CN103977586A - Separation, enrichment and determination method of desulfurized organic components in flue gas desulphurization aqueous solution - Google Patents
Separation, enrichment and determination method of desulfurized organic components in flue gas desulphurization aqueous solution Download PDFInfo
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Abstract
The invention provides a separation, enrichment and determination method of desulfurized organic components in a flue gas desulphurization aqueous solution. The separation and enrichment comprises the following steps: measuring the solution, adjusting the solution to form a highly acidic solution, and evaporating to remove most water; cooling, adjusting the obtained residual solution to form a highly alkaline solution, and carrying out first time distillation; and cooling, washing with water, immersing residues obtained after the second time distillation, and carrying out secondary distillation. The determination method comprises the following steps: determining fractions obtained after the second and third time distillation by using at least one of gas chromatography-mass spectrometry, gas chromatography, liquid chromatography and liquid chromatography-mass spectrometry, and calculating to obtain the content of organic components. The separation, enrichment and determination method enables the desulfurized organic components contained in various aqueous solution samples comprising absorbing tower condensed water, absorbing tower rainfall, resin washing water, stripper condensed water and the like generated in the key links of absorption, stripping, resin desalination and the like of a flue gas desulphurization system to be effectively separated and enriched, and the content of the desulfurized organic components to be precisely and accurately measured, and the detection process is fast and convenient.
Description
Technical field
The present invention relates to detect the method for analyzing desulfurization organic component in the various aqueous solution that flue gas desulphurization system running produces.Specifically, the present invention relates to a kind ofly can carry out separation and concentration and method for measuring to measuring contained desulfurization organic component in the various aqueous sample such as absorption tower condensed water that flue gas desulfurization production run process produces at several places critical process links such as absorption, parsing and resin desalination and position, absorption tower precipitation, resin washings, Analytic Tower condensed water.
Background technology
For controlling and solve sulfur dioxide pollution problem, at present China initial development a kind of formulated flue gas desulfurization solutions such as one or more organic amine compounds and water and other antioxidant that adopt, for circulating absorbing and removing and reclaim the Novel desulphurization technology of the multiple industrial smoke sulfur dioxide such as metallurgy sintered, this desulfur technology also can be described as renewable flue gas desulphurization process conventionally.In flue gas desulphurization system production run process, need to monitor at any time and detect contained desulfurization organic component content in various aqueous sample such as analyzing the absorption tower condensed water that produces at several places critical process links such as absorption, parsing and resin desalination and position, absorption tower precipitation, resin washings, Analytic Tower condensed water.Because, desulfurization organic component content very low (for example, can be low to moderate ppm level) in the aqueous sample such as absorption tower condensed water, absorption tower precipitation, resin washings, Analytic Tower condensed water, therefore, prior art is difficult to wherein desulfurization organic component content of Measurement accuracy.In addition also there is the problems such as Measuring Time is long in prior art.
Summary of the invention
The object of the invention is to solve at least one in the problem that prior art exists.
For example, one of object of the present invention is to provide a kind of method that can measure desulfurization organic component content in the flue gas desulfurization aqueous solution.
Inventor finds through research: due to the characteristic that the flue gas desulfurization aqueous solution (also can referred to as the desulfurization aqueous solution or the aqueous solution) possesses itself, cause directly it being carried out to conventional distillation and cannot record the organic component content in flue gas desulfurization solution at all.
Specifically, because the boiling point of the desulfurization organic amine component of initial molecule form is 300 DEG C of left and right, stability is stronger, volatility is originally just well below moisture, in addition absorb and generate the reaction strengthening of sulfuric acid and be reacted into after chelate ion with the complexing of metal ion that enters desulfuration solution through the circulation desulfurization process of flue gas desulphurization system, the volatility that is present in the organic component in the various aqueous solution to be measured with stable ionic forms is lower, and stability strengthens.Therefore, inventor is through attempting, find: the methods such as the water-bath used of prior art documents and materials, oil bath or directly heating, rotary distillation, high temperature distillation are all difficult to effectively the organic amine component that is ionic forms be separated from the aqueous solution, and in still-process along with moisture reduce, the sulfuric acid with higher boiling, strong oxidizing property, dehydration property being concentrated obviously strengthens organic amine component oxygenolysis, and final organic component remaines in container with solid forms and can not fully effectively be distilled.That is to say, for the method for desulfurization organic component in detecting the flue gas desulfurization aqueous solution, need to overcome the inorganic anions such as the sulfate radical, inferior sulfate radical, carbonate, chlorine root, nitrate anion of contained higher concentration in this flue gas desulfurization aqueous solution, an interference effect difficult problem for the various metal cations such as Yi Jitie, copper, nickel, chromium, calcium, magnesium, sodium.In addition, for example, because the concentration of contained desulfurization organic component in the aqueous solution such as common Analytic Tower precipitation, resin washings is very low (, be about under normal circumstances the concentration level of a few millionths (being ppm level)), therefore, desulfurization organic component is wherein measured and also had larger difficulty.
