CN103182244A - Dephosphorization catalytic reaction technology of yellow phosphorus tail gas and apparatus - Google Patents
Dephosphorization catalytic reaction technology of yellow phosphorus tail gas and apparatus Download PDFInfo
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- CN103182244A CN103182244A CN2011104560530A CN201110456053A CN103182244A CN 103182244 A CN103182244 A CN 103182244A CN 2011104560530 A CN2011104560530 A CN 2011104560530A CN 201110456053 A CN201110456053 A CN 201110456053A CN 103182244 A CN103182244 A CN 103182244A
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- phosphoric tail
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Abstract
The invention provides a dephosphorization catalytic reaction technology of yellow phosphorus tail gas and an apparatus. The technology comprises the following steps: the yellow phosphorus tail gas through filter dust is pressurized to a preset air pressure value, liquid water or water vapor is injected according to preset volume percentage to form a gas-water mixture; the gas-water mixture is preheated to convert to a gaseous state, and a catalytic reaction is carried out under a preset temperature to generate phosphorus oxide, phosphorus oxide can generate phosphoric acid after being mixed with water vapor, desorption is carried out under preset bed layer temperature, and the phosphoric acid can flow out by following with reaction tail gas in a gaseous state form. According to the invention, yellow phosphorus tail gas can be consecutively purified, and the catalyst is not required for regenerating.
Description
Technical field
The present invention relates to catalytic reaction technology, particularly relate to a kind of dephosphorization catalytic reaction technology and device of yellow phosphoric tail gas.
Background technology
Phosphorus has purposes widely in industries such as washing agent, agricultural chemicals, bio-pharmaceuticals.Produce 2500～3000m from 1 ton of yellow phosphorus of the every refinement of natural phosphorus ore
3Tail gas, its classical group becomes to see the following form.
| Composition | Content | Composition | Content |
| CO | 85％～95％ | CH 4 | ～0.3％ |
| N 2 | 2～5％ | Total sulfur (H 2S, organic sulfur) | 500～3000ppm |
| H 2O | ～5％ | Total phosphorus (PH 3+P 4) | 500～1500ppm |
| H 2 | 1～8％ | HF | ～100ppm |
| CO 2 | 1～4％ | AsH 3 | ～50ppm |
| O 2 | ～1％ |
Pollutant kind in the yellow phosphoric tail gas is many, toxicity is big, can not directly discharge, and its major impurity is total phosphorus and total sulfur.Early stage external main come reproducibility component total phosphorus (DE2213483 especially in the oxidation yellow phosphoric tail gas with the acid solution that contains heavy metal such as Hg, Cr, Cu salt; SU570386; SU618124) reaching emission request, but the mode of this liquid phase oxidation will be brought the problem of heavy metal pollution again.
Along with the transfer to less developed country of the yellow phosphorus industry of high energy consumption, high pollution, China becomes phosphorus production big country, has concentrated the output phosphor of the whole world more than 80%.Each enterprise is quite general to the simple extensive burning of igniting the torch of yellow phosphoric tail gas (being commonly called as " point day lamp "), and this processing mode not only wastes a large amount of heat energy, and total phosphorus, total sulfur change into phosphorous oxides and SO
2Cause that also acid gas pollutes.Environmental Protection in China requires increasingly stringent in recent years, and is extremely urgent to the recycling behind the purifying exhausting gas of yellow phosphorus.Be example with Yunnan Province, the whole province's phosphorus output was 290,000 tons in 2006, contained 9.6 hundred million m in the yellow phosphoric tail gas of discharging only
3CO is if can utilize the heat energy even the purification CO that wherein comprise will bring huge economy and the value of environmental protection as the synthetic unstripped gas of carbonyl.But the composition complexity of yellow phosphoric tail gas, it is big, the most key with removing of total phosphorus especially to purify difficulty, and the relevant purification techniques with feasibility is very few.
