CN111103267A

CN111103267A - Water-carrying atomic fluorescence analysis device and atomic fluorescence analysis method

Info

Publication number: CN111103267A
Application number: CN201811271724.4A
Authority: CN
Inventors: 龚治湘; 杨梅; 龚晖
Original assignee: Chongqing Mintai New Agrotech Development Group Co ltd
Current assignee: Chongqing Mintai New Agrotech Development Group Co ltd
Priority date: 2018-10-29
Filing date: 2018-10-29
Publication date: 2020-05-05

Abstract

The invention relates to a water-carrying flow atomic fluorescence analysis device and an analysis method, belonging to the atomic fluorescence analysis in the field of analytical chemistry. The device is highly integrated, compact in structure and convenient to assemble, adjust, operate and maintain, the analysis method can effectively overcome the memory effect, improves the measurement sensitivity and accuracy, breaks through the constraint of the traditional atomic fluorescence analysis, and is an innovation of the atomic fluorescence analysis technology.

Description

Water-carrying atomic fluorescence analysis device and atomic fluorescence analysis method

Technical Field

The invention belongs to the field of analytical chemistry, and relates to atomic fluorescence analysis. It breaks through the atomic fluorescence analysis technology, in particular to the improvement of the existing atomic fluorescence instrument and the atomic fluorescence analysis method.

Background art scene

Atomic fluorescence analysis has been widely used for the determination of trace amounts of As, Sb, Bi, Hg, Se, and the like. The basic principle is that ions of an element to be detected in an acidic medium (usually hydrochloric acid) react with a strong reducing agent (usually potassium borohydride or sodium borohydride) to be reduced into gaseous hydride or atoms, and a large amount of hydrogen is generated. The hydride molecules are dissociated into ground state atoms in the high-temperature hydrogen flame and excited to a high energy state by radiation of a specific frequency of an excitation light source, and the excited state atoms emit fluorescence of a characteristic wavelength in the form of light radiation in the de-excitation process due to extreme instability of the high energy level. The fluorescence intensity is correlated with the concentration of the element to be detected, and the concentration of the element to be detected is obtained by measuring the fluorescence signal of the element to be detected by a detector (usually a photomultiplier).

The atomic fluorescence analysis device (also called atomic fluorescence instrument and atomic fluorescence photometer) designed according to the principle mainly comprises a transfusion system, a steam generation system (or called reactor), an atomizer, an excitation light source, a detector and a control system. The liquid conveying system is used for conveying the test liquid and the reducing agent, chemical reaction is carried out in the vapor generating system to generate gaseous hydride molecules and hydrogen (becoming vapor), the atomizer is used for enabling the hydride molecules to become atoms, the excitation light source and the detector are used for generating fluorescence and collecting fluorescence signals, and the detection result is reported through the operation of the control system.

Since the existence of commercial instruments, the atomic fluorescence analysis uses HCl-NaBH4(KBH4) as a current-carrying conveying test solution, and a reaction product is introduced into hydrogen flame from an inner tube of a quartz furnace along with small-flow Ar gas. The Ar gas introduced into the outer tube plays a shielding role and is called shielding gas. The hydrogen continuously generated in the measuring process keeps the hydrogen flame constant, so that a large amount of high-purity HCl and reducing agent are consumed, and accordingly, the problems of long sample introduction and measuring time, high furnace body temperature, large memory effect, no complete signal spectrogram, difficult ignition of the hydrogen flame and the like are caused. Meanwhile, most of the instruments do not have applicable lamp position adjusting devices; the control of the carrier gas by the solenoid valve often fails; the operating software is complicated; a large lamp current and a negative high voltage are required to achieve a high sensitivity, etc. All of the above negatively affect the detection by atomic fluorescence.

Disclosure of Invention

The invention aims to provide an atomic fluorescence analysis device with a brand-new concept so as to effectively solve the problems.

The invention provides a water-borne flow atomic fluorescence analysis device, which comprises a liquid conveying system and an instrument main body, wherein the instrument main body comprises an outer cover, a reactor, an atomizer, an optical ring, an excitation light source, a detector, a circuit and gas circuit integrated system and the like, wherein the reactor, the atomizer, the optical ring, the excitation light source, the detector, the circuit and gas circuit integrated system and the like are assembled in the outer cover, and the liquid conveying system: the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a sample inlet pipe; the reagent bottle is used for containing a reducing agent and is communicated with the reactor through a reagent inlet pipe; the water outlet of the water bottle is respectively communicated with the inlet of the sample inlet pipe and the inlet of the reagent inlet pipe through a water inlet pipe, and the water inlet is controlled by switching the water inlet pipe; and the infusion system does not contain a matched device for infusing the carrier acid.

In the water current-carrying atomic fluorescence analysis device, the sample inlet pipe and the reagent inlet pipe are liquid inlet capillary tubes, the water bottle is changed into two water cups, one water cup is used for containing cleaning water, the other water cup is used for containing water current, and the liquid inlet capillary tubes are alternately inserted in the two water cups.

In the water-carrying atomic fluorescence analysis device, a liquid inlet capillary is connected into a reactor through a peristaltic pump, and the peristaltic pump is used for controlling the conveying speed and the transfusion quantity of a liquid inlet capillary sample liquid, a reagent, cleaning water and carrying flow water.

In the water-carrying atomic fluorescence analysis device, an air outlet pipeline of the reactor is connected to an outer pipe joint of a quartz furnace in the atomizer, and an inner pipe joint of the quartz furnace is connected with an argon pipeline as auxiliary air.

In the water current-carrying atomic fluorescence analysis device, the atomizer comprises a furnace body support, a furnace core, a quartz furnace sleeved in the furnace core, a furnace body outer cover sleeved outside the furnace core, a ceramic cover plate, an electric furnace wire and other parts, and is characterized in that the furnace core and the furnace body outer cover are made of insulating heat-resistant non-metal materials, and the parts are clamped or fixed without screws.

In the water current-carrying atomic fluorescence analysis device, at least two clamping grooves are formed in the upper end of the furnace body outer cover, the side edge of the ceramic cover plate is aligned to form a buckle, and the buckle and the clamping grooves are buckled to clamp the upper end of the furnace body outer cover and the ceramic cover plate.

In the water current-carrying atomic fluorescence analysis device, the electric furnace wire is inserted between the ceramic cover plate and the quartz furnace pipe orifice, a ceramic heat-insulating layer instead of asbestos is arranged between the ceramic cover plate and the top end surface of the furnace core, and the electric furnace wire is supported and positioned at the pipe orifice of the quartz furnace by the ceramic heat-insulating layer.

In the water current-carrying atomic fluorescence analysis device, a groove body and a step are arranged at the upper part of a furnace body support, and two slotted holes are formed in the side wall of the groove body; the lower part of the furnace core is provided with a bulge which is embedded in the groove body; the inner pipe joint and the outer pipe joint at the lower part of the quartz furnace are clamped in the slotted holes and extend out to the side surface; the quartz furnace is sleeved in the furnace core cavity, and a pipe orifice of the quartz furnace extends upwards out of the top end surface of the furnace core; the furnace body outer cover is sleeved on the periphery of the furnace core, and the bottom of the furnace body outer cover abuts against and is seated on the step of the furnace body support.

In the water current carrying atomic fluorescence analysis device, the optical ring comprises a shell, one side of the shell is provided with a mounting hole for mounting an excitation light source and a detector respectively, and the opposite side of the shell on the side where the mounting hole is located is provided with a side cutting groove for transmitting light emitted by the excitation light source.

In the water current-carrying atomic fluorescence analysis device, the size of the side cutting groove is matched with the adjusting range of the excitation light source, so that the characteristic spectrum emitted by the excitation light source cannot irradiate the shell of the optical ring.

In the water current-carrying atomic fluorescence analysis device, light absorption paper coated with black light absorption materials is laid on the inner side of the atomic fluorescence instrument shell towards which the side cut groove of the shell faces.

In the water current-carrying atomic fluorescence analysis device, the circuit gas path integrated system is an integral module and comprises a bottom plate, a switch power supply and a vertical frame type circuit gas path integrated module, wherein the switch power supply and the vertical frame type circuit gas path integrated module are arranged on the bottom plate; the power panel modulates the power provided by the switching power supply into DC power supplies in different ranges to be supplied to the control mainboard and the pneumatic control module.

In the water current-carrying atomic fluorescence analysis device, the bottom plate and the bottom of the instrument main body realize displacement by nesting a slide rail and a groove.

In the water current carrying atomic fluorescence analysis device, a large display screen is arranged on a front panel of an outer cover of the instrument main body and is used for displaying contents of a desktop system.

In the water current-carrying atomic fluorescence analysis device, the instrument main body also comprises a lamp tube position adjusting device which is used for adjusting the excitation light source in the horizontal direction and the vertical direction, and the adjusting knob is positioned on the side edge of the outer shell of the instrument main body.

