CN105152509B - The supercritical processing methods of supercritical reaction device, supercritical reaction system and sludge - Google Patents
The supercritical processing methods of supercritical reaction device, supercritical reaction system and sludge Download PDFInfo
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Abstract
The present invention discloses the supercritical processing methods of a kind of supercritical reaction device, supercritical reaction system and sludge, it is related to processing and its engineering device technique field of sludge, the speed that the water in carbon containing slurry is changed into supercriticality in warm by normal state can be improved.Supercritical reaction device includes inner cylinder and outer barrel, the circular region of inner cylinder is reaction zone, and the region formed between the bottom of inner cylinder and the outer barrel is chill zone, and supercritical reaction device also includes heat transfer zone, and heat transfer zone connects with the reaction zone, the chill zone respectively, heat-exchanger rig is provided with heat transfer zone.The supercritical reaction system includes the supercritical reaction device that above-mentioned technical proposal provides.The supercritical processing methods of the sludge are handled sludge using above-mentioned supercritical reaction system.The supercritical processing methods of supercritical reaction device provided by the invention, supercritical reaction system and sludge are used for the purified treatment of sludge.
Description
Technical field
The present invention relates to the processing of sludge and its engineering device technique field, more particularly to it is a kind of supercritical reaction device, overcritical
The supercritical processing methods of reaction system and sludge.
Background technology
At present, with shortage of water resources the problem of, is increasingly serious, how to realize recycling as current society for water resource
The Important Problems that can develop.Realize that recycling for water resource needs to carry out purified treatment to sewage, and at the purification
A large amount of sludge will be produced during reason, so as to need that further these sludge are handled, due to containing in these sludge
(difference of the quality of moisture is referred to as butt quality in sludge gross mass and sludge, then organic pollution for substantial amounts of organic pollution
Quality generally accounts for more than the 30% of butt quality), therefore, the processing method of conventional landfill or burning will be made to soil or air
Into secondary pollution, the living environment of the mankind is had a strong impact on.And in contrast, supercritical oxidation technology then can be in a short time
By the organic pollution materials complete oxidation in sludge, in the absence of secondary pollution problem.Therefore, the supercritical processing methods day of sludge
Benefit is concerned by people.
In the prior art, the first supercritical processing of sludge is typically carried out in supercritical reaction device, is specially：By certain ratio
Example mixes sludge with water, is made carbon containing slurry, and by carbon containing slurry be forced into critical point temperature and critical point pressure with
Upper (generally, critical point temperature is 374.3 DEG C, and critical point pressure is 22.1MPa) so that the water in carbon containing slurry is converted into super face
Boundary's water, and then the organic pollution in sludge is aoxidized and removed by supercritical oxidation reaction.
In supercritical oxidation reaction, when temperature of reaction system is more than critical point temperature, supercritical oxidation reaction can
Pass through the lasting progress of self-heat generation maintenance reaction.Because the calorific value of sludge is (caused by i.e. after the sludge oxidation of unit mass
Heat) it is smaller, and the temperature of carbon containing slurry is increased to more than critical point temperature need to absorb substantial amounts of heat by normal temperature, therefore
Directly the carbon containing slurry of normal temperature, which is imported in supercritical reaction device, reduces the temperature for causing reaction system, causes supercritical oxidation
Reaction spontaneous can not be carried out.Therefore, prior art is by carbon containing slurry generally before supercritical reaction device is passed through, using overcritical anti-
Carbon containing slurry is preheated to close to critical point temperature by the product for answering device to export, to maintain the supercritical oxidation in supercritical reaction device
The lasting progress of reaction.
However, the temperature of the reaction product of supercritical reaction device output is usually less than above-mentioned critical point temperature, therefore, generally
In the case of, in the warm of carbon containing slurry, the temperature of carbon containing slurry is closer to critical point temperature, the temperature of above-mentioned reaction product
The temperature difference of degree and carbon containing slurry is with regard to smaller, and heat exchange between the two is more difficult to, so as to cause the water in carbon containing slurry to exist
Be changed into that the speed of supercriticality is slower in warm by normal state, cause sludge first supercritical processing efficiency compared with
It is low.
The content of the invention
It is an object of the invention to provide the first supercritical processing of a kind of supercritical reaction device, supercritical reaction system and sludge
Method, it is changed into the speed of supercriticality, Jin Erti by normal state to improve the water in carbon containing slurry in warm
The efficiency of the first supercritical processing of high sludge.
To achieve these goals, the present invention provides following technical scheme：
In a first aspect, the invention provides a kind of supercritical reaction device, for handling carbon containing slurry, including inner cylinder
And outer barrel, the circular region of the inner cylinder are reaction zone, the region formed between the bottom of the inner cylinder and the outer barrel is sharp
Cold-zone, the supercritical reaction device also include heat transfer zone, and the heat transfer zone connects with the reaction zone, the chill zone respectively,
Heat-exchanger rig is provided with the heat transfer zone；
The heat-exchanger rig is used to import the carbon containing slurry into the reaction zone；The heat transfer zone is used for from described anti-
Answer area to receive a product of supercritical oxidation reaction generation, and the heat exchange is filled by the heat energy that a product contains
The carbon containing slurry in putting is preheated.
