CN1312866A - Automatic regulation and control of cleansing baths - Google Patents

Automatic regulation and control of cleansing baths Download PDF

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Publication number
CN1312866A
CN1312866A CN99809555A CN99809555A CN1312866A CN 1312866 A CN1312866 A CN 1312866A CN 99809555 A CN99809555 A CN 99809555A CN 99809555 A CN99809555 A CN 99809555A CN 1312866 A CN1312866 A CN 1312866A
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analysis
sample
result
content
analyze
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伊波尔亚·巴蒂克－希姆勒尔
沃尔夫岗·克利
维尔纳·奥皮茨
卢茨·胡泽曼
贝恩德·申泽尔
彼得·屈姆
德特勒夫·博恩霍斯特
阿努尔夫·维勒斯
赫伯特·普德巴赫
汉斯－维利·克林
赖纳·莫尔
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
    • G05D21/00—Control of chemical or physico-chemical variables, e.g. pH value
    • G05D21/02—Control of chemical or physico-chemical variables, e.g. pH value characterised by the use of electric means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1826—Organic contamination in water
    • G01N33/1846—Total carbon analysis

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  • General Chemical & Material Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Immunology (AREA)
  • Food Science & Technology (AREA)
  • Automation & Control Theory (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

The invention relates to a method for controlling cleansing baths, characterized in that at least two of i)tenside contents, ii)inorganically and/or organically bound carbon load, iii)alkalinity, are measured in a program-controlled manner and in that a)depending on the result of the measurements additional components are added and/or one or more bath maintenance measures are initiated and/or b)the results of the measurements and/or data derived from the measurement results are transmitted to at least one remote destination which is situated in a room different from the one housing the device for carrying out the above measurements.

