CN102557229A - Constant volume internal combustion type supercritical fluid oxidation device and oxidation method thereof - Google Patents
Constant volume internal combustion type supercritical fluid oxidation device and oxidation method thereof Download PDFInfo
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Abstract
The invention relates to a constant volume internal combustion type supercritical fluid oxidation device and an oxidation method thereof. According to the constant volume internal combustion type supercritical fluid oxidation device, a fuel input pipe and an oxidant input pipe penetrate through a reactor shell, an inorganic polymer and a reactor liner and is communicated with a reactor inner cavity; a discharge pipe and a safety valve are arranged on the lower part of a phase separator; and an upper thermometer, a lower thermometer and a pressure gauge are arranged in the reactor inner cavity. According to the constant volume internal combustion type supercritical fluid oxidation device, a reactor is heated and pressurized in a constant volume internal combustion mode, so that various reaction regulators are added easily, energy consumption is reduced, harmful organic matters are treated harmlessly, and the problems of quick corrosion of materials on the inner wall surface of the reactor, salt attachment to a reaction flow path and the inner wall of the reactor, high equipment cost and running cost and the like in the conventional supercritical water oxidation technology which cannot solve the problems are solved radically. Compared with the prior art, the constant volume internal combustion type supercritical fluid oxidation device has the advantages of simple structure of the reactor, wide treatment range, high efficiency, no secondary pollution, energy conservation, high possibility of separating inorganic salt and the like.
Description
Technical field:
The present invention relates to a kind of supercutical fluid oxide treatment harmful organic substances technology; Especially the efficient generation of the mixture of supercritical water and supercritical co and use the method for this supercutical fluid oxide treatment harmful organic substances; Specifically relate to come subcritical water in the heating and pressurizing constant volume container, oxygenant and harmful organic substance, make the temperature and pressure of these materials surpass stagnation point (temperature＞374 ℃ of water with the mode of internal combustion; Pressure＞22.1MPa).
Background technology:
(supercritical water oxidation, SCWO) technology is to handle the very effective technology of liquid harmful organic substances to supercritical water oxidation.M.D.Bermejo and M.J.Cocero (Supercritical Water Oxidation:A Technical Review; AIChE is (2006) 3933-3951 J.52) to have summarized this technology and can efficiently handle harmful organic substances (like utmost point poisonous substance matter PCBs) up hill and dale and can reach 99.9999% with interior rate of decomposition at 60 seconds, this is that existing other treatment technologies are beyond one's reach.But; Because common small-sized intermittent type (Batch system); Like Veriansyah Bambang; Kim Jae-duck (Supercritical water oxidation for the destruction of toxic organic wastewaters:A Review; J.of Environmental Sciences19 (2007) 512-522) said, such SCWO treatment system is to come the material in the heating container to make it the stagnation point that increasing temperature and pressure surpasses water through indirect heating constant volume reactor drum, and oxygenant under the environment of supercritical water in the container and harmful organic substance reaction reach innoxious.This will ask the wall surface material of reactor drum promptly will have the high heat transfer function to have highly corrosion resistant again, high withstand voltage function.
Philip A.Marrone; Glenn T.Hong (Review:Corrosion control methods in superitical water oxidation and gasification processes, J.of Supercritical Fluids 51 (2009) 83-103) spells out does not also have a kind of material to have all these functions till now.In addition, the salt of organic oxidation generation can be separated out attached to increasing wall surface material corrosion and thermal conduction resistance on the reaction vessel.
In addition; Continous way (Continuous flow system) SCWO treatment system is that (Transpiring wall reactor is to come the reacting by heating material with internal combustion like B.Wellig et al. (Hydrothermal methanol diffusion flame as internal heat source in a SCWO reactor J.of Supercritical Fluids49 (2009) 59-70) TWR) for habitual level pressure external heating mode (like the SUWOX of Germany) or level pressure infiltration wall formula.But this must use a plurality of high energy consumption HPPs all participation RMs (fuel, oxygenant, organic liquor, water etc.) of pumping under overcritical pressure (being higher than 25MPa), although available liquid oxidizer is (like H
2O
2) directly join and reduce HPP in the organic liquor and use number, but this to make during heating organism and oxidant reaction generate salt be very expensive (like H attached to the price of minimizing pre-heat effect and liquid oxidizer on the inwall of stream and the reactor wall
2O
2Price can be high and tens times of oxygen).These continuous reaction systems prevent adhering to of serious corrosion and salt to have used a large amount of pure water to separate reaction product and reactor wall and increase the problem of separating out of the solubleness control salt of salt with very high WP, and being to use WP like S.Baur et al. (The destruction of industrial aqueous waste containing biocides in supercritical water:development of the SUWOX process for the technical application J.of Supercritical Fluids33 (2005) 149-157) is 70MPa.The price of HPP is that the maximum pumpage with HPP is similar to exponential relationship, and it is too high that this just makes existing supercritical water oxidation handle the cost of liquid harmful organic substances.Particularly the enforcement of extensiveization is very difficult.
