CN106334506A - Supercritical reactor and supercritical treating system - Google Patents
Supercritical reactor and supercritical treating system Download PDFInfo
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- CN106334506A CN106334506A CN201610940179.8A CN201610940179A CN106334506A CN 106334506 A CN106334506 A CN 106334506A CN 201610940179 A CN201610940179 A CN 201610940179A CN 106334506 A CN106334506 A CN 106334506A
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- inner core
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00099—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor the reactor being immersed in the heat exchange medium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
- B01J2219/00259—Preventing runaway of the chemical reaction
- B01J2219/00263—Preventing explosion of the chemical mixture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
- B01J2219/0236—Metal based
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The embodiment of the invention provides a supercritical reactor and a supercritical treating system and relates to the field of supercritical treatment. The risk that the supercritical reactor produces detonation in the starting process can be reduced. The supercritical reactor comprises an outer cylinder and an inner cylinder arranged in the outer cylinder, wherein a cooling water inlet and a material outlet are formed in the outer cylinder, the inner cylinder is made from a corrosion-resistant material, the inner wall of the inner cylinder is coated with a sacrificial layer, and the sacrificial layer is greater than the inner cylinder in high-temperature oxidation resisting capability. The supercritical treating system is used for the supercritical reactor.
Description
Technical field
The present invention relates to first supercritical processing field, more particularly, to a kind of supercritical reaction device and supercritical processing system.
Background technology
Supercritical water oxidation method treatment technology is by the use of supercritical water as medium, under high-temperature and high-pressure conditions, by waste water
Or contained Organic substance oxygen resolves into the simply nontoxic micromolecular compound such as water, carbon dioxide in sewage.Faced due to super
Boundary's water oxidation treatment technology nearly reaches 100% to contained Organic substance clearance rate in waste water or sewage, and in totally-enclosed shape
State Organic substance is fully oxidized, non-secondary pollution, and therefore, technique is increasingly subject to the attention of people.But this High Temperature High Pressure
The requirement to equipment for the reaction condition higher, and the corrosive ion containing in material can produce violent corrosion to reactor,
A variety of materials can be produced strong spot corrosion, greatly reduce service life of equipment and economy by especially chloride ion.
For solving the above problems, devise a kind of double-deck reactor of water cooled wall type in prior art, that is, internal layer is not hold
The inner sleeve of pressure, predominantly material reaction area；Outer layer plays pressure-bearing effect, leads to cooling water between outer layer and internal layer, reduces inner tube wall
Temperature.For tackling the corrosion to reactor for the chloride ion containing in material, internal layer generally selects the excellent titanium of chlorine-resistant property or titanium
Alloy makes.But find through research practice, titanium or titanium alloy can occur violent combustion under the pure oxygen environment more than 500 DEG C
Burn.Before supercritical reaction starts, generally need to introduce fuel and rise and temperature with pressure change, and in control pressure change
And during flow disturbance, the temperature of system can intermittent reduce, for making up the impact that temperature reduction causes to system, often
Fuel and combustion adjuvant (usually oxygen) is supplemented into system.Have certain hysteresis quality because temperature shows, lead to temperature to raise
Still there is excessive combustion adjuvant to supplement afterwards, make inevitably to produce a certain degree of detonation in reactor.If detonation is sent out
When life is near inner core, high temperature and the oxygen-enriched situation coexisting will be produced in this regional area, titanium or titanium alloy so can be made to occur
Vigorous oxidation or even burning, bring greater risk and loss for producing.Although by continuous to control condition in prior art
Optimize, this influence of fluctuations can be controlled within certain limits so that detonation will not occur during reactor stable operation, but in reaction
During device starts, because the temperature in reactor, pressure and oxygen content all can occur great variety, still suffer from reactor
Larger detonation risk.
Content of the invention
Embodiments of the invention provide a kind of supercritical reaction device and supercritical processing system, can reduce supercritical reaction
There is the risk of detonation in device in start-up course.
