CN102590394A - Method for pretreating aqueous solution containing organic amine compounds and determination method - Google Patents
Method for pretreating aqueous solution containing organic amine compounds and determination method Download PDFInfo
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Abstract
The invention provides a method for pretreating an aqueous solution containing organic amine compounds and a determination method. The method for pretreating the aqueous solution containing the organic amine compounds comprises the following steps of: adding sodium hydroxide into the aqueous solution, and regulating the pH value of the aqueous solution to be more than 11 so as to ensure that metal ions in the aqueous solution are subjected to chemical reaction to obtain a metal hydroxide precipitate; dry-filtering to obtain a filtrate and the metal hydroxide precipitate, washing the metal hydroxide precipitate and a precipitation reaction container, and collecting a washing liquid into the filtrate; reducing the temperature of the filtrate to ensure that inorganic salts in the filtrate are crystallized and precipitated from the filtrate; and dry-filtering the filtrate which is subjected to temperature reduction to remove inorganic salt crystals and obtain a clear liquid, namely a sample solution. The determination method comprises the following step of: performing assay determination on the sample solution by one or more methods of gas chromatography-mass spectrometry, gas chromatography, liquid chromatography, and liquid chromatography-mass spectrometry to obtain the content of the organic amine compounds.
Description
Technical field
The present invention relates to the solution that contains organic amine compound is carried out check and analysis; Specifically; Relate to a kind of can passing through and eliminate of the influence of inorganic salts such as solution metal ion, hydrogen ion and sodium sulphate, thereby accurately measure the method for organic amine compound content in the solution the mensuration organic amine compound.
Background technology
In the prior art, organic amine compound is meant the organic compound that organic type of material and ammonia generation chemical reaction generate, and generally being divided into fatty amine, hydramine, acid amides, aliphatic cyclic amine, aromatic amine, naphthalene is seven big classifications such as amine, other amine.For example, organic amine compound comprises: methylamine, ethamine, n-propylamine, tert-butylamine base ethanol (TBE), tert-butylamine base oxethyl ethanol (TBEE), 2-send pyridine ethanol (PE), 2-amino-2-methyl-1-propanol (AMP), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine, n-propanol amine, diisopropanolamine (DIPA), dimethyl formamide (DMF), N-methyl-ethanolamine (MMEA), N methyldiethanol amine (MDEA), AEEA (AEE), N-tert-butylamine base monoethanolamine (TBMEA), N-n-butylamine-based monoethanolamine (BMEA), TETA (triethylene tetramine), DETA (diethylenetriamine), sulfolane (SF), 4-(2-hydroxyethyl)-2-piperazine ketone, triethylenediamine, cyclic ethylene imines, morpholine, piperazine, hydroxyethyl to send organic compounds such as piperazine, dimethyl sulfoxide (DMSO) (DMSO), naphthylamines, azanol.
Organic amine compound is widely used in aspects such as medicine, dyestuff, surfactant, solvent, rubber ingredients, the agent of polyurethane rib, hardening agent, ion exchange resin, corrosion inhibitor, acid gas absorbent; The organic amine compound and the complex of deriving thereof are one type of important function molecular materials; It is common sequestrant; They all have strong sequestering power with a lot of metallic ions, all have important use and researching value at the simulation of water correction, industrial cleaning, antidote, compartment analysis, metalloenzyme, the aspects such as exploitation of new material.
Particularly as acid gas absorbent, amine process flue gas desulfurization belongs to emerging regeneration type flue gas SO
2Isolation technics, bibliographical information have abroad been developed respectively with monoethanolamine (MEA), diethanolamine (DEA), diisopropanolamine (DIPA) or the methyldiethanolamine desulfurizing agent as solvent; The domestic research report that employing N methyldiethanol amine (MDEA), dimethyl sulfoxide (DMSO), ethylenediamine, diethylenetriamine, triethylene tetramine etc. are arranged as desulfurizing agent, and the novel desulfurizing agent of organic amine is to sinter fume and boiler smoke SO
2Removing with the research of regenerating is just becoming focus, and domestic certain enterprise has carried out 1000m
3The commerical test of/h flue gas treatment capacity.
