CN1253577A

CN1253577A - Method and apparatus for treating wastes by gasification

Info

Publication number: CN1253577A
Application number: CN97182129A
Authority: CN
Inventors: 藤村宏幸; 平山详郎; 藤并晶作; 高野和夫; 入江正昭; 广势哲久; 永东秀一; 大下孝裕; 福田俊男
Original assignee: Ebara Corp; Ube Industries Ltd
Current assignee: Ebara Corp; Ube Corp
Priority date: 1997-04-22
Filing date: 1997-10-22
Publication date: 2000-05-17
Anticipated expiration: 2017-10-22
Also published as: ES2229339T3; WO1998047985A1; EP0979262B1; DE69730870D1; DE69730870T2; CN1137249C; EP0979262A1

Abstract

A method and apparatus for treating wastes by two-stage gasification recovers metals or ash content in the wastes in such a state that they can be recycled, and gases containing carbon monoxide (CO) and hydrogen gas (H2) for use as synthesis gas of ammonia (NH3) or production of hydrogen gas. The wastes are gasified in a fluidized-bed reactor (3) at a low temperature. Then, gaseous material and char produced in the fluidized-bed reactor (3) are introduced into the high-temperature combustor (17), and gasified at a high temperature and ash content is converted into molten slag. After water scrubbing and CO conversion reaction, the gas is separated into H2 and residual gas. The residual gas is then supplied to the fluidized-bed reactor (3) as a fluidizing gas.

Description

Method and apparatus for treating waste by gasification

Technical Field

The present invention relates to a method and apparatus for treating wastes by gasification, and more particularly, to a method and apparatus for treating wastes, which recovers metals or ash and gases in the wastes by a two-stage gasification process, and the resulting metals or ash are in a reusable state, and the gases are mainly composed of carbon monoxide (CO) and hydrogen (H)₂) Composition, usable as hydrogen or ammonia (NH)₃) The synthesis gas of (2).

Background

Ammonia is a basic raw material for mass production for the production of nitric acid, fertilizers including ammonium nitrate, ammonium sulfate and urea, acrylonitrile, caprolactam, etc. Ammonia is under high pressure conditionsUnder nitrogen (N)₂) And hydrogen (H)₂) The catalyst is synthesized by catalysis. Hydrogen may be produced by steam reforming of natural gas or naphtha or by partial combustion, i.e. by gasification of hydrocarbons such as crude oil, heavy oil, foots, coal, bitumen or petroleum coke.

The introduction of most of the raw materials for hydrogen production from abroad has led to a loss of competitiveness of ammonia-derived chemical products in the world market after the oil crisis. Therefore, the raw materials which are cheap and easily available at home are urgently needed to be obtained.

Until now, when organic wastes such as municipal wastes, plastic wastes including Fiber Reinforced Plastics (FRP), biological wastes, and automobile wastes are treated, it has been customary to reduce their recycling volume by incineration or to dispose of them in a landfill without treatment.

Therefore, only a small amount of resources are recovered from the organic waste for reuse, regardless of direct or indirect utilization.

On the other hand, incineration of organic wastes has some disadvantages for the following reasons:

until now, automatic coal-feeding furnaces or fluidized-bed furnaces were used for incineration of organic wastes. However, such incineration is problematic in terms of environmental protection or in terms of recycling of resources or energy. More specifically, a large amount of exhaust gas containing a large amount of air and toxic dioxins is discharged. In addition, the metal discharged from the furnace isalready heavily oxidized and unsuitable for reuse, and landfill sites are also reduced year by year. Recently, the number of waste treatment plants in combination with ash melting plants is increasing, but problems are encountered in increasing the construction costs and/or the operating costs of these waste treatment plants. There has also recently developed a trend to more efficiently utilize waste energy.

Landfills are becoming more difficult at desired sites without disposal and are also not allowed from an environmental point of view due to the scarcity of landfills. Therefore, the problem of landfill of hazardous waste such as scrap of discarded automobiles becomes worse.

In addition, when a large amount of steam and oxygen (O) is used₂) When used together as a gasifying agent in a fluidized-bed reactor, the operation cost increases. Even if the air used as the gasifying agent is easily available, the amount of air is limited because the amount of nitrogen in the synthesis ammonia is limited.

Description of the invention

Accordingly, it is an object of the present invention to provide a method and apparatus for treating wastes by a two-stage gasification process, which can recover resources in the wastes to reuse, produce a synthesis gas capable of synthesizing ammonia by a partial combustion process, solve various problems caused by incineration or landfill of organic wastes, and obtain a low-cost hydrogen or ammonia synthesis gas.

To achieve the above object, according to one aspect of the present invention, there is provided a method for treating wastes by a gasification method, the method comprising: gasifying the waste in a fluidized bed reactor at a relatively low temperature; introducing a gaseous feedstock and char produced in a fluidized bed reactor into a high temperature combustor; producing synthesis gas at a relatively high temperature in a high temperature combustor; after acid components are removed by leaching, the synthesis gas is converted by CO conversion reaction; producing hydrogen by a gas separation process; and supplying the remaining gas to a fluidized bed in the fluidized bed reactor.

The gas separation process may be performed by pressure swing adsorption (pressure adsorption) or a hydrogen separation membrane.

According to another aspect of the present invention, there is provided a method of treating waste by a gasification process, the method comprising: gasifying the waste in a fluidized bed reactor at a relatively low temperature; introducing a gaseous feedstock and char produced in a fluidized bed reactor into a high temperature combustor; producing synthesis gas at a relatively high temperature in a high temperature combustor; converting the synthesis gas by CO shift reaction; removing acidic components from the gas obtained from the CO shift reaction to obtain hydrogen; part of the gas from which the acidic component is removed is supplied to the fluidized-bed reactor. The above-mentioned CO shift reaction may also be carried out after removing acidic components in the synthesis gas.

According to another aspect of the present invention, there is provided an apparatus for treating wastes by a gasification method, the apparatus comprising: a fluidized bed reactor for gasifying the wastes at a relatively low temperature to produce a gaseous raw material and charcoal; a high temperature combustor for producing synthesis gas at a relatively high temperature; a water cooled chamber for cooling the syngas; a water shower for removing an acidic component from the gas from the cooling chamber; performing CO shift reaction to remove CO and H in gas from water leaching chamber₂Conversion of O to CO₂、H₂The CO shift converter of (1); a gas separator that separates the gas into hydrogen gas and a remaining gas; the remaining gas is supplied to the line of the fluidized-bed reactor.

According to still another aspect of the present invention, there is provided an apparatus for treating wastes by a gasification method, the apparatus comprising: a fluidized bed reactor for gasifying the wastes at a relatively low temperature to produce a gaseous raw material and charcoal; a high temperature combustor that introduces syngas at a relatively high temperature; a water cooled chamber for cooling the syngas; performing CO shift reaction to make CO and H in the gas from the cooling chamber₂Conversion of O to CO₂、H₂The CO shift converter of (1); an acid gas remover for removing acid components from the gas after completion of the CO shift reaction; and a line for supplying a portion of the acidic component to the fluidized bed reactor.

The acid gas removal chamber may be disposed between the cooling chamber and the CO shift converter.

The two-stage gasification process in the present invention may be carried out under normal pressure, but it is economical to carry out it in a pressure range of 5 to 90atm, preferably 10 to 40 atm. As the gasifying agent, air and/or oxygen obtained by air separation can be used. In addition, steam or carbon dioxide (CO) may be used₂) Adding into the mixture.

