CN105277534A - Method for analyzing trace amounts of carbonyl iron and nickel carbonyl in methanation raw gas and system thereof - Google Patents
Method for analyzing trace amounts of carbonyl iron and nickel carbonyl in methanation raw gas and system thereof Download PDFInfo
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- CN105277534A CN105277534A CN201410272426.2A CN201410272426A CN105277534A CN 105277534 A CN105277534 A CN 105277534A CN 201410272426 A CN201410272426 A CN 201410272426A CN 105277534 A CN105277534 A CN 105277534A
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- wash solution
- atomic absorption
- methanation
- unstripped gas
- drexel bottle
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Abstract
The invention provides a method for analyzing trace amounts of carbonyl iron and nickel carbonyl in methanation raw gas by flameless atomic absorption spectrometry. The method comprises the following steps: (1) carrying out absorption treatment on methanation raw gas by the use of a washing solution so as to obtain a washing solution which has absorbed carbonyl iron and nickel carbonyl in the methanation raw gas, and recording pressure and flow of the methanation raw gas; and (2) transferring the washing solution obtained from the step (1) into a measuring cylinder, recording volume and analyzing by flameless atomic absorption spectrometry. According to the method, gas absorbing capacity is increased, measurement error is minimized, data accuracy is guaranteed, analytical accuracy, precision and work efficiency of operators are enhanced, and the lowest limit of detection of carbonyl iron and nickel carbonyl can reach 0.005 vpm.
Description
Technical field
The present invention relates to chemical industry methanation technology field.Particularly, the present invention relates to a kind of trace analysis methods and system, particularly one utilizes flameless atomic absorption spectrometry (AAS) to measure the method for trace iron carbonyi and carbonyl nickel in methanation unstripped gas, and realizes the system of the method.
Background technology
China's coal preparing natural gas, olefin hydrocarbon making by coal, ammonia from coal are flourish, and most Coal Chemical Industry technique adopts Coal Gasification producing synthesis gas to be converted into the Organic chemical products such as methyl alcohol, alkene, ethylene glycol.
In coal preparing natural gas production run to methanation unstripped gas in each component concentration require more and more stricter, especially effective catalyst is produced to the iron carbonyi and carbonyl nickel of poisoning, the iron carbonyi contained in unstripped gas and carbonyl nickel are easy to generate under lower than the condition of temperature of reactor, can decompose at the reaction temperatures again and be deposited on catalyst surface, cover catalyst surface and blocking hole, even make the activity of catalyst activity reduce inactivation, reaction Heat of Formation can not be taken away in time, reaction bed temperature can be made to raise, catalyst poisoning can be caused, affect the serviceable life of catalyzer.But also cause some subsidiary reactions, have impact on the long-term operation of device to a great extent.
This is because, CO contained in unstripped gas and a small amount of CO
2add H
2generate CH in the presence of a nickel catalyst
4and H
2o, chemical equation is:
CO+3H
2＝CH
4+H
20△H
0298＝-206KJ/mol
CO
2+4H
2＝CH4+2H
20△H
0298＝-165KJ/mol
If iron, the nickel containing trace in gas in this course of reaction, iron, nickel can under comparatively temperate condition directly and CO gas reaction generate carbonyls Fe (CO)
5with Ni (CO)
4, its reaction equation is:
Fe(s)+5CO(g)→Fe(CO)
5(g)
Ni(s)+4CO(g)→Ni(CO)
4(g)
At present, the iron carbonyi in the method mensuration methanation unstripped gas and carbonyl nickel is not still adopted in prior art.The main method measuring iron carbonyi and carbonyl nickel in other industry has sampling Graphite Furnace Atomic Absorption, ICP, ICP-MS.Wherein in ICP mensuration process because adding the torch that to go out when organic solvent causes inorganic sampling system to be lighted a fire, need change organic solvent sampling system, needing to consume a large amount of argon gas in measuring process increases testing cost, and the detection limit of ICP is higher compared with graphite oven atomic absorption simultaneously.And the detection limit of ICP-MS is too low, the background interference of solvent is comparatively large, and repeatability is not good.The present invention creatively adopts iron carbonyi and carbonyl nickel in graphite furnace atomic absorption spectrometry methanation unstripped gas.
