CN109292855A - CO2The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal - Google Patents
CO2The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/125—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using screw filters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/46—Solid fuels essentially based on materials of non-mineral origin on sewage, house, or town refuse
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
-
- 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
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
Abstract
CO2The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal is sufficiently mixed the biomass and the water ratio of 1:5~1:50 in mass ratio, is put into reaction kettle, and be passed through CO into kettle according to the method2, heat pressure in kettle up to 4~7MPa, opening electric heater, set reaction temperature as 250~290 DEG C, the reaction time is 100~200 minutes, continues thereafter with the CO for leading into reaction kettle and being pre-heated to temperature of reaction kettle2Make in kettle pressure up to 17~22MPa, and continue to heat, temperature is set as 330~350 DEG C, time is 200~400 minutes, two sections of heating ramp rates of reaction kettle are 10~20 DEG C/min, after reaction, squeeze separation, it is burnt to obtain the porous hydro-thermal of extremely low ash content, the concentrated isolated formic acid of liquid, methanol, potassium formate, sodium formate, calcium formate, mode through the invention, while realizing CO2It seals up for safekeeping and is activated with hydro-thermal coke deliming.
Description
Technical field
The invention belongs to biomass cleanizations to utilize field, in particular to a kind of CO2Joint biomass by hydro-thermal realizes hydro-thermal
The method of burnt step deliming activation.
Background technique
Biomass by hydro-thermal carbonization technology, can produce hydro-thermal coke.Its reaction condition is mild, simple process, handles fast.
Alkali (soil) metal (K, Na, Ca, Mg etc.) is the important component of biomass ash, is during biomass fuel thermochemical study
Extremely harmful, contamination, deposition and corrosion of equipment of heating surface etc. are easily caused, causes system to be unable to operate normally, very
To by forced-stopping machine.And in biomass by hydro-thermal carbonisation, organic acid of alkali (soil) metal in part in water self-ionization and generation
Can be soluble in water under collective effect, it is the slagging and contamination behavior when fuel uses so as to improve solid hydro-thermal Jiaozhuo.But alkali
(soil) metal removal degree and raw material components and reaction condition are closely related, and alkali metal can be to hydro-thermal coke in transition process
Pore development generates positive influence.How hydrothermal reaction condition is made full use of, makes biomass alkali (soil) during hydrothermal carbonization
It is this field technical problem to be solved that metal, which effectively removes while activating hydro-thermal coke,.
CO2As the important component of carbon cycle, it is widely present in atmosphere.In recent years, due to greenhouse effects, CO2's
Emission reduction flutters collection and using receiving very big concern.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of CO2Joint biomass by hydro-thermal realizes hydro-thermal coke one
The method of deliming activation is walked, it can be achieved that CO2It seals up for safekeeping and biomass efficient carbonization converts while removing alkali metal and effective activation.
This method process is simple, and properties of product are excellent, and solid product is suitable as fuel cleaning burning, water body or heavy metal in soil
Adsorbent material, product liquid can be used as liquid fuel and industrial chemicals.
To achieve the goals above, the invention adopts the following technical scheme: CO2Joint biomass by hydro-thermal realizes hydro-thermal coke one
The method for walking deliming activation, includes the following steps:
(1) biomass and water are sufficiently mixed, mixture is put into reaction kettle, closed autoclave body, and be passed through into kettle
CO2, pressurized, heated carry out in pressure hydrothermal carbonization reaction；
(2) hydrothermal carbonization after reaction, continues to be passed through CO into reaction kettle2, make pressure rise in kettle, raise simultaneously anti-
Temperature is answered, the alkali metal in biomass is promoted to be converted into corresponding salt removing at high temperature under high pressure, meanwhile, promote CO2With generation
Hydro-thermal coke carry out oxide etch reaction, improve hydro-thermal coke porosity；
(3) after reaction, it cools down immediately, gained solid-liquid mix products extruding-desiccation machine is dehydrated, be dehydrated separating obtained
Solid product, that is, hydro-thermal is burnt, is dehydrated the concentrated separation of separating obtained product liquid, obtains by-product.