CN1730414 discloses " a kind of method of using supercritical water oxidation to handle waste water ", is that waste water is forced into 22.1-30MPa, is preheated to 300-370 ℃; Under the condition that keeps uniform pressure, the input of the waste water after preheating desalination plant is warming up to 450-650 ℃ carries out desalination; To contain oxidant fluid and be forced into 22.1-30MPa; Be warming up to 550-650 ℃; Contain oxidant fluid by the oxygenant molar weight be the theoretical aerobic molar weight of organism complete oxidation 2-6 doubly with step (2) desalination after waste water be mixed into the supercritical reaction device, controlled temperature is 550-650 ℃, pressure is 22.1-30MPa; The residence time is 10-40 second, carries out supercritical water oxidation.
CN101182065 discloses " a kind of vinylformic acid is produced the method that the middle and high concentration organic wastewater is handled " (1) and oxygenant and deionized water has been hybridly prepared into oxidizing agent solution, and places in the oxygenant jar; (2) acrylic acid production waste water and clear water are placed respectively in waste water and the clear water jar, and in waste water, add catalyzer; (3) at first preheater is heated to 300-400 ℃, reactor drum is heated to 400-600 ℃; (4) open the high pressure plunger pump sample introduction; Waste water and oxidizing agent solution get in the reactor drum micropore ceramic tube after preheating, pressurization respectively; Under 374 ℃-600 ℃ of pressure 22-28MPa and temperature, carry out supercritical water oxidation, clear water is by in the ceramic membrane outer wall infiltration into microporous vitrified pipe; (5) treat effluent can realize qualified discharge after cooling and gas-liquid separation.
CN101928080A disclose " a kind of supercritical water oxidation treatment method of high concentrated organic wastewater " comprise boost, process such as preheating, supercritical water oxidation.Content through cl ions and salt in the qualification waste water stops up equipment corrosion and pipeline and is controlled in the scope that can bear; The COD concentration of control waste water makes oxidizing reaction reach reaction self-heating.
Above-mentioned existing technology all is operation under high-temperature and high-pressure conditions, and treatment facility is difficult to maximize.When hanging down PH, under the condition that especially cl ions exists, equipment corrosion is serious, and general material is difficult to satisfy equipment requirements.Salt in the supercritical water oxidation process in the equipment is almost all separated out, and causes the obstruction of pipeline easily, causes equipment to move continuously.
Summary of the invention:
The object of the invention just is the deficiency to above-mentioned prior art, and a kind of constant volume internal combustion type supercutical fluid oxidizer unit is provided;
Another object of the present invention just is to provide a kind of method for oxidation of constant volume internal combustion type supercutical fluid oxidizer unit.
The objective of the invention is to realize through following technical scheme:
Constant volume internal combustion type supercutical fluid oxidizer unit; Be to pass shell of reactor 14, geopolymer 15 and reactor inner container 17 by fuel inlet pipe 1 through fuel under high pressure volume pump 2 and fuel transfer valve 3 to communicate with reactor drum inner chamber 12, and fixing with reactor inner container 17 with shell of reactor 14 welding; Oxygenant input tube 4 passes shell of reactor 14, inorganic polymer 15 and reactor inner container 17 through oxygenant transfer valve 5 and communicates with reactor drum inner chamber 12, and fixing with shell of reactor 14 welding with reactor inner container 17; Organic liquid waste input tube 10 passes shell of reactor 14, geopolymer 15 and reactor inner container 17 through high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8 and communicates with reactor drum inner chamber 12, and fixing with shell of reactor 14 welding with reactor inner container 17; The top of phase separator 24 is passed shell of reactor 14, geopolymer 15 and reactor inner container 17 through pipeline through reactant outlet valve 18 or SV 19 respectively and is communicated with reactor drum inner chamber 12 bottoms, and fixing with shell of reactor 14 welding with reactor inner container 17; Outlet valve 25 and vent pipe 26 are equipped with in the bottom of phase separator 24; The upper side of phase separator 24 links to each other with gas-liquid separator 22 with reducing valve 20 through pipeline; Gas-liquid separator 22 tops are provided with gas outlet pipe 21; Gas-liquid separator 22 bottoms are provided with liquid discharge tube 23; Upper temp meter 11 is equipped with on reactor drum inner chamber 12 tops, and temperature of lower meter 13 is equipped with in reactor drum inner chamber 12 bottoms, and reactor drum inner chamber 12 middle parts are equipped with pressure warning unit 16 and are constituted.
On the fuel inlet pipe 1 of fuel transfer valve 3 bottoms, fuel heater 6 is housed, organic liquid waste well heater 7 is housed at the front end of organic liquid waste transfer valve 8.
Fuel heater 6 is solar heater or electric heater with organic liquid waste well heater 7.
