CN101045824A - Molecular marked compound for organic solvent system - Google Patents
Molecular marked compound for organic solvent system Download PDFInfo
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- CN101045824A CN101045824A CN 200710097055 CN200710097055A CN101045824A CN 101045824 A CN101045824 A CN 101045824A CN 200710097055 CN200710097055 CN 200710097055 CN 200710097055 A CN200710097055 A CN 200710097055A CN 101045824 A CN101045824 A CN 101045824A
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Abstract
This invention relates to a colorless marker used in petroleum product and its test method.
Description
The application be that August 28 calendar year 2001, application number are 200510077839.6 the applying date, denomination of invention divides an application for the application for a patent for invention of " molecular marked compound that is used for organic solvent system ", and the latter be that August 28 calendar year 2001, application number are 018235816 the applying date, denomination of invention divides an application for the application for a patent for invention of " molecular marked compound that is used for organic solvent system ".
Background of invention
In the present invention, disclose the new molecular marked compound of chemical substance that add lustre to as organic solvent solution (particularly petroleum products).Also disclose a kind of synthetic, detect and the quantitative method of these novel substances.These detection methods provide the new improvement technology of a kind of detection and more quantitative known mark materials.Use the present invention, can in containing the single_phase system of petroleum products, present color or fluorescence, do not need independent extraction step.
Under strength of solution less than about 20 micrograms per litre, give the chemical substance of accepting proton of very little color of organic solvent or non-obvious color, be used as marker or marker in many occasions, especially for the fuel that obtains by oil.This marker is dissolved in the liquid to be identified, then carries out simple physics or chemical assay is detected by liquid to this mark.Marker is used for guaranteeing other fuel of a specific order is taken over suitable tax by government organs sometimes.The oil company is the people of their product of mark to help determining those dilutions or to change its product also.The petroleum products that these companies often pay a high price with the brand that guarantees to beat them satisfies some specification, for example volatility and octane value, and provide the effective additives that contains scale remover and other component combination for their petroleum products.The human consumer relies on the title of these products and quality explanation to guarantee that the product of buying has required quality.
Usually, by with can not be miscible moisture of acidic substance or contain the described petroleum products of solution extraction of big water gaging, detect and the existing of optional quantitatively these materials (its accuracy is different with the characteristic of marker).The reaction of described acid and basic cpd produces dark positively charged ion that be easy to see, more or less, these positively charged ions be dissolved in aqueous acids mutually in.This technology is in U.S. Pat 5,145, description arranged in 573.
The amount of mark substance in extract also can be measured, and for example by the visible absorption spectrum method, then its result compared with reference standard, thereby determines the initial concentration of alkali label thing in fuel.For fully quantitatively, need repetition (being generally 2 times or 3 times) extraction fuel sometimes to reclaim all markers that exist at first.Therefore, marker is removed also simple relatively from the fuel of mark by this reaction.This is the weakness of these prior art neutral and alkali mark substances; Those want that the dishonest personnel that cheat revenue department or individual consumer can more easily remove them from fuel.For example, can the mark in the low octane gasoline of mark be removed through washing, thereby sell once more with the excellent fuel of unlabelled higher price.Perhaps, will remove as the marker in the #2 fuel oil of the mark of the tax-free sale of family's heated oil or railway or agriculture diesel oil, so that it is sold as road, diesel-fuel once more with higher after-tax price.Therefore legal tax revenue mechanism has lost their tax revenue.In the U.S., owing to carried out the mark program in 1993, these tax revenues have increased about 2,000,000,000 dollars.
In addition, the separation of described extraction belongs to Hazardous wastes mutually, and has safety problem and legal processes problem, particularly when in " on the spot " when detecting.And the fuel that is in contact with it can be hygroscopicity, makes it be difficult to get back to its initial source, and therefore has other waste disposal problem.
The hydrocarbon of the developer of the application of the invention, particularly organic phosphoric acid or sulfonic acid or alcoholic solution can extract from petroleum products and make the indication color of marker or fluorescence is clear and immediately as seen, and can be quantitative.
Quick and definite determination step is very important to actual detected, and it can transport the delay of vehicle and the wrong degree of the end that drops to of detaining.Also can use isotopic labeling as the assistant analysis step, thereby confirm to analyze by adding lustre to the result who obtains independently.