Because organic amine itself has and forms chelate easily with many metallic ions and the pH value is characteristics such as strong basicity; Therefore the organic amine WS in use (for example; Comprising that the organic amine desulfurizing agent removes the metallurgy sintered use that waits in the application such as sulphuric dioxide in the industrial smoke) in; The organic amine component easily with the complexing of metal ion reaction form metallo-chelate, and the hydrogen ion neutralization reaction changed inorganic salts such as having generated high concentration sulfate after strong basicity that organic amine appeared originally and the absorbing sulfur dioxide, all organic amine component in the mensuration solution such as chromatography has been caused serious disturbing effect.
Therefore; Be used for measuring the analytical approachs such as gas chromatography and chemistry titration of the WS organic amine of pure and inclusion-free influence at present, can't be applicable to that mensuration receives the organic amine compound component (also becoming the organic amine component) in the fume desulfurizing agent (being also referred to as flue gas desulfurization solution) under the complex system of the serious disturbing effects of inorganic salts such as hydrogen ion, metallic ion and sodium sulphate.
And; The water wettability of organic amine compound is extremely strong; Solubleness is much larger than other polarity or non-polar organic solvent in water or ethanol; Therefore and ethanol and water dissolve each other and separate, and are difficult to find that certain is suitable, water-insoluble, can whole organic amine compound components to be measured organic solvent that separation and Extraction is come out from the sample substrate WS that has interference impurity; In addition, organic amine compound volatility to be measured very a little less than, be weaker than moisture, be difficult for coming out, so also should not adopt pressure volatilization methods such as purge and trap, headspace sampling or rotary distillation prior to the water preferential volatilization.
The application for a patent for invention that disclosed publication number was CN102288700A on Dec 21st, 2011 discloses the preprocess method and the detection method of the liquid desulfurizing agent solution of a kind of flue gas.This method comprises: in the liquid desulfurizing agent of flue gas, add solid alkaline reagent gradually; Alkaline reagent is dissolved in the liquid desulfurizing agent of flue gas fully; Repeatable operation makes that interfering component sufficient chemical reaction takes place and generates precipitate metal hydroxides in alkaline reagent and the flue gas liquid state desulfurizing agent in the pH value of the liquid desulfurizing agent with flue gas is regulated 9.5～10.5 the scope of being controlled at; Then, separate the precipitate metal hydroxides of removing generation, thereby make the sample solution of the liquid desulfurizing agent of flue gas that is used to detect.This method can be removed the high efficiency separation from sample substrate of the component with interference effect; And the still harmless lost territory of organic component to be measured is remained in the sample substrate of having removed interfering component, thereby guaranteed accuracy to the liquid desulfurizing agent active principle of flue gas testing result.Yet; Use alkaline reagent to eliminate the disturbing effect that metallic ion and hydrogen ion cause though this patented claim is open; But not only do not solve the problem that influences of inorganic salts such as sulfate; More because of using alkali metal ions such as the newly-increased sodium of having introduced high concentration of alkaline reagent, potassium, cause the concentration of inorganic salts such as sodium sulphate in the prepared sample solution significantly to rise on the contrary, and this can cause when GC or GC-MS isochromatic spectrum analytical instrument organic amine component; Under injection port high temperature with solution in the gasification of organic component to be measured and moisture introduce in the chromatographic resolution capillary column; The inorganic salts that can't gasify is in a large number formed solid particle attached to sample introduction glass bushing pipe and capillary column port by evaporate to dryness, promptly causes sample introduction glass bushing pipe or capillary column to stop up after often measuring several samples, needs frequent clean glass bushing pipe or cutting to change that section capillary column of obstruction; Influence the precision level of check and analysis, reduce the serviceable life of expensive capillary column greatly.
Summary of the invention
To the deficiency that prior art exists, one of the object of the invention is to provide a kind of can eliminate inorganic salts such as metallic ion, hydrogen ion and sodium sulphate in the WS that contains organic amine compound to the preprocess method and the detection method thereof of the influence of measuring the organic amine compound in the said WS.