Based on above-mentioned discovery, inventor has finally drawn technical scheme of the present invention through creative work.
One aspect of the present invention provides the method for separating and concentrating of desulfurization organic component in a kind of flue gas desulfurization aqueous solution.Described method for separating and concentrating comprises the following steps: measure the flue gas desulfurization aqueous solution and be adjusted to highly acid, then, in the system of opening wide, the flue gas desulfurization aqueous solution being evaporated to remove wherein most of moisture; After cooling, regulate the remaining flue gas desulfurization aqueous solution to strong basicity, in enclosed system, the remaining flue gas desulfurization aqueous solution is distilled for the first time, until no longer produce dense white flue gas, obtain the first cut; After cooling, water is injected and distills for the first time container used, wash, soak the residue in this container, in enclosed system, this container is distilled for the second time, until no longer produce dense white smog in container, obtain the second cut; Wherein, the aqueous solution that contains desulfurization organic component of the described flue gas desulfurization aqueous solution for producing in flue gas desulphurization system running.
Another aspect of the present invention provides the assay method of desulfurization organic component in the flue gas desulfurization aqueous solution.Described assay method comprises the following steps: adopt method for separating and concentrating as above to carry out separation and concentration processing to the flue gas desulfurization aqueous solution to be measured, obtain the first cut and the second cut; Adopt at least one the first cut and the second cut sum that directly mensuration obtains in GC-MS, gas chromatography, liquid chromatography, Liquid Chromatography-Mass Spectrometry, calculate the content that obtains desulfurization organic component in the flue gas desulfurization aqueous solution to be measured.
Compared with prior art, beneficial effect of the present invention comprises: can absorb flue gas desulfurization production run process, the absorption tower condensed water that several places critical process links such as parsing and resin desalination and position produce, absorption tower precipitation, resin washings, in the various aqueous sample such as Analytic Tower condensed water, the content of contained desulfurization organic component carries out separation and concentration and measurement, thereby realize from complex system, disturb in matrix by 1,000,000/concentration level (ppm level) with ion, the desulfurization organic component that the various forms such as molecule or metallo-chelate exist is effectively separated and obtains abundant enrichment, there is good preci-sion and accuracy, and testing process is efficient and convenient.
Brief description of the drawings
Fig. 1 shows the detection spectrogram that does not adopt the flue gas desulfurization aqueous solution that the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution of the present invention processes;
Fig. 2 shows and adopts the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution of the present invention to carry out detection spectrogram after treatment to the corresponding flue gas desulfurization aqueous solution of Fig. 1.
Detailed description of the invention
Hereinafter, describe method for separating and concentrating (also can be described as flue gas desulfurization aqueous solution preprocess method) and the assay method of desulfurization organic component in the flue gas desulfurization aqueous solution of the present invention in detail in connection with exemplary embodiment.
The method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to an aspect of the present invention, comprise step: measure the flue gas desulfurization aqueous solution and be adjusted to highly acid, then, in the system of opening wide, the flue gas desulfurization aqueous solution is evaporated to remove wherein most of moisture; After cooling, regulate the remaining flue gas desulfurization aqueous solution to strong basicity, in enclosed system, the remaining flue gas desulfurization aqueous solution is distilled for the first time, until no longer produce dense white flue gas, obtain the first cut; After cooling, water is injected and distills for the first time container used, wash, soak the residue in this container, in enclosed system, this container is distilled for the second time, until no longer produce dense white smog in container, obtain the second cut.Wherein, the aqueous solution that contains desulfurization organic component of the described flue gas desulfurization aqueous solution for producing in flue gas desulphurization system running, for example, the flue gas desulfurization aqueous solution can be that flue gas desulphurization system is absorbing, the various aqueous solution that several places critical process links such as parsing and resin desalination and position produce, generally include: the absorption tower condensed water producing in sulfur dioxide absorbing tower, absorption tower precipitation, the resin washings that produce in ion exchange resin desalting processing operation, and the various aqueous solution such as the Analytic Tower condensed water producing at Analytic Tower place that the sulfur dioxide having absorbed in desulfuration solution is parsed.
In method for separating and concentrating of the present invention, all kinds of inorganic interfering material that in the complex matrices of flue gas desulfurization aqueous sample, existing impact detection is analyzed (for example, chlorine root, nitrate anion, fluorine root, carbonate, sulfate radical, one or more in the inorganic anions such as inferior sulfate radical, and nickel, chromium, calcium, magnesium, potassium, sodium, iron, copper, plumbous, one or more in the metal cations such as aluminium), except carbonate at regulator solution to overflowing with acid reaction and with carbon dioxide form in highly acid step, all the other disturb impurity all with sulfate, chlorate, nitrate, fluoride salt, the inorganic salts such as carbonate, precipitate metal hydroxides, the solid particles such as dust and other form that is difficult to the inorganic compound of volatilization residue in former container for evaporation.
