CN101735011B - Process for gasification-liquefaction disposal of domestic garbage and organic waste - Google Patents
Process for gasification-liquefaction disposal of domestic garbage and organic waste Download PDFInfo
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- CN101735011B CN101735011B CN2009102582862A CN200910258286A CN101735011B CN 101735011 B CN101735011 B CN 101735011B CN 2009102582862 A CN2009102582862 A CN 2009102582862A CN 200910258286 A CN200910258286 A CN 200910258286A CN 101735011 B CN101735011 B CN 101735011B
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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
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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
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention discloses a process for gasification-liquefaction disposal of domestic garbage and organic waste, which relates to disposal technology of the domestic garbage and the organic waste. The process comprises the steps of: performing oxygen-free gasification on the domestic garbage or the organic waste in a plasma gasification furnace to produce hydrogen-rich syngas which does not contain oxygen and takes CO and H2 as main components, wherein the conditions of the formation of dioxin are avoided; then sending the hydrogen-rich syngas taken as feed gas into a methanol synthesis reactor to catalytically synthesize a methanol product after temperature reduction and dust removal/ purification; then drawing the methanol product out of the reactor to mix with lime water for terminal purification operation; and using calcium hydroxide as an absorbent to ensure that pollutants and purities which are not eliminated in a dust removal/purification working procedure and comprise the dioxin are removed. The process almost has no the discharge of the pollutants during the whole disposal process, and is suitable for harmless disposal of municipal domestic waste, rural domestic refuse, medical waste, industrial polymer waste, agricultural and forestry waste, composting leftovers and refuse sorting field waste.
Description
Technical field
The present invention relates to the disposal technology of domestic refuse, organic waste, particularly relate to a kind of method of solid waste harmlessness disposing.
Background technology
Domestic refuse and organic waste are along with the continuous expansion of the development of Chinese national economy and city size and increase sharply, cause rubbish to overflow, current, the garbage-surrounded city phenomenon has all appearred in many cities of China, has had influence on the Sustainable development of Chinese national economy and the development in restriction city.Domestic refuse and organic waste contain many objectionable constituent, as process badly, will pollute the environment, and threaten that the people's is healthy.At present, process domestic refuse and mainly contain refuse classification comprehensive utilization, Sanitary Landfill Technology, compost (biochemistry) technology and incineration technology, wherein, refuse classification needs public participation and cooperation, China does not also carry out at present, if can reach separate waste collection, comprehensive utilization, still 40～50% amount needs burning disposal in addition; China's most areas adopts sanitary landfill method to process domestic waste, and this not only need take a large amount of land resources, and easy contaminated land and underground water; Adopt composting process only to utilize organism about 40%, remaining 60% also need make burning disposal or landfill disposal, has equally the problem of secondary pollution; Adopt burning method to process domestic refuse, to have accomplished minimizing, recycling treatment domestic refuse to the eye, but be actually the mode of ground solid contaminant with flue gas shifted in the atmosphere, these transfer to pollutent in the atmosphere along with convection of air, terrestrial gravitation are got back on the ground, the life and health that impact is human, some pollutent is got back on the ground in the mode of making acid rain, and the carbonic acid gas that quantity discharged is maximum then plays the living environment that Greenhouse effect destroy people.Also there is the problem that generates easily carcinogenic violent in toxicity-dioxin contaminate environment, harm person health in disposal process in burning method, also lack at present effective reliable terminal cleaning process technology and eliminate dioxin, though incineration plant has flue gas purification system, all be difficult to eliminate.
