CN107694359A - A kind of preparation facilities and preparation method of hydrogen deuterium Standard Gases - Google Patents
A kind of preparation facilities and preparation method of hydrogen deuterium Standard Gases Download PDFInfo
- Publication number
- CN107694359A CN107694359A CN201711006965.1A CN201711006965A CN107694359A CN 107694359 A CN107694359 A CN 107694359A CN 201711006965 A CN201711006965 A CN 201711006965A CN 107694359 A CN107694359 A CN 107694359A
- Authority
- CN
- China
- Prior art keywords
- gas
- hydrogen
- deuterium
- gas cylinder
- preparation facilities
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007789 gas Substances 0.000 title claims abstract description 263
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 115
- 239000001257 hydrogen Substances 0.000 title claims abstract description 115
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 title claims abstract description 109
- 229910052805 deuterium Inorganic materials 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 87
- 150000002431 hydrogen Chemical class 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000012546 transfer Methods 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003113 dilution method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/10—Mixing gases with gases
- B01F23/19—Mixing systems, i.e. flow charts or diagrams; Arrangements, e.g. comprising controlling means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/20—Measuring; Control or regulation
- B01F35/21—Measuring
- B01F35/211—Measuring of the operational parameters
- B01F35/2113—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/20—Measuring; Control or regulation
- B01F35/22—Control or regulation
- B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
- B01F35/2213—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/20—Measuring; Control or regulation
- B01F35/22—Control or regulation
- B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
- B01F35/2217—Volume of at least one component to be mixed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/20—Measuring; Control or regulation
- B01F35/22—Control or regulation
- B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
- B01F35/2218—Weight of at least one component to be mixed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/80—Forming a predetermined ratio of the substances to be mixed
- B01F35/88—Forming a predetermined ratio of the substances to be mixed by feeding the materials batchwise
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/80—Forming a predetermined ratio of the substances to be mixed
- B01F35/88—Forming a predetermined ratio of the substances to be mixed by feeding the materials batchwise
- B01F35/881—Forming a predetermined ratio of the substances to be mixed by feeding the materials batchwise by weighing, e.g. with automatic discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/80—Forming a predetermined ratio of the substances to be mixed
- B01F35/88—Forming a predetermined ratio of the substances to be mixed by feeding the materials batchwise
- B01F35/882—Forming a predetermined ratio of the substances to be mixed by feeding the materials batchwise using measuring chambers, e.g. volumetric pumps, for feeding the substances
- B01F35/8821—Forming a predetermined ratio of the substances to be mixed by feeding the materials batchwise using measuring chambers, e.g. volumetric pumps, for feeding the substances involving controlling
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0006—Calibrating gas analysers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/30—Driving arrangements; Transmissions; Couplings; Brakes
- B01F2035/35—Use of other general mechanical engineering elements in mixing devices
- B01F2035/351—Sealings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/23—Mixing of laboratory samples e.g. in preparation of analysing or testing properties of materials
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
- Sampling And Sample Adjustment (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
Abstract
The invention belongs to calibrating gas preparing technical field, is related to a kind of preparation facilities and preparation method of hydrogen deuterium Standard Gases.Described preparation facilities include hydrogen feed gas cylinder, deuterium raw material gas cylinder, hydrogen delivery tube road, deuterium transfer pipeline, gas delivery main road, gas conveying bypass conduit, ordinarily manometer, high-precision pressure gauge, with gas cylinder, vacuum pump set, mass comparator, reference gas cylinder, valve.Utilize the preparation facilities and preparation method of the hydrogen deuterium Standard Gases of the present invention, can be when precision preparation requires high, gravimetric method is used when preparing low abundance hydrogen deuterium Standard Gases (D abundance is less than or equal to 1%), volumetric method is used during high abundance hydrogen deuterium Standard Gases (D abundance is more than 1%) in preparation；When precision preparation is less demanding, a kind of preparation of carry out hydrogen deuterium Standard Gases in optional gravimetric method or volumetric method.
Description
Technical field
The invention belongs to calibrating gas preparing technical field, is related to a kind of preparation facilities of hydrogen deuterium Standard Gases and preparation side
Method.
Background technology
Hydrogen is the main raw material of industry, and important industrial gasses and special gas, and hydrogen isotope gas is in state
Important role is played in anti-industry.In many projects, the accurate quantitative analysis technical process of analytical equipment need to be utilized each
Hydrogen isotope abundance in stage sample, to be monitored to process, product abundance is measured.Obtain the same position of hydrogen
The plain accurate isotope abundance value of gas, first have to carry out phase to analytical equipment using the hydrogen isotope reference sample of known composition
Close calibration.