The temperature of the fluidized bed reactor is preferably in the temperature range of 450 ℃ to 950 ℃. The lower limit of the average calorific value of the waste is preferably 3500kcal/kg or more. If the lower average calorific value of the wastes is 3500kcal/kg or less, a supplementary fuel may be added to the wastes so that the lower average calorific value thereof is 3500kcal/kg or more. As the compensation fuel, afossil fuel such as coal or petroleum coke, which is generally used, may be used.

As the fluidized bed reactor used in the present invention, a circulating flow type (revlvingflow-type) fluidized bed reactor is preferable. In a circulating type fluidized bed reactor, a circulating flow of a fluidizing medium is formed in a fluidized bed by controlling the linear velocity of a fluidizing gas. The circulating type fluidized bed is superior to the bubbling type fluidized bed in that the linear velocity of the fluidizing gas is uniform in the function of dispersing and pulverizing charcoal. In addition, compared with the fluidized bed reactor with external circulation, the fluidized bed reactor with the circulating flow type has simple structure and smaller size. The circulating flow type fluidized bed reactor is preferably a vertical cylindrical one because it is operated under pressurized conditions.

In the high temperature combustor, a gaseous feedstock containing ash and char produced in a fluidized bed reactor is gasified at a temperature above the melting point of the ash. The temperature in the high temperature combustor is 1200 c or higher.

In the present invention, the total amount of oxygen supplied to the fluidized-bed reactor and the high-temperature combustor may be in the range of 0.1 to 0.6 times the theoretical oxygen demand for combustion. The amount of oxygen supplied to the fluidized bed reactor may range from 0.1 to 0.3 times the theoretical oxygen demand for combustion.

The fluidized-bed reactor is operated under reduced pressure, so that the metals in the waste can be recovered from the bottom of the fluidized-bed reactor in an uncorroded state. In addition, the temperature inside the high temperature combustor is set to 1200 ℃ or more so that the temperature inside the high temperature combustor is 50-100 ℃ higher than the melting point of ash, and thus theash is discharged from the bottom of the combustor in the form of slag.

In the present invention, a gas separation device for separating air into nitrogen and oxygen is provided. In the production of ammonia, there may be provided a means for supplying the separated nitrogen gas to the ammonia synthesis reactor, a means for supplying the separated oxygen gas to the fluidized bed reactor and/or the high temperature combustor.

The waste used in the present invention may be municipal refuse, plastic waste including Fiber Reinforced Plastics (FRP), biological waste, automobile waste, low-grade coal, waste oil, and other fuels such as RDF (fuel extracted from refuse) and SWM (solid-water mixture) made from the above waste.

Other fuels include fuel extracted from refuse obtained by pulverizing and classifying municipal refuse, adding quicklime and compacting and granulating, and solid-water mixture obtained by crushing municipal refuse, mixing with water, and then converting into oily fuel by reaction with hot water. Biological waste includes waste from waterworks or sewage treatment plants (misplaced materials, residues on screens, sewage sludge, etc.), agricultural waste (rice hulls, rice straw, surplus products, etc.), forestry waste (sawdust, bark, chipped wood, etc.), industrial waste (pulp-chips, etc.), and construction waste. The low-rank coal includes peat having a low calorific value or waste in coal dressing.

The present invention is also applicable to organic materials including oil shale, food offal, animal carcasses, waste clothing, waste paper, and other materials.

The above and other objects, features and advantages of the present invention will become more apparent upon reading the following specification in conjunction with the accompanying drawings which illustrate by way of example preferred embodiments of thepresent invention.

Brief description of the drawings

FIG. 1 is a schematic diagram of an apparatus for carrying out the treatment process according to the first embodiment of the present invention;

FIG. 2 is a schematic diagram of an apparatus for carrying out the treatment process according to the second embodiment of the present invention;

FIG. 3 is a schematic diagram of an apparatus for carrying out the treatment process according to the third embodiment of the present invention;

FIG. 4 is a diagram of ammonia (NH) synthesis from waste according to an embodiment of the present invention₃) A flow chart of (1);

FIG. 5 is a process for producing ammonia (NH) from waste according to another embodiment of the present invention₃) A process block diagram of (a);

FIG. 6 is a diagram of hydrogen (H) production from waste according to an embodiment of the present invention₂) Another process block diagram of (a);

FIG. 7 is a schematic view of a known apparatus for gasifying and combusting wastes;

FIG. 8 is a graph showing the pyrolysis characteristics of RDF in a nitrogen atmosphere.

Best Mode for Carrying Out The Invention

The method and apparatus for treating wastes by gasification according to the present invention will be described with reference to the accompanying drawings.

In the present invention, organic wastes that can be used are one or more of municipal wastes, fuels extracted from refuse, solid-water mixtures, plastic wastes, wastes of fiber-reinforced plastics, biological wastes, automobile wastes, low-grade coals, and waste oils. Depending on the nature of the organic waste, fossil fuels such as coal or petroleum coke may be added to the organic waste as a compensation fuel.

The two-stage gasification method of the present invention is a combination of gasification at a relatively low temperature and gasification at a relatively high temperature, and uses a fluidized bed reactor for gasification at a relatively low temperature and a high temperature combustor for gasification at a relatively high temperature. In the fluidized-bed reactor for low-temperature gasification, the fluidized-bed is maintained at a temperature range of 450-950 ℃ to perform partial combustion, i.e., gasification of the introduced wastes. Metals in the waste, such as iron or copper, can be recovered from the fluidized-bed reactor in an uncorroded state. The reason why the metal is not oxidized is that a low pressure is formed in the fluidized-bed reactor. The typical combined metal and plastic material is a cable, and the plastic covering the surface of the copper wire in the fluidized bed reactor is pyrolyzed and completely removed, and only the copper wire is recovered in a reusable, non-corrosive state. In a high-temperature combustor for high-temperature gasification, a gas containing char and tar from a fluidized-bed reactor is partially combusted, i.e., instantaneously gasified at a temperature of 1200 ℃ or higher, and ash is discharged as slag from the bottom of the high-temperature combustor.

In the case of using a swirl type burner as the high temperature burner, high load combustion can be performed, so that the size of the burner can be reduced. Because the vortex generates centrifugal force, slag smoke generated by charcoal combustion is attached to the inner wall of the combustor to form a slag phase, and therefore, the recovery range of 80-90% of the slag canbe reached. This reduces the load on the heat recovery device and the soot collector arranged downstream of the burner. It is therefore preferred to use a swirl type burner.

In the synthesis of ammonia, the gasifying agent used in the fluidized bed reactor is the mixture of oxygen obtained through steam and air separation, and the nitrogen obtained through air separation can be used for synthesizing ammonia. Cryogenic separation processes, adsorption processes such as PSA or TSA, and processes using separation membranes can all be used for air separation.

In addition, air is used as partial gasifying agent, H in the produced gas₂And N₂Is prepared from (A) and (B)The molar ratio is 3: 1, so that the produced gas can be used for synthesizing ammonia. That is, in order to avoid sintering or caking, the oxygen content of the gasifying agent supplied to the fluidized-bed reactor must be reduced to a range of 20 to 30%. If a mixture of oxygen and steam is used as the gasifying agent, a relatively large amount of steam is required. But in the case of ammonia production as the final product, air may be used. This is due to the fact that if nitrogen is present in the produced gas, and H₂And N₂In a molar ratio of 3: 1, the gas produced is just usable for the synthesis of ammonia.