Dioxin is that a kind of chloride strong toxic organic is learned material, this class material is highly stable, water insoluble, it is the lipid-soluble substance of colorless and odorless, so be very easy in vivo accumulation, natural microorganism and hydrolytic action are less on the molecular structure impact of dioxin, and therefore, the De dioxin is difficult to the natural degradation elimination in the environment.Its toxicity is more than 1000 times of potassium cyanide, and the title of " poison in century " is arranged, and is classified as human one-level carcinogens by IARC.Domestic refuse, industrial organic waste and medical waste all can produce dioxin in burning process, rubbish following approach: a. that is formed with of dioxin in burning process forms dioxin by chloride precursors such as plastic containing chlorine, chloride pesticide/herbicide/wood preservative/SYNTHETIC OPTICAL WHITNER/food, polychlorobiphenyl by molecular transposition, free radical condensation, dechlorination or other molecular reaction in combustion processes; B. when burning when insufficient, chloride rubbish incomplete combustion produces the too much material that do not burn in the flue gas, meets the heavy metal such as the material of strong catalytic such as cupric chloride, iron(ic) chloride, nickel oxide, aluminum oxide and He Cheng dioxin; C. it is not destroyed in burning itself to contain the De dioxin in the fuel, is present in the flue gas after the burning; D. carbon residue, oxygen, hydrogen, chlorine etc. are at flying dust surface catalysis synthetic mesophase product Huo dioxin in the solid flying dust, or the precursor in the gas phase is at flying dust surface catalysis Sheng Cheng dioxin; E. flue gas drops to low temperature from high temperature decomposed dioxin can resynthesis between 250～500 ℃ the time; F. other unknown cause Sheng Cheng dioxin.Generally contain chlorine source, organic matter and heavy metal in the domestic refuse, therefore, in flue gas, flying dust and slag that incinerator produces, often contain dioxin.There are some researches show that the concentration of precursor concentration, chlorine, temperature, oxygen level, sulphur content and heavy metal have material impact as the existence of unconscious catalyzer to the Production and emission of De dioxin in the incineration process of domestic garbage.The measure of control that waste incineration reduces the dioxin generation have: 1. before rubbish enters incinerator, take the refuse classification technology, sort out the metals such as iron in the rubbish, copper, nickel, cut off the catalytic media in the Refuse Incineration Process, reduce the amount of chlorinated organics, reduce the source of waste incineration Sheng Cheng dioxin from the source; 2. for the control of combustion conditions, keep the rubbish combustion around more than 850 ℃, gas residence time was greater than 2 seconds, the peroxide amount is controlled at below 8%, realizes " 3T+E " the work principle, namely, 1T-temperature of combustion (Temperature), the 2T-residence time (Time), 3T-turbulence level (Turbulence), E-peroxide control (Excess); 3. add to suppress dioxin and generate agent, in stove, add sulfocompound and suppress the formation of dioxin; 4. quenching, the flue gas that will draw in the incinerator is plummeted to below 250 ℃ by 450 ℃ with interior at 3s, to reduce the residence time of flue gas in regenerating 250 ℃ of-400 ℃ of peak district temperature ranges of dioxin; 5. fully deacidification uses absorption agent to slough De dioxin precursor in the flue gas; 6. avoid dust, dust is the carrier of catalyzer, makes flue-gas temperature reach 450 ℃ of before a large amount of dust contents that reduce in the flue gases by rational boiler design; 7. avoid the outer low temperature resynthesis of stove, adopt the mode of half dry type scrubber tower and sack cleaner collocation, the spent air temperture of operating device entrance is not less than 232 ℃ simultaneously.More than these measures, can only be the formation that relatively reduces dioxin, waste incineration still can produce the dioxin contaminate environment inevitably: one of reason is that its burning of burning method processing domestic refuse must just can make abundant burning above under 6% the condition in the peroxide amount, otherwise it will be more serious polluting, and peroxide is one of condition that forms dioxin, the concentration of peroxide environment Zhong dioxin increases greatly, the concentration of anaerobic environment Zhong dioxin can descend, do not have oxygen then not have dioxin synthetic, oxygen level is 6～12% in the standard GB/T 18485-2001 regulation incinerator outlet flue gas; Former two is that the flue gas that burns must be to contact with metal heated of the equipment such as superheater, boiler, heat exchanger, air preheater therefore, and these metal heated faces all can become the catalytic media that forms dioxin; Former three is be difficult to realize fully deacidification therefore, still has a certain amount of dioxin precursor in the flue gas; Former four is that ubiquity has carbon residue, oxygen, hydrogen, chlorine and flying dust in the flue gas of waste incineration therefore, inevitably can be outside stove low temperature resynthesis dioxin; More than four cause descriptions in the flue gas of burning away the refuse, must have a certain amount of dioxin, it is unapproachable dioxin being eliminated from flue gas again, it will be along with the discharging of flue gas contaminate environment, standard GB/T 18485-2001 regulation domestic waste incineration Air Pollutant Emission De dioxin limit value is 1ngTEQ/m
3, but in fact discharge beyond standards in the majority, still more this 1ngTEQ/m
3De dioxin emission limit value is not to be the patient value of environment, but looks after present technical deficiency.Because dioxin is difficult to degraded, its transformation period is 14-273, substantially be considered as not degrading, its accumulation in people's living environment and in the human body can get more and more, the large national capital of many burnings is out of joint, the probability that the local resident gets cancer is large a lot, and the content of De dioxin and other toxic substances is all high many in air and the soil, Japan such as the Daxing waste incineration, De dioxin content has reached 10 times of advanced industrial country in the atmosphere, and Japan has turned off more than 70% incinerator.China's present De dioxin total amount of pollutants discharge also is not very serious, but the generation of China's solid waste and clinical waste and treatment capacity are all in continuous increase in recent years, concentrated burning facility is set up or established in various places one after another, growth momentum is swift and violent, serious De dioxin pollution problem may be brought, enough attention should be caused.