The hydrogen isotope calibrating gas of the existing related concentrations of foreign countries, but be not easy to buy, and it is domestic be difficult to obtain hydrogen at present it is same
The plain calibrating gas in position, also no pertinent literature can consult.With reference to the preparation data of other Standard Gases, with reference to hydrogen isotope from
Body feature, it is mainly weighing method and partial pressure method to prepare calibration with the more feasible method of hydrogen deuterium hybrid standard gas.
Weighing method prepares calibration gas mixture, is that unstrpped gas quantitatively is transferred into gaseous mixture gas cylinder from raw material gas cylinder to have come
Into, unstrpped gas can be pure gas or main constituent, by weighing method prepare gaseous mixture.Gas component
Addition be to fill front and rear gas bottle or raw material gas bottle match somebody with somebody by weighing to determine, the difference of weighing is equal to twice
Addition.The uncertainty of weighing method is mainly derived from：(1) uncertainty of balance weighing value；(2) buoyancy effect introduces not
Degree of certainty；(3) the introduced uncertainty of mass change caused by gas cylinder disassembly process；(4) caused by Multi-stage dilution not
The accumulation of degree of certainty.Although weighing method compared with other methods is not the best way in production efficiency, it is with quality list
Position is foundation, can be traceable to the measurement of fundamental quantity, reliable in precision, therefore is preparation gas mark generally acknowledged in the world
The basic skills of quasi- material, the preparation of the reference gas of every country are substantially using weighing method.
Partial pressure method (also known as pressure method or pressure application) is a kind of static method, and can largely prepare standard with pressure with this method mixes
Gas.Component A, B, C etc. and carrier gas be filled with successively one be assumed to constant volume closed vessel in, this container answer pre-wash and
Evacuate (expansion for ignoring the container caused by internal pressure changes).Every time after inflation, container pressure is measured.Partial pressure method
Physical basis are dalton (Dalton) laws, i.e., standard (mixing) gas each component partial pressure sum is equal to the stagnation pressure of calibrating gas
Power, and the partial pressure of component is equal to the molar fraction of the component and the product of gross pressure.The uncertainty of partial pressure method is mainly derived from：
(1) uncertainty of piezometry (pressure gauge value)；(2) pressure ratio is converted into the uncertainty of molar concentration introducing；(3) press
The uncertainty that contracting heat introduces.
The content of the invention
The present invention primary and foremost purpose be to provide a kind of preparation facilities of hydrogen deuterium Standard Gases, with can use the preparation facilities with
When required precision processed is high, gravimetric method is used when preparing low abundance hydrogen deuterium Standard Gases (D abundance is less than or equal to 1%), in preparation
High abundance hydrogen deuterium Standard Gases use volumetric method when (D abundance is more than 1%)；When precision preparation is less demanding, optional gravimetric method or
A kind of preparation of carry out hydrogen deuterium Standard Gases in volumetric method.
In order to achieve this, in the embodiment on basis, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, institute
The preparation facilities stated includes hydrogen feed gas cylinder, deuterium raw material gas cylinder, hydrogen delivery tube road, deuterium transfer pipeline, gas
Convey main line, gas conveying bypass conduit, ordinarily manometer, high-precision pressure gauge, with gas cylinder, vacuum pump set, mass ratio compared with
Instrument, reference gas cylinder, valve,
The hydrogen feed gas and deuterium unstripped gas that described hydrogen feed gas cylinder and deuterium raw material gas cylinder provides respectively,
Respectively behind described hydrogen delivery tube road and the conveying of deuterium transfer pipeline, it is defeated to share described gas delivery main road progress
Send, the end on described gas delivery main road is connected with the described vacuum pump set for vacuumizing；
The gas delivery main road described in one end connection of gas conveying bypass conduit described in each bar, the other end connect respectively
Described ordinarily manometer, high-precision pressure gauge, with gas cylinder, reference gas cylinder；
Described gas cylinder of matching somebody with somebody is used to prepare described hydrogen deuterium Standard Gases；
Described mass comparator is used to weigh the described weight with gas cylinder together with wherein gas；
Described reference gas cylinder is with described identical with gas cylinder specification, for the weighing results and ginseng according to mass comparator
More described than the weight difference calculating of gas cylinder matches somebody with somebody the weight that gas is filled with gas cylinder；
It is other that described valve is arranged on described hydrogen delivery tube road, deuterium transfer pipeline, the gas conveying described in each bar
Road pipeline, and described gas delivery main road connect the pipeline before and after the gas conveying bypass conduit described in each bar
On.
In a preferred embodiment, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, wherein described
The relative error of high-precision pressure gauge measurement is less than 0.1%.
In a preferred embodiment, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, wherein described
High-precision pressure gauge has two pieces, is connected in different described gas conveying bypass conduits.