Description

The automatic monitoring and the control of cleaner bath
The present invention relates to a kind of automatic monitoring and the cleaner bath of method, particularly metal-processing industry of control cleaner bath or the cleaner bath in the automobile making.Core content of the present invention is, automatically and in programme controlled mode analyzes the controlled variable of at least two kinds of selections, and the higher apsis of the result that will analyze and/or the data transmission to that derived by analytical results and cleaner bath direct neighbor.Result according to analyzing further analyzes and/or bathes treatment measures and can carry out or carry out according to apogean requirement in programme controlled mode.In addition, the result according to analyzing can or compare measurement as required in programme controlled mode.Here, the higher apsis can be positioned at, for example, and a place of the control center of advanced processes Controlling System, factory's cleaner bath or factory outside.
Metal parts is a kind of routine work in the metal-processing industry in the cleaning of its further first being processed.Metal parts may be contaminated, for example, and by pollutions such as pigment dirt, dust, scrap metal, anti-corrosive oil, cooling lubricant or denaturants.In further first being processed, for example particularly before corrosionproof protection is handled (for example, phosphatization, chromaking, anodizing, with the complex fluorides reaction etc.) or japanning before, these impurity substances must be removed by suitable scavenging solution.Spray method, immerse method or their combination treatment can be used for this purpose.
Industrial cleaning agent in the metal-processing industry is generally alkalescence (scope of pH value is on 7, for example between 9-12).Their basal component is alkali (alkali metal hydroxide, carbonate, silicate, phosphoric acid salt, borate), and nonionic and/or anion surfactant.Usually contain complexing agent (gluconate, poly-phosphate, amino acid salts as additional ancillary component scavenging solution; as edetate or nitrilotriacetic acid(NTA) salt; phosphonate is the salt of hydroxyl ethane di 2 ethylhexyl phosphonic acid, phosphinylidyne butane tricarboxylic acid or other phosphonic acids or phosphono-carboxylic acids for example; carboxylate salt, alkanolamine and froth suppressor that resist for example contains 6-12 carbon atom for example contain the sealing end group and the alkoxy compound or the alcohol of 6 to 16 carbon atoms are arranged in alkyl group.If cleaner bath does not contain anion surfactant, also can use cats product.
As nonionogenic tenside, scavenging solution generally contains the alcohol that 6 to 16 carbon atoms are arranged or ethoxy compound, propoxylation compound and/or the ethoxy compound/propoxylation compound of alkylamine in its alkyl, wherein also can contain the sealing end group.Alkyl-sulphate and alkylsulfonate are widely used as anion surfactant.Also can use alkylbenzene sulfonate, although be disadvantageous from environmental point of view.Contain at least one alkyl and 8 or the kation alkyl ammonium compound of more carbon atoms be especially suitable for use as cats product.
Alkali in the cleaner bath has promoted its cleansing power.For example, therefore the saponifiable impurity of their saponification as fat, and make that these impurity are soluble in water.They have also promoted insoluble dust particles to remove from the metallic surface, and they absorb OH by the metallic surface -Ion makes it be the negative electricity state, therefore plays the Coulomb repulsion effect.Fan Ying result is like this, and also traction goes out again, and alkali can consume, so cleaning performance can slacken in time.Therefore, the basicity in the cleaner bath is checked at specified time traditionally, if desired, replenish the solution that contains activeconstituents or upgrade cleaner bath fully.This inspection can manually carry out or use a cover autotitrator to carry out in the locality.The measurement of basicity here uses the strong acid titration to carry out usually.Operator serve as that the basis is estimated basicity and started required measure with the consumption of acid, as replenishing or renewal of solution.This traditional method requires operator must be positioned near the cleaner bath when checking.Need the interval of monitoring short more, the operator that required monitoring is measured are just many more.
EP-A-806244 discloses a kind of method of pH value of automatic analytical solution, and adds acid or alkali automatically when deviation takes place.In this document, its target is that the pH value with liquid flow remains on the preset value.The acid base titration reaction does not take place in this method.Need field monitoring to clean factory's task performance here.It is impossible interfering pH pH-value determination pH or input measure from afar.
In previous technology, people use colored indicator to containing aqueous cleaning, analyze as the nonionogenic tenside in the cleaner bath.Normally can add in the sample from scavenging solution, take out with the reagent that nonionogenic tenside forms colored complex a kind of.This colored complex preferably is extracted in the organic solvent that is immiscible in water, then with the absorbance value under the photometric determination specific wavelength.For example, the tetrabromophenolphthalein ethyl ester can be used as the reagent that colored complex forms.Before being extracted into organic solvent, preferably be extracted in the hydrochloric ether, the buffered soln of pH7 is joined in this scavenging solution.
People also analyze nonionogenic tenside in the presence of ionogenic surfactant.Here, ionogenic surfactant is by ion-exchanger and sample separation.Last bonded nonionogenic tenside is analyzed by the specific refractory power of the solution of outflow exchange column in the ion-exchanger.Preferably, specific refractory power is measured as the function of elution time, measures the partial product score value of deviation of the refractive index curve of pure elutriant, and this deviation integration value and correcting measuring income value are compared.
But in addition, less accurate method relates to the extremum of measuring specific refractory power and by the mensuration surfactant content of comparing with calibration curve.
Negatively charged ion in the aqueous solution and cats product can be measured, for example, and by volumetry " Hyamin 1622 ", (Hyamin Be chlorination N-benzyl-N, N-dimethyl-N-(1,1,3,3-tetramethyl--butyl)-phenoxy group-ethoxyethyl ammonium) and the terminal point potentiometry measure.For this purpose, the sodium lauryl sulphate of known quantity joins in the sample, uses the Hyamin titration, uses a kind of ion-sensitive electrode to measure titrating terminal point.
In addition, the also available chlorination 1 of anion surfactant, 3-didecyl-glyoxal ethyline salt titration determination.A kind of electrode that has ion sensitive membrane is used as detector.Electropotential is a function of measuring ionic concn in the solution.
According to the result that this tensio-active agent is analyzed, this analysis relates to a large amount of personal expenditures, and factory personnel is added one or more auxiliary compositions in scavenging solution.Therefore this method needs the operator at least should be at the factory scene when tensio-active agent is analyzed.Therefore, it is a kind of method that consumes a large amount of manpowers, particularly under the situation of multistage operations.The destination file of quality control and quality-guarantee needs extra-pay.
The result of clean is that the fouling products composition of removing from the handled thing surface just accumulates in the scavenging solution.The pigment dust can produce the content of inorganic carbon.Anti-corrosive oil, cooling lubricant or modification agent as the lubricating grease of brushing and/or dissolved or the organic coating or the sticky object of flush away, produce the content of total organic carbon in the scavenging solution.Because of total organic carbon mainly exists with the form of mineral oil, mineral fat, or come from the oil and the fat of animal or plant, generally be abbreviated as scavenging solution " fat content ".Such oil and fat main form with emulsion in scavenging solution exists.Yet the oil and the fat that come from animal or plant may be at least in part by the alkaline cleaning fluid hydrolysis.Then, hydrolysate just can occur in scavenging solution with the dissolved form.The content of TOC is too high in the scavenging solution, just can not guarantee that scavenging solution can clean to the grease on the parts degree of requirement.Or exist the grease that has washed and to come back to the danger that cleaning part gets on.Therefore, must guarantee that the fat content in the scavenging solution is lower than a critical maximum value, this critical maximum value by the further use of cleaning part and scavenging solution become to assign to determine.Under the situation of high lipid content, can increase the content of tensio-active agent in the scavenging solution, with the dissolving power of the fat that increases scavenging solution.Or be that the fat content that reduces in the scavenging solution can start the bath treatment measures.In any case, in the higher limit of in advance fat content, all must start and bathe treatment measures.Under the simplest situation, all or part of the draining of scavenging solution meeting, and by fresh scavenging solution replacement or additional.Yet, owing to can produce waste water and need clean water, therefore to from scavenging solution, separate fuel-displaced and fat as possible, and continue to use these scavenging solutions, also can add activeconstituents.For reaching this purpose, suitable device in the prior art can be used as separator or membrane filter appts.
At first, based on the result who cleans, estimate the cleaning efficiency of scavenging solution routinely intuitively.The operator of factory estimate cleaning efficiency and implement desired measure, as the renewal that replenishes or bathe of bathing.The universal method of present this routine requires operator near must being positioned at cleaner bath the detection time that requires.The timed interval of wish detecting is short more, requires staff's the workload of visual evaluation just big more.
In the former technology, people proposed cleaner bath single controlled variable can with programme controlled mode analyze and with the result transmission analyzed to the higher apsis, according to the result who analyzes, by higher apsis start-up control technology and/or bathe treatment technology or also can automatically and in programme controlled mode start.The method of surfactant content has description in a kind of automatic monitoring and the control aqueous cleaning in H3267, the automatic analysis method that contains carbon content in the aqueous cleaning has description in H3268, the method for monitoring and control cleaner bath by the basicity analysis automatically has description in German patent application DE19802725.7.The present invention is based on these methods, and interrelated with these methods.In three files mentioning, described the mode of implementing single analysis in detail in the above.Therefore it is of the present invention open that the content of these three files also can be expressed as formation.
The place that an object of the present invention is make to place cleaner bath does not need operator and realizes monitoring to cleaner bath, preferred control.
Preferably, the measuring apparatus that is adopted can self-check and self calibration, and can be when breaking down to the higher apsis signal that gives the alarm.In addition, preferably it can put performance and the measurement result of checking measuring apparatus in distant.In addition, it can be put measuring process in distant and bathe treatment measures and intervene.By the expectation Long-distance Control, the expenditure of carrying out the operator of cleaner bath bath monitoring and bath control can reduce.Here provide and analyze two parameters at least, analysis cleaner bath performance and/or dirt amount by these parameters just can detect.So that a plurality of measurands are taken into account, just can start than when only knowing a single-measurement variable, more there being purpose to bathe treatment measures.
This purpose can realize by the method for monitoring cleaner bath, it is characterized in that two kinds in the following at least analysis can carry out in programme controlled mode:
(ⅰ) analysis of surfactant content;
(ⅱ) analysis of inorganic carbon and/or total content of organic carbon; With
(ⅲ) basicity analysis; And
(a), can start adding and/or one or more bath treatment measures of extra ancillary component according to analytical results;
And/or
(b) result that will analyze and/or the data transmission that derived by the result who analyzes are at least one higher apsis, and this higher apsis is positioned at the different room of device with the realization analysis.
For example, surfactant content and total content of organic carbon and/or inorganic carbon content can be analyzed.Or surfactant content and basicity can be analyzed.Or total content of organic carbon and/or inorganic carbon content and basicity can be analyzed.Yet, preferably analyze all three parameters to obtain the profile completely of cleaner bath state.
In the file that a kind of special mode is mentioned detailed description is arranged in the above, in this ad hoc base, these analyses can be carried out in programme controlled mode.These analyses can be carried out or also successive analysis one by one substantially simultaneously.
The result who analyzes can be stored on the data carrier.And these data also can form the basis of further calculating.Result who analyzes or further result calculated are transferred to higher apsis (promptly arriving place far away), put it in distant and are stored on the data carrier once more and/or output.Method said " higher apsis " or " place far away " among the present invention not can be understood as not the place that directly contacts with cleaning solution, perhaps are less than the place that visually contacts with treatment soln at least.For example, the higher apsis can be central process control system, and it is the part that metal part surface is handled whole process, as its monitoring of a subtask and control cleaner bath.Should " higher apsis " also can be an observation control center, can control and monitor whole process by it, and it be to be positioned in the room different with cleaner bath.But, should " higher apsis " also can be the place that is positioned at outside the factory that is provided with cleaner bath.Adopt this mode, make the expert place oneself in the midst of outside the factory that wherein is provided with cleaner bath, just can check and control scavenging solution.Consequently, the expert has reduced widely time of placing oneself in the midst of the cleaner bath site.