In addition, another object of the present invention is to provide a kind of can accurately measure the content of the organic amine compound in the WS and not influence the life-span of follow-up measuring equipment and the method for precision level.
In addition, another object of the present invention is to provide a kind of preprocess method and the detection method thereof that can eliminate the inorganic salts such as fume desulfurizing agent solution metal ion, hydrogen ion and sodium sulphate that contain organic amine compound to the influence of measuring the organic amine compound in the said flue gas desulfurization agent solution.
In addition, another object of the present invention is to provide a kind of and can eliminate inorganic salts such as sodium sulphate in the WS that contains organic amine compound the preprocess method and the detection method thereof of the influence of measuring the organic amine compound in the said WS.
One side of the present invention provides a kind of preprocess method that contains the WS of organic amine compound.Said preprocess method may further comprise the steps: in the said WS, add NaOH and regulate said pH value of aqueous solution greater than 11, so that the metallic ion generation chemical reaction in the NaOH and the said WS and generate precipitate metal hydroxides; Do and filter, wash said precipitate metal hydroxides and precipitation reaction container then, and cleansing solution is collected in the said filtrating to form filtrating and precipitate metal hydroxides; To the processing of lowering the temperature of said filtrating, so that the inorganic salts crystallization in the said filtrating and from filtrating, separating out; Do and filter the filtrating of handling, to remove the inorganic salts crystal and to obtain clear liquid through said cooling; Make the clear liquid temperature return to room temperature, be sample solution.
In one exemplary embodiment of the present invention, said inorganic salts comprise sulfate and chloride.
In one exemplary embodiment of the present invention; Said preprocess method also is included under the situation of the sulfate ion deficiency that can generate deposition with the sodion reaction in the said WS, before processed steps that filtrating is lowered the temperature, in solution, introduces sulfate ion to remove the sodion in the WS.
In one exemplary embodiment of the present invention, the step of said washing precipitate metal hydroxides and precipitation reaction container comprises that the moisture that uses scheduled volume becomes washing precipitate metal hydroxides and precipitation reaction container 3～5 times.
In one exemplary embodiment of the present invention, said the filtrating processed steps of lowering the temperature is reduced to 3～10 ℃ with the temperature of said filtrating.
A kind of preprocess method that contains the WS of organic amine compound is provided according to a further aspect in the invention; Contain sodion or sulfate ion in the said WS; Said preprocess method may further comprise the steps: to the processing of lowering the temperature of the said WS, so that the inorganic salts crystallization in the said WS and separating out; Do and filter the WS of handling through said cooling, to remove the inorganic salts crystal and to obtain clear liquid; Make the clear liquid temperature return to room temperature, be sample solution.
In one exemplary embodiment of the present invention, the said WS be contain one or more organic amine compounds and can absorb and the desorb industrial smoke in the WS of oxysulfide gas.For example, this WS can be for containing the flue gas desulfurization agent solution of one or more organic amine compounds.
A kind of method of measuring the organic amine compound content in the WS is provided according to another aspect of the invention.Said method comprising the steps of: adopt according to above-mentioned one side of the present invention or described on the other hand preprocess method and form sample solution; Adopt one or more methods in GC-MS (abbreviating the GC-MS method as), vapor-phase chromatography (abbreviating the GC method as), liquid phase chromatography (abbreviating the LC method as) and the liquid chromatograph mass spectrography method (abbreviating the LC-MS method as) that said sample solution is carried out assay determination, to record the content of the organic amine compound in the said WS.
Compared with prior art, the present invention includes following beneficial effect:
First; Through water precipitate metal hydroxides and the container (also can be described as the precipitation reaction container) that carries out precipitation reaction (are for example washed; Can adopt a small amount of mode repeatedly to wash), reclaim organic amine component to be measured residual or that be adsorbed, cleansing solution is collected in the former filtrating; Thereby the loss of the component of having avoided because of precipitate metal hydroxides the absorption of organic amine component being caused to be measured has improved the accuracy of measuring.
