CN107011946A - The technique that biomass is converted into methanol with combustible in rubbish - Google Patents
The technique that biomass is converted into methanol with combustible in rubbish Download PDFInfo
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- CN107011946A CN107011946A CN201610051824.0A CN201610051824A CN107011946A CN 107011946 A CN107011946 A CN 107011946A CN 201610051824 A CN201610051824 A CN 201610051824A CN 107011946 A CN107011946 A CN 107011946A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
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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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
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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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
House refuse is by sorting, it is impossible to which the combustible of recycling is mixed with biomass material, biomass in mixed material is accounted for more than 60%.It is aqueous less than 20% that raw material, which is spontaneously dried,.Make gasifying agent raw material with the oxygen-containing 70-95% of air separation by PSA oxygen rich gas.Flammable raw material in biomass and rubbish is converted into crude synthesis gas and lime-ash with gasification furnace.Carbon residue in lime-ash returns to gasification furnace after being pulled out from lime-ash pond.Crude synthesis gas after cooling enters the fixed bed calcium oxide particle filter of two series connection, carries out two-stage dry cleaning.5-10MPa is compressed to, into methanol synthesis reactor.Synthesizing methanol uses existing ripe technology.
Description
The invention belongs to derived energy chemical field for technical field.
Background technology is petered out with fossil energy, and the mankind can be carried by the use of methanol and its derivative as the energy
The intermediate of body and multi-chemical, to substitute and produce past oil product, across the oil gas epoch, realizes sustainable development
Exhibition, is the common recognition of multinational scientist.China scientist Ni Wei bucket academicians, also propose to develop " methanol and dimethyl ether " warp to country
Ji, the energy strategy of the western and eastern's cooperative development.Biomass is flammable in carbon containing, hydrogen, the organic compound based on oxygen element, rubbish
Thing is in addition to a part is biomass, the organic matter also synthesized, and they are by synthesis gas approach, i.e., by gasification --- synthesis gas
Purification --- methanol-fueled CLC, can be converted into methanol by solid combustible.
It is ripe technology by synthesis gas synthesizing methanol.The difficult point for being converted into methanol with combustible in rubbish by biomass is
The gasification of raw material and the purification technique of crude synthesis gas.Different from conventional Coal Gasification, purified synthesis gas, biomass material has it only
Special physicochemical properties, in general gasification, it is difficult to set up a stable gasification reaction layer, it is also difficult to stable
Ground is produced causes the failure of process without tar synthesis gas.For the utilization biomass energy of modernization, many people study this
Technical process proposes different solutions.There is the chemical composition of complexity in rubbish in combustible, particularly containing some chlorine
The material of element, makes its gasification product different from Coal Gasification product, therefore can not apply mechanically a purification method.
Biomass is converted into methanol with combustible in rubbish, and manufacture synthesis gas is a crucial step, using partial oxidation process
Biomass and other organic matters are converted into synthesis gas by one step, are the preferred technical schemes of Many researchers, but it is at present in skill
It is also very unripe in art.Inst. of Energy, Shandong Prov. Academy of China proposes a kind of method by repeatedly improvement.Invention name
Claim：A kind of biomass gasification method.Number of patent application：CN201010139473.1.The main technical characteristic of the invention is：It is biological
The undergone dry thermal cracking of matter gasification, burning reduction, three different areas of the several steps of gas reforming in same gasification furnace
Between separate and be carried out continuously relatively, while in whole gasification points 3 points be continuously passed through gasifying agent, the equivalent of total gasifying agent
Than for 0.2-0.35, the mass ratio between gasifying agent, second gasification agent, three gasifying agents is (0-0.8): (2-3.5):
(0.7-1.5).By control the mutual ratio between biomass material, gasifying agent, second gasification agent, three gasifying agents come
The temperature and reaction depth of each subregion in stove are controlled, so as to control the quality of final products gas.In the patent of invention, biomass
The realization of gasification has three steps：
1st, under indirect heat exchange effect dry thermal cracking and partial gasification reaction occur for biomass and a gasifying agent.(and
In gasification for the purpose of production synthesis gas, a gasifying agent is not passed through)；
Burning and reduction reaction occur for semicoke and the second gasification agent that is passed through the 2, after pyrolysis and partial gasification；
3rd, pyrolysis and partial gasification after gaseous state thing (contain a large amount of tar) and by with second gasification agent burning reduce after
Gaseous products are mixed with three gasifying agents being passed through jointly, are occurred incomplete oxidation reaction, are realized gas high temperature reformation.Final
To the product gas of high-quality.
I extremely respects the achievement in research and their contribution of Inst. of Energy, Shandong Prov. Academy, but is also considered as the hair
The synthesis gas of open-birth production, it is former if during using methyl formate route synthesizing methanol, the content of the carbon dioxide in synthesis gas is higher
Material dry thermal cracking under indirect heat exchange effect is not largely effective.If gasification is simpler, device fabrication will be more
Easily, manufacturing cost will be more lower.If wider to biomass and the accommodation of flammable raw material in rubbish, Jiu Huigeng
Plus it is practical.By experiment and improvement for many years, I employs different gasification process.