Analytical results and control command are transmitted by the suitable data circuit, are known in the former technology.The output of analytical results or further calculate is interpreted as and the result is delivered to a super process control system or shows on a screen and the mode that can understand with people prints.Local or the output result's of display result place can be corresponding to previously defined " higher apsis ".Preferably the result with single analysis is stored on the data carrier, at least can be subsequently calculate these individual datas at interval at the fixed time, for example with the form of quality assurance inspection.Yet analytical results does not need so direct output or is stored on the data carrier.On the contrary, the result of these analyses can be directly as the basis of further calculating, and these further result calculated can show or store.For example, under the situation of instantaneous content, trend that can display density and/or its relative variation.Also instantaneous concentration can be converted into " percentage ratio of demarcating concentration " or " percentage ratio of peak concentration ".
Here, the higher apsis can be positioned at the place from least 500 meters far away in the device of implementing to analyze.Under the particular case, it also can be positioned at the outside of the factory of monitoring cleaner bath.Therefore, the higher apsis monitoring need not operator directly near cleaner bath.
Here, it provides, when the data that obtain the new result who measures and/or derive by measurement result, automatically the result that will analyze and/or by the data transmission of analytical results derivation to the higher apsis.And it can provide according to apogean requirement, and the data transmission that derives with the result that analyzes and/or by analytical results is to the higher apsis.
On the one hand, single analysis can repeat at interval at preset time.And it also provides a kind of time variable control, and when having than big difference between twice successive analysis result, the timed interval that single analysis repeats is just short more.Here it also provides, and when first analysis of measuring variable produces predetermined threshold value maybe when the predetermined variation value generation between twice analysis of this mensuration variable, starts second analysis of measuring variable.Like this, the beginning of mensuration variable analysis can be depended on the analytical results of another mensuration variable.
In other words: the method among the present invention can realize in such a way, promptly in programme controlled mode, when be selected from analysis (ⅰ), (ⅱ) and (ⅲ) in the 1st kind of result that analysis provides surpass predetermined maximum value be lower than predetermined minimum value or departed from this 1st kind of analysis before result's predetermined minimum value the time, be selected from analysis (ⅰ), (ⅱ) and (ⅲ) in second kind of analysis just begin.
Very natural, it also provides according to apogean requirement carries out analytical work.
In a kind of embodiment of the present invention, the method among the present invention is characterised in that in programme controlled mode carries out:
(ⅰ) analysis of surfactant content is performed such:
(a) sample of taking-up pre-determined volume from aqueous cleaning;
(b) if desired, from sample, isolate solid.
(c) if desired, in ratio predefined or that determine according to the initial analysis result, the dilute with water sample, and
(d) surfactant content is measured by selective adsorption, electrochemistry, chromatographic process, by being diverted to volatile compound, separate sucking-off and detect these volatile compounds and measure, or by adding reagent, these reagent can change the reaction between sample and electromagnetic radiation, its change value and surfactant content are proportional, measure the variation of this reaction and measure.
The another kind of embodiment of the inventive method is characterized in that:
(ⅱ) the analysis follow procedure control mode of inorganic carbon content and/or total content of organic carbon realizes;
(a) sample of taking-up pre-determined volume from aqueous cleaning;
(b) if desired, from this sample, isolate solid matter and/or spare matter;
(c) if desired, according to the ratio of prior setting or the ratio of determining according to the initial analysis result, dilute with water sample;
(d) with organic carbon and/or total organic carbon amount in the known methods analyst sample.
According to the form of step (d), can analyze inorganic carbon content (IC), total content of organic carbon (TOC), or their sum total carbon content (TC).Particularly the ratio of oleophilic substance can detect in the cleaner bath, if as a part of analyzing, use a kind of extracting process can only make oleophilic substance extract from cleaner bath and analyze in step subsequently.
Another kind of embodiment of the present invention is characterized in that:
(ⅲ), analyze the basicity of cleaner bath in programme controlled mode by carrying out the acid-alkali reaction with acid:
(a) sample of taking-up pre-determined volume from scavenging solution;
(b) if desired, from sample, isolate solid matter;
(c) be to analyze free alkali and/or total alkali, make one's options;
And
(d) sample comes titration or acid as initial substance with adding acid, comes titration with sample.
In each sampling procedure (a), the volume of sampling can for good and all be arranged in the program of control section of measuring apparatus used in the method.Preferably, the big I of sample volume is changed by the higher apsis.In addition, sequence of control can be designed to such mode, and it can make the volume of specimen in use determine according to the previous result who measures.For example, the substances content that will analyze in the scavenging solution is low more, and it is just big more that sample volume is selected.Therefore the accuracy of analyzing has obtained optimization.
Between sampling and practical measurement, might in each optional step (b), from sample, remove solid matter.This only contains under the situation of hanging down amount of solid in scavenging solution is unnecessary.Yet under the very high situation of amount of solid, the valve of measuring apparatus may begin blocked, and transmitter can be contaminated.Therefore, solid matter is removed in suggestion from sample.This step can be undertaken by automatic filtration, perhaps, also can use centrifugal or swirler.
Before the parameter of selecting began to analyze, if desired, sample can dilute by water, and thinning ratio is to preestablish or determine according to the result of initial analysis.In step (d), actual analysis will be carried out according to different methods, will describe these methods below in detail.
Under the simplest situation, the method among the present invention is work like this, and specific analysis repeats after the preset time interval.Preset time will can comprise the timed interval of any needs of the scope that several minutes arrives several days according to cleaner bath operator's requirement decision at interval.In order to ensure the quality of products, preferably preset time at interval can, for example, between 5 minutes to 2 hours time, changed.For example, a kind of measurement can be carried out once in per 15 minutes.
Yet the method among the present invention can realize in such a way that also the result's of twice successive analysis difference is big more, and the particular analysis multiple timed interval is short more.The Controlling System of the method among the present invention thereby the timed interval that can decide in its sole discretion between each analysis are to reduce or increase.Usually, under discrepant situation between the successive analysis, select time program at interval must be arranged in the Controlling System in advance.
Here, two or three different analyses (ⅰ), (ⅱ), (ⅲ) needn't always carry out by this order one by one continuously.But might a kind ofly analyze than another kind analysis carry out more frequent.In practice, parameter is than coming to this under the faster situation of the variation of another parameter.For example, frequent many of the analysis that the content analysis of tensio-active agent may specific alkalinity.Or factory is programmed to, and whether decision begins the result that first analysis is depended in another analysis.For example, it can provide and surpass predetermined limit value up to the cleaner bath carbon content and just begin the analysis of basicity.Perhaps basicity can only when having surpassed lower value, the content of cleaner bath tensio-active agent analyzed.By this way, for example, can select is only to add surfactant component or also can add the component composition in cleaner bath.
And the method among the present invention can realize by this way that also specific analysis can be carried out in desired time according to external demand.By this way, for example,, just can start surfactant content, basicity and/or fat content in the monitoring cleaner bath immediately if in treating processes subsequently, find out defective in qualityly.Therefore, select the mensuration of situational variables to carry out (regular time at interval) or the mode of incident control is carried out (depend on whether change or response external requires) in the mode of time control.
(ⅰ) analysis of surfactant content
Method among the present invention can be designed to like this, and the tensio-active agent that will analyze its content in the cleaner bath is a nonionogenic tenside.The analysis of this surfactant content can be carried out like this, (d) adds a kind of reagent in step, it can change reacting to each other between sample and electromagnetic radiation, and the content of this change and nonionogenic tenside is proportional, and then measures the changing value in this reaction.
For example, this reagent can be made up of the complex compound of two kinds of substance A and B, and nonionogenic tenside replaces substance B and combines with substance A from complex compound, and therefore the fluorescent characteristic of substance B or color can change.For example, substance B may by a kind of fluorescent substance or a kind of can with for example, form as the dyestuff that the dextran or the starch of the example of substance A forms complex compound.As the composition of this complex compound, substance B has special color or fluorescent characteristic.If this material replaces from complex compound, these characteristics will change.By measure light absorption or fluorescent radiation, the substance B that just can determine how many ratios does not form complex compound with A.The nonionogenic tenside of adding is depended in the selection of substance A here, and substance B is substituted out from complex compound, and forms the complex compound that replaces with nonionogenic tenside.Yet it is proportional to be replaced the amount of nonionogenic tenside of the amount of the B that and adding by A from complex compound.The photoabsorption that causes by the amount that discharges B or the variation of fluorescent characteristic just can be extrapolated the amount of the nonionogenic tenside of adding.
For example, the salt that contains the cationic dyestuff of tetraphenyl acid anion can be used as this reagent.Nonionogenic tenside can replace dyestuff when forming cationic complex when adding barium ion in this salt and with barium ion from this salt.This method that nonionogenic tenside is converted into the complex compound of positive ion and therefore makes them be easy to react is called " activation " of nonionogenic tenside in the literature.Vytras K., Dvorakova V and Zeeman I are described this method in " Analyst " (1989,114, P, 1435 ff) as an example.The amount of the amount of the cationic dyestuff that discharges from reagent and the anion surfactant of existence is proportional.If variation has taken place absorption spectrum when dyestuff discharges, the amount that dyestuff discharges just can be analyzed with the photometer device of a suitable absorption wave band.
If a kind ofly only be only soluble in salt with the cationic dyestuff of the not miscible organic solvent of water as reagent, and the dyestuff that discharges itself is water-soluble and cause the water colour developing, and this analytical procedure just can be simplified.Usually and above-mentionedly also be fine on the contrary: use a kind of water-soluble salt of organic dye, and the dyestuff that discharges is only soluble in organic phase.By the exchange of released dye and nonionogenic tenside, the dyestuff of release be extracted into other one mutually in, this dyestuff just can carry out photometric analysis with a kind of simple method.
This analytical procedure also is suitable for the analysis of cats product.Because these cats products itself are positively charged, above-described just the activation with the barium positively charged ion there is no need.
In addition, reagent can comprise a kind of material, and with anion surfactant, itself forms a kind of complex compound, and this complex compound has different colours or fluorescent characteristic to free reagent.For example, reagent can be colourless in the light zone, and it and nonionogenic tenside bonded complex compound absorb electric and magnetic oscillation in the light zone, thereby has color.Perhaps, the maximum value of the photoabsorption of binding reagents is not that color is different from the color with the complex compound of nonionogenic tenside.Yet this reagent also can have specific fluorescent characteristic, can change this fluorescent characteristic when it combines the formation complex compound with nonionogenic tenside.In all cases, by measuring in the photoabsorption of measuring wavelength or by measuring fluorescent radiation, just can analytical reagent and the concentration of the complex compound of nonionogenic tenside, thereby can analyze the concentration of nonionogenic tenside itself.