In the water current-carrying atomic fluorescence analysis apparatus, the lamp position adjusting apparatus includes: a lamp tube holder for mounting a lamp tube; a support base, on the upper surface of which a lamp tube seat is arranged; the horizontal adjusting mechanism is of a gear combination structure and is used for converting the rotation of the horizontal knob into the movement of the lamp tube seat provided with the lamp tube in the horizontal direction; the vertical adjusting mechanism comprises a lead screw and a scissor structure connected with the lead screw through a lead screw nut assembly, and is used for converting the rotation of the lead screw into the change of the angle of the scissor structure so as to push the supporting seat supported on the scissor structure to vertically move up and down; and the fixing frame is used for supporting the horizontal adjusting mechanism and the vertical adjusting mechanism.

Elastic clamping pieces are fixed on two sides of the lamp tube seat respectively, the lower ends of the two clamping pieces are fixed on the side edges of the lamp tube seat, the upper ends of the two clamping pieces are bent to the outer side, and the two clamping pieces form an arc-shaped containing space with an upper opening and a narrow upper part and a lower opening for installing the lamp tube.

The horizontal adjustment mechanism includes: the rack is fixed at the bottom of the lamp tube seat; the straight gear is provided with an integrated sleeve and is meshed with the rack; the lower end of the straight rack adjusting shaft is rotatably arranged on a supporting beam, two ends of the supporting beam are fixed on the fixed frame, and the upper end of the straight rack adjusting shaft is used for penetrating and sleeving a sleeve of the straight gear and is in matched connection with the plane of the sleeve of the straight gear; the bevel gears in the horizontal direction are fixed on the straight gear adjusting shaft, and the vertical bevel gears are fixed at the end parts of the bevel gear adjusting shafts; and the horizontal knob is connected to the bevel gear adjusting shaft through a coupler.

The supporting seat comprises a horizontal plate and a first side plate vertically arranged on two sides of the horizontal plate, the straight gear is fixed in a groove formed in the bottom of the lamp tube seat, two sliding sleeves are respectively fixed on two sides of the groove in the bottom of the lamp tube seat, and the sliding sleeves can be slidably sleeved in third sliding grooves formed in the horizontal plate.

The fixing frame comprises a base, supporting plates fixed at two ends of the base and second side plates arranged on two sides of the base, and mounting holes and first sliding grooves are formed in the second side plates and used for supporting the vertical adjusting mechanism.

The vertical adjustment mechanism includes: the two supporting connecting rods form a scissor-type structure, fixed rods are respectively arranged at two corners on the left side of the scissor-type structure in a penetrating manner, sliding rods are respectively arranged at two corners on the right side of the scissor-type structure in a penetrating manner, and two ends of each fixed rod respectively penetrate through the mounting holes of the second side plate and the first side plate to be fixed; two ends of the sliding rod can respectively and slidably penetrate and sleeve the second sliding groove of the second side plate and the first sliding groove of the first side plate; the lead screw and wear to overlap on the lead screw and rather than threaded connection's lead screw nut component, the lead screw head passes bearing, backup pad, lead screw nut component in proper order and is fixed in the left side bearing, and the lead screw afterbody passes through a shaft coupling and connects perpendicular knob, and the shear mode structure upper end that two support connecting rods formed withstands the horizontal plate of supporting seat, and a slide bar in the shear mode structure passes behind the lead screw nut slidable and wears to overlap in the second spout of second curb plate.

The atomic fluorescence analysis method provided by the invention uses the water current-carrying atomic fluorescence analysis device, and comprises the process of taking water as current-carrying after the sampling of the liquid conveying system, and carrying out sample injection from the outer tube of the quartz furnace in the atomization process until the detection is finished.

In the atomic fluorescence analysis method, the outer tube sample injection refers to introducing hydride and hydrogen mixed gas carried by carrier gas from a reactor into an outer tube of a quartz furnace, introducing auxiliary gas (Ar gas) into an inner tube of the quartz furnace, and controlling the flow rate.

In the atomic fluorescence analysis method, the flow rate of the carrier gas (Ar gas also can be used) carrying the mixed gas is increased to 1000-1200ml/min, and the flow rate of the auxiliary gas (Ar gas) is reduced to 400-600ml/min or the auxiliary gas is not introduced (namely the flow rate is 0 ml/min).

In the atomic fluorescence analysis method, the sampling refers to simultaneously and respectively introducing a test solution with certain acidity (preferably, the concentration range of hydrochloric acid is 4% -10%) and a reagent with certain concentration, and the taking of water as a current carrier refers to respectively carrying and pushing the test solution and the reagent into a reactor by taking purified water as the current carrier.

In the atomic fluorescence analysis method, the sampling time is 4-5 seconds, and the time from the water carrying to the detection ending is 8-10 seconds.

In the atomic fluorescence analysis method, two water cups are used for holding purified water, a capillary tube for conveying a test solution and a reagent is switched between the two cups of water after sampling, the sampling/delay/switching/measuring time is 4-5/0/2-3/8-10 seconds respectively, namely the sampling time is 4-5 seconds, the delay is zero seconds, the switching time is 2-3, and the time from current carrying to measurement ending is 8-10 seconds.

In the atomic fluorescence analysis method, the detection process also comprises a process of controlling the intermittent ignition of the hydrogen flame, and the excitation light source and the detector work within the combustion time of the hydrogen flame.

By adopting the scheme, the device is highly integrated, has a compact structure, and is convenient to assemble, adjust, operate and maintain, the analysis method can effectively overcome the memory effect, improve the measurement sensitivity and accuracy, break through the constraint of the traditional atomic fluorescence analysis, is an innovation of the atomic fluorescence analysis technology, and has epoch-making significance.

The invention is described in detail below with reference to the figures and examples.

Drawings

FIG. 1A is a schematic view of the overall appearance of the water-borne atomic fluorescence analyzer according to the present invention;

FIG. 1B is a schematic view of a part structure of the water-borne atomic fluorescence analyzer according to the present invention;

FIG. 2A is a schematic view showing the configuration of a liquid feeding system in the atomic fluorescence analyzer according to the present invention;

FIG. 2B is a simplified configuration and schematic view of an infusion system in the atomic fluorescence analyzer of the present invention;

FIG. 3A is a schematic diagram of an atomizer sub-assembly of the atomic fluorescence analyzer of the present invention;

FIG. 3B is a schematic cross-sectional view of an atomizer in the atomic fluorescence analyzer of the present invention;

FIG. 3C is a schematic diagram of the appearance structure of an atomizer in the atomic fluorescence analyzer of the present invention;

FIG. 3D is a schematic diagram of the outer tube sample injection method of the present invention in atomic fluorescence analysis;

FIG. 3E is a schematic diagram of the original sample injection mode of a quartz furnace in atomic fluorescence analysis;

FIG. 4-1 is a perspective view showing a lamp position adjusting apparatus in the atomic fluorescence analyzer according to the present invention;

FIG. 4-2 is an exploded view of the lamp position adjusting device of the atomic fluorescence analyzer of the present invention;

FIG. 4-3 is a schematic view showing the structure of a horizontal adjustment mechanism in the atomic fluorescence analyzer of the present invention;

FIGS. 4 to 4 are schematic structural views of a vertical adjustment mechanism in the atomic fluorescence analysis apparatus according to the present invention;

FIGS. 4 to 5 are longitudinal sectional views of a lamp position adjusting device in the atomic fluorescence analyzing apparatus according to the present invention;

FIGS. 4-6 are schematic diagrams of the lamp position adjusting device and the lamp in the atomic fluorescence analyzer according to the present invention;

FIGS. 4 to 7 are schematic views showing the state of the horizontal adjustment mechanism in the atomic fluorescence analyzer according to the present invention when the tube holder is at the uppermost position;

FIG. 5-1 is a first schematic view of the installation structure of the optical ring in the atomic fluorescence instrument;

FIG. 5-2 is a schematic diagram of the installation structure of the optical ring in the atomic fluorescence instrument;

FIG. 5-3 is a schematic perspective view of an optical ring of the atomic fluorescence analyzer of the present invention;

FIGS. 5-4 are rear views of the optical ring in the atomic fluorescence analysis device of the present invention;

FIGS. 5 to 5 are side views of the optical ring in the atomic fluorescence analysis device of the present invention;

FIG. 6-1 is a schematic structural diagram of a circuit and gas circuit integrated system in the atomic fluorescence analyzer of the present invention;

FIG. 6-2 is a schematic diagram of a vertical frame structure in the circuit gas path integrated system of FIG. 6-1;

FIG. 6-3 is a schematic view of the electrical circuit gas path integrated system of FIG. 6-1 assembled in an atomic fluorescence instrument;

FIG. 7A is a plot of the peak value of Cd measured in assay example 1 (fluorescence value versus time);

FIG. 7B is a standard curve (fluorescence value-concentration) of 0.1-0.5ng/mL for Cd determination in test example 1;

FIG. 8A is a graph showing the peak value (fluorescence value versus time) of Hg/As measured simultaneously in detection example 2;

FIG. 8B is a standard curve (fluorescence value-concentration) of a mixed solution of 0.1 to 0.5ng/ml Hg and 10 to 50ng/ml As in detection example 2 in which Hg/As is measured simultaneously.

FIG. 9A is a graph showing the peak value of Pb measured in detection example 3 (fluorescence value versus time);

FIG. 9B is a standard curve (fluorescence value vs. concentration) of 0.1-0.5ng/mL for Cd determination in detection example 3;

FIG. 10 is a data screenshot showing the detection limit and reproducibility of Hg measured by the atomic fluorescence analyzer of the present invention.