In the present invention, the apparatus includes a fluidized-bed reactor for partially combusting organic wastes, a gasification chamber in a high-temperature combustor for partially combusting a gas raw material and charcoal from the fluidized-bed reactor under a high-temperature condition, and a cooling chamber for cooling the gas from the gasification chamber. For cooling the gas, the quench gas is preferably contacted directly with water. High-temperature gas of 1300 ℃ or higher is instantaneously cooled to about 200 ℃ by direct quenching, thus preventing the re-synthesis ofdioxin in the downstream process because the high-temperature gas rapidly passes through the temperature range of 300 ℃ for the re-synthesis of dioxin and 500 ℃, and a catalyst such as CuCl for the re-synthesis of dioxin₂It is also completely recovered from the gas by direct quenching (revalued). The apparatus further comprises a cooling chamber disposed downstream of the cooling chamber for removing HCl and soot from the gasA shower chamber for removing CO and H from the gas₂Conversion of O to CO₂And H₂CO converter for absorbing acid gases such as CO₂、H₂Acid gas removal chamber for S and COS, for removing CO and CO detrimental to ammonia synthesis catalyst₂Or CO and CO₂Gas purification chamber for converting H into harmless substance, and method for purifying H₂And N₂Reaction for synthesis of NH₃The reactor of (1).

In addition, the apparatus preferably comprises an air separator, and means for introducing the separated oxygen into the fluidized bed reactor and/or the high temperature combustor.

As a new waste treatment technology suitable for environmental protection instead of incineration, a gasification and high-temperature combustion system was developed, and the apparatus of the present invention mainly uses this system. If used for waste treatment, the system has the following advantages:

1. since the gas combustion replaces the conventional solid combustion, the combustion is performed at a low air ratio of about 1.3 and the amount of exhaust gas is greatly reduced.

2. Due to the high temperature combustion, dioxin and its precursors in the exhaust gas can be decomposed.

3. The ash in the waste can be recovered as harmless slag, and the harmful materials in the waste do not need to be eluted and removed. The service life of the recycling land (reclaimed land) can be extended and the recycled slag can be used as paving material.

4. Since the decomposition function of dioxin and the melting function of ash are combined into the system, the overall size of the equipment is reduced, and the construction cost is lower than that of the conventional incineration equipment added with the two functions. The reduction in the amount of exhaust gas leads to a reduction in the cost of the exhaust gas treatment equipment.

5. The operating costs are significantly reduced because the energy of the gases, char and tar produced in the fluidized bed reactor can be effectively used to produce slag, thereby saving the electrical energy necessary for the ash melting equipment.

6. The system may be used in a high efficiency power generation system.

7. Metals such as iron and copper can be recovered in a non-corroded state suitable for reuse.

8. Since the gas generated by high-temperature gasification is cooled by direct quenching, the refined synthesis gas does not contain dioxin.

Although air is used as the oxygen source for the incineration process, pure oxygen or oxygen-enriched air is used in the present invention for partially combusting the waste, and thus the combustible gas recovered is mainly composed of CO and H₂And (4) forming. According to the present invention, the gasification and high-temperature combustion system can be combined with a hydrogen production apparatus and an ammonia production apparatus, so that organic wastes including municipal wastes, plastic wastes, wastes of fiber-reinforced plastics, low-grade coal and waste oil are gasified in large quantities, thereby solving the problems caused by incineration or burial of the organic wastes and effectively utilizing the organicwastes.

It is preferred to use a gasification and high temperature combustion system in conjunction with a fluidized bed reactor and a high temperature combustor. In the fluidized-bed reactor, as a fluidizing medium, sand such as silica or olivine sand, alumina, iron particles, limestone, dolomite, etc. can be used.

Among these wastes, municipal wastes, biological wastes, plastic wastes, and automobile wastes are roughly pulverized into a particle size of about 30 cm. The fuel and solid-water mixture extracted from the reject is used untreated. The low-rank coal is pulverized into a particle size of 40mm or less.

The above wastes are separated and put into several tanks, and well stirred and mixed in each tank, and then fed into the fluidized-bed reactor. The wastes in the tank may be supplied to the fluidized-bed reactors separately or may be mixed and supplied to the fluidized-bed reactors.

Coal or petroleum coke may be added to the waste as a compensation fuel to suppress fluctuations in the calorific value of the waste according to the quality (calorific value and humidity) of the organic waste to be gasified. The amount of make-up fuel added is determined by waste mass. According to a tentative calculation, the lower limit of the average calorific value of the organic waste as the raw material is 3500kcal/kg or more from the viewpoint of economy.

The organic wastes are fed into a fluidized-bed reactor, gasified in a fluidized-bed at a temperature range of 450-950 ℃ and further gasified at a temperature of 1200 ℃ or more in a high-temperature combustor. As a gasifying agent, oxygen, air and steam are mixed, and if necessary, preheated. Carbon dioxide may additionally be used instead of steam. The necessary heat in each gasification stage can be obtained by partial combustion of the waste. This is called "internal heat extraction type". Gas, tar and char are produced by gasification in a fluidized bed. At lower bed temperatures, the rate of gas produced decreases as the rate of tar and char produced increases. The metal having a melting point higher than the temperature of the fluidized bed is not vaporized and is discharged from the bottom of the fluidized bed reactor together with the fluidizing medium and crushed stone. The discharged material is fed to a classifier, where it is classified into large-sized, metal-containing incombustibles above the screen and small-sized fluidized media below the screen. Valuable, e.g., metals, are separated from the non-combustibles and the fluidizing medium is returned to the fluidized-bed reactor. The fluidized bed reactor has a portion with a large diameter at the upper part of the fluidized bed, which is called a "dilute phase zone". The freeboard zone prevents entrainment of the fluidizing agent and char, thereby suppressing pressure fluctuations. In the present invention, a portion of the gasifying agent may be added to the freeboard zone to gasify the gas and char in the freeboard zone at a temperature in the range of 600 ℃ to 950 ℃, while the fluidized bed is maintained at a temperature in the range of 450 ℃ to 650 ℃ to recover metals having relatively low melting points, such as aluminum. In the subsequent high-temperature burner, the gasification of the material is carried out at a temperature of 1200 ℃ or more, so that the product gas consists mainly of H₂、CO、CO₂、N₂And H₂And (C) O. If air is not used as a gasifying agent, N is not contained in the product gas₂. The ash is converted into slag, which is discharged from the bottom of the gasification chamber and is in contact with water in the cooling chamber for quenching,the granulated slag can be used as aggregate or other building materials.

In addition, the reason for maintaining the fluidized bed inthe fluidized bed reactor in the temperature range of 450 ℃ and 950 ℃ will be described below.

FIG. 8 shows the pyrolysis characteristics of RDF in a nitrogen atmosphere. During the first stage gasification in a fluidized bed reactor, it is desirable to produce as much gaseous components including gas and tar as possible and as little solid components including combustible materials and ash as possible. The solid component, i.e., the smaller diameter charcoal, is fed in the fluidized bed reactor with the upward flow of product gas to the high temperature combustor, but the larger diameter solid component is discharged from the bottom of the reactor along with the non-combustibles.

As the pyrolysis temperature decreases, the ratio of the generated solid component increases. If the ratio of the produced solid component is high, the amount of the solid component discharged from the bottom of the reactor is increased accordingly in order to prevent the solid component from accumulating inside the fluidized bed. The solid component discharged from the reactor may be reused after removing sand and incombustibles therein, but it is desirable to reduce the amount of the solid component discharged from the reactor. In addition, at a temperature of 450 ℃ or less, the pyrolysis reaction rate is extremely low, and undecomposed raw materials tend to accumulate in the fluidized bed, so that the operation of the fluidized bed reactor becomes difficult. Conversely, as the temperature of the fluidized bed increases, the ratio of the solid components produced decreases, favoring gasification of the waste.