Preferably, add a kind of reagent in step (d), with nonionogenic tenside, form a kind of complex compound, this complex compound can be extracted in a kind of water-fast organic solvent.Then, nonionogenic tenside and the complex compound that adds reagent are extracted in the water-fast organic solvent.This process may be by the mixed process influence of two-phase intensive, the influence of for example being vibrated or preferably stirring.After finishing this extraction step, it is mixed to stop two-phase, and such one separately enters the aqueous solution mutually and organic phase occurs.If desired, the degree that is separated can be monitored by suitable method, for example specific conductivity analysis or by photoabsorption or scatterometry turbidity.
Back to back is the practical measurement of nonionogenic tenside content.For this purpose, the organic phase that contains the complex compound of nonionogenic tenside and interpolation reagent is exposed in the electromagnetic radiation, this electromagnetic radiation and the complex compound that is dissolved in the organic phase interact.For example, visible or uv-radiation can be used as electromagnetic radiation, analyzes by the absorption of the complex compound of nonionogenic tenside and interpolation reagent.Yet, also can use, the complex compound of for example a kind of reagent itself and nonionogenic tenside provides the characteristic signal in a kind of nuclear resonance or the electron spin resonance measurement.Sort signal intensity shows as slackening of electric and magnetic oscillation at certain frequency band (absorption), can be relevant with the concentration of complex compound.Without assimilation effect, launching effect also can be used for analytical concentration.For example, can select a kind of reagent, it and the nonionogenic tenside complex compound in organic solvent absorbs the electromagnetic radiation of specific wavelength and the intensity of emission is measured in the electromagnetic radiation of the bigger wavelength of emission conversely.An example of this respect is, when sample during with visible light or ultraviolet radiation, and the mensuration of fluorescent radiation.
On principle, followed by finishing of being separated in the container of implementing to be separated, organic phase and electromagnetic radiation interactional mixed can generation.Yet,,, preferably take out and transfer in the actual measurement device through a pipeline to organic phase or its part according to the interactional measuring method of analyzing between organic phase and the electromagnetic radiation.In such mode, particularly can provide suitable cuvette to be used for measuring.Therefore, one of the present invention preferred embodiment is that according to step (f), organic phase is isolated and forwarded to the measuring apparatus from aqueous phase.To this separation of organic phase, the water-fast organic solvent of ad hoc proposal is to contain to have the Halogen solvent bigger than the density of water.Be separated finish after, organic phase is positioned at the Lower Half of container, just can take away from the bottom.
For example, methylene dichloride or high boiling point halohydrocarbon, particularly Chlorofluorocarbons (CFCs), such as, Freon 113 uses as the Halogen solvent.These solvents should be handled after use according to the local law regulation.Because, may expend greatlyyer like this, might handle again used solvent, for example, handle with activated carbon treatment and/or distillation, be reused for the mensuration process.
Of the present invention one preferred embodiment in, add a kind of material that in organic phase, forms color reaction with nonionogenic tenside.Measurement is reacting to each other between organic phase and electromagnetic radiation in the photoabsorption of predetermined wavelength.A kind of traditional photometer is suitable for this measurement.For example, tetrabromo-phenolphthalein ethyl ester just can be used as colouring reagents.In this case, pH is that 7 buffer system should be added in the sample of aqueous cleaning.The sort buffer system can by, for example, the aqueous solution of biphosphate and hydrophosphate is formed.Here, a kind of preferred operation amount that is buffered soln will surpass the amount of the scavenging solution sample that contains tensio-active agent significantly.
When tetrabromophenolphthalein ethylester was used as developer, in step (g), the measurement of photoabsorption was preferably carried out at the 610nm wavelength.
3,3,5, the 5-tetrabromophenolphthalein ethylester is as in the preferred implementation of developer, and the content of nonionogenic tenside can be analyzed as follows:
With 100 milligram 3,3,5, the 5-tetrabromophenolphthalein ethylester is dissolved in 100 milliliters of ethanol, the preparation indicator solution.By being that commodity buffered soln 200 milliliters (potassium primary phosphate/Sodium phosphate dibasics) and 500 milliliters of termolecular Klorvess Liquids of 7 are mixed in 1000 ml waters with pH, preparation buffered soln.
For carrying out this analysis, begin to get 18 milliliters of buffered soln in a suitable containers.In this container, add 2 milliliters of indicator solutions again.The sample solution that adds 50 microlitres again.This mixed solution stirred 3 minutes, added 20 milliliters of methylene dichloride then.Miscellany in the container is fierce mixed one minute then.Be separated etc. pending, possible, for example, wait 20 minutes.Remove organic phase then, at 610nm wavelength place photometer measurement.For example, a 10mm cuvette is suitable as to analyze and uses cuvette.The content of tensio-active agent determines by comparing with typical curve in the sample solution.
Analyze if the content of tensio-active agent is too little and to become unreliablely, just can increase the sample volume that is used to measure.Photoabsorption occurs in more than 0.9 if the content of tensio-active agent is too high, suggestion dilute sample before mensuration.
No matter which type of method of selection is calibrated by the surfactant soln with concentration known, just can set up and store the concentration of nonionogenic tenside and the dependency between the measure signal intensity in advance.When measuring photoabsorption, correction may be by suitable coloured glass influence.As optionally, before proofreading and correct, surfactant content can be extrapolated or calculate by reacting to each other of accumulation and replication and electromagnetic radiation repeatedly by the tensio-active agent/reagent complex compound that adds concentration known in the sample.
As an alternative, with a kind of interaction of electromagnetic radiation of reagent, this reagent combines with nonionogenic tenside or is replaced from complex compound, just can analyze the content of nonionogenic tenside with chromatography.Any oil that may exist in the sample for this purpose, and fat are at first preferably removed.This possibility, for example, the absorption agent influence that is used.With this sample, optionally contain ionogenic surfactant then, transfer to negatively charged ion-and/or cationic exchange coloum, preferably with the form of high pressure/liquid-phase chromatographic column.The concentration of nonionogenic tenside in the solution does not contain ionogenic surfactant, flows out from exchange column, preferably by the refractive index analysis.Here external standard method is preferably used in quantitative analysis.Mensuration is relatively to carry out by the solvent phase that contains the material that will analyze in neat solvent in the reference cell and the detectors measure pond.Water or water-methanol miscellany are as solvent.
Before a series of mensuration of beginning, similar HPLC ion exchange system must proofread and correct and also detector in reference cell must be with solvent washing 20 minutes.The solution of the different concns of the nonionogenic tenside of analyzing is used for calibrating.Calibration solution and sample solution must outgas in ultrasonic bath, for example,, outgas 5 minutes before similar HPLC system at sample introduction.Because specific refractory power detects the sensitivity problem to the different solvents quality, the degassing of saying previously is extremely important.
If added methyl alcohol before sample solution is transferred to similar HPLC ion exchange column, insoluble salt can precipitate.These throw outs should filter with micro-filtration before sample is delivered to the HPLC system.
In the off-line analysis of the unsulfonated composition of this method in organic sulfate or sulfonate (DIN EN 8799) is known.
Following method also is suitable for the analysis of nonionogenic tenside: nonionogenic tenside decomposes with hydrogen halide, preferably uses hydrogen iodide, so form volatile alkyl halides thing, preferably haloalkane.Flow in the sample by blowing a gas, the volatility haloalkane is purged out and is detected with suitable detector.For example, electron capture detector just is fit to do this analysis.This method is known as the laboratory characterization method (DGF standard method H-III 17 (1994)) that fat alcohol ethoxyl compound detects.
Tensio-active agent also can be an anion surfactant.Its content in sample solution is analyzed in step (d), preferably uses electrochemical method.For this purpose, and then the change of the electromotive force of suitable potential electrode takes place with suitable reagent titration in anion surfactant after the titration.
For example, people can carry out by this way, and the pH value of sample is fixed between the 3-4, are preferably 3.5, and sample carries out titration with a titration reagent in the presence of the ion selectivity membrane electrode, the variation of potential electrode electromotive force.The sensitivity of this method can improve in the sample that adds the alcohol that contains 1 to 3 carbon atom, preferably contains methyl alcohol, chlorination 1, and 3-didecyl-glyoxal ethyline salt is preferably used as titrating solution.A kind of ion selectivity membrane electrode preferably has the PVC film, as potential electrode.Such electrode is known as " highly sensitive electrode ".A kind of silver electrode is preferably used as reference electrode.Interact between the ion in ionophore that contains in the PVC film and the mensuration solution that will analyze, the electromotive force current potential has just formed.This interaction, with a kind of form of balanced reaction, the ion that causes measuring shifts to film from measure solution, therefore, has formed potential difference at mensuration solution/membrane boundary.This potential difference can be carried out potential measurement (no current ground) with reference electrode, and the amount that ion is moved on the film from mensuration solution is relevant with concentration.The dependency of measuring between ionic concentration and the current potential can be described with Nernst (this spy of energy) equation in theory.Yet, owing to have interference, preferably calibrate by reference solution, measure the dependency between electrode potential and the mensuration ionic concn.
Except anion surfactant, also can analyze the cats product in the scavenging solution that to monitor.The method that is fit to the analysis of anions tensio-active agent also can be used to analyze cats product.And in the method, analyze and also realize by electrochemistry: the sodium laurylsulfonate of a predetermined amount joins in the sample, sample arquad Hyamin (N-benzyl-N, N-dimethyl-N-4 (1,1,3,3-tetramethyl--butyl) benzene oxygen-ethoxy second ammonium chlorine) titration, and titration end point is measured with an electrode to the ionogenic surfactant sensitivity.
Except previously described method, certain methods, wherein SURFACTANT ADSORPTION is measured the influence of the top coat of tensio-active agent on a suitable surface, just is fit to the analytical table surface-active agent.When the tensio-active agent top coat when saturation limit is following, can think proportional with surfactant content, after suitable correction, the content of the tensio-active agent in the sample solution can be calculated out by the change that scribbles the tensio-active agent surface properties.
For example, tensio-active agent can be adsorbed on the surface of oscillating crystal, measures the change of the oscillation frequency of oscillating crystal.Another method includes SURFACTANT ADSORPTION on the pretreated optical semiconductor of the process of any appropriate surface.This will cause the change of light from the specific refractory power of optical semiconductor medium transmission towards periphery, and the change that causes the light conductivity of optical semiconductor self.According to specific refractory power, the light in the optical semiconductor can be attenuated in various degree, perhaps, is losing fully under the refractive situation, does not have light to display fully at the end of optical semiconductor., just can measure the degree of optical semiconductor surface-coated tensio-active agent, thereby can measure the content of tensio-active agent in the surrounding medium by terminal light intensity that penetrates of optical semiconductor and the light intensity that begins to enter optical semiconductor by relatively.The forfeiture of total reflection occurs in a specific threshold values of surfactant content, similarly can be used for characterizing the cleaner bath surfactant content.
ⅱ) carbon quantitative analysis
The method of describing in detail among the available German patent application H 3268 of the analysis of inorganic carbon and/or total content of organic carbon is carried out.Before beginning this parameter analysis, the even quality sample of suggestion for example, passes through high degree of agitation.This can make the organic impurity homogenizing that may exist with the form of thick oil or fat granule and well distribute.
If desired, in step (c), with sample with specific ratio dilute with water.This ratio can be a fixed, but can change from the higher apsis.Certainly, Dilution ratio also can be determined according to the result who analyzes in advance of inorganic carbon and/or total organic carbon amount.Can guarantee that like this carbon content in the sample solution is located in the optimized analysis scope that allows in the method that is adopted.
In step (d), inorganic carbon and/or total organic carbon can be analyzed like this, for example, and by it is converted into CO 2And the CO that measure to form quantitatively 2And mensuration inorganic carbon and/or total organic carbon amount.