In a kind of more preferred embodiment, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, wherein two
The range of high-precision pressure gauge described in block is respectively 0-1000Torr and 0-100Torr.
In a preferred embodiment, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, wherein described
Material with gas cylinder and described reference gas cylinder is aluminum alloy materials, and pressure-resistant is 25Mpa.
In a preferred embodiment, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, wherein described
The range of mass comparator is 5200g, precision 0.2mg.
In a preferred embodiment, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, wherein described
Preparation facilities also includes isotope mass spectrometer, for being quantified to the hydrogen deuterium Standard Gases prepared；Gas described in one is defeated
Bypass conduit is sent to connect described isotope mass spectrometer in end by described valve.
In a preferred embodiment, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, wherein described
Preparation facilities also includes leak test plant, for determine in described preparation facilities each pipeline, part whether gas leakage, so as to ensure
The gas tightness for the preparation facilities stated is good.
In a preferred embodiment, the present invention provides a kind of preparation facilities of hydrogen deuterium Standard Gases, wherein described
The range of pressure gauge is 0-25MPa.
Second object of the present invention is to provide the method that the preparation facilities of foregoing hydrogen deuterium Standard Gases prepares hydrogen deuterium Standard Gases,
So that weight can be used when preparing low abundance hydrogen deuterium Standard Gases (D abundance is less than or equal to 1%) when precision preparation requires high
Method, volumetric method is used during high abundance hydrogen deuterium Standard Gases (D abundance is more than 1%) in preparation；When precision preparation is less demanding,
The preparation of optional gravimetric method or a kind of carry out hydrogen deuterium Standard Gases in volumetric method.
In order to achieve this, in the embodiment on basis, the present invention provides the preparation facilities system of foregoing hydrogen deuterium Standard Gases
The method of standby hydrogen deuterium Standard Gases, comprises the following steps：
1) to hydrogen delivery tube road, deuterium transfer pipeline, gas delivery main road and/or each before being filled with or conveying gas
Gas conveying bypass conduit carries out vacuumize process with described vacuum pump set respectively；
2) hydrogen and deuterium are filled with sequentially adjustable in gas cylinder to described, according in the hydrogen deuterium Standard Gases of required preparation
The required proportioning of hydrogen and deuterium, control are filled with the described difference weighed with gas cylinder and/or described height before and after every kind of gas
Precision pressure table measures the difference of pressure.
In a preferred embodiment, the preparation facilities of the foregoing hydrogen deuterium Standard Gases of present invention offer prepares hydrogen deuterium standard
The method of gas, wherein also hunted leak to described preparation facilities before the step 1), cleaned to described with gas cylinder and height
Pure hydrogen Passivation Treatment.
In a kind of more preferred embodiment, the preparation facilities that the present invention provides foregoing hydrogen deuterium Standard Gases prepares hydrogen deuterium
The method of Standard Gases, wherein the time of described high-purity hydrogen Passivation Treatment is 48 hours.
In a preferred embodiment, the preparation facilities of the foregoing hydrogen deuterium Standard Gases of present invention offer prepares hydrogen deuterium standard
The method of gas, wherein before step 2) is filled with gas, match somebody with somebody gas cylinder described at least 6 times dismounting, mass comparator is weighed, so as to most
The uncertainty that may be introduced with gas cylinder disassembly process described in the reduction of limits.
The beneficial effects of the present invention are, can using the preparation facilities and preparation method of the hydrogen deuterium Standard Gases of the present invention
When precision preparation requires high, gravimetric method is used when preparing low abundance hydrogen deuterium Standard Gases (D abundance is less than or equal to 1%), with
In system volumetric method is used during high abundance hydrogen deuterium Standard Gases (D abundance is more than 1%)；When precision preparation is less demanding, optional weight
A kind of preparation of carry out hydrogen deuterium Standard Gases in method or volumetric method.Best hydrogen deuterium mark can be so obtained in the range of full abundance
Quasi- gas prepares product without changing air distributing device, and can also choose any one kind of them air distributing method system when requirement is not high
Gas.
The preparation facilities of the hydrogen deuterium Standard Gases of the present invention can prepare hydrogen deuterium Standard Gases with weighing method and partial pressure method simultaneously, and
Simple in construction, operation is easy, and prepared hydrogen deuterium Standard Gases error is less than 1%, is less than 1% with respect to expanded uncertainty, meets
Demand for analytical equipment calibration.The present invention compensate for the blank of hydrogen isotope Standard Gases preparation field.
Brief description of the drawings
Fig. 1 is the composition figure of the preparation facilities of exemplary hydrogen deuterium Standard Gases of the invention.