However, the temperature rise of pyrolysis can cause special problems with the fluidized bed, such as agglomeration or burning of the clinker. Therefore, the critical temperature at which the above phenomenon does not occur is about 950 ℃ depending on the types of the waste and the fluidizing medium. Therefore, the maximum value of the fluidized bed temperature was set to 950 ℃.

Most of the waste contains metals and it is important to recover the metals in an uncorroded state suitable for reuse. Among metals, in order to recover aluminum having a melting point of 660 ℃, the temperature of the fluidized bed is required to be lower than the melting point of aluminum.

However, when gasification is carried out under pressurized conditions, the gasification temperature in the fluidized-bed reactor is raised in some cases to ensure a certain reaction rate even at the expense of recovering aluminum.

Generally, in the production of synthesis gas for use as a chemical feedstock, gasification is at a pressure of 5 to 90atmWithin the force range. It is considered that gasification is carried out under normal pressure and that purification of the product gas is carried out in a pressure range of 30 to 40atm after CO shift. As the gasifying agent for the fluidized bed reactor, pure oxygen (O) obtained by low-temperature air separation is generally used₂) Mixture with steam, but CO recovered by removal of acid gases₂May be added to the oxygen. Nitrogen obtained by cryogenic air separation can be used for ammonia (NH) synthesis₃). In addition, air may be used as part of the gasifying agent. Controlling the combination ratio of gasifying agents to ensure that the H in the gas produced after CO shift₂And N₂The ratio of (a) to (b) is 3: 1, making it possible to use the product gas directly for ammonia synthesis. However, this method has a disadvantage in that when the flow rate of the product gas is increased, the size of the gas refining apparatus is increased.

In using organic waste as H₂Or ammonia synthesis gas, the amount of waste must be ensured and the quality of the waste must be stabilized. In addition, variationsin waste quality during system operation must be addressed.

In order to solve the above problems, according to the present invention, when the system cannot be stably operated using only wastes or when the system is in a driving stage, a solid fuel such as a fuel having a higher calorific value and stable performance, which is actually used for producing H, can be used₂The coal and petroleum coke of (2) are added to the waste. That is, the gasification raw material can be made to have stable quality and quantity by adding coal, petroleum coke or heavy oil to the waste to make its total content 20-40%. When the waste quality is reduced for some reason during the operation, H is contained in the produced gas₂Or the concentration of CO is decreased, the gas properties can be stabilized by increasing the mixing ratio of the solid fuel. The coal used in the system is not low-rank coal, which is a waste, but low-smoke coal or bituminous coal having a higher calorific value.

Figure 7 shows a reference embodiment of a gasification and high temperature combustion system for an incineration, i.e. complete combustion, waste process.

The apparatus shown in fig. 7 comprises a feed hopper 1, a steady state feeder 2 for feeding waste and a fluidized bed reactor 3 having a fluidized bed 4 therein. The fluidized-bed reactor 3 hasDilute phase zone 5 and burner 6, and is connected to a trommel 7, and trommel 7 is connected to a bucket conveyor 8. The device also comprises a vortex type high-temperature combustor 9, wherein the combustor 9 is provided with a primary combustion chamber 10, a secondary combustion chamber 11 and a slag separation chamber 12. The swirl type high temperature combustor 9 has a combustor 13.In FIG. 7, "a" represents organic waste, "b" represents fluidizing air, "b '" represents air supplied to the freeboard zone, "b'" represents air for the high-temperature combustor 9, "c" represents large-sized incombustibles, "d" represents silica sand, "e" represents generated gas₁"represents off-gas" and "f" represents slag.

If necessary, the organic wastes "a" may be pulverized and fed into the hopper 1 and then fed into the fluidized-bed reactor 3 through the steady-state feeder 2. Air "b" as a gasifying agent is introduced into the reactor from the bottom of the fluidized-bed reactor 3, and a fluidized bed 4 of silica sand is formed above the distributor inside the fluidized-bed reactor 3.

The organic wastes "a" are fed into the fluidized-bed 4, contacted with oxygen in the air inside the fluidized-bed 4, rapidly pyrolyzed and gasified, and the fluidized-bed 4 is maintained at a temperature range of 450-650 ℃. The fluidized medium and incombustibles are discharged from the bottom of the fluidized-bed reactor 3 and introduced into the trommel 7, and the incombustibles "c" are removed through the trommel 7. The separated silica sand "d" is returned from the upper end of the fluidized-bed reactor 3 to the fluidized-bed reactor through a bucket conveyor 8. The discharged incombustibles "c" contain metals. The fluidized bed 4 is maintained at a temperature in the range of 500 ℃ to 600 ℃ so that iron, copper and aluminum can be recovered in an unetched state.

When the waste "a" is gasified in the fluidized-bed 4, gas, tar and charcoal are generated. The gas and tar rise in the fluidized-bed reactor 3. The charcoal is ground to a powder by the agitation of the fluidized bed 4. Since the charcoal is porous and light, it can be entrained by the upward flowing gas. Since the fluidizing medium of the fluidized bed 3 is hard silica sand, the pulverization of charcoal is promoted. Air "b'" is blown into the freeboard zone 5 to gasify the gas, tar and char in the temperature range of 600-.

The product gas "e" discharged from the fluidized-bed reactor 3 is introduced into the first combustion chamber 10 of the swirling-type high-temperature combustor 9, mixed with preheated air "b" in a swirling flow, and burned at a high temperature of 1200 c or more. Combustion is completed in the second combustion chamber 11, and exhaust gas "e" is produced₁"is discharged from the slag separation chamber 12. Because the temperature in the vortex type high-temperature combustion chamber 9 is high, ash in the charcoal is converted into slag smoke and is combusted by the centrifugal force of the vortex for the first timeThe slag phase on the inner walls of the chamber 10 is trapped. The slag on the inner wall flows down into the second combustion chamber 11, where slag "f" is discharged from the bottom of the slag separation chamber 12. The first and second combustion chambers 1O and 11 are each provided with a burner 13 for starting the vehicle. In this way, combustion is carried out at an air ratio of about 1.3, while the ash is converted into slag.

The present invention will be described in detail below with reference to the accompanying drawings.

FIG. 1 is a two-stage gasification system of the present invention. The system shown in FIG. 1 is used to produce ammonia synthesis gas at pressures in the range of 5-90 atm.

In the following description, the same or similar elements or portions as those in fig. 7 will be denoted by the same reference numerals. The system comprises a fluidized bed reactor 3 and a vortex type high temperature combustor 17. The fluidized bed reactor 3 is connected to a rock feed hopper 14, and the feed hopper 14 is connected to a screen 15. A vortex type high temperature burner 17 is also connected to a rock feed hopper 14'. The screen 15 is connected to the fluidized-bed reactor 3 via a fluidizing medium circulating line 16. The swirl type high temperature combustor 17 has a high temperature gasificationchamber 18 and a cooling chamber 19 inside. In fig. 1, "a '" represents coal or petroleum coke used as a compensation fuel, "g" represents a mixture of oxygen and air used as a gasifying agent, and "g'" represents oxygen.

The crushed waste "a" is fed to the fluidized-bed reactor 3 through a rock hopper (not shown) at a constant rate. A mixture of oxygen and air is introduced as a gasifying agent "g" from the bottom of the fluidized-bed reactor 3, forming a fluidized bed 4 of silica sand above the sparger in the fluidized-bed reactor 3. The wastes "a" are introduced into the fluidized-bed 4, contacted with the gasifying agent "g" in the fluidized-bed 4 maintained at a temperature range of 750-850 deg.C, and rapidly pyrolyzed and gasified at a pressure of 40 atm.