Method by oxidation changes into CO with carbon 2Of course, for example, undertaken by the burning in the gas phase under comparatively high temps.Comparatively high temps preferably is higher than about 600 ℃ during burning, for example about 680 ℃.Preferably, burning is to carry out under the effect that catalyzer is arranged in reaction tubes with air or oxygen.Appropriate catalyst has, and for example, metal oxide containing precious metals or other metal oxide are as vanadate, vanadium oxide, chromic oxide, manganese oxide or ferric oxide.Be deposited on also useful as catalysts of platinum on the aluminum oxide or palladium.This process directly provides a kind of CO of containing 2Burning gas, CO wherein 2Determination on content is as described below.
Except burning in gas phase, another kind of method is by the wet-chemical means carbon to be converted into CO 2Here, the extensive chemical oxygenant of the carbon in the sample as hydrogen peroxide or persulphate, carries out oxidation.If desired, this wet-chemical oxidizing reaction also can use the catalyzer and/or the ultraviolet radiation of type that the front is chatted to quicken.In this case, preferably with air-flow from sample, carry out acidifying in case of necessity, the CO that discharge to form 2So that it is carried out quantitative assay.With carbonate or CO 2The carbon that form exists also can detect.
No matter which kind of adopts produce gaseous state CO 2Method, can come quantitative assay CO by a kind of in the following method 2When the amount of known sample, from then on inorganic carbon and/or total organic carbon just can calculate in scavenging solution.In addition, adopt predetermined gain factor, if there is no inorganic carbon or remove before this, the result of analysis just provides with the form of fat content in every liter of scavenging solution.
Diverse ways can be used for measuring the CO in the resulting air-flow in the prior art 2Content.For example, this gas can pass through an absorbent solution, and for example, the weight that absorbent solution increases just can be measured out.For example, potassium hydroxide aqueous solution absorbs CO 2Form salt of wormwood and just be suitable for this purpose.Except the increase of measuring weight, CO can absorbed 2The method of the change of the electric conductivity in the mensuration absorbent solution of back or the change of its residual basicity is determined the content of carbon.
The CO that forms 2Can absorb by suitable solid, measure the weight that solid increases.For example, soda-asbestos just is suitable for this situation.Certainly, when they use up and no longer can absorb CO 2The time, just be necessary to replace absorbent solution and solid absorbent.
But,, come CO in the quantitative assay gas by measuring infrared absorption for the process of automatic operation 2Content is fairly simple.The mensuration of infrared absorption can, for example, be 4.26 μ m at wavelength, corresponding wave number is 2349cm -1Shi Jinhang.Can carry out the burning of sample and the device of infrared absorption measurement is known in the prior art.The TOC system of Shimadzu company is exactly an example.
For to combustion gases and from sample the CO in the expellant gas 2Content carries out photometric analysis, not only can use the infrared spectrometer of chromatic dispersion operation, also can use dispersionless photometer.These be exactly known " NDIR device ".Such device exists, and for example, narration is arranged among the DE-A-4405881.
In this analytical procedure, the ratio from the carbon in the activeconstituents of accurate interpolation in the scavenging solution also can detect.Tensio-active agent, organic corrosion inhibitor and organic complex form agent and can be used as example.But the content of the mentioned component in scavenging solution is known in certain fluctuation range or can measures respectively.Therefore, can from analytical results, get rid of from the ratio of the total organic carbon in these activeconstituentss.Thereby obtain to be derived from the ratio of the impurity that enters.In fact, the ratio that will be present in the carbon in the activeconstituents form in the carbon analysis is taken into account and is not main.On the contrary, often determine the upper limit of an enough big carbon content in the scavenging solution, itself takes into account this upper limit the content of activeconstituents.Can determine that by means of the analysis of carbon carbon content is to be higher or lower than this threshold limit value.
The ratio that is present in the total organic carbon in the oleophilic substance form can be definite like this, promptly water-fast oleophilic substance can be extracted in the organic solvent.After solvent was evaporated, oleophilic substance is left to get off and can carry out gravimetric analysis.But preferably, the infrared absorption of the oleophilic substance in the extract is carried out photometric analysis.Particularly halohydrocarbon can be used as organic solvent, and it is water insoluble.Preferred example is 1,1, the 2-Refrigerant R 113.This method is based on DIN 38409 the 17th part, but different with this method be that behind organic solvent evaporation, the ratio of oleophilic substance is not to use the weighting method analysis in the sample, but organic solvent is carried out photometric analysis.This quantitative analysis method is preferably as described in DIN 38409 the 18th part, by measuring in the extract oleophilic substance at CH 2Infrared absorption under the eigen vibration frequency of base is carried out.Here, suggestion is used not contain CH when extraction 2The organic solvent of group.For example, 3.42 μ m (2924cm -1) infrared absorption band located can be used for this photometric analysis.All contain CH 2Group and the organic substance that can be extracted in the organic solvent can detect.Partly they are the tensio-active agent in the scavenging solution.If can not detect this tensio-active agent, can measure separately with another kind of method, and from the long and, deduct.If necessary, the partition ratio of tensio-active agent between scavenging solution and water-fast organic solvent must be determined in advance.But, in practice, give maximum value of permission content setting of the scavenging solution that contains oleophilic substance just enough, wherein extra takes into account surfactant component.If surpassed this maximum value, just start and bathe treatment measures.
As the part of this method, suggestion is calibrated infrared photometer with a kind of oleophilic substance of known quantity.For example, can use at 100 milliliter 1,1, the solution that contains 400-500 milligram methyl palmitate in the 2-Refrigerant R 113 is as calibration solution.This calibration solution equally also is used to detect the photometric function of IR-.
Here, preferably at first the phosphoric acid Adlerika is added in the sample of scavenging solution.This solution is dissolved in the deionized water by the phosphoric acid with 220 gram crystal sal epsom and 125 milliliter of 85 weight %, and then additional deionized water to 1000 gram and preparing.Sample solution mixes mutually with about 20 milliliters phosphoric acid sal epsom.Then, add 50 milliliters of water-fast organic solvents, preferred 1,1, the 2-Refrigerant R 113.Water and organic phase are carried out the separation of phase after mixing, and isolate organic phase.Preferably this organic phase is washed with the phosphoric acid Adlerika again, carry out the separation of a second phase again, isolate organic phase.Organic phase is changed in the measuring tube, at CH 2The vibration frequency band of base is measured infrared absorption down.Proper measuring tube comprises, for example, has the quartz glass tube of 1mm thick coating.By comparing with working curve, wherein also comprise photometric blind value, just can determine the content of oleophilic substance in the sample according to infrared absorption.
In the implementation process of the inventive method, might wish both to have detected inorganic carbon and also detect total organic carbon (TOC).For example, when being used for the analysis of carbon content, sample combustion is exactly this situation.If CO under the temperature of combustion of selecting 2Cracking is come out from carbonate, here dissolved CO 2Or to detect in addition with the carbon that carbonate form exists.If the inorganic carbon amount does not detect in addition in this case, just can it be extracted acidified sample the CO of formation 2Can go out with gas such as air or nitrogen purging.If " the fat content " that only needs under special circumstances to detect in the cleaner bath is that hope is such.When the carbon content that exists with the oleophilic substance form detects according to the extracting process of foregoing description, just can not automatically detect inorganic carbon.
To volatile organic compounds, in implementation step (d) before, with gas such as air or nitrogen flooding by and from sample, discharge.For example, before carrying out the carbon analysis, volatile solvent can be removed in this way.
ⅲ) the analysis of basicity
For the analysis of basicity, can carry out according to the method for describing among the German patent application DE19802725.7.
At step (c), particularly for this method, must make one's options, be to measure free alkali and/or total alkalinity.This can permanently be input in the program flow.For example, can in a mensuration circulation, both measure free alkalinity and also can measure total alkalinity.But, this program also can determine to measure in these two values one than another more frequency.For example, when previous measurement result show in these two values one than another change faster the time, a kind of situation that comes to this.Usually, can be to analyze free alkali or total alkali also by the requirement decision of outside." external demand " both can be understood as can also can intervene automatic analytic process by a data line artificially by an advanced processes Controlling System.
The definition of term " free alkali " and " total alkali " is not very clear, because of user's difference deals with different.For example, can define specific pH value and can begin up to titration, to measure free alkali or total alkali, for example pH8 measures free alkali, and pH4.5 measures total alkali.In order to carry out automatic analytic process, these previously selected pH values must be input in the Controlling System.Except specific pH value, the transition point that also will select specific indicator is with definition free alkali and total alkali.But, the point of equivalent of free alkali or total alkali can be selected and define to the flex point in the pH curve.
In step (d), when actual analysis basicity, can carry out the acid-alkali reaction with acid.Preferably carry out acid-base reaction with strong acid.Here, to free alkali or also can be with adding the acidometric titration sample up to given threshold value to total alkali.Also can begin and come Titrable acid from acid with sample.
Different transmitters is suitable for coming the acid-alkali in the titrating scavenging solution to react with acid.In present existing technology, the pH-sensitive electrode as glass electrode, will preferably use.It provides the voltage signal relevant with the pH value, can do further to analyze to this signal.See that from the angle of device it is special simple using such electrode, therefore preferably is used.
Yet and then the acid-base reaction in the step (d) also can use a kind of indicator, can measure this indicator electromagnetic radiation interaction relevant with pH.For example, this indicator can be the colored indicator of classics, and its change in color can be measured with luminosity.In addition, also can use a kind of optical pickocff.This comprises, for example, contains the organic polymer or the inorganic polymer film of fixed dye, changes its color under specific pH.As under the situation of the colored indicator of classics, the change of color is based on such principle, and promptly hydrogen ion or hydroxide ion can be diffused in the film and with dye molecule and react.The change of the optical characteristics of this film can be used photometer measurement.In addition, can use film, organic polymer for example, the change of its refractive index is the function of pH.If, for example, scribble a kind of optical conductor of this polymkeric substance, one side in optical conductor the threshold value of refractive index just can obtain total reflection, so just can propagate a branch of light.Yet, but there is not total reflection to take place at the other side of refractive index threshold value, light beam is just fled from away from optical conductor like this.Whether just can detect at the end of optical semiconductor like this has light to propagate from optical conductor or do not propagate.A kind of like this device is referred to as " optronics ".
Inorganic or organic solid, its electrology characteristic changes with the change of the pH of solution on every side, also can be used as transmitter.For example, specific conductivity is with H +Or OH -A kind of ionophore that ionic concn changes can be used as this transmitter.By the direct current or the AC Permeability of survey sensor, just can extrapolate the pH value of surrounding medium.Correction/contrast is measured
Method among the present invention is preferably carried out like this, be used for the measuring apparatus of single analysis can self-monitoring and, if desired can also self-correction.For this purpose, behind the preset time interval or after the predetermined analysis times or, measure, check the work capacity of the measuring apparatus of use by the contrast of one or more standardized solution according to external demand.For the purpose of checking is measured the known standardized solution of location parameter value.If the composition of the composition of a standard cleaning liquid and the scavenging solution that will detect is approaching as much as possible, this standard cleaning liquid is used to check to be best as standardized solution.
If, contrasting with standardized solution when measuring, the value that measuring apparatus is measured and demarcate concentration differently reach predetermined minimum, this measuring apparatus can be at the locality or the signal that preferably gives the alarm in distant.Warning signal here can comprise a kind of intervention of being selected by the measuring apparatus sequence of control and advise or advised by the intervention that the advanced procedures Controlling System is selected.