In a word, it is not a good way that burning method is disposed domestic refuse, sanitary landfill exists again land occupation and pollution hidden trouble, refuse classification, composting process also will be in the face of not utilizing the problem of outlet of part, and headachy " garbage-surrounded city " problem must solve, therefore, the human urgent perfect technical scheme of disposing domestic refuse of wishing to have.
Summary of the invention
The objective of the invention is to solve burning method and bring the pollution problem of De dioxin; overcome burning method and dispose the shortcoming of living garbage pollution environment; propose a kind of domestic refuse, organic waste to be disposed with the method for gasification-liquefaction; establishment comprises that the pollutent of dioxin forms; in whole disposal process, do not discharge pollutants; preserve the ecological environment, simultaneously domestic refuse, organic waste are converted into a kind of clean energy.
In order to achieve the above object, the one way of life rubbish that the present invention takes, the technique of organic waste gasifying-liquefying treatment, comprise terminal purification techniques, can avoid the formation condition of dioxin, suppress effectively to comprise that the pollutent of dioxin produces, even minute quantity De generation of dioxin is arranged, also be eliminated in the easy product liquid endways, its technical process is: domestic refuse or organic waste are carried out the anaerobic gasification in the plasma gasification stove, produce oxygen-free gas with CO and H
2Hydrogen-rich synthetic gas for main component, again hydrogen-rich synthetic gas is passed through cooling, send into methanol sythesis reactor as unstripped gas after dedusting/purification, catalyze and synthesize methanol product, owing in the purified synthesis gas operation, can not accomplish thoroughly to clear the pollution off, may there be a small amount of pollutent that comprises dioxin and impurity in the unstripped gas, these pollutents and impurity will mix with methanol product, again methanol product being drawn reactor mixes with liming and carries out terminal cleansing operation, as absorption agent, the pollutent that comprises dioxin and the impurity of failing to eliminate at dedusting/cleaning section are removed with calcium hydroxide.Described liming is the Ca (OH) of clarification
2Saturated solution.The method of terminal cleansing operation is: the liming of the methyl alcohol of the pollutent that comprises dioxin from reactor may carry out and impurity with at least 2 times is fully mixed in the mixing tank that seals, the temperature of liquid was 40～60 ℃ after control mixed, working pressure is 0～1Mpa, because dioxin dissolves in the methyl alcohol, and methyl alcohol is very easily miscible with water, therefore, De dioxin wherein, muriate, fluorochemical, sulfide is present in methyl alcohol and the liquid that liming mixes with ionic species, by with the chemical reaction of calcium hydroxide, generate respectively the calcium chloride of removing easily, Calcium Fluoride (Fluorspan), calcium sulfate, reach the purification purpose, then in separator, the gaseous state thing of end reaction separated and send synthesis reactor back to and carry out circulating reaction, because the boiling point of methyl alcohol is 64.7 ℃ and can react with calcium hydroxide, the boiling point of water is 100 ℃ (water begins to have a small amount of vaporization more than 80 ℃), so be easy to a separating methanol out by distillation, the mixed solution of methanol product and liming is sent into distillation tower, in distillation tower, mixed solution is warmed up to 68 ± 2 ℃, steam methyl alcohol, again gaseous methanol is become liquid methanol by cooling, liquid methanol is cooled to sends into the methyl alcohol basin below 40 ℃, as the raw material of producing alcohol-group fuel or be refined methanol by rectification and purification again; The liming that contains foreign material is carried out scrubbing by hydrocyclone, carry out recycle sending mixing tank back to after the clear liming cooling again.Have a small amount of nitrogen component in the domestic refuse itself, the mobile meeting by synthetic gas after gasification is accumulated in the tail gas, uses endways the synthetic ammonia technology in the cleaning section and produces ammonia the N of accumulation
2Consume, as N from the separator unreacting gas out of end
2When surpassing 5%, unreacting gas is sent into reactors for synthesis of ammonia, use the way of producing synthetic ammonia N
2Consume, again ammonia is separated, the unreacting gas after the denitrogenation is sent back to methanol sythesis reactor carry out circulating reaction; As CO from separator unreacting gas out
2When surpassing 10%, isolated unreacting gas in the terminal cleaning section is shunted 50% feed back to and melt down processing in the vapourizing furnace, make CO in the hot environment in stove more than 1000 ℃
2Be reduced to CO, the not clear organic gas in the tail gas also becomes valuable gases by cracking or molecular transposition simultaneously.