The content of the invention：
First, the technical characteristic of the gasification of combustible material method present invention is in biomass and rubbish：What gasification of biomass was undergone
The two different intervals of dry thermal cracking, burning reduction, the several steps of gas reforming in same gasification furnace separate and connected relatively
It is continuous to carry out, while being continuously passed through oxygen in gasifying agent, total gasifying agent in three diverse locations in three times in whole gasification
Equivalent proportion is 0.2-0.35, and gasifying agent, second gasification agent, three gasifying agents account for the percentage difference of gasifying agent total oxygen demand
For：70-80%, 5-20%, 0-15%.Specific implementation step is：
1st, combustible in gasified raw material biomass and rubbish, it is desirable to which water content is less than 20%, equivalent grade is less than 20 lis
Rice, that is, the raw material that fine day is collected are basic without drying again, and most of raw material is without broken.The total amount of biomass is big in raw material
In 60%.
2nd, raw material enters gasification furnace, while being passed through a gasifying agent (richness for oxygen or oxygen content more than 70% of preheating
Oxygen), a gasifying agent is with 1 --- and the speed of 100 meter per seconds is injected directly into raw material layer, after raw material and material gasification pyrolysis
The high temperature that gas burning at combustion reaction, a gasifying agent nozzle produces more than 2000 DEG C occurs for gaseous products, and hot gas is rapid
Raw material is set to heat up, because the fineness ratio of raw material is larger, heat transfer is not that quickly, feed particles inside and outside temperature difference is very big, once
Mean temperature is 600-900 DEG C in gasifying agent reaction zone, stove.Raw material rapid draing, gasification and pyrolysis, generation gaseous state tar, dioxy
Change carbon, carbon monoxide, methane, hydrogen, vapor and charcoal (semicoke).
3rd, gaseous products and charcoal (semicoke) stove in cocurrent of the raw material by a gasifying agent reaction generation, charcoal movement
Speed is less than gas velocity, and now a gasifying agent has exhausted, and is participated in without oxygen, hot charcoal and vapor and titanium dioxide
Carbon is reacted, and its decomposition rate is substantially reduced, artificial in gasification furnace to form one relative to charcoal filtering that is stable, slowly moving
Layer.Its length is 0.3-2 meters.The gaseous products of gasifying agent reaction generation through longer one section of charcoal filtering layer, again with
After charcoal occurs reduction reaction and reformed, come out of the stove in the middle part of charcoal filtering layer as product gas.
4th, preheating second gasification agent (oxygen+vapor, ratio is 1: 0.5-1.5), with slow speed (0.001-
1 meter per second) feed in gasification furnace charcoal filtering layer stage casing, second gasification agent feed direction, reaction after airflow direction with wood
Charcoal moving direction is vertical.Second gasification agent is charcoal layer heating with charcoal reaction, makes the product gas outlet of charcoal filtering layer middle part
Neighbouring layer of charcoal temperature maintains 900 DEG C -1100 DEG C, and its reaction product gas composition is mainly carbon monoxide and hydrogen, and it is with one
The gaseous product that secondary gasification reaction is produced mixed flow in charcoal layer, it is common through one section of charcoal layer, come out of the stove as product gas.
5th, three gasifying agents (oxygen+vapor, ratio is 1: 0.5-3.5), with slow speed (0.001-0.1 meter/
Second) feeding the endpiece of charcoal filtering layer in gasification furnace, three gasifying agents feed airflow direction and charcoal shifting after direction, reaction
It is dynamic in opposite direction.Three times gasifying agent is not preheated, and it passes through ash bed, cools down lime-ash, forms solid slag.Third time gasification reaction
Make the basic after-flame of charcoal of remaining.Gaseous product is carbon monoxide and hydrogen, and it is also reverse through one section of charcoal filtering layer, from charcoal
Come out of the stove via product gas outlet at the middle part of filter layer.
Have in gasification furnace of the present invention between two reaction zones：One is gasifying agent oxygen and feed stock for blast furnace reaction interval,
The high temperature hot gas body that the burned reaction of raw material herein is produced quickly is heated, and is produced preliminary gasifying gas and hot charcoal, can be claimed
Be char zone；Second reaction interval is the charcoal filtering layer for the red heat set up, and its formation is with once gasifying in raw material
Constantly produce, loss constantly being exhausted with carbonaceous after the reaction of third time gasifying agent after agent reaction.The charcoal of red heat is both reaction
Agent is tar cracking catalyst again, and all product gas all go out gasification furnace, two after the layer filtering reaction of this charcoal filtering
The ratio of carbonoxide and the water reduction decomposition in this activity very high charcoal layer is more thoroughly.As long as the temperature dimension of charcoal layer under normal pressure
Hold at 900 DEG C -1100 DEG C, the equilibrium partial pressure of carbon dioxide is very low in product gas.That is, at ambient pressure, as long as
Control product gas outlet layer of charcoal temperature at 900 DEG C -1100 DEG C, main component only has carbon monoxide and hydrogen in product gas.