Number be CN1128000C as Chinese patent application, name is called the method that removes phosphorus, phosphide, sulfide from yellow phosphoric tail gas, and the patent application on April 24th, 2002 in open day has disclosed a kind of alternating temperature pressure swing adsorption purge technology.Through alkali cleaning remove acidic components and remove with carbon absorbent elemental phosphorous after, utilize alternating temperature transformation adsorbing and removing hydrogen phosphide and hydrogen sulfide to purify back gas.The regeneration of adsorbent is by reversely putting pressure, adding series of steps such as heat flush, cold blowing, pressurising and realize.
Number be CN1398658A as Chinese patent application, name is called the method that the yellow phosphoric tail gas fixed bed catalytic oxidation purifies, and the patent application on February 26th, 2003 in open day has disclosed a kind of fixed bed catalytic oxidation process for purifying.Yellow phosphoric tail gas is tentatively removed small part phosphorus, sulphur and almost all after the fluoride impurities through alkali cleaning, change remaining most of phosphorus, sulfide into phosphorous oxides and sulphur respectively through a catalytic oxidation fixed bed again after sorption on beds.The catalyst that lost efficacy after a period of time is regenerated after hot-air activation, steam activation, washing, drying.
More than these concrete representational prior aries have following problems: adsorbent or catalyst needed to regenerate after using a period of time to lose efficacy, regenerative process has not only increased the complexity of equipment and operation, simultaneously for catalyst, to such an extent as to repeated regeneration also can cause the final inactivation of the loss gradually of catalytic active center.
Therefore, need the urgent technical problem that solves of those skilled in the art to be exactly at present: a kind of dephosphorization catalytic reaction technology of yellow phosphoric tail gas is provided, makes the purifying exhausting gas of yellow phosphorus can continuous carrying out, catalyst also need not regeneration.
Summary of the invention
Technical problem to be solved by this invention provides a kind of dephosphorization catalytic reaction technology of yellow phosphoric tail gas, makes the purifying exhausting gas of yellow phosphorus can continuous carrying out, and catalyst need not regeneration.
Accordingly, the present invention also provides the dephosphorization catalyst reaction device of yellow phosphoric tail gas, in order to guarantee said method realization and application in practice.
In order to address the above problem, the invention discloses a kind of dephosphorization catalytic reaction technology of yellow phosphoric tail gas, it is characterized in that, comprising:
To dust after filtration and be pressurized to the yellow phosphoric tail gas of default atmospheric pressure value, inject aqueous water or steam according to default percent by volume, form air-water mixture;
Described air-water mixture after changing gaseous state into, is carried out catalytic reaction in preheating.
Preferably, described catalytic reaction comprises:
By default air speed described yellow phosphoric tail gas through preheating is passed through catalyst, total phosphorus is wherein generated phosphorous oxides by catalytic oxidation, and after chance steam generated phosphoric acid, desorption under default bed temperature flowed out with reaction end gas with gaseous form.
Preferably, the dephosphorization catalytic reaction technology of described yellow phosphoric tail gas also comprises:
Described yellow phosphoric tail gas after catalytic reaction is condensed into phosphoric acid solution.
Preferably, the mode of described injection aqueous water or steam is to inject aqueous water or directly inject steam through the water filling steaming plant through water injection equipment; Described aqueous water comprises distilled water.
Preferably, described default atmospheric pressure value is arbitrary value among 0.05MPa～0.5MPa.
Preferably, the preset vol percentage of described aqueous water or steam and yellow phosphoric tail gas is arbitrary value in 10: 90～50: 50.
Preferably, the preset vol percentage of described aqueous water or steam and yellow phosphoric tail gas is 30: 70.
Preferably, the described temperature that air-water mixture is carried out preheating is arbitrary value in 300～500 ℃.
Preferably, default bed temperature is arbitrary value in 300～500 ℃ in the described catalytic reaction.
Preferably, default bed temperature is 380 ℃ in the described catalytic reaction.
Preferably, default air speed is 500～10000h in the described catalytic reaction
-1In arbitrary value.
Preferably, default air speed is 5000h in the described catalytic reaction
-1
Preferably, described catalyst is surface treated activated carbon supported type catalyst.
Preferably, the temperature that adopts of described condensation is arbitrary value in 0～60 ℃.
