CN109540815A - A kind of novel seal acidification aeration hydrogen sulfide detector - Google Patents

A kind of novel seal acidification aeration hydrogen sulfide detector Download PDF

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Publication number
CN109540815A
CN109540815A CN201910094622.8A CN201910094622A CN109540815A CN 109540815 A CN109540815 A CN 109540815A CN 201910094622 A CN201910094622 A CN 201910094622A CN 109540815 A CN109540815 A CN 109540815A
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China
Prior art keywords
bottle
hydrogen sulfide
gas
liquid
pipeline
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CN201910094622.8A
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Chinese (zh)
Inventor
谢素梅
陈嘉浩
翟家骥
郝永刚
李椿方
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BEIJING XIANQU WEIFENG TECHNOLOGY DEVELOPMENT Co.,Ltd.
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谢素梅
陈嘉浩
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Priority to CN201910094622.8A priority Critical patent/CN109540815A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/783Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • G01N2021/0106General arrangement of respective parts
    • G01N2021/0112Apparatus in one mechanical, optical or electronic block

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention discloses a kind of sealings to be acidified aeration hydrogen sulfide detector, the measurement of sulfide content suitable for the samples such as environment, chemical industry.Instrument includes circulating pump, sealing gas circuit, gas-liquid separation lid, peristaltic pump, pressure bottle and electric control part.Peristaltic pump 9 squeezes into liquid in releasing agent bottle 7 in sample bottle 3, and circulating pump 5 provides gas circulation power by gas circuit 2,4,6, and the trace hydrogen sulfide of release is brought into absorption bottle 1.The absorbing liquid that unabsorbed hydrogen sulfide is repeatedly absorbed in bottle by gas circuit circulation absorbs.Gas-liquid separation lid 11,12 has also been devised in the present apparatus, while ensuring system integral sealing, ensure that liquid does not enter circulation line in sample bottle and absorption bottle.The design of integral sealing ensures that hydrogen sulfide will not lose because absorbing not exclusively, and does not need to be further added by external air source, and preci-sion and accuracy is high, easy to operate.Six channel patterns are such as used, then are greatly improved analysis efficiency.