Reaction zone is connected with heat transfer zone in supercritical reaction device provided by the invention, and heat-exchanger rig is provided with heat transfer zone, is led to
Cross heat-exchanger rig and the carbon containing slurry for needing to preheat is imported into reaction zone.By above-mentioned setting, supercritical oxidation reacts the one of gained
Secondary product directly can enter heat transfer zone from reaction zone, the heat energy contained by a product by the tube wall of heat-exchanger rig conduct to
In heat-exchanger rig, and then the carbon containing slurry exchanged in thermal is preheated.Therefore, reacted with supercritical oxidation in the prior art
Product supercritical reaction device is being exported after supercooling, but preheating is carried out to carbon containing slurry and compared, in the present invention, once
Product can need not directly preheat through supercooling in heat transfer zone to carbon containing slurry, and now the temperature of a product is far above
The temperature of carbon containing slurry, even if so as to be preheated by a product to carbon containing slurry, the temperature of a product also will not
It is down to close to critical point temperature.Therefore, during being preheated to carbon containing slurry, carbon containing slurry and supercritical oxidation of the invention
The temperature difference that reaction generates a product is larger, so that the water in carbon containing slurry is changed into supercriticality by normal state
Speed be improved, and then improve sludge first supercritical processing efficiency.
Further, since a product of above-mentioned supercritical oxidation reaction not through supercooling and is exporting supercritical reaction device
Carbon containing slurry is preheated afterwards, but directly carbon containing slurry preheated in supercritical reaction device, therefore can will be by
More heat energy in the heat energy of supercritical oxidation reaction generation is applied in the preheating to carbon containing slurry, and therefore, the present invention provides
Supercritical reaction device can also mitigate supercritical oxidation reaction caused by heat energy waste.
Second aspect, the embodiment of the present invention additionally provides a kind of supercritical reaction system, to carbon containing slurry
Reason, including the supercritical reaction device described in above-mentioned technical proposal, the supercritical reaction device include reaction zone, heat transfer zone and Quench
Area, heat-exchanger rig is provided with the heat transfer zone；Wherein,
The heat-exchanger rig is used to import carbon containing slurry into the reaction zone；The reaction zone is used to make the carbon containing material
Slurry carries out supercritical oxidation reaction, to generate a product；The heat transfer zone is used to once produce from described in reaction zone reception
Thing, and the heat energy contained by a product preheats to the carbon containing slurry in the heat-exchanger rig；The chill zone
For receiving a product from the reaction zone and the heat transfer zone, and a product is cooled down, with generation
Secondary product.
Relative to prior art, supercritical processing system provided by the invention has the advantage that and above-mentioned supercritical reaction device
It is same relative to Dominant Facies possessed by prior art, it will not be repeated here.
The third aspect, present invention also offers a kind of supercritical processing methods of sludge, using described in above-mentioned technical proposal
Supercritical reaction system, the supercritical processing methods of the sludge include：
By heat-exchanger rig, the carbon containing slurry is imported into reaction zone；
The carbon containing slurry is set to carry out supercritical oxidation reaction in the reaction zone, to generate a product；
Heat transfer zone receives a product from the reaction zone, and the heat energy contained by a product is to described
The carbon containing slurry in heat-exchanger rig is preheated；
Chill zone receives a product from the reaction zone and the heat transfer zone, and a product is carried out cold
But, to generate secondary product.
Relative to prior art, the supercritical processing methods of sludge provided by the invention have the advantage that with it is above-mentioned overcritical
Reaction system is same relative to Dominant Facies possessed by prior art, will not be repeated here.
Brief description of the drawings
Accompanying drawing described herein is used for providing a further understanding of the present invention, forms the part of the present invention, this hair
Bright schematic description and description is used to explain the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the structure chart of supercritical reaction device provided in an embodiment of the present invention；
Fig. 2 is the annexation figure between each part of supercritical reaction system provided in an embodiment of the present invention；
Fig. 3 is the flow chart of the supercritical processing methods of sludge provided in an embodiment of the present invention；
Fig. 4 is in the flow of the supercritical processing methods of the sludge shown in Fig. 3, utilizes the heat energy contained by a product
Obtain the method flow diagram of steam.
Reference：
100- supercritical reaction devices, 110- reaction zones,
120- heat transfer zones, 121- heat-exchanger rigs,
130- chill zones, 210- raw material storage tanks,
220- liquid oxygen tanks, 310- steam turbines,
The water pots of 320- first, 410- vapor heat exchangers,
The separators of 420- first, the separators of 430- second,
510- deslagging lock hoppers, 520- liquid nitrogen containers,
The water pots of 530- second, the water pots of 540- the 3rd.
Embodiment
In order to further illustrate the super of supercritical reaction device provided in an embodiment of the present invention, supercritical reaction system and sludge
Critical processing method, is described in detail with reference to Figure of description.It should be noted that in each of the embodiments described below, respectively
Connected relation between part can be realized by modes such as pipelines, control valve can be installed on every pipeline, with the company to pipeline
Logical or block is controlled, if inessential, following each embodiments are not described in detail to the control valve on specific pipeline and pipeline,
Those skilled in the art voluntarily can be configured to the control valve on pipeline and pipeline as needed.
Referring to Fig. 1, supercritical reaction device provided in an embodiment of the present invention is used for the first supercritical processing of sludge, it includes interior
Cylinder and outer barrel, wherein, inner cylinder is hollow cylinder；Outer barrel includes the hollow cylinder around inner cylinder, and hollow with outer barrel
The hollow cone that cylinder is coaxially disposed and bottom surface external diameter is suitable with the external diameter of outer barrel, the bottom surface of the hollow cone and outer barrel
The bottom surface of hollow cylinder overlap ground connection, it is to be understood that the above is only that the shape of outer barrel is described, actual
On, outer barrel, which is alternatively, to be integrally formed, and the circular region of inner cylinder is formed between reaction zone 110, the bottom of inner cylinder and the outer barrel
Region be that the circular region of hollow cone of outer barrel is chill zone 130.Further, supercritical reaction provided by the invention
Device also includes heat transfer zone 120, and heat transfer zone 120 connects with reaction zone 110, chill zone 130 respectively, and heat exchange is provided with heat transfer zone 120
Device 121.Heat-exchanger rig 121 is used to be passed through carbon containing slurry into reaction zone 110；Heat transfer zone 120 is used to receive from reaction zone 110
Product of supercritical oxidation reaction generation, and the carbon containing material that the heat energy contained by a product is exchanged in thermal 121
Slurry is preheated.