Second; NaOH has increased Na ion concentration in the solution; Could fully effectively utilize sodium sulphate solubleness along with temperature descends and the rapid characteristic that reduces; Remove sulfate anion, introduce original sodion in the sodion and the WS by NaOH with the freezing and crystallizing mode, other can't reach this target like various alkaline reagents such as potassium hydroxide, calcium hydroxide, magnesium hydroxides.
The 3rd, handle through cooling, the present invention can utilize the Changing Pattern of inorganic salts (for example, sodium sulphate and sodium chloride etc.) solubility with temperature, removes inorganic anion in the said filtrating (for example, whole sulfate ion and chlorion partly).
The 4th, method of the present invention is greater than 11 with the pH regulator of the WS, can fully remove the metallic ion in the WS, and along with the increase of pH value of water solution, solution alkalescence strengthens, and more helps precipitated metal and removes up hill and dale.And prior art is because of alkali-metal ions such as the sodium that can not eliminate alkaline reagent and introduce, potassium, avoids its excessive concentration in order to control in the solution sodion etc., therefore the pH value of solution is controlled in 9.5～10.5 the scope.
The 5th; Method of the present invention has been eliminated the disturbing effects to measuring such as alkali metal cation that negative ion such as metallic ion, hydrogen ion, sulfate radical in the WS and newly-increased alkaline reagent are introduced simultaneously, has simplified solution matrix, reduces obstruction, the corrosion of inorganic salts to capillary column; Reduction to the maintaining frequency of equipment, prolong the serviceable life of expensive components such as capillary column; Reduce the check and analysis cost, improve the continuous operation stability of detecting instrument, improve the analysis result precision level.
Embodiment
Hereinafter, will specify preprocess method of the present invention and assay method with reference to exemplary embodiment.
In one exemplary embodiment of the present invention; The preprocess method that contains the WS of organic amine compound may further comprise the steps: in the said WS, add NaOH and regulate said pH value of aqueous solution greater than 11, so that the metallic ion generation chemical reaction in the NaOH and the said WS and generate precipitate metal hydroxides; Do and filter, wash said precipitate metal hydroxides and precipitation reaction container then, and cleansing solution is collected in the said filtrating to form filtrating and precipitate metal hydroxides; To the processing of lowering the temperature of said filtrating, so that the inorganic salts crystallization in the said filtrating and from filtrating, separating out; Do and filter the filtrating of handling, to remove the inorganic salts crystal and to obtain clear liquid through said cooling; Make the clear liquid temperature return to room temperature, be sample solution.
In one exemplary embodiment of the present invention; The step of said washing precipitate metal hydroxides and precipitation reaction container comprises that the moisture that uses scheduled volume becomes washing precipitate metal hydroxides and precipitation reaction container 3～5 times; With reclaim by the organic amine component of precipitate metal hydroxides absorption with remain in the organic amine component in the precipitation reaction container, thereby can improve the accuracy of detection.
The principle that reduces according to the solubility with temperature in the filtrating such as the inorganic salts of sodium sulphate, (for example, the solubleness of sodium sulphate and the relation of temperature can for: 0 ℃, 4.9g/100mL; 10 ℃, 9.1g/100mL; 20 ℃, 19.5g/100mL; 30 ℃, 40.8g/100mL; 40 ℃, 48.8g/100mL; 60 ℃, 45.3g/100mL; 80 ℃, 43.7g/100mL; 100 ℃; 42.5g/100mL; Therefore in addition, sodium chloride solubleness temperature influence is less relatively, handles its solubleness is diminished and amount that crystallization is separated out is less relatively through cooling); Remove inorganic salts such as sodium sulphate to avoid solution to be frozen simultaneously icing for crystallization to greatest extent, and the preprocess method of the present invention target temperature of handling of can lowering the temperature is set to solidifying point and alap temperature greater than said filtrating.For example, remove inorganic salts such as sodium sulphate for crystallization to large extent and avoid solution to be frozen simultaneously and freeze, the method for the present invention target temperature of handling of will lowering the temperature is arranged in 3～10 ℃ of scopes, and this moment can be with the freezing preservation of filtrating 1.5～2.5 hours.In the method for the invention, along with the reduction of filtrating temperature, other sulfate and other chloride also can crystallization separate out and be removed.In addition; After low-temperature condition taking-up filtrating; Can take advantage of low-temperature condition do immediately isolated by filtration remove decrystallize separate out such as inorganic salts crystal such as sodium sulphate, sodium chloride, avoid Yin Wendu to rise and the inorganic salts crystal such as sodium sulphate that cause having separated out dissolve again.