The plasma gasification stove designs by following principle:
At least be divided into the pyrolysis zone of effusion volatile matter and the gasification zone of fixed carbon gasification in the plasma gasification stove, directly communicate between each district, rubbish material from entering vapourizing furnace to the flow process of discharging lime-ash that is gasified totally is: rubbish material is first through oven dry/preheating, then enter pyrolysis zone, after pyrolysis zone is overflowed volatile matter fully, fixed carbon directly enters the gasification zone, acceptance is washed away from the high-temperature water vapor activator of plasma torch ejection, making the carbon in the fixed carbon is synthetic gas with high-temperature water vapor activator chemical combination all, realization is gasified totally, the ash content of vapourizing furnace end gives melting with plasma arc, and slag is discharged by the water seal mouth;
Because dioxin is to connect 2 phenyl ring that replaced by the chlorine atom by 2 or 1 Sauerstoffatom to be formed, and in the situation of anaerobic, even have the precursor of dioxin, catalytic condition to exist, also can not synthesize dioxin.In order to make oxygen-free gas composition in the hydrogen-rich synthetic gas that produces in the vapourizing furnace, the condition of avoiding dioxin to form, can improve simultaneously the quality of hydrogen-rich synthetic gas, to satisfy the application requiring as the synthesizing methanol unstripped gas, this technique does not provide air or oxygen combustion-supporting in vapourizing furnace, the required heat energy of gasification is provided by the plasma torch that is installed in the gasification zone in the vapourizing furnace, temperature distribution in the vapourizing furnace with end for the highest, direction to the rubbish material entrance reduces gradually, wherein: terminal ash melting position is 1300～1600 ℃, the gasification zone is 1000～1300 ℃, and pyrolysis zone is 300～1000 ℃, and oven dry/preheating position is 120～300 ℃;
Gaseous state thing in the vapourizing furnace carries heat energy and solid-state rubbish material inverse motion, and is regional to pyrolysis zone, oven dry/preheating the thermal energy transfer of vapourizing furnace end and gasification zone; Draw via the regional position of oven dry/preheating as the part gaseous state thing of heat-transfer medium whole volatile matter gases that pyrolysis zone produces and gasification zone, 1300 ℃ of zones then sending the gasification zone back to circulate cracking, gasify, disintegrate dioxin.
During the operation of plasma gasification stove, be heated to the gasification zone that sprays into behind the generation activator more than 3000 ℃ in the vapourizing furnace with water vapor by plasma torch as vaporized chemical and working gas, carry out completely gasification reaction with the rubbish biomass charcoal, domestic refuse or organic waste pass through respectively 300～1000 ℃ pyrolysis environment, 1000～1600 ℃ plasma gasification environment in the plasma gasification stove, be implemented in the situation of anaerobic input and be gasified totally, draw at the position that hydrogen-rich synthetic gas is 1000 ℃ from the gasification zone; The residence time of solid materials in vapourizing furnace is more than 30 minutes; Draw and feed back to the gaseous state thing in vapourizing furnace plasma gasification district from pyrolysis zone, the time of being detained in stove for the second time is more than 1.5 seconds; Working pressure in the vapourizing furnace be controlled at negative pressure 30Pa～malleation 50Pa near in the normal pressure scope.
The present invention also sprays into the calcium oxide powder in 300～1000 ℃ of pyrolysis environment in the plasma gasification stove, as the measure of sloughing the dioxin precursor in the stove, and double as dechlorination/desulfurization/defluorinating agent and use, the direction of motion of calcium oxide powder in stove is consistent with the direction of gaseous state thing motion in the stove, the particle diameter of calcium oxide powder is 20～50 microns, the recycle of calcium oxide powder, the stove amount that is recycled into of calcium oxide powder is 150～200kg during one ton of rubbish of every disposal.
In the above-mentioned technical process, 1000 ℃ of hydrogen-rich synthetic gas of drawing from vapourizing furnace adopt conventional duct type waste heat boiler to carry out indirect type heat exchange cooling, make hydrogen-rich synthetic gas cool to 232 ℃, then send into dedusting/cleaning section and carry out dedusting and purifying treatment.Dedusting/cleaning section is used conventional dry cleaning technology, and its composition form is dry method absorption reactor thermally+sack cleaner, with Ca (OH)
2Powder is absorption agent, and the rear 232 ℃ hydrogen-rich synthetic gas of lowering the temperature enters into the dry method absorption reactor thermally, muriate wherein, sulfide and other pollutent and Ca (OH)
2Powder generation chemical reaction and being absorbed, the gas-solid biphasic mixture of discharging from the dry method absorption reactor thermally enters sack cleaner and is able to high-efficient purification after the pre-dedusting of the common tornado dust collector of one-level, hydrogen-rich synthetic gas after the purification is used as the unstripped gas of synthesizing methanol, the absorption agent recycle of being caught by fly-ash separator.Make the Ca (OH) that absorption agent is used
2The thickness of powder cooperate particle diameter be 0.2～0.8 micron account for 40%, 1～10 micron account for 60%, Ca (OH)
2The dutycycle of powder in absorption reactor thermally is 20～25%.