Summary of the invention
For above-mentioned technological deficiency, the object of this invention is to provide a kind of method utilizing flameless atomic absorption spectrometry to analyze trace iron carbonyi and carbonyl nickel in methanation unstripped gas, and realize the system of the method.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
On the one hand, the invention provides a kind of method utilizing flameless atomic absorption spectrometry to analyze trace iron carbonyi and carbonyl nickel in methanation unstripped gas, the method comprises the following steps:
(1) absorption process is carried out to methanation unstripped gas, the wash solution of iron carbonyi and carbonyl nickel in the described methanation unstripped gas that has been absorbed with wash solution, and record the flow of described methanation unstripped gas;
(2) wash solution that step (1) obtains is transferred in graduated cylinder, after recording volume, utilizes flameless atomic absorption spectrometry analysis.
In method of the present invention, the absorption process in described step (1) is that the method by comprising the following steps realizes:
A methanation unstripped gas is passed at least one of being connected successively by connecting pipe and the Drexel bottle of wash solution is housed and at least one is equipped with the Drexel bottle of deionized water by ();
B (), with Drexel bottles all in a little methanol wash step (a) and connecting pipe, obtains cleaning fluid;
C the cleaning fluid obtained in the wash solution obtained in step (a), step (b) joins in graduated cylinder by (), the wash solution of iron carbonyi and carbonyl nickel in the described methanation unstripped gas that has been absorbed.
The described Drexel bottle that wash solution is housed is 2 ~ 6.Preferably, the Drexel bottle that wash solution is housed described in is 4.More preferably, the Drexel bottle that deionized water is housed described in is 1.
In method of the present invention, described wash solution is iodo-hydroiodic acid mixed liquor, and the wash solution in each Drexel bottle is identical.
On the other hand, the present invention also provides a kind of system for realizing said method, this system comprises absorption treating device and atomic absorption analysis device, described absorption treating device comprise at least one of being connected successively by connecting pipe be equipped with wash solution Drexel bottle, at least one is equipped with Drexel bottle and the flowmeter of deionized water; Described atomic absorption analysis device comprises graduated cylinder and Atomic Absorption Spectrometer.
The Drexel bottle that wash solution is housed is 2 ~ 6, is preferably 4, is more preferably 1.
In one embodiment, absorption treating device also comprises the needle valve be connected with the inlet end described in first, the Drexel bottle of wash solution being housed.
Atomic absorption analysis device also comprises sampler measuring cup in one embodiment.
Described flow counts gas meter in one embodiment, is preferably wet test meter.
In method of the present invention, described wash solution is iodo-hydroiodic acid mixed liquor, and the wash solution in each Drexel bottle is identical.
Should be understood that, conventional method can be adopted to record the flow of methanation unstripped gas, such as, can adopt gas meter.But the present invention is not by the restriction of gas meter, every gas meter that can measure methanation feed gas volume all can be used for the present invention, such as, can adopt LMF-2 wet test meter (Beijing Jin Zhiye instrument and equipment Ltd).
Compared with prior art, the present invention at least has following beneficial effect: increase gas absorption amount, reduce error at measurment, ensure that the accuracy of data, improve the work efficiency of accuracy of analysis, precision and operator, iron carbonyi and carbonyl nickel minimum detectability can reach 0.005ppm.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 is the structural representation of a present system preferred embodiment;
Fig. 2 is according to one embodiment of present invention with the typical curve that iron (Fe) standard solution is drawn;
Fig. 3 is according to one embodiment of present invention with the typical curve that nickel (Ni) standard solution is drawn.
description of reference numerals:
1 – needle valve, 2,3,4,5 – wash solution Drexel bottles, 6 – deionized water Drexel bottles, 7 – wet test meters, 8 – methanation unstripped gas outlets.
Embodiment
Further illustrate the present invention below by specific embodiment, but should be understood to these embodiments is only use for specifically describing more in detail, and should not be construed as limiting the present invention in any form.
As shown in Figure 1, absorption treating device of the present invention comprises the wash solution Drexel bottle 2,3,4,5 and deionized water Drexel bottle 6 of being connected successively by connecting pipe.Deionized water Drexel bottle 6 other end is communicated with wet test meter 7.
When analyzing, first 70mL wash solution being added to respectively in 250mL wash solution Drexel bottle 2,3,4,5,70mL deionized water being joined in deionized water Drexel bottle 6, read the initial number of degrees of wet test meter 7, be designated as M
1(L), by sampling needle valve 1, sample flow is controlled between 40 ~ 50L/h, prolong in the Drexel bottle flow to subsequently to avoid wash solution.Methanation unstripped gas is connected with the needle valve 1 of device, pass into the methanation unstripped gas of about 150L (if the concentration level of carbonyl is estimated very high, then go easy gas), carry out absorption process to it, the gas discharging of simultaneously methanation unstripped gas outlet 8 being discharged is to safety area.Stop ventilation, read the final number of degrees, the pressure and temperature of wet gas meter 7, be designated as M respectively
2(L), P
1and T (DEG C) (kPa).