Specifically,, in method for separating and concentrating of the present invention, by the flue gas desulfurization aqueous solution is adjusted to highly acid, thereby can make organic amine component there is good stability and be difficult for the feature of volatilization loss.For example, through overtesting, inventor finds: the flue gas desulfurization aqueous solution, also cannot be by contained organic component separated out up to more than 500 DEG C temperature in Muffle furnace in acidity and metal ion medium, the ashing until last organic component is all decomposed.Therefore, method of the present invention is in the process of evaporative removal moisture, can not cause the situation that causes Lower result because of the loss of organic component, that is to say, evaporation in method of the present invention can select higher temperature to remove moisture, boil under temperature conditions and evaporate and needn't be controlled at 100 DEG C of following Asias, so greatly shortened distillation time.For example, the preferred temperature of evaporation can be 100 DEG C～180 DEG C.But this not says that the temperature of the evaporation in method of the present invention must be controlled in the scope of 100 DEG C～180 DEG C, certainly, also can be higher or lower than this temperature range.
The residue flue gas desulfurization aqueous solution after evaporation is adjusted to strong basicity, can impel organic amine component wherein from react generated molecule with hydrogen ion or metal ion, in ion or metallo-chelate ion, dissociate and recover original molecular structure and have form, recapture original boiling characteristics, then can be by organic component from comprising sulfate radical through high temperature distillation for the second time, chlorine root, the inorganic anion of nitrate anion etc., and iron, copper, nickel, chromium, calcium, magnesium, potassium, in the various inorganic salts interference effects of the metal cations such as sodium in interior complex sample matrix, separate completely, thoroughly eliminate the impact of all inorganic interfering materials.
In addition, in method for separating and concentrating of the present invention, by residue obtainedly washing, soak to cooled distillation for the first time, and in enclosed system, distill for the second time subsequently, can reach following effect: the organic amine component a small amount of to be measured that may wrap up in distillation leftover for the first time is again dissolved and is distilled out; The steam that distillation produces for the second time and condensed water thereof also can play and rinse the residual organic component to be measured being got off by the condensation again that is evaporated in distilling apparatus pipeline, thereby have avoided organic component to be measured to residue in the loss causing in solid inorganic salt and distilling apparatus pipeline.
For method for separating and concentrating of the present invention, the temperature of distillation for the first time and distillation for the second time can adopt higher temperature, can make like this separated organic component time greatly reduce, shorten thus whole analysis process, improve detection speed, more can meet the on-the-spot fast pace of uninterrupted circulating flue gas desulfurization and produce the requirement to detection speed.And because distillation time shortens greatly, method of the present invention is measured the more flue gas desulfurization aqueous solution as solution to be measured, thereby can improve enrichment method ratio, and then not only can improve detection speed, and can improve the flue gas desulfurization aqueous solution of desulfurization organic component concentration lower (1,000,000/(ppm level) following concentration) is detected to precision and the accuracy analyzed.For example, preferably, the temperature of distillation can be 200 DEG C～300 DEG C for the first time, and the temperature of distillation can be 300 DEG C～350 DEG C for the second time, but, the invention is not restricted to this.
In an exemplary embodiment of method for separating and concentrating of the present invention, preferably, the step of evaporation is removed the moisture that accounts for the front flue gas desulfurization aqueous solution volume 80%～95% of evaporation.It is to obtain high as far as possible enrichment ratio in order to guarantee to treat the Accurate Determining of micrometer amount or trace desulfurization organic amine component that moisture removal amount is set to 80%～95% benefit, effectively avoids after excessively concentrated causing the oxidized decomposition of desulfurization organic component in the strength sulfuric acid medium generating simultaneously.For evaporation step, it can save the reagent dosage that regulates acidity, but saving and regulating the reagent dosage of acidity is not main purpose, the key effect of this step is that rapid evaporation is removed moisture in the system of opening wide, fully concentrated desulfurization organic component to be measured, not only greatly shorten second, third airtight distillation required time, and be more conducive to measure the desulfurization component of trace or trace level.Therefore, evaporation specifically need to be removed how much moisture is advisable, need the comprehensive height of saving desulfurization organic component content in follow-up distillation time and solution to be measured, if desulfurization constituent content is high in solution, moisture removal amount can be set and can be less than 80%, also enough ensure that the analytical methods such as follow-up GC-MS can Accurate Determining because the highly enriched ratio of its content is less.But method of the present invention is not limited to this, for example, the amount of moisture of removal also can be lower than 80% of flue gas desulfurization aqueous solution volume before evaporation, and unnecessary moisture can be processing in still-process for the first time; Certainly, also can be higher than 95% of flue gas desulfurization aqueous solution volume before evaporation, as long as the desulfurization organic component in the surplus solution that evaporation obtains is unlikely to occur to decompose.
