CN101081303B - Method for fathering submarine discharge gas through air self-cleaning - Google Patents

Abstract

The present invention relates to waste gas treating method, and is especially method of treating waste gas of submarine. The method is one liquid phase catalytic method, in which various harmful gases are eliminated effectively with air itself. Under normal temperature or in heating condition, hydrogen, CO, SO2, hydrogen halide, NOx and other harmful gases in the waste gas are reacted with oxygen in the air and water in the apparatus under the action of the catalyst to produce CO2, water, inorganic acid capable of dissolving in water or other non-toxic matter. The method can eliminate harmful gas effectively without secondary pollution, and has reusable catalyst, low power consumption and low operation cost.

Description

The method of fathering submarine discharge gas through air self-cleaning

Technical field

The present invention relates to a kind of method of administering waste gas, particularly relate to a kind of method of administering submarine waste gas.

Background technology

Submarine particularly nuclear submarine because long-term diving closed operation, reasons such as body running, personnel's breathing and human body natural distribute produce a large amount of harmful gass, as multiclass toxic gas such as hydrogen, carbon monoxide, sulfur dioxide, chlorine, hydrogen halides, nitrogen oxide, ammonia, formaldehyde, formic acid, acrylic aldehyde, lactic acid, as untimely processing, the healthy of staff will be had a strong impact on.At present, nuclear submarine is Palladium monoxide and active carbon filter gas mainly adopting manganese dioxide, palladium powder aspect the improvement waste gas, and fluorine Lyons purifies, plasma, ethanolamine absorbent and catalytic oxidation degasification.The method that has is to handle single-minded harmful gas, acts on single; The special absorbent of the needs that have, the cost height; And these methods all exist the problem of bigger adsorption equilibrium of trend and chemical equilibrium, can't reach the high standard of toxic gas zero-emission.The device that the degasification method that has adopts is the cost height then, and one-time investment is big, the energy consumption height.

Summary of the invention

The objective of the invention is provides a kind of employing liquid catalytic at the above-mentioned defective that exists in the prior art, utilizes air self to eliminate the method for the fathering submarine discharge gas through air self-cleaning of multiple harmful gas effectively.

The present invention realizes above-mentioned purpose by the following technical solutions: the method for this fathering submarine discharge gas through air self-cleaning, the step that comprises following order: (1) is sent into the waste gas in the submarine bay in the device of the improvement waste gas that filler is housed, and adds water and oxidation state metallic salt catalyst in the device; (2) at normal temperatures, the water in the hydrogen in the waste gas, carbon monoxide, sulfur dioxide, hydrogen halides, nitrogen oxide and airborne oxygen and the device generates nontoxic carbon dioxide, water or the water-soluble inorganic acids material of energy under the effect of catalyst; Chlorine in the waste gas also reacts to each other with hydrogen and carbon monoxide respectively and generates carbon dioxide and hydrochloric acid; Ammonia in the waste gas is then absorbed by the acid medium in the device, generates the ammonium salt nontoxic and soluble in water to catalyst, and further eremacausis gets nitrogen; (3) under the effect of heating of the heater in device and catalyst, formaldehyde in exhaust gas, formic acid, acrylic aldehyde and the reaction of airborne oxygen generate nontoxic carbon dioxide and water; (4) the oxidation state auxiliary agent of adding valence variation element in device, the reaction back transforms the then oxidized attitude auxiliary agent of as-reduced metal salt catalyst that obtains and is recovered to active oxidation state metal salt catalyst in the device; After this ortho states auxiliary agent of going back then is recovered to the oxidation state auxiliary agent by airborne oxygen with the chlorine oxidation that is mixed with; (5) be discharged in the body of cabin through the clean gas outlet passage of controlling device cleaned air passes in device, if air in purification process because of must heating needing after heating up to cool off, by entering in the body of cabin after the cooling of the condensation reflux unit in the clean gas outlet passage, the aqueous solvent of vaporization is condensed into aqueous water through condensation reflux unit and passes back in the device again; When the water in the device amasss too much, enable water knockout drum and carry out branch water; When gas must not purify, enable bypass pipe and directly air is played back in the body of cabin.

