CN1128001C - Method for removing phosphorus, phosphide, surfide and recovering phosphorus from yellow phosphorus tail gas - Google Patents
Method for removing phosphorus, phosphide, surfide and recovering phosphorus from yellow phosphorus tail gas Download PDFInfo
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- CN1128001C CN1128001C CN 00116137 CN00116137A CN1128001C CN 1128001 C CN1128001 C CN 1128001C CN 00116137 CN00116137 CN 00116137 CN 00116137 A CN00116137 A CN 00116137A CN 1128001 C CN1128001 C CN 1128001C
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- yellow phosphoric
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Abstract
The present invention relates to a gas separation method, particularly to a method for purifying yellow phosphorus tail gas and recovering phosphorus. In the method, an acidic component is eliminated by a caustic washing procedure, the phosphorus is washed and recovered by industrial water in a low-temperature water washing procedure, phosphide and sulphide are adsorbed and eliminated by an adsorbent in a pressure-variable and temperature-variable adsorbing procedure so that purified gas is obtained, the regeneration of the adsorbent is realized by the steps of reverse pressure release, heating and washing, cold blowing and pressurization, and regenerated waste gas exhausts after the acidic component is eliminated by the caustic washing procedure. The present invention has the advantages of simple process and convenient use, and is suitable for purifying the yellow phosphorus tail gas and other kinds of mixed gas containing phosphorus, hydrogen phosphate, hydrogen sulfide and carbon oxysulfide. The content of the phosphorus and the compound thereof in the purified gas is less than 1 ppm, and the content of the sulphide is less than 1 ppm.
Description
The present invention relates to gas separation method, particularly the method for the purification of yellow phosphoric tail gas and recovery phosphorus.
Yellow phosphoric tail gas is the source of the gas that is rich in carbon monoxide, because it contains impurity such as sulphur, phosphorus, arsenic, fluorine, the comprehensive utilization technique of yellow phosphoric tail gas normally after preliminary purification, absorbs production oxalic acid etc. as fuel or soda ash.Therefore the comprehensive utilization of yellow phosphoric tail gas is restricted.
The existing method that removes phosphorus and phosphide thereof from yellow phosphoric tail gas mainly contains:
(1) solution oxide absorption process
This method is to utilize the solution that contains oxidant (such as hydrogen peroxide, clorox) that the component to be clean of phosphorus and hydrogen phosphide etc. is carried out oxidation, absorbs by alkaline solution behind the oxide of generation phosphorus.Shortcoming is to consume oxidant, and clean-up effect and oxidant are active and alkali absorption efficiency relation is very big, and the device operability is relatively poor.
(2) alkaline solution washing method
Adopt alkaline solution absorptions such as milk of lime.Shortcoming is the acidic components that can only remove in the yellow phosphoric tail gas, and it is not high to purify precision.
(3) active carbon oxidation absorption method
Employing reducing impurity component generation catalytic reaction such as the phosphorus in oxygen and the yellow phosphoric tail gas, hydrogen phosphide and the mechanism that is adsorbed removes reducing impurity components such as phosphorus, hydrogen phosphide on activated carbon surface.Shortcoming is to need strict quantitative oxygen or the air added in yellow phosphoric tail gas.The device poor operability, and adsorbent can not be regenerated.Cause the secondary pollution of phosphorous active carbon.
Above several method all exists and takes off that the phosphide precision is not high, energy consumption is high, flow process is complicated, investment is big or defectives such as secondary pollution are arranged.
Given this, the purpose of this invention is to provide a kind of phosphorus, phosphide, sulfide of from yellow phosphoric tail gas, removing, and reclaim the method for phosphorus.
The present invention adopts yellow phosphoric tail gas is carried out alkali cleaning, low temperature washing, pressure and temperature varying absorption successively, the back alkali washing process process of regeneration off gases is realized its purpose.