Embodiment
The embodiment of the present invention is further illustrated below in conjunction with accompanying drawing.
The preparation facilities of exemplary hydrogen deuterium Standard Gases of the invention is as shown in figure 1, including hydrogen feed gas cylinder 1, deuterium
Gas raw material gas cylinder 2, the steel cylinder of standby raw material gas 3, pressure gauge 4 (range 0-25MPa), (the range 0- of high-grade pressure gauge 5
1000Torr, measurement relative error be less than 0.1%), high-grade pressure gauge 6 (range 0-100Torr, measurement relative error be less than
0.1%), isotope mass spectrometer 7, (also serve as standby with gas cylinder 8 (material is aluminum alloy materials, and pressure-resistant is 25Mpa), reference gas cylinder 9
With with gas cylinder, material is aluminum alloy materials, and pressure-resistant is 25Mpa), vacuum pump set 10, hydrogen delivery tube road 11, deuterium transfer pipeline
12nd, standby raw material letter shoot road 13, gas delivery main road 14, gas conveying bypass conduit 15, (range is mass comparator
Be not drawn into 5200g, precision 0.2mg, Fig. 1), leak test plant, the valve V1-V11 (for VCR joints valve) on each pipeline,
Valve V12 is carried with gas cylinder, reference gas cylinder carries valve V13.
Hydrogen feed gas that hydrogen feed gas cylinder 1, deuterium raw material gas cylinder 2, the steel cylinder of standby raw material gas 3 provide respectively,
Deuterium unstripped gas and standby raw material gas, it is defeated through described hydrogen delivery tube road 11, deuterium transfer pipeline 12, standby raw material gas respectively
After sending pipeline 13 to convey, common gas conveying main line 14 is conveyed.The end on gas delivery main road 14, which is connected with, to be used for
The vacuum pump set 10 vacuumized.
Each bar gas conveying bypass conduit 15 one end connection gas delivery main road 13, the other end connects usual pressure respectively
Table 4, high-precision pressure gauge 5, high-precision pressure gauge 6, isotope mass spectrometer 7 (are used to determine the hydrogen deuterium Standard Gases prepared
Amount), with gas cylinder 8, reference gas cylinder 9.
It is used to match somebody with somebody hydrogen manufacturing deuterium Standard Gases with gas cylinder 8.
Mass comparator is used to weigh the weight with gas cylinder 8 together with wherein gas.
Reference gas cylinder 9 is identical with the specification of gas cylinder 8, for the weighing results according to mass comparator and reference gas cylinder 9
Weight difference calculates the weight matched somebody with somebody and gas is filled with gas cylinder 8.
Leak test plant be used to determine in described preparation facilities each pipeline, part whether gas leakage, so as to ensure preparation facilities
Gas tightness it is good.
Valve V1 is arranged on hydrogen delivery tube road 11；Valve V2 is arranged on deuterium transfer pipeline 12；Valve V3 is set
On standby raw material letter shoot road 13；Valve V4, V11 are separately positioned on the front-end and back-end on gas delivery main road 14；Valve
Door V5-V10 is separately positioned on connection pressure gauge 4, high-precision pressure gauge 5, high-precision pressure gauge 6, isotope mass spectrometer 7, distribution
Bottle 8, the gas of reference gas cylinder 9 are conveyed in bypass conduit 15.
Exemplary hydrogen deuterium Standard Gases system is carried out using the preparation facilities of the hydrogen deuterium Standard Gases of the invention of above-mentioned example
Standby method is as follows.
(1) gravimetric method
This method application top load mass comparator weighs the hydrogen that is fitted into aluminium alloy gas cylinder and deuterium, according to hydrogen with
The mass ratio of deuterium, calculate the concentration of gas cylinder Plays gas.This method compared with other method is not most in production efficiency
Good method, but it is using mass unit as foundation, it is reliable in precision, therefore, it is considered to be prepare the master of reference gas
Method is wanted, the preparation of the reference gas of every country uses gravimetric method substantially.
1. being hunted leak using leak test plant to whole device, leak rate is less than 10-11atm·ml/s。
2. determine deuterium concentration and final charge pressure.
3. a pair reference gas cylinder 9 pre-processes, dirt is removed with wipes of alcohol gas washing bottle surface, gas cylinder valve V13 is opened, allows
Gas cylinder internal and atmospheric equilibrium 24 hours, tighten valve V13.
4. pair being pre-processed with gas cylinder 8, dirt is removed with wipes of alcohol gas washing bottle surface, is put into heating under reduced pressure in baking oven,
Steam is removed after cooling.
5. gas cylinder 8 is matched somebody with somebody in installation, gas cylinder is soaked 48 hours with high-purity hydrogen to be passivated gas cylinder.