Gasification implementation steps are found out more than, biomass of the present invention and the gasification process of combustible in rubbish, with Shandong Province
The biomass gasification method of Energy Research Institute of academy of sciences invention is different in technical measures.Their principle is identical,
All it is that based on partial oxidation, the oxidation reaction of heat release is combined with the vapor and CO 2 reforming reaction absorbed heat
It is common to carry out, make generally thermodynamic equilibrium.Biomass is once converted into synthesis gas under self-heat condition.
Appended drawings 1 are the process schematic representations of biomass and gasification of combustible material method in rubbish.
2nd, in a kind of biomass and rubbish gasification of combustible material stove in order to implement the gasification process described in the present invention one, this hair
Bright two be a kind of gasification furnace of the flammable raw material suitable for biomass and rubbish, and its construction is characterized in：Body of heater is a water
The steel length cylinder of placing flat, section is circular.Liner flame retardant coating, outer layer is jacket boiler.
Body of heater one end connects the charging cylinder of a steel, and the internal diameter for feeding cylinder is equal with the internal diameter of flame retardant coating in body of heater
Or smaller, the feeder that is driven by motor and speed reducer, (it can be screw type or reciprocating-piston
), it is connected with the other end of charging cylinder；The other end closing of body of heater, sealing surface is observed provided with the glass for having sealing gland
Hole；It is product gas outlet to be opened upwards in the middle part of body of heater；The flame retardant coating of the lower half circle of corresponding product gas outlet is micropore in the middle part of body of heater
There are 2-6 gasifying agent shower nozzles in the second gasification agent distribution grid of ceramics, the body of heater of feed end, body of heater blind end has one
Three gasifying agent air inlet pipe.Body of heater postmedian, opens exported for lime-ash downwards.The lime-ash pond that lime-ash outlet is submerged in downwards
The water surface below, what there was 8 ° -22 ° of inclination angle lime-ash pond side drags for slag spiral.Opposite side has charcoal retracting device.
The operating characteristic of the gasification furnace is：Gasification furnace micro-pressure operation.Raw material is forced into charging cylinder, quilt by feeder
Extruding forms a closely knit stock column, is moved into gasification furnace.Feed closely knit stock column cut-off gasification furnace and air in cylinder
UNICOM.When raw material reaches flame retardant coating position in stove, a gasifying agent (richness for oxygen or oxygen content more than 70% having been warmed up
Oxygen) raw material post is sprayed at a high speed from periphery different directions, it is anti-to occur violent burning with the gaseous products after raw material and gasification and pyrolysis
Answer, more than 2000 DEG C of high temperature is produced at nozzle, hot gas rapidly cracks raw material avalanche, volume-diminished separates out gaseous state thing, by
Gradual change matter is semicoke or charcoal, and mean temperature reaches 600-900 DEG C in a gasifying agent reaction zone, stove.
Flowed due to feeding the gas in the material envelope effect of cylinder, stove to the relatively low product gas outlet direction of air pressure；Solid-state
Charcoal or semicoke be that the extruding of the solid feed that is constantly entered promotes motion, that is, stove internal solid material is all charging
What device was promoted, although volume constantly reduces after raw material reacts through a gasifying agent, but the charcoal constantly produced is under mutual push
Furnace chamber is still filled with, the movement velocity charcoal filtering layer slower than gas is formd.The gaseous products of gasifying agent reaction generation
Through longer one section of charcoal filtering layer, after occurring reduction reaction with charcoal again and reform, from charcoal filtering layer stage casing top
Product gas outlet is come out of the stove.
Second gasification agent, by micropore ceramics distribution grid, the charcoal filtering in gasification furnace is fed with slow speed upwards
The middle pars infrasegmentalis of layer, occurring burning reduction reaction with charcoal heats charcoal layer, makes the layer of charcoal temperature of product gas near exit
Maintain 900 DEG C -1100 DEG C.The gas for reacting generation flows in charcoal layer with a gasification reaction gas mixing, wears jointly
One section of layer of charcoal is crossed, is come out of the stove as product gas.
Three gasifying agents are fed in the peep hole of gasification furnace blind end, because lime-ash outlet is water seal, three gasifications
Agent is moved through lime-ash to charcoal layer.Three times gasifying agent is not preheated, and it, which cools down lime-ash, makes its solid-state discharge furnace chamber, falls into clinker water
In the water in pond, pulled out by dragging for slag spiral, separation and recovery useful metal and sylvite.The carbon residue of floating pulls return gasification furnace out.
Appended drawings 2 are biomass and the structural representation of gasification of combustible material stove in rubbish.In figure：1 is charging
Device.2. feed cylinder.3. it is a gasification agent nozzle.4. flame retardant coating.5. jacket boiler.6. body of heater.7. the secondary gas of micropore ceramics
Agent branch plate.8. second gasification agent import.9. three gasifying agent imports.10. product gas outlet.11. lime-ash outlet.12.
Glass peephole.13. lime-ash pond.14. drag for slag spiral.15. charcoal retracting device.
The present invention one, two has following beneficial effect：
1st, gasification process process is simple, and adaptability to raw material is strong.
2nd, gasification furnace apparatus is simple, and air-tightness is reliable, reliable.Maintenance is small.
3rd, technical process is easily controllable.The content of carbon monoxide and hydrogen is high in product gas.