Detailed Description

On the basis of the original atomic fluorescence instrument, the invention takes the sampling mode adjustment of a transfusion system as a starting point, combines the change of the sampling mode of a quartz furnace of an atomizer, and is matched with the perfection of various aspects such as assembly, adjustment, automatic control and the like of all parts, finally provides a novel atomic fluorescence device which breaks through the constraint of the traditional concept, and forms a novel atomic fluorescence detection technology by matching.

Similar to the traditional atomic fluorescence instrument, the atomic fluorescence analysis device mainly comprises a transfusion system, a steam generation system (or called reactor), an atomizer, an excitation light source, a detector and a control system, wherein the functions and functions of all the parts are the same as those of the original atomic fluorescence instrument, but the atomic fluorescence analysis device has special design and unique combination and comprises the following parts:

A. the method of abandoning HCL-NaBH4 as a current carrying method adopts pure water as the current carrying;

B. adopting an outer tube sample introduction technology;

C. intermittently heating the furnace wire;

D. adopting a newly developed nonmetal furnace body;

E. using an open optic ring;

F. removing peripheral equipment, and assembling in a gathering manner;

G. the asbestos pad is discarded, and a ceramic heat-insulating layer is adopted;

H. adopting a rapid sample introduction and detection program; the desktop system integrates measurement, display, printing and storage into a whole and is rapid;

I. a device for quickly adjusting the lamp position is adopted;

J. the current limiting technique is used to allow the ground state atoms or hydrides to pass through the quartz furnace at a slower rate.

The following are described separately.

Infusion system

The invention has the characteristic A that the method of removing HCL-NaBH4 as the current carrying adopts pure water as the current carrying. The infusion system designed according to the method can be seen in fig. 2A, and comprises: the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a sample inlet pipe; the reagent bottle is used for containing a reducing agent and is communicated with the reactor through a reagent inlet pipe; the water outlet of the water bottle is communicated with the inlet of the sample inlet pipe and the inlet of the reagent inlet pipe respectively through the water inlet pipe, and the water inlet is controlled by switching the water inlet pipe. The infusion system is unique in design that the infusion system does not comprise a matched device for infusing hydrochloric acid, and is obviously distinguished and obviously different from the known infusion system.

A simplified infusion system is shown in fig. 2B, comprising: the device comprises a test solution bottle for containing a sample solution to be tested and a reagent bottle for containing a reducing agent, wherein the test solution bottle and the reagent bottle are communicated with a reactor through a liquid inlet capillary; the two water bottles are used for containing purified water, one water bottle (water cup 1) contains cleaning water for cleaning a capillary tube, and the other water bottle (water cup 2) contains carrier flow water as a carrier flow. In the atomic fluorescence analysis transfusion process, a peristaltic pump can be used, after a sample solution and a reagent are respectively input into a sample storage ring (called as sampling) through two capillaries under the action of the peristaltic pump, the front sections of the two capillaries near the head ends are transferred into cleaning purified water of a water cup 1 to be cleaned (shown by a dotted line in a figure 2B), then the head ends of the two capillaries are transferred into a water cup 2 (shown by a dotted line in a figure 2B and called as replacement insertion), and the sample solution and the reagent in the sample storage ring are carried by carrier purified water to be pushed into a reactor.

By utilizing the simplified infusion system, after a test solution and a reagent are conveyed, the capillary tube is immediately placed in a first cup of water (water cup 1) to clean a solution which is possibly attached to the outer wall of the capillary tube, and then is placed in a second cup of water (water cup 2) to carry the solution with water until the measurement is finished. The specific operation can be as follows:

A1) sampling: inserting the ends of two liquid inlet capillaries into a test solution (blank solution, standard solution or sample solution) and a reagent (NaBH)₄) Sampling in the solution, and stopping the peristaltic pump after 4-5 seconds;

A2) and (3) replacement and insertion: taking out the ends of the two capillaries, putting the two capillaries into water for cleaning, immediately transferring the capillaries into current-carrying water of the other water cup, and restarting the peristaltic pump;

A3) current carrying measurement: the carrier water carries the test solution and the reagent into the reactor respectively, and the instrument simultaneously determines the fluorescence signal of the test solution.

In the operation, the sampling/delay/interpolation/measurement time is respectively 4-5/0/2-3/8-10 seconds, namely, A1) the sampling time is 4-5 seconds, the delay is zero seconds, A2) the interpolation time is 2-3, and A3) the current-carrying measurement time is 8-10 seconds.

The invention utilizes the transfusion system, creatively uses water As the current-carrying in the atomic fluorescence analysis, ends the history of using HCl and NaBH4 As the current-carrying for more than 30 years, can detect trace or trace As, Sb, Bi, Pb, Se, Cd and Hg in the test solution, shows that the transfusion technology using water to replace HCl and reducing agent As the current-carrying can be used in the atomic fluorescence analysis, and has the advantages that: different from HCl and NaBH4 which are used as current carriers, the ultrapure water does not contain a component to be measured, does not have any chemical reaction with a test solution or a reducing agent in the infusion process, does not have a large number of bubbles (caused by hydrogen generated by acid and the reducing agent) adhered to the tube wall of the flow path, and can ensure that all infusion flow paths are thoroughly washed. Therefore, the atomic fluorescence analysis with water as a carrier current effectively overcomes the memory effect, improves the sensitivity and accuracy of the determination, saves a large amount of high-purity HCl and a reducing agent NaBH4, greatly reduces the analysis cost, and obviously improves the operation environment.

Atomizer

The invention is characterized in that D adopts a newly developed nonmetal furnace body, G adopts a ceramic heat-insulating layer for removing asbestos pads, B adopts an outer tube sample introduction technology, J adopts a current limiting technology, C adopts intermittent heating on furnace wires, and the characteristics are reflected in the improvement and the use of an atomizer.

Features D and G relate to the novel atomizer 30 designed by the present invention, the appearance structure of which is shown in fig. 1B and 3C, the constitution and structure of which are shown in fig. 3A-3C, including: the furnace comprises a furnace core 31, a quartz furnace 33 sleeved in the furnace core 31, a furnace body outer cover 32 sleeved outside the furnace core 31, a ceramic cover plate 34 clamped with the upper end of the furnace body outer cover, an electric furnace wire 37 embedded between the ceramic cover plate 34 and a pipe orifice of the quartz furnace 33, and a ceramic heat insulation layer 36 filled between the ceramic cover plate 34 and the top end surface of the furnace core 31, wherein the furnace body part is formed by the above components, and a furnace body support 35 is arranged at the bottom of the furnace body and used for supporting the furnace body. Here: the quartz furnace 33 is a commercially available product, and is a sleeve composed of a central tube (inner tube) and an outer tube which are separated from each other, and the inner tube and the outer tube are respectively connected with hydride and hydrogen (carried by carrier gas) generated by the reactor and shielding gas through an inner tube joint 331 and an outer tube joint 332. The furnace core 31 is an I-shaped cavity member as a whole, the quartz furnace 33 is sleeved in the cavity, the pipe orifice 333 of the quartz furnace extends upwards out of the top end surface 313 of the furnace core 31, the shape and the size of the lower bulge 311 of the furnace core 31 are matched with the upper groove body 351 of the furnace body support 35, and the bulge 311 is embedded in the groove body 351. The upper portion of the core 31 may be formed with an inner recess 312 for receiving the ceramic insulation 36. Two slots 352 are opened on the side wall of the upper tank 351 of the furnace body support 35, and the inner pipe joint 331 and the outer pipe joint 332 of the quartz furnace 33 extend to the side through the slots 352. The furnace body outer cover 32 is cylindrical and is sleeved on the periphery of the furnace core 31, the bottom 321 of the furnace body outer cover is abutted against the step 353 of the furnace body support, and the upper part of the furnace body outer cover is provided with at least two clamping grooves 322 which are clamped and buckled with the buckles 342 arranged on the side edge of the ceramic cover plate 34. The electric furnace wire 37 is mounted on the inner side of the ceramic cover plate 34 in a penetrating way, and is supported and fixed on the periphery of the nozzle 333 of the quartz furnace 33 through the ceramic heat insulation layer 36 filled between the ceramic cover plate 34 and the top end surface of the furnace core 31. The shape of the ceramic thermal insulation layer 36 varies with the shape of the filling gap, and may be one or a combination of a plurality of thermal insulation materials (without asbestos material), such as ceramic sheets, ceramic fibers, mica sheets, etc., as shown in fig. 3B, a ceramic thermal insulation layer composed of a ceramic fiber rope 363, mica sheets 362 and ceramic fibers 361 stacked in sequence is provided, wherein the ceramic fiber rope 363 is embedded into the inner groove 312 provided at the upper portion of the furnace core 31.