The method of improvement submarine waste gas of the present invention adopts liquid-phase catalysis air self-cleaning method that airborne gas is interacted and generates nontoxic carbon dioxide, water and can reach the purpose of eliminating toxic gas by water-soluble materials such as mineral acid by add the heater heating of entry and catalyst and use device in device.The method of this improvement submarine waste gas can effectively be removed multiple harmful gas, essentially no secondary pollution; Catalyst once drops into, the life-time service activity as before, so energy consumption is low, standing charges are low.And the isolated plant that adopts this method is simple in structure, volume is little, in light weight, cost is low, easy to operate, operating technology is easily grasped.

Description of drawings

Fig. 1 is the structural representation that the present invention administers the isolated plant of submarine waste gas.

The specific embodiment

Below in conjunction with accompanying drawing isolated plant of the present invention is described.

Referring to Fig. 1, this device comprises the main body 1 that packing material is housed in, and a side is connected with waste gas inlet channel 14 in the bottom of main body 1, and opposite side is connected with catalyst outlet passage 12.Be provided with gas transmission device 8 on waste gas inlet channel 14, the waste gas in the cabin is sent in the main body 1 by gas transmission device 8 and is purified.On catalyst outlet passage 12, be provided with valve 13, when needs reduce or discharge catalyst, promptly open valve 13.Bottom in main body 1 is provided with heater 2, when needs heat, can use this heater.Be provided with adding material device 9 at the top of main body 1, catalyst adding material device mouth thus inserts, and is provided with valve 11 on the interface channel of adding material device 9 and main body 1, in the time of need inserting catalyst etc., opens this valve; Be provided with barometric pipe 10 between the top of adding material device 9 and bottom, the air pressure in main body 1 causes adding material greater than atmospheric pressure and falls at need, can play the effect of equilibrium air pressure.As seen from Figure 1, the top of main body 1 also is provided with a liquid level observation window 3.

From Fig. 1, be also shown in, be communicated with clean gas outlet passage 17 at the top of main body 1.Being connected with on clean gas outlet passage 17 with the horizontal line angle of inclination is to be less than or equal to 90 condensation reflux units 4 of spending greater than zero degree; The inner passage of condensation reflux unit 4 communicates with clean gas outlet passage 17, the inner passage of condensation reflux unit 4 is covered with shell, the bottom of shell is connected with cooling water outlet pipe 15, top is connected with cooling water inlet pipe 16, when the heating cleaned air passes is flowed through condensation reflux unit in main body 1, be cooled and be discharged in the cabin again after the water cooling, because cooling water is the bottom that enters shell from the top of shell, so water, QI rising in reverse order stream carry out favourable heat exchange.The bottom, lower end of the inner passage of condensation reflux unit 4 is connected with water knockout drum 5, and the top of water knockout drum 5 and bottom are respectively equipped with valve 6 and valve 7, next door are provided with liquid level indicator 23.If it is long-pending too much to observe the water that main body 1 endogenous cause of ill hydrogen transforms from liquid level observation window 3, just valve 6 to be opened, at this moment valve-off 7 is used for collecting the condensed water of reflux; Observe condensed water by the liquid level indicator 23 on the water knockout drum 5 and collect when a certain amount of, valve-off 6 is opened valve 7, and condensed water is discharged.

Can see also that from Fig. 1 be provided with bypass pipe 18 in the import department of waste gas inlet channel 14, the outlet of bypass pipe 18 links to each other with clean gas outlet passage 17, the import and export place of bypass pipe 18 is provided with valve 22 and valve 20 respectively; The branched bottom that waste gas inlet channel 14 enters main body 1 is provided with valve 21, and also is provided with valve 19 on clean gas outlet passage 17 and the branched bottom that condensation reflux unit 4 communicates.When detecting air when very clean, but valve-off 21 and valve 19 are opened valve 22 and valve 20, and at this moment air is handled and directly is discharged in the cabin without emission-control equipment; If air needs purified treatment, then open valve 21 and valve 19, valve-off 22 and valve 20, air admission emission-control equipment carry out being discharged in the cabin after the purified treatment again.