For reaching above-mentioned purpose, embodiments of the invention adopt the following technical scheme that
On the one hand, the embodiment of the present invention provide a kind of supercritical reaction device, include outer tube be arranged on described outer barrel
Inner core, described outer tube is provided with cooling water inlet and material outlet, described inner core is made up of resistant material, described inner core
Inwall on be coated with sacrifice layer, the high temperature oxidation resisting ability of described sacrifice layer is more than the high temperature oxidation resisting ability of described inner core.
Optionally, the material of described inner core is titanium or titanium alloy, and the material of described sacrifice layer is carbon steel, rustless steel or Ni-based
Alloy.
Optionally, the thickness of described sacrifice layer is 1.5mm～2.5mm.
Optionally, when the ratio of height to diameter h/d of described inner core is 2.7～3.2, the inner side of described sacrifice layer is provided with benefit in one week
Repay layer, the rational height of described layer of compensation is 0.28h～0.36h；
The high temperature oxidation resisting ability of described layer of compensation is more than the high temperature oxidation resisting ability of described inner core.
Optionally, the width of described layer of compensation is 20mm～50mm.
Optionally, the thickness of described layer of compensation is 1.4mm～2.5mm.
Optionally, the material of described inner core is titanium or titanium alloy, and the material of described layer of compensation is carbon steel, rustless steel or Ni-based
Alloy.
Optionally, described sacrifice layer is produced on the inwall of described inner core by explosion composite method.
Optionally, described inner core includes taper necking, is provided between the side wall of described outer tube and described taper necking
Distribution grid, is distributed with multiple through holes on described distribution grid, inclined with the side wall of described taper necking in the perforate direction of described through hole
Tilted direction is consistent.
On the other hand, the embodiment of the present invention provides a kind of supercritical processing system, including any one described surpassing above-mentioned
Critical reaction device.
Supercritical reaction device provided in an embodiment of the present invention and supercritical processing system, described supercritical reaction device includes outer
Cylinder and the inner core being arranged on outer barrel, outer tube are provided with cooling water inlet and material outlet, inner core is by resistant material system
Become, the inwall of inner core is coated with sacrifice layer, the high temperature oxidation resisting ability of sacrifice layer is more than the high temperature oxidation resisting ability of inner core.Phase
Compared with prior art, the embodiment of the present invention passes through to cover sacrifice layer on the inwall of the inner core of supercritical reaction device, due to sacrificing
The high temperature oxidation resisting ability of layer is more than the high temperature oxidation resisting ability of inner core, thus using the higher sacrifice layer of high temperature oxidation resisting ability
Inner core is kept apart with the oxygen enriched environment in reactor, so in supercritical reaction device start-up course, even if supercritical reaction
The local of device produces high temperature and oxygen enriched environment, and supercritical reaction device also will not occur detonation risk, that is, reduce supercritical reaction
There is the risk of detonation in device in start-up course.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, acceptable
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is a kind of structural representation of supercritical reaction device provided in an embodiment of the present invention.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation description is it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of not making creative work
Embodiment, broadly falls into the scope of protection of the invention.
The embodiment of the present invention provides a kind of supercritical reaction device, and with reference to shown in Fig. 1, described supercritical reaction device includes outer tube
1 and be arranged on inner core 2 within outer tube 1, outer tube 1 is provided with cooling water inlet 3 and material outlet 4, inner core 2 is by corrosion-resistant material
Material is made, and the inwall of inner core 2 is coated with sacrifice layer 5, and the high temperature oxidation resisting ability of sacrifice layer 5 is more than the high temperature resistant oxygen of inner core 2
Change ability.
With reference to shown in Fig. 1, during supercritical reaction device starts, high temperature resistant due to being coated with the inwall of inner core 2
The sacrifice layer 5 of oxidation, accordingly even when the local of inner core 2 creates high temperature and oxygen enriched environment, does not result in the burning of inner core 2 yet,
Thus protecting the normal operation of inner core 2.With the gradually stable operation of supercritical reaction device, the supercritical water oxidation in inner core 2
The corrosive ions such as the chloride ion in environment and oxidant can corrode to sacrifice layer 5, and sacrifice layer 5 is gradually eroded and naked
Expose inner core 2, now supercritical reaction device is stable, inner core 2 just can play its excellent decay resistance and no longer have
The danger of detonation, thus ensure that supercritical reaction device being capable of stable operation.