Although the 4, raw material is without pulverizing processing, there is carbon residue in lime-ash.But it can be recycled in the lime-ash pond of setting.Charcoal profit
It is high with rate.
Specific implementation method：
For example：Gasified raw material is stalk (such as corn stalk, wheat straw, cotton straw, rice seedling) after crop harvesting, agricultural
The biomass material such as processing waste (such as rice wheat peanut shell, wood chip, shell) and leaf, branch is a kind of or arbitrarily mixes
Thing is mixed with combustible in the rubbish by sorting, it is desirable to which water content is less than 20%, that is, the raw material that fine day is collected is substantially not
With drying, unless the larger branch of volume, timber etc. are needed outside broken, most of raw material is without broken.Biomass in raw material
Total amount is more than 60%.When namely combustible plastic components are excessive in municipal refuse, to be incorporated some can generate more carbonaceous
Biomass material.
Oxygen-enriched with air separation by PSA oxygen-containing 90% is that the equivalent proportion of the total gasifying agent oxygen of gasifying agent is 0.25-0.28.
Gasifying agent is oxygen-enriched, and its consumption accounts for 75-the 80% of total oxygen demand；Second gasification agent is oxygen-enriched+vapor, ratio is 1: 1-
1.2, the consumption of oxygen accounts for 8-the 12% of total oxygen demand；Three times gasifying agent is oxygen-enriched+vapor, and ratio is 1: 1-1.5, the use of oxygen
Amount, accounts for 8-the 15% of total oxygen demand.
Raw material is promoted by plug feeder, quantitatively into gasification furnace, 450-600 DEG C of a gasifying agent is preheated to, with 30
The speed of meter per second is injected directly into raw material layer, and combustion reaction occurs for the gaseous products after being pyrolyzed in gasification furnace with material gasification,
Gas burning produces more than 2000 DEG C of high temperature at nozzle, and hot gas diffuses rapidly into raw material layer, feed particles internal and external temperature
Difference is very big, and mean temperature is 800-900 DEG C in a gasifying agent reaction zone, stove.Raw material rapid draing, gasification and pyrolysis, generation
Gaseous state tar, carbon dioxide, carbon monoxide, methane, hydrogen, vapor and charcoal (semicoke).
The gaseous products of generation flow to the less product gas outlet direction of pressure, and charcoal (semicoke) is not breaking the original of stove
Material extruding is moved under promoting to lime-ash Way out.The two cocurrent in stove, charcoal translational speed is less than gas velocity, now existed
It is artificial in gasification furnace to form one relative to charcoal filtering layer that is stable, slowly moving.Its length is 0.4-1 meters.Gasifying agent
The gaseous products of generation are reacted because velocity ratio charcoal is fast, and it occurs also through 0.3-0.6 meters of charcoal filtering layer length with charcoal
Original reaction as product gas with after reformation, coming out of the stove.
450-600 DEG C of second gasification agent is preheated to, by micropore ceramics distribution grid, is fed upwards with slow speed
The middle pars infrasegmentalis of charcoal filtering layer in gasification furnace, is charcoal layer heating, maintains the layer of charcoal temperature of product gas near exit
At 900 DEG C -1100 DEG C.Gas mixing of the gas of generation in charcoal layer with generation of once gasifying is reacted, from product gas outlet
Come out of the stove.
Three gasifying agents of natural temperature are fed by the peep hole of gasification furnace tail end, and it passes through ash bed, cools down lime-ash,
Make its dry ash extraction.Third time gasification reaction makes the basic after-flame of charcoal of remaining.Gaseous product is inversely through 0.1 meter of charcoal filtering
Come out of the stove after layer length, lime-ash falls into lime-ash pond via lime-ash delivery channel, and lime-ash pulls separation and recovery useful metal out by spiral,
The carbon residue of floating is pulled return out and used again.
Product gas tapping temperature is 950-1050 DEG C.The volume content of product gas composition is：Carbon monoxide 32-38%,
Hydrogen 45-60%, carbon dioxide 1-5%, methane 1-2%, nitrogen 5-10%, oxygen is less than 0.6%. hydrogen chloride and is less than 2%, vulcanization
Hydrogen is micro.The gas can be used for synthesizing methanol after purification.
3rd, the technology characteristics that combustible is converted into the technique present invention of methanol in biomass and rubbish are：House refuse is passed through
Sorting is crossed, noncombustibles, the material of recoverable and the combustible that can not be recycled is isolated.By can not be sharp again in rubbish
Combustible is mixed with the agriculture and forestry organic waste material raw material collected in addition, biomass in mixed material is accounted for more than 60%.
It is aqueous less than 20% that raw material, which is spontaneously dried,.The bulk materials that equivalent diameter is more than gasification furnace charging drum diameter 1/5th are needed
It is broken.
PSA oxygen-enriching devices are provided with technique.Make gasifying agent with the oxygen rich gas of air separation by PSA oxygen-containing 70-95% former
Material.
Flammable raw material in biomass and rubbish is converted into crude synthesis gas and lime-ash with gasification furnace.Lime-ash reclaim metal and
Stored up after sylvite.Carbon residue in lime-ash returns to gasification furnace after being pulled out from lime-ash pond.