The method that the present invention adopts above-mentioned isolated plant to administer submarine waste gas then comprises the step of following order:

(1) waste gas in the submarine bay is sent in the device main body 1 of the improvement waste gas that filler is housed, from the adding material device 9 at apparatus main body 1 top, added water and oxidation state metallic salt catalyst in main body 1;

(2) at normal temperatures, the water in the hydrogen in the waste gas, carbon monoxide, sulfur dioxide, hydrogen halides, nitrogen oxide and airborne oxygen and the device generates nontoxic carbon dioxide, water or the water-soluble inorganic acids material of energy under the effect of catalyst; Chlorine in the waste gas also reacts to each other with hydrogen and carbon monoxide respectively and generates carbon dioxide and hydrochloric acid; Ammonia in the waste gas is then absorbed by the acid medium in the device, generates the ammonium salt nontoxic and soluble in water to catalyst, and further eremacausis gets nitrogen;

(3) under the effect of heating of the heater in device and catalyst, formaldehyde in exhaust gas, formic acid, acrylic aldehyde and the reaction of airborne oxygen generate nontoxic carbon dioxide and water;

(4) the oxidation state auxiliary agent of adding valence variation element in apparatus main body 1, the reaction back transforms the then oxidized attitude auxiliary agent of as-reduced metal salt catalyst that obtains and is recovered to active oxidation state metal salt catalyst in the device; After this ortho states auxiliary agent of going back then is recovered to the oxidation state auxiliary agent by airborne oxygen with the chlorine oxidation that is mixed with;

(5) be discharged in the body of cabin through the clean gas outlet passage 17 of controlling device cleaned air passes in device, if air in purification process because of must heating needing after heating up to cool off, can be by entering again in the body of cabin after 4 coolings of the condensation reflux unit in the clean gas outlet passage, the aqueous solvent of vaporization is condensed into aqueous water through condensation reflux unit 4 and passes back in the device main body 1; When the water in the apparatus main body 1 amasss too much, enable water knockout drum 5 and carry out branch water; When gas must not purify, enable bypass pipe 18 and directly exhaust air in the body of cabin.

(1) metallic element of step in the described oxidation state metal salt catalyst is a kind of in Pt, Pd, the Os element in the said method, and the valence variation element in the oxidation state auxiliary agent of above-mentioned described valence variation element of (4) step is one or more in Fe, Mo, Cu, As, P, the V element.

The temperature that above-mentioned catalyst uses is greater than 0 ℃, and pH is less than 3.

The chemical reaction that is taken place in the purification process in (2) step in the said method can be represented with following equation:

(1) catalytic reaction of air cleaning carbon monoxide:

(2) catalytic reaction of air oxidation hydrogen:

(3) cleaning principle of aqueous solvent dissolving hydrogen halides:

Product enters purifier can be strengthened except that useless effect.

(4) catalytic reaction of air oxidation sulfur dioxide:

H ₂SO ₄Entering purifier strengthens except that useless effect.

(5) reaction of air oxidation nitrogen oxide:

HNO ₃Entering purifier strengthens except that useless effect.

(6) catalytic reaction removed mutually of hydrogen and chlorine toxic gas:

HCl enters purifier can be strengthened except that useless effect

(7) catalytic reaction removed mutually of carbon monoxide and chlorine toxic gas:

(8) medium absorbs the cleaning principle of ammonia:

NH ₄ ⁺Enter the harmless effect of giving up of removing of purifier.

The chemical reaction that is taken place in the purification process in (3) step in the said method can be represented with following equation:

(1) catalytic reaction of air oxidation formaldehyde (aldehydes):

(2) catalytic reaction of air oxidation formic acid:

(3) catalytic reaction of air oxidation acrylic aldehyde:

Be that example illustrates Catalysis Principles of the present invention with airborne toxic gas carbon monoxide and hydrogen below:

(1) oxidation state slaine oxidizing carbon monoxide and hydrogen are reduced into the as-reduced metal, and its chemical equation is:

Can calculate above-mentioned equilibrium constant of reaction K ≈ 10 according to chemical thermodynamics rudimentary knowledge ²⁵

In like manner can calculate above-mentioned equilibrium constant of reaction K ≈ 10 ²¹

And then the dividing potential drop of carbon monoxide, hydrogen (content) as can be known:

$p\left(\mathrm{CO}\right)=\frac{p\left({\mathrm{co}}_2\right)\×{\left[H^{+}\right]}^2}{\left[M\left(\mathrm{II}\right)\right]\×K}\≈{10}^{-22}\mathrm{Pa}$

$p\left(H_2\right)=\frac{{\left[H^{+}\right]}^2}{\left[M\left(\mathrm{II}\right)\right]\×K}\≈{10}^{-20}\mathrm{Pa}$

(2) as-reduced metal M (0) is by auxiliary agent N ^N+Oxidation and be recovered to the oxidation state slaine:

(3) go back ortho states auxiliary agent N ^(n-1)+By air or chlorine oxidation and be recovered to oxidation state auxiliary agent N ^N+

Experiment shows Cl ₂Compare O ₂Easilier carry out this reaction.Wherein: M represents Pd, Pt, Os element; N represents Fe, Mo, Cu, As, P, V element.

