CN102311301A - Copper salt absorption liquid for desorbing arsenic hydride from ethane and propene in gas phase and application thereof - Google Patents
Copper salt absorption liquid for desorbing arsenic hydride from ethane and propene in gas phase and application thereof Download PDFInfo
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- CN102311301A CN102311301A CN2010102123154A CN201010212315A CN102311301A CN 102311301 A CN102311301 A CN 102311301A CN 2010102123154 A CN2010102123154 A CN 2010102123154A CN 201010212315 A CN201010212315 A CN 201010212315A CN 102311301 A CN102311301 A CN 102311301A
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- propylene
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Abstract
The invention relates to a copper salt absorption liquid for desorbing arsenic hydride from ethane and propene in gas phase and an online monitoring system. The absorption liquid is composed of the mixed liquid of bromine water, hydrogen peroxide, copper salt and inorganic acid. The online monitoring system comprises a sampling system, a gas-phase chromatographic separation system and a mass spectrum analysis system, wherein a six-way valve of the sampling system is used for sampling continuously; and the gas-phase chromatographic separation system is used for separating the arsenic hydride from the ethane and the propene, and then the mass spectrum analysis system is used for monitoring quantitatively. The absorption liquid provided by the invention has the advantages of simple ingredient and low cost. The arsenic hydride in the ethane and the propene can be desorbed to a content of smaller than 30ppb. The online monitoring system has the advantages of high sensitivity, low limit of detection and capability of rapidly reflecting the absorbing and purifying effect of the absorption liquid.
Description
Technical field
The present invention relates to a kind of solution, and the decontamination effect improving of absorbent solution is monitored, to guarantee purifying back hydrogen arsenide content less than 30ppb through on-line monitoring system through arsine gas in catalysed oxidation processes purification gaseous ethene, the propylene.
Background technology
Ethene, propylene gas are to produce polyolefinic virgin gas, so Vilaterm, polyacrylic performance are decided by that polymerization process also is decided by material purity and foreign matter content.Arsenide is typical polyolefin catalyst poisonous substance, and the many catalyzer that use in the industry are all very responsive to arsenide, and the arsenide of minute quantity (1,000,000/zero point is several) just can make the poisoning of catalyst inactivation.Improving constantly of the variation of domestic refinery crude oil, the improvement of deep process technology and working ability causes arsenide to be present in the different refined oil products.In polyolefin industry was produced, the existence of arsenic all had great influence to the consumption and the quality product of catalyzer, and the hydrogen arsenide of minute quantity just can make the poisoning of catalyst inactivation, and external polyolefin device explicitly calls for the arsenic content in ethene, the propylene.
Existing a lot of about the patent of dearsenic agent at present, the overwhelming majority is used for liquid hydrocarbon and oil product removes arsenide, all discloses a kind of supported dearsenic agent like Chinese patent CN101590418A and Chinese patent CN1259560A.But this dearsenic agent is not to develop to ethene, propylene feedstocks specially, and its dearsenification efficient can not satisfy the requirement (the efficient polyolefin catalyst of a new generation to hydrogen arsenide content requirement in olefin feedstock be not more than 30ppb (volume(tric)fraction)) of polyolefin catalyst to raw material.In addition, the Monitoring systems imperfection of state's nonterminal olefin refining plant leans on experience to calculate mostly and uses purification system.When purification system lost efficacy or Water purification descends and do not have timely replacing to bring greater loss to production equipment.Thereby the hydrogen arsenide of trace in the olefin feedstock is removed and set up Monitoring systems is very necessary.
Summary of the invention
The object of the present invention is to provide a kind of can hydrogen arsenide content in gaseous ethene, the propylene purification to be removed to the absorption liquid less than 30ppb (volume(tric)fraction), its composition is simple, cheap.On-line monitoring is investigated absorption liquid and is purified assimilation effect simultaneously.
Solving the scheme that technical problem of the present invention takes is:
1, the absorption liquid that absorbs hydrogen arsenide in ethene, the propylene is made up of the mixed solution of bromine water, ydrogen peroxide 50, mantoquita and suitable mineral acid (pH value regulator), and wherein mantoquita concentration is that 0.02～0.2mol/L, bromine water concentration are that 0.05～0.26mol/L, hydrogen peroxide concentration are 1-8mol/L.Preferred concentration range for: mantoquita concentration is that 0.02～0.04mol/L, bromine water concentration are that 0.09～0.12mol/L, hydrogen peroxide concentration are 3-4mol/L, pH value 2～4.Mantoquita can be chosen any one in copper sulfate, cupric nitrate, cupric chloride, the neutralized verdigris.Mantoquita is water-soluble, again with after bromine water and ydrogen peroxide 50 are mixed, regulate pH value to 2～4 with the concentrated hydrochloric acid of 1: 1 (volume ratio) and concentrated nitric acid and be made into absorption liquid.Absorption liquid pack in the airtight tourie and the mode that adopts plural serial stage in 20～80 ℃ of scopes to propylene in hydrogen arsenide absorb.