The above components are assembled in such a way that: the upper part of the quartz furnace 33 is sleeved into the inner cavity of the furnace core 31 from bottom to top, the furnace core 31 and the bottom of the quartz furnace 33 are sleeved into the upper groove body 351 of the furnace body support, and the inner pipe joint 331 and the outer pipe joint 332 of the quartz furnace 33 are clamped into the slotted hole 352; the ceramic cover plate 34 provided with the electric furnace wire 37 is clamped at the upper end of the furnace body outer cover 32, a ceramic heat-insulating layer 36 is filled in the space from the upper end of the furnace core 31 to the pipe orifice of the quartz furnace 32, and finally the furnace body outer cover 32 is sleeved outside the furnace core 31 and is seated on the step 353 of the furnace body support 35. The atomizer that the assembly was accomplished like this uses structures such as draw-in groove to realize fixing between the part in the assembly, need not the screw.

In the atomizer, the furnace core 31 and the furnace body outer cover 32 are both made of insulating and heat-resistant non-metallic materials, and metal materials are not used. The furnace body is made of a non-metallic material which has excellent heat dissipation performance and is completely insulated, the furnace body can be maintained without cooling after stopping working, the temperature of the furnace body is not too high in the working process, the phenomenon of baseline drift is avoided, and the working stability of the instrument is good; all the components are assembled in a matching way, and the mounting does not need to be fastened by screws, so that the whole body can be disassembled, assembled and maintained; the pipe orifice of the quartz furnace adopts heat insulation materials such as mica, ceramic and the like, thereby eliminating carcinogenic asbestos and integrally improving the quality of the atomizer.

In the aspect of using an atomizer, the characteristic D relates to a unique method of the invention and provides an outer tube sampling mode, and the characteristic J further combines and uses a current limiting technology. Referring to fig. 3D and comparing with fig. 3E, the present invention replaces the hydride and hydrogen mixed gas (generated in the gas-liquid separator) carried by the carrier gas (argon) originally connected to the inner tube of the quartz furnace with the outer tube, and at the same time replaces the shielding gas (Ar gas) tube of the outer tube with the inner tube as the auxiliary gas; on the other hand, the flow rate of the carrier gas (also Ar gas) carrying the mixed gas is increased to 1000-1200ml/min, the flow rate of the shielding gas (Ar gas) is reduced from 1000ml/min in the original mode to 400-600ml/min, and some elements can be measured even without introducing the auxiliary gas (i.e. 0 ml/min). The use of current limiting techniques to allow ground-state atoms or hydrides to pass through the quartz furnace at a slower rate allows the hydrogen flame to be more stable and maintained for a longer period of time.

The outer tube sample injection mode changes the mode of introducing hydride (or Hg atoms) from the inner tube in the atomic fluorescence analysis. The mechanism is as follows: gaseous atoms or molecules and hydrogen generated by the chemical reduction reaction are introduced from the outer tube of the quartz furnace along with the carrier gas Ar gas carrier, the mixed gas of the element hydride (or mercury atoms) to be detected and the hydrogen rises along the inner wall of the outer tube of the quartz furnace, the hydrogen is immediately ignited by heating at the mouth of the quartz furnace, and the hydride is dissociated under the action of oxyhydrogen flame at high temperature in the Ar gas atmosphere. The auxiliary gas (usually argon) entering the inner tube pulls the hydrogen flame upward, and the hydrogen flame formed is much larger than the inner tube sample (see fig. 3D). Thus, hydrogen is heated by the furnace wire at the mouth of the outer tube, the hydrogen flame is easy to ignite, the formed hydrogen flame has large and stable shape, the determination sensitivity is obviously improved, and the method is particularly suitable for detecting elements (such as Pb) which generate less hydrogen in the reaction.

In a word, the outer tube sampling technology enables the ignition of hydrogen flame to be very easy, and the flame has a large shape, a large light-emitting solid angle and high sensitivity; this is particularly advantageous for reaction systems with low hydrogen generation, such as Pb lamps.

The characteristic C relates to the change of the heating mode of the furnace wire, and changes the mode of keeping the hydrogen flame continuously in the original analysis process into intermittent heating, wherein the intermittent heating means that the hydrogen flame is only ignited for a period of time when a signal is measured, and the furnace is in a cooling period for about half of the time, so that the phenomenon of baseline drift caused by the temperature rise of the furnace body in the atomic fluorescence analysis is overcome.

Lamp tube position adjusting device

The invention is characterized in that the lamp position is quickly adjusted, and the vertical position and the horizontal position of an emission light source (a hollow cathode lamp) can be quickly adjusted by using two knobs outside a case. This feature is achieved by the specially designed lamp position adjustment device 60 of the present invention (see fig. 1B). Aiming at the problems of inconvenient operation, difficult guarantee of the position of a lamp tube and the like of the conventional lamp tube position adjusting device in a screw mode, the invention provides the lamp tube position adjusting device which is convenient to operate and can realize continuous adjustment.

The structure of the lamp tube position adjusting device is shown in fig. 4-1 to 4-7, wherein the reference numbers in the figure are as follows:

01: tube holder, 011: a sliding sleeve;

02: mount, 021: base, 022: support plate, 023: second side plate, 0231: a second chute;

03: supporting seat, 031: horizontal plate, 0311: a third chute; 032: first curb plate, 0321: a first chute;

04: horizontal adjustment mechanism, 041: rack, 042: spur gear, 043: straight gear adjusting pump, 044: bevel gear, 045: bevel gear adjustment shaft, 046: support beam, 047: a horizontal knob;

05: vertical adjustment mechanism, 051: support link, 052: fixed bar, 053: slide bar, 054: lead screw, 055: screw nut assembly, 056: a vertical knob;

06: a clamping piece;

07: a lamp tube.

Referring to fig. 4-1 and 4-5, the lamp position adjusting device of the present invention is used to install the lamp 07 as an excitation light source and adjust the position thereof so that the excitation spectrum emitted by the lamp 07 is irradiated to the flame center ignited at the outlet of the atomizer. The lamp tube position adjusting device comprises a horizontal adjusting mechanism 04, a vertical adjusting mechanism 05, a supporting seat 03, a lamp tube seat 01 and a fixing frame 02 for supporting the horizontal adjusting mechanism 04 and the vertical adjusting mechanism 05, wherein a lamp tube 07 is fixed on the lamp tube seat 01 through a clamping piece 06 (see figures 4-6), the lamp tube seat 01 is installed on the supporting seat 03, the horizontal adjusting mechanism 04 adopts a gear combination structure to convert the rotation of a horizontal knob 047 into the movement of the lamp tube seat 01 provided with the lamp tube 07 in the horizontal direction, the vertical adjusting mechanism 05 adopts a lead screw 054 and a shear type structure connected with the lead screw through a lead screw nut component 055, the rotation of the lead screw 054 is converted into the change of the angle of the shear type structure, and therefore the supporting seat 03 supported on the shear type structure is pushed to.

As shown in fig. 4-1, the lamp tube base 01 is a block structure, the upper end of the lamp tube base 01 is provided with an arc-shaped groove for accommodating the lamp tube 07, the two sides of the lamp tube base 01, which are located in the arc-shaped groove, are respectively fixed with elastic clamping pieces 06, the lower ends of the clamping pieces 06 are fixed at the side edges of the lamp tube base 01, the upper ends of the two clamping pieces are bent to the outside, and the two clamping pieces 06 form an arc-shaped accommodating space with a narrow upper part and a wide lower. When the lamp tube 07 is installed, the lamp tube 07 is pressed downwards from the opening of the arc-shaped accommodating space, the clamping pieces 06 are opened outwards due to the elastic action, and when the bottom of the lamp tube 07 is contacted with the arc-shaped groove of the lamp tube seat 01, the clamping pieces 06 rebound to clamp the lamp tube 07, so that the lamp tube 07 is fixed.

Referring to fig. 4-2, 4-3 and 4-5, the horizontal adjustment mechanism 04 comprises a rack 041 fixed at the bottom of the lamp holder 01, a spur gear 042 engaged with the rack 041, a spur gear adjustment shaft 043 for sleeving the spur gear 042, a bevel gear 044 fixed on the spur gear adjustment shaft 043 and a bevel gear 044 fixed on the bevel gear adjustment shaft 045, wherein the two bevel gears 044 are vertically arranged and engaged; the straight gear 042 is provided with an integrated sleeve, the sleeve is sleeved on the upper part of the straight gear adjusting shaft 043 in a penetrating way and is connected in a plane matching way, the straight gear 042 can rotate along with the straight gear adjusting shaft 043, the lower end of the straight gear adjusting shaft 043 is rotatably arranged on a supporting beam 046, and two ends of the supporting beam 046 are fixed on the fixing frame 02; the bevel gear adjustment shaft 045 is connected to the horizontal knob 047 via a coupling. The bevel gear 044 can transmit the rotation of the bevel gear adjusting shaft 045 through the bevel gear 044 to drive the straight gear adjusting shaft 043 and the straight gear 042 to rotate, so as to drive the rack 041 meshed with the straight gear 042 and the lamp holder 01 fixed with the rack 041 to horizontally move, and thus, the lamp tube 07 fixed on the lamp holder 01 through the clamping piece 06 can horizontally move.