The temperature that catalyst in the above-mentioned reaction uses is greater than 0 ℃, and pH is less than 3.Catalyst heatproof moisture-proof corrosion resistance is strong, almost can forever use removing submarine waste gas, handles easily regeneration where necessary a little.

Below by experiment the present invention is done further argumentation:

Concrete operation method is as follows:

Catalytic reaction is propped up in the test tube at the large size tool that is filled with glass fibre and is carried out, and catalyst amount 30mL[contains 0.6gPd (II)/100gH ₂O] aqueous solution, pH=0,20 ℃ of reaction temperatures, reaction gas consists of 0.5%CO (NH ₃, SO ₂, H ₂, HCl), 20%O ₂(dilution of Ar gas, flow 100mL/min), product (detects NH through the concentrated sulphuric acid drying ₃The time use the soda lime drying) back analyzes with GC-8A gas chromatograph (thermal conductivity cell detector).

After adopting technology of the present invention to experimentize, to CO, SO ₂, H ₂, thing such as HCl carries out the GC gas Chromatographic Determination, do not detect measured object.

Catalysqt deactivation and regeneration tests:

Only feed catalyst, the catalyst effective ingredient is transformed into entirely goes back ortho states and complete deactivation with CO.Bubbling air only in the catalyst of complete deactivation, the going back that ortho states is transformed into oxidation state entirely of catalyst effective ingredient and bringing back to life fully.

Catalyst experiment in service life:

Behind repetition catalysqt deactivation and the regeneration tests 300 times, the catalytic activity of catalyst as before.

In air, sneak into 0.5%CO, at room temperature fed catalyst continuously 90 days, do not see catalyst failure.

Claims (2)

1. the method for a fathering submarine discharge gas through air self-cleaning is characterized in that comprising the step of following order:

(1) waste gas in the submarine bay is sent in the device of the improvement waste gas that filler is housed, added water and oxidation state metallic salt catalyst in the device; Metallic element in the described oxidation state metallic salt catalyst is a kind of in Pt, Pd, the Os element;

(2) at normal temperatures, the water in the hydrogen in the waste gas, carbon monoxide, sulfur dioxide, hydrogen halides, nitrogen oxide and airborne oxygen and the device generates nontoxic carbon dioxide, water or the water-soluble inorganic acids material of energy under the effect of catalyst; Chlorine in the waste gas also reacts to each other with hydrogen and carbon monoxide respectively and generates carbon dioxide and hydrochloric acid; Ammonia in the waste gas is then absorbed by the acid medium in the device, generates the ammonium salt nontoxic and soluble in water to catalyst, and further eremacausis gets nitrogen;

(3) under the effect of heating of the heater in device and catalyst, formaldehyde in exhaust gas, formic acid, acrylic aldehyde and the reaction of airborne oxygen generate nontoxic carbon dioxide and water;

(4) the oxidation state auxiliary agent of adding valence variation element in device, the reaction back transforms the then oxidized attitude auxiliary agent of as-reduced metal salt catalyst that obtains and is recovered to active oxidation state metal salt catalyst in the device; After this ortho states auxiliary agent of going back then is recovered to the oxidation state auxiliary agent by airborne oxygen with the chlorine oxidation that is mixed with; Valence variation element in the oxidation state auxiliary agent of described valence variation element is one or more in Fe, Mo, Cu, As, P, the V element.

(5) be discharged in the body of cabin through the clean gas outlet passage of controlling device cleaned air passes in device, if air in purification process because of must heating needing after heating up to cool off, by entering in the body of cabin after the cooling of the condensation reflux unit in the clean gas outlet passage, the aqueous solvent of vaporization is condensed into aqueous water through condensation reflux unit and passes back in the device again; When the water in the device amasss too much, enable water knockout drum and carry out branch water; When gas must not purify, enable bypass pipe and directly exhaust air in the body of cabin.

2. the method for fathering submarine discharge gas through air self-cleaning according to claim 1 is characterized in that: the temperature that catalyst uses is greater than 0 ℃, and pH is less than 3.

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