The mode of 2, packing into absorption liquid in the airtight tourie and adopting plural serial stage in 20～80 ℃ of scopes to ethene, propylene in hydrogen arsenide absorb.
3, on-line monitoring system is made up of sampling system, gc separation system, mass spectrometry system.Wherein the six-way valve in the sampling system can be realized continuous sample introduction, and gas chromatography system separates ethene, propylene again with hydrogen arsenide and carries out Quantitative Monitoring by mass spectrum.Chromatographic condition: chromatographic column: capillary column column length 60m internal diameter 0.32mm column temperature: 50 ℃ of initial temperatures; Constant temperature 6min, 150 ℃ of carrier gas of top temperature: helium 2.0mL/min constant current mode mass spectrum: quadrupole temperature: 150 ℃ of ion source temperatures: 230 ℃ of quantitative manner: select ion mode (SIM).
The invention has the beneficial effects as follows: a kind of absorption liquid and on-line monitoring system that removes hydrogen arsenide in gaseous ethene, the propylene is provided; Liquid absorption element is simple; Obtain easily, use cost is low, can the hydrogen arsenide in gaseous ethene, the propylene be purified extremely less than 30ppb (volume(tric)fraction).On-line monitoring system is highly sensitive, can monitor the hydrogen arsenide content that is not less than 10ppb (volume(tric)fraction) in ethene, the propylene.
Description of drawings
Fig. 1 removes hydrogen arsenide absorption liquid and on-line monitoring system schematic flow sheet in gaseous ethene, the propylene
The propylene feedstocks that Fig. 2 contains 910ppb (volume(tric)fraction) and hydrogen arsenide 96ppb (volume(tric)fraction) hydrogen arsenide purifies absorption front and back makings Monitoring systems comparison diagram.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described further:
Crude propylene is 910ppb (volume(tric)fraction) through its hydrogen arsenide content after the rough purification, with 0.26mol/L bromine aqueous solution: 30%H
2O
2Solution: the 0.2mol/L Cupric Chloride Solution is 3: 3: 1 mixed by volume; Bromine water concentration is that 0.11mol/L, hydrogen peroxide concentration are that 3.7mol/L, cupric chloride concentration are 0.03mol/L in the mixing solutions; Use 1: 1 concentrated hydrochloric acid and concentrated nitric acid to regulate the diameter 60mm that packs into after the pH value to 3 again; In the airtight purification resorber of long 250mm, mixing solutions keeps 70 ℃ of temperature.The propylene that contains hydrogen arsenide 910ppb (volume(tric)fraction) purifies the sample introduction six-way valve (3) of the direct connection monitoring system in absorption back through the absorption liquid (1) of one-level with the flow velocity of 100mL/min; Six-way valve is equipped with quantifying ring and realizes the continuous and quantitative sample introduction, and sampling interval is 20 minutes.The sample of propylene that contains the fixed amount hydrogen arsenide gets into chromatogram capillary column system (4) propylene major constituent through six-way valve separates with hydrogen arsenide, and hydrogen arsenide gets into mass spectrum (5) quantitative Analysis.The monitoring time of a sample is 20 minutes.Fig. 2 passes through the surveillance map after the one-level absorption liquid purifies for the propylene feedstocks that contains 910ppb (volume(tric)fraction) hydrogen arsenide; The makings peak area that can find out the hydrogen arsenide of 910ppb (volume(tric)fraction) through monitoring diminishes, and is 96ppb (volume(tric)fraction) through calculating hydrogen arsenide content.Explaining only to absorb through one-level also has the hydrogen arsenide of trace residual.