Specifically, the process of the first supercritical processing of sludge is carried out using supercritical reaction device provided in an embodiment of the present invention
For：Sludge is configured to aqueous carbon containing slurry first, and carbon containing slurry is forced into carbon containing slurry by high-pressure diaphragm pump
Pressure is more than critical point pressure (be usually 22.1MPa), then by heat-exchanger rig 121 by carbon containing slurry pipeline transport to reaction zone
The nozzle entrance of 110 tops, reaction zone 110 is injected by nozzle entrance, while oxygen (oxygen pressure is passed through into reaction zone 110
More than critical point pressure), supercritical oxidation reaction is carried out in reaction zone 110 and generates a product；The generation is once
Product enters from reaction zone 110 will produce heat exchange (i.e. heat contained by a product between heat transfer zone 120, with carbon containing slurry
Amount conducts the tube wall via steam heat exchanging tube into carbon containing slurry), because the temperature of a product is far above heat-exchanger rig 121
In carbon containing slurry temperature, therefore carbon containing slurry promptly can be preheated to temperature close to critical point temperature by a product
(being usually 374.3 DEG C).It should be noted that a product includes oxidation product, the nothing that organic pollution is oxidized and generated
Water under machine salt, solid particle, supercriticality, the oxygen and organic matter that are not reacted completely including part also sometimes etc..
In above process, chill zone 130 actually connects reaction zone 110 with heat transfer zone 120, so, a product
After chill zone 130 is entered, the product reflux of part one time to heat transfer zone 120, exchange in the heat-exchanger rig 121 in hot-zone 120
Carbon containing slurry is preheated；Further, because in above-mentioned warm, the temperature of a product is higher, its density is got over
It is low, therefore the product that temperature reduces in warm will drop to chill zone 130 from heat transfer zone 120, and temperature is higher
A product will rise to heat transfer zone 120 from chill zone 130 so that chill zone 130 can be constantly to heat transfer zone 120
There is provided a higher product of temperature, further improve the efficiency that a product preheats to carbon containing slurry.
Further, due to solid particle and inorganic salts in carbon containing slurry be present, and inorganic salts are in supercritical water
Will separate out, if therefore a product is directly exported from supercritical reaction device, above-mentioned solid particle and precipitation it is inorganic
Salt may blocks transmission pipeline.Therefore, in supercritical reaction device provided in an embodiment of the present invention, below reaction zone 110
Chill zone 130 is additionally provided with, the chill zone 130 is used for a product after reception preheats to carbon containing slurry and partly from anti-
Answer area 110 to be directly entered a product of chill zone 130, and an above-mentioned product is cooled down so that in chill zone 130
Water is cooled to subcritical state, and inorganic salts dissolve again in subcritical water, and solid particle can also be deposited on the bottom of chill zone 130
Portion, so as to generate secondary product and steam.Prevent phenomenon that above-mentioned transmission pipeline is blocked from occurring by above-mentioned means, it is necessary to
Illustrate, the composition of secondary product and a product is identical, including organic pollution is oxidized and oxidation product, the nothing of generation
Water under machine salt, solid particle, supercriticality, the oxygen and organic matter that are not reacted completely including part also sometimes etc., two
The difference of product of secondary product is that secondary product reclaimed water is in subcritical state (temperature is below critical point temperature).
It is understood that reaction zone 110 is the region for carrying out supercritical oxidation reaction, in the effect of supercritical water
Under, the moieties in carbon containing slurry in reaction zone 110 have extremely strong corrosivity, maintain the supercriticality institute of water in addition
Necessary high temperature and high pressure environment, cause the environment in reaction zone 110 extremely harsh.Therefore, in embodiments of the present invention, it is necessary to profit
Manufacture inwall with high temperature high voltage resistant and corrosion-resistant material (such as some nichromes etc.), by reaction zone 110 with it is overcritical
Other zone isolations in reactor come.Similarly, because a product of generation in reaction zone 110 need to enter heat transfer zone 120,
To avoid or mitigating the damage for the grade part of heat-exchanger rig 121 that the material of severe corrosive is exchanged in hot-zone 120, heat-exchanger rig 121
Also to be made up of above-mentioned high temperature high voltage resistant and corrosion-resistant material.Further, can be in the company of reaction zone 110 Yu heat transfer zone 120
Logical place sets the outlet (such as valve) of controllable switch, and the outlet is closed during supercritical oxidation reaction is carried out, with
Product of control enters the time of heat transfer zone 120, reduces the reactant entered in heat transfer zone 120, further mitigates reactant
The corrosion phenomenon for the part exchanged in hot-zone 120.
In the parameter designing of reaction zone 110, volume and ratio of height to diameter (height of reaction zone 110 and the diameter of the bottom surface of reaction zone 110
Ratio) it is more important.The specific design of volume and ratio of height to diameter is according to as follows.The volume of reaction zone 110 is by carbon containing slurry super
Residence time and supercritical reaction device in critical reaction device within the unit interval the amount of treatable carbon containing slurry determine,
It is different according to the requirement of specific Treatment of Sludge and reaction condition, the volume.In general, carbon containing slurry is in supercritical reaction
Residence time in device is 20-30s.Ratio of height to diameter need to determine according to the Flow Field Distribution in reaction zone 110, the stream in reaction zone 110
Field is generally divided into fluerics, tri- parts in recirculating zone and Guan Liuqu, fluerics substantially conical area, the summit position of conical area
In nozzle entrance, the cross section of the bottom surface substantially reaction zone 110 of conical area；In the substantially reaction zone 110 of recirculating zone, by justifying
The plane where the summit in region is bored between the bottom surface of conical area, the part in addition to conical area；Guan Liuqu, which is located at, to be penetrated
Flow the lower section of area and recirculating zone.According to reaction conditions such as the composition of carbon containing slurry and temperature and pressure, you can reasonably set
Flow Field Distribution in reaction zone 110, and then the ratio of height to diameter of reaction zone 110 is reasonably set.