Biomass in the step (1) is rice straw, straw, millet stalk, any one or a few in cornstalk, length
For 1~10cm.
In the step (1), reaction pressure be 4~7MPa, reaction temperature be 250~290 DEG C, the reaction time be 100~
200 minutes.
Reaction kettle heating rate in step (1) step (2) is 10~20 DEG C/min.
Extrusion dehydration uses screw extrusion dewaterer, 7~30kW of power, 16~8r/ of revolution speed of screw in the step (3)
min。
Concentration and separation use nanofiltration membrane in the step (3), and aperture is 1~2nm, and molecular cut off is 40~900, operation
Pressure is 3~10bar.
The hydro-thermal charred ashes that the step (3) obtains divides K content to be less than or equal to 12mg/kg, and Na content is less than or equal to 4mg/kg,
Aperture surface area is more than or equal to 785m2/g。
In step (2), the pressure of reaction kettle is 7~22MPa, and reaction temperature is 330~350 DEG C, the reaction time is 200~
400 minutes.
By-product in step (3) includes formic acid, methanol, potassium formate, sodium formate, calcium formate.
In step (1), the ratio of biomass and water 1:5~50 in mass ratio is sufficiently mixed.
The utility model has the advantages that
(1) the present invention provides a kind of CO2The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, the party
Method operating process is simple, utilizes CO2Hydro-thermal reaction characteristic combination hydro-thermal intermediate product is to CO2Absorption property, it is anti-in hydrothermal carbonization
It answers in device, by the Reasonable Regulation And Control of technological parameter, with CO2As reaction atmosphere, in reaction in two steps: medium temperature and medium pressure first, benefit
With CO2 hydro-thermal reaction characteristic, hemicellulose, cellulose and the abundant hydrothermal carbonization of lignin in catalysis biomass reduce intermediate produce
Object excessive decomposition then proceedes to be passed through CO2, under high-temperature and high-pressure conditions, promotes in biomass different shape alkali metal in CO2 gas
Orientation converts and aoxidizes to form the organic alkali metals salt such as potassium formate, calcium formate under atmosphere, is directly realized by biomass by hydro-thermal carbonisation
The removing of middle alkali metal, while realizing alkali metal in transition process and CO2The etching activation to hydro-thermal coke is reacted with alkali metal,
It is burnt can to directly obtain ashless porous hydro-thermal for control through reasonable design and processes parameter；The present invention by step (1)~
(3) in, CO is controlled2Intake and pressure are to sufficiently promote the migration of alkali metal and the development of hydro-thermal coke hole in biomass.?
CO in step (2)2It after being first heated to the reaction temperature in reaction kettle, then boosts and is passed through reaction kettle, realize reaction kettle intermediary
Matter is reacted rapidly without the temperature difference, improves CO2Etching performance, increase reaction rate.
(2) the achievable CO of the present invention2Seal up for safekeeping with processing while biomass waste, have application potential and environmental benefit；
The organic alkali metal salt being dissolved in reaction solution is alternatively arranged as potential chemicals, is used for chemical industry or soil conditioner；
(3) present invention is by adjusting CO2Concentration and reaction condition promote CO2Oxide etch is carried out with hydro-thermal coke to react,
Develop the pore structure of hydro-thermal coke, hydro-thermal coke obtained has the characteristics that even pore distribution, content of ashes are extremely low, especially water
K and Na mass fraction in hot coke is lower than 0.3%, is not required to subsequent processing；
(4) CO provided by the invention2The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, technique letter
It is single, environmental-friendly, it is the cutting edge technology that biomass recycling use is paid close attention in the world at present.
Specific embodiment
To be best understood from the present invention, the present invention is further described in detail below by embodiment.