As shown in fig. 4-2, the supporting seat 03 includes a horizontal plate 031 and a first side plate 032 vertically disposed on two sides of the horizontal plate 031, the horizontal plate 031 is provided with a through hole (see fig. 4-5) for passing through a spur gear adjusting shaft 043, and two sides of the through hole are respectively provided with a third sliding groove 0311; the bottom of the lamp holder 01 is provided with a groove for accommodating the rack 041 and the straight gear 042, the straight gear 042 is fixed in the groove of the lamp holder 01, the straight gear 042 is meshed with the rack 041, meanwhile, two sides of the groove at the bottom of the lamp holder 01 are fixed with the sliding sleeve 011, the sliding sleeve 011 can slidably penetrate and sleeve in the third sliding groove 0311, the lamp holder 01 fixed with the rack 041 can be driven to move when the straight gear 042 rotates, and the sliding sleeve 011 slides in the third sliding groove 0311.

As shown in fig. 4-2, the fixing frame 02 as a supporting mechanism of the lamp tube position adjusting device includes a base 021, supporting plates 022 fixed at two ends of the base, and second side plates 024 disposed at two sides of the base, wherein the second side plates 024 are provided with mounting holes and first sliding grooves 0321.

Referring to fig. 4-2, 4-4 and 4-5, the vertical adjustment mechanism 05 includes a scissor structure formed by two support links 051, two corners on the left side of the scissor structure are respectively provided with a fixing rod 052 in a penetrating manner, two corners on the right side are respectively provided with a sliding rod 053 in a penetrating manner, two ends of the fixing rod 052 respectively penetrate through a second side plate 024 of the fixing frame 02 and a mounting hole of a first side plate 032 of the supporting seat 03 for fixing, and two ends of the sliding rod 053 respectively slidably penetrate through a second chute 0241 of the second side plate 024 and a first chute 0321 of the first side plate 032; vertical adjustment mechanism 05 still includes a lead screw 054 and wears the cover on lead screw 054 and rather than threaded connection's lead screw nut subassembly 055, lead screw nut subassembly 055 includes lead screw nut and the sleeve of connection on lead screw nut, lead screw 054 head passes right side bearing in proper order, backup pad 022, the sleeve of lead screw nut subassembly 055 and is fixed in the left side bearing, lead screw 054 afterbody passes through a shaft coupling and connects perpendicular knob 056, the shear mode structure upper end that two support connecting rods 051 formed withstands the horizontal plate 031 of supporting seat 03, and slidable wears to overlap in the second spout of second curb plate 024 behind lead screw nut 056 in the shear mode structure of a slide bar 053. When rotating perpendicular knob 056, perpendicular knob 056 drives lead screw 054 and rotates, and then drives lead screw nut subassembly 055 and moves along the lead screw to drive the horizontal angle grow of scissor construction or diminish, scissor construction's upper end will support seat 03 jack-up or drop, simultaneously, slide bar 053 removes in corresponding spout.

The lamp tube position adjusting device assembled by the components according to the connection relationship has the following characteristics:

(1) the device adopts a gear combination structure, the rotation of a bevel gear adjusting shaft 045 is converted into the horizontal rotation of a straight gear adjusting shaft 043 and a straight gear 042 through a bevel gear 044, and then a lamp tube seat 01 provided with a lamp tube 07 is driven to move horizontally through a rack 041 meshed with the straight gear 042.

(2) In the vertical adjusting mechanism 05 of the device, a shear type structure formed by two supporting connecting rods 051 is connected with a lead screw 054 through a lead screw nut component 055, the lead screw 054 is in threaded connection with the lead screw nut component 055, the lead screw 054 and the lead screw nut component 055 move relatively to drive the angle change of the shear type structure of the two supporting connecting rods 051, so that a supporting seat 03 and a lamp tube seat 01 which are supported at the upper end of the shear type structure are driven to vertically move up and down, and meanwhile, a straight gear 042 vertically moves up and down along the upper part of a straight gear adjusting shaft 043.

(3) The vertical adjusting mechanism 05 and the horizontal adjusting mechanism 04 are supported on the fixing frame 02 and are arranged in a crossed manner in space without interference, the vertical adjusting mechanism 05 is respectively connected with a second side plate 024 of the fixing frame 02 and a first side plate 032 of the supporting seat 03 through a fixed rod 052 arranged at the left corner of the scissor structure, and is respectively connected with sliding chutes on the second side plate 024 of the fixing frame 02 and the first side plate 032 of the supporting seat 03 through a sliding rod 053 arranged at the right side of the scissor structure; the horizontal knob 047 and the vertical knob 056 of the device are both arranged outside the shell of the atomic fluorescence instrument, the structure is compact, the position adjustment is convenient, and the continuous adjustment can be realized.

(4) The lamp tube 07 is fixed through the two clamping pieces 06 fixed on the lamp tube seat 01, the lamp tube 07 is arranged in the arc-shaped accommodating space which is narrow at the top and wide at the bottom and formed by the two clamping pieces 06, the lamp tube 07 is clamped and fixed by utilizing the elasticity of the clamping pieces 06, and the lamp tube 07 can be automatically clamped and fixed only by slightly pressing the lamp tube 07 to be arranged in the arc-shaped accommodating space formed by the clamping pieces, so that extra operation is not needed.

Optical ring

The invention is characterized in that the open optical ring 10 (see figure 1B) is designed, the radiation of the excitation light source (hollow cathode lamp) is moved out of the furnace, the influence of diffuse reflection light on the measurement can be effectively reduced, and the installation and the maintenance of the furnace body are more convenient. This optical ring's under shed installation atomizer, the atomizer export is located the optical ring, and casing one side of optical ring is provided with the mounting hole of installation excitation light source and detector, and the mounting hole opposite side is seted up the side grooving, and the characteristic spectrum of excitation light source transmission shines to the atomic fluorescence appearance shell inboard that is separated by one end distance through the side grooving, can not have light to get into in the detector to optical interference has been reduced, the structure has been simplified simultaneously, the installation maintenance of being convenient for.

The installation and structure of the optical ring are shown in fig. 5-1 to 5-5. The reference numbers in the figures denote:

50: chimney, 30: an atomizer;

10: optical ring, 101: a housing, 102: upper opening, 103: lower opening, 104: side cut groove, 105: first mounting hole, 106: second mounting hole, 107: a third mounting hole;

20: a first excitation light source;

20': a second excitation light source;

40: a detector.

As shown in fig. 5-3 to 5-5, the optical ring 10 includes a housing 101, the housing 101 is a cylindrical structure, an upper opening 102 and a lower opening 103 of the housing 101 are respectively used for installing the chimney 50 and the atomizer 30, three installation holes, namely a first installation hole 105, a second installation hole 106 and a third installation hole 107, are sequentially arranged on the same horizontal plane on one side of the housing 101 and are respectively used for installing the first excitation light source 20, the detector 40 and the second excitation light source 20 '(see fig. 5-2), a side slot 104 is formed on the opposite side of the installation hole on the housing 101, and the size of the side slot 104 matches with the adjustment range of the first excitation light source 20 and the second excitation light source 20', so that the characteristic spectrum emitted by the excitation light source can be irradiated to the inner side of the housing of the atomic fluorescence instrument through the side slot 104 without being irradiated to the housing 101.

When the atomizer 30 is installed, the atomizer 30 extends into the casing 101 of the optical ring 10, the characteristic spectra emitted by the first excitation light source 20 and the second excitation light source 20 'are opposite to the center of a flame ignited at the outlet of the atomizer 30, the light path inlets of the detector 40 are positioned on the same horizontal plane as the center of the flame, the emission ports of the first excitation light source 20 and the second excitation light source 20' and the light path inlets of the detector 40 are opposite to the side cut groove 104 of the optical ring 10, and the side cut groove 104 faces the inner side (such as the rear side of the display screen 74) of the front cover plate 71 (see fig. 1B) of the atomic fluorescence instrument. Preferably, the optical ring 10 has a light absorbing paper coated with black light absorbing material on the opposite side of the housing from the side where the side cut groove 104 is located, and the light absorbing paper can be directly attached to the inside of the housing of the atomic fluorescence instrument, for example, the rear side of the display screen.

In operation, the characteristic spectra emitted by the first excitation light source 20 and the second excitation light source 20' are directly irradiated to the rear side of the display screen at a distance from the optical ring 10 through the side cut groove 104 of the optical ring 10, and light basically does not enter the light path inlet of the detector 40, and stray light is not formed. After the light absorption paper is laid on the rear side of the display screen, most of light is absorbed, and the reflection effect is avoided, so that the optical background is reduced.

According to the optical ring 10, the side cutting groove 104 is formed in the opposite side of the excitation light source emission port and the light path inlet of the detector 40, so that the characteristic spectrum emitted by the excitation light source is irradiated to the inner side of the shell of the atomic fluorescence instrument through the side cutting groove 104, stray light cannot enter the detector, optical noise is reduced, and the influence of light diffusion on the detection result is avoided; by providing the side cut groove 104 on one side of the optical ring 10, a reflector for removing stray light is omitted, the structure is simplified, and maintenance can be performed without dismantling.

Circuit gas circuit integration and control system

The characteristic F is that the atomic fluorescence instrument of the invention goes to the peripheral equipment, every part has adopted the modular form, can realize the assembled assembly, characteristic H adopts and advances the sample and detects the procedure fast, collect and determine, display, print, store as an organic whole and swift desktop system; the instrument has the advantages of tidy appearance, reasonable and compact internal configuration and small volume, an advanced electrical control system is adopted, a large display screen 74 (see figure 1B) and a simple and clear desktop system are used, the sampling and measuring time is less than 20 seconds, and the instrument can be carried on a vehicle to carry out emergency detection on site.