6. opening V9, V11, V12,10 will be evacuated to gas cylinder 8-5Pa；V9, V11, V12 are closed, pulls down with gas cylinder 8, uses
Mass comparator is weighed, the m of poor quality of record and reference gas cylinder 90。
7. reinstalling with gas cylinder 8, V4, V5, V9, V11 are opened, distribution pipeline is evacuated to 10-5Continue to take out very after Pa
It is empty 30 minutes.
8. turning off V11, V12 is opened, slowly opens V2, the pointer position of pressure gauge 4 is observed, is closed after reaching both constant-pressures
V2, V9, V12, pull down with gas cylinder 8, weighed with mass comparator, record now matches somebody with somebody the m of poor quality of gas cylinder 8 and reference gas cylinder 91,
m1-m0It is the filling quality of deuterium.
9. reinstalling with gas cylinder 8, V4, V5, V9, V11 are opened, distribution pipeline is evacuated to 10-5Continue to take out very after Pa
It is empty 4 hours.
10. turning off V11, V1 is slowly opened, observes the pointer position of pressure gauge 4, ensures that now loine pressure is more than and matches somebody with somebody gas cylinder 8
The charge pressure of middle deuterium, V12 is opened, V1, V9, V12 is closed after reaching both constant-pressures, pulls down gas cylinder 8, claimed with mass comparator
Weight, record now match somebody with somebody the m of poor quality of gas cylinder 8 and reference gas cylinder 92, m2-m1It is the filling quality of hydrogen.
11. mix balance 2 days.
12. using the concentration of deuterium in the Mass Calculation institute gas distribution for filling hydrogen and deuterium of record, to whole distribution
The uncertainty of process is calculated, and is strictly controlling preparation process, on the premise of avoiding the surface of gas cylinder from staiing and collide, mainly
Consider the uncertainty of deuterium unstripped gas purity and the uncertainty that mass comparator weighs.
13. being compared Par value to the hydrogen deuterium Standard Gases of preparation with the isotope mass spectrometer 7 calibrated, and carry out stabilization
The checking of property and uniformity.
14. if matched somebody with somebody deuterium concentration is relatively low, need to be prepared using Multi-stage dilution method, the intermediate concentration that will now prepare
Hydrogen deuterium Standard Gases as unstripped gas, contained with reference gas cylinder 9 and final match somebody with somebody hydrogen deuterium Standard Gases, preparation method and step 1-
13 is identical.
By way of improving charge pressure and being prepared using Multi-stage dilution, full abundance scope is prepared using above-mentioned gravimetric method
The preparation error of hydrogen deuterium Standard Gases is less than 0.5%, and with respect to expanded uncertainty, (related definition and computational methods are shown in GB/T 5274-
2008 " gas analysis calibration prepares weighing method with mixed gas ") it is less than 0.5% (Coverage factor k=2).
(2) volumetric method
It is to be filled with the deuterium of concentration known and hydrogen successively to be assumed to constant volume that volumetric method, which prepares hydrogen deuterium Standard Gases,
In closed container, this container answers pre-wash and evacuates and (ignore the container caused by internal pressure increase to expand), every time
After inflation, container inner pressure is measured, standard gas concentration is represented with pressure ratio, and it is equal to the partial pressure for being filled with the component and matches somebody with somebody standard
The ratio between gas gross pressure.Specific implementation step is as follows：
1. being hunted leak using leak test plant to whole device, leak rate is less than 10-11atm·ml/s。
2. determine deuterium concentration and final charge pressure.
3. pair being pre-processed with gas cylinder 8, dirt is removed with wipes of alcohol gas washing bottle surface, is put into heating under reduced pressure in baking oven,
Steam is removed after cooling；
4. gas cylinder 8 match somebody with somebody in installation, with high-purity hydrogen immersion gas cylinder and air distributing device 48 hours to be passivated gas cylinder.
5. opening V4, V6, V9, V11, V12, pipeline and gas bottle to be matched somebody with somebody are evacuated simultaneously with vacuum pump set 10, is evacuated to 10- 5Pa, V11 is closed, whether the observation registration of high-grade pressure gauge 5 is stablized, if registration is unstable, continues to vacuumize until stabilizing to
Only, the registration P of pressure gauge 5 is recorded0, close V11.
6. slowly opening V2, the registration of high-grade pressure gauge 5 is observed, after reaching predetermined pressure, V2 is closed, treats that registration is steady
It is fixed, record pressure value P shown in pressure gauge 51, P1-P0It is then the charge pressure of deuterium.Close V12.
