CN102311301B - 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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- CN102311301B CN102311301B CN 201010212315 CN201010212315A CN102311301B CN 102311301 B CN102311301 B CN 102311301B CN 201010212315 CN201010212315 CN 201010212315 CN 201010212315 A CN201010212315 A CN 201010212315A CN 102311301 B CN102311301 B CN 102311301B
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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 by arsine gas in catalysed oxidation processes purification gaseous ethene, the propylene, and by on-line monitoring system the decontamination effect improving of absorbent solution is monitored, to guarantee purifying back hydrogen arsenide content less than 30ppb.
Background technology
Ethene, propylene gas are to produce polyolefinic unstripped gas, so polyethylene, 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 many catalyzer of industrial use 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 had great influence to 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 removes arsenide for liquid hydrocarbon and oil product, all discloses a kind of supported dearsenic agent as Chinese patent CN101590418A and Chinese patent CN1259560A.But this dearsenic agent is not to develop at ethene, propylene feedstocks specially, and its dearsenification efficient can not satisfy polyolefin catalyst to the requirement (the efficient polyolefin catalyst of a new generation is not more than 30ppb (volume fraction) to the hydrogen arsenide content requirement in the olefin feedstock) of raw material.In addition, the Monitoring systems imperfection of state's internal olefin refining plant is calculated by experience mostly and is used purification system.When purification system lost efficacy or cleaning action 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 absorption liquid that hydrogen arsenide content purification in gaseous ethene, the propylene can be removed to less than 30ppb (volume 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, hydrogen peroxide, mantoquita and suitable mineral acid (pH value conditioning agent), 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 hydrogen peroxide 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, absorption liquid being packed 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, gas-chromatography 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, the hydrogen arsenide in gaseous ethene, the propylene can be purified extremely less than 30ppb (volume fraction).On-line monitoring system is highly sensitive, can monitor the hydrogen arsenide content that is not less than 10ppb (volume 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 fraction) and hydrogen arsenide 96ppb (volume fraction) hydrogen arsenide purifies absorption front and back makings Monitoring systems comparison diagram.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described:
Crude propylene is 910ppb (volume 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 fraction) purifies the sample introduction six-way valve (3) of the direct connection monitoring system in absorption back by the absorption liquid (1) of one-level with the flow velocity of 100mL/min, six-way valve is equipped with quantitative 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 enters chromatogram capillary column system (4) propylene major constituent by six-way valve separates with hydrogen arsenide, and hydrogen arsenide enters mass spectrum (5) quantitative Analysis.The monitoring time of a sample is 20 minutes.Fig. 2 is the surveillance map of the propylene feedstocks that contains 910ppb (volume fraction) hydrogen arsenide after purifying by the one-level absorption liquid, the makings peak area of the hydrogen arsenide of 910ppb (volume fraction) diminishes by monitoring as can be seen, is 96ppb (volume fraction) through calculating hydrogen arsenide content.Illustrating 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 fraction) purifies the sample introduction six-way valve (3) that absorbs by bypass moisture eliminator (2) connection monitoring system with the flow velocity of the 1.2L/min absorption liquid (1) by three grades of series connection, six-way valve is equipped with quantitative 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 enters chromatogram capillary column system (4) propylene major constituent by six-way valve separates with hydrogen arsenide, and hydrogen arsenide enters mass spectrum (5) quantitative Analysis.The monitoring time of a sample is 20 minutes.Fig. 2 is the surveillance map of the propylene feedstocks that contains 910ppb (volume fraction) hydrogen arsenide after purifying by absorption liquid, the peak of the hydrogen arsenide of 910ppb (volume fraction) disappears by monitoring as can be seen, illustrates that the hydrogen arsenide content that purifies the back propylene is less than 10ppb (volume fraction).
Crude propylene finds that through monitoring after the rough purification hydrogen arsenide content is 910ppb (volume 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 fraction) purifies the sample introduction six-way valve (3) of the direct connection monitoring system in absorption back by the absorption liquid (1) of one-level with the flow velocity of 80mL/min, six-way valve is equipped with quantitative 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 enters chromatogram capillary column system (4) propylene major constituent by six-way valve separates with hydrogen arsenide, and hydrogen arsenide enters mass spectrum (5) quantitative Analysis.The monitoring time of a sample is 20 minutes.Fig. 2 is the surveillance map of the propylene feedstocks that contains 910ppb (volume fraction) hydrogen arsenide after purifying by absorption liquid, the peak of the hydrogen arsenide of 910ppb (volume fraction) disappears by monitoring as can be seen, illustrates that the hydrogen arsenide content that purifies the back propylene is less than 10ppb (volume 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 fraction) purifies the sample introduction six-way valve (3) that absorbs by bypass moisture eliminator (2) connection monitoring system with the flow velocity of the 1.2L/min absorption liquid (1) by three grades of series connection, six-way valve is equipped with quantitative 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 enters chromatogram capillary column system (4) propylene major constituent by six-way valve separates with hydrogen arsenide, and hydrogen arsenide enters mass spectrum (5) quantitative Analysis.The monitoring time of a sample is 20 minutes.Fig. 2 is the surveillance map of the propylene feedstocks that contains 910ppb (volume fraction) hydrogen arsenide after purifying by absorption liquid, the peak of the hydrogen arsenide of 910ppb (volume fraction) disappears by monitoring as can be seen, illustrates that the hydrogen arsenide content that purifies the back propylene is less than 10ppb (volume fraction).
Claims (4)
1. absorption liquid that absorbs hydrogen arsenide in ethene, the propylene, mixed solution by bromine water, hydrogen peroxide, 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; Described mantoquita is copper sulfate or cupric chloride.
2. a kind of absorption liquid that absorbs hydrogen arsenide in ethene, the propylene according to claim 1, 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. method that absorbs hydrogen arsenide in ethene, the propylene, pack into claim 1 or 2 described absorption liquids in the airtight tourie and the mode that adopts plural serial stage in 20~80 ℃ of scopes to ethene, propylene in hydrogen arsenide absorb.
4. a kind of preparation method who absorbs the absorption liquid of hydrogen arsenide in ethene, the propylene according to claim 1, in copper sulfate, the cupric chloride any one is water-soluble, again with after bromine water and hydrogen peroxide are mixed, be that 1: 1 concentrated hydrochloric acid and concentrated nitric acid are regulated pH value to 2~4 and be made into absorption liquid with volume ratio.
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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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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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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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杨万龙等.气相色谱-质谱联用分析法.《仪器分析实验》.2008,第238页. * |
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