With 0.26mol/L bromine aqueous solution: 30%H
2O
2Solution: the 0.2mol/L Cupric Chloride Solution is 3: 3: 1 mixed by volume; Bromine water concentration is that 0.11mol/L, hydrogen peroxide concentration are that 3.7mol/L, cupric chloride concentration are 0.03mol/L in the mixing solutions; Use 1: 1 concentrated hydrochloric acid and concentrated nitric acid to regulate three the diameter 0.1m that pack into behind the pH value to 3 again; In the purification adsorber of long 1m, mixing solutions keeps 30 ℃ of temperature.The crude propylene that contains hydrogen arsenide 910ppb (volume(tric)fraction) purifies through three grades of placed in-line absorption liquids (1) with the flow velocity of 1.2L/min and absorbs after the sample introduction six-way valve (3) of bypass moisture eliminator (2) connection monitoring system; Six-way valve is equipped with quantifying ring and realizes the continuous and quantitative sample introduction, and sampling interval is 20 minutes.The sample of propylene that contains fixed amount trace hydrogen arsenide gets into chromatogram capillary column system (4) propylene major constituent through six-way valve separates with hydrogen arsenide, and hydrogen arsenide gets into mass spectrum (5) quantitative Analysis.The monitoring time of a sample is 20 minutes.Fig. 2 passes through the surveillance map after absorption liquid purifies for the propylene feedstocks that contains 910ppb (volume(tric)fraction) hydrogen arsenide; The peak that can find out the hydrogen arsenide of 910ppb (volume(tric)fraction) through monitoring disappears, and explains that the hydrogen arsenide content that purifies the back propylene is less than 10ppb (volume(tric)fraction).
Crude propylene finds that through monitoring after the rough purification hydrogen arsenide content is 910ppb (volume(tric)fraction), with 0.26mol/L bromine aqueous solution: 30%H
2O
2Solution: the 0.2mol/L copper-bath is 4: 4: 1 mixed by volume; Bromine water concentration is that 0.12mol/L, hydrogen peroxide concentration are that 3.9mol/L, concentration of copper sulfate are 0.02mol/L in the mixing solutions; Use 1: 1 concentrated hydrochloric acid and concentrated nitric acid to regulate the diameter 60mm that packs into after the pH value to 2 again; In the purification adsorber of long 250mm, mixing solutions keeps 70 ℃ of temperature.The propylene that contains trace hydrogen arsenide 910ppb (volume(tric)fraction) purifies the sample introduction six-way valve (3) of the direct connection monitoring system in absorption back through the absorption liquid (1) of one-level with the flow velocity of 80mL/min; Six-way valve is equipped with quantifying ring and realizes the continuous and quantitative sample introduction, and sampling interval is 20 minutes.The sample of propylene that contains the fixed amount hydrogen arsenide gets into chromatogram capillary column system (4) propylene major constituent through six-way valve separates with hydrogen arsenide, and hydrogen arsenide gets into mass spectrum (5) quantitative Analysis.The monitoring time of a sample is 20 minutes.Fig. 2 passes through the surveillance map after absorption liquid purifies for the propylene feedstocks that contains 910ppb (volume(tric)fraction) hydrogen arsenide; The peak that can find out the hydrogen arsenide of 910ppb (volume(tric)fraction) through monitoring disappears, and explains that the hydrogen arsenide content that purifies the back propylene is less than 10ppb (volume(tric)fraction).
With 0.26mol/L bromine aqueous solution: 30%H
2O
2Solution: the 0.2mol/L copper-bath is 4: 4: 1 mixed by volume; Bromine water concentration is that 0.12mol/L, hydrogen peroxide concentration are that 3.9mol/L, concentration of copper sulfate are 0.02mol/L in the mixing solutions; Use 1: 1 concentrated hydrochloric acid and concentrated nitric acid to regulate three the diameter 0.1m that pack into after the pH value to 2 again; In the purification adsorber of long 1m, mixing solutions keeps 30 ℃ of temperature.The crude propylene that contains hydrogen arsenide 910ppb (volume(tric)fraction) purifies through three grades of placed in-line absorption liquids (1) with the flow velocity of 1.2L/min and absorbs after the sample introduction six-way valve (3) of bypass moisture eliminator (2) connection monitoring system; Six-way valve is equipped with quantifying ring and realizes the continuous and quantitative sample introduction, and sampling interval is 20 minutes.The sample of propylene that contains fixed amount trace hydrogen arsenide gets into chromatogram capillary column system (4) propylene major constituent through six-way valve separates with hydrogen arsenide, and hydrogen arsenide gets into mass spectrum (5) quantitative Analysis.The monitoring time of a sample is 20 minutes.Fig. 2 passes through the surveillance map after absorption liquid purifies for the propylene feedstocks that contains 910ppb (volume(tric)fraction) hydrogen arsenide; The peak that can find out the hydrogen arsenide of 910ppb (volume(tric)fraction) through monitoring disappears, and explains that the hydrogen arsenide content that purifies the back propylene is less than 10ppb (volume(tric)fraction).