A principal character of the inspection of the work capacity of basicity measuring apparatus is to monitor its employed transmitter.For example, this transmitter can include a pH-sensitive electrode, particularly glass electrode.Use a kind of buffered soln to make standardized solution, just can check whether electrode provides predetermined voltage, whether responds at interval at preset time, with and gradient (=voltage changes with pH) whether be positioned at the scope of expectation.A kind of if not so situation, measuring apparatus are just at local or the signal that preferably gives the alarm in distant.Warning signal here can include intervention suggestion of being selected by the measuring apparatus sequence of control or the intervention suggestion of being selected by the advanced procedures Controlling System.For example, it can advise cleaning or to change electrode.
In the method for the invention, reach predetermined amount if twice continuously measured result differs, it also can provide the work capacity of being checked the measuring apparatus of use by the measurement of comparison of one or more standardized solution.Whether the deviation that can distinguish the content in the cleaner bath of foundation like this is very and whether needs to bathe treatment measures or whether they have simulated the fault in the measuring system.
According to the result that used measuring apparatus is checked, the analysis of carrying out between current measurement and measurement of comparison before this can provide the condition identifier of the reliability that can indicate these analyses.For example, show that its operation is normal if be used for the continuous measurement of comparison of check measurement device, then this analysis can provide status identifier " OK ".If the measurement of comparison result is different with the minimum value of being scheduled to, then interference analysis for example provides status identifier " suspicious ".
In addition, it also provides, check result according to used measuring apparatus, continue the automatic analysis of measuring parameter and/or carry out one or more following action: termination, status signal or the warning signal that the analysis of the error of formation, the correction of measuring apparatus, measurement of correlation parameter are analyzed is to the transmission of advanced procedures Controlling System or monitoring device, promptly to apogean transmission.Therefore, if necessary, whether this measuring apparatus can self decide it to have enough work capacity to make these analyses proceed according to predetermined standard, perhaps whether produces abnormal conditions and needs artificial intervention.
Preferably, the design of measuring system that is used for the inventive method becomes such form, and it can monitor the consumption of concentration and/or agents useful for same and solvent automatically, and washing soln, and when not reaching predetermined minimum sandards, will send warning signal.In this way, just can prevent that measuring apparatus is owing to lacking the required chemical agent cisco unity malfunction that becomes.These Determination on content can realize with known method.For example, the container that has a chemical agent can be placed on the scale card of the specified weight that has write down these chemical agents.Perhaps insert buoy.Another kind method is to adopt the conductivity electrode that is immersed in the container that contains chemical agent to check Cmin.The warning signal that is sent by measuring apparatus preferably is sent to the higher apsis, so just can start adequate measures therefrom.Usually, in the method for the invention, preferably the result of the result of result that will analyze and/or measurement of comparison and/or calibration and/or status signal are sent to the higher apsis continuously, perhaps at preset time at interval and/or be sent to the higher apsis as required.Adopt this mode, the monitor staff needn't place oneself in the midst of the field position of cleaner bath, just can constantly obtain the information of the instant level of alkalinity of relevant cleaner bath.According to the result who analyzes and the result of measurement of comparison, can automatically also can take necessary corrective action by sequence control system by manual intervention.
As the part in the inventive method it provide to be selected from analysis (ⅰ), (ⅱ) and (ⅲ) in each analysis, behind the preset time interval or after the predetermined analysis times or, can check the work capacity of used measuring apparatus and check result is sent to the higher apsis by the measurement of comparison of one or more standardized solution according to apogean requirement.In addition, when the result of twice successive analysis and predetermined amount have difference, just can start inspection corresponding to used measuring apparatus work capacity.The result of this inspection preferably is sent to the higher apsis.According to the check result to used measuring apparatus, a kind of situation feature provides the reliability of the analysis of the measurement of correlation parameter of carrying out between current and before this measurement of comparison.
Method of the present invention, it also further provides, according to be selected from analysis (ⅰ), (ⅱ) and (ⅲ) in the result of one or more analyses, the interpolation of extra ancillary component and/or one or more bath treatment measures can be started by the higher apsis.It also provide according to be selected from analysis (ⅰ), (ⅱ) and (ⅲ) in the result of one or more analyses, the interpolation of extra ancillary component and/or a plurality of bath treatment measures can start in programme controlled mode.
In addition, in the method for the invention, when be selected from analysis (ⅰ), (ⅱ) and (ⅲ) in the result of at least two analyses between when predetermined correlation having occurred, it can provide, the interpolation of extra ancillary component and/or one or more bath treatment measures start in programme controlled mode.Therefore, analyze (ⅰ), (ⅱ) and (ⅲ) in each separate analysis between specific dependency in the sequence of control of handling, pre-set, when dependency above-mentioned occurs, just start and additionally add ancillary component and/or start the bath treatment measures.Thus, this decision is based on two different bath parametric measurement results rather than is made by single measured value.Here can change by the higher apsis about the relation curve that starts that measure, for example operating experience be taken into account.For example, a kind of measure (bathe all or part of renewal, remove fat and/or oil and/or pass through membrane filtering method from bathe by separator) that realizes reducing the fat content in the cleaner bath can be provided, if, on the one hand, the content of total organic carbon has surpassed predetermined maximum level, on the other hand, the content end of tensio-active agent reaches predetermined minimum content.Perhaps the summation of giving surfactant content and fat content is with a specific maximum value, and top bath treatment measures just can automatically start.
According to the required measured value or the variation of in measured value, being set up, can start following one or more corrective actions.Proofread and correct and bathe treatment measures
The simplest bath treatment measures are such, according to surpassing inorganic carbon and/or total organic carbon predetermined maximum value or according to the requirement of an outside, and a kind of device that triggers the activation, it can be added to one or more ancillary components (solution or powder) in the cleaner bath.For example, this can realize with automated manner, according to the carbon content of measuring, supplies with the assisted solution and the adjuvant powders of specific quantity in cleaner bath.Can change the size of the ratio of adding here, perhaps, under the situation that fixedly adds ratio, change the timed interval between each interpolation operation.For example, this can realize by means of volume pump or the mode that also can control weight.Therefore, in the method for the invention, it can provide, and (particularly when the function of measuring apparatus be when being determined by measurement of comparison) occurring under the situation of offrating, a certain amount of auxiliary component is added to be added in the scavenging solution extraly.In addition, when reaching the minimum change of predetermined carbon content, just can carry out these and bathe the measure of replenishing.This additional adding also can answer outside need to carry out, and for example according to apogean requirement, and needn't consider current carbon content but on the other hand.For example, replenish and to add tensio-active agent and increased the carbon content in the cleaner bath.In the analysis of next carbon content, must take into account with a suitable manner, it can automatically carry out.The interpolation of tensio-active agent has increased oil in the cleaner bath-and the carrying capacity of fat.Therefore, must increase the maximum bearing value of carbon content, surpass this value and just start the next treatment measures of bathing.This can provide automatically by sequence of control.
Do not adopt the extra interpolation of bathing component,, or when surpassing the predetermined maximum value of inorganic carbon and/or total content of organic carbon, can start and bathe the content of treatment measures with inorganic carbon and/or organic carbon in the reduction scavenging solution as tensio-active agent.The purpose of such bath treatment measures particularly reduces fat and oily content in the scavenging solution.In simple example, scavenging solution can discharge whole or in part and replace with fresh scavenging solution.Yet more economical is by measure known in the art oil and fat to be removed from scavenging solution, for example, separates or the membrane filtration separation by separator.Because in these processes, be that the tensio-active agent of part is discharged at least, so additional clean liquid suitably.The enforcement of these measures is not only relevant with the absolute carbon content of scavenging solution, and relevant with the predetermined variation of carbon content.
In order to monitor content and/or the basicity with the control surface promoting agent, in the time of can reaching the predetermined minimum value of content at the end or according to external demand, trigger a kind of device, this device is added to one or more auxiliary components in the scavenging solution.For example, a kind of assisted solution that contains all activeconstituentss in the cleaner bath than under can be used as auxiliary component in correct quantity.Therefore, assisted solution not only can include the thing of monitoring, also can further comprise the activeconstituents in the scavenging solution, such as tensio-active agent, builder material, alkali, complexing agent and corrosion inhibitor.In addition, auxiliary solution may only contain tensio-active agent or only contain alkali and other activeconstituents in the scavenging solution according to the time time control or Material control mode independent analysis additionally add again when needed.
Here, can change interpolation quantity or, under fixing situation of adding quantity, changes timed interval of interpolation respectively twice.For example, this can carry out by chemicals feed pump or by the weight control mode.Therefore, on the one hand, in the method for the invention, it provides when departing from the calibration value certain value (particularly when finding that by measurement of comparison the function of measuring apparatus has problem), and the ancillary component of specified quantitative additionally is added in the scavenging solution.Yet, on the other hand, also can additionally add medicament according to external demand, for example, from the higher apsis, and no matter the content of tensio-active agent and/or the content of alkali at that time.In another kind of embodiment of the present invention, bathe treatment solution and be in the mode that depends on through-put and add by the feed intake amount of predetermined ancillary component of per unit.For example, be used in cleaner bath under the situation of body of a motor car, can come the given amount that will add ancillary component according to the vehicle body of each cleaning.In the present invention, the monitoring of surfactant content or basicity play monitoring and write down this predetermined success of adding and, add by small dispensing and the discontinuous of alkali that relies on the result, reach a kind of more stable cleaner bath operator scheme.Therefore reduced the fluctuation of quality.
Usually, the method among the present invention needs proper device.This comprises a control unit, computer control unit for example, and it can time-dependent manner and/or event mode control survey process.It also must comprise reagent container, pipeline, valve, dispensing and the measuring apparatus etc. of the control that is used for sample flow and the measurement of some necessity.These materials should be fit to intended purpose, and for example, they should be to be made by high-quality steel and/or plastics.The control electronic unit of measuring apparatus should have a kind of suitable I, can get in touch with the higher apsis like this.
On the one hand, method of the present invention makes the content of scavenging solution to check at the scene, and starts predetermined corrective action and need not human intervention.Adopt this mode, the security of process just is improved, and can obtain continuously reliable wash result.The situation of offrating can obtain detecting in stage early, before the result who cleans is slackened, and automatically or manual synchronizing.On the other hand, the data of measurement preferably are transferred to the higher apsis, even operator or monitor staff be not near cleaner bath like this, also can obtain the information of cleaner bath state often.The personnel's disbursement that is used for cleaner bath monitoring and control just can reduce on significance ground.The file of the data that the inventive method is collected meets the requirement of modern quality-guarantee.The consumption of chemical substance can be recorded files and optimization.