CO2The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, includes the following steps:
(1) biomass and the water ratio of 1:5~1:50 in mass ratio are sufficiently mixed, mixture are put into reaction kettle,
Closed autoclave body, and CO is passed through into kettle2, make 4~7MPa of pressure in kettle, heated by heater, set reaction temperature as 250
~290 DEG C, the reaction time is 100~200 minutes；
(2) step (1) after reaction, continues to be passed through CO into reaction kettle2, make 17~22MPa of pressure in kettle, then
Reaction temperature is set as 330~350 DEG C, the reaction time is 200~400 minutes；
(3) step (2) after reaction, is passed through cooling water cooling immediately, and gained solid-liquid mix products feeding spiral is squeezed
Pressing dehydrator dehydration is dehydrated separating obtained solid product i.e. hydro-thermal coke, is dehydrated the concentrated separation of separating obtained product liquid, obtains
Formic acid, methanol, potassium formate, sodium formate, calcium formate.
Biomass in the step (1) is one or more of rice straw, straw, millet stalk, cornstalk, length 1
~10cm.
Reaction kettle heating rate in step (1) step (2) is 10~20 DEG C/min.
CO in the step (2)2After being first heated to the reaction temperature in reaction kettle, boosting is passed through reaction kettle.
Screw extrusion dewaterer 7~30kW of power, 16~8r/min of revolution speed of screw in the step (3).
Concentration and separation use nanofiltration membrane in the step (3), and aperture is 1~2nm, and molecular cut off is 40~900, operation
Pressure is 3~10bar.
The hydro-thermal coke that the step (3) obtains is that low ash point or the porous hydro-thermal of extremely low ash content are burnt, cleans and burns as fuel
Or heavy-metal adsorption material application.
Concentration and separation gained formic acid, methanol can be used as liquid fuel, and potassium formate, sodium formate, calcium formate can be used as chemical industry use
Product are applied.
In step (1)~(3), CO2Intake and pressure should sufficiently promote the migration of alkali metal and water in biomass
The development of hot coke hole.
Embodiment 1
Rice straw 30g and water 150g are sufficiently mixed, are put into reaction kettle, closed autoclave body is passed through CO into kettle2Make to press in kettle
Power rises to 4MPa, is heated by heater, and heater heating rate is 10 DEG C/min, is heated to reaction temperature and is 250 DEG C and protects
Temperature 200 minutes, will then be preheated to 250 DEG C of CO2Continue to be passed through in kettle, so that pressure in kettle is risen to 17MPa, heater keeps 10
DEG C/heating rate of min makes reaction temperature rise to 330 DEG C, 400min is kept the temperature, CO is made2It is abundant under hydrothermal conditions with biomass
Reaction leads to cooling water cooling immediately, obtains solid-liquid mix products after reaction；Gained solid-liquid mix products are sent into power
7KW, the screw extrusion dewaterer that revolving speed is 16 turns are dehydrated, and obtain dewatered solid product i.e. hydro-thermal coke, product liquid is through hole
The nanofiltration membrane that diameter is 1nm is concentrated and separated, and obtains formic acid, methanol, potassium formate, sodium formate, calcium formate.
It is tested and analyzed it is found that K content is 12mg/kg in the present embodiment hydro-thermal coke, Na content is 4mg/kg, aperture surface area
Up to 785m2/g。
Embodiment 2
Straw 30g and water 1500g are sufficiently mixed, are put into reaction kettle, closed autoclave body is passed through CO into kettle2Make in kettle
Pressure rises to 7MPa, is heated by heater, heater heating rate be 20 DEG C/min, be heated to reaction temperature be 290 DEG C simultaneously
Heat preservation 100 minutes, will then be preheated to 290 DEG C of CO2Continue to be passed through in kettle, so that pressure in kettle is risen to 22MPa, heater is kept
The heating rate of 20 DEG C/min makes reaction temperature rise to 350 DEG C, keeps the temperature 200min, makes CO2It is filled under hydrothermal conditions with biomass
Divide reaction, after reaction, leads to cooling water cooling immediately, obtain solid-liquid mix products；Gained solid-liquid mix products are sent into power
The screw extrusion dewaterer for being 16 turns for 7KW, revolving speed is dehydrated, and dewatered solid product i.e. hydro-thermal coke, product liquid warp are obtained
The nanofiltration membrane that aperture is 1nm is concentrated and separated, and obtains formic acid, methanol, potassium formate, sodium formate, calcium formate.