The method that removes phosphorus, phosphide, sulfide from yellow phosphoric tail gas of the present invention has following operation:
(1) caustic wash process: in caustic wash tower, remove acidic components in the yellow phosphoric tail gas with alkali cleaning after, send into the low temperature washing step;
(2) low temperature washing step: in the low temperature water scrubber, be after 1 ℃～-15 ℃ washings washings yellow phosphoric tail gas reclaims phosphorus, to send into the pressure and temperature varying absorption process with temperature;
(3) pressure and temperature varying absorption process: in the circular flow system of at least two adsorbent beds that are filled with adsorbent, each adsorbent bed of operation each time of system carries out adsorption step and regeneration step successively, wherein, adsorption step is with phosphide in the adsorbents adsorb yellow phosphoric tail gas and sulfide and be trapped in the adsorbent bed, the purified gas that obtains is discharged system, regeneration step successively through reversely put pressure, add heat flush, cold blowing, pressurising step reproducing adsorbent, the regeneration off gases of generation is sent into the back caustic wash process;
(4) back caustic wash process in the caustic wash tower of back, removes discharge system behind the acidic components in the regeneration off gases with alkali cleaning.
The pressure of above-mentioned adsorption step is 0.02～1.5MPa, and said regeneration step temperature is 60 ℃～150 ℃, contain phosphide and sulfide that the nitrogen of oxygen 0.01～5% or purified gas, desorb that adsorbent bed is discharged are adsorbed agent absorption.
Above-mentioned pressurising step is boosted or/and boost with the feed end of unstripped gas from adsorbent bed with the product end of purified gas from adsorbent bed.
The washings of above-mentioned low temperature washing step are water or brine ice, and the cleaning solution that washing produces stands the phosphorus groove and reclaims phosphorus.
Adsorbent in the above-mentioned pressure and temperature varying absorption process is at least a in active carbon, aluminium oxide, silica gel, the molecular sieve.
Alkali in above-mentioned caustic wash process and the back caustic wash process is milk of lime or soda ash solution or soda bath.
Pressure and temperature varying absorption process of the present invention is formed a continuous movement system by at least two adsorbent beds, and each adsorbent bed in them once must experience following steps in the circulation successively:
(1) absorption
Unstripped gas sent into from bottom to up have 0.02MPa～adsorb in the adsorbent bed of 1.5MPa pressure, the adsorbent in the adsorbent bed adsorbs phosphide, sulfide, purified gas is discharged from the adsorbent bed top.When the forward position of adsorption zone is moved upwards up to the certain position of bed, phosphide, sulfide reach normal concentration in Purge gas after, end to enter unstripped gas, stop absorption, unstripped gas entered cooled another adsorbent bed of regenerating and adsorbed this moment.
(2) the reverse pressure of putting
Make adsorbent bed reverse pressure of putting under adsorptive pressure, gas is emitted from the bottom reach atmosphere pressure state.
(3) add heat flush
With containing oxygen 0.01～5% nitrogen, or a part of purified gas of another adsorbent bed discharge, be heated to 60～150 ℃ with 0.01MPa～0.5MPa pressure through heater, from top to bottom pass through bed, make the phosphide, the sulfide desorb that are adsorbed, reproducibility components such as hydrogen phosphide, phosphorus are oxidized simultaneously, and adsorbent obtains regeneration.
(4) cold blowing
In order to prepare to enter adsorption step, must make bed be cooled to environment temperature, promptly stop to heat and continue to wash, cool off with the cold air after purifying.
(5) pressurising
With purified gas bed is boosted to adsorptive pressure.
Each adsorbent bed all will experience identical step, just diverge mutually on the sequential, carry out continuously to guarantee separation process.
The inventive method adopts caustic wash process, removes acidic componentses such as hydrogen sulfide a large amount of in the yellow phosphoric tail gas with alkali; Adopt the low temperature washing step with cold washing water washing yellow phosphoric tail gas, wash the gained cleaning solution and stand phosphorus groove recovery phosphorus.Adopt the pressure and temperature varying absorption process to remove phosphide and sulfide with adsorbents such as active carbon, aluminium oxide, silica gel, molecular sieves; Emptying behind the acidic componentses such as hydrogen sulfide after adopting in the caustic wash process regenerated from washing waste gas and phosphorous oxide.Therefore, have following substantive distinguishing features and positive effect compared with the prior art:
One, adopt the method for the present invention can be with the content of phosphorus, hydrogen phosphide, hydrogen sulfide in the yellow phosphoric tail gas from 50～15000mg/m
3, all can be removed to 5mg/m
3Below, the minimum 1mg/m that reaches
3, the rate of recovery with the precision height that removes phosphorus and phosphide, phosphorus can be up to 80% advantage.And the washings behind the recovery phosphorus recycle after can reducing temperature by cooler.