Then, the cleansing solution be equipped with in the Drexel bottle 2,3,4,5 of wash solution is joined in the beaker of 500mL, joined in described beaker by cleaning fluid with all Drexel bottles of a small amount of washed with methanol and connecting pipe, be absorbed the wash solution of iron carbonyi and carbonyl nickel again.
Then, the solution in beaker is transferred in 500mL graduated cylinder, record volume now.Subsequently according to the typical curve of iron carbonyi and carbonyl nickel, direct injection analysis on flameless atomic absorption spectrometry (AAS) instrument.
Concrete analytical procedure is:
Instrument and reagent
1. methanol solution: get 30ml hydrochloric acid methanol solution and be diluted to 1000mL.
2. iodine-hydroiodic acid solution: dissolve 20g iodine crystal in 70mL hydroiodic acid.In volumetric flask with methanol dilution to 500mL.
3. gas absorption solution: 140mL iodine-hydroiodic acid solution (2) is moved in the volumetric flask of a 1000mL, then use methanol solution (1) to be diluted to scale.
4. standard reserving solution (AAS), iron content is 1000mg/L.
5. standard reserving solution (AAS), nickel content is 1000mg/L.
6. the standard solution of iron and nickel: 5.0ppm, moves into the flask of a 100mL by the iron standard solution (AAS) (iron content is 1000mg/L) of 0.50mL and the nickel standard solution (AAS) (nickel content is 1000mg/L) of 0.50ml with transfer pipet.Mark is added into the wash solution got ready.
The preparation of instrument:
1) assemble absorption plant, refer to (Fig. 1).
2) instrument and running parameter PEAA800 Atomic Absorption Spectrometer, operating room's temperature 20 ± 2 DEG C, relative humidity less than 80%, measures wavelength coverage 190nm-900nm.
3) condition of work: slit width 0.2nm, nebulizer gas pressure 60psi carrier gas flux 250ml/min, sample size 5 μ L, the atomization temperature of Fe and Ni is respectively 2100/2300 DEG C.The analytical wavelengths of Fe and Ni is respectively 302.1/232.0nm
Instrument measuring:
1) check that whether all circuit, gas circuit be normal.Open carrier gas (Ar), regulate carrier gas flux.Open AA800 atomic absorption instrument, carry out graphite furnace operation.Set for the instrument parameter of carrying out iron, nickel is analyzed.
2) 0,0.2,0.50,0.6,0.8 and the 5ppm nickel of 1.0mL and ferrous solution is respectively moved into transfer pipet at the volumetric flask of six 50ml.Each bottle mark is added into by the absorbent solution got ready.These solution will respectively containing nickel and the iron of 0,20,50,60,80 and 100 μ g/L (parts per billion (ppb)).
3) with washed with de-ionized water seven self-actuated sampler measuring cups, then by wherein six standard working solution being all filled with iron and nickel, the 7th then fills sample solution.
4) be that the standard absorption solution of 0ppb uses as blank solution using iron, nickel content.
5) each standard solution and sample solution injecting 5 μ L equal portions, often kind of solution at least injects twice, carries out replication.
6) if sample solution exceedes the highest limit of absorbance, then sample is made after diluting this sample by absorbent solution.
7) obtain corresponding result by drawing standard curve, then calculate content according to the uptake of gas.Figure 2 shows that the typical curve drawn with iron (Fe) standard solution, Figure 3 shows that the typical curve drawn with nickel (Ni) standard solution, and table 1 corresponds to the absorption parameter of iron (Fe) standard solution drawing standard curve shown in Fig. 2, table 2 corresponds to shown in Fig. 3 with the absorption parameter of nickel (Ni) standard solution drawing standard curve.
Table 1 is with the absorption parameter of iron (Fe) standard solution drawing standard curve
Table 2 is with the absorption parameter of the standard solution drawing standard curve of nickel (Ni)
Result calculates
1 by gas sample amount (V
0) be corrected to 0 DEG C and 101.325kPa (760mmHg) time volume.
Wherein: M
2represent the final number of degrees of gasometer, unit is L;
M
1represent gasometer initial reading, unit is L;
P
1represent atmospheric pressure, unit is kPa;
T represents gasometer temperature, and unit is DEG C.
Iron carbonyi Fe (CO)
5,
Carbonyl nickel (CO)
4,
Wherein: C represents iron in solution or nickel, and unit is μ g/L;
V represents the volume of absorbent solution, and unit is mL;
V
0represent the volume by gas, unit is L;
0.005vpm can be reached by the minimum detectability calculating known this method.