Between reactor inner container 17 and the shell of reactor 14 apart from 0.3--10cm; Filling geopolymer 15 between reactor inner container 17 and the shell of reactor 14, geopolymer (Geopolymer) 15 can be made up of a series of inorganic polymer, usually can be by alukalin (metakaolin); Fine grinding water-granulated slag, flyash; Alkali (KOH), sodium silicate and water are formed, with the above-mentioned materials mixing of weighing by a certain percentage; Be poured between reactor inner container 17 and the shell of reactor 14 after being stirred into slurry, form material high temperature resistant, high pressure resistant, anticorrosive and that have good heat-proof quality through the maintenance sclerosis.The pressure that reactor inner container 17 is born passes to shell of reactor 14 effectively.The geopolymer proportioning by weight ratio that the present invention selects for use is: alukalin: fine mill slag: alkali: sodium silicate: water=80: 10: 6: 17: 21; Or fine mill slag: alkali: sodium silicate: water=125: 8: 21: 52; Or fine mill slag: flyash: alkali: sodium silicate: water=150: 100: 16: 43: 53, alkali re-used after will water-solublely in advance processing solution.
The preferred KOH of described alkali, NaOH, K
2CO
3Or Na
2CO
3
The starting material that adopt are: I level flyash, slag are the S105 levels, and the modulus of water glass is 2.8.
The method for oxidation of constant volume internal combustion type supercutical fluid oxidizer unit comprises following order and step:
A, at first close fuel transfer valve 3, organic liquid waste transfer valve 8, reactant outlet valve 18 and SV 19; After reactor drum inner chamber 12 injects the 0.3-0.5MPa oxygenant, close oxygenant transfer valve 5 through oxygenant input tube 4 and oxygenant transfer valve 5, stop oxygenant and inject;
B, open organic liquid waste transfer valve 8; Inject organic liquid waste through organic liquid waste input tube 10 and high pressure organic liquid waste volume pump 9 to reactor drum inner chamber 12; When the pressure of reactor drum inner chamber (12) reaches 5-8MPa, close high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8, stop organic liquid waste and inject; , heat to organic liquid waste to the process that reactor drum inner chamber 12 injects at organic liquid waste through organic liquid waste well heater 7;
D, open fuel transfer valve 3; Inject fuel through fuel inlet pipe 1 and fuel under high pressure volume pump 2 to reactor drum inner chamber 12; In the process of fuel to 12 injections of reactor drum inner chamber; Be heated to above 500 ℃ through well heater 6 to fuel, inject fuel spontaneous ignition under the help of oxygenant of reaction vessel inner chamber 12;
E, the response behaviour of keeping watch on the material in the reactor drum inner chambers 12 through upper temp meter 11, temperature of lower meter 13 and pressure warning unit 16; Temperature in reactor drum inner chamber 12, pressure have surpassed the stagnation point of water; To be upper temp meter 11 with the temperature of temperature of lower meter 13 all reach is higher than 500 ℃; Close fuel under high pressure volume pump 2 and fuel transfer valve 3 when the pressure of pressure warning unit 16 reaches 30MPa-40MPa, stop fuel feed, kept 30 seconds;
F, open the safety-valve 19 then; Give the reactor drum inner chamber 12 decompressions,, open reactant outlet valve 18 when the pressure of reactor drum inner chamber 12 drops to 20MPa closed safe valve 19 when following; Let the material in the reactor drum inner chamber 12 spray into phase separator 24, make solid salt and fluid separation;
G, open reducing valve 20 fluids and get into gas-liquid separator 22, gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe 21
2O discharges through liquid discharge tube 23;
H, open outlet valve 25 at last, contain saline solution and discharge through vent pipe 26, use TOC (Total organic carbon) analysis meter (Sievers InnovOx Lab) to measure discharge opeing, the TOC transformation efficiency is higher than 99.3%.
Described oxygenant is an oxygen.
Described fuel is methanol aqueous solution (28wt%CH
3OH+72wt%H
2O) self-ignition temperature of fuel is less than 500 ℃.
The benefit effect: the present invention supplies with oxygen and supplies with organic liquor at the low pressure downhill reaction device of 2.0-5.0MPa to the constant volume reactor drum under the low pressure of 0.3-0.5MPa; Fuel is pumped in the reaction vessel and the oxygen mix burning with high pressure measurement, makes material in the reactor drum surpass stagnation point (temperature＞374 ℃ of water; Pressure＞22.1MPa).The energy consumption of material from the subcritical state to the supercritical state reduced significantly in the reactor drum, and this makes that the running cost of device is reduced significantly.Reactor inner container 17 of the present invention adopts the alloy625 steel alloy of heat-and corrosion-resistant; Geopolymer 15 is heat insulation transmission pressure material; Shell of reactor 14 adopts the SS316 stainless steel; Satisfy high temperature resistant, corrosion-resistant, heat insulation and high voltage bearing requirement, also make the manufacturing cost of device reduce significantly simultaneously.Because reactor drum is a constant volume internal combustion type heating and pressurizing, even there is the salt of separating out can not produce big influence to rate of heating in adhering to also of inner-wall surface.Various reaction adjustment agent are added in the easy mass-producing of such reactor drum easily.This is that existing supercritical water oxidation treatment technology is not available.Use energy consumption of the present invention low, efficient is high, harmless treatment completely harmful organic substances.Solved three problems in the existing supercritical water oxidation technology: the corrosion of (1) reactor wall flooring is too fast; (2) reaction stream and reactor wall salt adheres to; (3) the too high problem of equipment cost and running cost.Compared with prior art, the present invention has advantages such as structure of reactor is simple, and process range is wide, and efficient is high, and non-secondary pollution is saved the energy, and inorganic salt are easily separated.