Two, adopt this method deep purifying yellow phosphoric tail gas, the carbon monoxide content of the purified gas of acquisition can reach 99.5%, and it is synthetic to be directly used in carbonyl, has the advantage of the comprehensive utilization of widening yellow phosphoric tail gas.
Three, adopt the inventive method, can exempt and adopt combustion method to handle the pollution of yellow phosphoric tail gas atmosphere.Because vent gas is cleaned, and has the advantage that reduces greatly atmosphere pollution.
Method of the present invention is applicable to that yellow phosphoric tail gas and other contain the gaseous mixture of phosphide or sulfide, for example, and the purified treatment of lime-kiln gas, power plant's waste gas.
Below, with embodiment and accompanying drawing the present invention is elaborated again.
Brief description of drawings:
Fig. 1 is a kind of flow chart that removes phosphorus, phosphide, sulfide and reclaim the method for phosphorus from yellow phosphoric tail gas of the present invention.
Fig. 2 is that another kind of the present invention removes phosphorus, phosphide, sulfide and reclaims the flow chart of the method for phosphorus from yellow phosphoric tail gas.
Embodiment 1:
A kind of method that removes phosphorus, phosphide, sulfide and reclaim phosphorus from yellow phosphoric tail gas of the present invention, its technological process as shown in Figure 1.This method is carried out four following operations successively.
One, caustic wash process
With yellow phosphoric tail gas 500Nm
3/ h is after air blast is forced into 0.08MPa, send into the caustic wash tower of caustic wash process through pipeline, caustic wash tower adopts the tower bubble type washing of spray absorption plant, alkali adopts milk of lime or alkaline solutions such as soda ash solution or soda bath, and the washing yellow phosphoric tail gas is to remove acidic componentses such as hydrogen sulfide a large amount of in the yellow phosphoric tail gas.Yellow phosphoric tail gas after alkali cleaning is admitted to the low temperature washing step.
Two, low temperature washing step
In the low temperature washing step, adopting common low temperature water scrubber temperature is 1 ℃～-15 ℃ washings washings yellow phosphoric tail gas, and phosphorus is tentatively removed.Washings can be selected water or brine ice for use.The cleaning solution that washing is produced reclaims phosphorus through the common phosphorus groove that is subjected to.Washings behind the recovery phosphorus recycle after reducing temperature by cooler.
Three, pressure and temperature varying absorption process (PTSA)
The pressure and temperature varying absorption process adopts two tower pressure and temperature varying adsorption systems of common structure, and the adsorbent that loads in adsorption tower A tower and B tower is selected for use has the acticarbon that enriches pore structure and appropriate bore distribution.
Two tower pressure and temperature varying absorbing process step time-scales are as shown in table 1.To after alkali cleaning and the preliminary purification of low temperature washing step, pressure be the yellow phosphoric tail gas of 0.05MPa, and send into the A tower or send into the B tower through valve 2A by pipeline with through valve 1A.When the A tower was in adsorption step, valve 1A, the 2A that links with the A tower opened, and 3A, 4A close, the phosphorus in the yellow phosphoric tail gas, hydrogen sulfide, and sulfide by the adsorbents adsorb of filling in the tower, the purified gas that obtains is sent system reserve through pipeline again through valve 2A.
When the A tower was in adsorption step, the B tower was in regeneration step.The B tower first step is the reverse pressure step of putting during regeneration, and valve 1B, the 2B, 3B and the 4B that link to each other with the B tower all close, and the adsorbent in the B tower has been inhaled saturated phosphide and sulfide, and then open valve 3B is that the gas of 0.05MPa is discharged by pipeline with B tower internal pressure.Second step was the heating rinsing step, open valve 4B, allow the nitrogen heater via E that contains 0.5% oxygen, be heated to 100 ℃, enter the B tower through pipeline and valve 4B, add heat-adsorbent, and then outside valve 3B and pipeline discharge tower, along with whole adsorbent constantly is heated, the phosphide that is adsorbed, sulfide are also constantly by desorb, phosphorus and hydrogen phosphide are oxidized, and stripping gas is discharged through pipeline.The 3rd step was the cold blowing step, stopped heating this moment, and cold regeneration gas is taken away the heat that accumulates in the B tower by the whole bed of adsorbent bed, and cooling is closed 4B, 3B then till environment temperature.The 4th step was the pressurising step, and open valve 2B, purified gas are progressively to the pressurising of B tower, and be identical with the A tower until its pressure, and reach till the adsorptive pressure, immediately shut off valve 2B.