For example, supercritical reaction device provided in an embodiment of the present invention is used for the processing of municipal sludge, if carbon containing slurry exists
Residence time 30s in supercritical oxidation device, the carbon containing slurry being passed through per hour in reaction zone 110 are 10 tons, in carbon containing slurry
Sludge mass fraction be 10%, then the volume of its reaction zone 110 be at least 0.6m3Left and right, it is settable more for the volume
The ratio of height to diameter of kind reaction zone 110, the ratio of height to diameter general control is 8:1-12:1, specific ratio of height to diameter needs to combine nozzle and reaction
The flow field formed in area 110 determines.
In addition, during the sludge in exchanging thermal 121 is preheated, water is changed into overcritical by normal state
State is a kind of phase transition process, and the process needs to absorb substantial amounts of heat, but temperature change is little, thus, if carbon containing slurry
The remote super critical point temperature of temperature, then it can ensure that the water in carbon containing slurry is basically completed and supercriticality be changed into by normal state
Phase transformation.Therefore, the temperature of carbon containing slurry should be made as far as possible close to above-mentioned critical point temperature before carbon containing slurry enters reaction zone 110
Degree, to ensure that the water in carbon containing slurry is basically completed above-mentioned phase transition process, the water of carbon containing slurry is avoided after reaction zone 110 is entered
Amount of heat is absorbed to carry out above-mentioned phase transformation, causes supercritical oxidation reaction can not continue to carry out.It is understood that in this hair
In bright embodiment, it can not lead to according to the amount for the carbon containing slurry being passed through in the unit interval into reaction zone 110 and a product and
Enter the factors such as the temperature of carbon containing slurry in heat-exchanger rig 121, material and heat exchange gross area of heat-exchanger rig 121 etc. be set,
The temperature reached is preheated in heat-exchanger rig 121 with the carbon containing slurry of indirect control.
It is understood that the carbon containing slurry in the present invention is not limited to be made up of sludge, for example, industry, aquaculture institute
The more mixture of caused content of organics also can supercritical reaction device provided by the present invention handled.
In supercritical reaction device provided in an embodiment of the present invention, generated using the supercritical reaction in reaction zone 110
Product, directly exchange the carbon containing slurry in hot-zone 120 in heat-exchanger rig 121 and preheated, the temperature of a product is remote
Higher than the critical point temperature of supercritical water.Therefore, exported after the cooling period with the product of the reaction of supercritical oxidation in the prior art super
Critical reaction device, preheating then is carried out to carbon containing slurry and compared, in embodiments of the present invention, even if carbon containing slurry has been preheated to
Close to or up the critical point temperature of supercritical water, the larger temperature difference is still suffered between a product and carbon containing slurry, so that
Obtaining a product can continue and promptly provide conduction heat to carbon containing slurry, and then the water improved in carbon containing slurry is preheating
During be changed into the speed of supercriticality, the efficiency of the final first supercritical processing for improving sludge by normal state.
In addition, in the prior art, needed from the product of the supercritical oxidation reaction of supercritical reaction device output through supercooling
But, therefore when being preheated using the product to carbon containing slurry, most of heat in the heat that the product carries is cooled
Process is consumed.And heat transfer zone 120 is arranged on inside supercritical reaction device by the present invention, once produced caused by reaction zone 110
The carbon containing slurry that thing is directly exchanged in thermal 121 is preheated, therefore can all use the heat entrained by a product
In the preheating of carbon containing slurry, so as to can also significantly mitigate the waste of heat energy caused by supercritical oxidation reaction.
Referring to Fig. 1, in embodiments of the present invention, heat transfer zone 120 is located at supercritical reaction device around reaction zone 110
Outer wall and reaction zone 110 between, so that the outer wall of reaction zone 110 and supercritical reaction device be separated by heat transfer zone 120, this
Sample, pass through the heat exchange between an above-mentioned product and carbon containing slurry so that the temperature of a product significantly reduces, and then to change
Temperature in hot-zone 120 is significantly lower than the temperature in reaction zone 110, and in other words, heat transfer zone 120 potentially acts as water-cooling wall, to super
The outer wall of critical reaction device is cooled.Therefore, in embodiments of the present invention, the temperature of the outer wall of supercritical reaction device is far below
Temperature in reaction zone 110, so as to mitigate high temperature to parts such as the flanges at the outer wall of supercritical reaction device and outer wall sealing
Injury, and then provided convenience condition for the selection of the device such as reactor outer wall and flange.
Further, reaction zone can be helically wrapped in as heat-exchanger rig 121, the heat exchange coil using heat exchange coil
110 peripheral (spring-likes), arrangement height (length for being similar to spring) and the reaction zone 110 of the spiral helicine heat exchange coil
It is highly consistent, namely the side wall of the whole reaction zone 110 of heat exchange coil encirclement, so that heat exchange coil can not only be from heat transfer zone
Heat is absorbed in a product in 120, additionally it is possible to heat is absorbed from the side wall of reaction zone 110, so as to improve heat exchange
The efficiency of heating surface of carbon containing slurry in coil pipe, and can enough more effectively cool to the outer wall of reaction zone 110, and then reduce high temperature
Harm to supercritical reaction device.