Due to containing part polyolefine material in rubbish, the volume content of crude synthesis gas gas componant is substantially：One oxidation
Carbon 32-38%, hydrogen 45-60%, carbon dioxide 1-5%, methane 1-2%, nitrogen 5-10%, it is small that oxygen is less than 0.6%. hydrogen chloride
In 2%, hydrogen sulfide is less than 0.5%.The ratio of carbon monoxide and hydrogen is adapted to synthesizing methanol close to 2.Due to containing hydrogen chloride, slightly
Synthesize gas corrosion metal.High temperature is more very.
The crude synthesis gas temperature for going out gasification furnace is 950-1100 DEG C, and it is changed by the pipeline of lined ceramicses into enamel
After hot device exchanges heat with gasifying agent, via enamel normal-pressure boiler, temperature is down to 200 DEG C or so.Exchange heat, cool as 90 DEG C of left sides with water again
It is right.
Crude synthesis gas after cooling enters the fixed bed calcium oxide particle filter of two series connection, carries out two-stage dry method net
Change.Fixed bed calcium oxide particle filter sets three altogether, wherein two tandem workings, another offline oxidation for changing failure
Calcium particle.In calcium oxide particle filter, directly with filtrate chemistry occurs for sour gas hydrogen sulfide, hydrogen chloride, carbon dioxide
React and be removed.Control crude synthesis gas flow velocity and residence time in the filter more than 30-60s, moisture and other miscellaneous
Matter is also filtered out.Monitor hydrogen chloride content in the quality of First calcium oxide particle filter outlet gas, synthesis gas on-line steady
Surely it is less than 0.5 × 10-6Clean-up effect can meet technological requirement.
Synthesis gas after purification is compressed to 5-10MPa via gas compressor, into methanol synthesis reactor.
Synthesizing methanol uses existing ripe technology.Use copper zinc catalyst.Using paste state bed reactor.Lived by reduction
Powdered copper zinc catalyst after change is dispersed in liquid paraffin or other inert hydrocarbon oils, catalyst solid content 5-35%.
Synthesis gas simply blasts reactor bottom, controls 5-10MPa of reaction pressure, 220~280 DEG C of reaction temperature, and air speed 50-
500l/h. methanol-fueled CLCs are strong exothermal reactions, and the tubular boiler sunk in a liquid using paste state bed reactor is moved with vapor
Synthesising reacting heat is removed, control synthetic reaction is carried out under approximately constant temperature.
It is methanol steam to go out in the product gas of paste state bed reactor about 85-90%, containing only a small amount of unreacted synthesis gas
And inert gas.It enters after high pressure condenser, and liquid is stablized into low-pressure condenser, and the liquid of collection is exactly fuel-grade
Absolute methanol.It need not be re-refined as fuel.On-condensible gas is periodically seted off.
Appended drawings 3 are the schematic flow sheets for the technique that biomass is converted into methanol with combustible in rubbish.
The present invention has following beneficial effect：
1st, realize biomass and the free of contamination resource recycling of rubbish is utilized.Alleviate social energy shortage.
2nd, realize that garbage disposal has an economic benefit.Promote economic development.Present invention gasification and gas purification process simply may be used
Lean on, equipment investment is few, calcium oxide is inexpensive, whole flow process running cost compared is relatively low.It is raw under the existing methanol fuel market price
Production has an economic benefit.
3rd, there are social benefit and environmental benefit.It more thoroughly eliminates pollution of the rubbish to environment.The combustion that it is provided
Material, CO2 emission is approximately zero.Alcohol ether is clean fuel, can reduce air pollution.It can promote garbage disposal society
Change and Run on commercial basis.Rubbish volume reduction, few land occupation.
Specific implementation method
For example：Contain substantial amounts of leaf in autumn and winter, domestic waste, now combustible components of biomass in rubbish
More than 60% is accounted for, without mixing other biomass materials again.House refuse isolates noncombustibles, recyclable profit by sorting
Material and the combustible that can not be recycled.By the combustible that can not be recycled in rubbish spontaneously dry for aqueous 20% with
Under.
Make gasifying agent raw material with the oxygen rich gas of air separation by PSA oxygen-containing 70-95%.
Using the gasification process condition and method described in the present invention one, i.e., the equivalent proportion of total gasifying agent oxygen for 0.25-
0.28.Gasifying agent is oxygen-enriched, and its consumption accounts for 75-the 80% of total oxygen demand；Second gasification agent is oxygen-enriched+vapor, and ratio is
1: 1-1.2, oxygen amount accounts for 8-the 12% of total oxygen demand；Three times gasifying agent is oxygen-enriched+vapor, and ratio is 1: 1-1.5, oxygen consumption
Account for 8-the 15% of total oxygen demand.Flammable raw material in biomass and rubbish is converted into crude synthesis gas and lime-ash in gasification furnace.Ash
Slag is stored up after reclaiming metal and sylvite.Carbon residue in lime-ash returns to gasification furnace after being pulled out from lime-ash pond.