The time of above-mentioned adsorption step is 6 hours, in the regeneration step reverse put press 5 minutes, added heat flush 3 hours, cold blowing flushing 2.5 hours, pressurising 25 minutes.Add heat flush and cold blowing and all carry out under 0.02MPa pressure, temperature is controlled at 100 ℃ when adding heat flush, contains phosphide＜1mg/m in the Purge gas
3, sulfur compound＜1mg/m
3
Table 1 two tower pressure and temperature varying absorbing process step time-scales
| The A tower | Absorption | The reverse pressure of putting | Add heat flush | Cold blowing | Pressurising | |||
| The B tower | The reverse pressure of putting | Add heat flush | Cold blowing | Pressurising | Absorption | |||
The reverse of this operation put the discharge gas of pressing step and heats the stripping gas general designation regeneration off gases that rinsing step is discharged, caustic wash process after pipeline 40 is sent into.
Four, back caustic wash process
The back caustic wash tower of back caustic wash process adopts spray column or bubble type washing absorption plant, alkali adopts milk of lime or alkaline solutions such as soda ash solution or soda bath, washing removes acidic componentses such as hydrogen sulfide in the regeneration off gases, phosphorous oxide, reduce the pollution of regeneration off gases, purified gas emptying to atmosphere.
Embodiment 2:
A kind of method that removes phosphorus, phosphide, sulfide from yellow phosphoric tail gas of the present invention, its technological process as shown in Figure 2.This method is substantially the same manner as Example 1.Be characterized in adopting three tower pressure and temperature varying adsorption systems at the pressure and temperature varying absorption process.Three tower pressure and temperature varying absorbing process step time-scales, as shown in table 2.
Table 2 three tower pressure and temperature varying absorbing process step time-scales
| The A tower | Absorption | The reverse pressure of putting | Add heat flush | Isolate | Cold blowing | Pressurising | |||
| The B tower | Isolate | Cold blowing | Pressurising | Absorption | The reverse pressure of putting | Add heat flush | Isolate | ||
| The C tower | The reverse pressure of putting | Add heat flush | Isolate | Cold blowing | Pressurising | Absorption | |||
Present embodiment is with 3000Nm
3After the yellow phosphoric tail gas of/h is sent into caustic wash process after water-ring vacuum pump is forced into 0.05MPa caustic wash tower removes acidic componentses such as hydrogen sulfide, after the low temperature water scrubber of sending into the low temperature washing step removes and reclaims phosphorus, enter three tower pressure and temperature varying adsorption systems yellow phosphoric tail gas is entered deep purifying, adsorbent adopts the special-purpose activated charcoal that carries 1% sodium and 0.4% iron, the time of adsorption step is 4 hours, contraryly in the regeneration step puts 5 minutes, add heat flush 3.5 hours, cold blowing flushing 3.5 hours, pressurising 25 minutes.Add heat flush and cold blowing flushing and all carry out under 0.01MPa pressure, adding the heat flush temperature is 105 ℃.Purify in the gas of back and contain phosphide＜5mg/m
3Sulfur compound＜5mg/m
3Reversely put the discharge gas of pressing step and stripping gas emptying after the back caustic wash tower washing of back caustic wash process of heating rinsing step.
Claims (6)
1, from yellow phosphoric tail gas, remove phosphorus, phosphide, sulfide and reclaim the method for phosphorus, it is characterized in that having following operation:
(1) caustic wash process: in caustic wash tower, remove acidic components in the yellow phosphoric tail gas with alkali cleaning after, send into the low temperature washing step;
(2) low temperature washing step: in the low temperature water scrubber, be 1 ℃～-15 ℃ washings washings yellow phosphoric tail gas with temperature, condensation of phosphorus steam and precipitation and reclaim phosphorus, the yellow phosphoric tail gas after the washing is sent into the pressure and temperature varying absorption process;
(3) pressure and temperature varying absorption process: in the circular flow system of at least two adsorbent beds that are filled with adsorbent, each adsorbent bed of operation each time of system carries out adsorption step and regeneration step successively, wherein, adsorption step is with phosphide in the adsorbents adsorb yellow phosphoric tail gas and sulfide and be trapped in the adsorbent bed, the purified gas that obtains is discharged system, regeneration step is successively through reversely putting pressure, adding the heat flush reproducing adsorbent, again through cold blowing, pressurising absorption preparation process, the regeneration off gases that produces is sent into the back caustic wash process;
(4) back caustic wash process: in the caustic wash tower of back, remove discharge system behind the acidic components in the regeneration off gases with alkali cleaning.