As a preferred scheme of above-mentioned heat-exchanger rig 121, in embodiments of the present invention, by helical form around reaction zone
The distance between adjacent heat exchange coil is referred to as gap of arranging in 110 heat exchange coil, then the arrangement gap is no more than heat exchange disk
The 1/4 of pipe external diameter, the efficiency of heat is absorbed to improve heat exchange coil to greatest extent from reaction zone 110.
Refer to Fig. 2, the embodiment of the present invention additionally provides a kind of supercritical reaction system, to carbon containing slurry
Reason, including the supercritical reaction device 100 that any of the above-described technical scheme is provided, supercritical reaction device 100 include reaction zone
110th, heat transfer zone 120 and chill zone 130, heat transfer zone 120 is interior to be provided with heat-exchanger rig 121；Wherein, heat-exchanger rig 121 is used for anti-
Answer and carbon containing slurry is imported in area 110；Reaction zone 110 is used to make carbon containing slurry carry out supercritical oxidation reaction, is once produced with generation
Thing；Heat transfer zone 120 is used to receive a product from reaction zone 110, and the heat energy contained by a product exchanges thermal 121
Interior carbon containing slurry is preheated；Chill zone 130 is used to receive a product from reaction zone 110 and heat transfer zone 120, and to once
Product is cooled down, to generate secondary product.
Relative to prior art, supercritical processing system provided in an embodiment of the present invention have the advantage that with it is above-mentioned overcritical
Reactor 100 is same relative to Dominant Facies possessed by prior art, will not be repeated here.
Referring to Fig. 2, alternatively, supercritical reaction system also includes raw material storage tank 210 and liquid oxygen tank 220, wherein, raw material
Storage tank 210 is connected by the heat-exchanger rig 121 in heat transfer zone 120 with reaction zone 110, for storing carbon containing slurry；Liquid oxygen tank 220
Connected with reaction zone 110, for storing liquid oxygen.Specifically, raw material storage tank 210 is used to store the carbon containing slurry configured, is anti-
Only the mud granule in carbon containing slurry is settled, and the device being stirred automatically, raw material storage tank are typically provided in raw material storage tank 210
High-pressure diaphragm pump can be also provided between 210 and heat-exchanger rig 121, the high-pressure diaphragm pump is used to enter reaction zone in carbon containing slurry
Before 110, carbon containing slurry is boosted into more than 25MPa, so that carbon containing slurry can smoothly enter reaction zone 110；Liquid oxygen tank 220
The liquid oxygen under high pressure conditions is inside stored, the purpose for setting liquid oxygen tank 220 is, avoids normobaric oxygen in sludge handling process
The huge energy consumption more than gas direct weighting to critical point pressure consumed.
Referring to Fig. 2, a prioritization scheme as above-mentioned technical proposal, supercritical reaction system also includes saturating with steam
Flat 310 and first water pot 320, steam turbine 310 connected with the first water pot 320 by steam heat exchanging tube, some vapor heat exchanger tube
In chill zone 130；Wherein, the first water pot 320 is used to provide evaporation liquid to steam heat exchanging tube, and steam heat exchanging tube is used to make to swash
Evaporation liquid heat exchange in a product and steam heat exchanging tube in cold-zone so that evaporation liquid is changed into steam, and steam turbine 310 is used for
Steam is received from steam heat exchanging tube, and the heat energy contained in steam is converted into mechanical energy.
Specifically, to steam heat exchanging tube offer evaporation liquid, (evaporation liquid can be the relatively low liquid of boiling point such as water to the first water pot 320
Body), steam heat-exchanging tube portion is located in chill zone 130, and evaporation liquid is in the steam heat-exchanging being located at by the part in chill zone 130
A product outside Guan Shi, with steam heat exchanging tube is exchanged heat, and forms the steam of high temperature.The steam continues through steam heat-exchanging
Pipe, is finally delivered to steam turbine 310 (can use impulse turbine), and the steam expands in nozzle, speed increase, temperature pressure
Power reduces, and is sprayed from nozzle, drives working-blade rotation, so as to obtain kinetic energy from the blade of rotation.Pass through above-mentioned means, energy
It is enough more fully to utilize the heat energy contained in a product, reduce the waste of heat energy in supercritical oxidation reaction.It is appreciated that
It is during making a product cooling in chill zone 130, according to the side for making a product and coolant hybrid cooling
Formula, then a large amount of steam can be also produced during the hybrid cooling, therefore, the gaseous phase outlet on supercritical reaction device can be passed through
And with circuits, an above-mentioned product is mixed with coolant caused by steam export chill zone, evaporated with above-mentioned evaporation liquid
Caused steam is together delivered to steam turbine 310 and is used.
Fig. 2, further is referred to, supercritical reaction system provided by the invention also includes vapor heat exchanger 410, first
The separator 430 of separator 420 and second；Vapor heat exchanger 410 includes some vapor heat exchange in heat exchanger chamber and heat exchanger chamber
Pipe, and some vapor heat exchanger tube in heat exchanger chamber be located at some vapor heat exchanger tube in chill zone and first water pot it
Between；Wherein, the first separator 420 is connected by heat exchanger chamber with chill zone 130, and the first separator 420 is used to receive and separate
Secondary product, generate gaseous product three times and three times product liquid；Second separator 430 connects with the first separator 420, is used for
To receiving and separating product liquid three times, carbon dioxide and the first pulp water are generated, vapor heat exchanger is used to make steam heat-exchanging
Evaporation liquid in pipe exchanges heat with the secondary product in heat exchanger chamber.