7. opening hydrogen pressure-reducing valve, decompression valve outlet pressure is set to be much larger than P1(two magnitudes), slowly opens V1, and observation is high
The registration of precision pressure meter 5, after reaching predetermined pressure, V1 is closed, treat that registration is stable, record pressure value P shown in pressure gauge 52, P2-
P1It is then the charge pressure of hydrogen.
8. mix balance 2 days.
9. using the concentration of deuterium in the pressure value calculating institute gas distribution for filling hydrogen and deuterium of record, to whole distribution
The uncertainty of process is calculated, in strictly control preparation process, the main uncertainty for considering deuterium unstripped gas purity and
The uncertainty of pressure gauge reading.
10. being compared Par value to the hydrogen deuterium Standard Gases of preparation with the isotope mass spectrometer 7 calibrated, and carry out stabilization
The checking of property and uniformity.
11. if matched somebody with somebody deuterium concentration is relatively low, need to be prepared using Multi-stage dilution method, the intermediate concentration that will now prepare
Hydrogen deuterium Standard Gases as unstripped gas, contained with reference gas cylinder 9 and final match somebody with somebody hydrogen deuterium Standard Gases, preparation method and step 1-
10 is identical.
By using the mode of Multi-stage dilution, preparing low abundance hydrogen deuterium Standard Gases using above-mentioned volumetric method, (D abundance is less than
Equal to 1%) when, prepare error be less than 1%, be less than 0.5% (k=2) with respect to expanded uncertainty；High abundance hydrogen deuterium mark in preparation
During quasi- gas (D abundance is more than 1%), prepare error and be less than 0.5%, be less than 0.2% (k=2) with respect to expanded uncertainty.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention
God and scope.So, if belonging to the model of the claims in the present invention and its equivalent technology to these modifications and variations of the present invention
Within enclosing, then the present invention is also intended to comprising including these changes and modification.Above-described embodiment or embodiment are simply to the present invention
For example, the present invention can also be implemented with other ad hoc fashions or other particular forms, without departing from the present invention's
Main idea or substantive characteristics.Therefore, it is regarded as from the point of view of the embodiment of description is in terms of any illustrative and non-limiting.This
The scope of invention should be illustrated that any change equivalent with the intention of claim and scope should also include by appended claims
Within the scope of the invention.
Claims (10)
- A kind of 1. preparation facilities of hydrogen deuterium Standard Gases, it is characterised in that：Described preparation facilities includes hydrogen feed gas cylinder, deuterium Gas raw material gas cylinder, hydrogen delivery tube road, deuterium transfer pipeline, gas delivery main road, gas conveying bypass conduit, common pressure Power table, high-precision pressure gauge, with gas cylinder, vacuum pump set, mass comparator, reference gas cylinder, valve,The hydrogen feed gas and deuterium unstripped gas that described hydrogen feed gas cylinder and deuterium raw material gas cylinder provides respectively, respectively Behind described hydrogen delivery tube road and the conveying of deuterium transfer pipeline, share described gas delivery main road and conveyed, institute The end on the gas delivery main road stated is connected with the described vacuum pump set for vacuumizing；The gas delivery main road described in one end connection of gas conveying bypass conduit described in each bar, the other end connects described respectively Ordinarily manometer, high-precision pressure gauge, with gas cylinder, reference gas cylinder；Described gas cylinder of matching somebody with somebody is used to prepare described hydrogen deuterium Standard Gases；Described mass comparator is used to weigh the described weight with gas cylinder together with wherein gas；Described reference gas cylinder is with described identical with gas cylinder specification, for the weighing results and reference gas according to mass comparator Match somebody with somebody the weight that gas is filled with gas cylinder described in the weight difference calculating of bottle；Described valve is arranged on described hydrogen delivery tube road, deuterium transfer pipeline, the gas conveying shunt valve described in each bar Road, and described gas delivery main road are connected on the pipeline before and after the gas conveying bypass conduit described in each bar.
- 2. preparation facilities according to claim 1, it is characterised in that：The relative error of described high-precision pressure gauge measurement Less than 0.1%.
- 3. preparation facilities according to claim 1, it is characterised in that：Described high-precision pressure gauge has two pieces, connects respectively It is connected in different described gas conveying bypass conduits.
- 4. preparation facilities according to claim 3, it is characterised in that：The range difference of high-precision pressure gauge described in two pieces For 0-1000Torr and 0-100Torr.
- 5. preparation facilities according to claim 1, it is characterised in that：The described material with gas cylinder and described reference gas cylinder Matter is aluminum alloy materials, and pressure-resistant is 25Mpa.
- 6. preparation facilities according to claim 1, it is characterised in that：The range of described mass comparator is 5200g, essence Spend for 0.2mg.