In an exemplary embodiment of method for separating and concentrating of the present invention, preferably, be adjusted to highly acid step the pH value of the flue gas desulfurization aqueous solution is adjusted to 1～3.The pH value that is adjusted to highly acid step is not limited to this, for example, also can suitably exceed a bit this pH value scope and also be fine, just exceed lower limit and regulate acid used to increase, and the increase of the concentrated ratio of impact, need to consider to avoid component to be measured by strong acid oxidation Decomposition; Suitably exceeds the upper limit but still be also fine for acidity, but pH value is too high, in solution desulfurization constituent content compared with Gao Shiyou in evaporation process by the risk of evaporation, decomposition volatilization loss.In addition, in fact, along with the removal of moisture, the pH value of solution declines gradually, is also that acidity increases.In a word, scope can suitably be relaxed.Be adjusted to highly acid step can be by adding acid to realize in the flue gas desulfurization aqueous solution, for example, can select any or multiple in the conventional mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, and its purity can be chemical pure or analyze any Quality Grades such as pure.
In an exemplary embodiment of method for separating and concentrating of the present invention, preferably, regulate the remaining flue gas desulfurization aqueous solution to alkaline step that the pH value of the flue gas desulfurization aqueous solution is adjusted to 10～12.Certainly, also can suitably amplify this alkaline range.Regulate the consumption of the alkaline reagents such as acidity NaOH used to increase if pH value is greater than 12, the corrosiveness of glass equipment is also increased, and cause nonvolatile salt residue in solution also to increase; If pH value is less than 10, need to consider whether precipitation by metallic ion completely and from the chelate of desulfurization component and metal ion generation again dissociates and discharge desulfurization component whether can be complete.Extremely alkaline step can be by adding alkali to realize in the remaining flue gas desulfurization aqueous solution to regulate the remaining flue gas desulfurization aqueous solution, for example, solid or its saturated solution that can select any strong basic reagent such as NaOH, potassium hydroxide, its purity can be chemical pure or analyze any Quality Grades such as pure.
In an exemplary embodiment of method for separating and concentrating of the present invention, preferably, the step that obtains the second cut is carried out more than twice repeatedly.For example, more for inorganic salts in the flue gas desulfurization aqueous solution, or the higher situation of the concentration of organic component to be measured in the flue gas desulfurization aqueous solution, still fail to solve completely organic component because of residual problem of losing for avoiding the distillation for the second time of rinsing inorganic salts and distilling apparatus pipeline, affect the situation of the testing result degree of accuracy, can select the repeated multiple times step that obtains the second cut.
Method of the present invention can be measured flue gas desulphurization system and absorb, the absorption tower condensed water that several places critical process links such as parsing and resin desalination and position produce, absorption tower precipitation, resin washings, contained trace in the various aqueous solution such as Analytic Tower condensed water, when the concentration content of trace organic amine desulfurization component, take evaporation and concentration enrichment respectively under different acid-alkali mediums and different temperatures controlled condition in three steps, the method that separated is extracted, by owing to there is the organic component that loses boiling characteristics with the various forms such as ion or metallo-chelate, from the aqueous solution to be measured, separated is out completely, exist the organic component to be measured of form from complex system, to disturb in matrix separation and concentration out 1,000,000/concentration level (ppm level) various thereby realize, and measure the object of its concentration content with analytical methods such as GC-MS, effectively solve original aqueous solution normal condition to be measured and be difficult to distillation, or water consumption overlong time is removed in the evaporation of boiling of low temperature Asia, and component to be measured is in inorganic salts and the distillation residual deficiency that waits in pipeline.
In the flue gas desulfurization aqueous solution according to a further aspect of the invention, the detection method of desulfurization organic amine component comprises the following steps: according to method described above, aqueous sample to be measured is carried out to separated processing; Adopt cut that at least one in GC-MS (GC-MS), gas chromatography (GC), liquid chromatography (LC), Liquid Chromatography-Mass Spectrometry (LC-MS) directly measure the condensation collection of separated processing institute (, the first cut and the second cut sum), thus the concentration content that obtains the organic amine component to be measured in the aqueous solution calculated.