The present invention also provides a kind of dephosphorization catalyst reaction device of yellow phosphoric tail gas, comprising:
The filter of Lian Jieing, gas boosting equipment, fixed bed catalytic reactor in turn; And, being connected the preheater between described gas boosting equipment and the fixed bed catalytic reactor, described preheater is circumscribed with water injection pipe;
Yellow phosphoric tail gas enters described filter after filtration behind the dust, is pressurized to default atmospheric pressure value through gas boosting equipment; Inject aqueous water or steam according to default percent by volume from water injection pipe, the yellow phosphoric tail gas after the described supercharging and aqueous water or steam form air-water mixture; After described air-water mixture enters preheater and is converted into gaseous state, enter fixed bed catalytic reactor and carry out catalytic reaction.
Preferably, described water injection pipe is water injection equipment or water filling steaming plant, and described aqueous water comprises distilled water.
Preferably, the dephosphorization catalyst reaction device of described yellow phosphoric tail gas also comprises:
The condenser that is connected with described fixed bed catalytic reactor;
Described yellow phosphoric tail gas after catalytic reaction is condensed into phosphoric acid solution at condenser.
Preferably, the dephosphorization catalyst reaction device of described yellow phosphoric tail gas also comprises:
Be connected the surge tank between described gas boosting equipment and the preheater;
The described yellow phosphoric tail gas that is pressurized to default atmospheric pressure value enters preheater behind described surge tank steady air flow.
Preferably, described default atmospheric pressure value is arbitrary value among 0.05MPa～0.5MPa.
Preferably, the default percent by volume of described aqueous water or steam and yellow phosphoric tail gas is arbitrary value in 10: 90～50: 50.
Preferably, the default percent by volume of described aqueous water or steam and yellow phosphoric tail gas is 30: 70.
Preferably, the temperature of the preheating adopted of described preheater is arbitrary value in 300～500 ℃.
Preferably, the bed temperature that adopts of described fixed bed catalytic reactor is arbitrary value in 300～500 ℃.
Preferably, the bed temperature that adopts of described fixed bed catalytic reactor is 380 ℃.
Preferably, the air speed that adopts of described fixed bed catalytic reactor is 500～10000h
-1In arbitrary value.
Preferably, the air speed that adopts of described fixed bed catalytic reactor is 5000h
-1
Preferably, the catalyst that adopts of described fixed bed catalytic reactor is activated carbon supported type catalyst.
Preferably, the temperature that adopts of described condenser is arbitrary value in 0～60 ℃.
Compared with prior art, the present invention includes following advantage:
The embodiment of the invention provides a kind of continuous catalysis dephosphorization technology for purifying exhausting gas of yellow phosphorus, by in yellow phosphoric tail gas, adding a certain proportion of aqueous water or steam, phosphorous oxides that total phosphorus in the yellow phosphoric tail gas generates through catalytic oxidation is shifted out with the form of gaseous state phosphoric acid, thereby make catalytic reaction to carry out continuously, therefore catalyst need not regenerated, and prolong service life greatly.The equipment of this technology and operation are all more simple, have saved permanent plant investment and operating cost.
In addition, total phosphorus impurities and total sulphur impurity are separately handled among the present invention, and total phosphorus impurities is directly collected with the form of dilute phosphoric acid solution, can concentrate the back reuse, has solved secondary pollution problem; Major impurity only is sulfide in the yellow phosphoric tail gas behind the process dephosphorization, can easily be removed by the sulfur removal technology of various maturations.
Description of drawings
Fig. 1 is the flow chart of steps of the dephosphorization catalytic reaction process implementing example 1 of a kind of yellow phosphoric tail gas of the present invention;
Fig. 2 is the flow chart of steps of the dephosphorization catalytic reaction process implementing example 2 of a kind of yellow phosphoric tail gas of the present invention;
Fig. 3 is the structured flowchart of the dephosphorization catalyst reaction device embodiment of a kind of yellow phosphoric tail gas of the present invention.
Fig. 4 is the structure chart of an example of the dephosphorization catalyst reaction device embodiment of a kind of yellow phosphoric tail gas of the present invention.