The circuit gas path integrated system 80 (see fig. 1B and 6-1) of the invention is designed mainly for solving the problems of inconvenient installation and maintenance, incapability of quick disassembly and assembly, large occupied space and the like caused by the horizontal arrangement of the circuit gas path in the original atomic fluorescence instrument.

The circuit gas path integrated system 80 is constructed as shown in fig. 6-1 to 6-3. The reference numbers in the figures denote:

810: vertical frame type circuit gas circuit integrated module, 811: power supply board, 812: control motherboard, 813: a support plate; 82: a gas pressure gauge; 83: a pneumatic control module; 84: an isolation column; 70: a chassis; 86: a switching power supply; 87: a base plate.

Referring to fig. 6-1 to 6-3, the circuit-air path integrated system includes a bottom plate 87, and a switching power supply 86 and a vertical frame type circuit-air path integrated module 810 which are disposed on the bottom plate 87, wherein the switching power supply 86 supplies power to the vertical frame type circuit-air path integrated module 810.

As shown in fig. 6-2, the vertical frame type circuit gas circuit integrated module 810 is a vertical frame type modular structure, and includes a power board 811, a control main board 812 and a support board 813 which are sequentially arranged from bottom to top at intervals, a gas control module 83 and a gas pressure gauge 82 are installed on the support board 813, the gas control module 83 includes two gas channels for respectively conveying a carrier gas and an auxiliary gas, the carrier gas and the auxiliary gas are generally argon gas, the argon gas is connected to the gas channel of the gas control module 83 through the gas pressure gauge 82 via a pipeline, the gas pressure gauge 82 is used for controlling the pressure of the introduced argon gas, and is generally controlled at 0.3MPa, and the control main board 812 (loaded with a control system) controls the flow of the two gas channels of the gas control module 83; the power supplied from the switching power supply 86 is modulated into DC power of different ranges by the circuit of the power board 811 to be supplied to the control main board 812 and the air control module 83.

The vertical frame structure in the vertical frame type electric circuit and air circuit integrated module 810 is not limited to three layers, and the arrangement order of layers and the distance between adjacent layers are not limited.

The base plate 87 may be secured to the chassis 70 of the atomic fluorescence instrument. In order to facilitate the circuit and gas circuit integrated system 80 to be conveniently taken out for maintenance or device replacement, the bottom of the case 70 is provided with a raised rail, the bottom surface of the bottom plate 87 is provided with a groove matched with the raised rail of the case 70, and the bottom plate 7 can slide along the raised rail of the case 70, slide in and slide out, and facilitate installation and maintenance.

The circuit gas path integrated system 80 is integrally arranged in the chassis 70 of the atomic fluorescence instrument, the power panel 811, the control main board 812 and the supporting plate 813 form a vertical frame structure through the isolation column 84, and the switching power supply 86, the power panel 811, the control main board 812 and the gas control module 83 are electrically connected through a wire or a flat wire, so that the vertical frame structure fully utilizes the limited space in the chassis 70, has a compact structure and is beneficial to the miniaturization of the atomic fluorescence instrument; the push-pull structure formed by the bottom plate 87 and the bottom of the case 70 is convenient for disassembly and maintenance.

The water-borne flow atomic fluorescence analysis device is assembled by components including the systems, the appearance of an instrument main body (not including a transfusion system) is shown in figure 1A, and the appearance of the instrument main body is shown in figure 1B in a split structure. The instrument shell comprises a case 70, a rear cover plate 72, an upper cover plate 73 and a front cover plate 71, wherein a large-size display screen 74 is arranged on the front cover plate 71, and a desktop operating system is presented through the display screen 74 to realize man-machine conversation; the peristaltic pump 91 of the infusion system is arranged near the front lower part of the side plate of the case 70, the argon conveying pipeline hole 92 is arranged, the small-sized printing output equipment (the right side in the figure is omitted) can be arranged at the other side, the horizontal knob 047 and the vertical knob 056 (combined with the figure 4-1) of the lamp tube position adjusting mechanism are arranged near the upper part, and the horizontal or vertical position of the lamp tube can be conveniently adjusted through the knob arranged outside the case. The reactor 90 is arranged in the case 70 and adjacent to the peristaltic pump 91, and the test solution and reagent output pipes of the peristaltic pump 91 are connected into the reactor 90; a fixing frame 93 is fixed with the supporting frame in the case 70, the atomizer 30 is installed on the fixing frame 93, the gas outlet pipe of the reactor 90 is connected to the outer pipe joint of the quartz furnace of the atomizer 30, and the inner pipe joint of the quartz furnace is connected with the argon pipe as the auxiliary gas; the optical ring 10 is sleeved outside the atomizer 30 and fixed in the case 70, and the chimney 50 is arranged above the optical ring 10 and extends outwards from the upper cover plate 73 corresponding to the gap; the circuit and gas circuit integrated system 80 is integrally arranged at the bottom in the case 70, the lamp tube position adjusting device 60 and the excitation light source 20 (or 20') are arranged on a support frame in the case 70 and are fixed (the lamp tube can move horizontally or vertically), and the detector 40 is fixed on the support frame in the case 70; fixing the components, connecting the wires, installing the front cover plate 71, the rear cover plate 72 and the upper cover plate 73, and completing the assembly of the instrument main body. The instrument main body is matched with a transfusion system to form the water current-carrying atomic fluorescence analysis device.

When the water-borne flow atomic fluorescence analysis device is used for atomic fluorescence analysis, all analysis operation processes are completed on the display screen, and the structure, the function and the using method of a desktop system can be displayed on the display screen.

The desktop system is divided into five pages, namely a first page, a setting page, a standard curve making page, a sample testing page and an instrument performance index testing page. The 'home page' recommends different element analysis conditions, and a user needs to prepare required test solutions and reagents before testing by taking the conditions as reference.

The test work was carried out as follows:

1, turning on a power supply, and selecting a single channel (A or B) or a double channel (A + B) on a 'setting' page, wherein Hg/As, As/Sb and Bi/Hg can be measured by using the double channels in general; se, Pb and Cd are measured by a single channel; setting lamp current, negative high voltage; the pump speed, the Ar gas flow, and the operation time may in principle be left unmodified;

2, turning on a lamp power supply, preheating the hollow cathode lamp for 5-10min, and carefully adjusting a light spot of the hollow cathode lamp during the preheating, wherein the light spot is positioned in the center of the quartz furnace, the height of the light spot is 8-10mm away from the center of a clear aperture of the lens at the pipe orifice of the quartz furnace, the specific number is related to the element concentration, for a sample with extremely low concentration, As can be 8mm, Hg can be 10mm, and Hg/As is measured according to the sample type, such As soil, so that the fluorescence value is reduced.

3, opening a main valve of the Ar gas steel cylinder, and controlling the pressure of the primary pressure reducing valve to 0.4MPa and the pressure of the secondary pressure reducing valve to 0.3 MPa;

4, after the instrument is preheated, opening ventilation, switching on a power supply of an electric furnace wire, and placing the test solution, the reagent and two cups of water in a sample tray;

inserting two transfusion capillary tubes of a peristaltic pump into purified water respectively, clicking a blank on a page of 'standard curve making', cleaning a transfusion flow path twice through test water, then inserting the capillary tubes into a blank solution and a NaBH4 solution, taking samples, immediately taking the capillary tubes out of a test solution and a reagent solution, placing the capillary tubes in a first cup for quick cleaning, then placing the capillary tubes in a second cup for water, sucking water by the pump, carrying the test solution and the reagent for chemical reduction reaction, introducing Hg atoms or hydride into hydrogen flame of an atomizer, recording a blank fluorescence value by a detector, and taking a blank average value until the difference of secondary measurement values is not more than 5; the fluorescence value of each solution in the series is then determined in concentration order from low to high (typically twice). And inputting the concentration of the step series in the concentration column, and clicking the average value and the curve below to display the slope and the intercept of the standard curve and the linear equation.

6 after preparing the standard curve, the sample concentration is measured on the "sample" page. Before the test solution is measured, the capillary tube needs to be inserted into water again, washed twice according to the running program, and then the fluorescence value of the blank is measured by using a standard blank solution and a reagent blank solution and is averaged. Then the fluorescence value of each test solution is measured one by one, the corresponding concentration of the test solution is obtained, the sample weighing or sampling volume and the volume fraction of the preparation solution are input into the corresponding column, and the content of the measured sample is obtained by clicking 'enter'. If the number of samples exceeds 10, the test is continued with pages 2-4.

And 7, enabling a right-side printing or storing key to print or store the standard curve or sample result, wherein the stored data can be read or stored on a computer.

8, after the test is finished, the flow path needs to be washed by water for 2-3 times.

9, closing the hollow cathode lamp, the furnace wire power supply, the Ar gas, the ventilation and the host power supply one by one, loosening the peristaltic pump clamp plate, and finally closing the Ar gas steel cylinder valve.

The above operation is used as an examination example to illustrate the effect of the fluorescence analysis of the element atoms using the apparatus of the present invention. In the examples, "%" of reagent concentration is expressed as mass percent concentration.