The volume content of crude synthesis gas gas componant is substantially：Carbon monoxide 32-38%, hydrogen 45-60%, carbon dioxide
1-5%, methane 1-2%, nitrogen 5-10%, oxygen is less than 0.6%. hydrogen chloride and is less than 2%, and hydrogen sulfide is less than 0.5%.One oxidation
The ratio of carbon and hydrogen is adapted to synthesizing methanol close to 2.Due to containing hydrogen chloride, crude synthesis gas corrosion metal.High temperature is more very.
The crude synthesis gas temperature for going out gasification furnace is 950--1100 DEG C, and it is changed by the pipeline of lined ceramicses into enamel
After hot device exchanges heat with gasifying agent, via enamel normal-pressure boiler, temperature is down to 200 DEG C or so.Exchange heat, cool as 90 DEG C of left sides with water again
It is right.
Crude synthesis gas after cooling enters the fixed bed calcium oxide particle filter of two series connection, carries out two-stage dry method net
Change.Fixed bed calcium oxide particle filter sets three altogether, wherein two tandem workings, another offline oxidation for changing failure
Calcium particle.In calcium oxide particle filter, directly with filtrate chemistry occurs for sour gas hydrogen sulfide, hydrogen chloride, carbon dioxide
React and be removed.Control crude synthesis gas flow velocity and residence time in the filter more than 30-60s, moisture and other miscellaneous
Matter is also filtered out.Monitor hydrogen chloride content in the quality of First calcium oxide particle filter outlet gas, synthesis gas on-line steady
Surely it is less than 0.5 × 10-6Clean-up effect can meet technological requirement.
Synthesis gas after purification is compressed to 5-10MPa via gas compressor, into methanol synthesis reactor.
Synthesizing methanol uses copper zinc catalyst.Using paste state bed reactor.Powdered copper zinc after reduction activation
Catalyst is dispersed in liquid paraffin or other inert hydrocarbon oils, catalyst solid content 5-35%.Synthesis gas blasts reactor bottom
Portion, 5-10MPa of reaction pressure, 220--280 DEG C of reaction temperature, air speed 500l/h. methanol-fueled CLCs are strong exothermal reactions, utilize slurry
The tubular boiler of state bed reactor sinking in a liquid removes synthesising reacting heat with vapor, and control synthetic reaction is in approximately constant temperature
It is lower to carry out.
It is methanol steam to go out about 85--90% in the product gas of paste state bed reactor, containing only a small amount of unreacted synthesis gas
And inert gas.It enters after high pressure condenser, and liquid enters low pressure and condenses stabilizer, and the liquid of collection is exactly fuel-grade anhydrous
Methanol.It need not be re-refined as fuel.
Claims (1)
1. the first, the technical characteristic of the gasification of combustible material method present invention is in biomass and rubbish：It is dry that gasification of biomass is undergone
The two different intervals of scorching solution, burning reduction, the several steps of gas reforming in same gasification furnace are separated and continuous relatively
Carry out, while being continuously passed through working as oxygen in gasifying agent, total gasifying agent in three diverse locations in three times in whole gasification
Amount ratio is 0.2-0.35, and the percentage that gasifying agent, second gasification agent, three gasifying agents account for gasifying agent total oxygen demand is respectively：
70-80%, 5-20%, 0-15%.Specific implementation step is：
1st, combustible in gasified raw material biomass and rubbish, it is desirable to which water content is less than 20%, equivalent grade is less than 20 centimetres,
It is exactly that the raw material collected of fine day is basic without drying again, most of raw material is without broken.The total amount of biomass is more than in raw material
60%.
2nd, raw material enters gasification furnace, while being passed through a gasifying agent (oxygen or oxygen content more than 70% oxygen-enriched) for preheating, one
Secondary gasifying agent is injected directly into raw material layer with the speed of 1-100 meter per seconds, is sent out with the gaseous products after raw material and material gasification pyrolysis
Gas burning produces more than 2000 DEG C of high temperature at raw combustion reaction, a gasifying agent nozzle, and hot gas makes raw material heat up rapidly,
Because the fineness ratio of raw material is larger, heat transfer is not that quickly, feed particles inside and outside temperature difference is very big, in a gasifying agent reaction
Mean temperature is 600-900 DEG C in area, stove.Raw material rapid draing, gasification and pyrolysis, generation gaseous state tar, carbon dioxide, an oxidation
Carbon, methane, hydrogen, vapor and charcoal (semicoke).
3rd, gaseous products and charcoal (semicoke) stove in cocurrent of the raw material by a gasifying agent reaction generation, charcoal translational speed
Less than gas velocity, now a gasifying agent has exhausted, and is participated in without oxygen, and hot charcoal is only anti-with vapor and carbon dioxide
Should, its decomposition rate is substantially reduced, artificial in gasification furnace to form one relative to charcoal filtering layer that is stable, slowly moving.Its
Length is 0.3-2 meters.The gaseous products of gasifying agent reaction generation are sent out with charcoal again through longer one section of charcoal filtering layer
Raw reduction reaction in the middle part of charcoal filtering layer as product gas with after reformation, coming out of the stove.