In the above-mentioned technique, the synthesis reactor that the synthetic employing of methyl alcohol is conventional or employing China Patent No. are 200710166618.5 electrocatalysis synthesis reactor, when adopting conventional synthesis reactor, use the Cu/Zn/Al catalyzer, synthesizing methanol in the environment of 210～280 ℃ of working pressure 3～15Mpa, service temperature; When adopting electrocatalysis synthesis reactor, use the Cu/Zn/Al catalyzer, synthesizing methanol in the environment of 120～400 ℃ of working pressure 0～1Mpa, service temperature.
In the above-mentioned technique, water vapor decomposes in plasma torch and the equation that activates is:
e
*+ H
2O → H
2O
*+ e or e
*+ H
2O → H
2O
++ 2e
H
2O
*+e→H
2O
++2e
H
2O
++e→H
++OH
-
H
++e→H OH
--e→H+O
H+H→H
2
O+O→O
2
In the formula: e
*-acceleration electronics, e-stall electronics, H
2The O-water molecules, H
2O
*The water molecules of-activation, H
2O
+-water molecules ion,
H
+-hydrogen ion, OH
--hydroxide ion, H-hydrogen atom, O-Sauerstoffatom, H
2-hydrogen molecule, O
2-oxygen molecule.
In the plasma gasification stove, the gasification reaction formula of solid-state rubbish, organic waste is mainly:
(C
6H
10O
5)
n(s) → gC (s)+xC
6H
10O
5(s)+zC
nH
m(g)+... heat absorption
C
6H
10O
5(s) → C (s)+CO (g)+H
2(g)+CH
4(g)+... heat absorption
C(s)+O
2(g)→CO
2(g) ΔH＝+406.96kj/mol
C(s)+2H
2(g)→CH
4(g) ΔH＝+75.6kj/mol
C(s)+H
2O(g)→CO(g)+H
2(g) ΔH＝-131.2kj/mol
C(s)+H
2O
*(g)→CO(g)+H
2(g)
CH
4(g)+H
2O(g)→CO(g)+3H
2(g) ΔH＝-205.8kj/mol
CH
4(g)+CO
2(g)→2CO(g)+2H
2(g) ΔH＝-247.8kj/mol
C(s)+CO
2(g)→2CO(g) ΔH＝-172.2kj/mol
C
nH
m(g) → nC (s)+m/2H
2(g) heat absorption
C
nH
m(g)+nH
2O (g) → nCO (g)+(n+m/2) H
2(g) thermo-negative reaction
CO(g)+H
2O(g)→CO
2(g)+H
2(g) ΔH＝+42kj/mol
CaO(s)+CO
2(g)→CaCO
3(s) ΔH＝+178.8kj/mol
……
The reaction formula of making absorption agent with calcium hydroxide in scavenging process is mainly:
Ca(OH)
2(ι)+2HCl(g)＝CaCl
2(s)+2H
2O
Ca(OH)
2(ι)+SO
2(g)＝CaSO
3(s)+H
2O
Ca(OH)
2(ι)+2SO
2(g)＝Ca(HSO
3)
2(s)
Ca(OH)
2(ι)+2H
2SO
3(ι)＝Ca(HSO
3)
2(s)+2H
2O
Ca(OH)
2(ι)+2HF(g)＝CaF
2(s)+2H
2O
Ca(OH)
2(ι)+CO
2(g)＝CaCO
3(s)+H
2O
Reaction formula in methanol sythesis reactor is: CO+2H
2=CH
3OH+102.5kj/mol
Among the present invention, the molten ash of discharging from vapourizing furnace becomes the particulate matter as the vitreum when entering the hydrolock slag bath, can directly do the building materials utilization; For the production of non-burning brick or send into special plasma body skull melting furnace and carry out melting treatment, domestic refuse enters the isolated inorganics in stokehold and can be used for producing non-burning brick or do general the processing isolated waste residue in the flying dust of collecting from waste heat boiler, fly-ash separator, the treating plant.
The invention has the beneficial effects as follows: domestic refuse, organic waste are disposed by the operational path of gasification-liquefaction, can avoid the condition that dioxin forms, discharge pollutants hardly in the whole disposal process, the methanol product of producing can be made industrial chemicals or industrial fuel, and the economic benefit of obtaining is much higher than burning electricity generation.The present invention compares with burning method: one. and burning method has a large amount of carbon dioxides and other pollutant emission, and contaminate environment is made Greenhouse effect and acid rain, and the present invention does not discharge flue gas, does not pollute the environment; Two. burning method can form the violent in toxicity dioxin inevitably, and is difficult to eliminate, and enters atmosphere with flue gas, the health of harm humans, the present invention can avoid forming dioxin, even there is the dioxin of minute quantity to occur, also removes in the purification process endways easily; Three. burning method affects people's health owing to discharge pollutants, and has been subjected to the common people's resistance, and the present invention can realize eco-friendly disposal domestic refuse, will be subject to welcome and the support of the common people and governments at all levels; Four. burning electricity generation enterprise does not have economic benefit, must rely on government finance to help, and the present invention is owing to the output value advantage, and the economic return that can obtain can attract nongovernmental fund investment construction project, for government removes difficulties and alleviates sufferings; Five. the burning electricity generation project must reach certain scale, is not suitable for samll cities and towns, is difficult to popularize, and project of the present invention is changeable, can spread to villages and towns in rural areas.The present invention is fit to the harmlessness disposing of domestic waste, life in the countryside rubbish, medical waste, industrial high molecular waste material, agriculture and forestry organic waste material, composting process residuum, garbage sorting field waste.