It is tested and analyzed it is found that K content is 10mg/kg in the present embodiment hydro-thermal coke, Na content is 2mg/kg, aperture surface area
Up to 815m2/g。
Embodiment 3
Millet stalk 30g and water 500g are sufficiently mixed, are put into reaction kettle, closed autoclave body is passed through CO into kettle2Make in kettle
Pressure rises to 5MPa, is heated by heater, heater heating rate be 15 DEG C/min, be heated to reaction temperature be 260 DEG C simultaneously
Heat preservation 150 minutes, will then be preheated to 260 DEG C of CO2Continue to be passed through in kettle, so that pressure in kettle is risen to 18MPa, heater is kept
The heating rate of 15 DEG C/min makes reaction temperature rise to 340 DEG C, keeps the temperature 300min, makes CO2It is filled under hydrothermal conditions with biomass
Divide reaction, after reaction, leads to cooling water cooling immediately, obtain solid-liquid mix products；Gained solid-liquid mix products are sent into power
The screw extrusion dewaterer for being 8 turns for 30KW, revolving speed is dehydrated, and dewatered solid product i.e. hydro-thermal coke, product liquid warp are obtained
The nanofiltration membrane that aperture is 1.5nm is concentrated and separated, and obtains formic acid, methanol, potassium formate, sodium formate, calcium formate.
It is tested and analyzed it is found that K content is 11mg/kg in the present embodiment hydro-thermal coke, Na content is 3mg/kg, aperture surface area
Up to 805m2/g。
Embodiment 4
Cornstalk 30g and water 900g are sufficiently mixed, are put into reaction kettle, closed autoclave body is passed through CO into kettle2Make in kettle
Pressure rises to 6MPa, is heated by heater, heater heating rate be 12 DEG C/min, be heated to reaction temperature be 270 DEG C simultaneously
Heat preservation 120 minutes, will then be preheated to 270 DEG C of CO2Continue to be passed through in kettle, so that pressure in kettle is risen to 17MPa, heater is kept
The heating rate of 12 DEG C/min makes reaction temperature rise to 335 DEG C, keeps the temperature 240min, makes CO2It is filled under hydrothermal conditions with biomass
Divide reaction, after reaction, leads to cooling water cooling immediately, obtain solid-liquid mix products；Gained solid-liquid mix products are sent into power
The screw extrusion dewaterer for being 16 turns for 7KW, revolving speed is dehydrated, and dewatered solid product i.e. hydro-thermal coke, product liquid warp are obtained
The nanofiltration membrane that aperture is 2nm is concentrated and separated, and obtains formic acid, methanol, potassium formate, sodium formate, calcium formate.
It is tested and analyzed it is found that K content is 8mg/kg in the present embodiment hydro-thermal coke, Na content is 2mg/kg, aperture surface area
Up to 825m2/g。
Embodiment 5
Rice straw and the total 30g of millet stalk and water 1200g are sufficiently mixed, are put into reaction kettle, closed autoclave body is passed through into kettle
CO2So that pressure in kettle is risen to 4MPa, heated by heater, heater heating rate is 10 DEG C/min, is heated to reaction temperature
For 250 DEG C and 200 minutes are kept the temperature, will then be preheated to 250 DEG C of CO2Continue to be passed through in kettle, pressure in kettle made to rise to 17MPa,
Heater keeps the heating rate of 10 DEG C/min that reaction temperature is made to rise to 350 DEG C, keeps the temperature 400min, makes CO2With biomass in water
It is sufficiently reacted under heat condition, after reaction, leads to cooling water cooling immediately, obtain solid-liquid mix products；The mixing of gained solid-liquid produces
Object feeding power is 7KW, the screw extrusion dewaterer that revolving speed is 16 turns is dehydrated, and obtains dewatered solid product i.e. hydro-thermal coke,
The nanofiltration membrane that product liquid via hole diameter is 1.2nm is concentrated and separated, and obtains formic acid, methanol, potassium formate, sodium formate, calcium formate.