Description

A kind of novel seal acidification aeration hydrogen sulfide detector
Technical field
The measurement of present invention sulfide content suitable for the samples such as environment, petroleum, chemical industry, the energy such as water, soil, is consolidated Body waste, petroleum, coal etc..
Background technique
In the fields such as environment, petroleum, chemical industry, the energy, the micro sulfide to trace is usually contained, because sulfide has play Poison, and just capable of discharging in carbonic acid acidification, therefore, sulfide are that surface water, seawater, Drinking Water, soil, solid are useless Required test item in the fields such as gurry, petroleum, coal.In these samples, water sample often has the disturbing factors such as color, muddiness and deposits It is even more directly to measure in, petroleum and other solid samples.Its pretreatment technology is usually to be acidified aeration absorption process at present.
It is provided in GB 5749-2006 standard, sulfide is the " sensory properties and general in " the unconventional index of water quality " Chemical index ", limit value 0.02mg/L.In its standard detecting method GB/T 5750.5-2006, aeration partition method is only advised The preci-sion and accuracy of 0.08mg/L or more is determined.Under limit value or lower concentration, not well-tolerated recycling.
Provided in GB 3838-2002 standard, sulfide be " water environment quality standard elementary item ", from I class~ Its limit value of V class water quality is followed successively by 0.05,0.1,0.2,0.5,1.0mg/L.In its standard detecting method GB/T 16489-1996 In, aeration partition method specifies only the preci-sion and accuracy of 0.148~0.600mg/L, tetra- groups of samples.In detection limit or limit value Hereinafter, recycling can not preferably be absorbed.
It is provided in GB 3097-1997 standard, sulfide is one of seawater quality project, from the first kind~the 4th class sea Its limit value of water water quality is followed successively by 0.02,0.05,0.10,0.25mg/L.The 18.1 of its standard detecting method GB 17378-2007 In, aeration partition method specifies only the repeatability and reproducibility of 0.427mg/L sample.In detection limit or limit value hereinafter, can not Preferably absorb recycling.
Above-mentioned tradition aeration partition method is purged using nitrogen, and device is complicated, and the degree of automation such as acid adding are not high, operates numerous It is trivial, to the more demanding of operator.And since in aeration process, the gas-liquid mass transfer of bubble and liquid has certain resistance, cause Absorb not exclusively, preci-sion and accuracy it is difficult to ensure that.
Summary of the invention
The present invention is absorbed as principle to seal acidification aeration, proposes that a kind of sealing, circulation and the small hydrogen sulfide of dead volume contain Analyzer is measured, solves above-mentioned technical problem.
For the assay for solving the problems, such as sulfide, sulfide content analyzer of the present invention is with following component: circulating pump, Seal gas circuit, gas-liquid separation lid, peristaltic pump, pressure bottle and electric control part.Circulating pump is used to hydrogen sulfide chemical inert material, but It is not limited to EPDM ethylene propylene diene rubber, VITON fluorubber, polytetrafluoroethylene (PTFE), high density poly propylene, brushless motor driving.Sealing Gas circuit is integrally used to hydrogen sulfide chemical inert material, but be not limited to silica gel, polytetrafluoroethylene (PTFE) etc..Gas-liquid separation lid is used to sulphur Change Hydrochemistry inert material, processed using numerically-controlled machine tool, there is gas liquid separating function, material is not limited to polytetrafluoroethylene (PTFE), highly dense Spend polypropylene etc..Peristaltic pump is driven using brush motor, the acid resistances bullet such as silica gel, EPDM ethylene propylene diene rubber, VITON fluorubber Property material.Pressure bottle is using materials such as high borosilicate, high density poly propylene, polytetrafluoroethylene (PTFE).Electric control part is prolonged using metal-oxide-semiconductor circulation The control loops time such as Shi Kaiguan.
Acid or other releasing agents is added to pressure-resistant sample bottle in peristaltic pump, and hydrogen sulfide is released at molecular state in sample bottle Come, aeration is then bubbled by circulating pump and is purged out, until pressure-resistant absorption bottle, is absorbed agent absorption, unabsorbed hydrogen sulfide It continues cycling through, until absorbing complete.Releasing agent is added in peristaltic pump and circulation time passes through two metal-oxide-semiconductor circulation delay switch respectively Control.
Detailed description of the invention
Fig. 1 is single channel of the present invention sealing aeration separation hydrogen sulfide content analyzer schematic device.
Fig. 2 is two hole gas-liquid separation lid schematic diagrames of the invention.
Fig. 3 is three hole gas-liquid separation lid schematic diagrames of the invention.
In figure: 1, absorbing pressure bottle;2,4,6, guide pipeline;3, sample bottle;5, circulating pump;8,10, releasing agent fluid path;9, Peristaltic pump;11,12, gas-liquid separation lid.
Specific embodiment
Single channel sealing acidification aeration separation hydrogen sulfide content analyzer --- methylenum careuleum mode determination
N, N- diethyl p-phenylenediamine's solution: weighing 0.75gN, and N- diethyl p-phenylenediamine's hydrochloride is dissolved in 900mL pure water, Sulfuric acid (1+1) 100mL is added.It is stored in brown bottle, if color reddens, need to reconfigure.
Sodium hydroxide (0.1mol/L): weighing 4g sodium hydroxide, is dissolved in 1000mL water.
Ferric chloride solution: weighing 10g ferric chloride hexahydrate, is dissolved in 900mL pure water, and sulfuric acid (1+1) 100mL is added.
Releasing agent: (1+3) hydrochloric acid.
As shown in Figure 1, precision pipettes 10mL sodium hydroxide (0.1mol/L) in absorbing in pressure bottle, successively drawing concentration is The sulfide standard solution 0.00 of 2.00mg/L, 2.00,4.00,6.00,8.00,10.00mL are in sample bottle, for drawing mark Directrix curve.Start circulating pump, while starting peristaltic pump and releasing agent is added.The time that circulating pump is opened is 5 minutes, flow velocity 1L/ min.The time that peristaltic pump is opened is 10 seconds, flow velocity 60mL/min.After absorbing completely, N, N- diethyl are added in absorption bottle Base p-phenylenediamine solution 10.00mL is added ferric chloride solution 5.00mL, shakes up, after placing 20min, the colorimetric at 665nm.It should Method draws standard curve y=0.0177x+0.0057, linearly dependent coefficient R2=0.9985.
Directly draw sulfide standard solution 0.00,2.00,4.00,6.00,8.00 that concentration is 2.00mg/L, N, N- diethyl p-phenylenediamine solution 10.00mL is added in 10.00mL, and ferric chloride solution 5.00mL is added, shakes up, and places 20min Afterwards, the colorimetric at 665nm.This method draws standard curve y=0.0178x+0.0015, linearly dependent coefficient R2=0.9994.
The standard curve of two methods configuration is not different, it was demonstrated that using system and does not use system not have difference.
The tap water of 500mL is drawn again, EDTA solution 1mL and ascorbic acid solution 2mL is added, measuring its blank value is 0.00mg/L.The 2.00mg/L sulfide standard solution (it is horizontal to be equivalent to 0.004mg/L sulfide concentration) of 2.00mL is added, follows The time that ring pump is opened is 15 minutes, flow velocity 6L/min.The time that peristaltic pump is opened is 30 seconds, flow velocity 60mL/min. It is measured in parallel 6 times, precision relative standard deviation is 2.6%, and the rate of recovery is 93.9~100.0%.
Six channels sealing aeration separation hydrogen sulfide content analyzer --- conductivity mode
Lead nitrate solution: nitric acid lead concentration is 20mg/L, and Hydrochloric Standard Titration is added, makes 1.5 μm of ol/L of its concentration.
Releasing agent: the citric acid solution of the 200g/L of pH 4.00.
Precision pipettes 50.00mL lead nitrate solution in absorbing in pressure bottle, successively draws the vulcanization that concentration is 10.00mg/L Object standard solution 0.00,2.00,4.00,6.00,8.00,10.00mL are in sample bottle, for drawing standard curve.Starting follows Ring pump, while starting peristaltic pump and releasing agent is added.The time that circulating pump is opened is 5 minutes, flow velocity 1L/min.Peristaltic pump is opened Time be 10 seconds, flow velocity 60mL/min.This method draws standard curve y=0.3832x+25.9234, linear correlation system Number R2=0.9951.
Certain industrial wastewater 50.00mL is drawn again, EDTA solution 1mL and ascorbic acid solution 2mL is added, and is measured in parallel six It is secondary, average value 0.064mg/L, precision 1.0%.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.