In above embodiment, the interfering component in the said WS comprises negative ion such as metallic ion, hydrogen ion, sulfate radical and small amounts of chlorine root.For example; The said WS can or be used for the organic amine compound of other purpose and the mixed solution of water for fume desulfurizing agent solution; Said flue gas desulfurization agent solution is for being used for circulation and absorbing and what remove industrial smoke sulphur oxide gas (for example, sulphuric dioxide and/or sulfuric anhydride) such as metallurgy sintered being the solution of desulfurization active principle with the organic amine compound.
In addition; If do not exist sulfate radical or its concentration very low in the said WS; Only receive the influence of hydrogen ion or metallic ion, then need be in solution suitably extraly add metal sulfate such as ferrous sulphate, and then adopt in the NaOH and hydrogen ion and precipitate and separate metallic ion (comprising metallic ion) by the new introducing of metal sulfate; Impelling the sulfate ion that enough concentration is arranged to combine, and then remove inorganic salts such as sodium sulphate through the mode of freezing and crystallizing with sodion.Specifically, at this moment, the preprocess method that contains the WS of organic amine compound of the present invention also is included in filtrating lowered the temperature introduces sulfate ion before the processed steps to remove the sodion in the WS in solution.For example, can introduce sulfate ion through the mode that adds ferrous sulphate.
In addition; If fume desulfurizing agents etc. contain the disturbing effect that the WS of organic amine component does not receive hydrogen ion and metallic ion; Only receive the influence of sodion and sulfate ion; Preprocess method then of the present invention can omit and add in the NaOH and the step of hydrogen ion and precipitate and separate metallic ion, and directly removes inorganic salts such as sodium sulphate through the mode of freezing and crystallizing.Specifically, at this moment, the preprocess method that contains the WS of organic amine compound of the present invention may further comprise the steps: to the processing of lowering the temperature of the said WS, so that the inorganic salts crystallization in the said WS and separating out; Do and filter the WS of handling through said cooling, to remove the inorganic salts crystal and to obtain clear liquid; Make the clear liquid temperature return to room temperature, be sample solution.
In one exemplary embodiment of the present invention, the method for measuring the organic amine compound content in the WS may further comprise the steps: adopt according to the described preprocess method of above-mentioned any embodiment and form sample solution; Adopt one or more methods in GC-MS, vapor-phase chromatography, liquid phase chromatography and the liquid chromatograph mass spectrography method that said sample solution is carried out assay determination, to record the content of the organic amine compound in the said WS.
In one exemplary embodiment; The preprocess method that contains the WS of organic amine compound of the present invention also can be realized through following steps: at first; Measure desulfurizing agent 80～120mL in the 250mL conical flask; Add purity greater than solid sodium hydroxide (NaOH) 10～20g of 96.0% and cover stopper, vibration dissolving and regulator solution pH＞11; Acutely shook 3～5 minutes, and impelled hydrogen ion in hydroxide ion and the solution, free metal ion and organic amine metallo-chelate to carry out abundant chemical reaction, isolated by filtration is removed the precipitate metal hydroxides that is produced then.Filtrating is collected in the 150mL volumetric flask; And adopt a small amount of mode repeatedly to become conical flask and the precipitate metal hydroxides of 3～5 washings as the precipitation reaction container with 15～20mL moisture; Wash solution is collected among the former filtrating in the lump, with water dilution constant volume, shake up.Then, filtrating is transferred in the sub-containers of uncovered not capping plug such as 250mL conical flask, and placed cold compartment of refrigerator or other sub-cooled equipment, be controlled under 3～10 ℃ the low-temperature condition continuous freezing preservation 1.5～2.5 hours.At last; Take out filtrating and taking advantage of low-temperature condition to do the isolated by filtration crystallization immediately crystal such as the sodium sulphate of separating out, sodium chloride; After treating that the clear liquid temperature rises to room temperature, this clear liquid is preparation gained sample solution, is used for the dense change content that detection method such as GC-MS is analyzed the organic amine component.