Although present invention has been description to a certain degree, significantly, under the condition not departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Be appreciated that and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the equivalent replacement of described each factor.
Claims (10)
1. utilize flameless atomic absorption spectrometry to analyze a method for trace iron carbonyi and carbonyl nickel in methanation unstripped gas, the method comprises the following steps:
(1) absorption process is carried out to methanation unstripped gas, the wash solution of iron carbonyi and carbonyl nickel in the described methanation unstripped gas that has been absorbed with wash solution, and record the flow of described methanation unstripped gas;
(2) wash solution that step (1) obtains is transferred in graduated cylinder, after recording volume, utilizes flameless atomic absorption spectrometry analysis.
2. method according to claim 1, is characterized in that, the absorption process in described step (1) is that the method by comprising the following steps realizes:
A methanation unstripped gas is passed at least one of being connected successively by connecting pipe and the Drexel bottle of wash solution is housed and at least one is equipped with the Drexel bottle of deionized water by ();
B (), with all Drexel bottles and connecting pipe in washed with de-ionized water step (a), obtains cleaning fluid;
C the cleaning fluid obtained in the wash solution obtained in step (a) and step (b) is added in graduated cylinder by (), the wash solution of iron carbonyi and carbonyl nickel in the described methanation unstripped gas that has been absorbed.
3. method according to claim 2, is characterized in that, described in wash solution is housed Drexel bottle be 2 ~ 6, be preferably 4, be more preferably 1.
4. according to the method in any one of claims 1 to 3, it is characterized in that, described wash solution is iodo-hydroiodic acid mixed liquor.
5. one kind for realizing the system of method according to any one of Claims 1-4, this system comprises absorption treating device and atomic absorption analysis device, described absorption treating device comprise at least one of being connected successively by connecting pipe be equipped with wash solution Drexel bottle, at least one is equipped with Drexel bottle and the flowmeter of deionized water;
Described atomic absorption analysis device comprises graduated cylinder and Atomic Absorption Spectrometer.
6. system according to claim 5, is characterized in that, described in wash solution is housed Drexel bottle be 2 ~ 6, be preferably 4, be more preferably 1.
7. the system according to claim 5 or 6, is characterized in that, described absorption treating device also comprises the needle valve be connected with the inlet end described in first, the Drexel bottle of wash solution being housed.
8. the system according to any one of claim 5 ~ 7, is characterized in that, described atomic absorption analysis device also comprises sampler measuring cup.
9. the system according to any one of claim 5-8, is characterized in that, described flow counts gas meter, is preferably wet test meter.
10. the system according to any one of claim 5 ~ 9, is characterized in that, described wash solution is iodo-hydroiodic acid mixed liquor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410272426.2A CN105277534A (en) | 2014-06-18 | 2014-06-18 | Method for analyzing trace amounts of carbonyl iron and nickel carbonyl in methanation raw gas and system thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410272426.2A CN105277534A (en) | 2014-06-18 | 2014-06-18 | Method for analyzing trace amounts of carbonyl iron and nickel carbonyl in methanation raw gas and system thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106018664A (en) * | 2016-08-16 | 2016-10-12 | 王宏铭 | Method for evaluating inactivation performance of nickel catalyst in laboratory |
| CN108507901A (en) * | 2018-06-21 | 2018-09-07 | 河南省煤气(集团)有限责任公司义马气化厂 | The analysis method of trace carbinol in a kind of purified gas |
| CN109253996A (en) * | 2018-10-31 | 2019-01-22 | 中国石油天然气股份有限公司 | A kind of the mercury isotope test method and its device of crude oil |
-
2014
- 2014-06-18 CN CN201410272426.2A patent/CN105277534A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 刘阳等: "《煤制合成气中羰基镍和羰基铁的测定》", 《辽宁化工》 * |
| 王丹侠等: "《工作场所空气中五拨基铁的石墨炉原子吸收测定方法研究》", 《现代科学仪器》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106018664A (en) * | 2016-08-16 | 2016-10-12 | 王宏铭 | Method for evaluating inactivation performance of nickel catalyst in laboratory |
| CN108507901A (en) * | 2018-06-21 | 2018-09-07 | 河南省煤气(集团)有限责任公司义马气化厂 | The analysis method of trace carbinol in a kind of purified gas |
| CN109253996A (en) * | 2018-10-31 | 2019-01-22 | 中国石油天然气股份有限公司 | A kind of the mercury isotope test method and its device of crude oil |
| CN109253996B (en) * | 2018-10-31 | 2021-05-28 | 中国石油天然气股份有限公司 | Mercury isotope testing method and device for crude oil |
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Application publication date: 20160127 |