The specific embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
For prior art, when yellow phosphoric tail gas was carried out the dephosphorization catalytic reaction, catalysate was attached on the catalyst, made catalyst need to regenerate after use a period of time, and reaction can not be carried out continuously, the complexity of increase equipment and operation.In view of this, the inventor herein creatively proposes one of core idea of the embodiment of the invention and is, in through the yellow phosphoric tail gas after filtering supercharging, inject aqueous water or steam, form air-water mixture and change gas into by preheating, carry out catalytic reaction again, the phosphorous oxides that reaction generates and water reaction change phosphoric acid into, behind the catalyst surface desorption, migrate out bed with gaseous form at a certain temperature, thereby make that purifying exhausting gas of yellow phosphorus reaction can continuous carrying out, catalyst also need not regeneration.
With reference to figure 1, show the flow chart of a kind of embodiment 1 of the present invention, specifically can may further comprise the steps:
As the concrete a kind of preferred exemplary used of the embodiment of the invention, described aqueous water can be distilled water.
In concrete the application, Chalk-dust filtering is in order to remove the solid impurity particle in the yellow phosphoric tail gas, to prevent from its obstruction bed or be adsorbed onto influencing catalytic activity on the catalyst; Supercharging is in order to make yellow phosphoric tail gas and steam or aqueous water better mixing under certain pressure even, can make gas overcome the resistance in the technical process simultaneously and flows through each operation smoothly.
Adopt the embodiment of the invention, need in yellow phosphoric tail gas, inject aqueous water or steam, form air-water mixture, after changing gaseous state into, comprise yellow phosphoric tail gas and water in the gas that forms, gaseous mixture carried out the total phosphorus in the yellow phosphoric tail gas is behind catalytic oxidation after the catalysis, the phosphorus oxidation compound of generation is adsorbed on the catalyst, simultaneously can with gaseous mixture in water in conjunction with generating phosphoric acid.At a certain temperature, phosphoric acid can enter the tail gas with gaseous form behind the beds desorption.Like this, the phosphorus oxidation compound that total phosphorus in the yellow phosphoric tail gas generates migrates out from beds, can not influence activity of such catalysts, thereby also just remove the step of catalyst regeneration from, realized carrying out continuously of catalytic reaction, made greatly prolong the service life of catalyst simultaneously.
In embodiments of the present invention, what inject to yellow phosphoric tail gas can be distilled water or steam, or other forms of water, such as: ultra-pure water, demineralized water, deionized water etc. perhaps exist with different states, such as: gaseous state, liquid state, gas-liquid mixed attitude.Can inject aqueous water or directly inject steam through the water filling steaming plant through water injection equipment, water injection equipment can be plunger displacement pump, and the water filling steaming plant can be steam pipe line, and the present invention does not limit this.
With reference to figure 2, show the flow chart of a kind of embodiment 2 of the present invention, specifically can may further comprise the steps:
As the concrete a kind of preferred exemplary used of the embodiment of the invention, described aqueous water can be distilled water.
In a kind of preferred embodiment of the present invention, described default atmospheric pressure value can be arbitrary value among 0.05MPa～0.5MPa.
In a kind of preferred embodiment of the present invention, the preset vol percentage of described aqueous water or steam and yellow phosphoric tail gas can be arbitrary value in 10: 90～50: 50.In concrete example, the best preset vol percentage of described aqueous water or steam and yellow phosphoric tail gas is 30: 70.
In embodiments of the present invention, described catalytic reaction can for, by default air speed with described yellow phosphoric tail gas through preheating by catalyst, total phosphorus is wherein generated phosphorous oxides by catalytic oxidation, after meeting steam generation phosphoric acid, flowing out with gaseous form behind the desorption under the default bed temperature.
In the preferred embodiment of the invention, the catalyst that loads in the fixed bed catalytic reactor is surface treated activated carbon supported type catalyst.The catalyst that the present invention relates to is just in patent application.As a kind of example in the concrete application, described absorbent charcoal carrier can be surface treated ature of coal charcoal or coconut husk charcoal, and the active component of described load can be cupric phosphate, cupric pyrophosphate, ferric phosphate or ferric pyrophosphate.