Description of drawings:
Accompanying drawing is a constant volume internal combustion type supercutical fluid oxidizer unit structure iron
1 fuel inlet pipe, 2 petrolifts, 3 fuel transfer valves, 4 oxygenant input tubes, 5 oxygenant transfer valves, 6 fuel heaters; 7 organic liquid waste well heaters, 8 organic liquid waste transfer valves, 9 organic liquid waste front pumps, 10 organic liquid waste input tubes, 11 upper temp meters; 12 reactor drum inner chambers, 13 temperature of lower meters, 14 shell of reactor, 15 inorganic polymers, 16 pressure warning units; 17 reactor inner container, 18 reactant outlet valves, 19 SV, 20 reducing valve, 21 gas outlet pipes; 22 vapour liquid separators, 23 liquid discharge tubes, 24 phase separators, 25 outlet valves, 26 vent pipes
Embodiment:
Do further detailed description below in conjunction with accompanying drawing and embodiment:
Embodiment 1
Constant volume internal combustion type supercutical fluid oxidizer unit; Be to pass shell of reactor 14, geopolymer 15 and reactor inner container 17 by fuel inlet pipe 1 through fuel under high pressure volume pump 2 and fuel transfer valve 3 to communicate with reactor drum inner chamber 12; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Oxygenant input tube 4 passes shell of reactor 14, geopolymer 15 and reactor inner container 17 through oxygenant transfer valve 5 and communicates with reactor drum inner chamber 12; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Organic liquid waste input tube 10 passes shell of reactor 14, geopolymer 15 and reactor inner container 17 through high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8 and communicates with reactor drum inner chamber 12, and fixing with shell of reactor 14 welding with reactor inner container 17, and the top of phase separator 24 is passed shell of reactor 14, geopolymer 15 and reactor inner container 17 through pipeline through reactant outlet valve 18 and SV 19 respectively and communicated with reactor drum inner chamber 12 bottoms; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Vent pipe 26 and outlet valve 25 are equipped with in the bottom of phase separator 24, and the upper side of phase separator 24 links to each other with gas-liquid separator 22 with reducing valve 20 through pipeline, and gas-liquid separator 22 tops are provided with gas outlet pipe 21; Gas-liquid separator 22 bottoms are provided with liquid discharge tube 23; In the reactor drum, upper temp meter 11 is equipped with on 12 tops, and upper temp meter 11 links to each other with reactor drum is outside through the outer wall of lead along oxygenant input tube 4; Temperature of lower meter 13 is equipped with in reactor drum inner chamber 12 bottoms, and temperature of lower meter 13 links to each other with reactor drum is outside through the outer wall of lead along the reactant vent pipe; Pressure warning unit 16 is equipped with at reactor drum inner chamber 12 middle parts, and pressure warning unit 16 is through the outer wall and reactor drum outside link to each other formation of lead along organic liquid waste input tube 10.
On the fuel inlet pipe 1 of fuel transfer valve 3 bottoms, fuel heater 6 is housed, organic liquid waste well heater 7 is housed at the front end of organic liquid waste transfer valve 8.Fuel heater 6 is an electric heater with organic liquid waste well heater 7.Reactor inner container 17 adopts the alloy625 steel alloy of heat-and corrosion-resistant, and shell of reactor 14 adopts the SS316 stainless steel.Between reactor inner container 17 and the shell of reactor 14 apart from 2cm, the geopolymer Geopolymer between reactor inner container 17 and the shell of reactor 14) be to mix by 800g alukalin, 200g fine mill slag, 60gKOH, 170g sodium silicate, 210g water to constitute; Through being stirred into the slurry after-pouring between reactor inner container 17 and the shell of reactor 14; Form high temperature resistant, high pressure resistant, anticorrosive and have the inorganic materials of good heat-proof quality through maintenance sclerosis; The pressure that reactor inner container 17 is born passes to shell of reactor 14 effectively; Through test, ultimate compression strength is 65MPa.In advance KOH is processed the aqueous solution re-uses.