The fluidized medium and incombustibles are discharged from the bottom of the fluidized-bed reactor 3, passed through a rock hopper 14, and then fed into a screen 15 to separate out incombustibles "c". The silica sand "d" under the screen 15 is transported by a fluidizing medium circulating line 16 including a bucket conveyor and then returned to the fluidized-bed reactor 3 through a rock hopper (not shown). The discharged incombustibles "c" contain metals, and iron, copper, etc. can be recovered in an uncorroded state.

When the waste "a" is gasified in the fluidized-bed 4, gas, tar and charcoal are generated. The gas and tar are vaporized and rise in the fluidized-bed reactor 3. The charcoal is pulverized by the vigorous agitation of the fluidized bed 4 and then entrained by the upward flowing product gas. The use of hard silica sand as the fluidizing medium promotes the powdering action of the charcoal.

Product gas "e" discharged from the fluidized-bed reactor 3₂The high-temperature gasification gas enters a high-temperature gasification chamber 18 of a vortex type high-temperature combustor 17, contacts with a gasification agent g' in a vortex inside the high-temperature gasification chamber, and is gasified at a high temperature of 1300 ℃ or higher. Due to the high temperature in the swirling-type high-temperature combustor 17, ash in the generated gas is converted into slag fume, and the slag fume enters the cooling chamber 19 together with the gas. In the cooling chamber 19, the slag "f" is quenched into granulated slag which is discharged from the high temperature combustor 17 through the rock hopper 14'.

FIG. 2 is a schematic view of an embodiment of the present invention, including a fluidized bed reactor, a vortex type high temperature combustor and its peripheral equipment. The apparatus shown in figure 2 is used to produce synthesis gas at a pressure of about 40 atm.

The apparatus includes a fluidized-bed reactor 3 of a circulating flow type and a vortex type high-temperature combustor 17. The apparatus shown in fig. 2 is different from the apparatus shown in fig. 1 in that the fluidized-bed reactor 3 is of an internal circulation type, the material discharged from the bottom of the fluidized-bed reactor 3 is separated by means of a screen 15, and large-sized incombustibles "c" located above the screen and a fluidized medium d located below the screen are depressurized through a rock hopper 14, respectively and independently. This embodiment has the following advantages: even when coarsely crushed waste is fed to the fluidised bed, it is consumed in the bed and does not accumulate in the bed. Since the charcoal is uniformly dispersed in the fluidized bed, the gasification of the charcoal is promoted. The powdered char is entrained in the circulating stream of fluidizing medium. The incombustibles "c" of large size are smoothly discharged from the fluidized-bed. Since no hot spots are generated in the fluidized bed, problems such as agglomeration or burning of clinker are prevented. Problems may occur herein discharging large-sized incombustibles, but by first separating the incombustibles from the fluidizing medium, the large-sized incombustibles are discharged through a special rock hopper which can prevent the incombustibles from bridging, while the fine fluidizing medium is discharged through a rock hopper which is generally used for high-temperature fine particles, thus improving the reliability of the system.

FIG. 3 is a schematic diagram of a two-stage gasification system according to another embodiment of the present invention, including a fluidized bed reactor, a high temperature burner of the swirling type, and its peripheral equipment. The apparatus shown in figure 3 is used to produce synthesis gas at a pressure of about 40 atm.

The apparatus shown in fig. 3 includes a fluidized-bed reactor 3 of a circulating flow type and a vortex type high-temperature combustor 9. The apparatus shown in fig. 3 is different from the apparatus shown in fig. 2 in that the material discharged from the fluidized-bed reactor 3 is separated by a screen 15 after being depressurized by a rock hopper 14, and a vortex type high temperature combustor has two high

temperature gasification chambers

10 and 11. In this embodiment, since it is estimated that large-sized incombustibles "c" are not contained in the waste, the material discharged from the bottom of the fluidized-bed reactor is depressurized through a rock hopper 14, which is generally used for high-temperature fine particles, and then separated into incombustibles "c" and a fluidized medium "d" by a sieve 15. The high temperature burner is not a single vertical cylindrical chamber but is composed of a vertical chamber 10 and an outer chamber 11. The slag can therefore remain in the burner for a longer period of time, which may reduce unburned carbon and promote evaporation of low melting point metals such as zinc and lead.

FIG. 4 is a diagram of ammonia (NH) production from organic waste according to an embodiment of the present invention₃) Is described.

As shown in fig. 4, the process includes a gasification step 100, a CO shift step 200, an acid gas removal step 300, a gas refining step 400 using liquid nitrogen, an ammonia synthesis step 500, and a sulfur recovery step 600. In FIG. 4, the gasifying agent supplied to the fluidized-bed reactor is a mixture of oxygen and steam. The apparatus for performing the above process includes a gas washer 21, a low temperature air separator 23, a fluidized bed reactor 24 for performing first-stage gasification of organic wastes, a high temperature burner 25 for performing second-stage gasification at a high temperature, a CO converter 36, an absorption tower 40, a condensing tank 41, a CO converter 36, a condensing tower 41, a gas-liquid separator, a₂Stripping column 44, H₂The system comprises an S stripping tower 50, an absorption tower 53, a liquid nitrogen leaching device 56 and a cooler 57. The plant also includes a nitrogen compressor 58, an oxygen compressor 59, a syngas compressor 60, an ammonia synthesis column 62, an ammonia chiller 68, an ammonia separator 70, and an ammonia storage tank 72. The apparatus further includes

heat exchangers

38, 39, 48, 52, 64, and 66, pumps 30, 46, and 54. In FIG. 4, symbols i, j and q represent air and oxygen (O), respectively₂) And sulfur (S).

The air "i" is separated into oxygen "j" and nitrogen "k" by the air separator 23. The oxygen gas obtained by the separation is compressed by a compressor 59 and then supplied as a gasifying agent to the fluidized-bed reactor 24 and the high-temperature combustor 25. The nitrogen "k" is compressed by compressor 58 and used for ammonia synthesis. Air is typically separated using cryogenic separation processes.

In the gasification step 100, the organic wastes"a" and the supplementary fuel "a" are gasified in the fluidized-bed reactor 24 at a pressure of 40atm and a temperature range of 750-850 deg.C, and then reacted with oxygen "j" and steam "m" at a temperature of 1200 deg.C or more in the high-temperature combustor 25 to generate main components including CO, H₂、H₂O and CO₂The gas of (2). The temperature in the high temperature combustor 25 is mainly regulated by controlling the feed rate of oxygen. The high temperature combustor 25 is of a direct cold quenching type, and has a high temperature gasification chamber 18 at an upper portion thereof and a cooling chamber 19 at a lower portion thereof. Product gasAnd is directly cooled by contact with water in the cooling chamber 19 and then discharged from the high temperature combustor 25. By cold quenching, a large amount of steam is generated to mix with the product gas. Most of the slag generated in the high temperature gasification chamber 18 is removed. The slurry mixture of slag and water is sent to a slag treatment process (not shown). The product gas, accompanied by a large amount of steam, is discharged from the cooling chamber 19, cleaned in a venturi scrubber (not shown), and then subjected to smoke removal in a gas scrubber chamber 21. The gas then enters the CO shift step 200. The shower water from the bottom of the water washer 21 is pumped back to the cooling chamber 19 by a circulation pump 30 and part of the shower water is fed to the slag treatment process (not shown).