Description of drawings
Accompanying drawing is the technological process block-diagram of one way of life rubbish of the present invention, organic waste gasifying-liquefying treatment.
Embodiment
Embodiment 1: present embodiment is before domestic refuse enters vapourizing furnace, by dehydration, large part fragmentation, removal metal object and inorganics, the air-dry pre-treatment of hot blast, make the content of its inorganics in 5%, water content is below 15%, calorific value reaches more than the 9000kj/kg, purify with energy consumption and the favourable rear class that reduces in the vapourizing furnace, the domestic refuse pre-treatment is adopted routine techniques or is used the technology of Chinese patent ZL 2008201391055 " pretreatment system and equipment that domestic garbage as fuel utilizes "; The plasma gasification stove is used the vapourizing furnace of the 10th embodiment in Chinese patent ZL 2008202082326 " gasification system of rubbish, organic waste and the equipment ", and the structure of this vapourizing furnace can reach processing requirement of the present invention.Sending in the stove from the opening for feed of top of gasification furnace through pretreated domestic refuse or organic waste, simultaneously the water vapor of 0.5～1Mpa is sent into plasma torch and be heated to more than 3000 ℃, make water molecules be decomposed into oxygen, hydrogen and activity chemistry thing H
2O
*Then spray into gasification one district, gasification two districts and burnt zone in the vapourizing furnace, carry out gasification reaction with the rubbish fixed carbon and generate carbon monoxide and hydrogen, and the rubbish carbon residue burnt, the lime-ash that burns enters the hydrolock slag bath from slag-drip opening, and the hydrogen-rich synthetic gas of the oxygen-free gas composition that produces in the stove is drawn from the accumulation of heat chamber of vapourizing furnace.Garbage fuel moves from top to bottom according to own wt in stove, the gaseous state thing that generates in gasification one district is under the graviational interaction of stove outer circulation blower fan, gap and garbage fuel antikinesis by garbage fuel, the gaseous state thing offers the part heat of gasification one district, gasification two districts and burnt zone generation pyrolysis and the baking needed of garbage fuel simultaneously as thermophore in the mode of transmission of heat by convection; Gas (vapour) the attitude mixture that generates at gasification one district, pyrolysis zone and baking zone, comprise that tar, coal smoke (carbon particle), carbon monoxide, carbonic acid gas, methane, hydrogen and water vapor are drawn from the gas phase loop exit on vapourizing furnace top, gasification two districts and burnt zone by the circulation airduct outside the stove and recirculation blower turn back to the stove bottom carry out cycle gasification; During gasifier operation, the service temperature of control oven dry/preheating zone is between 120～300 ℃, the service temperature of pyrolysis zone is between 300～1000 ℃, the service temperature in gasification one district is between 1000～1200 ℃, the service temperature in gasification two districts is between 1200～1300 ℃, the service temperature of burnt zone is between 1300～1600 ℃, the working pressure of oven dry/preheating zone is negative pressure 30Pa, the working pressure in gasification two districts is greater than malleation 20Pa, the control of working pressure and service temperature is by regulating input speed in the stove, the input of water vapor, the internal circulating load of circulation gaseous state thing and the amount of drawing of synthetic gas realize that the ratio of carbon monoxide and hydrogen is allocated by the input of adjusting water vapor and the power of plasma torch in the synthetic gas.1000 ℃ of hydrogen-rich synthetic gas of drawing from the plasma gasification stove are carried out indirect type heat exchange cooling by the duct type waste heat boiler, make hydrogen-rich synthetic gas cool to 232 ℃, then send into the dry method absorption reactor thermally, with Ca (OH)
2Powder is absorption agent, makes muriate, sulfide and other pollutent and Ca (OH) in the synthetic gas
2Powder generation chemical reaction and being absorbed is able to high-efficient purification by entering sack cleaner behind the pre-chalk dust removing of tornado dust collector, and the hydrogen-rich synthetic gas after the purification is used as the unstripped gas of synthesizing methanol, the absorption agent recycle of being caught by fly-ash separator.Make the Ca (OH) that absorption agent is used