4th, preheating second gasification agent (oxygen+vapor, ratio is 1: 0.5-1.5), with slow speed (0.001-1 meters/
Second) feeding the stage casing of charcoal filtering layer in gasification furnace, second gasification agent feeds airflow direction and charcoal shifting after direction, reaction
Dynamic direction is vertical.Second gasification agent is charcoal layer heating with charcoal reaction, makes charcoal filtering layer middle part product gas near exit
Layer of charcoal temperature maintain 900 DEG C -1100 DEG C, its reaction product gas composition is mainly carbon monoxide and hydrogen, it and once gas
Change and react the gaseous product produced mixed flow in charcoal layer, it is common through one section of charcoal layer, come out of the stove as product gas.
5th, three gasifying agents (oxygen+vapor, ratio is 1: 0.5-3.5), are given with slow speed (0.001-0.1 meter per seconds)
Enter the endpiece of the charcoal filtering layer in gasification furnace, three gasifying agents feed airflow direction and charcoal movement side after direction, reaction
To opposite.Three times gasifying agent is not preheated, and it passes through ash bed, cools down lime-ash, forms solid slag.Third time gasification reaction makes residual
The basic after-flame of charcoal deposited.Gaseous product is carbon monoxide and hydrogen, and it is also reverse through one section of charcoal filtering layer, from charcoal filtering
Come out of the stove via product gas outlet at the middle part of layer.
Have in gasification furnace of the present invention between two reaction zones：One is a gasifying agent oxygen and feed stock for blast furnace reaction interval, at this
In the high temperature hot gas body that produces of the burned reaction of raw material quickly heat, produce preliminary gasifying gas and hot charcoal, can be referred to as
Char zone；Second reaction interval is the charcoal filtering layer for the red heat set up, and its formation is anti-in raw material and a gasifying agent
It rear should constantly produce, loss constantly being exhausted with carbonaceous after the reaction of third time gasifying agent.The charcoal of red heat be both reactant again
It is tar cracking catalyst, all product gas all go out gasification furnace after the layer filtering reaction of this charcoal filtering.
2nd, its construction of gasification of combustible material stove is characterized in a kind of biomass and rubbish：Body of heater is the steel of a horizontal positioned
Long cylinder, section is circular.Liner flame retardant coating, outer layer is jacket boiler.Boiler outer layer is heat-insulation layer.
Body of heater one end connects the charging cylinder of a steel, and the internal diameter of charging cylinder is equal with the internal diameter of flame retardant coating in body of heater or omits
It is small, the feeder that is driven by motor and speed reducer, (it can be screw type or reciprocating-piston), with
The other end of charging cylinder is connected；The other end closing of body of heater, sealing surface is provided with a glass peephole for having sealing gland；Body of heater
It is product gas outlet that middle part is opened upwards；The flame retardant coating of the lower half circle of corresponding product gas outlet is the two of micropore ceramics in the middle part of body of heater
There are a 2-6 gasifying agent shower nozzles in secondary gasifying agent distribution grid, the body of heater of feed end, body of heater blind end there are three gasifying agents
Air inlet pipe.Body of heater postmedian, opens exported for lime-ash downwards.The water surface in the lime-ash pond that lime-ash outlet is submerged in downwards with
Under, what there was 8 ° -22 ° of inclination angle lime-ash pond side drags for slag spiral.Opposite side drags for charcoal device.
The operating characteristic of the gasification furnace is：Gasification furnace micro-pressure operation.Raw material is forced into charging cylinder by feeder, is extruded
A closely knit stock column is formed, is moved into gasification furnace.Feed the UNICOM that stock column closely knit in cylinder separates gasification furnace and air.
When raw material reaches flame retardant coating position in stove, the gasifying agent (oxygen or oxygen content more than 70% oxygen-enriched) having been warmed up is from week
Side different directions spray to raw material post at a high speed, occur violent combustion reaction, nozzle with the gaseous products after raw material and gasification and pyrolysis
Place produces more than 2000 DEG C of high temperature, and hot gas rapidly cracks raw material avalanche, and volume-diminished separates out gaseous state thing, gradually gone bad
For semicoke or charcoal, mean temperature reaches 600--900 DEG C in a gasifying agent reaction zone, stove.
Flowed due to feeding the gas in the material envelope effect of cylinder, stove to the relatively low product gas outlet direction of air pressure；The wood of solid-state
Charcoal or semicoke are that the extruding of the solid feed constantly entered promotes motion, that is, stove internal solid material is all that feeder is pushed away
It is dynamic, although volume constantly reduces after raw material reacts through a gasifying agent, but the charcoal constantly produced under mutual push still
Full of furnace chamber, the movement velocity charcoal filtering layer slower than gas is formd.The gaseous products of gasifying agent reaction generation are passed through
Longer one section of charcoal filtering layer, after occurring reduction reaction with charcoal again and reform, the product from charcoal filtering layer stage casing top
Gas is come out of the stove.
Second gasification agent, by micropore ceramics distribution grid, charcoal filtering layer in gasification furnace is fed with slow speed upwards
Middle pars infrasegmentalis, occurring burning reduction reaction with charcoal heats charcoal layer, maintains the layer of charcoal temperature of product gas near exit
At 900 DEG C -1100 DEG C.The gas for reacting generation flows in charcoal layer with a gasification reaction gas mixing, jointly through one
Section layer of charcoal, comes out of the stove as product gas.