Claims (6)
1. absorption liquid that absorbs hydrogen arsenide in ethene, the propylene; Mixed solution by bromine water, ydrogen peroxide 50, mantoquita and suitable mineral acid is formed; Wherein mantoquita concentration is that 0.02～0.2mol/L, bromine water concentration are that 0.05～0.26mol/L, hydrogen peroxide concentration are 1-8mol/L, pH value 2～4.
2. kind according to claim 1 absorbs the absorption liquid of hydrogen arsenide in ethene, the propylene, and wherein mantoquita concentration is that 0.02～0.04mol/L, bromine water concentration are that 0.09～0.12mol/L, hydrogen peroxide concentration are 3-4mol/L.
3. kind according to claim 1 and 2 absorbs the absorption liquid of hydrogen arsenide in ethene, the propylene, and said mantoquita is any one in copper sulfate, cupric nitrate, cupric chloride, the neutralized verdigris.
4. method that absorbs hydrogen arsenide in ethene, the propylene, with claim 1 or 2 described absorption liquids pack in the airtight tourie and the mode that adopts plural serial stage in 20～80 ℃ of scopes to ethene, propylene in hydrogen arsenide absorb.
5. on-line monitoring system that removes hydrogen arsenide in gaseous ethene, the propylene; Be made up of sampling system, gc separation system, mass spectrometry system, wherein gas chromatography system separates ethene, propylene again with hydrogen arsenide through claim 1 or 2 said absorption liquids and carries out Quantitative Monitoring by mass spectrum.
6. the described kind of claim 1 absorbs the preparation method of the absorption liquid of hydrogen arsenide in ethene, the propylene; Just any one in copper sulfate, cupric nitrate, cupric chloride, the neutralized verdigris is water-soluble; Again with after bromine water and ydrogen peroxide 50 are mixed, regulate pH value to 2～4 with the concentrated hydrochloric acid of 1: 1 (volume ratio) and concentrated nitric acid and be made into absorption liquid.
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| CN 201010212315 CN102311301B (en) | 2010-06-29 | 2010-06-29 | Copper salt absorption liquid for desorbing arsenic hydride from ethane and propene in gas phase and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102854267A (en) * | 2012-09-28 | 2013-01-02 | 神华集团有限责任公司 | Measuring method of trace oxy-compound in liquid-phase propylene |
| CN106370713A (en) * | 2016-08-18 | 2017-02-01 | 华东理工大学 | Light gas olefin arsenic content detection method |
| CN109211654A (en) * | 2017-07-05 | 2019-01-15 | 中国石油天然气股份有限公司 | Method for detecting trace impurity ions in light olefin gas and absorption liquid used for method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337157A (en) * | 2008-08-12 | 2009-01-07 | 昆明理工大学 | Purification method of low concentration phosphine waste gas |
| CN101574618A (en) * | 2009-05-22 | 2009-11-11 | 昆明理工大学 | Absorption liquid used for purifying hydrogen phosphide by wet-catalytic oxidation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337157A (en) * | 2008-08-12 | 2009-01-07 | 昆明理工大学 | Purification method of low concentration phosphine waste gas |
| CN101574618A (en) * | 2009-05-22 | 2009-11-11 | 昆明理工大学 | Absorption liquid used for purifying hydrogen phosphide by wet-catalytic oxidation |
Non-Patent Citations (1)
| Title |
|---|
| 杨万龙等: "《仪器分析实验》", 31 March 2008 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102854267A (en) * | 2012-09-28 | 2013-01-02 | 神华集团有限责任公司 | Measuring method of trace oxy-compound in liquid-phase propylene |
| CN102854267B (en) * | 2012-09-28 | 2014-05-07 | 神华集团有限责任公司 | Measuring method of trace oxy-compound in liquid-phase propylene |
| CN106370713A (en) * | 2016-08-18 | 2017-02-01 | 华东理工大学 | Light gas olefin arsenic content detection method |
| CN109211654A (en) * | 2017-07-05 | 2019-01-15 | 中国石油天然气股份有限公司 | Method for detecting trace impurity ions in light olefin gas and absorption liquid used for method |
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| CN102311301B (en) | 2013-09-25 |
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