So, compared to prior art, the embodiment of the present invention is passed through on the inwall of the inner core of supercritical reaction device
Cover sacrifice layer, because the high temperature oxidation resisting ability of sacrifice layer is more than the high temperature oxidation resisting ability of inner core, thus using high temperature resistant
Inner core is kept apart by the higher sacrifice layer of oxidability with the oxygen enriched environment in reactor, so starts in supercritical reaction device
Cheng Zhong, even if the local of supercritical reaction device produces high temperature and oxygen enriched environment, supercritical reaction device also will not occur detonation risk,
Reduce the risk that supercritical reaction device occurs detonation in start-up course.
In actual applications, because the corrosion resistance of titanium or titanium alloy is strong, especially anti-chlorine ion corrosion performance is strong, because
And the material of inner core 2 typically selects titanium or titanium alloy, and titanium or titanium alloy under high-temperature oxygen-enriched environment, easy vigorous oxidation is even
Burning, thus the sacrifice layer 5 of high temperature oxidation resisting is covered on the inwall of inner core 2, its material is generally carbon steel, rustless steel or Ni-based
Alloy, thus protect inner core 2 to avoid its oxidation or burn.
Due to the solderable poor-performing between titanium or titanium alloy and other kinds of metal material, thus can be using blast
Sacrifice layer 5 is produced on the inwall of inner core 2 composite algorithm.Particularly as follows: inner core 2 and sacrifice layer 5 are made first with explosion composite method
It is made the composite plate structure of bilayer, then by composite plate rolling into barrel-shape, accomplish fluently groove in outer, successively weld.Due to water
The version of cold wall type is to inner core 2 no bearing requirements, thus welding and requirement of mechanical strength to inner core 2 are relatively low.In reality
In application, using interference composite algorithm, sacrifice layer 5 can also be produced on the inwall of inner core 2, the embodiment of the present invention is not made to this
Limit.
It should be noted that because sacrifice layer 5 gradually can be eroded in supercritical reaction device running, thus
Have no progeny in each long-play of supercritical reaction device, inner core 2 should be taken out, sacrifice layer is again coated on the inwall of inner core 2
5, just can put into use next time.
In supercritical reaction device running, the change due to hot-zone during supercritical reaction device internal oxidition can lead to temperature
Interval change, the degree that the sacrifice layer 5 of therefore diverse location is corroded is different.Additionally, making the material of sacrifice layer 5 not
With corrosion rate also can be otherwise varied.Consider from economy point, general selection is opened for 24 hours as supercritical reaction device
The wave time of temperature when dynamic.In this wave time section, coat completely and not exposed to ensure that inner core 2 is sacrificed layer 5, sacrificial
The material of domestic animal layer 5 typically chooses stainless steel 304 or Stainless steel 316, and its thickness is generally 1.5～2.5mm.
With reference to shown in Fig. 1, for making to corrode heavier region concentration and narrower width as far as possible, supercritical reaction in sacrifice layer 5
The ratio of height to diameter h/d of the inner core 2 of device is typically designed between 2.7～3.2.Now, in order that the diverse location of sacrifice layer 5 is corroded
Degree is more uniform, can in the inner side of sacrifice layer 5 one week setting layer of compensation 6, the rational height of layer of compensation 6 be 0.28h～
0.36h (with the side wall bottom of inner core 2 for horizontal 0 point)；The high temperature oxidation resisting ability of layer of compensation 6 is more than the high temperature resistant oxygen of inner core 2
Change ability.Layer of compensation 6 can compensate for corroding heavier region in sacrifice layer 5 so that the exposed time of inner core 2 diverse location more connects
Closely.In the case of the setting scope of the ratio of height to diameter considering supercritical reaction device, the width general control of layer of compensation 6 is in 20mm
～50mm, the thickness general control of layer of compensation 6 is in 1.4mm～2.5mm.