In a kind of preferred embodiment of the present invention, the described temperature that air-water mixture is carried out preheating can be arbitrary value in 300～500 ℃.
In a kind of preferred embodiment of the present invention, default bed temperature can be arbitrary value in 300～500 ℃ in the described catalytic reaction.In concrete example, best bed temperature is 380 ℃.
In a kind of preferred embodiment of the present invention, air speed default in the described catalytic reaction can be 500～10000h
-1In arbitrary value.In concrete example, best air speed is 5000h
-1
Along with reaction end gas is taken out of reaction bed, can be condensed into phosphoric acid in condenser behind the phosphoric acid desorption, collection phosphoric acid also concentrates, and can utilize again, can not produce secondary pollution.
The catalyst that the present invention relates to demonstrates good anti-sulphur ability.The existence of sulfur species is to the not influence of catalysis dephosphorization in the yellow phosphoric tail gas in the above-mentioned catalytic reaction, and total sulfur self reacts under this reaction condition hardly, all flows out bed with reaction end gas, major impurity remaining total sulfur only in the reaction end gas.Total sulfur can be removed by the sulfur removal technology of various maturations.
In a kind of preferred embodiment of the present invention, the temperature that described condensation is adopted is arbitrary value in 0～60 ℃.
For making those skilled in the art understand the present invention better, below provide the specific implementation process of the dephosphorization catalytic reaction technology that an example illustrates yellow phosphoric tail gas.
The load active component of catalyst adopts cupric phosphate in this example, and absorbent charcoal carrier is surface treated ature of coal charcoal, and this kind of 200g ature of coal charcoal load cupric phosphate catalyst is seated in the fixed bed catalytic reactor.Advance distilled water with plunger displacement pump, the steam after the gasification and the percent by volume of yellow phosphoric tail gas were set in 40: 60; Default atmospheric pressure value is for being pressurized to 0.2MPa; The preheater temperature is set in 390 ℃; The fixed bed catalytic reactor temperature is set in 380 ℃; Air speed is set in 6000h
-1Condenser places room temperature environment.
To dust after filtration and be pressurized to the yellow phosphoric tail gas of 0.2MPa, be 40: 60 according to the percent by volume of steam and yellow phosphoric tail gas, inject distilled water or steam, form air-water mixture; In preheater, change gaseous state under 390 ℃ the temperature, then at 6000h
-1Air speed, under 380 ℃ of temperature, carry out catalytic reaction.Yellow phosphoric tail gas after catalytic reaction at room temperature is condensed into phosphoric acid solution.
Before the purification, the detected content of total phosphorus is 770mg/m in the yellow phosphoric tail gas
3, total sulfur is 3500mg/m
3After feeding the fixed bed reactors purification, the content of total phosphorus is 18mg/m in the yellow phosphoric tail gas
3, the content of total sulfur is constant substantially.Successive reaction 500h, the catalytic activity no change does not need catalyst regeneration, has realized the continuous purification of yellow phosphoric tail gas.
As the another kind of example of the embodiment of the invention, the load active component of catalyst adopts ferric pyrophosphate, and absorbent charcoal carrier is surface treated coconut husk charcoal, and concrete process for purifying is:
200g coconut husk charcoal load ferric pyrophosphate catalyst is seated in the fixed bed reactors.Introduce steam with the Boiler Steam pipeline in yellow phosphoric tail gas, the percent by volume of steam and yellow phosphoric tail gas was set in 30: 70; Default atmospheric pressure value is for being pressurized to 0.2MPa; The preheater temperature is set in 400 ℃; Temperature of reactor is set in 420 ℃; Air speed is set in 5000h
-1Condenser places room temperature environment.
To dust after filtration and be pressurized to the yellow phosphoric tail gas of 0.2MPa, be 30: 70 according to the percent by volume of steam and yellow phosphoric tail gas, inject distilled water or steam, form air-water mixture; In preheater, change gaseous state under 400 ℃ the temperature, then at 5000h
-1Air speed, under 420 ℃ of temperature, carry out catalytic reaction.Phosphoric acid steam in the yellow phosphoric tail gas after catalytic reaction at room temperature is condensed into phosphoric acid solution.