Below, with contain organic amine compound, can absorb and the desorb industrial smoke in the flue gas desulfurization agent solution (also can be described as organic amine desulfurizer solution) of oxysulfide gas come exemplarily to explain preprocess method of the present invention and detection method for the WS to be measured.
In the example below; Used and analyzed other quality percentage composition of pure level and be no less than 96.0% solid sodium hydroxide (NaOH); Freezing equipment uses be the normal domestic use refrigerator reefer and can be at auxiliary its refrigerated storage temperature of control of regulating down of thermometer, used GC-MS is the Claus of U.S. P-E company 500 type gas chromatograph-mass spectrometer (GCMS)s.
Example 1
Pre-service prepares the sample solution of organic amine desulfurizer solution
Measure 80mL organic amine desulfurizer solution (below be called primary sample 1) and place the 250mL conical flask, vibration dissolving and regulator solution pH＞11 after adding the 10g solid sodium hydroxide and covering stopper; Continue acutely to shake conical flask 3 minutes; Impel that sufficient chemical reaction takes place interfering component in NaOH and the desulfurizing agent; The isolated by filtration precipitate metal hydroxides, filtrating is collected in the 150mL volumetric flask, becomes washing conical flask and precipitate metal hydroxides 3 times with 15mL moisture; Wash solution is collected in the former filtrating, dilutes constant volume, shakes up with water.
Filtrating is transferred to the 250mL conical flask, place cold compartment of refrigerator, be controlled under 10 ℃ the low-temperature condition continuous freezing preservation 1.5 hours.At last, take out filtrating and taking advantage of low-temperature condition to do the isolated by filtration crystallization immediately crystal such as the sodium sulphate of separating out, sodium chloride, treat that the clear liquid temperature rises to room temperature after, the clear liquid that is obtained is exactly the sample solution of the fume desulfurizing agent of pre-service preparation, is designated as sample solution 1.
Measure the sample solution of fume desulfurizing agent with GC-MS
Prepared flue gas desulfurization sample solution as detection means, directly, simultaneously carries out assay determination to organic amine component to be measured with GC-MS.The GC-MS determination step is undertaken by usual manner, and wherein, each parameter is provided with as follows:
Chromatographic parameter: sample size 5 microlitres; 300 ℃ of injector temperatures; Quartz capillary chromatographic column is the Elite-5MS (N9316282) that U.S. PE company produces, column length 30m, diameter 250 μ m;
Post case heating schedule: initial 200 ℃ and keep 30min;
Carrier gas: high-pure helium, 1.00mL/min, split ratio 1: 15;
The mass spectrum parameter: the transmission line temperature is 230 ℃; Ion source temperature is 210 ℃; The ion gun pattern is electron ionization sources EI+, energy 70ev; The photomultiplier transit tube voltage is 320v; The scanning of the mass spectrum time is 30min; Solvent delay reaches 3.0min; The scanning of the mass spectrum mass range is 80～500; Reach 0.20sec sweep time; Sweep interval is 0.10sec.
Example 2
Measure 120mL organic amine desulfurizer solution (below be called primary sample 2), add 20g NaOH and regulate pH＞11; Shake after 5 minutes the filtering metal precipitation of hydroxide and with 20mL moisture 5 washings conical flask and deposition.Filtrating was descended freezing 2.5 hours at 3 ℃.In addition, all the other are all according to carrying out with example 1 same procedure, to make sample solution to be detected, obtain sample solution 2 and measure with GC-MS.
Example 3
Measure 100mL organic amine desulfurizer solution (below be called primary sample 3), add 15g NaOH and regulate pH＞11; Shake after 4 minutes the filtering metal precipitation of hydroxide and with 18mL moisture 4 washings conical flask and deposition.Filtrating was descended freezing 2 hours at 7 ℃.In addition, all the other are all according to carrying out with example 1 same procedure, to make sample solution to be detected, obtain sample solution 3 and measure with GC-MS.