Owing to only being formed by the organic substance such as organic amine component to be measured or other a small amount of antioxidant and the water that are molecular conformation in distillation fraction, component to be measured is purified and enrichment, various inorganic salts materials all residue in evaporative flask and thoroughly effectively separate with component to be measured, not only avoid the interference effect to the testing result degree of accuracy, precision, and avoid entering GC, GC-MS, LC or LC-MS detecting instrument because of a large amount of inorganic salts, reduce the service life of expensive chromatographic column, increase instrument maintenance maintenance difficulty and analysis cost.
In an exemplary embodiment of the present invention, in the described flue gas desulfurization aqueous solution, the detection method of desulfurization organic amine component can adopt following steps to realize:
Measure 100mL～500mL aqueous solution to be measured, add the conventional mineral acid of any kinds such as hydrochloric acid to regulate and control the highly acid scope of solution in PH=1～3, at 100 DEG C～180 DEG C temperature, open wide evaporation in system and remove fast the most of moisture in solution, until the volume of residual solution is only original volume 5%～20% in container; Be cooled to after 60 DEG C～80 DEG C, add the strong basic reagent of any kinds such as NaOH, regulate the strong basicity scope of controlling solution PH=10～12, connect airtight distillation condensing unit and at 200 DEG C～300 DEG C temperature, distill for the first time also condensation collection cut, until no longer produce dense white flue gas in container for evaporation.Take off cooling 80 DEG C～90 DEG C, with 5mL～10mL water washing bottle wall and solid inorganic salt, again connect airtight condensation gathering-device and at 300 DEG C～350 DEG C temperature, distill for the second time and merge condensation collection cut, until no longer produce dense white flue gas in container.Collected cut is from all kinds of aqueous sample enrichment method and disturbs separation and Extraction matrix out to return the organic component to be measured of initial molecule form from sample, then uses the organic analysis instruments such as GC-MS, GC, LC, LC-MS directly organic component to be measured to be measured.
Describe in detail and adopt method of the present invention to carry out separation and concentration and detect the situation of organic component in the various aqueous solution such as absorption tower condensed water that flue gas desulphurization system produces, absorption tower precipitation, resin washings, Analytic Tower condensed water below in conjunction with concrete example.
In following concrete example, the nitric acid using or other acid are the concentrated acid % of analytically pure not diluted, and the content analytically pure solid sodium hydroxide or the potassium hydroxide that are greater than 96.0%, rotary distillation device, GC-MS is the U.S. Claus500 of P-E company type GC-MS, but the invention is not restricted to this.
Because the present invention concentrates separated out completely by organic component to be measured from the complex sample matrix of the primary sample aqueous solution, therefore measure the concentration content of the how many and contained interfering material of the volume of the aqueous solution, and add the detection of how many organic amine components of all distillation being collected of the alkaline reagent consumptions such as NaOH to analyze not produce any impact, only that the aqueous sample volume that measures is larger, consume the alkaline reagent consumptions such as NaOH larger, when separated, the spent time is longer.So, if the concentration content of organic component to be measured is lower than the concentration level of 1,000,000/(being ppm level) in the aqueous solution, if really need to detect the organic component to be measured of analyzing low content like this, can be arbitrarily the volume of recruitment water intaking solution example unrestrictedly, with the component to be measured of distilling enrichment sufficient amount for analytical instrument.
example 1
detect and analyze absorption tower precipitation
Measure 100mL absorption tower precipitation (being below called sample No. 1) in distilling flask, add hydrochloric acid to regulate and control solution PH=1, at 100 DEG C, open wide in system and evaporate, by directly discarded emptying removing until residual 10mL solution only in container of the moisture of evaporation; Be cooled to 60 DEG C and add sodium hydrate regulator solution PH=10, connect rotary evaporator and distillation for the first time condensation collection cut at 200 DEG C, until be cooled to 80 DEG C after no longer producing dense white flue gas in container for evaporation, with 5mL water washing bottle wall and inorganic salts, again connect rotary evaporator distillation for the second time and merging condensation collection cut at 300 DEG C, until no longer produce dense white flue gas in container.
Collected cut is enrichment method, separated organic component to be measured out in the precipitation of absorption tower, adopts GC-MS directly to measure each component and concentration thereof.GC-MS determination step carries out in the usual way.Wherein, chromatographic parameter: sample size (5 microlitre); Injector temperature (300 DEG C); Capillary chromatographic column (Elite-5MS of PE company of the U.S., column length 30m, diameter 250 μ are m); Column temperature rise program (180 DEG C keep 15min); Carrier gas (high-pure helium, 1.00mL/min, split ratio 1:15); Mass spectrum parameter: transmission line temperature (200 DEG C); Ion source temperature (180 DEG C); Ion gun pattern (EI+, energy 70ev); Photomultiplier transit tube voltage (300v); The scanning of the mass spectrum time (15min); Solvent delay (2.5min); Scanning of the mass spectrum mass range (70～550); Sweep time (0.20sec); Sweep interval (0.10sec).