Summary of the invention
The invention provides such composition, it comprises a kind of petroleum products that forms organic phase, a kind ofly is dissolved in the mark substance in this petroleum products and a kind ofly combines to show the anhydrous acid of detectable color with described mark substance in organic phase.It also comprises such composition, and it comprises a kind of the form petroleum products of organic phase, a kind of mark substance and a kind of combination with mark substance and petroleum products to show the acid of detectable color or fluorescence in organic phase that is dissolved in this petroleum products.
The marker that is used for petroleum products also is provided.They have following structure:
Wherein A, B and C are the aromatic carbocyclic part independently of one another, and N is a nitrogen, and R is alkyl or hydrogen atom.And, the invention provides contain can with the authentication method of the petroleum products of the marker of acid-respons, it comprise at first obtain to contain can with the sample of the petroleum products of the marker of acid-respons, in this sample, add a kind of developer that contains anhydrous acid or its solution then, thereby formation acid and marker combination are to present the single-phase of a kind of detectable color.
Detailed Description Of The Invention
The developer that the invention provides new molecular marked compound or marker and use together with them.Described developer also can use with marker acid-respons with preexist.Basically cannot see when these markers are present in the liquid petroleum product with effective usage quantity, but when contacting with suitable developer of the present invention, described marker presents clearly color and/or fluorescence.The step of the present invention that presents color or fluorescence is simple in actual use, and the reagent that is used to described color is manifested is easy to handle and reclaim.
Use the present invention,, detect with the step of quantitative acid-respons marker and can directly in petroleum products, carry out, do not need aqueous phase extracted deriving from the composition of oil.The preferred use of described reaction can be finished with the miscible anhydrous organic acid soln of petroleum products.This combination make mark substance existence immediately as seen, perhaps if necessary, adopt the existence of instrument cue mark material.Described marker concentrations can accurately be measured by for example standard colour chart step.For producing quantitative result, step of the present invention is than using aqueous acids extraction (time that acquisition is separated fully is long) to want fast and more convenient.Described new step has also reduced the potential environmental disposal problem, and this is because the product of colour developing and mark can be got back to its origin; Optional, for example with can sour developer being neutralized with the miscible aliphatic amine of described petroleum products.Can also use can with the mark substance (under the aqueous acids condition, being not easy from petroleum products, to extract) of acid-respons.
Developer of the present invention represents with R-OH that usually wherein the OH group is the part of acid moieties, its pK
aValue is 3.5 or littler, and R is monoalkyl or aryl sulfonic acid part or monoalkyl or dialkyl group phosphoric acid.
The acid of preferred described marker colour developing usefulness be can with those of petroleum products complete miscibility.In addition, in order to carry out quantitative analysis, the salt that they and the reaction of described mark substance form also should be dissolved in the described fuel fully.
The final selection of acid can change at the difference of different systems with solubility parameter.For example, high octane gasoline contains a large amount of aromatic hydrocarbons usually, and these aromatic hydrocarbons have good solvency power to mark substance and developer.On the contrary, kerosene stock and lubricating oil are to belong to aliphatic series and/or alicyclic in itself basically, and it is relative with the solvency power of the salt of acid-respons gained relatively poor to many mark substances and they.
Although can use organic sulfonic acid such as methylsulfonic acid,, preferably has the acid of more complicated organo-functional group in order to realize good mixing.The Phenylsulfonic acid, particularly C of preferred especially senior alkylization
10-C
20The Phenylsulfonic acid that alkyl replaces, what wherein use most convenient is Witco 1298 Soft Acid.This compound as the basis of many laundries and other washing composition by mass production.Its dodecyl chain can be a straight or branched, and since the easier biological degradation of straight chain compound, therefore preferred straight chain compound, but the two is all in full force and effect in the present invention.
As the substitute of this class sulfonic acid, can use the monoalkyl of phosphoric acid or dialkyl group or aryl ester as developer or detection agent.Many can industry acquisition the in these compounds, and for organic sulfonic acid, the consistency of the special fuel and the system of mensuration is depended in final selection.Two (2-ethylhexyl) ester of phosphoric acid is owing to have the consistency of broad, thereby is particularly preferred a kind of compound.