The method for oxidation of constant volume internal combustion type supercutical fluid oxidizer unit comprises following order and step:
A, at first close fuel transfer valve 3, organic liquid waste transfer valve 8, reactant outlet valve 18 and SV 19; Inject the oxygen of 0.5MPa to reactor drum inner chamber 12 through oxygenant input tube 4 and oxygenant transfer valve 5; After close oxygenant transfer valve 5, stop oxygen and inject; SV 19 WPs are 60MPa;
B, open organic liquid waste transfer valve 8; Is the phenol organic liquid waste of 1wt.% through organic liquid waste input tube 10 to reactor drum inner chamber 12 implantation concentrations with high pressure organic liquid waste volume pump 9;, the pressure of reactor drum inner chamber (12) closes organic liquid waste transfer valve 8 when reaching 5MPa; Stop the organic liquid waste input, to the process that input reactor inner chamber 12 injects, be heated to 350 ℃ to organic liquid waste through organic liquid waste well heater 7 at organic liquid waste; High pressure organic liquid waste volume pump (NP-KX-720: peak pressure 10MPa; 0.2-200ml/min)
C, open fuel transfer valve 3; Inject methanol aqueous solution through fuel inlet pipe 1 and fuel under high pressure volume pump 2 to reactor drum inner chamber 12; Inject the process of methanol aqueous solution to reactor drum inner chamber 12 at fuel under high pressure volume pump 2; Be heated to above 500 ℃ through well heater 6 to methanol aqueous solution, inject methanol aqueous solution spontaneous ignition burning under the help of oxygen of reaction vessel inner chamber 12; Fuel under high pressure volume pump 2 (NP-KX-520: maximum 60MPa; 0.2-20ml/min)
D, the response behaviour of keeping watch on the material in the reactor drum inner chambers 12 through upper temp meter 11, temperature of lower meter 13 and pressure warning unit 16; Temperature, pressure in reactor drum inner chamber 12 has surpassed the stagnation point of water; The temperature that is upper temp meter 11 and temperature of lower meter 13 all is higher than 500 ℃; The pressure of pressure warning unit 16 is closed fuel under high pressure volume pump 2 and fuel transfer valve 3 after being higher than 30MPa, stops methanol aqueous solution and supplies with, and keeps 30 seconds;
E, open the safety-valve 19 then; Give the reactor drum inner chamber 12 decompressions,, open reactant outlet valve 18 when the pressure of reactor drum inner chamber 12 drops to 20MPa closed safe valve 19 when following; Let the material in the reactor drum inner chamber 12 spray into phase separator 24, make solid salt and fluid separation;
F, open reducing valve 20 fluids and get into gas-liquid separator 22, gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe 21
2O discharges through liquid discharge tube 23;
G, open outlet valve 25 at last, contain saline solution and discharge through vent pipe 26, use TOC (Total organic carbon) analysis meter (Sievers InnovOx Lab) to measure discharge opeing, the TOC transformation efficiency is higher than 99.5%.
Embodiment 2
Constant volume internal combustion type supercutical fluid oxidizer unit; Be to pass shell of reactor 14, geopolymer 15 and reactor inner container 17 by fuel inlet pipe 1 through fuel under high pressure volume pump 2 and fuel transfer valve 3 to communicate with reactor drum inner chamber 12; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Oxygenant input tube 4 passes shell of reactor 14, geopolymer 15 and reactor inner container 17 through oxygenant transfer valve 5 and communicates with reactor drum inner chamber 12; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Organic liquid waste input tube 10 passes shell of reactor 14, geopolymer 15 and reactor inner container 17 through high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8 and communicates with reactor drum inner chamber 12, and fixing with shell of reactor 14 welding with reactor inner container 17, and the top of phase separator 24 is passed shell of reactor 14, geopolymer 15 and reactor inner container 17 through pipeline through reactant outlet valve 18 and SV 19 respectively and communicated with reactor drum inner chamber 12 bottoms; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Vent pipe 26 and outlet valve 25 are equipped with in the bottom of phase separator 24, and the upper side of phase separator 24 links to each other with gas-liquid separator 22 with reducing valve 20 through pipeline, and gas-liquid separator 22 tops are provided with gas outlet pipe 21; Gas-liquid separator 22 bottoms are provided with liquid discharge tube 23; In the reactor drum, upper temp meter 11 is equipped with on 12 tops, and upper temp meter 11 links to each other with reactor drum is outside through the outer wall of lead along oxygenant input tube 4; Temperature of lower meter 13 is equipped with in reactor drum inner chamber 12 bottoms, and temperature of lower meter 13 links to each other with reactor drum is outside through the outer wall of lead along the reactant vent pipe; Pressure warning unit 16 is equipped with at reactor drum inner chamber 12 middle parts, and pressure warning unit 16 is through the outer wall and reactor drum outside link to each other formation of lead along organic liquid waste input tube 10.
On the fuel inlet pipe 1 of fuel transfer valve 3 bottoms, fuel heater 6 is housed, organic liquid waste well heater 7 is housed at the front end of organic liquid waste transfer valve 8.Fuel heater 6 is an electric heater with organic liquid waste well heater 7.Reactor inner container 17 adopts the alloy625 steel alloy of heat-and corrosion-resistant, and shell of reactor 14 adopts the SS316 stainless steel.
Between reactor inner container 17 and the shell of reactor 14 apart from 4.0cm, the geopolymer (Geopolymer) between reactor inner container 17 and the shell of reactor 14 is by 1000g fine mill slag, 162g K
2CO
3, 210g water and 168g sodium silicate mix and constitute; Through being stirred into the slurry after-pouring between reactor inner container 17 and the shell of reactor 14; Form high temperature resistant, high pressure resistant, anticorrosive and have the inorganic materials of good heat-proof quality through maintenance sclerosis; The pressure that reactor inner container 17 is born passes to shell of reactor 14 effectively; Through test ultimate compression strength is 90MPa.K
2CO
3Soluble in waterly in advance process solution re-uses.