Claims (17)

1. method of monitoring cleaner bath is characterized in that carrying out at least two kinds of analyses in the following analysis with program controlled mode:
(ⅰ) analysis of surfactant content;
(ⅱ) inorganic carbon and/or total organic carbon quantitative analysis;
(ⅲ) analysis of basicity;
And,
(a), start extra interpolation and/or one or more bath treatment measures of ancillary component according to the result who analyzes;
And/or
(b) result that will analyze and/or the data transmission that derived by analytical results are at least one higher apsis, and this higher apsis is arranged in the room different with analytical instrument.
2. according to the process of claim 1 wherein that the higher apsis is positioned at apart from the place of 500 meters far away of analytical instrument at least.
3. according to the method for claim 1 or 2, wherein whenever the data that obtain new analytical results and/or derived by analytical results, the transmission of its analytical results and/or the data that derived by analytical results is automatically carried out.
4. according to the method for claim 1 or 2, wherein the transmission of analytical results and/or the data that derived by analytical results is carried out according to apogean requirement.
5. according to the arbitrary method in the claim 1 to 4, wherein single analysis repeats behind the preset time interval.
6. according to the arbitrary method in the claim 1 to 4, repeat after the wherein single analysis at certain time intervals, two analytical results gaps of carrying out continuously are big more, and this timed interval is short more.
7. according to the arbitrary method in the claim 1 to 4, analysis wherein should be carried out in apogean requirement.
8. according to the arbitrary method in the claim 1 to 4, when analyze (ⅰ), (ⅱ) and (ⅲ) in the result of the 1st analysis selecting exceed predetermined maximum value or when not reaching predetermined minimum value or difference being arranged by previous the 1st analytical results and predetermined minimum value, analysis (ⅰ), (ⅱ) and (ⅲ) in the 2nd analysis selecting will carry out in programme controlled mode.
9. according to the arbitrary method in the claim 1 to 8, wherein according to programme controlled mode,
(ⅰ) carry out the analysis of surfactant content, wherein
(a) sample of a pre-determined volume of taking-up from aqueous cleaning;
(b) if desired, remove solid matter in the sample;
(c) if desired, sample is according to predefined or by the ratio dilute with water of initial analysis result decision; With
(d) surfactant content is analyzed by selective adsorption, electrochemistry, chromatographic process; By injecting volatile compound, extrude and check that these waving property compounds analyze; Or by adding reagent, this reagent can change the interaction of sample and electromagnetic radiation, and this interactional variation and surfactant content are proportional, measure this interactional variation and analyze.
10. according to the arbitrary method in the claim 1 to 8, wherein
(ⅱ) inorganic carbon or total organic carbon quantitative analysis are carried out with program controlled mode, wherein:
(a) sample of taking-up pre-determined volume from aqueous cleaning,
(b) if desired, remove solid matter and/or homogeneous in the sample;
(c) if desired, sample is according to predefined or by the ratio dilute with water of initial analysis result decision; And
(d) the known methods analyst of inorganic carbon or the total organic carbon content in sample.
11. according to the arbitrary method in the claim 1 to 8, wherein
(ⅲ) according to programme controlled mode, the basicity of cleaner bath is analyzed by acid-base reaction with acid, wherein:
(a) sample of taking-up pre-determined volume from scavenging solution,
(b) if desired, remove solid matter in the sample;
(c) to being to analyze free alkalinity and/or total alkalinity makes one's options, and
(d) sample is by adding acidometric titration or acid being come titration as parent material with sample.
12. according to the arbitrary method in the claim 1 to 11, wherein for analyze (ⅰ), (ⅱ) and (ⅲ) in any one analysis, a back, preset time interval or after a predetermined analysis times or according to apogean requirement, the serviceability of used measuring apparatus is proofreaied and correct result transmission to the higher apsis by the contrast measurement update of one or more standardized solution.
13. according to the arbitrary method in the claim 1 to 11, wherein for analyze (ⅰ), (ⅱ) and (ⅲ) in any one analysis, when the analytical results that carries out continuously for twice differs a preset value, the serviceability of used measuring apparatus is proofreaied and correct result transmission to the higher apsis by the contrast measurement update of one or more standardized solution.
14.,, provide the state characteristic of these measurement reliabilities of indication in analysis current and that last time, contrast was done between measuring wherein according to check result to used measuring apparatus according to the method for claim 12 or 13.
15. according to the arbitrary method in the claim 1 to 14, wherein according to be selected from analysiss (ⅰ), (ⅱ) and (ⅲ) in one or more analytical resultss, additionally add ancillary component and/or one or more bath treatment measures by the higher apsis startup.
16. according to the arbitrary method in the claim 1 to 14, wherein according to be selected from analysis (ⅱ), (ⅱ) and (ⅲ) in one or more analytical resultss, start in programme controlled mode and additionally to add ancillary component and/or one or more bath treatment measures.
17. according to the arbitrary method in the claim 1 to 14, wherein when be selected from analysis (ⅰ), (ⅱ) and (ⅲ) in when predetermined relation occurs between the result of at least two analyses, start with program controlled mode and additionally to add ancillary component and/or one or more bath treatment measures.
CN99809555A 1998-08-13 1999-08-04 Automatic regulation and control of cleansing baths Pending CN1312866A (en)