example 2
detect and analyze absorption tower condensed water
Measure 500mL absorption tower condensed water (being below called sample No. 2), add hydrochloric acid to regulate PH=3, at 180 DEG C evaporation except anhydrating until residual 25mL solution only in container; Be cooled to 80 DEG C and add potassium hydroxide regulate PH=12, connect rotary evaporator distillation for the first time condensation collection cut at 300 DEG C, until be cooled to 80 DEG C after no longer producing dense white flue gas in container for evaporation, with 10mL water washing bottle wall and inorganic salts, again connect rotary evaporator distillation for the second time and merging condensation collection cut at 350 DEG C, until no longer produce dense white flue gas in container.In addition, detect cut according to the method enrichment method identical with the method for example 1, separated absorption tower condensed water and with GC-MS.
example 3
detect and analyze washings
Measure 250mL washings (being below called sample No. 3), add nitric acid to regulate PH=2, at 150 DEG C evaporation except anhydrating until residual 15mL solution only in container; Be cooled to 70 DEG C and add NaOH regulate PH=11, connect rotary evaporator distillation for the first time condensation collection cut at 250 DEG C, until be cooled to 80 DEG C after no longer producing dense white flue gas in container for evaporation, with 10mL water washing bottle wall and inorganic salts, again connect rotary evaporator distillation for the second time and merging condensation collection cut at 320 DEG C, until no longer produce dense white flue gas in container.In addition, detect cut according to the method enrichment method identical with the method for example 1, separated washings and with GC-MS.
example 4
detect and analyze Analytic Tower condensed water
Measure 400mL Analytic Tower condensed water (being below called sample No. 4), add hydrochloric acid to regulate PH=1, at 150 DEG C evaporation except anhydrating until residual 20mL solution only in container; Be cooled to 70 DEG C and add potassium hydroxide regulate PH=12, connect rotary evaporator distillation for the first time condensation collection cut at 280 DEG C, until be cooled to 90 DEG C after no longer producing dense white flue gas in container for evaporation, with 5mL water washing bottle wall and inorganic salts, again connect rotary evaporator distillation for the second time and merging condensation collection cut at 300 DEG C, until no longer produce dense white flue gas in container.Again be cooled to 90 DEG C, again with 5mL water washing bottle wall and inorganic salts, again connect rotary evaporator the 4th distillation and merging condensation collection cut at 350 DEG C, until no longer produce dense white flue gas in container.In addition, detect cut according to the method enrichment method identical with the method for example 1, separated absorption tower condensed water and with GC-MS.
example 5
detect and analyze absorption tower precipitation
Measure 350mL absorption tower precipitation (being below called sample No. 5), add nitric acid to regulate PH=2, at 180 DEG C evaporation except anhydrating until residual 20mL solution only in container; Be cooled to 70 DEG C and add potassium hydroxide regulate PH=10, connect rotary evaporator distillation for the first time condensation collection cut at 300 DEG C, until be cooled to 80 DEG C after no longer producing dense white flue gas in container for evaporation, with 5mL water washing bottle wall and inorganic salts, again connect rotary evaporator distillation for the second time and merging condensation collection cut at 350 DEG C, until no longer produce dense white flue gas in container.In addition, detect cut according to the method enrichment method identical with the method for example 1, separated absorption tower precipitation and with GC-MS.
example 6
detect and analyze washings
Measure 500mL washings (being below called sample No. 6), add hydrochloric acid to regulate PH=1, at 180 DEG C evaporation except anhydrating until residual 25mL solution only in container; Be cooled to 70 DEG C and add NaOH regulate PH=10, connect rotary evaporator distillation for the first time condensation collection cut at 300 DEG C, until be cooled to 80 DEG C after no longer producing dense white flue gas in container for evaporation, with 10mL water washing bottle wall and inorganic salts, again connect rotary evaporator distillation for the second time and merging condensation collection cut at 350 DEG C, until no longer produce dense white flue gas in container.In addition, detect cut according to the method enrichment method identical with the method for example 1, separated washings and with GC-MS.
example 7
detect and analyze absorption tower condensed water
Measure 800mL absorption tower condensed water (being below called sample No. 7), add hydrochloric acid to regulate PH=2, at 180 DEG C evaporation except anhydrating until residual 20mL solution only in container; Be cooled to 70 DEG C and add NaOH regulate PH=12, connect rotary evaporator distillation for the first time condensation collection cut at 300 DEG C, until be cooled to 80 DEG C after no longer producing dense white flue gas in container for evaporation, with 10mL water washing bottle wall and inorganic salts, again connect rotary evaporator distillation for the second time and merging condensation collection cut at 350 DEG C, until no longer produce dense white flue gas in container.In addition, detect cut according to the method enrichment method identical with the method for example 1, separated absorption tower condensed water and with GC-MS.
flue gas desulfurization aqueous solution preprocess method recruitment evaluation
For assessing the elimination ability of desulfuration solution preprocess method of the present invention to interference effect factor, its practical application effect is carried out to demonstration test.
