaccharides that its gross mass 15 ~ 20% is sprayed on stalk
Sugar aqueous solution, takes out standby after stalk is fully absorbed;
(4)Heat carbonization treatment:
By step(3)Stalk after processing, which is put into carbide furnace, carries out carbonization treatment, first control heating speed for 20 ~ 23 DEG C/
Min, 400 DEG C are risen to by the temperature in carbide furnace by normal temperature, and the speed for then adjusting heating is 8 ~ 13 DEG C/min, by carbide furnace
Temperature rise to 550 DEG C by 400 DEG C, after the completion of carbonization stalk is taken out.
2. a kind of method for reclaiming stalk preparation biological carbon of utilization wicker products according to claim 1, its feature exists
In step(2)Described in water vapour in zinc chloride mass percent be 12 ~ 17%.
3. a kind of method for reclaiming stalk preparation biological carbon of utilization wicker products according to claim 1, its feature exists
In step(2)Described in release to be cooled to used in the whole process of normal temperature and pressure duration control be 10 ~ 15min.
4. a kind of method for reclaiming stalk preparation biological carbon of utilization wicker products according to claim 1, its feature exists
In step(3)Described in soy oligosaccharides sugar aqueous solution in soyabean oligosaccharides mass percent be 2 ~ 5%.
5. a kind of method for reclaiming stalk preparation biological carbon of utilization wicker products according to claim 1, its feature exists
In step(4)Described in carbonization treatment whole process in maintain carbide furnace in pressure be 0.3 ~ 0.5MPa.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108611097A (en) * | 2018-06-11 | 2018-10-02 | 阜南县中信柳木工艺品有限公司 | A kind of recycling method of waste and old wicker plaiting article raw material |
CN108812194A (en) * | 2018-06-14 | 2018-11-16 | 安徽省霍山县农伯乐开发有限公司 | A kind of cultivation matrix promoting dendrobium nutrient value and yield |
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CN103055898A (en) * | 2012-10-23 | 2013-04-24 | 河北工业大学 | Biomass carbon-based catalyst prepared by utilizing wastes in furfural production in recycling manner and application thereof |
CN104371748A (en) * | 2014-10-24 | 2015-02-25 | 东华大学 | Preparation method of high-yield biochar |
WO2017049090A1 (en) * | 2015-09-16 | 2017-03-23 | Sweetwater Energy, Inc. | Specialized activated carbon derived from pretreated biomass |
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2017
- 2017-04-18 CN CN201710253831.3A patent/CN106987259B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103055898A (en) * | 2012-10-23 | 2013-04-24 | 河北工业大学 | Biomass carbon-based catalyst prepared by utilizing wastes in furfural production in recycling manner and application thereof |
CN104371748A (en) * | 2014-10-24 | 2015-02-25 | 东华大学 | Preparation method of high-yield biochar |
WO2017049090A1 (en) * | 2015-09-16 | 2017-03-23 | Sweetwater Energy, Inc. | Specialized activated carbon derived from pretreated biomass |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108611097A (en) * | 2018-06-11 | 2018-10-02 | 阜南县中信柳木工艺品有限公司 | A kind of recycling method of waste and old wicker plaiting article raw material |
CN108812194A (en) * | 2018-06-14 | 2018-11-16 | 安徽省霍山县农伯乐开发有限公司 | A kind of cultivation matrix promoting dendrobium nutrient value and yield |
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