CN1128000C - Method for removing phosphorus, phosphide and surfide from yellow phosphorus tail gas - Google Patents
Method for removing phosphorus, phosphide and surfide from yellow phosphorus tail gas Download PDFInfo
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- CN1128000C CN1128000C CN 00116136 CN00116136A CN1128000C CN 1128000 C CN1128000 C CN 1128000C CN 00116136 CN00116136 CN 00116136 CN 00116136 A CN00116136 A CN 00116136A CN 1128000 C CN1128000 C CN 1128000C
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- tail gas
- phosphide
- phosphorus
- adsorbent
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Abstract
The present invention relates to a gas separation method, particularly to a method for purifying yellow phosphorus tail gas. In the method, acidic components are removed in a caustic washing procedure, phosphorus is removed by a carbonaceous adsorbent in a pretreatment procedure, phosphide and sulphide are adsorbed and removed by an adsorbent in a variable-pressure and variable-temperature adsorption procedure so that purified gas is acquired, the regeneration of the adsorbent is realized by the steps of reverse pressure release, heating and flushing, cold blowing and pressurization, and regenerated waste gas is evacuated after the acidic components are removed in a subsequent caustic washing procedure. The present invention has the advantages of simple process and convenient operation, the content of the phosphorus and other compounds in the purified gas is less than 1 ppm, and the content of sulphide is less than 1 ppm. The present invention is suitable for purifying the yellow phosphorus tail gas and other kinds of mixed gas containing phosphorus, phosphine, hydrogen sulfide and carbon sulfide.
Description
The present invention relates to gas separation method, particularly the purification method of yellow phosphoric tail gas.
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 such as the phosphorus in oxygen and the yellow phosphoric tail gas, hydrogen phosphide on activated carbon surface reacts and the mechanism that is adsorbed removes reducing impurity components such as phosphorus and hydrogen phosphide thereof.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, carbonaceous adsorbent preliminary treatment, 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 pretreatment process;
(2) pretreatment process: in pretreater, behind the phosphorus in the carbonaceous adsorbent adsorbing and removing yellow phosphoric tail gas, send 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, the adsorption step yellow phosphoric tail gas passes through adsorbent bed, phosphide in the yellow phosphoric tail gas and sulfide are adsorbed agent absorption and are trapped in the adsorbent bed, thereby obtain purified gas and discharge system, regeneration step successively through reversely put pressure, add heat flush, cold blowing, pressurising step reproducing adsorbent, 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.
The pressure of above-mentioned adsorption step is 0.02～2.0MPa, and said regeneration step temperature is 60 ℃～150 ℃ the nitrogen that contains oxygen 0.5～5% or the purified gas of above-mentioned adsorbent bed discharge, and desorb is adsorbed the phosphide and the sulfide of agent absorption.
Carbonaceous adsorbent in the above-mentioned pretreatment process is coke or active carbon.
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 2.0MPa 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
Be heated to 60～150 ℃ with nitrogen that contains oxygen 0.5%～5% or the inert gas that contains oxygen 0.5%～5% 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 present invention adopts caustic wash process, removes acidic componentses such as hydrogen sulfide a large amount of in the yellow phosphoric tail gas with alkali; The phosphorus of employing pretreatment process in the carbonaceous adsorbent adsorbing and removing yellow phosphoric tail gas; 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; Acidic componentses such as hydrogen sulfide after adopting in the caustic wash process regenerated from washing waste gas and phosphorous oxide.
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, be removed to 5mg/m
3Below, the minimum 1mg/m that reaches
3, have the efficient that removes phosphorus and phosphide and can reach 80%～99% advantage, and the saturated adsorbent under changing can send the reduction of yellow phosphorus stove to reclaim phosphorus again.
Two, adopt this method deep purifying yellow phosphoric tail gas, the carbon monoxide content height of the purified gas of acquisition, 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 are phosphorous, the purified treatment of the gaseous mixture of hydrogen phosphide, hydrogen sulfide, sulphur oxygen carbon.
Below, the present invention is described in detail to use embodiment and accompanying drawing thereof again.
Brief description of drawings:
Fig. 1 is a kind of flow chart that removes the method for phosphorus, phosphide, sulfide from yellow phosphoric tail gas of the present invention.
Fig. 2 is another kind of the present invention removes the method for phosphorus, phosphide, sulfide from yellow phosphoric tail gas a flow chart.
Embodiment 1:
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 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 0.05MPa, send into the caustic wash tower of caustic wash process through pipeline 10, 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 pretreatment process.