Claims (6)

1. a kind of sealing acidification aeration hydrogen sulfide detector, it is characterised in that including circulating pump, sealing gas circuit, gas-liquid separation lid, Peristaltic pump, pressure bottle and electric control part, peristaltic pump 9 squeeze into liquid in releasing agent bottle 7 in sample bottle 3, and circulating pump 5 passes through gas circuit 2,4,6 provide gas circulation power, the trace hydrogen sulfide of release are brought into absorption bottle 1, unabsorbed hydrogen sulfide passes through gas Road circulation is repeatedly absorbed the absorbing liquid in bottle and absorbs.
2. according to claim 1, circulating pump is used to hydrogen sulfide chemical inert material, but is not limited to EPDM ethylene-propylene-diene monomer Glue, VITON fluorubber, polytetrafluoroethylene (PTFE), high density poly propylene, brushless motor driving.
It uses 3. according to claim 1, sealing gas circuit 2,4,6 is whole to hydrogen sulfide chemical inert material, but is not limited to silicon Glue, polytetrafluoroethylene (PTFE) etc., wherein pipeline 2 is in one end of sample bottle 3 under sample solution liquid level, and pipeline 2 is in one end of absorption bottle On absorbing liquid liquid level;Pipeline 4 in one end of sample bottle 3 on sample solution liquid level, the import of pipeline 4 other end and circulating pump End connection;In one end of absorption bottle under absorbing liquid liquid level, the outlet end of 6 other end of pipeline and circulating pump connects pipeline 6.
It, will 4. according to claim 1, gas-liquid separation lid 11,12, using to hydrogen sulfide chemical inert material, are machined with skewed slot Vent line port is higher than the bottom surface of separation lid, has gas liquid separating function, prevents solution in bottle from entering circulation line, gas-liquid point Material from lid is not limited to polytetrafluoroethylene (PTFE), high density poly propylene etc..
5. according to claim 1, carrying out automatic past sample bottle using peristaltic pump 9 is added releasing agent, peristaltic pump, which uses, brush Motor driven, the acid resistances elastic materials such as silica gel, EPDM ethylene propylene diene rubber, VITON fluorubber, pipeline 8 is in releasing agent bottle 7 Under liquid level of solution, the other end of pipeline 8 is connect with peristaltic pump input end for one end;Pipeline 10 is in one end of sample bottle 3 in sample On liquid level of solution, the other end of pipeline 10 is connect with peristaltic pump outlet end.
6. according to claim 1, pressure bottle is using materials such as high borosilicate, high density poly propylene, polytetrafluoroethylene (PTFE).
CN201910094622.8A 2019-01-31 2019-01-31 A kind of novel seal acidification aeration hydrogen sulfide detector Pending CN109540815A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114112776A (en) * 2021-11-24 2022-03-01 西安镭博赛因科学仪器有限公司 Based on closed circulation absorption measurement H in natural gas2Method for S content

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101737040A (en) * 2008-11-18 2010-06-16 长春吉大·小天鹅仪器有限公司 Device and method for detecting hydrogen sulfide on oil drilling site
CN103210300A (en) * 2010-11-30 2013-07-17 福斯分析股份公司 Determination of sulphur dioxide in a liquid
CN209961681U (en) * 2019-01-31 2020-01-17 谢素梅 Novel sealed acidizing aeration hydrogen sulfide determinator

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101737040A (en) * 2008-11-18 2010-06-16 长春吉大·小天鹅仪器有限公司 Device and method for detecting hydrogen sulfide on oil drilling site
CN103210300A (en) * 2010-11-30 2013-07-17 福斯分析股份公司 Determination of sulphur dioxide in a liquid
US20130236976A1 (en) * 2010-11-30 2013-09-12 Foss Analytical A/S Determination of sulphur dioxide in a liquid
CN209961681U (en) * 2019-01-31 2020-01-17 谢素梅 Novel sealed acidizing aeration hydrogen sulfide determinator

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114112776A (en) * 2021-11-24 2022-03-01 西安镭博赛因科学仪器有限公司 Based on closed circulation absorption measurement H in natural gas2Method for S content

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