Before the purification, the detected content of total phosphorus is 890mg/m in the yellow phosphoric tail gas
3, total sulfur is 3000mg/m
3After feeding the fixed bed reactors purification, the content of total phosphorus is 15mg/m in the yellow phosphoric tail gas
3, the content of total sulfur is constant substantially.Successive reaction 365h, the catalytic activity no change does not need catalyst regeneration, has realized the continuous purification of yellow phosphoric tail gas.
For method embodiment, for simple description, so it all is expressed as a series of combination of actions, but those skilled in the art should know, the present invention is not subjected to the restriction of described sequence of movement, because according to the present invention, some step can adopt other orders or carry out simultaneously.Secondly, those skilled in the art also should know, the embodiment described in the specification all belongs to preferred embodiment, and related action and parts might not be that the present invention is necessary.
With reference to figure 3, show the structured flowchart of a kind of embodiment of the present invention, specifically can comprise:
The filter 301 of Lian Jieing, gas boosting equipment 302, fixed bed catalytic reactor 304 in turn; And, being connected the preheater 303 between described gas boosting equipment 302 and the fixed bed catalytic reactor 304, described preheater is circumscribed with water injection pipe 305;
Yellow phosphoric tail gas enters described filter after filtration behind the dust, is pressurized to default atmospheric pressure value through gas boosting equipment; The yellow phosphoric tail gas that is pressurized to default atmospheric pressure value enters preheater behind described surge tank steady air flow, inject aqueous water or steam according to default percent by volume from water injection pipe, the yellow phosphoric tail gas after the described supercharging and aqueous water or steam form air-water mixture; After described air-water mixture enters preheater and is converted into gaseous state, enter fixed bed catalytic reactor and carry out catalytic reaction.
In a kind of preferred embodiment of the present invention, described device can comprise also that with the condenser that described fixed bed catalytic reactor is connected, described condenser is condensed into phosphoric acid solution with the phosphoric acid steam in the yellow phosphoric tail gas after catalytic reaction.
In a kind of preferred embodiment of the present invention, described device can also comprise, is connected the surge tank between described gas boosting equipment and the preheater, is used for making the yellow phosphoric tail gas after the pressurization to enter preheater with air-flow stably.In the concrete realization, can between surge tank and preheater, add flowmeter, for detection of the flow of yellow phosphoric tail gas, with the state of monitoring air-flow.
In a kind of preferred embodiment of the present invention, described water injection pipe can be water injection equipment or water filling steaming plant.
In a kind of preferred embodiment of the present invention, described default atmospheric pressure value can be arbitrary value among 0.05MPa～0.5MPa, and gas boosting equipment can be booster pump.
In a kind of preferred embodiment of the present invention, described aqueous water or steam can be than being arbitrary value in 10: 90～50: 50 with the default volume percentage of yellow phosphoric tail gas.In the concrete realization, optimal volume percentage is 30: 70.
In a kind of preferred embodiment of the present invention, the temperature of the preheating that described preheater adopts can be arbitrary value in 300～500 ℃.
In a kind of preferred embodiment of the present invention, the bed temperature that described fixed bed catalytic reactor adopts can be arbitrary value in 300～500 ℃.In the concrete realization, best bed temperature is 380 ℃.
In a kind of preferred embodiment of the present invention, the air speed that described fixed bed catalytic reactor adopts can be 500～10000h
-1In arbitrary value.In the concrete realization, best air speed is 5000h
-1
In a kind of preferred embodiment of the present invention, the catalyst that described fixed bed catalytic reactor adopts can be surface treated activated carbon supported type catalyst.In the concrete realization, the absorbent charcoal carrier that described activated carbon supported type catalyst adopts can be surface treated ature of coal charcoal or coconut husk charcoal, and the active component of the load that described catalyst adopts can be cupric phosphate, cupric pyrophosphate or ferric phosphate, ferric pyrophosphate.
In a kind of preferred embodiment of the present invention, the temperature that described condenser adopts can be arbitrary value in 0～60 ℃.