The steam-containing gas from the gasification step 100 enters the CO shift step 200. The gas from the water scrubber 21 is preheated to a temperature suitable for CO shift by heat exchange with the gas from the first stage catalyst bed via a heat exchanger 38 and then enters the CO converter 36. In the CO converter 36, carbon monoxide (CO) and accompanying steam (H) in the gas are reacted in the presence of a catalyst₂O) reaction to produce hydrogen (H)₂) And carbon dioxide (CO)₂). The CO converter 36 has two catalyst beds. As an example, the inlet gas temperature of the first stage catalyst bed was 300 ℃ and the outlet gas temperature was 480 ℃.

As an example, the inlet gas temperature of the second stage catalyst bed was 300 ℃. The total conversion in the first and second catalyst beds is 90% or more and the CO concentration in the dry gas from the CO converter 36 is 1-2%. The CO shift reaction can be represented by the following formula:

this is an exothermic reaction, and the high temperature gas from the first stage catalyst bed is cooled by the heat exchange with the gas entering the CO converter 36, and then enters the second stage catalyst bed. In the second section of catalyst bed, the CO shift reaction is continued.

The gas passing through the CO converter 36 is cooled to about 40 ℃ by a heat exchanger 39, and then separated into condensed water and gas in a condensing tank 41The mass, which is then cooled to-17 c by heat exchange with a portion of the purge gas from the top of the liquid nitrogen washer 56. The cooled gas then enters an acid gas removal step 300 in which a physical absorption process, i.e. a methanol absorption process, is carried out to remove hydrogen sulfide (H) from the gas from the CO shift step 200₂S), carbonyl sulfide (COS) and carbon dioxide (CO)₂) Impurities in the interior.

The gas cooled to-17 c is introduced into the absorption tower 40, and the acid gas is absorbed in the absorption tower 40 by being countercurrently contacted with liquid methanol at about-60 c. So that carbon dioxide (CO) contained in the gas discharged from the absorption tower 40₂) In the range of 10-20ppm, hydrogen sulfide (H)₂S) was about 0.1 ppm. After acidic gases are removed from methanol used as an absorbent, the temperature of methanol rises and its absorption capacity decreases. Thus, methanol is withdrawn from the absorption tower 40, cooled with the ammonia coolant and the cooled methanol, and then returned to the absorption tower 40.

In the methanol taken out from the absorption tower 40, carbon dioxide (CO) is removed₂) And hydrogen sulfide (H)₂S) in addition, hydrogen (H) is also dissolved₂) And carbon monoxide (CO). To recover hydrogen (H) from methanol₂) And carbon monoxide (CO), and the methanol is decompressed to make hydrogen (H) therein₂) And carbon monoxide (CO) vaporization. The vaporized hydrogen and carbon monoxide are compressed by a recycle compressor. On the other hand, in order to recover high purity carbon dioxide (CO) absorbed by methanol₂) Methanol is added to CO₂In a stripper 44, which is then depressurized and stripped with nitrogen, carbon dioxide (CO) in methanol₂) Most of it is evaporated and if necessary recovered. The recovered carbon dioxide can be used for synthesizing urea or producing liquid carbon dioxide.

From CO₂The bottoms of stripper 44 are withdrawn containing condensed hydrogen sulfide (H)₂S) methanol is sent by pump 46 to heat exchanger 48. After preheating by heat exchanger 48, methanol enters H₂S stripper 50, where methanol is indirectly regenerated using steam in column 50. From H₂The top of the S stripping tower 50 is dischargedIs cooled by the heat exchanger 52 and then fed to the sulfur recovery step 600 where sulfur "q" is recovered. From H₂Methanol taken out of the bottom of the S stripper 50 is cooled and then sent to the top of the absorption column 40 by the circulation pump 54.

The hydrogen-rich gas from the absorber 40 contains a small amount of carbon monoxide (CO) and a trace amount of carbon dioxide (CO)₂) The gas is passed through an absorption column 53 from which methanol and carbon dioxide are removed, and cooled to about-190 c by a cooler 57, and then fed to a liquid nitrogen washer 56. In the gas refining step 400 using liquid nitrogen, the gas containing trace amounts of carbon monoxide (CO) and carbon dioxide (CO) is cleaned using supercooled liquid nitrogen₂) Argon (Ar) and methane (CH)₄) To remove these gas components. Hydrogen is not absorbed by liquid nitrogen because hydrogen has a lower boiling point than nitrogen. The purified hydrogen-rich gas obtained from the top of the liquid nitrogen scrubber 56 thus contains nitrogen.

The purified gas obtained from the top of the liquid nitrogen scrubber 56 is mixed with high-pressure nitrogen gas compressed by the compressor 58 after passing through the cooler 57, so that the molar ratio of hydrogen to nitrogen gas is adjusted to about 3 to be suitable for ammonia synthesis, and the mixed gas is supplied to the ammonia synthesis step 500. Part of the nitrogen gas compressed by the compressor 58 is cooled and liquefied by the cooler 57 and then supplied to the liquid nitrogen scrubber 56, and in the liquid nitrogen scrubber 56, the added nitrogen gas is in counter-current contact with the gas added from the bottom of the liquid nitrogen scrubber 56, and the gas includes carbon monoxide (CO), carbon dioxide (CO), and the like₂) Argon (Ar) and methane (CH)₄) Impurities in the liquid nitrogen are absorbed and removed by the liquid nitrogen. Absorbing impurities such as carbon monoxide (CO) and carbon dioxide (CO)₂) Argon (Ar) and methane (CH)₄) The liquid nitrogen is extracted from the bottom of the liquid nitrogen scrubber 56 and depressurized for use as boiler fuel. As an example, the gas provided from the gas refiningstep 400 is compressed to 150atm in the first stage of the compressor 60, and then the compressed gas is mixed with the recycle gas from the ammonia separator 70. The mixed gas is then compressed to 165atm in the second stage of the compressor 60 and then supplied to the ammonia synthesis column 62. The ammonia converter has two sections formed by iron-based catalystThe catalyst bed of (2).The inlet gas pressure of the ammonia synthesis column 62 was 164atm, and the temperature was 250 ℃. The ammonia synthesis reaction is carried out as the synthesis gas passes through the catalyst bed. The reaction is represented by the following formula:

while the gas passes through the catalyst bed, its temperature may exceed 500 ℃, but it is cooled by the cold recycle gas introduced into the ammonia synthesis column 62.

The ammonia pressure from the ammonia synthesis column 62 is 160atm and the temperature is 450 ℃. The ammonia is cooled to around room temperature by the

heat exchangers

64 and 66 and then further cooled by an ammonia refrigerator 68, so that most of the ammonia is condensed. The condensed ammonia is separated into liquid ammonia and gas in the ammonia separator 70, and the liquid ammonia enters the ammonia storage tank 72. The separated gas enters the second stage of the compressor 60, is compressed to a pressure of 165atm, and is then fed to the ammonia synthesis column 62 for recycling.

In the above process, a mixture of oxygen and steam is used as a gasifying agent. However, the gasifying agent is not limited to the above-mentioned species, and a mixture of air and oxygen may be used. In this case, the amount of air depends on the amount of nitrogen required for synthesizing ammonia. Since the product gas comprises nitrogen gas required for synthesis of ammonia, methanation is preferred for gas refining processes using liquid nitrogen.

Fig. 5 is a block diagram showing a process in which the product gas obtained by two-stage gasification of the wastes is separated into hydrogen and residual gas, and the resulting residual gas is reused as the fluidizing gas for the fluidized-bed reactor 110. As shown in fig. 5, the process includes a first gasification stage in a fluidized bed reactor 110, a second gasification stage in a swirling high temperature combustor 112, a water scrubber 114, an acid gas removal step 116, a CO shift step 118, a hydrogen separation step 120, a recycle gas compressor 122. In FIG. 5, "a" represents waste and "g'" represents oxygen.