2, the method that from yellow phosphoric tail gas, removes phosphorus, phosphide, sulfide and reclaim phosphorus according to claim 1, the pressure that it is characterized in that said adsorption step is 0.02～1.5MPa, and said regeneration step temperature is 60 ℃～150 ℃, contain phosphide and sulfide that the nitrogen of oxygen 0.01～5%mol or purified gas, desorb that adsorbent bed is discharged are adsorbed agent absorption.
3, the method that removes phosphorus, phosphide, sulfide and reclaim phosphorus from yellow phosphoric tail gas according to claim 1 and 2 is characterized in that said pressurising step boosts or/and boost with the feed end of unstripped gas from adsorbent bed with the product end of purified gas from adsorbent bed.
4, the method that from yellow phosphoric tail gas, removes phosphorus, phosphide, sulfide and reclaim phosphorus according to claim 1 and 2, the washings that it is characterized in that said low temperature washing step are water or brine ice, the cleaning solution that washing produces stands the phosphorus groove and reclaims phosphorus.
5, the method that removes phosphorus, phosphide, sulfide and reclaim phosphorus from yellow phosphoric tail gas according to claim 1 and 2 is characterized in that adsorbent in the said pressure and temperature varying absorption process is at least a in active carbon, aluminium oxide, silica gel, the molecular sieve.
6, the method that removes phosphorus, phosphide, sulfide and reclaim phosphorus from yellow phosphoric tail gas according to claim 1 and 2 is characterized in that the alkali in said caustic wash process and the back caustic wash process is milk of lime or soda ash solution or soda bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00116137 CN1128001C (en) | 2000-09-29 | 2000-09-29 | Method for removing phosphorus, phosphide, surfide and recovering phosphorus from yellow phosphorus tail gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00116137 CN1128001C (en) | 2000-09-29 | 2000-09-29 | Method for removing phosphorus, phosphide, surfide and recovering phosphorus from yellow phosphorus tail gas |
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|---|---|
| CN1345620A CN1345620A (en) | 2002-04-24 |
| CN1128001C true CN1128001C (en) | 2003-11-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516028B (en) * | 2011-11-17 | 2014-06-11 | 四川天一科技股份有限公司 | Method for preparing methanol and dimethyl ether by taking calcium carbide furnace tail gas and sodium chlorate tail gas as well as other hydrogen-containing gas sources as raw materials |
| CN103011079B (en) * | 2012-12-20 | 2014-09-03 | 贵州开磷（集团）有限责任公司 | Method for treating waste carbide slag and waste hydrochloric acid |
| CN103466575B (en) * | 2013-09-09 | 2015-06-17 | 湖北泰盛化工有限公司 | Novel phosphorus pressing method and equipment in production of phosphorus trichloride |
| CN103657329B (en) * | 2013-12-25 | 2016-05-04 | 贵州开磷集团股份有限公司 | A kind of yellow phosphoric tail gas centralized Control reclaims and purifier |
| CN103994944B (en) * | 2014-05-28 | 2016-05-25 | 天津大学 | A kind of testing arrangement and method of hydrogen phosphide burst size of red phosphorus flame-retardant polymeric material |
| CN105402991B (en) * | 2015-12-28 | 2018-03-23 | 苟仲武 | Condensation recovery discharge gas chemical composition and the method and apparatus to generate electricity |
| CN108341405A (en) * | 2018-01-16 | 2018-07-31 | 湖北兴福电子材料有限公司 | A kind of device and method that the phosphorous off-gas recovery of yellow phosphorus storage tank recycles |
| CN111234883A (en) * | 2020-01-20 | 2020-06-05 | 河北燕钢科技有限公司 | Coal gas double-tower washing and purifying system |
| CN111514701B (en) * | 2020-04-30 | 2021-07-27 | 昆明理工大学 | Method for purifying CO in yellow phosphorus tail gas through magnetic-assisted pressure swing adsorption |
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