Example 4
Measure 90mL organic amine desulfurizer solution (below be called primary sample 4), add 12g NaOH and regulate pH＞11; Shake after 4 minutes the filtering metal precipitation of hydroxide and with 20mL moisture 4 washings conical flask and deposition.Filtrating was descended freezing 2 hours at 8 ℃.In addition, all the other are all according to carrying out with example 1 same procedure, to make sample solution to be detected, obtain sample solution 4 and measure with GC-MS.
Example 5
Measure 110mL organic amine desulfurizer solution (below be called primary sample 5), add 16g NaOH and regulate pH＞11; Shake after 5 minutes the filtering metal precipitation of hydroxide and with 20mL moisture 5 washings conical flask and deposition.Filtrating was descended freezing 2.5 hours at 10 ℃.In addition, all the other are all according to carrying out with example 1 same procedure, to make sample solution to be detected, obtain sample solution 5 and measure with GC-MS.
Example 6
The removal efficient of 1 to 5 pair of metallic ion of table 1 example
Use metallic element check and analysis method and chemical analysis methods such as ICP-AES; Respectively primary sample 1 to 5 and the common metal ion that after pre-service of the present invention, is contained in the prepared sample solution 1 to 5 and the concentration content of sulfate anion are measured, and calculated the removal efficient of the present invention metallic ion and sulfate ion.The result sees table 1 and table 2.
The removal efficient of 1 to 5 pair of sodium sulphate of table 2 example
| Sample number | Sodium sulphate |
| Primary sample 1 (mg/mL) | 102 |
| Sample solution 1 (mg/mL) | 5.1 |
| The metal sulfate ion of example 1 is removed efficient (%) | 95.0 |
| Primary sample 2 (mg/mL) | 110 |
| Sample solution 2 (mg/mL) | 7.7 |
| The sulfate ion of example 2 is removed efficient (%) | 93.0 |
| Primary sample 3 (mg/mL) | 94 |
| Sample solution 3 (mg/mL) | 5.0 |
| The sulfate ion of example 3 is removed efficient (%) | 94.6 |
| Primary sample 4 (mg/mL) | 66 |
| Sample solution 4 (mg/mL) | 6.5 |
| The sulfate ion of example 4 is removed efficient (%) | 90.2 |
| Primary sample 5 (mg/mL) | 79 |
| Sample solution 5 (mg/mL) | 6 |
| The sulfate ion of example 5 is removed efficient (%) | 92.4 |
Can find out through above-mentioned table 1 and table 2; The sample pretreatment effect that example 1 according to the present invention to example 5 is eliminated interfering component such as metallic ion and sulfate ion in the desulfurizing agent is obvious; Remove efficient all more than 90%; Eliminated the influence of interfering material effectively to measuring; Greatly reduce GOLD FROM PLATING SOLUTION and belong to the concentration of ion and sodium sulphate etc., improved the analysis result accurate reliability, the sample solution of pre-service preparation meets the requirement of modern precision organic analysis instrument detecting such as GC-MS more.
Example 7
Primary sample 2 and 4 is repeated 8 independently pre-service and assay determinations according to example 2 and example 4,8 measurement results are carried out statistical treatment, to assess precision of method of the present invention according to relative standard deviation (RSD).The result sees table 3.
Table 3 degree of accuracy test (n=8) (%)
Remarks: still locate confidential state because of the prescription composition of fume desulfurizing agent, inconvenience discloses clear and definite its and is specially which kind of organic amine material, and this sentences A, B, C replacement.
Visible from table 3; Owing to eliminated the congestion affects of inorganic salts such as sodium sulphate to sample introduction glass bushing pipe, capillary column etc.; Improved the stability of instrument sample introduction greatly; Reduced the influence to capillary column internal fixation liquid, the accuracy level of analysis result is good, RSD＜4% that continuous replication is 8 times.