In the low temperature fluidized bed reactor 110, waste crushed to the desired particle size is fed above a fluidized bed of hard silica sand. As a gasifying agent, oxygen "g'" and a fluidizing gas (described below) are fed to the lower portion of the fluidized-bed reactor 110. The fluidized bed was maintained at a temperature in the range of 450 ℃ and 950 ℃. Under these conditions, the waste is rapidly pyrolyzed and gasified by partial oxidation.

In the fluidized-bed reactor 110, gas, tar and charcoal are generated by gasification of the wastes "a". Most of the tar and char are entrained by the upward flowing product gas into the vortex type high temperature combustor 112 and then decomposed into unrefined gas mainly composed of carbon monoxide (CO), carbon dioxide (CO) by partial oxidation at a temperature of 1350 deg.C and a pressure of 40atm₂) Hydrogen (H)₂) And water (H)₂O) is added. In the cooling chamber at the lower portion of the swirling-type high-temperature combustor 112, the high-temperature unrefined gas is quenched, and then washed in the water washer 114 to remove impurities such as hydrogen chloride (HCl) and dusts.

In the acid gas removal step 116, acid gases, such as carbon dioxide (CO), are removed from the gas₂) Hydrogen sulfide (H)₂S) and carbonyl sulfide (COS). In the subsequent CO shift step 118, CO and H are reacted by CO shift reaction in the presence of a catalyst₂Conversion of O to H₂And CO₂. If necessary, steam for CO shift is added to the gas in a saturator (not shown) in the CO shift step 118.

Since the desulfurized gas is supplied to the CO shift step, either a high-temperature shift catalyst (Fe-based) or a low-temperature catalyst (Cu-based) can be used as a catalyst for CO shift, thereby improving the CO shift rate. The refined gas from the CO shift step 118 is composed of H₂、CO₂、H₂O and a small amount of CO, and separating the gas into high-purity H by using a pressure swing adsorption method or a hydrogen separation membrane₂And a residual gas consisting essentially of CO₂And CO. The remaining gas is compressed by the recycle gas compressor 122 and then introduced into the fluidized-bed reactor 110 together with oxygen g' from the bottom of the fluidized-bed reactor 110 as a part of the fluidizing gas.

If a large amount of steam is used as the gasifying agent, the operation cost of the apparatus increases.In contrast, if air is used as the gasifying agent, the product gas will contain a large amount of nitrogen. In order to avoid the above disadvantage, it is preferable to reuse the surplus gas as a part of the gasifying agent. N from an air separation unit (not shown)₂Is added to the hydrogen separated in the hydrogen separation step 120 and is sent to the ammonia synthesis step. In addition, N may not be added₂While withdrawing H from the hydrogen separation step 120₂。

In any of the above embodiments, it is desirable to exclude N₂And H₂In addition, the content of inert gasAs small as possible, thereby reducing the amount of purge gas used. In the two-stage gasification process of the present invention, when the wastes "a" are pyrolyzed and gasified in the low-temperature fluidized-bed reactor 110, the product gas contains a large amount of hydrocarbons. In the vortex type high temperature combustor 112, the product gas is partially combusted and reacted with steam to convert into CO, CO₂、H₂And H₂And O. When the vaporization temperature in the swirling-type high-temperature combustor 112 is not sufficiently high, the product gas discharged from the swirling-type high-temperature combustor 112 contains unreacted hydrocarbons such as CH₄Or C₂H₄. When the methanation process is carried out in the subsequent step, the unreacted hydrocarbon acts as inert gas for the ammonia synthesis step. Therefore, in order to reduce the amount of unreacted hydrocarbons, the vaporization temperature in the swirling-type high-temperature combustor 112 is preferably 1300 ℃ or higher.

The block of figure 6 is another embodiment of figure 5 of the present invention. After separation of hydrogen from the product gas from the gas purification step, the remaining acid gas is mainly CO₂The gas is reused as fluidizing gas for the fluidized-bed reactor. As shown in fig. 6, the process includes a first stage gasification in a fluidized bed reactor 110, a second stage gasification in a swirling high temperature combustor 112, a water scrubber 114, an acid gas removal step (first) 116, a CO shift step 118, an acid gas removal step (second) 121, and a recycle gas compressor 122. In FIG. 6, "a" represents waste, "g'" represents oxygen.

The waste "a" having been crushed to a desired particle size is fed into the fluidized-bed reactor 110 above the fluidized bed of the hard silica sand. Theinternal pressure of the fluidized-bed reactor 110 is about 40 atm.

As a gasifying agent, oxygen "g'" is fed into the lower portion of the fluidized-bed reactor 110 together with the fluidizing gas (see below in detail) supplied from the circulating gas compressor 122. The temperature of the fluidized bed was maintained within the temperature range of 450 ℃ and 950 ℃. Under these conditions, the waste is rapidly pyrolyzed and gasified by partial oxidation.

In the fluidized-bed reactor 110, gas, tar and charcoal are generated by gasification of the wastes "a". Most of the charcoal is pulverized, entrained by the upward flowing gas into the high temperature combustor 112, and decomposed into unrefined gas mainly composed of CO, CO by partial oxidation at 1350 deg.C and 40atm pressure in the high temperature combustor₂、H₂And H₂And (C) O. High-temperature unrefined gas in a cooling chamber at the lower part of the swirl type burner 112The bodies are quenched and then rinsed in a water washer to remove impurities such as hydrogen chloride (HCl) and dust.

In the acid gas removal step (first) 116, acid gases such as CO are removed from the gas₂、H₂S and COS. In the subsequent CO shift step 118, CO is reacted by CO shift reaction in the presence of a catalyst₂And H₂Conversion of O to H₂And CO₂. In the CO shift step 118, steam for CO shift is added to the gas in a saturator (not shown).

The refined gas produced in the CO shift step 118 contains H₂、CO₂、H₂O and a small amount of CO, and CO is removed therefrom in the acid gas removal step (second) 121₂Thereby obtaining a catalyst mainly containing H₂The gas of (2). CO removed in acid gas removal step 121₂Compressed by the recycle gas compressor 122 and then fed to the bottom of the fluidized bed reactor 110 together with oxygen "g'" as part of the fluidizing gas. The gas obtained contains mainly H₂Optionally, N may not be added₂Is taken out in the case of (1). In addition, N is added₂Then, H₂Is sent to the ammonia synthesis step for productionAmmonia. For the obtained H₂The use and application of (A) is not limited.

As described above, the method and apparatus for treating wastes by the two-stage gasification method according to the present invention have the following advantages:

1. can utilize cheap and easily-obtained organic waste of our country to produce synthetic ammonia (NH)₃) Hydrogen as a raw material of (3). The production cost of hydrogen is significantly reduced.

2. Various problems associated with conventional incineration processes may be solved by gasifying organic wastes to produce hydrogen. Namely, the amount of exhaust gas is greatly reduced and dioxin and its precursor are not generated. In addition, since ash in the wastes is converted into harmless slag, the life span of the recycling site can be extended, and the recycled slag can be used as paving material.

3. Metals such as iron or copper can be recovered in a non-corroded state suitable for reuse.

From the viewpoint of effective utilization of wastes and environmental protection, the gasification apparatus, the hydrogen production apparatus, and the ammonia synthesis apparatus are disposed adjacent to each other, and are organically combined in terms of utilization of raw materials, thereby enhancing the functions of all the apparatuses as the entire system.