The method for oxidation of constant volume internal combustion type supercutical fluid oxidizer unit comprises following order and step:
A, at first close fuel transfer valve 3, organic liquid waste transfer valve 8, reactant outlet valve 18 and SV 19; Inject 0.4MPa oxygen through oxygenant input tube 4 and oxygenant transfer valve 5 to reactor drum inner chamber 12; After close oxygenant transfer valve 5, stop oxygen and inject; SV 19 WPs are 60MPa;
B, open organic liquid waste transfer valve 8; Is acetone (acetone) organic liquid waste of 1wt.% through organic liquid waste input tube 10 to reactor drum inner chamber 12 implantation concentrations with high pressure organic liquid waste volume pump 9;, the pressure of reactor drum inner chamber (12) closes organic liquid waste transfer valve 8 when reaching 6MPa; Stop the organic liquid waste input, to the process that input reactor inner chamber 12 injects, be heated to 350 ℃ to organic liquid waste through organic liquid waste well heater 7 at organic liquid waste;
C, open fuel transfer valve 3; Inject methanol aqueous solution through fuel inlet pipe 1 and fuel under high pressure volume pump 2 to reactor drum inner chamber 12; Inject the process of methanol aqueous solution to reactor drum inner chamber 12 at fuel under high pressure volume pump 2; Be heated to above 500 ℃ through well heater 6 to methanol aqueous solution, spray into the methanol aqueous solution spontaneous ignition burning under the help of oxygenant in the reaction vessel inner chamber 12;
D, the response behaviour of keeping watch on the material in the reactor drum inner chambers 12 through upper temp meter 11, temperature of lower meter 13 and pressure warning unit 16; Temperature, pressure in reactor drum inner chamber 12 has surpassed the stagnation point of water; To be upper temp meter 11 with the temperature of temperature of lower meter 13 reach is higher than 500 ℃; The pressure of pressure warning unit 16 is closed fuel under high pressure volume pump 2 and fuel transfer valve 3 after being higher than 30MPa, stops methanol aqueous solution and supplies with, and keeps 30 seconds;
E, open the safety-valve 19 then; Give the reactor drum inner chamber 12 decompressions,, open reactant outlet valve 18 when the pressure of reactor drum inner chamber 12 drops to 20MPa closed safe valve 19 when following; Let the material in the reactor drum inner chamber 12 spray into phase separator 24, make solid salt and fluid separation;
F, open reducing valve 20 fluids and get into gas-liquid separator 22, gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe 21
2O discharges through liquid discharge tube 23;
G, open outlet valve 25 at last, contain saline solution and discharge through vent pipe 26, use TOC (Total organic carbon) analysis meter (Sievers InnovOx Lab) to measure discharge opeing, the TOC transformation efficiency is higher than 99.8%.
Embodiment 3
Constant volume internal combustion type supercutical fluid oxidizer unit; Be to pass shell of reactor 14, geopolymer 15 and reactor inner container 17 by fuel inlet pipe 1 through fuel under high pressure volume pump 2 and fuel transfer valve 3 to communicate with reactor drum inner chamber 12; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Oxygenant input tube 4 passes shell of reactor 14, geopolymer 15 and reactor inner container 17 through oxygenant transfer valve 5 and communicates with reactor drum inner chamber 12; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Organic liquid waste input tube 10 passes shell of reactor 14, geopolymer 15 and reactor inner container 17 through high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8 and communicates with reactor drum inner chamber 12, and fixing with shell of reactor 14 welding with reactor inner container 17, and the top of phase separator 24 is passed shell of reactor 14, geopolymer 15 and reactor inner container 17 through pipeline through reactant outlet valve 18 and SV 19 respectively and communicated with reactor drum inner chamber 12 bottoms; And it is fixing with shell of reactor 14 welding with reactor inner container 17; Vent pipe 26 and outlet valve 25 are equipped with in the bottom of phase separator 24, and the upper side of phase separator 24 links to each other with gas-liquid separator 22 with reducing valve 20 through pipeline, and gas-liquid separator 22 tops are provided with gas outlet pipe 21; Gas-liquid separator 22 bottoms are provided with liquid discharge tube 23; In the reactor drum, upper temp meter 11 is equipped with on 12 tops, and upper temp meter 11 links to each other with reactor drum is outside through the outer wall of lead along oxygenant input tube 4; Temperature of lower meter 13 is equipped with in reactor drum inner chamber 12 bottoms, and temperature of lower meter 13 links to each other with reactor drum is outside through the outer wall of lead along the reactant vent pipe; Pressure warning unit 16 is equipped with at reactor drum inner chamber 12 middle parts, and pressure warning unit 16 is through the outer wall and reactor drum outside link to each other formation of lead along organic liquid waste input tube 10.