In the detailed process for the first supercritical processing that application supercritical reaction system provided by the invention carries out sludge, once
Product is cooled in chill zone 130, and the secondary product of generation exports discharge admittedly by the liquid on supercritical reaction device 100, and leads to
Cross and be imported into heat exchanger chamber with circuits, and then be imported into the first separator 420, connect heat exchanger chamber and the first separator 420
Pipeline on can be provided with the dropping equipment such as pressure-reducing valve orifice plate, the pressure of secondary product is down to below critical point pressure.Due to this
When secondary product still have far above usual atmospheric pressure pressure, therefore first separator 420 can be high-pressure separator it is (right
The device that the higher mixture of pressure is separated), preferably to be separated to secondary product.In first separator 420
In the presence of, secondary product is separated into gaseous product three times and three times product liquid, wherein, gaseous product includes a small amount of three times
Fuel gas, such as CO gas, hydrogen and methane, therefore after appropriate decompression, gaseous product can be made three times
Used for fuel；Product liquid then includes water, a small amount of carbon dioxide being dissolved in water and a small amount of solid residue three times.
In above process, secondary product is needed by changing in vapor heat exchanger 410 before the first separator 420 is entered
Hot cavity, due to being additionally provided with steam heat exchanging tube in heat exchanger chamber, by evaporating liquid in steam heat exchanging tube, evaporation liquid is preferably soft water
Etc. the liquid for being not easy to make pipeline produce obstruction.In vapor heat exchanger 410, the secondary product in heat exchanger chamber will be with steam heat-exchanging
Evaporation liquid heat exchange in pipe, so as to further reduce the temperature of secondary product, to carry out follow-up Pipe transfer and separation
Process etc.；Also, secondary product preheats in coolant before chill zone 130 is entered to coolant, so that coolant
There is higher initial temperature before by the steam heat exchanging tube in chill zone 130, be converted into so as to improve evaporation liquid
The efficiency of steam,
The above-mentioned product liquid three times generated in the first separator 420 enters the second separator 430, the company by pipeline
The dropping equipments such as pressure-reducing valve orifice plate can be provided with the pipeline of logical first separator 420 and the second separator 430, further to reduce
The pressure of product liquid three times, it is relatively low to be passed through the pressure of the product liquid three times of the second separator 430, therefore the second separator
430 can be low pressure separator (device that the mixture relatively low to pressure is separated), so as to this, product liquid is carried out three times
Separation.In the presence of the second separator 430, product liquid is separated into carbon dioxide and the first pulp water three times, wherein,
Carbon dioxide can be used as industrial unstrpped gas, and the first pulp water includes water and a small amount of solid residue, can discharged after filtration.
Fig. 2, the another prioritization scheme as above-mentioned technical proposal are referred to, supercritical reaction system also includes deslagging lock hopper
510, and liquid nitrogen container 520, the second water pot 530 and the 3rd water pot 540 being respectively communicated with deslagging lock hopper 510；Deslagging lock hopper 510
Connected with the chill zone 130 in supercritical reaction device 100, for receiving solid residue from chill zone 130；Liquid nitrogen container 520 is used for
Nitrogen is filled with to deslagging lock hopper 510, so that the air pressure in deslagging lock hopper 510 is equal with the air pressure in chill zone 130；Second water pot
530 also connect with chill zone 130, for when supercritical oxidation reactor is run, to the offer coolant of chill zone 130, and the
Two water pots 530 are additionally operable to when being cleaned to chill zone 130, and cleaning fluid is provided to chill zone 130 and deslagging lock hopper 510, right
Chill zone 130 and deslagging lock hopper 510 are cleaned and generate the second pulp water；3rd water pot 540 connects with deslagging lock hopper 510, uses
In reclaiming the second pulp water.Wherein：
Deslagging lock hopper 510 includes the parts such as pipe connecting flange, lining, cone cylinder, dome head and connection component.It act as clearly
The solid residue in chill zone 130 is managed, in embodiments of the present invention, deslagging lock hopper 510 may be provided at the bottom of chill zone 130,
For intermittently clearing up the solid residue in chill zone 130, lime-ash accumulation and salinity in chill zone 130 is avoided to increase
Add.In specific cleared up, liquid nitrogen container 520 need to be first passed through and be passed through high pressure nitrogen to deslagging lock hopper 510, so that deslagging lock hopper
Air pressure in 510 is equal to the air pressure in chill zone 130, chill zone 130 is connected with deslagging lock hopper 510, and pass through second
Water pot 530 provides cleaning fluid into deslagging lock hopper 510 and chill zone 130 respectively, and (cleaning fluid can be that water etc. is relatively clean
Industrial water, need to be pressurizeed by increasing apparatus such as high-pressure pumps before deslagging institute and chill zone 130 is entered, so that cleaning liquid energy
It is enough smoothly to enter chill zone 130 and deslagging lock hopper 510), the residue in deslagging lock hopper 510 and chill zone 130 is rinsed, rushed
Contain solid residue in cleaning fluid after washing, as above-mentioned second pulp water, the second pulp water is received by the 3rd water pot 540 and can be in mistake
Discharged after filter.
In addition, according to making the method that the first product mixes with coolant the first product is cooled, then it can also pass through second
Water pot 530 provides coolant to chill zone 130, to make full use of the liquid storage function of the second water pot 530, reduces supercritical reaction system
The manufacturing cost of system, it is to be understood that increasing apparatus is provided with the pipeline of the second water pot 530 and chill zone 130, with logical
Cross chill zone 130 from the second water pot 530 to supercritical reaction device provide cleaning fluid when, coolant is smoothly entered chill zone
130。
Referring to Fig. 2, further, it is preferable to liquid nitrogen container 520 also connects with reaction zone 110.It is so designed that so that face super
When supercritical oxidation reaction in boundary's reactor 100 occurs abnormal, liquid oxygen tank 220 can be made to stop conveying oxygen into reaction zone 110
Gas, and make the supplying nitrogen into reaction zone 110 of liquid nitrogen container 520, with the normal premise of air pressure in supercritical reaction device 100 is kept
Under, the oxygen in supercritical reaction device is gradually replaced with nitrogen so that supercritical oxidation reaction stops, to improve supercritical oxidation
The security of device.