When the material of inner core 2 is titanium or titanium alloy, the material of layer of compensation 6 is generally carbon steel, rustless steel or nickel-base alloy.
It should be noted that the material of layer of compensation 6 can be identical with the material of sacrifice layer 5, also can be different from the material of sacrifice layer 5, this
Inventive embodiments do not limit to this.In actual applications, layer of compensation 6 is typically welded on sacrifice layer 5 using bead-welding technology.
Optionally, with reference to shown in Fig. 1, inner core 2 includes taper necking 21, between the side wall of outer tube 1 and taper necking 21
It is provided with distribution grid 7, multiple through holes, the perforate direction of described through hole and the side wall of taper necking 21 are distributed with distribution grid 7
Incline direction is consistent.
With reference to shown in Fig. 1, material is entered in the inner core 2 of supercritical reaction device by nozzle 8, and is contrary wherein
Should.Between the outer tube 1 and inner core 2 of supercritical reaction device, cooling water is imported for lowering the temperature to inner core 2 by cooling water inlet 3, and make
Outer tube 1 keeps low temperature.In inner core 2, reacted material is mixed with cooling water after taper necking 21, then by material outlet 4 row
Go out.In order to strengthen heat exchange, it is provided with distribution grid 7 between the side wall of outer tube 1 and taper necking 21, is distributed with many on distribution grid 7
Individual through hole, cooling water mixes with by the hot water that taper necking 21 is flowed out after the through hole on distribution grid 7 again.By described through hole
The setting of perforate direction is consistent with the incline direction of the side wall of taper necking 21, after so can strengthening cooling water further and reacting
Hot water between heat exchange.
Supercritical reaction device provided in an embodiment of the present invention, including outer tube and the inner core being arranged on outer barrel, on outer tube
It is provided with cooling water inlet and material outlet, inner core is made up of resistant material, the inwall of inner core is coated with sacrifice layer, sacrifice
The high temperature oxidation resisting ability of layer is more than the high temperature oxidation resisting ability of inner core.Compared to prior art, the embodiment of the present invention is passed through
Sacrifice layer is covered on the inwall of the inner core of supercritical reaction device, because the high temperature oxidation resisting ability of sacrifice layer is more than the resistance to height of inner core
Warm oxidability, thus using high temperature oxidation resisting ability higher sacrifice layer, inner core is isolated with the oxygen enriched environment in reactor
Open, so in supercritical reaction device start-up course, even if the local of supercritical reaction device produces high temperature and oxygen enriched environment, surpass and face
Boundary's reactor also will not occur detonation risk, that is, reduce the risk that supercritical reaction device occurs detonation in start-up course.
Another embodiment of the present invention provides a kind of supercritical processing system, anti-including any one described supercritical above-mentioned
Answer device.By covering sacrifice layer on the inwall of the inner core of described supercritical reaction device, due to the high temperature oxidation resisting energy of sacrifice layer
Power is more than the high temperature oxidation resisting ability of inner core, thus using the higher sacrifice layer of high temperature oxidation resisting ability by inner core and reactor
Oxygen enriched environment keep apart, so in supercritical reaction device start-up course, though supercritical reaction device local produce high temperature
And oxygen enriched environment, supercritical reaction device also will not occur detonation risk, that is, reduce supercritical reaction device and send out in start-up course
The risk of raw detonation, and then ensure that the normal operation of whole supercritical processing system.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, all should contain
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be defined by described scope of the claims.
Claims (10)
1. a kind of supercritical reaction device is it is characterised in that include outer tube and the inner core being arranged on described outer barrel, described outer tube
On be provided with cooling water inlet and material outlet, described inner core is made up of resistant material, and the inwall of described inner core is coated with
Sacrifice layer, the high temperature oxidation resisting ability of described sacrifice layer is more than the high temperature oxidation resisting ability of described inner core.