Detection example 1: analysis of Cd

Testing a sample: rice, soybean

And (3) manufacturing a cadmium standard curve: preparing 10ng/ml cadmium standard solution (prepared now), then respectively putting 0, 0.5, 1.0, 1.5, 2.0 and 2.5ml of the standard solution into a 50ml plastic quantitative bottle, respectively adding 4ml of 50% HCl solution and 5ml of 5% thiourea into each solution, diluting the solutions to a scale with water, wherein the concentrations of the standard series solutions are 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng/ml Cd. After shaking, the fluorescence signals of the blank and standard series solutions were measured as per the procedure to generate a standard curve (see FIG. 7B), and FIG. 7A shows the peak curve of Cd.

Preparation and determination of test solutions:

weighing 0.1-0.2g of rice or soybean sample, placing the rice or soybean sample in a 50ml plastic quantitative bottle, adding 50% HCl 4ml and 5% thiourea 5ml respectively, shaking for 5-10min, diluting with water to scale, shaking uniformly, measuring a fluorescence signal of the sample solution by using the sample solution as a test solution according to an operation process, and obtaining the concentration of Cd from a standard curve and converting the concentration of Cd into the content of Cd in the sample. The results of the determination of Cd in the food samples are shown in Table 1.

TABLE 1 test results (ng/g) for Cd in rice and soybean meal

As can be seen from the data in the table, under the conditions that the sample weighing (G) is greatly different and the HCl concentration is 4 percent, the test sample is not pretreated, cadmium in foods such as rice and the like can be rapidly measured by using the atomic fluorescence analysis of water carrying flow, and the content of Cd in the measured sample is consistent with the recommended value.

In the determination operation, only pure water (18.2M omega) is consumed without hydrochloric acid as a carrier, the sampling time is reduced by about 50 percent compared with the conventional method, and NaBH is reduced by about 50 percent₄The solution only needs to be used for participating in the reaction, and is saved by more than 75% compared with the conventional detection. The samples in Table 1 were tested sequentially from left to right, and it can be seen that the concentration of cadmium in the solution was high and low, and the test results were accurate, and it can be seen that the memory effect was eliminated by using water as the carrier, even after the high concentration standard solution was tested, because of the infusion systemThe system is cleaned by carrier water, and the determination of other concentration sample solution is not affected.

Detection example 2: simultaneous measurement of Hg/As

Testing a sample: soil(s)

Because the content of As in soil is much higher than Hg, the existing atomic fluorescence instrument can not simultaneously measure Hg and As in the sample. In this example, the device of the present invention is used to simultaneously detect two elements of Hg and As in the same sample.

And (3) preparing a standard curve: a mixed standard solution containing 500ng/ml As and 5ng/ml Hg was prepared in advance. Taking 0, 1, 2, 3, 4 and 5ml of the standard solution respectively, putting 5ml of 5% Vc-5% thiourea solution and 10ml of HCl with the concentration of 50% in 50ml plastic quantitative bottles, diluting the solutions to a scale with water, and obtaining series of standard solutions with the Hg concentration of 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng/ml and the As concentration of 0, 10, 20, 30, 40 and 50 ng/ml.

Selecting a double-channel method, simultaneously measuring the fluorescence signals of Hg and As in the blank and standard series solutions according to the operation process, and respectively making standard curves of 0.1-0.5ng/ml Hg and 10-50ng/ml As of the mixed standard solution. FIG. 8A is a peak curve of Hg/As and FIG. 8B is a standard curve of mixed standard solutions of Hg and As (the signal of the standard curve is calculated from the spectral area and the blank area has been subtracted).

Preparation and determination of test solutions: placing 0.1-0.2g of soil sample in a 50ml plastic quantitative bottle, adding 5ml of 5% Vc-5% thiourea solution and 10ml of HCl with the concentration of 50%, diluting with water to scale, shaking up, simultaneously measuring fluorescence signals of Hg and As of the sample solution by taking the sample solution As a test solution according to the operation process, and obtaining the concentrations of corresponding elements according to respective standard curves so As to calculate the respective contents in the sample. The results are shown in Table 2.

TABLE 2 results of simultaneous measurement of soil Hg/As

The data show that the difficulty of simultaneously measuring Hg and As in soil is solved using the present method and apparatus. Meanwhile, the Hg concentration in 6 samples (standard samples) has larger difference, and the results of the samples tested from top to bottom sequentially according to the table 2 are consistent with recommended values, which shows that the serious memory effect of Hg determination is eliminated by the detection of the device.

In the embodiment, two elements coexist in the test solution, the conveying system only needs to finish the conveying of the test solution once, the detection of the double-channel detection system is also finished once, and the determination operation takes water as a current carrier and does not need hydrochloric acid, NaBH₄The solution only needs 100ml to 250ml to participate in the reaction, and the time and the cost of the whole testing process are greatly reduced.

Detection example 3, analysis of Pb

Testing a sample: chemical reagents calcium chloride and calcium hydroxide

And (3) preparing a lead standard curve: preparing 100ng/ml lead standard solution, then respectively putting 0, 1, 2, 3, 4 and 5ml of the standard solution into a 50ml plastic quantitative bottle, respectively adding 10ml of 50% HCl solution and 5ml of 5% thiourea into each solution, and diluting the solutions to a scale by using water, wherein the concentrations of the standard series solutions are 0, 2, 4, 6, 8 and 10ng/ml Pb. After shaking, the fluorescence signals of the blank and standard series solutions were measured according to the procedure to prepare a calibration curve (see FIG. 9B), and FIG. 9A is a peak value curve of Pb. In the operation, the carrier gas and the auxiliary gas are Ar gas, the flow rate of the argon (outer tube) as the carrier gas is controlled to be 1000-1200ml/min, and the flow rate of the argon (inner tube) as the auxiliary gas is controlled to be 400-600 ml/min.

Preparation and determination of test solutions: weighing 0.2-0.3g of chemical reagent sample, dissolving, transferring into a 50ml plastic quantitative bottle, adding 10ml of 50% HCl and 5ml of 5% thiourea, shaking for 5-10min, diluting with water to a scale, shaking uniformly, measuring a fluorescence signal of the sample solution by using the sample solution as a test solution according to the same operation as that in the standard curve measurement, and obtaining the concentration of Pb from the standard curve and converting the concentration of Pb into the content of Pb in the sample. The results of the determination of Pb in the chemical reagent are shown in Table 3.

TABLE 3 determination of Pb in calcium chloride and calcium hydroxide (ng/g)

The acidity of the original atomic fluorescence analysis needs to be strictly controlled to be 2% in the determination of Pb, otherwise, no fluorescence signal can be detected, but the pre-treated test solution is difficult to meet the requirement, and moreover, the 2% acidity test solution generates less hydrogen after the reduction reaction and is difficult to ignite. In the embodiment, the carrier gas flow is increased while the outer tube sample injection is carried out, the hydrogen flame is easy to ignite, and the atomic fluorescence analysis is carried out on the Pb in the test solution with 10% acidity, so that an obvious Pb peak curve (see figure 9A) can be formed, the detection sensitivity is improved, and the determination of the Pb is realized.

The above detection examples show that the atomic fluorescence analysis using the novel atomic fluorescence analysis device can be successfully used for the determination of As, Hg, Pb and Cd in various samples. The detection limit and reproducibility data of the mercury are shown in FIG. 10, which shows that the stability of the detection is good.

Claims

1. Water current carries atomic fluorescence analytical equipment, including infusion system and instrument main part, the instrument main part includes the dustcoat and assembles reactor, atomizer, optical circle, excitation light source, detector and circuit gas circuit integrated system etc. in the dustcoat, the infusion system includes:

the test solution bottle is used for containing a sample solution to be tested and is communicated with the reactor through a sample inlet pipe;

the reagent bottle is used for containing a reducing agent and is communicated with the reactor through a reagent inlet pipe;

the water outlet of the water bottle is respectively communicated with the inlet of the sample inlet pipe and the inlet of the reagent inlet pipe through a water inlet pipe, and the water inlet is controlled by switching the water inlet pipe; and the number of the first and second electrodes,

the infusion system does not contain a matched device for infusing carrier acid.

2. The apparatus for flow-induced atomic fluorescence spectrometry of claim 1, wherein the sample inlet tube and the reagent inlet tube are liquid inlet capillary tubes, the water bottle is modified into two cups, one cup is used for containing washing water, the other cup is used for containing flow-induced water, and the liquid inlet capillary tubes are alternately inserted into the two cups.

3. The apparatus according to claim 2, wherein the liquid feed capillary is connected to the reactor by a peristaltic pump, and the peristaltic pump controls the transport speed and the amount of the liquid feed capillary, the reagent, the washing water, and the carrier water.

4. The apparatus for fluorescence analysis of water carrying atoms according to any one of claims 1 to 3, wherein the outlet pipe of the reactor is connected to the outer pipe joint of the quartz furnace in the atomizer, and the inner pipe joint of the quartz furnace is connected to the argon pipe as the auxiliary gas.

