CN103087779A - Method for recycling valuable by-product by pyrolysis treatment of organic residue and inorganic residue in multihearth - Google Patents
Method for recycling valuable by-product by pyrolysis treatment of organic residue and inorganic residue in multihearth Download PDFInfo
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- CN103087779A CN103087779A CN 201110463367 CN201110463367A CN103087779A CN 103087779 A CN103087779 A CN 103087779A CN 201110463367 CN201110463367 CN 201110463367 CN 201110463367 A CN201110463367 A CN 201110463367A CN 103087779 A CN103087779 A CN 103087779A
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Abstract
The invention discloses a method for recycling a valuable by-product by pyrolysis treatment of an organic residue and an inorganic residue in a multihearth, and relates to a method for reprocessing, recycling or separating a material or a waste material by means of direct pyrolysis which is called flameless pyrolysis in the multihearth. The method is characterized in that water vapor under lower pressure is injected into at least one area of the multihearth in a controlled manner so that uniform and precise temperature distribution state can be obtained both in a gas phase and a solid phase.
Description
Technical field
The present invention relates to the pyrolysis treating method in multiple bedded furnace (four à é tages) or multiple hearth furnace (four à soles multiples), is aspect the product of processing or in the suitable control of the temperature distribution state aspect gas phase (profil) no matter it combines.This method is applicable to the direct pyrolysis that wherein burner of reactor directly contacts with the gas produced by the method.
Background technology
Known pyrolysis is a kind of thermology method of the solid residue that solid and liquid substance is converted into to gaseous compound and consists of fixed carbon and inorganic substance.
So-called directly pyrolysis refers to a kind of method of utilizing following this stove: in this stove, burner is directly installed on this stove and produces flame.
Typical multiple bedded furnace comprises a series of circular siege (soles), and they are placed in a mode on another metal shell that is coated with refractory materials.Along the axis of this stove, vertical rotating shaft in place is furnished with rake teeth with a series of
rake arm (bras), it moves furnace charge through each siege according to helical flight.Pending material is packed in the position of upper siege and is stirred
pass siege on this by the perforate towards back to back lower siege, so analogize.After all sieges of process, treated material is discharged from furnace bottom.Hot gas in this stove usually the mode with adverse current circulate, in order to furnace charge is heated to its temperature of reaction and causes desirable reaction.Heat is by the burning of material in furnace charge itself or provides by auxiliary fuel.When the needs auxiliary fuel, the burner (direct roasting) by being positioned at specific siege place or indirectly via independently combustion chamber (roasting indirectly), cause burning directly.
The applicant has developed following this method a lot of years: directly pyrolysis in multistage stove (four multi-é tag é) is then the optional burning of fixed carbon.In this case, this classification (é tag é) thermal treatment need to be reequiped traditional multiple bedded furnace, and it should have:
The arid region of-treating material;
-the heating in oxygen-lean atmosphere and the zone of pyrolytic gasification volatile matter.After pyrolysis step, product is only containing inorganic substance and fixed carbon;
The combustion zone of-fixed carbon under excess air exists.
With the indirect thermal solution, compare, this direct pyrolysis method has some advantages.At first, direct method is carried out in multiple bedded furnace, and indirect method needs the stove of other types usually, rotary kiln.Therein, in view of intrinsic risk of explosion, the existence of gaseous substance need to make the entrance and exit of reactor become inertia.And the loss of energy is larger, because need to be with gas heating casing indirectly.Be finally to stir not goodly, and be difficult to process resistates, for example oil.
Direct pyrolysis method in multiple bedded furnace can be processed the abundant residues thing, such as the mud of purifying station or STEP, industrial sludge, by industrial resistates of the compositions of mixtures of organic substance and inorganic substance etc., and in numerous European countries (Germany, France, Switzerland etc.), obtained industrial application.
In traditional pyrolysis, the flammable volatile matter produced by the method contacts with the flame of burner.What the existence of remnant oxygen caused flame spreads (moment flame) and chain reaction.May and suffer from temperature out of control aspect the product of processing aspect gas phase, the partial melting of the product that consequence is stirred or the problem of sintering, be for example the form of slag, thereby need arrestment or abandon the pyrolysis for the treatment of some product fully.
The tradition pyrolysis method has formed the theme of numerous American-European publications.
Application WO2010/142397 discloses a kind of method of metal that reclaims from the streams that is rich in hydrocarbon and carbon-containing residue by means of processing section, comprise the following steps: this streams is sent to the first processing of carrying out in one or more steps, wherein said streams under fusing assistant exists in suitable equipment, at 80-180 ℃, preferably at the temperature of 100-160 ℃, processed, Gu and carry out liquid/separation, in order to obtain product and the cake piece (oil cake piece) of the purification basically formed by liquid, optionally the cake piece separated is carried out to drying, in order to remove the hydrocarbon composition of its boiling point lower than the temperature of 300-350 ℃ from the cake piece, this cake piece of optionally drying is delivered to the second thermal treatment, it comprises: at 400-800 ℃, preferably " nonflame " pyrolysis of the cake piece of 500-670 ℃ of realization, in oxidative environment at 400-800 ℃, the oxidation of the pyrolysis residue preferably realized at the temperature of 500-700 ℃.
Application WO2010/55489 discloses a kind of method and apparatus of material (as the waste and old electric card) of the mixture for the treatment of comprising plastic material and metallic substance.The method comprises the following steps: grind pending material; The material that pyrolysis grinds; Material through pyrolysis is carried out to the first magnetic separation, provide the ferrous metal part on the one hand, and non-iron resistates is provided on the other hand; Non-iron resistates is carried out to the second magnetic separation, provide the non-ferrous metal part on the one hand, and non magnetic resistates is provided on the other hand.
Application EP843142 discloses a kind of improved equipment and a kind of method, with at multiple bedded furnace by following mode material handling effectively, incinerating waste material for example, especially dewatered sludge: the drying or the heating region that oxygen jet are injected at a high speed to stove, with for strengthening the mixing of turbulent flow gas phase, hydrocarbon with promotion in gas phase and the perfect combustion of carbon monoxide, purpose is to realize discharge still less; With the convection current on drying process strengthens mud, purpose is to improve rate of drying; And, in drying process, making sludge incineration, purpose is further to improve its dryness factor.This equipment and method can improve mud discharge and reduce carbon monoxide, oxynitride and hydrocarbon discharge.
Application EP2083954 discloses the method for a kind of processing containing the waste material of precious metal, comprises following sequential step: waste material is contacted with the composition based on fusion of lead; The mixture of removing the scum silica frost of obtained mixture and removing removing dross by electrorefining is to reclaim precious metal.
U.S. Pat 4,261,268 disclose a kind of method and apparatus of processing waste material in counter-current furnace, and wherein material is introduced and discharges at the other end at an end of stove.Air is introduced at the same time in this stove and combustion gases are processed counter-current flow with respect to material and flow out at the first end of this stove.This stove has the aptitude in a kind of formation processing zone, starts sequentially to comprise zone, the combustion zone of fixed carbon and the cooled region of ash content of arid region, charing and volatile matter burning from the first end of this stove.The method comprises the middle part from this stove, discharges substantially the step of secondary waste gas between the zone of the combustion zone of fixed carbon and charing and volatile matter burning.According to a kind of embodiment of this invention, this secondary waste gas with add the air in this stove to carry out heat exchange.
U.S. Pat 4,046,086 discloses a kind of similar approach and equipment for the treatment of comprising alkali-metal waste material.In the surface of the bed that is close to treating material, the maximum temperature in this stove is held lower than about 1400 °F (760 ℃).
U.S. Pat 4, 118, 220 disclose the method for a kind of pack processing containing the material of heavy metal and carbonaceous material, comprise the steps: by entrance, pending waste material to be incorporated in the first stove continuously, add air simultaneously in described stove, add heat waste in stove, until it is the charing state and thus material is discharged from this stove and be sent in the second device, while combustion gas from this stove, in waste material by chemical leaching from this second treatment unit, reclaim and removal heavy metal, then the remainder of this waste material is delivered in the second stove, so that remaining carbonaceous material burning in waste material, and discharge respectively ash content and waste gas from this second stove.
Summary of the invention
The present invention is intended to overcome the problem of prior art.
Especially, the present invention is intended to process again or recirculation comprises organic substance as oily complicated waste material or resistates, in order to reclaim solid matter, especially inorganic substance (matieres min é rales) as precious metal or rare earth element from it.
The present invention also aims to control the process temperature in multiple bedded furnace.
The present invention also aims to the formation of the material of the crystalline transition of the material that will process again of restriction and slag, sintering.
main characteristic key element of the present invention
The present invention relates to a kind of for processing again by the direct pyrolysis that is known as " nonflame " pyrolysis method at multiple bedded furnace, the method of recirculation or separation of material (matieres) or waste material, wherein said material is introduced respectively and is discharged at first end and second end of this stove, described stove starts sequentially to comprise arid region from this first end, cause forming the gas phase that comprises volatile matter and comprising fixed carbon and the pyrolytic gasification zone of the solid phase of inorganic substance, and optionally, fixed carbon combustion zone under excess air, the heat output of furnace charge (charge) is by being directly injected into air and auxiliary fuel in this stove and obtaining, it is characterized in that, water vapor under low pressure is injected at least one zone of this multiple bedded furnace in a controlled manner, in order to no matter be to obtain in gas phase or in solid phase evenly and the temperature distribution state (profil) of accurate (precis).
According to special or preferred mode of the present invention, the method also comprises the appropriate combination of at least two features in one of following characteristics or following characteristics:
The pressure of-the water vapor that injects is the 1-5 bar;
-the water vapor that injects is dry steam;
-the water vapor that injects is saturation steam;
-in the situation that be the pyrolysis of fixed carbon burning subsequently, this water vapor is injected into the transit site (transition) between this pyrolytic gasification zone and this fixed carbon combustion zone;
-pyrolytic gasification carries out in reducing atmosphere;
-the temperature range that contains is between 150 to 1050 ℃;
-top temperature in this stove with use same procedure but not the situation of injected water steam compare at least 100 ℃ of reductions;
-the waste material of recirculation be waste electron wiring;
-the waste material of recirculation be the mud that comprises hydrocarbon and/or metal;
-the waste material of recirculation by the mineral (min é raux) of hydrocarbon and other volatile substance pollution;
-combustion gases and cigarette (fum é es) are processed the direction counter-current flow with respect to material;
-combustion gases and cigarette are extracted in the position on the top of stove, and the material through processing again is extracted in the position of the bottom of stove;
-combustion gases and cigarette are processed the direction concurrent flow with respect to material;
-combustion gases and cigarette and the material through processing again are extracted in the position of the bottom of stove, and this pyrolysis realizes under 150-500 ℃.
Another aspect of the present invention relates to multiple bedded furnace or the multiple hearth furnace for implementing aforesaid method, roasting (cuisson) siege or the plate that comprise a series of circle, they are placed in a mode on another outer steel shell that is coated with refractory materials, and comprise vertical rotating shaft, described vertical rotating shaft is along the axis arranged of this stove and with being furnished with rake teeth
rake arm (bras), it stirs furnace charge and moves furnace charge through each siege according to helical flight, pending product provides in the position of upper siege and is stirred
pass siege on this with the perforate for by leading to back to back lower siege, so analogize until the bottom of equipment (bas), in this bottom, the product of processing is discharged from, hot combustion gas circulates with for furnace charge being heated to its temperature of reaction and causing desirable reaction in this stove, especially the drying of strengthening, directly pyrolytic gasification and optional fixed carbon burning, heat output by or the burning of the composition of furnace charge itself or the auxiliary fuel that burns in burner produce, described burner is positioned at the position of one or more specific sieges, described multiple bedded furnace is characterised in that it also comprises the injection nozzle of the water vapor under the low pressure of the position that is positioned at one or more specific sieges.
Embodiment
the description of the preferred embodiment of the present invention
The present invention relates in multiple bedded furnace by " nonflame " method that directly pyrolysis (flameless pyrolysis) is more particularly heat-treated the material, waste material or the resistates that comprise inorganic substance and organic substance.No matter this method is all to need accurately to control temperature aspect gas phase or aspect solid phase.
According to the present invention, should " nonflame " pyrolysis by the steam by under low pressure controlled and classification inject multi-layered reactors and can be accurately and control equably the temperature distribution state of solid phase prod and gas phase (é tagee).The injection of steam has stoped the spreading and the not controlled increase of temperature of burning, flame of volatile matter.
The pressure of the dry or saturated water vapor injected is advantageously the 1-5 bar.According to the result of hope, water vapor also can be injected into one or more sieges of reactor.In the situation that be the pyrolytic gasification of fixed carbon burning subsequently, this steam preferably is injected into the siege of the transitional region between pyrolysis end and fixed carbon burning beginning.
According to the present invention, should can that is to say usually with the model application of adverse current operation by " nonflame " direct pyrolysis method, cigarette is extracted in the position on the top of reactor, and solid phase prod is extracted in the position of the bottom of reactor.But, for the application of the direct pyrolysis under low temperature (typically being 150-400 ℃), the method can also be in reactor with the model application of merging maneuver.Under this particular case, the two all is extracted cigarette and solid phase prod in the position of the bottom of reactor.
Method of the present invention can effectively be processed and be rich in hydrocarbon or utmost point acred is given birth to flammable volatile matter in the process of directly pyrolysis product.
No matter this method is mud and the resistates that is rich in hydrocarbon if can advantageously being applied to, or contaminated soil, electronic waste (" electronicscrap ") or by the mineral of hydrocarbon or other volatile substance pollution.
This method allow from 150 ℃ to be greater than in the temperature range of non-constant width of 1000 ℃ and atmosphere in the unusual gas phase of reductibility work.
The pattern of the layout of burner, their adjustment and the layout of steam introducing nozzle make it possible to optimize " nonflame " pyrolysis at the center of many sieges reactor.
Than direct traditional pyrolysis, the temperature distribution state obtained by this " nonflame " pyrolysis clearly illustrates that reasonableness of the present invention and its can be applicable to numerous resistatess and byproduct so that their increments.
embodiment 1: the mixture (table 1) of metal, glass fibre and epoxy resin
The purpose of processing is that metal and glass fibre are discharged from their epoxy substrate.The method is " nonflame " pyrolysis under low temperature.Table 1 provides the contrast between this " nonflame " pyrolysis and traditional pyrolysis.Can see, the method according to this invention can be avoided rising suddenly of temperature in time.
Excessive (or λ) expression minimum air capacity (or stoichiometry) required with perfect combustion of air compared excessive air capacity.Under reducing atmosphere, thereby lacking under air (λ<1) work at this.
Except this " nonflame " pyrolysis, can not control the temperature of gas phase and the temperature of solid phase inevitably, and this causes sintering and fusing in solid phase.
embodiment 2: mixed the processing (table 2) of the metal of oil and water
The purpose of processing is the temperature that discharges metal (for example, the oxide compound of tungsten) and again control gas phase, to avoid solid-state temperature, does not controllably raise.In logical snperoxiaized traditional method, temperature rises suddenly along with emitting of volatile matter.Fixed carbon is encapsulated by the covering of volatile matter.This method has been brought cooling problem.
Be somebody's turn to do " nonflame " pyrolysis and can accurately control the temperature of gas phase and solid phase.
embodiment 3: by the sludge treatment (table 3) of pyrolysis and fixed carbon burning
In the stove that for example has 6 sieges, the steam under the pressure of 2.5 bar is injected in siege 3.This steam enters just step-down fully of reactor from it.Should " nonflame " pyrolysis make it possible to be controlled in the transitional region between pyrolysis and fixed carbon burning, that is to say the temperature (Tfg) of gas phase of the position (referring to the grey of table 3) of siege 3 in the present circumstance.Do not measure the temperature of the solid phase prod stirred at this.The injection of steam make it possible to furnace charge reduce 100-150 ℃ temperature and thereby the risk of gas phase sintering (formation slag) is down to minimum, shown as following example.
table 1
The tradition pyrolysis
| Time (minute) | Temperature (℃) | λ |
| 0 | 552 | 0.87 |
| 17 | 741 | 0.97 |
| 35 | 732 | 0.73 |
| 50 | 713 | 0.73 |
" nonflame " pyrolysis (the present invention)
| Time (minute) | Temperature (℃) | λ |
| 0 | 643 | 0.72 |
| 10 | 547 | 0.75 |
| 20 | 576 | 0.77 |
| 30 | 542 | 0.74 |
| 40 | 514 | 0.71 |
table 2
The tradition pyrolysis
| Time (minute) | Temperature (℃) | λ |
| 0 | 559 | 0.67 |
| 15 | 542 | 069 |
| 30 | 637 | 0.75 |
| 60 | 713 | 0.74 |
| 90 | 737 | 0.61 |
" nonflame " pyrolysis (the present invention)
| Time (minute) | Temperature (℃) | λ |
| 0 | 670 | 0.54 |
| 30 | 559 | 0.77 |
| 45 | 587 | 0.77 |
| 60 | 594 | 0.74 |
| 90 | 581 | 0.74 |
Claims (16)
1. for processing again by the direct pyrolysis that is known as " nonflame " pyrolysis method at multiple bedded furnace, the method of recirculation or separation of material or waste material, wherein said material is introduced respectively and is discharged at first end and second end of this stove, described stove starts sequentially to comprise arid region from this first end, cause forming the gas phase that comprises volatile matter and comprising fixed carbon and the pyrolytic gasification zone of the solid phase of inorganic substance, and optionally, fixed carbon combustion zone under excess air, wherein the heat output of furnace charge is by being directly injected into air and auxiliary fuel in this stove and obtaining, it is characterized in that, water vapor under low pressure is injected at least one zone of this multiple bedded furnace in a controlled manner, in order to no matter be to obtain even and accurate temperature distribution state in gas phase or in solid phase.
2. the method for claim 1, is characterized in that, the pressure of the water vapor injected is the 1-5 bar.
3. the method for claim 1, is characterized in that, the water vapor injected is dry steam.
4. the method for claim 1, is characterized in that, the water vapor injected is saturation steam.
5. the method for claim 1, is characterized in that, in the situation that be the pyrolysis of fixed carbon burning subsequently, this water vapor is injected into the transit site between this pyrolytic gasification zone and this fixed carbon combustion zone.
6. the method for claim 1, is characterized in that, pyrolytic gasification carries out in reducing atmosphere.
7. the method for claim 1, is characterized in that, the temperature range contained is between 150 to 1050 ℃.
8. the method for claim 1, is characterized in that, the top temperature in this stove with use same procedure but not the situation of injected water steam compare at least 100 ℃ of reductions.
9. the method for claim 1, is characterized in that, the waste material of recirculation is waste electron wiring.
10. the method for claim 1, is characterized in that, the waste material of recirculation is the mud that comprises hydrocarbon and/or metal.
11. the method for claim 1, is characterized in that, the waste material of recirculation by the mineral of hydrocarbon and other volatile substance pollution.
12. the method for claim 1, is characterized in that, combustion gases and cigarette are processed the direction counter-current flow with respect to material.
13. the method for claim 12, is characterized in that, combustion gases and cigarette are extracted in the position on the top of stove, and the material through processing again is extracted in the position of the bottom of stove.
14. the method for claim 1, is characterized in that, combustion gases and cigarette are processed the direction concurrent flow with respect to material.
15. the method for claim 14, is characterized in that, combustion gases and cigarette and the material through processing again are extracted in the position of the bottom of stove, and this pyrolysis realizes under 150-500 ℃.
16. multiple bedded furnace or multiple hearth furnace for the method for implementing the claims any one, the roasting siege or the plate that comprise a series of circle, they are placed in a mode on another outer steel shell that is coated with refractory materials, and comprise vertical rotating shaft, described vertical rotating shaft is along the axis arranged of this stove and with the rake arm of being furnished with rake teeth, it stirs furnace charge and moves furnace charge through each siege according to helical flight, wherein pending product provides in the position of upper siege and is stirred with the perforate for by leading to back to back lower siege and pass siege on this, so analogize until the bottom of equipment, in this bottom, the product of processing is discharged from, hot combustion gas circulates with for furnace charge being heated to its temperature of reaction and causing desirable reaction in this stove, especially the drying of strengthening, directly pyrolytic gasification and optional fixed carbon burning, heat output by or the burning of the composition of furnace charge itself or the auxiliary fuel that burns in burner produce, described burner is positioned at the position of one or more specific sieges, described multiple bedded furnace is characterised in that it also comprises the injection nozzle of the water vapor under the low pressure of the position that is positioned at one or more specific sieges.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110463367 CN103087779A (en) | 2011-11-04 | 2011-11-04 | Method for recycling valuable by-product by pyrolysis treatment of organic residue and inorganic residue in multihearth |
| PCT/EP2012/070414 WO2013057073A1 (en) | 2011-10-21 | 2012-10-15 | Pyrolytic method for processing organic and inorganic residues in multiple-hearth furnace for recovering useful by-products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110463367 CN103087779A (en) | 2011-11-04 | 2011-11-04 | Method for recycling valuable by-product by pyrolysis treatment of organic residue and inorganic residue in multihearth |
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| CN103087779A true CN103087779A (en) | 2013-05-08 |
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| CN 201110463367 Pending CN103087779A (en) | 2011-10-21 | 2011-11-04 | Method for recycling valuable by-product by pyrolysis treatment of organic residue and inorganic residue in multihearth |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347634A (en) * | 2015-10-26 | 2016-02-24 | 徐明好 | Designing method of sludge processing apparatus and apparatus thereof |
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2011
- 2011-11-04 CN CN 201110463367 patent/CN103087779A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347634A (en) * | 2015-10-26 | 2016-02-24 | 徐明好 | Designing method of sludge processing apparatus and apparatus thereof |
| CN105347634B (en) * | 2015-10-26 | 2017-08-25 | 徐明好 | The design method and its device of a kind of sludge treatment equipment |
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Application publication date: 20130508 |