2. supercritical reaction device according to claim 1 it is characterised in that
The material of described inner core is titanium or titanium alloy, and the material of described sacrifice layer is carbon steel, rustless steel or nickel-base alloy.
3. supercritical reaction device according to claim 1 and 2 it is characterised in that
The thickness of described sacrifice layer is 1.5mm～2.5mm.
4. supercritical reaction device according to claim 1 it is characterised in that when described inner core ratio of height to diameter h/d be 2.7～
When 3.2, the inner side of described sacrifice layer is provided with layer of compensation for one week, and the rational height of described layer of compensation is 0.28h～0.36h；
The high temperature oxidation resisting ability of described layer of compensation is more than the high temperature oxidation resisting ability of described inner core.
5. supercritical reaction device according to claim 4 it is characterised in that
The width of described layer of compensation is 20mm～50mm.
6. supercritical reaction device according to claim 4 it is characterised in that
The thickness of described layer of compensation is 1.4mm～2.5mm.
7. supercritical reaction device according to claim 4 it is characterised in that
The material of described inner core is titanium or titanium alloy, and the material of described layer of compensation is carbon steel, rustless steel or nickel-base alloy.
8. supercritical reaction device according to claim 2 is it is characterised in that described sacrifice layer is made by explosion composite method
On the inwall of described inner core.
9. supercritical reaction device according to claim 1 is it is characterised in that described inner core includes taper necking, described
It is provided with distribution grid between the side wall of outer tube and described taper necking, multiple through holes, described through hole are distributed with described distribution grid
Perforate direction consistent with the incline direction of the side wall of described taper necking.
10. a kind of supercritical processing system is it is characterised in that to include supercritical described in any one in claim 1 to 9 anti-
Answer device.
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| CN201610940179.8A CN106334506B (en) | 2016-10-25 | 2016-10-25 | A kind of supercritical reaction device and supercritical processing system |
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| CN201610940179.8A CN106334506B (en) | 2016-10-25 | 2016-10-25 | A kind of supercritical reaction device and supercritical processing system |
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Citations (4)
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|---|---|---|---|---|
| US20030141301A1 (en) * | 2002-01-31 | 2003-07-31 | General Electric Crd | High temperature high pressure capsule for processing materials in supercritical fluids |
| CN101973621A (en) * | 2010-10-15 | 2011-02-16 | 西安交通大学 | Baffling tank type supercritical water treatment reactor with sacrificial lining |
| CN102751180A (en) * | 2011-04-19 | 2012-10-24 | 三星电子株式会社 | GaN film structure, method of fabricating the same, and semiconductor device including the same |
| CN103531487A (en) * | 2013-09-29 | 2014-01-22 | 南通富士通微电子股份有限公司 | Formation method of semiconductor packaging structure |
-
2016
- 2016-10-25 CN CN201610940179.8A patent/CN106334506B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030141301A1 (en) * | 2002-01-31 | 2003-07-31 | General Electric Crd | High temperature high pressure capsule for processing materials in supercritical fluids |
| CN101973621A (en) * | 2010-10-15 | 2011-02-16 | 西安交通大学 | Baffling tank type supercritical water treatment reactor with sacrificial lining |
| CN102751180A (en) * | 2011-04-19 | 2012-10-24 | 三星电子株式会社 | GaN film structure, method of fabricating the same, and semiconductor device including the same |
| CN103531487A (en) * | 2013-09-29 | 2014-01-22 | 南通富士通微电子股份有限公司 | Formation method of semiconductor packaging structure |
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| Title |
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Denomination of invention: A supercritical reactor and supercritical treatment system Effective date of registration: 20230303 Granted publication date: 20190802 Pledgee: Bank of Hebei Limited by Share Ltd. Langfang branch Pledgor: Xindi Environmental Protection Technology Co.,Ltd. Registration number: Y2023980033986 |
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