2The thickness of powder cooperate particle diameter be 0.2～0.8 micron account for 40%, 1～10 micron account for 60%, Ca (OH)
2The dutycycle of powder in absorption reactor thermally is 25%.Adjust H in the synthetic gas by the working parameter of regulating plasma torch
2: CO is equal to or greater than 2, or takes carbon monodixe conversion or hydrogenation measure to solve.H
2: the unstripped gas of CO 〉=2 is sent into electrocatalysis synthesis reactor, and using model is the Cu/Zn/Al catalyzer of NC301-1, synthesizing methanol product under the condition of 150 ℃ of working pressure 0.5Mpa, service temperature.The liming of the carbinol mixture of the pollutent that comprises dioxin from synthesis reactor may carry out and impurity with 3 times is fully mixed in the mixing tank of sealing, to be controlled to be 55 ± 5 ℃, working pressure be to carry out terminal cleansing operation under the 0.5Mpa condition to the temperature of liquid after mixing, and by separator unreacted gaseous state thing separated and sent back to synthesis reactor and carry out circulating reaction; Methanol product, liming mixed solution are warmed up to 68 ± 2 ℃ in distillation tower, steam methyl alcohol, again gaseous methanol is become liquid methanol by cooling and send into the methyl alcohol basin, as the raw material of producing alcohol-group fuel; The liming that contains foreign material is carried out scrubbing, cooling operation by hydrocyclone, more clear liming is sent back to mixing tank and carry out recycle; As N from separator unreacting gas out
2When surpassing 5%, unreacting gas is sent into reactors for synthesis of ammonia, use the way of producing synthetic ammonia N
2Consume, again ammonia is separated, the unreacting gas after the denitrogenation is sent back to methanol sythesis reactor carry out circulating reaction; As CO from separator unreacting gas out
2When surpassing 10%, processing is melted down in unreacting gas shunting 50% gasification zone that feeds back in the vapourizing furnace.In the present embodiment, from the isolated inorganics of domestic refuse pretreatment process for the production of non-burning brick, the molten ash of discharging from vapourizing furnace is delivered to the construction site do the aggregate application, isolated waste residue in the flying dust of collecting from waste heat boiler, fly-ash separator and the treating plant is carried out melting treatment with the plasma body skull melting furnace.
Embodiment 2: in the present embodiment, the plasma gasification stove that applicating adn implementing example 1 is same, the process dehydration, large part is broken, rubbish material behind removal metal object and the inorganics is sent into the plasma gasification stove, under the condition that oxygen or air are not provided, realize being gasified totally of rubbish material, generate the hydrogen-rich synthetic gas of oxygen-free gas composition, hydrogen-rich synthetic gas is drawn vapourizing furnace, after dedusting/purification, unstripped gas as synthesizing methanol is sent into methanol sythesis reactor, catalyze and synthesize methanol product, again methanol product is mixed with liming and carry out terminal cleansing operation, may there be the pollutents such as De dioxin in removal, then by alternating temperature operation, purification methanol product.The different of present embodiment and the first embodiment are: 20～50 microns calcium oxide powders are sprayed in the stove from the ventilation terminal that is arranged on gasification one district's side wall, as the dechlorinating agent and the sweetening agent that remove vapourizing furnace Nei dioxin precursor, the calcium oxide powder also can be in stove absorbing carbon dioxide generate calcium carbonate and emit heat and become heat producing element, to reduce the heating demand of plasma gun; Gas (vapour) the attitude mixture that generates at gasification one district, pyrolysis zone and baking zone, comprise that tar, coal smoke (carbon particle), carbon monoxide, carbonic acid gas, methane, hydrogen and water vapor are drawn from the gas phase loop exit on vapourizing furnace top, after tornado dust collector remove lower calcium oxide pulvis, gasification two districts and the burnt zone that turn back to the stove bottom by the circulation airduct outside the stove and recirculation blower again, carry out cycle gasification, the calcium oxide pulvis under tornado dust collector remove recycles; Methyl alcohol is synthetic uses conventional technology, and using model in the synthesis reactor is the Cu/Zn/Al catalyzer of NC301-1, synthesizing methanol product under the condition of 250 ℃ of working pressure 5Mpa, service temperature.