Metal impurities separating effect test mg/L in the table 1 desulphurization system aqueous solution
As seen from Table 1, metal ion hardly in the desulfuration solution after pretreatment separates, shows that preprocess method practical application effect of the present invention is good, has thoroughly eliminated under desulfuration solution complex system each metal ion species to detecting the interference effect of analyzing.
the assessment of disturbing factor eradicating efficacy
By under the same conditions, to adopting the present invention to carrying out the detection analysis of spectra before and after desulfuration solution pretreatment, the practical application effect of checking invention, in order to assess the elimination of the present invention to interference effect factor and the accumulation ability to component to be measured.
Fig. 1 shows the detection spectrogram that does not adopt the flue gas desulfurization aqueous solution that the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution of the present invention processes, wherein, comprise the detection spectrogram that does not use No. 1 sample of method for separating and concentrating processing of the present invention, No. 2 samples, No. 3 samples, No. 4 samples, No. 6 samples, No. 7 samples; Fig. 2 shows and adopts the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution of the present invention to carry out detection spectrogram after treatment to the corresponding flue gas desulfurization aqueous solution of Fig. 1, wherein, comprise the detection spectrogram that carries out enrichment method, separated No. 1 sample after treatment, No. 2 samples, No. 3 samples, No. 4 samples, No. 6 samples, No. 7 samples according to the method in example 1 to 7.
By comparison diagram 1 and Fig. 2, can find out, not by the analysis of spectra more complicated of the desulfurization aqueous solution of processing of the present invention, spectrum peak is numerous (according to the preparation of desulfuration solution, including antioxidant etc., organic component is no more than 5 kinds, wherein only have 2 to 3 kinds for desulfurization organic component to be measured, therefore compose peak and should be less than 5), this be due to due to disturbing, sensitivity, resolution ratio is all lower, impurity is many and change large, cannot effectively detect and accurate qualitative identification organic component to be desulfurization, more cannot quantitative analysis.In employing the present invention carries out mensuration spectrogram after treatment to desulfuration solution, high-visible disturbance spectrum peak all disappears, the spectrum peak of desulfurization organic component to be measured is obvious, separate completely with spectrum peak, left and right, realized and effectively having detected and the target of accurate qualitative identification and quantitative assay organic component to be desulfurization.
precision test
No. 3 samples and No. 7 samples are repeated to independently pretreatment preparation detection solution and analysis mensuration 8 times according to example 3 and example 7 respectively, 8 measurement results are carried out to statistical disposition, according to relative standard deviation (RSD) assessment invention precision.The results are shown in Table 2.
Table 2 precision test (n=8) (%)
As can be seen from Table 2, RSD of the present invention is less than 3%, shows that precision is higher, has good stability, workable.
Although showing, example above adopt GC-MS to detect the desulfurization organic component content that separation and concentration goes out from the flue gas desulfurization aqueous solution, but, method of the present invention also can use the Analytical Methods of Organic Compounds such as gas chromatography, liquid chromatography, Liquid Chromatography-Mass Spectrometry to detect organic component in the cut of condensation collection, can obtain equally testing result accurately.
To sum up, the present invention carries out the pretreatment of enrichment method and separated to various aqueous sample such as absorption tower precipitation, absorption tower condensed water, washings, Analytic Tower condensed waters, then measures the content of organic component to be measured in the cut that condensation collects.Owing to having carried out separating completely with complicated sample substrate, eliminated the impact that various inorganic interfering materials are measured organic component, simultaneous altitude enrichment method organic component to be measured, greatly improved the accurate reliability and the precision level that detect analysis result.In addition, the present invention has well and widely applicability, and sample solution prepared by pretreatment meets the requirement that modern precision organic analysis instrument detects.That is to say, the present invention has eliminated the anion such as the sulfate radical that exists in original solution, inferior sulfate radical, chlorine root, fluorine root, nitrate anion, the impact that the interfering materials such as the metal cations such as iron, copper, chromium, nickel, calcium, aluminium, zinc and dust solid particle, hydrogen ion, moisture cause, and avoided the sodium or the potassium plasma that in the precipitated separation technology of former employing, bring because of alkaline reagents such as use NaOH or potassium hydroxide to cause the detection that the increase of inorganic salts concentration causes to be disturbed; Component to be measured is separated from aqueous sample matrix, in the cut that condensation is collected, only formed by the simple organic substance such as organic component to be measured or minute quantity antioxidant that is molecular conformation, do not contain any inorganic substances, therefore the needs of the organic instrument of modern precision have been met better, not only improve and detect the preci-sion and accuracy of analyzing, and greatly reduced contamination and the loss to instrument, and extend the service life of the parts such as chromatographic column, reduce the frequency of maintaining instrument.