For making those skilled in the art understand the present invention better, the dephosphorization catalyst reaction device figure below in conjunction with yellow phosphoric tail gas shown in Figure 4 further specifies the present invention by a concrete example.
In this example, the dephosphorization catalyst reaction device of described yellow phosphoric tail gas comprises:
The filter 401 of Lian Jieing, booster pump 402, surge tank 403, preheater 404, fixed bed catalytic reactor 405, condenser 406 in turn; And be connected the outer plunger displacement pump 407 of described preheater.
Yellow phosphoric tail gas enters from import, through the filter Chalk-dust filtering, enter booster pump then and be pressurized to default atmospheric pressure value, yellow phosphoric tail gas after the supercharging enters preheater after entering the surge tank steady air flow, simultaneously inject aqueous water by plunger displacement pump to yellow phosphoric tail gas, form air-water mixture with yellow phosphoric tail gas, in preheater, be converted into gas, enter fixed bed catalytic reactor then and carry out catalytic reaction.Tail gas after catalysis enters and is condensed into phosphoric acid solution in the condenser.
In this example, can also inject industry water steam in the preheater, form air-water mixture with yellow phosphoric tail gas, the pressure of the steam that reduces to inject by the steam pressure-reducing valve.
In filter, tail gas is carried out dust removal by filtration in this example and enter behind the surge tank blowdown apparatus should be arranged; Also have drain, flowmeter, Pressure gauge and a detection mouth between surge tank and the preheater, drain is for the pressure by gas purging control air-flow; Flowmeter is used for monitoring the flow of yellow phosphoric tail gas, and Pressure gauge is used for the pressure condition of monitoring yellow phosphoric tail gas, detects mouthful content for detection of script total phosphorus and total sulfur in the yellow phosphoric tail gas.Being connected has individual flowmeter between plunger displacement pump and the preheater, be the amount for the distilled water of controlling injection; Condensator outlet also has one to detect mouthful, and the result of tail gas clean-up is detected, and calculates the content of total phosphorus total sulfur, with purify before compare the effect that obtains tail gas clean-up, tail gas enters another branch road and carries out follow-up sulphur removal process.
The described exhaust gas cleaner of this example also comprises a plurality of Pressure gauges, is in order to monitor the pressure condition of yellow phosphoric tail gas everywhere.
Because described device embodiment is substantially corresponding to the method embodiment shown in the preceding method, so not detailed part in the description of present embodiment can just not given unnecessary details at this referring to the related description in the previous embodiment.
More than the dephosphorization catalytic reaction technology of a kind of yellow phosphoric tail gas provided by the present invention and a kind of dephosphorization catalytic reaction process unit of yellow phosphoric tail gas are described in detail, used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (28)
1. the dephosphorization catalytic reaction technology of a yellow phosphoric tail gas is characterized in that, comprising:
To dust after filtration and be pressurized to the yellow phosphoric tail gas of default atmospheric pressure value, inject aqueous water or steam according to default percent by volume, form air-water mixture;
Described air-water mixture after changing gaseous state into, is carried out catalytic reaction in preheating.
2. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 1 is characterized in that described catalytic reaction comprises:
By default air speed described yellow phosphoric tail gas through preheating is passed through catalyst, total phosphorus is wherein generated phosphorous oxides by catalytic oxidation, and after chance steam generated phosphoric acid, desorption under default bed temperature flowed out with reaction end gas with gaseous form.
3. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 1 and 2 is characterized in that, also comprises:
Described yellow phosphoric tail gas after catalytic reaction is condensed into phosphoric acid solution.
4. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 3 is characterized in that, the mode of described injection aqueous water or steam is to inject aqueous water or directly inject steam through the water filling steaming plant through water injection equipment; Described aqueous water comprises distilled water.
5. according to the dephosphorization catalytic reaction technology of claim 1,2 or 4 described yellow phosphoric tail gas, it is characterized in that described default atmospheric pressure value is arbitrary value among 0.05MPa～0.5MPa.
6. according to the dephosphorization catalytic reaction technology of claim 1,2 or 4 described yellow phosphoric tail gas, it is characterized in that the preset vol percentage of described aqueous water or steam and yellow phosphoric tail gas is arbitrary value in 10: 90～50: 50.
7. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 6 is characterized in that, the preset vol percentage of described aqueous water or steam and yellow phosphoric tail gas is 30: 70.
8. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 1 is characterized in that, the described temperature that air-water mixture is carried out preheating is arbitrary value in 300～500 ℃.
9. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 2 is characterized in that, bed temperature default in the described catalytic reaction is arbitrary value in 300～500 ℃.
10. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 9 is characterized in that, bed temperature default in the described catalytic reaction is 380 ℃.
11. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 2 is characterized in that, air speed default in the described catalytic reaction is 500～10000h
-1In arbitrary value.
12. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 11 is characterized in that, air speed default in the described catalytic reaction is 5000h
-1
13. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 2 is characterized in that, described catalyst is surface treated activated carbon supported type catalyst.
14. the dephosphorization catalytic reaction technology of yellow phosphoric tail gas according to claim 3 is characterized in that, the temperature that described condensation is adopted is arbitrary value in 0～60 ℃.
15. the dephosphorization catalyst reaction device of a yellow phosphoric tail gas is characterized in that, comprising:
The filter of Lian Jieing, gas boosting equipment, fixed bed catalytic reactor in turn; And, being connected the preheater between described gas boosting equipment and the fixed bed catalytic reactor, described preheater is circumscribed with water injection pipe;
Yellow phosphoric tail gas enters described filter after filtration behind the dust, is pressurized to default atmospheric pressure value through gas boosting equipment; Inject aqueous water or steam according to default percent by volume from water injection pipe, the yellow phosphoric tail gas after the described supercharging and aqueous water or steam form air-water mixture; After described air-water mixture enters preheater and is converted into gaseous state, enter fixed bed catalytic reactor and carry out catalytic reaction.
16. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 15, described water injection pipe are water injection equipment or water filling steaming plant, described aqueous water comprises distilled water.
17. the dephosphorization catalyst reaction device according to claim 15 or 16 described yellow phosphoric tail gas is characterized in that, also comprises:
The condenser that is connected with described fixed bed catalytic reactor;
Described yellow phosphoric tail gas after catalytic reaction is condensed into phosphoric acid solution at condenser.
18. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 15 is characterized in that, also comprises:
Be connected the surge tank between described gas boosting equipment and the preheater;
The described yellow phosphoric tail gas that is pressurized to default atmospheric pressure value enters preheater behind described surge tank steady air flow.
19. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 15 is characterized in that, described default atmospheric pressure value is arbitrary value among 0.05MPa～0.5MPa.
20. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 15 is characterized in that, the default percent by volume of described aqueous water or steam and yellow phosphoric tail gas is arbitrary value in 10: 90～50: 50.
21. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 20 is characterized in that, the default percent by volume of described aqueous water or steam and yellow phosphoric tail gas is 30: 70.
22. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 15 is characterized in that, the temperature of the preheating that described preheater adopts is arbitrary value in 300～500 ℃.
23. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 15 is characterized in that, the bed temperature that described fixed bed catalytic reactor adopts is arbitrary value in 300～500 ℃.
24. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 23 is characterized in that, the bed temperature that described fixed bed catalytic reactor adopts is 380 ℃.
25. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 15 is characterized in that, the air speed that described fixed bed catalytic reactor adopts is 500～10000h
-1In arbitrary value.
26. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 25 is characterized in that, the air speed that described fixed bed catalytic reactor adopts is 5000h
-1
27. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 15 is characterized in that, the catalyst that described fixed bed catalytic reactor adopts is surface treated activated carbon supported type catalyst.
28. the dephosphorization catalyst reaction device of yellow phosphoric tail gas according to claim 17 is characterized in that, the temperature that described condenser adopts is arbitrary value in 0～60 ℃.
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| CN110813081A (en) * | 2019-11-04 | 2020-02-21 | 北京敬科科技发展有限公司 | Purification process of yellow phosphorus tail gas for combustion power generation |
| CN114588734A (en) * | 2022-01-28 | 2022-06-07 | 杨光华 | Method for purifying yellow phosphorus tail gas of electric furnace |
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