On the fuel inlet pipe 1 of fuel transfer valve 3 bottoms, fuel heater 6 is housed, organic liquid waste well heater 7 is housed at the front end of organic liquid waste transfer valve 8.Fuel heater 6 is the solar heat device with organic liquid waste well heater 7.Reactor inner container 17 adopts the alloy625 steel alloy of heat-and corrosion-resistant, and shell of reactor 14 adopts the SS316 stainless steel.
Between reactor inner container 17 and the shell of reactor 14 apart from 6.0cm, the geopolymer Geopolymer between reactor inner container 17 and the shell of reactor 14) be to mix by 600g fine mill slag, 400g flyash, 45gNaOH, 172g sodium silicate and 212g water to constitute; Through being stirred into the slurry after-pouring between reactor inner container 17 and the shell of reactor 14; Form high temperature resistant, high pressure resistant, anticorrosive and have the inorganic materials of good heat-proof quality through maintenance sclerosis; The pressure that reactor inner container 17 is born passes to shell of reactor 14 effectively, is 73Mpa through test ultimate compression strength.In advance NaOH is processed the aqueous solution re-uses.
The method for oxidation of constant volume internal combustion type supercutical fluid oxidizer unit comprises following order and step:
A, at first close fuel transfer valve 3, organic liquid waste transfer valve 8, reactant outlet valve 18 and SV 19; After reactor drum inner chamber 12 injects 0.3MPa oxygen, close oxygenant transfer valve 5 through oxygenant input tube 4 and oxygenant transfer valve 5, stop oxygen and inject;
B, open organic liquid waste transfer valve 8; Through organic liquid waste input tube 10 and high pressure organic liquid waste volume pump 9 NSC 2879s (2-chlorphenol) to reactor drum inner chamber 12 implantation concentration 1wt.%; Adhere at the reactor wall face for accelerated reaction and control corrosion and generation salt, add 50mg Na by the 1kg organic liquid waste
2CO
3Be metered into Na
2CO
3In reactor drum inner chamber 12;, the pressure of reactor drum inner chamber 12 closes high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8 when reaching 7MPa; Stop the organic liquid waste input; To the process that input reactor inner chamber 12 injects, be heated to 350 ℃ to organic liquid waste at organic liquid waste through organic liquid waste well heater 7;
C, open fuel transfer valve 3, inject methanol aqueous solutions through fuel inlet pipe 1 and fuel under high pressure volume pump 2 to reactor drum inner chamber 12, self-ignition temperature is less than 500 ℃.To the process that reactor drum inner chamber 12 injects, be heated to above 500 ℃ to methanol aqueous solution at methanol aqueous solution, spray into the methanol aqueous solution spontaneous ignition burning under the help of oxygenant in the reaction vessel inner chamber 12 through well heater 6;
D, the response behaviour of keeping watch on the material in the reactor drum inner chambers 12 through upper temp meter 11, temperature of lower meter 13 and pressure warning unit 16; Temperature, pressure in reactor drum inner chamber 12 has surpassed the stagnation point of water; To be upper temp meter 11 with the temperature of temperature of lower meter 13 reach is higher than 500 ℃; The pressure of pressure warning unit 16 is closed fuel under high pressure volume pump 2 and fuel transfer valve 3 after surpassing 35MPa, stops fuel feed, keeps 30 seconds;
E, open the safety-valve 19 then; Give the reactor drum inner chamber 12 decompressions,, open reactant outlet valve 18 when the pressure of reactor drum inner chamber 12 drops to 20MPa closed safe valve 19 when following; Let the material in the reactor drum inner chamber 12 spray into phase separator 24, make solid salt and fluid separation;
F, open reducing valve 20 fluids and get into gas-liquid separator 22, gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe 21
2O discharges through liquid discharge tube 23;
G, open outlet valve 25 at last, contain saline solution and discharge through vent pipe 26, use TOC (Total organic carbon) analysis meter (Sievers InnovOx Lab) to measure discharge opeing, the TOC transformation efficiency is higher than 99.9%.
Claims (8)
1. constant volume internal combustion type supercutical fluid oxidizer unit; It is characterized in that; Be to pass shell of reactor (14), geopolymer (15) and reactor inner container (17) by fuel inlet pipe (1) through fuel under high pressure volume pump (2) and fuel transfer valve (3) to communicate with reactor drum inner chamber (12); And it is fixing with reactor inner container (17) and shell of reactor (14) welding; Oxygenant input tube (4) passes shell of reactor (14), geopolymer (15) and reactor inner container (17) through oxygenant transfer valve (5) and communicates with reactor drum inner chamber (12); And it is fixing with reactor inner container (17) and shell of reactor (14) welding; Organic liquid waste input tube (10) passes shell of reactor (14), geopolymer (15) and reactor inner container (17) through high pressure organic liquid waste volume pump (9) and organic liquid waste transfer valve (8) and communicates with reactor drum inner chamber (12); And it is fixing with reactor inner container (17) and shell of reactor (14) welding; The top of phase separator (24) is passed shell of reactor (14), geopolymer (15) and reactor inner container (17) through pipeline through reactant outlet valve (18) or SV (19) respectively and is communicated with reactor drum inner chamber (12) bottom, and fixing with reactor inner container (17) and shell of reactor (14) welding, and vent pipe (26) and outlet valve (25) are equipped with in the bottom of phase separator (24); The upper portion side wall of phase separator (24) links to each other with vapour liquid separator (22) with reducing valve (20) through pipeline; Vapour liquid separator (22) top is provided with gas outlet pipe (21), and vapour liquid separator (22) bottom is provided with liquid discharge tube (23), and upper temp meter (11) is equipped with on reactor drum inner chamber (12) top; Temperature of lower meter (13) is equipped with in reactor drum inner chamber (12) bottom, and reactor drum inner chamber (12) middle part is equipped with pressure warning unit (16) and is constituted.