Although described the present invention with exemplary embodiment by reference to the accompanying drawings above, those of ordinary skill in the art should be clear, in the case of not departing from the spirit and scope of claim, can carry out various amendments to above-described embodiment.
Claims (10)
1. a method for separating and concentrating for desulfurization organic component in the flue gas desulfurization aqueous solution, is characterized in that, described method for separating and concentrating comprises the following steps:
Measure the flue gas desulfurization aqueous solution and be adjusted to highly acid, then, in the system of opening wide, the flue gas desulfurization aqueous solution being evaporated to remove wherein most of moisture;
After cooling, regulate the remaining flue gas desulfurization aqueous solution to strong basicity, in enclosed system, the remaining flue gas desulfurization aqueous solution is distilled for the first time, until no longer produce dense white flue gas, obtain the first cut;
After cooling, water is injected and distills for the first time container used, wash, soak the residue in this container, in enclosed system, this container is distilled for the second time, until no longer produce dense white smog in container, obtain the second cut;
Wherein, the aqueous solution that contains desulfurization organic component of the described flue gas desulfurization aqueous solution for producing in flue gas desulphurization system running.
2. the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to claim 1, is characterized in that, the step of described evaporation is removed the moisture that accounts for the front flue gas desulfurization aqueous solution volume 80%～95% of evaporation.
3. the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to claim 1, is characterized in that, described in be adjusted to highly acid step the pH value of the flue gas desulfurization aqueous solution be adjusted to 1～3.
4. the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to claim 1, is characterized in that, the remaining flue gas desulfurization aqueous solution of described adjusting to alkaline step is adjusted to 10～12 by the pH value of the flue gas desulfurization aqueous solution.
5. the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to claim 1, it is characterized in that absorption tower condensed water, absorption tower precipitation, resin washings or Analytic Tower condensed water that the described flue gas desulfurization aqueous solution produces in the operation of absorption, parsing and resin desalination for flue gas desulphurization system.
6. the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to claim 1, is characterized in that, described evaporation is carried out at 100 DEG C～180 DEG C.
7. the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to claim 1, is characterized in that, described distillation for the first time at 200 DEG C～300 DEG C carried out.
8. the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to claim 1, is characterized in that, described distillation for the second time at 300 DEG C～350 DEG C carried out.
9. the method for separating and concentrating of desulfurization organic component in the flue gas desulfurization aqueous solution according to claim 1, is characterized in that, described in obtain the second cut step repeatedly carry out more than twice.
10. an assay method for desulfurization organic component in the flue gas desulfurization aqueous solution, is characterized in that, described assay method comprises the following steps:
Adopt method for separating and concentrating as in one of claimed in any of claims 1 to 9 to carry out separation and concentration processing to the flue gas desulfurization aqueous solution to be measured, obtain the first cut and the second cut;
Adopt at least one the first cut and second cut that directly mensuration obtains in GC-MS, gas chromatography, liquid chromatography, Liquid Chromatography-Mass Spectrometry, calculate the content that obtains desulfurization organic component in the flue gas desulfurization aqueous solution to be measured.
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| CN101397164A (en) * | 2007-09-24 | 2009-04-01 | 宝山钢铁股份有限公司 | Processing method of flue gas cooling waste water during sintered flue gas desulfurization process and use of product after processing |
| CN102359990A (en) * | 2011-07-15 | 2012-02-22 | 攀钢集团有限公司 | Pre-treatment method for liquid desulfurizer solution of flue gas, and detection method thereof |
| US20130214202A1 (en) * | 2010-11-10 | 2013-08-22 | Rainald Forbert | Preparation of an amine based solvent contaminated by the introduction of sulfur oxides |
| CN103412065A (en) * | 2013-07-25 | 2013-11-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for measuring organic amine components in flue gas desulfurization solution |
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| CN101397164A (en) * | 2007-09-24 | 2009-04-01 | 宝山钢铁股份有限公司 | Processing method of flue gas cooling waste water during sintered flue gas desulfurization process and use of product after processing |
| US20130214202A1 (en) * | 2010-11-10 | 2013-08-22 | Rainald Forbert | Preparation of an amine based solvent contaminated by the introduction of sulfur oxides |
| CN102359990A (en) * | 2011-07-15 | 2012-02-22 | 攀钢集团有限公司 | Pre-treatment method for liquid desulfurizer solution of flue gas, and detection method thereof |
| CN103412065A (en) * | 2013-07-25 | 2013-11-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for measuring organic amine components in flue gas desulfurization solution |
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