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DE19836720.1 1998-08-13
DE19836720A DE19836720A1 (en) 1998-08-13 1998-08-13 Automatic testing and control of cleaning baths, as used in metal processing, e.g. for cleaning metal pieces before anti-corrosion processes

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CN103221152A (en) * 2010-10-26 2013-07-24 克朗斯股份公司 Apparatus and method for monitoring cleaning
CN103215605A (en) * 2013-04-18 2013-07-24 江门市瑞期精细化学工程有限公司 Magnesium-alloy alkaline membrane remover and chemical nickel plating pretreatment process
CN103424529A (en) * 2012-05-22 2013-12-04 韩国地质资源研究院 Unmanned automatic alkalinity measuring system and method
CN104685100A (en) * 2012-09-04 2015-06-03 汉高股份有限及两合公司 Method for corrosion-protective serial surface treatment of metallic components
CN109738429A (en) * 2019-01-15 2019-05-10 舍得酒业股份有限公司 The rapid detection method of alkali is analysed in a kind of glaze spraying vial

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19855957B4 (en) * 1998-12-04 2008-10-30 Henkel Ag & Co. Kgaa Automatic control of the hydrophilicity of a solid surface with infrared spectroscopy
DE19957997A1 (en) * 1999-12-02 2001-06-07 Wedeco Ag Device for measuring and monitoring the radiation power of UV lamps in a wastewater disinfection system
DE10209466B4 (en) * 2002-03-05 2004-03-11 Sita Messtechnik Gmbh Device for the continuous monitoring and control of process solution
US20220130652A1 (en) * 2018-08-31 2022-04-28 Shimadzu Corporation Analysis method, analysis device, and program
KR102359468B1 (en) * 2020-09-17 2022-02-07 서울과학기술대학교 산학협력단 Improve Total Organic Carbon Analysis Method with pretreatment and homogeneity evaluation of Sample
US20240017298A1 (en) * 2022-07-15 2024-01-18 Ecolab Usa Inc. Methods and systems for detecting and controlling the dosage and residual concentration of hard surface cleaners and rinse aids in an automotive parts washer

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4406249A (en) * 1979-11-14 1983-09-27 C. Uyemura & Co., Ltd. Apparatus for controlling electroless plating bath
US4374681A (en) * 1981-05-11 1983-02-22 Coral Chemical Company System for controlling the composition of chemical treatment baths
US4886590A (en) * 1987-11-02 1989-12-12 Man-Gill Chemical Company Chemical process control system
US5175502A (en) * 1990-09-14 1992-12-29 Armco Steel Company, L.P. Method and apparatus for determining acid concentration
US5439569A (en) * 1993-02-12 1995-08-08 Sematech, Inc. Concentration measurement and control of hydrogen peroxide and acid/base component in a semiconductor bath
DE19802725C1 (en) * 1998-01-24 1999-11-11 Henkel Kgaa Automatic control and control of detergent baths by determining the alkalinity

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CN103221152A (en) * 2010-10-26 2013-07-24 克朗斯股份公司 Apparatus and method for monitoring cleaning
CN103424529A (en) * 2012-05-22 2013-12-04 韩国地质资源研究院 Unmanned automatic alkalinity measuring system and method
CN104685100A (en) * 2012-09-04 2015-06-03 汉高股份有限及两合公司 Method for corrosion-protective serial surface treatment of metallic components
CN104685100B (en) * 2012-09-04 2016-10-19 汉高股份有限及两合公司 The method that hardware is carried out anticorrosion continuous surface process
CN103215605A (en) * 2013-04-18 2013-07-24 江门市瑞期精细化学工程有限公司 Magnesium-alloy alkaline membrane remover and chemical nickel plating pretreatment process
CN109738429A (en) * 2019-01-15 2019-05-10 舍得酒业股份有限公司 The rapid detection method of alkali is analysed in a kind of glaze spraying vial

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KR20010072441A (en) 2001-07-31
CA2369064A1 (en) 2000-02-24
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JP2002522647A (en) 2002-07-23
TR200100328T2 (en) 2001-07-23
AU5419499A (en) 2000-03-06
SI20535A (en) 2001-10-31
YU10901A (en) 2003-08-29
EP1109950A1 (en) 2001-06-27

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