4. By using a compensating fuel such as coal or petroleum coke for the waste, it is possible to solve the problem of fluctuations in the quality and quantity of the waste. Specifically, by increasing the mixing ratio of the compensation fuel, the gasification apparatus can be operated in a steady state without deterioration of the properties of the product gas.

5. The gas produced in the two-stage gasification process is refined and separated into hydrogen and a residual gas, which contains carbon monoxide and carbon dioxide, so that the residual gas obtained can be reused as fluidizing gas in the fluidized-bed reactor. Therefore, the problem of shortage of fluidizing gas caused by the enlargement of the apparatus can be solved.

Although preferred embodiments of the present invention have been described in detail, it should be understood that various changes and modifications may be made therein without departing from the scope of the appended claims.

Industrial applicability

The present invention is applicable to a waste treatment system in which wastes such as municipal wastes, plastic wastes or biological wastes are treated by a two-stage gasification method, metals or ashes in the wastes are recovered, and the metals or ashes are in a reusable state, and the gases are mainly composed of carbon monoxide (CO) and hydrogen (H)₂) Composition, can be used as hydrogen or ammonia (NH)₃) The synthesis gas of (2).

Claims

1. A method of treating waste by a gasification process, the method comprising:

gasifying the waste in a fluidized bed reactor under cryogenic conditions;

introducing a gaseous feedstock and char produced in the fluidized bed reactor into a high temperature combustor;

producing gas in the high temperature combustor under high temperature conditions;

after removal of the acidic components, subjecting the gas to a CO shift reaction;

separation of the gas obtained by CO shift reaction into H₂And a residual gas; and

the residual gas is supplied as fluidizing gas to the fluidized-bed reactor.

2. The process of claim 1 wherein said separation is by pressure swing adsorption or hydrogen separation membrane.

3. The method of claim 1, wherein said high temperature combustor comprises a vortex-type high temperature combustor.

4. The method of claim 1, wherein said fluidized-bed reactor comprises a circulating flow-type fluidized-bed reactor.

5. The process as claimed in claim 1, wherein the gasification stage in the fluidized-bed reactor and the gasification stage in the high-temperature combustor are each carried out in a pressure range of 5 to 90 atm.

6. The process as set forth in claim 1 wherein said low temperature in said fluidized bed reactor is in the range of 450 ℃ and 950 ℃.

7. The method of claim 1, wherein the high temperature within the high temperature combustor is 1200 ℃ or greater.

8. The method of claim 1, wherein the waste has a lower average calorific value of 3500kcal/kg or more.

9. The method of claim 1, wherein when the average lower calorific value of the waste is 3500kcal/kg or less, a supplementary fuel is added to the waste so that the average lower calorific value is 3500kcal/kg or more.

10. The method of claim 1, wherein oxygen or a mixture of oxygen and steam is used as a gasifying agent for the fluidized-bed reactor, and oxygen or a mixture of oxygen and steam is used as a gasifying agent for the high-temperature combustor.

11. A method of treating waste by a gasification process, the method comprising:

gasifying the waste in a fluidized bed reactor under cryogenic conditions;

subjecting the gas to a CO shift reaction;

removal of acidic components from gas from CO shift reaction to obtain H₂；

Supplying the removed portion of the acidic component as a fluidizing gas to the fluidized bed reactor.

12. The method of claim 11, wherein said high temperature combustor comprises a vortex-type high temperature combustor.

13. The method of claim 11, wherein said fluidized bed reactor comprises a circulating flow type fluidized bed reactor.

14. The method as claimed in claim 11, wherein the gasification stage in the fluidized-bed reactor and the gasification stage in the high-temperature combustor are eachperformed at a pressure ranging from 5 to 90 atm.

15. The process as set forth in claim 11 wherein said low temperature in said fluidized bed reactor is in the range of 450 ℃ and 950 ℃.

16. The method of claim 11, wherein the high temperature within the high temperature combustor is 1200 ℃ or greater.

17. The method of claim 11, wherein the waste has an average lower calorific value of 3500kcal/kg or more.

18. The method of claim 11, wherein when the average lower calorific value of the waste is 3500kcal/kg or less, a supplementary fuel is added to the waste so that the average lower calorific value is 3500kcal/kg or more.

19. The method of claim 11, wherein oxygen or a mixture of oxygen and steam is used as a gasifying agent for the fluidized-bed reactor, and oxygen or a mixture of oxygen and steam is used as a gasifying agent for the high-temperature combustor.

20. The method of claim 11, wherein a mixture of oxygen and air or a mixture of oxygen, air and steam is used as a gasifying agent for the fluidized-bed reactor, and oxygen or a mixture of oxygen and steam is used as a gasifying agent for the high-temperature combustorGasifying agent, whereby the gas produced in the high-temperature combustor contains CO, H₂And N₂And CO and H₂Addition of (A) and (B) and N₂Is about 3.

21. A method of treating waste by a gasification process, the method comprising:

gasifying the waste, which has been pulverized to a desired particle size range, by a two-stage gasification process to produce a gas; and

the produced gas is converted into hydrogen by a CO shift reaction.

22. The method of claim 21, wherein said waste comprises one or more of municipal waste, fuel extracted from reject, solid-water mixtures, plastic waste, biological waste, automotive waste, and low-rank coal.

23. The method of claim 21, wherein the two-stage gasification is a combination of low-temperature gasification and high-temperature gasification, and the low-temperature gasification is performed using a fluidized bed of a circulating flow type and the high-temperature gasification is performed using a high-temperature combustor of a vortex type.

24. An apparatus for treating waste by gasification, the apparatus comprising:

a fluidized bed reactor for gasifying the wastes at a low temperature to produce a gaseous raw material and charcoal;

a high-temperature gasification chamber for gasifying the gas raw material and charcoal at a high temperature in a high-temperature combustor;

a cooling chamber with water for quenching the gas in the high temperature combustor;

means for removing an acidic component from said gas from said cooling chamber;

a CO shift reactor for performing a CO shift reaction to shift a gas from the acid removal apparatus;

a separation device for separating the gas from the CO shift reaction into hydrogen and a residual gas;

a supply line for supplying the residual gas as a fluidizing gas to the fluidized-bed reactor.

25. The apparatus of claim 24, wherein said high temperature burner comprises a vortex-type high temperature burner.

26. The apparatus of claim 24, wherein said fluidized-bed reactor comprises a circulating flow-type fluidized-bed reactor.

27. The apparatus as set forth in claim 24 wherein said low temperature in said fluidized bed reactor is in the range of 450 ℃ and 950 ℃.

28. The apparatus of claim 24, wherein the high temperature in the high temperature combustor is 1200 ℃ or higher.

29. An apparatus for treating waste by gasification, the apparatus comprising:

a high temperature gasification chamber for producing gas at high temperature in a high temperature combustor;

a CO shift reactor for performing a CO shift reaction to shift the gas from the cooling chamber;

means for removing acidic components from said gas from said CO shift reaction; and

a supply line for supplying a portion of the acidic component as a fluidizing gas to the fluidized bed reactor.

30. The apparatus of claim 29, wherein said acid removal device is disposed between said cooling chamber and said CO shift reactor.

31. The apparatus of claim 29, wherein said high temperature burner comprises a vortex-type high temperature burner.

32. The apparatus of claim 29, wherein said fluidized-bed reactor comprises a circulating flow-type fluidized-bed reactor.

33. The apparatus as set forth in claim 29 wherein said low temperature in said fluidized bed reactor is in the range of 450 ℃ and 950 ℃.

34. The apparatus of claim 29, wherein said high temperature in said high temperature combustor is 1200 ℃ or higher.