The amount that is used to detect the developer of step is at least 1 molar equivalent/mole mark substance, and preferred excessive 2-5 doubly.The acid developer preferably adds with the form of the dilute solution in hydrocarbon, alcohol or the glycol ethers.Its reason is that the concentration of mark substance in petroleum products is 100mg/L or lower, and the molar weight of used developer acid will be very little, and is not easy to add with undiluted material.With regard to Fuel Petroleum, recommend the quite high solvent of volatility, for example toluene, dimethylbenzene, ethanol or n-propyl alcohol.With regard to the low fuel such as kerosene of volatility, preferably 2-Ethylhexyl Alcohol or 1-dodecane, this is because it has bigger consistency to this class system.These solvents also are applicable to lubricating oil and lubricating grease and use.Under one situation of back, owing to have other alkali, particularly mineral compound such as lithium hydroxide in lubricating grease, the concentration of Witco 1298 Soft Acid may must roll up.In general, acid can change in the concentration range of broad so that the colour developing optimizing of marker in different systems with the ratio of mark substance.The concentration of acid that is used for present method is more moisture or aqueous alcohol developer/extraction agent is much smaller than described in the prior art usually.
The active quantities of acid can be 0.05 mole or even lower among the present invention.Recommend the acid concentration of the 2.5-3.0 mole that uses to form contrast in this and the extraction step.Therefore, compared with prior art, particularly under the situation of field survey, the corrodibility of developer of the present invention is low, and the danger that exists is also much lower.
The suitable solvent of acid developer comprises aliphatic series and aromatic hydrocarbons, alcohols, glycols and glycol ethers.Preferred for this reason lower alcohols, for example methyl alcohol, ethanol and propyl alcohol, particularly when petroleum products is gasoline, hydro carbons most preferably still is as toluene or dimethylbenzene.In order to use, for example be used in combination the preferred low solvent of volatility with the diesel oil fuel of mark with other petroleum products.Usually, higher aliphatic and aromatic hydrocarbons are valuable especially in this respect, particularly octane-iso, dodecane and have other aliphatic hydrocarbon of required bonding properties, these bonding propertieies comprise good solvency power and with oil-fired miscibility, room temperature under low vapour pressure, high flash-point and do not have mutagenicity.This combination makes the harm of HUMAN HEALTH and fire hazard is minimized.
The concentration of acid in solution of the present invention can in very large range change.Preferably there are enough acid and all the marker reactions in the fuel sample.With regard to actual cause, be dissolved with about 0.5-10% in the preferred solvent, preferred about 1% acid solution.Therefore solvent accounts for about 90-99% of anhydrous developer usually.
Developer of the present invention for example can be with new mark substance of the present invention or marker of the prior art such as Solvent Yellow 56 or Solvent Yellow 124 uses.
Preferred new marker or mark substance of the present invention is the aromatic carbocyclic Monoazo compound, represented by following general formula:
Wherein A, B and C are the aromatic carbocyclic parts, preferably benzene or naphthalene, and N represents nitrogen-atoms, and R is alkyl or hydrogen atom.R is side chain or unbranched C preferably
1-C
20
Can choose wantonly by one or more not obvious other atom or groups of giving macromolecule water-solubility with the hydrogen atom that structural unit A, B link to each other with C and to replace.Typical substituting group can be halogen atom, nitro, alkyl, alkoxyl group or hydroxyl, carboxylicesters, carboxylic acid amides or sulphonamide functional group.Useful especially substituting group is alkyl for example, and alkyl improves the solubleness of alkali label material in organic solvent, particularly accounts in many oil fuels in the aliphatic hydrocarbon of the overwhelming majority.In addition, under a part of incendiary situation that mark substance is acted as a fuel, especially preferably its component is restricted to carbon, hydrogen, nitrogen and Sauerstoffatom, to avoid the discharging of issuable atmospheric polluting material such as sulfur oxide and hydrogen halide.
Monoazo tagged compound of the present invention can prepare by common process, this technology can comprise preferred carbocyclic ring uncle aromatic amine diazotization, then itself and N-arylamino aniline or N-aryl naphthylamines are carried out azo coupling reaction, the 4th of examining at virtue of described amine do not stand azo coupling reaction (is 1 with N arylamino substituting group).
For practical application and economic cause, preferred primary amine is aniline and cycloalkylation derivative, particularly dodecyl polyaniline.The ester of benzaminic acid is also valuable, and the major function of this ester group is to improve mark substance at hydrocarbon solvent, particularly the solubleness in aliphatic series, cycloparaffin series and clicyclic hydrocarbon (being the main ingredient in gasoline, diesel oil, family's heating and lubricating oil and the kerosene).
Perhaps, preferred compound of the present invention can also be by with 4-aminodiphenylamine diazotization, then the phenol of itself and phenol or replacement is carried out azo coupling reaction and synthesize.As coupling component, valuable especially is alkylphenol, suitably selects alkyl to guarantee that final compound has good solubleness in aforementioned aliphatic naphthenic hydrocarbon solvent and clicyclic hydrocarbon solvent thus.