Claims (5)
1. one way of life rubbish, the technique of organic waste gasifying-liquefying treatment, comprise terminal purification techniques, it is characterized in that domestic refuse, organic waste are disposed with the method for gasification-liquefaction, establishment comprises that the pollutent of dioxin forms, in whole disposal process, do not discharge pollutants, simultaneously domestic refuse, organic waste are converted into a kind of clean energy, its technical process is: domestic refuse or organic waste are carried out the anaerobic gasification in the plasma gasification stove, produce the hydrogen-rich synthetic gas of oxygen-free gas, again hydrogen-rich synthetic gas is passed through cooling, send into methanol sythesis reactor as unstripped gas after dedusting/purification, catalyze and synthesize methanol product, again methanol product being drawn reactor mixes with liming and carries out terminal cleansing operation, as absorption agent, the pollutent that comprises dioxin and the impurity of failing to eliminate at dedusting/cleaning section are removed with calcium hydroxide;
Wherein: be divided at least the pyrolysis zone of effusion volatile matter and the gasification zone of fixed carbon gasification in the plasma gasification stove, directly communicate between each district, rubbish material from entering vapourizing furnace to the flow process of discharging lime-ash that is gasified totally is: rubbish material is first through oven dry/preheating, then enter pyrolysis zone, after pyrolysis zone is overflowed volatile matter fully, fixed carbon directly enters the gasification zone, acceptance is washed away from the high-temperature water vapor activator of plasma torch ejection, making the carbon in the fixed carbon is synthetic gas with high-temperature water vapor activator chemical combination all, realization is gasified totally, the ash content of vapourizing furnace end gives melting with plasma arc, and slag is discharged by the water seal mouth; The required heat energy of gasification is provided by the plasma torch that is installed in the gasification zone in the vapourizing furnace, temperature distribution in the vapourizing furnace with end for the highest, direction to the rubbish material entrance reduces gradually, wherein: terminal ash melting position is 1300～1600 ℃, the gasification zone is 1000～1300 ℃, pyrolysis zone is 300～1000 ℃, and oven dry/preheating position is 120～300 ℃; Gaseous state thing in the vapourizing furnace carries heat energy and solid-state rubbish material inverse motion, and is regional to pyrolysis zone, oven dry/preheating the thermal energy transfer of vapourizing furnace end and gasification zone; Draw via the regional position of oven dry/preheating as the part gaseous state thing of heat-transfer medium whole volatile matter gases that pyrolysis zone produces and gasification zone, 1300 ℃ of zones then sending the gasification zone back to circulate cracking, gasify, disintegrate dioxin;
The method of described terminal cleansing operation is: the liming of the methyl alcohol of the pollutent that comprises dioxin from reactor carrying out and impurity with at least 2 times is fully mixed in the mixing tank of sealing, the temperature of liquid was 40～60 ℃ after control mixed, working pressure is 0～1MPa, make and mix wherein De dioxin, muriate, fluorochemical, sulfide is present in methyl alcohol and the liquid that liming mixes with ionic species, by with the chemical reaction of calcium hydroxide, generate respectively the calcium chloride of removing easily, Calcium Fluoride (Fluorspan), calcium sulfate, reach the purification purpose, then in separator, unreacted gaseous state thing separated and send synthesis reactor back to and carry out circulating reaction, in distillation tower, methanol product is separated, again the lime sewage that contains foreign material is carried out scrubbing by hydrocyclone, carry out recycle sending mixing tank back to after the clear liming cooling.
2. one way of life rubbish according to claim 1, organic waste gasifying-liquefying treatment technique is characterized in that using the N that the synthetic ammonia technology produces the accumulation of ammonia handle in the cleaning section endways
2Consume.
3. one way of life rubbish according to claim 1, organic waste gasifying-liquefying treatment technique is characterized in that isolated unreacting gas shunting 50% in the terminal cleaning section fed back to and melt down processing in the vapourizing furnace.
4. one way of life rubbish according to claim 1, organic waste gasifying-liquefying treatment technique, when it is characterized in that the operation of plasma gasification stove, be heated to the gasification zone that sprays into behind the generation activator more than 3000 ℃ in the vapourizing furnace with water vapor by plasma torch as vaporized chemical and working gas, carry out completely gasification reaction with the rubbish biomass charcoal, domestic refuse or the organic waste respectively pyrolysis environment by 300～1000 ℃, 1000～1600 ℃ plasma gasification environment in the plasma gasification stove are implemented in the situation of anaerobic input and are gasified totally.
5. according to claim 1 or 4 described one way of life rubbish, organic waste gasifying-liquefying treatment technique, it is characterized in that spraying into the calcium oxide powder in 300～1000 ℃ of pyrolysis environment in the plasma gasification stove, as the measure of sloughing the dioxin precursor in the stove, and doubling as dechlorination/desulfurization/defluorinating agent application, the direction of motion of calcium oxide powder in stove is consistent with the direction of gaseous state thing motion in the stove.
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| FR2971789B1 (en) * | 2011-02-22 | 2013-02-22 | Areva | PROCESS FOR PRODUCING METHANOL OR HYDROCARBONS FROM CARBONACEOUS MATERIAL WITH A REFORMING STEP WHOSE CONDITIONS OF OPERATION ARE SELECTIVELY ADJUSTED |
| CN102358851B (en) * | 2011-08-30 | 2013-07-24 | 张建超 | Horizontal plasma garbage gasification reaction chamber and gasification technology thereof |
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