Two, pretreatment process
In pretreatment process, adopt the pretreater of the absorber formula that is filled with carbonaceous adsorbents such as coke or active carbon, the phosphorus in the yellow phosphoric tail gas is tentatively removed.Can be removed 80%～99% by the phosphorus in the yellow phosphoric tail gas behind the pretreatment process.Adsorbent uses saturated back to change, and the adsorbent under changing send the yellow phosphorus stove to make reducing agent and reclaims phosphorus.
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 be the yellow phosphoric tail gas of 0.02MPa～2.0MPa through the pressure after alkali cleaning and the pretreatment process preliminary purification, and send into the A tower or send into the B tower through valve 2A by pipeline and 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 discharges the gas of 0.02MPa in the B tower～2.0MPa pressure by pipeline.Second step was the heating rinsing step, open valve 4B allows the nitrogen heater via E that contains 0.5% oxygen, is heated to 120 ℃, enter the B tower through pipeline and valve 4B, add heat-adsorbent, and then through valve 3B, pipeline is discharged outside the tower, along with whole adsorbent constantly is heated, the phosphide that is adsorbed, sulfide are also constantly by desorb, and 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 120 ℃ 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 discharge gas of pressing step and the stripping gas that heats the rinsing step discharge put of this operation is referred to as regeneration off gases, 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 pretreater of sending into pretreatment process 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 (5)
1, from yellow phosphoric tail gas, remove the method for phosphorus, phosphide, sulfide, 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 pretreatment process;
(2) pretreatment process: in pretreater, behind the phosphorus in the carbonaceous adsorbent adsorbing and removing yellow phosphoric tail gas, send 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, the adsorption step yellow phosphoric tail gas passes through adsorbent bed, phosphide in the yellow phosphoric tail gas and sulfide are adsorbed agent absorption and are trapped in the adsorbent bed, thereby obtain purified gas and discharge system, regeneration step is successively through the reverse pressure of putting, add heat flush, cold blowing, pressurising step reproducing adsorbent, the above-mentioned reverse pressure of putting, add heat flush, the sulfur compound that the cold blowing step produces and the regeneration off gases of phosphide are 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 according to claim 1, the pressure that it is characterized in that said adsorption step is 0.02～2.0MPa, said regeneration step temperature is 60 ℃～150 ℃ the nitrogen that contains oxygen 0.5～5%mol or the purified gas of above-mentioned adsorbent bed discharge, and desorb is adsorbed the phosphide and the sulfide of agent absorption.
3, the method that removes phosphorus, phosphide, sulfide from yellow phosphoric tail gas according to claim 1 and 2 is characterized in that the carbonaceous adsorbent in the said pretreatment process is coke or active carbon.
4, the method that removes phosphorus, phosphide, sulfide 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.
5, from yellow phosphoric tail gas, remove the method for phosphorus, phosphide, sulfide according to claim 1 or 2, it 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 00116136 CN1128000C (en) | 2000-09-29 | 2000-09-29 | Method for removing phosphorus, phosphide and surfide from yellow phosphorus tail gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00116136 CN1128000C (en) | 2000-09-29 | 2000-09-29 | Method for removing phosphorus, phosphide and surfide from yellow phosphorus tail gas |
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| CN1345619A CN1345619A (en) | 2002-04-24 |
| CN1128000C true CN1128000C (en) | 2003-11-19 |
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| CN 00116136 Expired - Lifetime CN1128000C (en) | 2000-09-29 | 2000-09-29 | Method for removing phosphorus, phosphide and surfide from yellow phosphorus tail gas |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369654C (en) * | 2006-05-10 | 2008-02-20 | 昆明理工大学 | Method for depriving arsenic fluorin phosphoric acid from tail gas of yellow phosphorus |
| CN101024140B (en) * | 2007-01-15 | 2010-06-02 | 左建国 | Method for purifying phosphor tail-gas |
| CN101590354B (en) * | 2008-05-30 | 2012-01-25 | 大连凯特利催化工程技术有限公司 | Dephosphorization agent for removing PH3 in yellow phosphorus tail gas, preparation method and application thereof |
| CN103182244B (en) * | 2011-12-30 | 2015-04-29 | 北京北大先锋科技有限公司 | Dephosphorization catalytic reaction technology of yellow phosphorus tail gas and apparatus |
| CN104069734B (en) * | 2013-03-26 | 2016-04-20 | 北京北大先锋科技有限公司 | A kind of dephosphorization catalytic reaction technique of yellow phosphoric tail gas and catalyst |
| CN105194996B (en) * | 2015-09-15 | 2017-09-05 | 华烁科技股份有限公司 | A kind of method of comprehensive utilization of yellow phosphoric tail gas |
| CN109316900B (en) * | 2018-11-13 | 2021-08-31 | 山东阿斯德科技有限公司 | Comprehensive utilization method of converter tail gas |
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