Fig. 3 is referred to, present invention also offers a kind of supercritical processing methods of sludge, using any of the above-described technical side
The supercritical reaction system that case is provided, is handled carbon containing slurry, and supercritical reaction system includes supercritical reaction device, is surpassed
Critical reaction device includes reaction zone, heat transfer zone and chill zone, and heat-exchanger rig, the supercritical processing methods of sludge are provided with heat transfer zone
Including：
Step 11, by heat-exchanger rig, import carbon containing slurry in the reaction zone into supercritical reaction device.Carbon containing slurry is
Sludge and the configuration of a certain amount of water form, and after carbon containing slurry is forced into more than critical point pressure, are passed into heat-exchanger rig,
And then in reaction zone, it is to be understood that while also need to be passed through oxygen into reaction zone, with to the organic contamination in carbon containing slurry
Thing is aoxidized.
Step 12, carbon containing slurry is set to carry out supercritical oxidation reaction in reaction zone, to generate a product.Usually,
Initial carbon containing slurry temperature when entering in reaction zone is relatively low, possibly can not spontaneously start supercritical oxidation reaction, therefore,
It may need to carry out a certain degree of heating to reaction zone when initial carbon containing slurry is passed through reaction zone, so as to supercritical oxidation
Reaction is proceeded by.
Step 13, heat transfer zone receive a product from reaction zone, and the heat energy contained by a product exchanges thermal
Interior carbon containing slurry is preheated.One time product includes oxide and some the carbon containing slurries and oxygen that are not consumed etc., due to
Supercritical oxidation reaction is a kind of exothermic reaction, therefore contains substantial amounts of heat energy in a product, and step in heat-exchanger rig be present
The carbon containing slurry being passed through in rapid 11, therefore, in heat transfer zone, a product and carbon containing slurry are carried out by the tube wall of heat-exchanger rig
Heat exchange, so that the temperature of a product is risen to close to critical point temperature.
Step 14, chill zone receive a product from reaction zone and heat transfer zone, and a product are cooled down, with generation
Secondary product and steam.Normally, coolant has been passed through in chill zone, the coolant and the product entered in chill zone mix
Close, a product is cooled rapidly and generate secondary product and steam.Wherein, coolant can be a water, then secondary product bag
Water, various non-aqueous oxides and solid residue etc. are included, when steam is that a product mixes with coolant, the water in coolant
Evaporate and caused vapor, wherein containing substantial amounts of heat energy.
Relative to prior art, the supercritical processing methods of sludge provided by the invention have the advantage that with it is above-mentioned overcritical
Reaction system is same relative to Dominant Facies possessed by prior art, will not be repeated here.
Fig. 4, further is referred to, in order to further utilize the heat energy contained in a product, in the embodiment of the present invention
In, supercritical reaction system also includes steam turbine and the first water pot, and steam turbine and the first water pot are connected by steam heat exchanging tube
Logical, then the supercritical processing methods of sludge also include：
Step 21, the first water pot provide evaporation liquid to steam heat exchanging tube.It can be relative to critical point temperature boiling point to evaporate liquid
Relatively low liquid, to be evaporated using the heat energy of a product and to produce steam.
Step 22, steam heat exchanging tube make a product in chill zone be exchanged heat with the evaporation liquid in steam heat exchanging tube so that
Evaporation liquid is changed into steam.In this step, evaporation liquid obtains heat energy from a product, so as to be able to heat up and evaporate, is formed
The steam of high temperature.It is understood that a product being evaporated to evaporation liquid, can be to be directly entered chill zone by reaction zone
The product of part one time, or to carbon containing slurry preheating finish, from heat transfer zone return chill zone a product.As long as once
The temperature of product is higher than the evaporation liquid temperature degree in chill zone, you can for making evaporation liquid heat up.
Step 23, steam turbine receive steam from steam heat exchanging tube, and the heat energy contained in steam are converted into mechanical energy.
Specifically, steam is discharged by the gaseous phase outlet on supercritical reaction device, and to steam turbine, (steam turbine can by Pipeline transport
Using impulse turbine), the steam is expanded in nozzle, and speed increase, temperature, pressure is reduced, sprayed from nozzle, band is started building
Make blade rotation, so as to obtain kinetic energy from the blade of rotation, and other plant equipment are driven using the kinetic energy of the acquisition.Pass through
Above-mentioned means, the heat energy contained in steam can be recycled, the heat energy in reduction supercritical oxidation reaction entrained by steam
Waste.
Each embodiment in this specification is described by the way of progressive, same or analogous between each embodiment
Part is mutually referring to what each embodiment stressed is the difference with other embodiment.Especially for method
For embodiment, because it is substantially similar to device embodiment, so describing fairly simple, related part is implemented referring to product
The part explanation of example.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (13)
- A kind of 1. supercritical reaction device, for handling carbon containing slurry, it is characterised in that described including inner cylinder and outer barrel The circular region of inner cylinder is reaction zone, and the region formed between the bottom of the inner cylinder and the outer barrel is chill zone, described super Critical reaction device also includes heat transfer zone, and the heat transfer zone connects with the reaction zone, the chill zone respectively, in the heat transfer zone Provided with heat-exchanger rig；The heat-exchanger rig is used to import the carbon containing slurry into the reaction zone；The heat transfer zone is used for from the reaction zone A product of supercritical oxidation reaction generation is received, and the heat energy contained by a product is in the heat-exchanger rig The carbon containing slurry preheated；The chill zone connects reaction zone with heat transfer zone.