In sum; The present invention is according to physicochemical properties such as the polarity of organic amine component and volatility; The technical measures that do not adopt normal organic analysis such as solvent extraction or distillation to separate interfering material; To hydrogen ion and characteristics of interference that metallic ion causes, adopt inorganic elements precipitate and separate purification techniques, component high efficiency separation from sample substrate that will have interference effect is removed; And organic component to be measured is remained in the sample substrate of having removed interfering component, thereby disturbing effect factors such as metal cation have been eliminated.And; The present invention further takes the mode of freezing and crystallizing to solve anionic interference such as sulfate radical and the interference of the sodium at high concentration ion that caused by NaOH; Thereby avoided inorganic salts to stop up glass bushing pipe and capillary column port, reduced glass cleaning bushing pipe frequency, need not to cut again the capillary column of changing obstruction; Improve the check and analysis precision level, prolonged the serviceable life of expensive capillary column greatly.
Although combined exemplary embodiment to describe the present invention above, it will be apparent to those skilled in the art that under the situation of spirit that does not break away from claim and limited and scope, can make various modifications to above-mentioned exemplary embodiment.
Claims (8)
1. preprocess method that contains the WS of organic amine compound, said preprocess method may further comprise the steps:
In the said WS, add NaOH and regulate said pH value of aqueous solution, so that the metallic ion generation chemical reaction in the NaOH and the said WS and generate precipitate metal hydroxides greater than 11;
Do and filter, wash said precipitate metal hydroxides and precipitation reaction container then, and cleansing solution is collected in the said filtrating to form filtrating and precipitate metal hydroxides;
To the processing of lowering the temperature of said filtrating, so that the inorganic salts crystallization in the said filtrating and from filtrating, separating out;
Do and filter the filtrating of handling, to remove the inorganic salts crystal and to obtain clear liquid through said cooling;
Make the clear liquid temperature return to room temperature, be sample solution.
2. the preprocess method that contains the WS of organic amine compound according to claim 1 is characterized in that said inorganic salts comprise sulfate and chloride.
3. the preprocess method that contains the WS of organic amine compound according to claim 2; It is characterized in that; Said preprocess method also is included under the situation of the sulfate ion deficiency that can generate deposition with the sodion reaction in the said WS, before processed steps that filtrating is lowered the temperature, in solution, introduces sulfate ion to remove the sodion in the WS.
4. according to claim 1 or the 3 described preprocess methods that contain the WS of organic amine compound; It is characterized in that the step of said washing precipitate metal hydroxides and precipitation reaction container comprises that the moisture that uses scheduled volume becomes washing precipitate metal hydroxides and precipitation reaction container 3～5 times.
5. according to claim 1 or the 3 described preprocess methods that contain the WS of organic amine compound, it is characterized in that, said the filtrating processed steps of lowering the temperature is reduced to 3～10 ℃ with the temperature of said filtrating.
6. a preprocess method that contains the WS of organic amine compound contains sodion or sulfate ion in the said WS, it is characterized in that, said preprocess method may further comprise the steps:
To the processing of lowering the temperature of the said WS, so that the inorganic salts crystallization in the said WS and separating out;
Do and filter the WS of handling through said cooling, to remove the inorganic salts crystal and to obtain clear liquid;
Make the clear liquid temperature return to room temperature, be sample solution.
7. according to claim 1 or the 6 described preprocess methods that contain the WS of organic amine compound; It is characterized in that, the said WS be contain one or more organic amine compounds and can absorb and the desorb industrial smoke in the WS of oxysulfide gas.
8. a method of measuring the organic amine compound content in the WS is characterized in that, said method comprising the steps of:
Employing forms sample solution according to any described preprocess method in the claim 1 to 7;
Adopt one or more methods in GC-MS, vapor-phase chromatography, liquid phase chromatography and the liquid chromatograph mass spectrography method that said sample solution is carried out assay determination, to record the content of the organic amine compound in the said WS.
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| CN106546694A (en) * | 2016-11-01 | 2017-03-29 | 青海盐湖工业股份有限公司 | A kind of method for determining organic amine content |
| CN114388776A (en) * | 2021-12-06 | 2022-04-22 | 宜宾光原锂电材料有限公司 | Method for removing impurity sodium by washing nickel-cobalt-manganese ternary precursor |
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