- 7. preparation facilities according to claim 1, it is characterised in that：Described preparation facilities also includes isotope mass spectrometry Instrument, for being quantified to the hydrogen deuterium Standard Gases prepared；Gas conveying bypass conduit described in one passes through described valve The described isotope mass spectrometer of connection in end.
- 8. preparation facilities according to claim 1, it is characterised in that：Described preparation facilities also includes leak test plant, uses In it is determined that in described preparation facilities each pipeline, part whether gas leakage, so as to ensure the gas tightness of described preparation facilities Well.
- 9. the method that the preparation facilities in a kind of 1-8 using claim described in any one prepares hydrogen deuterium Standard Gases, including such as Lower step：1) to hydrogen delivery tube road, deuterium transfer pipeline, gas delivery main road and/or each gas before being filled with or conveying gas Conveying bypass conduit carries out vacuumize process with described vacuum pump set respectively；2) hydrogen and deuterium are filled with sequentially adjustable in gas cylinder to described, according to hydrogen in the hydrogen deuterium Standard Gases of required preparation With the required proportioning of deuterium, control is filled with the described difference weighed with gas cylinder and/or described high accuracy before and after every kind of gas The difference of pressure gauges measure pressure.
- 10. according to the method for claim 9, it is characterised in that：Also described preparation facilities is examined before step 1) Leakage, cleaned to described with gas cylinder and high-purity hydrogen Passivation Treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711006965.1A CN107694359B (en) | 2017-10-25 | 2017-10-25 | Preparation device and preparation method of hydrogen deuterium standard gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711006965.1A CN107694359B (en) | 2017-10-25 | 2017-10-25 | Preparation device and preparation method of hydrogen deuterium standard gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107694359A true CN107694359A (en) | 2018-02-16 |
| CN107694359B CN107694359B (en) | 2024-07-23 |
Family
ID=61182300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711006965.1A Active CN107694359B (en) | 2017-10-25 | 2017-10-25 | Preparation device and preparation method of hydrogen deuterium standard gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107694359B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554207A (en) * | 2018-06-15 | 2018-09-21 | 上海雷密传感技术有限公司 | A kind of low concentration calibrating gas continues generating means and its method for generation |
| CN111017878A (en) * | 2019-12-18 | 2020-04-17 | 中国原子能科学研究院 | For preparing equilibrium state H2-HD-D2Apparatus and method for standard gas |
| CN111744423A (en) * | 2019-03-29 | 2020-10-09 | 中国石油天然气股份有限公司 | Preparation device and preparation method of standard mixed gas |
| CN113694820A (en) * | 2021-09-08 | 2021-11-26 | 中国工程物理研究院材料研究所 | Integrated device and method for rapidly preparing and detecting hydrogen isotope gas |
| CN115212738A (en) * | 2022-06-29 | 2022-10-21 | 广西电网有限责任公司电力科学研究院 | Multistage gas distribution device based on Dalton voltage division method |
| CN118032456A (en) * | 2024-02-23 | 2024-05-14 | 中国计量科学研究院 | Gas distribution system and method for greenhouse gas carbon dioxide isotope standard substance |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147612A (en) * | 1989-10-09 | 1992-09-15 | Raal Johan D | Apparatus for preparation of standard gas mixtures |
| CN203737125U (en) * | 2014-02-19 | 2014-07-30 | 昆明鹏翼达气体产品有限公司 | Portable standard gas configuration device |
| CN203829931U (en) * | 2014-02-19 | 2014-09-17 | 昆明鹏翼达气体产品有限公司 | Standard gas preparation device |
| CN204429223U (en) * | 2014-12-17 | 2015-07-01 | 大连光明特种气体有限公司 | High-precision standard gas distribution equipment |
| CN104888635A (en) * | 2015-06-11 | 2015-09-09 | 中国船舶重工集团公司第七一八研究所 | Device and method for compounding multiple cylinders of mixed gas |
| CN205627677U (en) * | 2016-05-25 | 2016-10-12 | 成都赛普生科技有限公司 | Continuous and steady distributing device of tolerance |
| CN207385222U (en) * | 2017-10-25 | 2018-05-22 | 中国原子能科学研究院 | A kind of preparation facilities of hydrogen deuterium Standard Gases |
-
2017
- 2017-10-25 CN CN201711006965.1A patent/CN107694359B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147612A (en) * | 1989-10-09 | 1992-09-15 | Raal Johan D | Apparatus for preparation of standard gas mixtures |
| CN203737125U (en) * | 2014-02-19 | 2014-07-30 | 昆明鹏翼达气体产品有限公司 | Portable standard gas configuration device |