The following examples are used for describing but do not limit the scope of the invention.
Embodiment 1
In 1 liter stirring-type vial, add 50 gram ice, then add 32% hydrochloric acid of 28.1 grams.Dropping is dissolved in the gram of 26.1 in 50ml dimethylbenzene dodecyl polyaniline, stirs this mixture down at 0 ℃ simultaneously.Next add 17.25 gram Sodium Nitrites (concentration), temperature is remained below 5 ℃ simultaneously with 40%.Carry out 10 minutes sulfone positive test (positivesulfone test) afterwards, add thionamic acid to remove excessive Sodium Nitrite.Pour in this reaction the pentanoic that is dissolved in the gram of 16.9 in the 50ml dimethylbenzene and stirring.Add sodium formiate its pH is adjusted to 3.Coupling finishes with ammoniacal liquor this reactant to be neutralized afterwards and leave standstill.Except that anhydrating and, obtaining 88.8% crude product with solvent evaporation.The described material that is dissolved in the dimethylbenzene with the concentration of 10mg/L becomes the brilliant violet look when reacting with Witco 1298 Soft Acid, locate to absorb maximum in 561 nanometers (nm).
Embodiment 2
In 1 liter stirring-type vial, add 50 gram ice, then add 32% hydrochloric acid of 28.1 grams.Dropping is dissolved in the gram of 26.1 in 50ml dimethylbenzene dodecyl polyaniline, stirs this mixture down at 0 ℃ simultaneously.Next add 17.25 gram Sodium Nitrites (concentration), temperature is remained below 5 ℃ simultaneously with 40%.After carrying out 10 minutes sulfone positive test, add thionamic acid to remove excessive Sodium Nitrite.Pour in this reaction and stirring with being dissolved in the gram of 18.3 in 50ml dimethylbenzene N-methyldiphenylamine.Add sodium formiate its pH is adjusted to 3.Coupling finishes with ammoniacal liquor this reactant to be neutralized afterwards and leave standstill.Except that anhydrating and, obtaining 92.1% crude product with solvent evaporation.This dyestuff and embodiment's 1 is closely similar, and just it shows rubescent slightly purple, absorbs maximum at the 559nm place.
Embodiment 3
45% sodium hydroxide and the 200ml water that add 12ml in 2 liters stirring-type vial then add 20.6 gram di sec-butylphenols.This container is heated to 70 ℃, is cooled to 50 ℃ then.In 1 liter of independent flask, add 32% hydrochloric acid of 200ml water, 28.1 grams and the 4-aminodiphenylamine alkali of 18.4 grams, then heating.In case described aminodiphenylamine is transformed into its hydrochloride, with this mixture be cooled to 10 ℃ and add 17.25 the gram Sodium Nitrites (concentration) with 40%.After carrying out 10 minutes sulfone positive test, add thionamic acid to remove excessive Sodium Nitrite.Described pentanoic diazonium solution stirring is become di sec-butylphenol solution, keep pH simultaneously more than 12.Add acetate after coupling finishes solution is acidified to pH3.Next the pH with this multi-phase solution is adjusted to 6.5.Except that anhydrating and, obtaining 93.0% crude product with solvent evaporation.Concentration is that the solution of the products therefrom of 10mg/L becomes reddish blue with 2-ethylhexyl-phosphatase reaction the time, and it absorbs maximum under 588 nanometers.
| Embodiment number | Diazo component | Coupling component | Visual appearance after protonated | Maximum absorption nm |
| 4 | Dodecyl polyaniline | 1-phenyl amino naphthalene | Blue | 616 |
| 5 | Dodecyl polyaniline | 3 methyl diphenylamine | Purple | 559 |
| 6 | Butyl 2-aminobenzoate | Pentanoic | Red | 543 |
| 7 | The 4-butyl aminobenzoate | Pentanoic | Blue red | 549 |
| 8 | The 4-aminodiphenylamine | The 4-nonylphenol | Hyacinthine | 599 |
Except aforesaid new azo mark substance, recommend in the prior art also can detect and quantitatively by technology of the present invention as other alkaline organic compound of dye marker, though before them only recommended be used to use moisture or contain big water gaging to the detection of proton reagent extraction etc.What deserves to be mentioned is usually colourless or the alkali of color slightly, as triarylmethane, xanthene, azine and other related dye.These alkali are by protonated ammonium ion, oxygen ion and the carbocation that forms dark color.The material that is easy to obtain comprises triarylmethane methyl alcohol class (as pentamethylpararosaniline), triarylmethane lactone (as crystal violet lactone and rhodamine B alkali) and amine (as victoria blue alkali and Nile red A).These compounds are present in the organic solvent with the concentration of 0.1-200mg/L, but preferred 1-20mg/L, can produce dark positively charged ion with anhydrous acid or anhydrous basically acid solution reaction, these positively charged ions absorb the light of the part wavelength in visible spectrums, can make thus fuel or lubricating oil have visible by yellow to brown color.Under the situation that is very black fuel etc., handle linear absorption spectrum by using differential to handle (particularly second-order differential processing), can improve to this mark substance quantitatively.
Embodiment 9
Rhodamine B alkali, the dilute solution of C.I. solvent red 49 in phenol second diether of aliquot are joined in the water white #1 kerosene lam-oil, make the rhodamine B alkaline solution of a colourless 2mg/L.1% the solution of technical grade Witco 1298 Soft Acid in dodecane of 10ml is joined in the described fuel of 100ml.Produce one and under 545 nanometers (nm), have a pink speed hyperfluorescence that has emission maximum under maximum absorption and the 565nm.By comparing with the correction reference standard, can the unknown concentration of rhodamine B alkali in the fuel is quantitative.When only having the rhodamine of unusual lower concentration, when perhaps fuel has high background color, by spectrofluorimetry than detecting by the easier realization of spectrophotometry and quantitatively.
Embodiment 10
0.1% pentamethylpararosaniline that 1 liter of white gasoline is joined 10ml is dissolved in the solution in the Denatured alcohol.This makes that the concentration of this fuel alkali is 10ml/L
-1With the described mark gasoline of 100ml and the unlabelled excellent gasoline thorough mixing of 900ml.In 1% the solution of the diethylhexyl phosphoric acid that then this mixture of 100ml is joined 10ml in dimethylbenzene.Present purple immediately, it can be by the spectrophotometric standard measure to confirm that the concentration of marker in the gasoline of described dilution is 1mg/L.If with the N of 1ml, the N-dimethylethanolamine joins in the described gasoline that presents purple, and this color disappears, and fuel recovers its initial outward appearance.
Embodiment 11
Repeat the step described in the embodiment 10, just with 1% 1,1,1-trichoroacetic acid(TCA) solution replacement two-2-ethylhexyl phosphoric acid.Realized to the methyl violet mark substance same quantitatively.
Embodiment 12
With 1 liter #2 family heated oil (painted with the concentration of 26mg/L), with the concentration mark of victoria blue B alkali with 5mg/L according to American I RS article with Unisol LiquidRed BNM.In the heated oil of the mark of 100ml, add in the solution of 1% concentration of Witco 1298 Soft Acid in 2-Ethylhexyl Alcohol of 10ml.The fuel outward appearance becomes purple by redness immediately.If the fuel sample after will developing the color scans, can measure red and blue relative concentration in absorption spectrophotometer.
Embodiment 13
If with the victoria blue B alkali enumerated among the embodiment 12 with the replacing of same concentrations according to embodiment 1 synthetic azo-compound, realized to orchil and marker similar quantitatively.
Embodiment 14
1% dodecylbenzenesulfonic acid solution that in family's heated oil (the C.I. solvent red 164 of usefulness 4mg/L and the C.I. solvent yellow 124 of 11mg/L are painted, according to the regulation of Ontario, Canada) of 100ml, adds 10ml.By the faint orange red darker garnet that becomes, this is because solvent yellow 124 alkali are transformed into pinkish red red positively charged ion to the outward appearance of fuel immediately.If the fuel sample after will developing the color scans in absorption spectrophotometer, and use second-order differential to handle or a plurality of component processing gained result, can the concentration in initial fuel carry out quantitatively solvent red 164 and solvent yellow 124.Compare with the prior art that comprises 2 or 3 times with aqueous hydrochloric acid continuous extraction fuel sample, this detection step is faster and more convenient, because in described prior art, need merge the isolated extract of each time, may also to filter the fuel droplet of wherein carrying secretly then, just can carry out spectrophotometric analysis then sample to remove.
Embodiment 15
By with N, between the N-diethyl-Tolylamine generation azo coupling reaction carries out diazotization to dodecyl polyaniline, synthesized a fuel marker sample according to the embodiment 6 of WO99/67346.The detection step of this mark substance comprises with 10N aqueous hydrochloric acid of equal-volume part and alcoholic acid mixture and extracts the fuel that contains this mark substance.By with the anhydrous dodecylbenzenesulfonic acid solution reaction described in identical mark substance and the top embodiment 10, can detect this mark substance more easily and reduce operational hazards.