5. The apparatus according to any one of claims 1 to 4, wherein the atomizer comprises a furnace body support, a furnace core, a quartz furnace sleeved in the furnace core, a furnace body outer cover sleeved outside the furnace core, a ceramic cover plate, an electric furnace wire and other parts, and is characterized in that the furnace core and the furnace body outer cover are made of insulating heat-resistant non-metallic materials, and the parts are clamped or fixed without screws.

6. The apparatus according to claim 5, wherein the furnace body housing has at least two slots, and the ceramic cover plate has a buckle at the side thereof, and the buckle engages with the slots to clamp the upper end of the furnace body housing to the ceramic cover plate.

7. The apparatus for fluorescence analysis of water-carrying atoms according to claim 6, wherein the electric furnace wire is inserted between the ceramic cover plate and the quartz furnace nozzle, and a ceramic heat insulating layer is provided between the ceramic cover plate and the top end surface of the furnace core instead of asbestos, and the ceramic heat insulating layer supports and positions the electric furnace wire at the quartz furnace nozzle.

8. The water current-carrying atomic fluorescence analysis device according to any one of claims 5 to 7, wherein a groove and a step are arranged at the upper part of the furnace body support, and two slotted holes are formed in the side wall of the groove; the lower part of the furnace core is provided with a bulge which is embedded in the groove body; the inner pipe joint and the outer pipe joint at the lower part of the quartz furnace are clamped in the slotted holes and extend out to the side surface; the quartz furnace is sleeved in the furnace core cavity, and a pipe orifice of the quartz furnace extends upwards out of the top end surface of the furnace core; the furnace body outer cover is sleeved on the periphery of the furnace core, and the bottom of the furnace body outer cover abuts against and is seated on the step of the furnace body support.

9. The apparatus according to any one of claims 1 to 8, wherein the optical ring comprises a housing, one side of the housing is provided with mounting holes for mounting the excitation light source and the detector, respectively, and the housing on the side of the mounting holes is provided with a side cutting groove on the opposite side for transmitting the light emitted from the excitation light source.

10. The fluorescence analyzer according to claim 9, wherein the lateral cut-out is sized to match the adjustment range of the excitation light source so that the excitation light source emits a characteristic spectrum that does not impinge on the housing of the optical ring.

11. An atomic fluorescence analyzer according to claim 9 or 10, characterized in that the lateral cut of the housing is faced towards the inside of the atomic fluorescence instrument housing and a black light absorbing material coated light absorbing paper is laid on the inside.

12. The water carrying atomic fluorescence analysis device according to any one of claims 1 to 11, wherein the circuit-gas path integrated system is an integral module, and comprises a bottom plate, a switching power supply and a vertical frame type circuit-gas path integrated module, the switching power supply and the vertical frame type circuit-gas path integrated module are mounted on the bottom plate, the vertical frame type circuit-gas path integrated module comprises a power supply board, a control main board and a support board, the power supply board, the control main board and the support board are fixed at intervals in the vertical direction, a gas control module and a gas pressure meter are mounted on the support board, and the control main board controls the; the power panel modulates the power provided by the switching power supply into DC power supplies in different ranges to be supplied to the control mainboard and the pneumatic control module.

13. The apparatus according to claim 12, wherein the bottom plate is displaceable in a sliding rail and groove nesting with the bottom of the instrument body.

14. The apparatus according to any one of claims 1 to 13, wherein a display screen is provided on a front panel of the housing of the instrument body for displaying contents of a desktop system.

15. The apparatus according to any one of claims 1 to 14, further comprising a lamp position adjusting device for adjusting the excitation light source in the horizontal direction and the vertical direction, wherein the adjusting knob is located at a side of the housing of the apparatus main body.

16. The apparatus for fluorescence analysis of water carrying atoms according to claim 15, wherein the lamp position adjusting means comprises:

a lamp tube holder for mounting a lamp tube;

a support base, on the upper surface of which a lamp tube seat is arranged;

the horizontal adjusting mechanism is of a gear combination structure and is used for converting the rotation of the horizontal knob into the movement of the lamp tube seat provided with the lamp tube in the horizontal direction;

the vertical adjusting mechanism comprises a lead screw and a scissor structure connected with the lead screw through a lead screw nut assembly, and is used for converting the rotation of the lead screw into the change of the angle of the scissor structure so as to push the supporting seat supported on the scissor structure to vertically move up and down;

and the fixing frame is used for supporting the horizontal adjusting mechanism and the vertical adjusting mechanism.

17. The apparatus according to claim 16, wherein the lamp holder has elastic clamping pieces fixed to both sides of the lamp holder, the clamping pieces having lower ends fixed to the sides of the lamp holder and upper ends bent outward, and the clamping pieces form an arc-shaped space with an upper opening and a narrow upper portion and a lower opening for mounting the lamp.

18. The apparatus for fluorescence analysis of water carrying atoms according to claim 16 or 17, wherein the level adjustment mechanism comprises:

the rack is fixed at the bottom of the lamp tube seat;

the straight gear is provided with an integrated sleeve and is meshed with the rack;

the lower end of the straight rack adjusting shaft is rotatably arranged on a supporting beam, two ends of the supporting beam are fixed on the fixed frame, and the upper end of the straight rack adjusting shaft is used for penetrating and sleeving a sleeve of the straight gear and is in matched connection with the plane of the sleeve of the straight gear;

the bevel gears in the horizontal direction are fixed on the straight gear adjusting shaft, and the vertical bevel gears are fixed at the end parts of the bevel gear adjusting shafts;

and the horizontal knob is connected to the bevel gear adjusting shaft through a coupler.

19. The apparatus according to claim 18, wherein the support comprises a horizontal plate and first side plates vertically disposed on both sides of the horizontal plate, the spur gear is fixed in a groove formed in the bottom of the tube holder, and a sliding sleeve is fixed on each of both sides of the groove in the bottom of the tube holder and slidably inserted in a third sliding groove formed in the horizontal plate.

20. The water-borne atomic fluorescence analysis device according to claim 19, wherein the fixing frame comprises a base, supporting plates fixed at two ends of the base, and second side plates disposed at two sides of the base, and the second side plates are provided with mounting holes and first sliding grooves for supporting the vertical adjustment mechanism.

21. The water-borne flux atomic fluorescence analysis device of claim 20, the vertical adjustment mechanism comprising:

the two supporting connecting rods form a scissor-type structure, fixed rods are respectively arranged at two corners on the left side of the scissor-type structure in a penetrating manner, sliding rods are respectively arranged at two corners on the right side of the scissor-type structure in a penetrating manner, and two ends of each fixed rod respectively penetrate through the mounting holes of the second side plate and the first side plate to be fixed; two ends of the sliding rod can respectively and slidably penetrate and sleeve the second sliding groove of the second side plate and the first sliding groove of the first side plate;

the lead screw and wear to overlap on the lead screw and rather than threaded connection's lead screw nut component, the lead screw head passes bearing, backup pad, lead screw nut component in proper order and is fixed in the left side bearing, and the lead screw afterbody passes through a shaft coupling and connects perpendicular knob, and the shear mode structure upper end that two support connecting rods formed withstands the horizontal plate of supporting seat, and a slide bar in the shear mode structure passes behind the lead screw nut slidable and wears to overlap in the second spout of second curb plate.

22. An atomic fluorescence analysis method using the water-carrying atomic fluorescence analysis device according to any one of claims 1 to 21, comprising a process of feeding the sample from an outer tube of a quartz furnace by using the liquid feeding system after sampling and using water as a carrier and an atomization process until detection is completed.

23. The atomic fluorescence analysis method according to claim 22, wherein the external tube injection is performed by introducing a mixed gas of a hydride and hydrogen carried by a carrier gas from a reactor into an external tube of a quartz furnace, introducing an auxiliary gas (Ar gas) into an internal tube of the quartz furnace, and controlling the flow rate.

24. The atomic fluorescence analysis method according to claim 23, wherein the flow rate of the carrier gas (Ar gas) carrying the mixed gas is increased to 1200ml/min and the flow rate of the auxiliary gas (Ar gas) is decreased to 600ml/min and 400 ml/min or no auxiliary gas is introduced (i.e. the flow rate is 0 ml/min).

25. An atomic fluorescence analysis method according to any one of claims 22 to 24, wherein the sampling is performed by introducing a test solution with a certain acidity (preferably, hydrochloric acid concentration in the range of 4% to 10%) and a reagent with a certain concentration, respectively, and the water as a carrier is performed by carrying and pushing the test solution and the reagent into the reactor with purified water as a carrier.

26. The atomic fluorescence analysis method according to claim 25, wherein the sampling time is 4 to 5 seconds, and the time from the water carrier flow to the end of detection is 8 to 10 seconds.

27. The atomic fluorescence analysis method of claim 25, wherein two cups are used to hold purified water, the capillary tube for delivering the sample solution and the reagent is inserted between the two cups of water after sampling, the sampling/delay/insertion/measurement time is 4-5/0/2-3/8-10 seconds respectively, i.e. the sampling time is 4-5 seconds, the delay is zero seconds, the insertion/replacement time is 2-3, and the time from current carrying to measurement ending is 8-10 seconds.

28. The atomic fluorescence analysis method according to any one of claims 22 to 27, wherein the detecting step further comprises controlling the intermittent ignition of the hydrogen flame, and the excitation light source and the detector are operated during the combustion time of the hydrogen flame.