It is tested and analyzed it is found that K content is 7mg/kg in the present embodiment hydro-thermal coke, Na content is 1mg/kg, aperture surface area
Up to 830m2/g。
Claims (10)
1.CO2The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, which comprises the steps of:
(1) biomass and water are sufficiently mixed, mixture is put into reaction kettle, closed autoclave body, and CO is passed through into kettle2, pressurization
Heating presses hydrothermal carbonization reaction in carrying out；
(2) hydrothermal carbonization after reaction, continues to be passed through CO into reaction kettle2, make pressure rise in kettle, raise simultaneously reaction temperature
Degree promotes the alkali metal in biomass to be converted into corresponding salt removing at high temperature under high pressure, meanwhile, promote CO2With the water of generation
Hot coke carries out oxide etch reaction, improves the porosity of hydro-thermal coke；
(3) after reaction, it cools down immediately, gained solid-liquid mix products extruding-desiccation machine is dehydrated, separating obtained solid is dehydrated
Product, that is, hydro-thermal is burnt, is dehydrated the concentrated separation of separating obtained product liquid, obtains by-product.
2. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: biomass in the step (1) is rice straw, straw, millet stalk, any one or a few in cornstalk, length 1
~10cm.
3. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: in the step (1), reaction pressure is 4~7MPa, and reaction temperature is 250~290 DEG C, and the reaction time is 100~200
Minute.
4. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: the reaction kettle heating rate in step (1) step (2) is 10~20 DEG C/min.
5. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: extrusion dehydration uses screw extrusion dewaterer, 7~30kW of power, 16~8r/min of revolution speed of screw in the step (3).
6. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: using nanofiltration membrane, aperture is 1~2nm for concentration and separation in the step (3), and molecular cut off is 40~900, operation pressure
Power is 3~10bar.
7. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: the hydro-thermal charred ashes that the step (3) obtains divides K content to be less than or equal to 12mg/kg, and Na content is less than or equal to 4mg/kg, hole
Surface area is more than or equal to 785m2/g。
8. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: in step (2), the pressure of reaction kettle is 7~22MPa, and reaction temperature is 330~350 DEG C, and the reaction time is 200~400
Minute.
9. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: the by-product in step (3) includes formic acid, methanol, potassium formate, sodium formate, calcium formate.
10. CO according to claim 12The method that joint biomass by hydro-thermal realizes the burnt step deliming activation of hydro-thermal, feature
Be: in step (1), the ratio of biomass and water 1:5~50 in mass ratio is sufficiently mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811248193.7A CN109292855B (en) | 2018-10-25 | 2018-10-25 | CO2Method for realizing hydrothermal coke one-step deliming activation by combining biomass hydrothermal method |
Applications Claiming Priority (1)
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| CN101774904A (en) * | 2009-12-01 | 2010-07-14 | 同济大学 | Method for preparing formic acid through hydrothermal reduction of CO2 by carbohydrate biomass |
| CN101886144A (en) * | 2010-07-13 | 2010-11-17 | 大连理工大学 | Method for preparing reducing sugar by catalyzing biomass hydrolysis with carbon dioxide |
| CN106824001A (en) * | 2017-01-23 | 2017-06-13 | 华中科技大学 | A kind of device of two-stage biological matter hydro-thermal catalytic activation reaction |
| CN106867614A (en) * | 2017-02-21 | 2017-06-20 | 上海理工大学 | Catalysis prepares biomass molding fuel method under a kind of hydrothermal condition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101774904A (en) * | 2009-12-01 | 2010-07-14 | 同济大学 | Method for preparing formic acid through hydrothermal reduction of CO2 by carbohydrate biomass |
| CN101886144A (en) * | 2010-07-13 | 2010-11-17 | 大连理工大学 | Method for preparing reducing sugar by catalyzing biomass hydrolysis with carbon dioxide |
| CN106824001A (en) * | 2017-01-23 | 2017-06-13 | 华中科技大学 | A kind of device of two-stage biological matter hydro-thermal catalytic activation reaction |
| CN106867614A (en) * | 2017-02-21 | 2017-06-20 | 上海理工大学 | Catalysis prepares biomass molding fuel method under a kind of hydrothermal condition |
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