Embodiment 16
As U.S. Pat 5,737,871 embodiment 2 carries out azo coupling reaction with the butyric ester and the diazotizing aniline of N-phenyl-N-ehtylethanolamine, makes a fuel marker.According to the claim 6 of same patent, detect the existence of this material in fuel by extracting with acidic aqueous solution.This material also can directly react with anhydrous acid of the present invention in fuel, thereby immediately it is detected with quantitative.This is more convenient, and is consuming time few, and than low with the risk level of aqueous acids extraction.
Applicant's invention has been described with reference to preferred implementation.In the case without departing from the scope of the present invention, can carry out many improvement to described invention.
Embodiment 17
With 4-amino-N-2 '-ethylhexyl benzsulfamide sample diazotization, then with N, N-Diethyl Aniline generation azo coupling reaction.Products therefrom is the yellow crystal solid, is soluble in most of hydro carbons.The dilute solution reaction of colourless gasoline solution of the 10mg/L of this product and Witco 1298 Soft Acid presents clarifying red color.
Being used for marker of the present invention also can represent with following formula:
Any hydrogen atom wherein in the described molecule can be replaced by D atom.Ring A can contain 0-2 substituting group, X and Y, and it represents not obvious any group of giving macromolecule water-solubility.X and Y for example can be (independently of one another) halogen atom, nitro, more preferably the ester class or the amides of alkyl and alkoxyl group or hydroxy-acid group.Can also use N-alkyl sulfonamide group.R
1And R
2Can be the hydroxyl of hydrogen or D atom or replacement, particularly by forming the group of ester functional moieties with alkyl carboxylic acid reaction or by forming the group of acetal functional moieties with the alkyl vinyl ether reaction.R
3Be alkyl, alkoxyl group or amido.
In another embodiment, marker of the present invention can be joined in the petroleum products that also contains a dyestuff.This mark substance can as mentioned above, need not independent extraction step with the acid colour developing in the petroleum products sample.In other words, the colour developing and the detection of mark substance among the present invention do not disturbed in the existence of dyestuff.Except mark substance, operable dyestuff comprises the C.I. solvent red 23, and its cycloalkylation homologue also can be used for the present invention.C.I. the cycloalkylation homologue of solvent red 23 comprises C.I. solvent red class 24,25,26,27,164 and 164:1.C.I. solvent yellow 124 also can be used for the present invention.
Claims (5)
1, a kind of marker that is used for petroleum products, it has following structure:
Wherein A, B and C are the aromatic carbocyclic part independently of one another, and N is a nitrogen, and R is alkyl or hydrogen atom.
2, marker as claimed in claim 1, wherein A, B and C are independently from each other benzene and naphthalene.
3, marker as claimed in claim 2, wherein R is side chain or unbranched C
1-C
20Alkyl.
4, marker as claimed in claim 3 is not wherein given tangible water miscible other atom of this molecule with the hydrogen atom that ring A, B link to each other with C by one or more or group replaces.
5, marker as claimed in claim 4, wherein C is selected from halogen atom, nitro, alkyl, alkoxyl group or hydroxyl, carboxylicesters, carboxylic acid amides or sulfuryl amine group.
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|---|---|---|---|
| CN 200710097055 CN101045824A (en) | 2001-08-28 | 2001-08-28 | Molecular marked compound for organic solvent system |
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|---|---|---|---|
| CN 200710097055 CN101045824A (en) | 2001-08-28 | 2001-08-28 | Molecular marked compound for organic solvent system |
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|---|---|---|---|
| CNA018235816A Division CN1545538A (en) | 2001-08-28 | 2001-08-28 | Molecular tag for organic solvent system |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116103517A (en) * | 2023-02-03 | 2023-05-12 | 哈尔滨工业大学（威海） | Extraction solvent and extraction method for extracting and separating titanium and/or iron from acidic solution containing titanium and/or iron |
-
2001
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116103517A (en) * | 2023-02-03 | 2023-05-12 | 哈尔滨工业大学（威海） | Extraction solvent and extraction method for extracting and separating titanium and/or iron from acidic solution containing titanium and/or iron |
| CN116103517B (en) * | 2023-02-03 | 2024-04-26 | 哈尔滨工业大学（威海） | Extraction solvent and extraction method for extracting and separating titanium and/or iron from acidic solution containing titanium and/or iron |
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