- 2. supercritical reaction device according to claim 1, it is characterised in that the heat transfer zone surround the reaction zone, and Between the outer wall and the reaction zone of the supercritical reaction device.
- 3. supercritical reaction device according to claim 1 or 2, it is characterised in that the heat-exchanger rig is heat exchange coil, institute The arrangement height that heat exchange coil is stated around the reaction zone and the heat exchange coil is highly consistent with the reaction zone.
- 4. supercritical reaction device according to claim 3, it is characterised in that the arrangement gap of the heat exchange coil is no more than The 1/4 of the heat exchange coil external diameter.
- 5. a kind of supercritical reaction system, for handling carbon containing slurry, it is characterised in that appoint including claim 1-4 Supercritical reaction device described in one, the supercritical reaction device include reaction zone, heat transfer zone and chill zone, in the heat transfer zone Provided with heat-exchanger rig；Wherein,The heat-exchanger rig is used to import carbon containing slurry into the reaction zone；The reaction zone is used to enter the carbon containing slurry Row supercritical oxidation reacts, to generate a product；The heat transfer zone is used to receive a product from the reaction zone, and The heat energy contained by a product preheats to the carbon containing slurry in the heat-exchanger rig；The chill zone be used for from The reaction zone and the heat transfer zone receive a product, and a product is cooled down, to generate secondary production Thing.
- 6. supercritical reaction system according to claim 5, it is characterised in that the supercritical reaction system also includes original Expect storage tank and liquid oxygen tank, wherein, the raw material storage tank is connected by the heat-exchanger rig in the heat transfer zone with the reaction zone, is used In the storage carbon containing slurry；The liquid oxygen tank connects with the reaction zone, for storing liquid oxygen.
- 7. the supercritical reaction system according to claim 5 or 6, it is characterised in that the supercritical reaction system is also wrapped Steam turbine and the first water pot are included, the steam turbine is connected with first water pot by steam heat exchanging tube, the part steaming Vapour heat exchanger tube is located in the chill zone；WhereinFirst water pot is used to provide evaporation liquid to the steam heat exchanging tube, and the steam heat exchanging tube is used to make the chill zone In a product and the steam heat exchanging tube in the evaporation liquid heat exchange so that it is described evaporation liquid be changed into steam, institute State steam turbine to be used to receive the steam from the steam heat exchanging tube, and the heat energy contained in the steam is converted into machinery Energy.
- 8. supercritical reaction system according to claim 7, it is characterised in that the supercritical reaction system also includes steaming Vapour heat exchanger, the first separator and the second separator；The vapor heat exchanger is included in heat exchanger chamber and the heat exchanger chamber The part steam heat exchanging tube, and the part steam heat exchanging tube in the heat exchanger chamber is located at the part in the chill zone Between the steam heat exchanging tube and first water pot；Wherein,First separator is connected by the heat exchanger chamber with the chill zone, and first separator is used to receive and divided From the secondary product, gaseous product three times and three times product liquid are generated；Second separator and first separator Connection, for receiving and separating the product liquid three times, generate carbon dioxide and the first pulp water；The vapor heat exchanger For making the evaporation liquid in the steam heat exchanging tube and the secondary product in the heat exchanger chamber exchange heat.
- 9. the supercritical reaction system according to claim 5 or 6, it is characterised in that the supercritical reaction system is also wrapped Deslagging lock hopper is included, and liquid nitrogen container, the second water pot being respectively communicated with the deslagging lock hopper；The deslagging lock hopper connects with the chill zone in the supercritical reaction device, for receiving solid from the chill zone Residue；The liquid nitrogen container is used to, when deslagging lock hopper receives the solid residue from chill zone, nitrogen is filled with to the deslagging lock hopper Gas, so that the air pressure in the deslagging lock hopper is equal with the air pressure in the chill zone.
- 10. supercritical reaction system according to claim 9, it is characterised in that second water pot also with the Quench Area connects, for when the supercritical oxidation reactor is run, coolant, and second water pot to be provided to the chill zone It is additionally operable to when being cleaned to the chill zone, cleaning fluid is provided to the chill zone and the deslagging lock hopper.
- 11. supercritical reaction system according to claim 9, it is characterised in that the liquid nitrogen container also with the reaction zone Connection, when being stopped for the supercritical reaction device, nitrogen is filled with into the reaction zone.
- 12. a kind of supercritical processing methods of sludge, it is characterised in that using overcritical described in claim any one of 5-11 Reaction system, the supercritical processing methods of the sludge include：By heat-exchanger rig, carbon containing slurry is imported into reaction zone；The carbon containing slurry is set to carry out supercritical oxidation reaction in the reaction zone, to generate a product；Heat transfer zone receives a product from the reaction zone, and the heat energy contained by a product is to the heat exchange The carbon containing slurry in device is preheated；Chill zone receives a product from the reaction zone and the heat transfer zone, and a product is cooled down, To generate secondary product.
- 13. the supercritical processing methods of sludge according to claim 12, it is characterised in that the supercritical reaction system Also include steam turbine and the first water pot, the steam turbine is connected with first water pot by steam heat exchanging tube, the dirt The supercritical processing methods of mud also include：First water pot provides evaporation liquid to the steam heat exchanging tube；The steam heat exchanging tube makes the product in the chill zone and the evaporation liquid in the steam heat exchanging tube Heat exchange so that the evaporation liquid is changed into steam；The steam turbine receives the steam from the steam heat exchanging tube, and the heat energy contained in the steam is converted into machine Tool energy.
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| WO2020156337A1 (en) * | 2019-02-03 | 2020-08-06 | 中国原子能科学研究院 | Supercritical water all-in-one machine and organic wastewater treatment method |
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