2. according to the described constant volume internal combustion type of claim 1 supercutical fluid oxidizer unit; It is characterized in that; On the fuel inlet pipe (1) of the bottom of fuel transfer valve (3), fuel heater (6) is housed, organic liquid waste well heater (7) is housed at the front end of organic liquid waste transfer valve (8).
3. according to the described constant volume internal combustion type of claim 2 supercutical fluid oxidizer unit, it is characterized in that fuel heater (6) and organic liquid waste well heater (7) are solar heater or electric heater.
4. according to the described constant volume internal combustion type of claim 1 supercutical fluid oxidizer unit; It is characterized in that; Distance between reactor inner container (17) and the shell of reactor (14) is 0.3--10cm; Filling geopolymer (15) therebetween, geopolymer (15) proportioning by weight ratio is: alukalin: fine mill slag: KOH: sodium silicate: water=80: 10: 6: 17: 21; Or fine mill slag: K
2C0
3: sodium silicate: water=500: 81: 105: 84; Or fine mill slag: flyash: NaOH: sodium silicate: water=600: 400: 45: 172: 212, alkali re-used after will water-solublely in advance processing solution.
5. according to the described constant volume internal combustion type of claim 4 supercutical fluid oxidizer unit, it is characterized in that the preferred KOH of described alkali, NaOH, K
2CO
3Or Na
2CO
3
6. the method for oxidation of a constant volume internal combustion type supercutical fluid oxidizer unit is characterized in that, comprises following order and step:
A, at first close fuel transfer valve (3), organic liquid waste transfer valve (8), reactant outlet valve (18) and SV (19); Inject the 0.3-0.5MPa oxygenant through oxygenant input tube (4) and oxygenant transfer valve (5) to reactor drum inner chamber (12); After close oxygenant transfer valve (5), stop oxygenant and inject;
B, open organic liquid waste transfer valve (8); Inject organic liquid waste through organic liquid waste input tube (10) and high pressure organic liquid waste volume pump (9) to reactor drum inner chamber (12);, the pressure of reactor drum inner chamber (12) closes organic liquid waste transfer valve (8) when reaching 5-8MPa; Stop the organic liquid waste input, to the process that reactor drum inner chamber (12) injects, heat to organic liquid waste through organic liquid waste well heater (7) at organic liquid waste;
C, open fuel transfer valve (3); Inject fuel through fuel inlet pipe (1) and fuel under high pressure volume pump (2) to reactor drum inner chamber (12); In the process of fuel to reactor drum inner chamber (12) injection; Be heated to above 500 ℃ through well heater (6) to fuel, spray into the fuel spontaneous ignition burning under the help of oxygenant in the reaction vessel inner chamber (12);
D, the response behaviour through the material in upper temp meter (11), temperature of lower meter (13) and pressure warning unit (16) the supervision reactor drum inner chamber (12); Temperature, pressure in reactor drum inner chamber (12) has surpassed the stagnation point of water; To be upper temp meter (11) with the temperature of temperature of lower meter (13) reach is higher than 500 ℃; Close fuel transfer valve (3) when the pressure of pressure warning unit (16) reaches 30MPa-40MPa, stop fuel feed, kept 20 seconds;
E, (19) then open the safety-valve; Give reactor drum inner chamber (12) decompression,, open reactant outlet valve (18) when the pressure of reactor drum inner chamber (12) drops to 20MPa closed safe valve (19) when following; Let the material in the reactor drum inner chamber (12) spray into phase separator (24), make solid salt and fluid separation;
F, open reducing valve (20) fluid and get into gas-liquid separator (22), gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe (21)
2O discharges through liquid discharge tube (23);
G, open outlet valve (25) at last, contain saline solution and discharge through vent pipe (26), fuel transforms (Totalorganic carbon (TOC)) and is higher than 99.95%.
7. according to the method for oxidation of the described constant volume internal combustion type of claim 5 supercutical fluid oxidizer unit, it is characterized in that described oxygenant is oxygen or H
2O
2
8. according to the method for oxidation of the described constant volume internal combustion type of claim 5 supercutical fluid oxidizer unit, it is characterized in that described fuel is methanol aqueous solution (28wt%CH
3OH+72wt%H
2O) self-ignition temperature of fuel is less than 500 ℃.
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