Third time gasifying agent is fed in the peep hole of gasification furnace blind end, because lime-ash outlet is water seal, three gasifying agents
Moved through lime-ash to charcoal layer.Three times gasifying agent is not preheated, and it, which cools down lime-ash, makes its solid-state discharge furnace chamber, falls into lime-ash pond
Water in.Lime-ash is pulled out by dragging for slag spiral, and separation and recovery useful metal after sylvite with storing up.The carbon residue of floating pulls return gasification out
Stove.
3rd, the technology characteristics that combustible is converted into the technique present invention of methanol in biomass and rubbish are：House refuse is through undue
Choosing, isolates noncombustibles, the material of recoverable and the combustible that can not be recycled.Can by what can not be recycled in rubbish
Combustion things are mixed with the agriculture and forestry organic waste material raw material collected in addition, biomass in mixed material is accounted for more than 60%.Raw material is certainly
So dry is aqueous less than 20%.The bulk materials that equivalent diameter is more than gasification furnace charging drum diameter 1/5th need to be crushed.
PSA oxygen-enriching devices are provided with technique.Make gasifying agent raw material with the oxygen-containing 70-95% of air separation by PSA oxygen rich gas.
Flammable raw material in biomass and rubbish is converted into crude synthesis gas and lime-ash in gasification furnace.Lime-ash reclaims metal and potassium
Stored up after salt.Carbon residue in lime-ash returns to gasification furnace after being pulled out from lime-ash pond.
Due to containing part polyolefine material in rubbish, the volume content of crude synthesis gas gas componant is substantially：Carbon monoxide 32-
38%, hydrogen 45-60%, carbon dioxide 1-5%, methane 1-2%, nitrogen 5-10%, oxygen are less than 0.6%. hydrogen chloride and are less than 2%, sulphur
Change hydrogen and be less than 0.5%.The ratio of carbon monoxide and hydrogen is adapted to synthesizing methanol close to 2.Due to containing hydrogen chloride, crude synthesis gas is rotten
Lose metal.High temperature is more very.
Go out gasification furnace crude synthesis gas temperature be 950-1100 DEG C, it by lined ceramicses pipeline, into enamel heat exchanger
After gasifying agent heat exchange, via enamel normal-pressure boiler, temperature is down to 200 DEG C -300 DEG C, then is exchanged heat with water, cools as 60-100
℃。
Crude synthesis gas after cooling enters the fixed bed calcium oxide particle filter of two series connection, carries out two-stage dry cleaning.Gu
Fixed bed calcium oxide particle filter sets three altogether, wherein two tandem workings, another offline calcium oxide for changing failure
Grain.In calcium oxide particle filter, sour gas hydrogen sulfide, hydrogen chloride, carbon dioxide directly chemically react with filtrate
And be removed.Control crude synthesis gas flow velocity and residence time in the filter more than 30-60s, moisture and other impurity
It is filtered out.Monitor hydrogen chloride content in the quality of First calcium oxide particle filter outlet gas, synthesis gas on-line and stablize small
In 0.5 × 10-6Clean-up effect can meet technological requirement.
Synthesis gas after purification is compressed to 3-10MPa via gas compressor, into methanol synthesis reactor.
Synthesizing methanol uses existing ripe technology.Use copper zinc catalyst.Using paste state bed reactor.After reduction activation
Powdered copper zinc catalyst be dispersed in liquid paraffin or other inert hydrocarbon oils, catalyst solid content 5-35%.Synthesis
Gas simply blasts reactor bottom, controls reaction pressure 3-10MPa, 220-280 DEG C of reaction temperature, air speed 50-5001/h. first
Alcohol synthesis is strong exothermal reaction, and the tubular boiler sunk in a liquid using paste state bed reactor removes synthetic reaction with vapor
Heat, control synthetic reaction is carried out under approximately constant temperature.
It is methanol steam to go out about 85-90% in the product gas of paste state bed reactor, containing only a small amount of unreacted synthesis gas and lazy
Property gas.It enters after high pressure condenser, and liquid enters low pressure and condenses stabilizer, and the liquid of collection is exactly fuel-grade anhydrous first
Alcohol.It need not be re-refined as fuel.On-condensible gas is periodically seted off.
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| CN201610051824.0A CN107011946A (en) | 2016-01-27 | 2016-01-27 | The technique that biomass is converted into methanol with combustible in rubbish |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020069146A1 (en) * | 2018-09-27 | 2020-04-02 | Maat Energy Company | Process for recovering heat at high temperatures in plasma reforming systems |
| CN113565681A (en) * | 2021-08-09 | 2021-10-29 | 国网浙江省电力有限公司电力科学研究院 | Coupling system using electric heating gasification furnace and multi-energy conversion method thereof |
-
2016
- 2016-01-27 CN CN201610051824.0A patent/CN107011946A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020069146A1 (en) * | 2018-09-27 | 2020-04-02 | Maat Energy Company | Process for recovering heat at high temperatures in plasma reforming systems |
| CN113565681A (en) * | 2021-08-09 | 2021-10-29 | 国网浙江省电力有限公司电力科学研究院 | Coupling system using electric heating gasification furnace and multi-energy conversion method thereof |
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