| CN203829931U (en) * | 2014-02-19 | 2014-09-17 | 昆明鹏翼达气体产品有限公司 | Standard gas preparation device |
| CN204429223U (en) * | 2014-12-17 | 2015-07-01 | 大连光明特种气体有限公司 | High-precision standard gas distribution equipment |
| CN104888635A (en) * | 2015-06-11 | 2015-09-09 | 中国船舶重工集团公司第七一八研究所 | Device and method for compounding multiple cylinders of mixed gas |
| CN205627677U (en) * | 2016-05-25 | 2016-10-12 | 成都赛普生科技有限公司 | Continuous and steady distributing device of tolerance |
| CN207385222U (en) * | 2017-10-25 | 2018-05-22 | 中国原子能科学研究院 | A kind of preparation facilities of hydrogen deuterium Standard Gases |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554207A (en) * | 2018-06-15 | 2018-09-21 | 上海雷密传感技术有限公司 | A kind of low concentration calibrating gas continues generating means and its method for generation |
| CN108554207B (en) * | 2018-06-15 | 2023-12-12 | 上海雷密传感技术有限公司 | Low-concentration standard gas continuous generation device and generation method thereof |
| CN111744423A (en) * | 2019-03-29 | 2020-10-09 | 中国石油天然气股份有限公司 | Preparation device and preparation method of standard mixed gas |
| CN111017878A (en) * | 2019-12-18 | 2020-04-17 | 中国原子能科学研究院 | For preparing equilibrium state H2-HD-D2Apparatus and method for standard gas |
| CN111017878B (en) * | 2019-12-18 | 2021-12-17 | 中国原子能科学研究院 | For preparing equilibrium state H2-HD-D2Apparatus and method for standard gas |
| CN113694820A (en) * | 2021-09-08 | 2021-11-26 | 中国工程物理研究院材料研究所 | Integrated device and method for rapidly preparing and detecting hydrogen isotope gas |
| CN113694820B (en) * | 2021-09-08 | 2023-04-07 | 中国工程物理研究院材料研究所 | Integrated device and method for rapidly preparing and detecting hydrogen isotope gas |
| CN115212738A (en) * | 2022-06-29 | 2022-10-21 | 广西电网有限责任公司电力科学研究院 | Multistage gas distribution device based on Dalton voltage division method |
| CN118032456A (en) * | 2024-02-23 | 2024-05-14 | 中国计量科学研究院 | Gas distribution system and method for greenhouse gas carbon dioxide isotope standard substance |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107694359B (en) | 2024-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107694359A (en) | A kind of preparation facilities and preparation method of hydrogen deuterium Standard Gases | |
| CN104888635B (en) | Device and method for compounding multiple cylinders of mixed gas | |
| CN204816244U (en) | Weigh device of many bottles of standard gas mixtures of cofabrication on line | |
| Valkiers et al. | Preparation of argon primary measurement standards for the calibration of ion current ratios measured in argon | |
| CN106501425B (en) | A kind of transformer online gc verification preparation method of standard oil | |
| CN207385222U (en) | A kind of preparation facilities of hydrogen deuterium Standard Gases | |
| CN104180861A (en) | Standard device and measuring method using mass method for detecting high-pressure gas filling flow | |
| US8636040B2 (en) | Installation for packaging NO using mass flow meters | |
| CN113866373B (en) | Method for measuring methane henry constant in water and measuring cavity | |
| CN203139972U (en) | Standard mixed gas preparation apparatus | |
| CN109781896B (en) | Standard series and gas sample analysis method based on internal standard method | |
| CN109745880B (en) | Trace gas transfer device and method | |
| CN111595408B (en) | Equipment for measuring liquid level in constant-temperature closed container, film coating device and method for measuring liquid level | |
| WO2018193444A1 (en) | Combined volumetric - gravimetric system and method for preparation of gas mixtures | |
| Picard et al. | Mass comparisons using air buoyancy artefacts | |
| Russe et al. | Synthetic isotope mixtures for the calibration of isotope amount ratio measurements of carbon | |
| CN208566179U (en) | More bottles of charging devices of Standard Gases | |
| CN111006926A (en) | Nitrogen dioxide gas standard substance in carbon dioxide and preparation method and application thereof | |
| CN105757448A (en) | Accurate gas sub-packaging device | |
| CN105954462B (en) | Solid moisture standards material and preparation method thereof | |
| RU2446005C1 (en) | Method for preparation of multi-component gas mixes | |
| CN112697632B (en) | Coal rock and shale bulk sample weight method isothermal adsorption measurement device and method | |
| CN112129799B (en) | Ppm-level dimethyl ether standard mixed gas configuration device and method | |
| JP2003065495A (en) | Mixed gas charging method and device | |
| RU2522629C1 (en) | Method of preparing multicomponent gas mixtures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |