CN210293842U - Multi-channel extraction device for pyrite sulfur in rock and soil samples - Google Patents
Multi-channel extraction device for pyrite sulfur in rock and soil samples Download PDFInfo
- Publication number
- CN210293842U CN210293842U CN201920974611.4U CN201920974611U CN210293842U CN 210293842 U CN210293842 U CN 210293842U CN 201920974611 U CN201920974611 U CN 201920974611U CN 210293842 U CN210293842 U CN 210293842U
- Authority
- CN
- China
- Prior art keywords
- ethylene propylene
- washing bottle
- spherical condensation
- flat
- gas washing
- 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.)
- Active
Links
Images
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
The utility model belongs to stable isotope composition mass spectrometer test field, concretely relates to a multichannel extraction device for pyrite sulfur in rock and soil samples, the device comprises a protective gas supply system, a sample reaction system and a product collection system, the protective gas supply system comprises a nitrogen steel cylinder gas, a nitrogen pressure reducing valve and a plurality of gas flow meters; the sample reaction system comprises a six-linked heating magnetic stirrer, flat-bottom triangular conical flasks, spherical condensation sampling devices and quark flow valves, wherein the number of the flat-bottom triangular conical flasks is the same as that of the gas flow meters, and the product collection system comprises two-stage absorption devices, the number of the two-stage absorption devices is the same as that of the gas flow meters. The utility model discloses a spherical condensation sampling device and flat end triangle erlenmeyer flask advance kind mode through quark flow valve and syringe, both guaranteed that the feeding does not expose in the atmosphere, can improve the device expansibility again, realize that the multichannel draws the pyrite sulphur in to a plurality of samples simultaneously.
Description
Technical Field
The utility model belongs to stable isotope composition mass spectrograph test field, concretely relates to multichannel extraction element that is arranged in rock, soil sample pyrite sulphur.
Background
Sulfur in rock and soil is classified into various forms such as Acid Volatile Sulfur (AVS), pyrite sulfur (CRS), Elemental Sulfur (ES), Organic Sulfur (OS), and the like. Accurate determination of pyrite sulfur (CRS) isotopes can provide more refined information for global sulfur cycles, paleoclimatic changes, and geological historical evolution. The method is characterized in that pyrite sulfur in rock and soil samples is separated from sulfur in equivalent states such as organic sulfur, sulfate sulfur and acid volatile sulfur, and the separated sulfur is converted into silver sulfide suitable for sulfur isotope determination, which is a precondition for accurate analysis of sulfur isotopes.
Currently, the extraction of pyrite sulfur is mainly divided into a thermal distillation method and a cold diffusion method. Compared with the cold diffusion method, the hot distillation method has the following advantages: 1. the reaction speed is high, the reaction time is only 2-3 hours, and the cold diffusion method needs 1-2 days and even longer; 2. the cold diffusion method places the sample in a closed container, the reaction process cannot be observed, and the hot distillation method can observe the reaction process at any time through the generation condition of the precipitate; 3. in the cold diffusion method, a sample is placed in a closed container for a long time, and the reaction process of generating hydrogen sulfide by completely reducing the pyrite sulfur is influenced probably because the air tightness of the container or the injection of protective gas in the operation process is insufficient, so that the inaccuracy of the experimental result is caused. Therefore, the hot distillation method can quickly and accurately extract the pyrite sulfur in the sample compared with the cold diffusion method.
However, the existing devices for extracting pyritic sulfur by the thermal distillation method have poor expansibility, are mostly single channels, and cannot prepare a plurality of samples at the same time, and part of the devices relate to the use of a plurality of glassware such as a separating funnel, a reactor, a gas washing bottle, a conical flask and the like, and the glassware is easy to damage and has poor operation convenience, so that the rapid thermal distillation method for treating a large number of pyritic sulfur samples faces a dilemma.
Disclosure of Invention
An object of the utility model is to provide a multichannel extraction element and extraction method for pyrite sulphur among rock, the soil sample, the device and method are simple, convenient, easy operation, are applicable to big batch, quick pyrite sulphur's preparation work of drawing.
Realize the utility model discloses the technical scheme of purpose: a multi-channel extraction device for pyrite sulfur in rock and soil samples comprises a shielding gas supply system, a sample reaction system and a product collection system, wherein the shielding gas supply system comprises nitrogen steel cylinder gas, a nitrogen pressure reducing valve and a plurality of gas flow meters; the sample reaction system comprises a six-linked heating magnetic stirrer, flat-bottom triangular conical flasks, spherical condensation sampling devices and quark flow valves, the quantity of the flat-bottom triangular conical flasks is the same as that of the gas flow meters, and the product collection system comprises two-stage absorption devices, the quantity of the two-stage absorption devices is the same as that of the gas flow meters; the gas outlet of the nitrogen gas steel cylinder gas of the protective gas supply system is communicated with the gas inlet of the nitrogen pressure reducing valve, and the gas outlet of the nitrogen pressure reducing valve is respectively communicated with the gas inlets of the plurality of gas flowmeters; the gas outlets of a plurality of gas flow meters of the protective gas supply system are respectively communicated with the gas inlet on one side of the top of the spherical condensation sample introduction device of the sample reaction system, the top of each spherical condensation sample introduction device is respectively provided with a quark flow valve, each spherical condensation sample introduction device is respectively arranged in a bottle mouth at the top of a flat-bottom triangular conical flask, and the bottoms of the flat-bottom triangular flasks are respectively placed on a six-linked magnetic stirrer with heating; and a sample outlet on one side of the top of each spherical condensation sample introduction device is respectively communicated with the gas inlets of a group of two-stage absorption devices of the product collection system.
The gas flowmeter of the protective gas supply system comprises a first gas flowmeter, a second gas flowmeter, a third gas flowmeter, a fourth gas flowmeter, a fifth gas flowmeter and a sixth gas flowmeter, and gas inlets of the first gas flowmeter, the second gas flowmeter, the third gas flowmeter, the fourth gas flowmeter, the fifth gas flowmeter and the sixth gas flowmeter are communicated with a gas outlet of the nitrogen pressure reducing valve.
The spherical condensation sample introduction device of the sample reaction system consists of a sample introduction pipe A and a branch pipe C, wherein the bottom of the sample introduction pipe A is provided with a grinding port D, one side of the top of the sample introduction pipe A is provided with a sample outlet B, the branch pipe C penetrates through the axis of the sample introduction pipe A, and the bottom of the branch pipe C is inserted into a flat-bottom triangular conical flask; the top of the branch pipe C is of a three-way structure, a transverse pipe of a three-way pipe at the top of the branch pipe C is communicated with an air outlet of the gas flowmeter, and a quark flow valve is arranged at the end part of a vertical pipe of the three-way pipe at the top of the branch pipe C; and a sample outlet B at the top of the sample inlet pipe A is communicated with the gas inlet of the two-stage absorption device.
The spherical condensation sampling device of the sample reaction system comprises a first spherical condensation sampling device, a second spherical condensation sampling device, a third spherical condensation sampling device, a fourth spherical condensation sampling device, a fifth spherical condensation sampling device and a sixth spherical condensation sampling device, the first spherical condensation sampling device, the second spherical condensation sampling device, the third spherical condensation sampling device, the fourth spherical condensation sampling device, the sample outlet B at the top of the sample inlet pipe A of the fifth spherical condensation sampling device and the sixth spherical condensation sampling device is respectively communicated with the sample inlets of a group of two-stage absorption devices, and the sample outlet of the two-stage absorption devices is sealed.
The flat-bottom triangular conical flasks of the sample reaction system comprise a first flat-bottom triangular conical flask, a second flat-bottom triangular conical flask, a third flat-bottom triangular conical flask, a fourth flat-bottom triangular conical flask, a fifth flat-bottom triangular conical flask and a sixth flat-bottom triangular conical flask, wherein the bottoms of the first flat-bottom triangular conical flask, the second flat-bottom triangular conical flask, the third flat-bottom triangular conical flask, the fourth flat-bottom triangular conical flask, the fifth flat-bottom triangular conical flask and the sixth flat-bottom triangular conical flask are all placed on a six-linked heating magnetic stirrer, and the glass grinding ports of the top bottle mouths of the first flat-bottom triangular conical flask, the second flat-bottom triangular conical flask, the third flat-bottom triangular conical flask, the fourth flat-bottom triangular conical flask, the fifth flat-bottom triangular conical flask and the sixth flat-bottom triangular conical flask are respectively connected with a first spherical condensation sample introduction device, a second spherical condensation sample introduction device and a third spherical condensation sample introduction device, And the bottom grinding ports D of the sample inlet pipes A of the fourth spherical condensation sample inlet device, the fifth spherical condensation sample inlet device and the sixth spherical condensation sample inlet device are connected.
The top parts of the first spherical condensation sample introduction device, the second spherical condensation sample introduction device, the third spherical condensation sample introduction device, the fourth spherical condensation sample introduction device, the fifth spherical condensation sample introduction device and the sixth spherical condensation sample introduction device are respectively connected with a first quark flow valve, a second quark flow valve, a third quark flow valve, a fourth quark flow valve, a fifth quark flow valve and a sixth quark flow valve.
The two-stage absorption device of the product collection system is six groups, and each two-stage absorption device is respectively formed by connecting two fluorinated ethylene propylene gas washing bottles in series.
The six groups of two-stage absorption devices are respectively formed by connecting a first fluorinated ethylene-propylene gas washing bottle, a seventh fluorinated ethylene-propylene gas washing bottle, a second fluorinated ethylene-propylene gas washing bottle, an eighth fluorinated ethylene-propylene gas washing bottle, a third fluorinated ethylene-propylene gas washing bottle, a ninth fluorinated ethylene-propylene gas washing bottle, a fourth fluorinated ethylene-propylene gas washing bottle, a tenth fluorinated ethylene-propylene gas washing bottle, a fifth fluorinated ethylene-propylene gas washing bottle, an eleventh fluorinated ethylene-propylene gas washing bottle, a sixth fluorinated ethylene-propylene gas washing bottle and a twelfth fluorinated ethylene-propylene gas washing bottle in series.
The sample outlet B at the top of the sample inlet pipe A of the first spherical condensation sample introduction device, the second spherical condensation sample introduction device, the third spherical condensation sample introduction device, the fourth spherical condensation sample introduction device, the fifth spherical condensation sample introduction device and the sixth spherical condensation sample introduction device of the sample reaction system is respectively communicated with the sample inlets of the first fluorinated ethylene propylene gas washing bottle, the second fluorinated ethylene propylene gas washing bottle, the third fluorinated ethylene propylene gas washing bottle, the fourth fluorinated ethylene propylene gas washing bottle, the fifth fluorinated ethylene propylene gas washing bottle and the sixth fluorinated ethylene propylene gas washing bottle of the product collection system, and the sample outlets of the first fluorinated ethylene propylene gas washing bottle, the second fluorinated ethylene propylene gas washing bottle, the third fluorinated ethylene propylene gas washing bottle, the fourth fluorinated ethylene propylene gas washing bottle, the fifth fluorinated ethylene propylene gas washing bottle and the sixth fluorinated ethylene propylene gas washing bottle are respectively communicated with the seventh fluorinated ethylene propylene gas washing bottle, The sample inlets of an eighth fluorinated ethylene propylene gas washing bottle, a ninth fluorinated ethylene propylene gas washing bottle, a tenth fluorinated ethylene propylene gas washing bottle, an eleventh fluorinated ethylene propylene gas washing bottle and a twelfth fluorinated ethylene propylene gas washing bottle are communicated; and sample outlets of a seventh fluorinated ethylene propylene gas washing bottle, an eighth fluorinated ethylene propylene gas washing bottle, a ninth fluorinated ethylene propylene gas washing bottle, a tenth fluorinated ethylene propylene gas washing bottle, an eleventh fluorinated ethylene propylene gas washing bottle and a twelfth fluorinated ethylene propylene gas washing bottle are sealed.
The nitrogen pressure reducing valve is connected with the nitrogen steel cylinder through a stainless steel adapter.
The utility model has the advantages of: the utility model discloses simplified reaction vessel's feed inlet, original reactor is connected with a plurality of feed arrangement, and the device is fragile, and the expansibility is poor, the utility model discloses a spherical condensation advances the device and triangle erlenmeyer flask at the flat end, advances the kind mode through top quark flow valve and syringe, both can guarantee that the feeding does not expose in the atmosphere, can improve the expansibility of device again, and then can realize the multichannel and to the extraction of pyrite sulphur in a plurality of samples simultaneously. The utility model discloses set up two-stage protection gas control system, carried out decompression once through the relief pressure valve to steel bottle gas, through the gas flow of every passageway of flowmeter accurate control. Such a design has two advantages: the expansibility is good, if a reaction system is added, only one flowmeter needs to be added; the reaction systems do not interfere with each other, and the independent control of the protective gas of each channel can be realized. The utility model discloses a gather the perfluoroethylene propylene gas washing bottle, it is durable to gather the perfluoroethylene propylene gas washing bottle than the glass gas washing bottle, and the gas washing bottle adopts the thread sealing mode, easy operation. The polyfluorinated ethylene propylene gas washing bottle has translucency, is convenient for observe the condition of precipitation generation during reaction, can monitor the condition of carrying out of reaction constantly, and this reactor is easy to fix, can be fixed in the backplate with the drinking cup frame, not only save space, but also be difficult for tumbling.
Drawings
Fig. 1 is a schematic view of a multi-channel extraction device for pyrite sulfur in rock and soil samples provided by the present invention;
FIG. 2 is a schematic structural view of the spherical condensation sample injection device provided by the present invention
In the figure:
1 is a nitrogen cylinder gas, 2 is a nitrogen pressure reducing valve, 3 is a six-gang heating magnetic stirrer, 4 is a first flat-bottomed triangular conical flask, 5 is a second flat-bottomed triangular conical flask, 6 is a third flat-bottomed triangular conical flask, 7 is a fourth flat-bottomed triangular conical flask, 8 is a fifth flat-bottomed triangular conical flask, 9 is a sixth flat-bottomed triangular conical flask, 10 is a first quark flow valve, 11 is a second quark flow valve, 12 is a third quark flow valve, 13 is a fourth quark flow valve, 14 is a fifth quark flow valve, 15 is a sixth quark flow valve, 16 is a first perfluoroethylene propylene copolymer washing gas cylinder, 17 is a second perfluoroethylene propylene washing gas cylinder, 18 is a third perfluoroethylene propylene washing gas cylinder, 19 is a fourth perfluoroethylene propylene washing gas cylinder, 20 is a fifth perfluoroethylene propylene washing gas cylinder, 21 is a sixth perfluoroethylene propylene washing gas cylinder, 22 is a seventh perfluoroethylene propylene washing gas cylinder, 23 is an eighth fluorinated ethylene propylene gas washing bottle, 24 is a ninth fluorinated ethylene propylene gas washing bottle, 25 is a tenth fluorinated ethylene propylene gas washing bottle, 26 is an eleventh fluorinated ethylene propylene gas washing bottle, 27 is a twelfth fluorinated ethylene propylene gas washing bottle, 28 is a first gas flow meter, 29 is a second gas flow meter, 30 is a third gas flow meter, 31 is a fourth gas flow meter, 32 is a fifth gas flow meter, 33 is a sixth gas flow meter, 34 is a first spherical condensation sample introduction device, 35 is a second spherical condensation sample introduction device, 36 is a third spherical condensation sample introduction device, 37 is a fourth spherical condensation sample introduction device, 38 is a fifth spherical condensation sample introduction device, and 39 is a sixth spherical condensation sample introduction device.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
As shown in figures 1 and 2, the utility model provides a multichannel extraction element for pyrite sulfur in rock, soil sample, the device includes shielding gas feed system, sample reaction system and result collecting system.
The protective gas supply system comprises a nitrogen steel cylinder gas 1, a nitrogen pressure reducing valve 2, a first gas flowmeter 28, a second gas flowmeter 29, a third gas flowmeter 30, a fourth gas flowmeter 31, a fifth gas flowmeter 32 and a sixth gas flowmeter 33, wherein a gas outlet of the nitrogen steel cylinder gas 1 is communicated with a gas inlet of the nitrogen pressure reducing valve 2 through a stainless steel adapter, and a gas outlet of the nitrogen pressure reducing valve 2 is respectively and sequentially connected with the first gas flowmeter 28, the second gas flowmeter 29, the third gas flowmeter 30, the fourth gas flowmeter 31, the fifth gas flowmeter 32 and a gas inlet of the sixth gas flowmeter 33 through a metal tee joint and a fluorine rubber pipe.
The sample reaction system comprises a six-linked heating magnetic stirrer 3, a first flat-bottom triangular conical flask 4, a second flat-bottom triangular conical flask 5, a third flat-bottom triangular conical flask 6, a fourth flat-bottom triangular conical flask 7, a fifth flat-bottom triangular conical flask 8, a sixth flat-bottom triangular conical flask 9, a first spherical condensation sample introduction device 34, a second spherical condensation sample introduction device 35, a third spherical condensation sample introduction device 36, a fourth spherical condensation sample introduction device 37, a fifth spherical condensation sample introduction device 38, a sixth spherical condensation sample introduction device 39, a first quark flow valve 10, a second quark flow valve 11, a third quark flow valve 12, a fourth quark flow valve 13, a fifth quark flow valve 14, a sixth quark flow valve 15, a first flat-bottom conical flask 4, a second flat-bottom triangular conical flask 5, a third flat-bottom conical flask 6, a fourth flat-bottom triangular conical flask 7, a third conical flask 6, a third flat-bottom conical flask 9, a first spherical condensation sample introduction device 34, the bottoms of a fifth flat-bottom triangular conical flask 8 and a sixth flat-bottom triangular conical flask 9 are all placed on a six-linked heating magnetic stirrer 3, the tops of the first flat-bottom triangular conical flask 4, the second flat-bottom triangular conical flask 5, the third flat-bottom triangular conical flask 6, the fourth flat-bottom triangular conical flask 7, the fifth flat-bottom triangular conical flask 8 and the sixth flat-bottom triangular conical flask 9 are respectively connected with the bottoms of a first spherical condensation sample introduction device 34, a second spherical condensation sample introduction device 35, a third spherical condensation sample introduction device 36, a fourth spherical condensation sample introduction device 37, a fifth spherical condensation sample introduction device 38 and a sixth spherical condensation sample introduction device 39 through glass grinding ports, and the first spherical condensation sample introduction device 34, the second spherical condensation sample introduction device 35, the third spherical condensation sample introduction device 36, the fourth spherical condensation sample introduction device 37, the fifth spherical condensation sample introduction device 38, The top of the sixth spherical condensation sampling device 39 is respectively connected with a first quark flow valve 10, a second quark flow valve 11, a third quark flow valve 12, a fourth quark flow valve 13, a fifth quark flow valve 14 and a sixth quark flow valve 15 through fluorine rubber pipes.
The spherical condensation sample introduction device comprises a sample introduction pipe A and a branch pipe C, wherein a ground port D is formed in the bottom of the sample introduction pipe A, a sample outlet B is formed in one side of the top of the sample introduction pipe A, the branch pipe C penetrates through the axis of the sample introduction pipe A, and the bottom of the branch pipe C is inserted into a flat-bottom triangular conical flask; the top of the branch pipe C is of a three-way structure, a transverse pipe of the three-way pipe at the top of the branch pipe C is communicated with a gas outlet of the gas flowmeter through a fluororubber pipe, and a quark flow valve is arranged at the end part of a vertical pipe of the three-way pipe at the top of the branch pipe C. The sample outlet B at the top of the sample inlet pipe A is communicated with the sample inlet of the fluorinated ethylene propylene gas washing bottle through a fluororubber pipe, and the sample outlet of the fluorinated ethylene propylene gas washing bottle is communicated with the sample inlet of the other fluorinated ethylene propylene gas washing bottle through the fluororubber pipe.
The bottom glass grinding opening D of the sample inlet pipe A of the spherical condensation sample injection device is identical to the top glass grinding opening D of the flat-bottom triangular conical flask in size, the bottom grinding opening of the sample inlet pipe A of the spherical condensation sample injection device is inserted into the top grinding opening of the flat-bottom triangular conical flask, and the sample inlet pipes of all the spherical condensation sample injection devices are respectively and tightly connected with the flat-bottom triangular conical flask through the glass grinding openings.
The product collecting system comprises a first perfluorinated ethylene propylene gas washing bottle 16, a second perfluorinated ethylene propylene gas washing bottle 17, a third perfluorinated ethylene propylene gas washing bottle 18, a fourth perfluorinated ethylene propylene gas washing bottle 19, a fifth perfluorinated ethylene propylene gas washing bottle 20, a sixth perfluorinated ethylene propylene gas washing bottle 21, a seventh perfluorinated ethylene propylene gas washing bottle 22, an eighth perfluorinated ethylene propylene gas washing bottle 23, a ninth perfluorinated ethylene propylene gas washing bottle 24, a tenth perfluorinated ethylene propylene gas washing bottle 25, an eleventh perfluorinated ethylene propylene gas washing bottle 26 and a twelfth perfluorinated ethylene propylene gas washing bottle 27, wherein the gas washing bottles are connected with the sample reaction system through fluororubber pipes. The sample outlets B at the tops of the sample inlet pipes A of the first spherical condensation sample introduction device 34, the second spherical condensation sample introduction device 35, the third spherical condensation sample introduction device 36, the fourth spherical condensation sample introduction device 37, the fifth spherical condensation sample introduction device 38 and the sixth spherical condensation sample introduction device 39 are respectively communicated with the sample outlets of the first perfluorinated ethylene propylene copolymer gas washing bottle 16, the second perfluorinated ethylene propylene copolymer gas washing bottle 17, the third perfluorinated ethylene propylene copolymer gas washing bottle 18, the fourth perfluorinated ethylene propylene copolymer gas washing bottle 19, the fifth perfluorinated ethylene propylene copolymer gas washing bottle 20 and the sixth perfluorinated ethylene propylene copolymer gas washing bottle 21 through fluorine rubber pipes, and the sample outlets of the first perfluorinated ethylene propylene copolymer gas washing bottle 16, the second perfluorinated ethylene propylene copolymer gas washing bottle 17, the third perfluorinated ethylene propylene copolymer gas washing bottle 18, the fourth perfluorinated ethylene propylene copolymer gas washing bottle 19, the fifth perfluorinated ethylene propylene copolymer gas washing bottle 20 and the sixth perfluorinated ethylene propylene copolymer gas washing bottle 21 are respectively communicated with the seventh perfluorinated ethylene propylene copolymer bottle 22, the sample outlets of the fourth perfluorinated ethylene propylene copolymer bottle 22, the second perfluorinated ethylene propylene copolymer bottle 19, the perfluorinated ethylene propylene copolymer, The sample inlets of an eighth fluorinated ethylene propylene gas washing bottle 23, a ninth fluorinated ethylene propylene gas washing bottle 24, a tenth fluorinated ethylene propylene gas washing bottle 25, an eleventh fluorinated ethylene propylene gas washing bottle 26 and a twelfth fluorinated ethylene propylene gas washing bottle 27 are communicated. And sample outlets of a seventh fluorinated ethylene propylene gas washing bottle 22, an eighth fluorinated ethylene propylene gas washing bottle 23, a ninth fluorinated ethylene propylene gas washing bottle 24, a tenth fluorinated ethylene propylene gas washing bottle 25, an eleventh fluorinated ethylene propylene gas washing bottle 26 and a twelfth fluorinated ethylene propylene gas washing bottle 27 are sealed. Except that being connected through the stainless steel adapter between nitrogen gas relief pressure valve 2 and the nitrogen gas steel bottle gas 1, the utility model provides a all the other parts of multichannel extraction element all adopt the fluororubber union coupling, and the fluororubber pipe internal diameter is 3mm, and the external diameter is 6mm, and the fluororubber union coupling adopts the metal clamp fixed.
The six-linked heating magnetic stirrer 3 can be heated at a temperature of 0-99 ℃.
The capacity of all the fluorinated ethylene propylene gas washing bottles is 250mL, and two gas washing bottles connected in series form a two-stage absorption device, so that the hydrogen sulfide generated by reaction can be completely absorbed, and no pollutant is discharged to the atmosphere. The gas-liquid separation device is characterized in that a first fluorinated ethylene propylene gas washing bottle 16 and a seventh fluorinated ethylene propylene gas washing bottle 22 are connected in series, a second fluorinated ethylene propylene gas washing bottle 17 and an eighth fluorinated ethylene propylene gas washing bottle 23 are connected in series, a third fluorinated ethylene propylene gas washing bottle 18 and a ninth fluorinated ethylene propylene gas washing bottle 24 are connected in series, a fourth fluorinated ethylene propylene gas washing bottle 19 and a tenth fluorinated ethylene propylene gas washing bottle 25 are connected in series, a fifth fluorinated ethylene propylene gas washing bottle 20 and an eleventh fluorinated ethylene propylene gas washing bottle 26 are connected in series, and a sixth fluorinated ethylene propylene gas washing bottle 21 and a twelfth fluorinated ethylene propylene gas washing bottle 27 are connected in series respectively to form six groups of two-stage absorption devices.
As shown in fig. 1 and 2, a method for operating a multichannel extraction device for pyrite sulfur in rock and soil samples specifically comprises the following steps:
step 1, removing natural sulfur and acid volatile sulfur in rock and soil samples
And acid soluble sulfate radicals, drying, crushing rock and soil samples to 200 meshes, and oscillating through dichloromethane for 12 hours to extract and remove natural sulfur in the samples; under the condition of introducing protective gas, adding 6mol/L HCl filtering solution to remove acid volatile sulfur and acid soluble sulfate radicals in the sample; and washing and drying the rest precipitate for later use.
Step 2, placing the rock and soil samples dried in the step 1 in a flat-bottom triangular conical flask, connecting the bottom of a spherical condensation sample injection device of the sample reaction system with the flat-bottom triangular conical flask, and communicating the top of the spherical condensation sample injection device of the sample reaction system with a gas flowmeter of a protective gas supply system
And (3) respectively placing the rock and soil samples dried in the step (1) into a first flat-bottom triangular conical flask 4, a second flat-bottom triangular conical flask 5, a third flat-bottom triangular conical flask 6, a fourth flat-bottom triangular conical flask 7, a fifth flat-bottom triangular conical flask 8 and a sixth flat-bottom triangular conical flask 9, and respectively adding magnetic rotors into all the flat-bottom triangular conical flasks. The bottom grinding ports D of sample inlet pipes A of a first spherical condensation sample introduction device 34, a second spherical condensation sample introduction device 35, a third spherical condensation sample introduction device 36, a fourth spherical condensation sample introduction device 37, a fifth spherical condensation sample introduction device 38 and a sixth spherical condensation sample introduction device 39 are respectively inserted into the top grinding ports of a first flat-bottom triangular conical flask 4, a second flat-bottom triangular conical flask 5, a third flat-bottom triangular conical flask 6, a fourth flat-bottom triangular conical flask 7, a fifth flat-bottom triangular conical flask 8 and a sixth flat-bottom triangular conical flask 9, and the transverse pipes of a branch pipe C top three-way pipe of the first spherical condensation sample introduction device 34, the second spherical condensation sample introduction device 35, the third spherical condensation sample introduction device 36, the fourth spherical condensation sample introduction device 37, the fifth spherical condensation sample introduction device 38 and the sixth spherical condensation sample introduction device 39 are respectively connected with a first gas flow meter 28, a second spherical condensation sample introduction device 35, a third spherical condensation sample introduction device 36, a fourth spherical condensation sample introduction device 37, The gas outlets of the second gas flow meter 29, the third gas flow meter 30, the fourth gas flow meter 31, the fifth gas flow meter 32 and the sixth gas flow meter 33 are communicated.
And opening a steel cylinder gas main valve 1, a nitrogen reducing valve 2, a first gas flow regulator 28, a second gas flow regulator 29, a third gas flow regulator 30, a fourth gas flow regulator 31, a fifth gas flow regulator 32 and a sixth gas flow regulator 33 in sequence, and respectively supplying protective gas to the first flat-bottom triangular conical flask 4, the second flat-bottom conical flask 5, the third flat-bottom triangular flask 6, the fourth flat-bottom triangular conical flask 7, the fifth flat-bottom conical flask 8 and the sixth flat-bottom triangular flask 9 through branch pipes C of a first spherical condensation sample introduction device 34, a second spherical condensation sample introduction device 35, a third spherical condensation sample introduction device 36, a fourth spherical condensation sample introduction device 37, a fifth spherical condensation sample introduction device 38 and a sixth spherical condensation sample introduction device 39 of a sample reaction system. The protective gas is nitrogen, in the process, the pressure of the LZB-2WB type gas flow regulator is ensured to be 40ml/min, and the gas flow regulator is purged for 10 minutes.
The two-stage absorption device is composed of two fluorinated ethylene propylene gas washing bottles which are connected in series. The added absorption liquid is cadmium acetate solution, and the cadmium acetate solution is prepared by dissolving 20g of cadmium acetate in 3.5mol/L acetic acid solution per liter. 200ml of cadmium acetate solution is filled into each perfluoroethylene propylene washing bottle.
The first fluorinated ethylene propylene gas washing bottle 16 and the seventh fluorinated ethylene propylene gas washing bottle 22, the second fluorinated ethylene propylene gas washing bottle 17 and the eighth fluorinated ethylene propylene gas washing bottle 23, the third fluorinated ethylene propylene gas washing bottle 18 and the ninth fluorinated ethylene propylene gas washing bottle 24, the fourth fluorinated ethylene propylene gas washing bottle 19 and the tenth fluorinated ethylene propylene gas washing bottle 25, the fifth fluorinated ethylene propylene gas washing bottle 20 and the eleventh fluorinated ethylene propylene gas washing bottle 26, and the sixth fluorinated ethylene propylene gas washing bottle 21 and the twelfth fluorinated ethylene propylene gas washing bottle 27 are respectively connected in series to form a group of two-stage absorption devices.
The sample outlet B at the top of the sample inlet pipe A of the first spherical condensation sample introduction device 34, the second spherical condensation sample introduction device 35, the third spherical condensation sample introduction device 36, the fourth spherical condensation sample introduction device 37, the fifth spherical condensation sample introduction device 38 and the sixth spherical condensation sample introduction device 39 of the sample reaction system is respectively communicated with the sample inlets of the first perfluorinated ethylene propylene copolymer gas washing bottle 16, the second perfluorinated ethylene propylene copolymer gas washing bottle 17, the third perfluorinated ethylene propylene gas washing bottle 18, the fourth perfluorinated ethylene propylene copolymer gas washing bottle 19, the fifth perfluorinated ethylene propylene copolymer gas washing bottle 20 and the sixth perfluorinated ethylene propylene copolymer gas washing bottle 21.
The first, second, third, fourth, fifth and sixth quark flow valves 10, 11, 12, 13, 14 and 15 were opened and the needle syringe was used to add the reagents into the first, second, fifth, third, fourth, fifth and sixth flat-bottomed triangular flasks 4, 5, 6, 7, 8 and 9, in that order, through the first, second, third, fourth, fifth and sixth quark flow valves 10, 11, 12, 13, 14 and 15.
The reagents included 20ml of 6.0mol/L HCl solution and 40ml of CrCl2And (3) solution. CrCl2The preparation method of the solution comprises the following steps: 133g of CrCl3·6H2O is dissolved in 500ml of 0.5mol/L HCl solutionCrCl3Putting the solution into a flat-bottom triangular conical flask, adding zinc particles treated by 2% mercuric nitrate solution into the flask, shaking and standing overnight to obtain the prepared CrCl2And (3) solution.
The first, second, third, fourth, fifth, and sixth quark flow valves 10, 11, 12, 13, 14, 15 are closed after the addition of the reactive agent is complete.
Step 6, starting the heating magnetic stirrer 3 for reaction, and generating H in the flat-bottom triangular conical flask2S is condensed by a spherical condensation sample introduction device and enters six groups of two-stage absorption devices to generate zinc sulfide precipitate, after the reaction is carried out for a period of time, after a sample reaction system is cooled, a gas flow regulator, a nitrogen pressure reducing valve 2 and a main valve of a nitrogen steel cylinder gas 1 are closed, and the six groups of two-stage absorption devices are taken down
Then the heating magnetic stirrer 3 is turned on to carry out the reaction. H generated in the first triangular flask with flat bottom 4, the second triangular flask with flat bottom 5, the third triangular flask 6, the fourth triangular flask with flat bottom 7, the fifth triangular flask with flat bottom 8 and the sixth triangular flask with flat bottom 92And S is condensed by a first spherical condensation sample introduction device 34, a second spherical condensation sample introduction device 35, a third spherical condensation sample introduction device 36, a fourth spherical condensation sample introduction device 37, a fifth spherical condensation sample introduction device 38 and a sixth spherical condensation sample introduction device 39, and then enters a fluorinated ethylene propylene gas washing bottle of six groups of two-stage absorption devices to generate zinc sulfide precipitate. After reacting for 2.5-3 h, after the sample reaction system is cooled, sequentially closing the first gas flow regulator 28, the second gas flow regulator 29, the third gas flow regulator 30, the fourth gas flow regulator 31, the fifth gas flow regulator 32, the sixth gas flow regulator 33, the nitrogen pressure reducing valve 2 and the main valve of the nitrogen steel cylinder gas 1, and then sequentially taking down the first polymerized perfluoroethylene propylene gas washing bottle 16, the second polymerized perfluoroethylene propylene gas washing bottle 17, the third polymerized perfluoroethylene propylene gas washing bottle 18, the fourth polymerized perfluoroethylene propylene gas washing bottle 19, the fifth polymerized perfluoroethylene propylene gas washing bottle 20, the sixth polymerized perfluoroethylene propylene gas washing bottle 21, the seventh polymerized ethylene propylene gas washing bottle 22, the eighth polymerized perfluoroethylene propylene gas washing bottle 18 in the six groups of two-stage absorption devicesA fluoroethylene-propylene gas washing bottle 23, a ninth perfluoroethylene-propylene gas washing bottle 24, a tenth perfluoroethylene-propylene gas washing bottle 25, an eleventh perfluoroethylene-propylene gas washing bottle 26 and a twelfth perfluoroethylene-propylene gas washing bottle 27.
7, separating zinc sulfide precipitation reactants in the six groups of two-stage absorption devices obtained in the step 6 to complete multi-channel extraction of the pyritic sulfur in the rock and soil samples
The method comprises the steps of transferring all solutions containing zinc sulfide precipitation reactants in a first fluorinated ethylene propylene gas washing bottle 16, a second fluorinated ethylene propylene gas washing bottle 17, a third fluorinated ethylene propylene gas washing bottle 18, a fourth fluorinated ethylene propylene gas washing bottle 19, a fifth fluorinated ethylene propylene gas washing bottle 20, a sixth fluorinated ethylene propylene gas washing bottle 21, a seventh fluorinated ethylene propylene gas washing bottle 22, an eighth fluorinated ethylene propylene gas washing bottle 23, a ninth fluorinated ethylene propylene gas washing bottle 24, a tenth fluorinated ethylene propylene gas washing bottle 25, an eleventh fluorinated ethylene propylene gas washing bottle 26 and a twelfth fluorinated ethylene propylene gas washing bottle 27 of six groups of two-stage absorption devices into a beaker, dripping 2% of silver nitrate solution into the beaker, and separating Ag in the beaker by a centrifugal method2S precipitation, washing once with ammonia water to separate Ag2S precipitation, then washing the Ag of ammonia water with distilled water2And washing the S precipitate until the pH value is neutral, and drying. Weighing Ag with balance2And (S) finishing the extraction of the pyritic sulfur in the rock and soil samples. After extraction, the composition of the sulfur isotope can be determined by adopting an EA-IRMS method.
The present invention has been described in detail with reference to the drawings and examples, but the present invention is not limited to the above examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. The present invention can adopt the prior art for the content which is not described in detail in the present invention.
Claims (10)
1. A multichannel extraction element that is arranged in rock, soil sample pyrite sulphur which characterized in that: the device comprises a protective gas supply system, a sample reaction system and a product collection system, wherein the protective gas supply system comprises a nitrogen steel cylinder gas (1), a nitrogen pressure reducing valve (2) and a plurality of gas flow meters; the sample reaction system comprises a six-linked heating magnetic stirrer (3), flat-bottom triangular conical flasks, spherical condensation sampling devices and quark flow valves, the number of the flat-bottom triangular conical flasks is the same as that of the gas flow meters, and the product collection system comprises two-stage absorption devices, the number of the two-stage absorption devices is the same as that of the gas flow meters; the gas outlet of a nitrogen steel cylinder gas (1) of the protective gas supply system is communicated with the gas inlet of a nitrogen pressure reducing valve (2), and the gas outlet of the nitrogen pressure reducing valve (2) is respectively communicated with the gas inlets of a plurality of gas flowmeters; the gas outlets of a plurality of gas flow meters of the protective gas supply system are respectively communicated with the gas inlet on one side of the top of the spherical condensation sample introduction device of the sample reaction system, the top of each spherical condensation sample introduction device is respectively provided with a quark flow valve, each spherical condensation sample introduction device is respectively arranged in a bottle mouth at the top of a flat-bottom triangular conical flask, and the bottoms of the flat-bottom triangular flasks are respectively placed on a six-linked heating magnetic stirrer (3); and a sample outlet on one side of the top of each spherical condensation sample introduction device is respectively communicated with the gas inlets of a group of two-stage absorption devices of the product collection system.
2. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 1, wherein: the gas flowmeter of the protective gas supply system comprises a first gas flowmeter (28), a second gas flowmeter (29), a third gas flowmeter (30), a fourth gas flowmeter (31), a fifth gas flowmeter (32) and a sixth gas flowmeter (33), wherein gas inlets of the first gas flowmeter (28), the second gas flowmeter (29), the third gas flowmeter (30), the fourth gas flowmeter (31), the fifth gas flowmeter (32) and the sixth gas flowmeter (33) are communicated with a gas outlet of the nitrogen reducing valve (2).
3. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 2, wherein: the spherical condensation sample introduction device of the sample reaction system consists of a sample introduction pipe A and a branch pipe C, wherein the bottom of the sample introduction pipe A is provided with a grinding port D, one side of the top of the sample introduction pipe A is provided with a sample outlet B, the branch pipe C penetrates through the axis of the sample introduction pipe A, and the bottom of the branch pipe C is inserted into a flat-bottom triangular conical flask; the top of the branch pipe C is of a three-way structure, a transverse pipe of a three-way pipe at the top of the branch pipe C is communicated with an air outlet of the gas flowmeter, and a quark flow valve is arranged at the end part of a vertical pipe of the three-way pipe at the top of the branch pipe C; and a sample outlet B at the top of the sample inlet pipe A is communicated with the gas inlet of the two-stage absorption device.
4. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 3, wherein: the spherical condensation sampling device of the sample reaction system comprises a first spherical condensation sampling device (34), a second spherical condensation sampling device (35), a third spherical condensation sampling device (36), a fourth spherical condensation sampling device (37), a fifth spherical condensation sampling device (38) and a sixth spherical condensation sampling device (39), wherein the sample outlet B at the top of the sample inlet pipe A of the first spherical condensation sampling device (34), the second spherical condensation sampling device (35), the third spherical condensation sampling device (36), the fourth spherical condensation sampling device (37), the fifth spherical condensation sampling device (38) and the sixth spherical condensation sampling device (39) is communicated with the sample inlets of a group of two-stage absorption devices respectively, and the sample outlets of the two-stage absorption devices are sealed.
5. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 4, wherein: the flat-bottom triangular conical flask of the sample reaction system comprises a first flat-bottom triangular conical flask (4), a second flat-bottom triangular conical flask (5), a third flat-bottom triangular conical flask (6), a fourth flat-bottom triangular conical flask (7), a fifth flat-bottom triangular conical flask (8) and a sixth flat-bottom triangular conical flask (9), the bottoms of the first flat-bottom triangular conical flask (4), the second flat-bottom triangular conical flask (5), the third flat-bottom triangular conical flask (6), the fourth flat-bottom triangular conical flask (7), the fifth flat-bottom triangular conical flask (8) and the sixth flat-bottom triangular conical flask (9) are all placed on a six-linked-belt heating magnetic stirrer (3), and the top glass grinding openings of the first flat-bottom triangular conical flask (4), the second flat-bottom conical flask (5), the third flat-bottom triangular conical flask (6), the fourth flat-bottom triangular conical flask (7), the fifth flat-bottom triangular flask (8) and the sixth flat-bottom triangular conical flask (9) are respectively ground with the first spherical glass grinding openings And the bottom grinding ports D of the sample inlet pipes A of the condensation sample inlet device (34), the second spherical condensation sample inlet device (35), the third spherical condensation sample inlet device (36), the fourth spherical condensation sample inlet device (37), the fifth spherical condensation sample inlet device (38) and the sixth spherical condensation sample inlet device (39) are connected.
6. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 5, wherein: the top parts of the first spherical condensation sample introduction device (34), the second spherical condensation sample introduction device (35), the third spherical condensation sample introduction device (36), the fourth spherical condensation sample introduction device (37), the fifth spherical condensation sample introduction device (38) and the sixth spherical condensation sample introduction device (39) are respectively connected with a first quark flow valve (10), a second quark flow valve (11), a third quark flow valve (12), a fourth quark flow valve (13), a fifth quark flow valve (14) and a sixth quark flow valve (15).
7. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 6, wherein: the two-stage absorption device of the product collection system is six groups, and each two-stage absorption device is respectively formed by connecting two fluorinated ethylene propylene gas washing bottles in series.
8. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 7, wherein: the six groups of two-stage absorption devices are respectively formed by connecting a first fluorinated ethylene propylene gas washing bottle (16) and a seventh fluorinated ethylene propylene gas washing bottle (22), a second fluorinated ethylene propylene gas washing bottle (17) and an eighth fluorinated ethylene propylene gas washing bottle (23), a third fluorinated ethylene propylene gas washing bottle (18) and a ninth fluorinated ethylene propylene gas washing bottle (24), a fourth fluorinated ethylene propylene gas washing bottle (19) and a tenth fluorinated ethylene propylene gas washing bottle (25), a fifth fluorinated ethylene propylene gas washing bottle (20) and an eleventh fluorinated ethylene propylene gas washing bottle (26), a sixth fluorinated ethylene propylene gas washing bottle (21) and a twelfth fluorinated ethylene propylene gas washing bottle (27) in series.
9. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 8, wherein: the sample reaction system comprises a first spherical condensation sample introduction device (34), a second spherical condensation sample introduction device (35), a third spherical condensation sample introduction device (36), a fourth spherical condensation sample introduction device (37), a fifth spherical condensation sample introduction device (38) and a sample introduction tube A of a sixth spherical condensation sample introduction device (39), wherein a sample outlet B at the top of the sample introduction tube A is respectively communicated with a first perfluorinated ethylene propylene gas washing bottle (16), a second perfluorinated ethylene propylene gas washing bottle (17), a third perfluorinated ethylene propylene gas washing bottle (18), a fourth perfluorinated ethylene propylene gas washing bottle (19), a fifth perfluorinated ethylene propylene gas washing bottle (20) and a sample introduction port of the sixth perfluorinated ethylene propylene gas washing bottle (21), the first perfluorinated ethylene propylene gas washing bottle (16), the second perfluorinated ethylene propylene gas washing bottle (17), the third perfluorinated ethylene propylene gas washing bottle (18), the fourth perfluorinated ethylene propylene gas washing bottle (19), Sample outlets of a fifth fluorinated ethylene propylene gas washing bottle (20) and a sixth fluorinated ethylene propylene gas washing bottle (21) are respectively communicated with sample inlets of a seventh fluorinated ethylene propylene gas washing bottle (22), an eighth fluorinated ethylene propylene gas washing bottle (23), a ninth fluorinated ethylene propylene gas washing bottle (24), a tenth fluorinated ethylene propylene gas washing bottle (25), an eleventh fluorinated ethylene propylene gas washing bottle (26) and a twelfth fluorinated ethylene propylene gas washing bottle (27); sample outlets of a seventh fluorinated ethylene propylene gas washing bottle (22), an eighth fluorinated ethylene propylene gas washing bottle (23), a ninth fluorinated ethylene propylene gas washing bottle (24), a tenth fluorinated ethylene propylene gas washing bottle (25), an eleventh fluorinated ethylene propylene gas washing bottle (26) and a twelfth fluorinated ethylene propylene gas washing bottle (27) are sealed.
10. The multi-channel extraction device for the pyrite sulfur in the rock and soil samples according to claim 9, wherein: the nitrogen pressure reducing valve (2) is connected with the nitrogen steel cylinder (1) through a stainless steel adapter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920974611.4U CN210293842U (en) | 2019-06-26 | 2019-06-26 | Multi-channel extraction device for pyrite sulfur in rock and soil samples |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920974611.4U CN210293842U (en) | 2019-06-26 | 2019-06-26 | Multi-channel extraction device for pyrite sulfur in rock and soil samples |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN210293842U true CN210293842U (en) | 2020-04-10 |
Family
ID=70098878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201920974611.4U Active CN210293842U (en) | 2019-06-26 | 2019-06-26 | Multi-channel extraction device for pyrite sulfur in rock and soil samples |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN210293842U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110208062A (en) * | 2019-06-26 | 2019-09-06 | 核工业北京地质研究院 | Multichannel extraction element and method for pyritic sulfur in rock, pedotheque |
-
2019
- 2019-06-26 CN CN201920974611.4U patent/CN210293842U/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110208062A (en) * | 2019-06-26 | 2019-09-06 | 核工业北京地质研究院 | Multichannel extraction element and method for pyritic sulfur in rock, pedotheque |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104181245B (en) | A kind of hydrogen isotope analysis method in fluid inclusion water | |
| CN109557225B (en) | A kind of C-O isotopes measuring method and its system | |
| CN204214707U (en) | A kind of pretreating device for analyzing trace impurity in trichlorosilane | |
| CN210293842U (en) | Multi-channel extraction device for pyrite sulfur in rock and soil samples | |
| CN201740738U (en) | Mercury vapor generator used for mercury vapor analyzer | |
| CN110208062A (en) | Multichannel extraction element and method for pyritic sulfur in rock, pedotheque | |
| CN206609782U (en) | A kind of edaphon respiration measuring device | |
| CN207081728U (en) | A kind of Soil Nitrogen circulating research device | |
| CN206950974U (en) | A kind of experimental provision for simulating industrial smoke dry desulfurization | |
| CN218766964U (en) | Multi-point-position multi-element full-automatic sampling, sample feeding, sampling and detecting system | |
| CN210166351U (en) | On-line sample introduction system for carbon and oxygen isotope determination of carbonate rock | |
| CN107037176A (en) | The method and apparatus of sulfide content in a kind of detection methane gas | |
| CN203658271U (en) | Multi-channel rapid detecting system for aminodithioformic acid ester pesticide residue | |
| CN206161642U (en) | Extraction and desorption device | |
| CN106769346B (en) | Method for analyzing hydrogen isotopes in water | |
| CN105784459A (en) | Pretreatment method for trace impurity element on chlorosilane and polycrystalline silicon body surface metal | |
| CN213313473U (en) | Novel lithium extraction system for adsorbing concentrated lithium-containing brine | |
| CN207816631U (en) | Overlying water and sediment interstitial water one harvester | |
| CN103675087A (en) | Analytic method of oxygen isotopes in sulfate radicals | |
| CN209443001U (en) | A kind of microorganism count device | |
| CN217878525U (en) | Gas well production sample collection device | |
| CN207730532U (en) | Core sample automatic separating apparatus | |
| CN205120418U (en) | A micro - interstitial water collection pipe that is used for aquatic attitude experiment deposit | |
| CN207036783U (en) | A kind of distilling apparatus for efficiently separating hydrogen sulfide in extract type spice | |
| CN205483764U (en) | Processing apparatus before purification - concentration of tealeaves pesticide residue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |