CN104237405B - The method of TATB synthetic intermediate and product in liquid chromatogram measuring waste water - Google Patents
The method of TATB synthetic intermediate and product in liquid chromatogram measuring waste water Download PDFInfo
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- CN104237405B CN104237405B CN201410453866.8A CN201410453866A CN104237405B CN 104237405 B CN104237405 B CN 104237405B CN 201410453866 A CN201410453866 A CN 201410453866A CN 104237405 B CN104237405 B CN 104237405B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 100
- JDFUJAMTCCQARF-UHFFFAOYSA-N tatb Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O JDFUJAMTCCQARF-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000007788 liquid Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000012086 standard solution Substances 0.000 claims abstract description 47
- 229960001553 phloroglucinol Drugs 0.000 claims abstract description 37
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 32
- 238000001514 detection method Methods 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 239000012982 microporous membrane Substances 0.000 claims abstract description 25
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 12
- 238000004458 analytical method Methods 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000005576 amination reaction Methods 0.000 claims description 27
- 238000006396 nitration reaction Methods 0.000 claims description 26
- 230000029936 alkylation Effects 0.000 claims description 25
- 238000005804 alkylation reaction Methods 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 25
- 239000012528 membrane Substances 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 13
- 230000001360 synchronised effect Effects 0.000 claims description 11
- 239000012044 organic layer Substances 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 6
- 230000001419 dependent effect Effects 0.000 claims description 5
- 238000010812 external standard method Methods 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000012925 reference material Substances 0.000 claims description 4
- 238000004811 liquid chromatography Methods 0.000 claims description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- WUCYBAXJJOWQFF-UHFFFAOYSA-N 2,4,6-trinitrobenzene-1,3,5-triol Chemical compound OC1=C([N+]([O-])=O)C(O)=C([N+]([O-])=O)C(O)=C1[N+]([O-])=O WUCYBAXJJOWQFF-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000004867 photoacoustic spectroscopy Methods 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The present invention relates to a kind of method of TATB synthetic intermediate and product in liquid chromatogram measuring waste water, belong to chemical analysis field.Described method is as follows: the standard solution one, preparing phloroglucin, TETNB and TATB standard substance with liquid chromatogram mobile phase; Two, described TATB waste water is processed: pH is adjusted to neutrality, extract test substance drying, then add liquid chromatogram mobile phase dissolving, then use filtering with microporous membrane removal of impurities, obtain liquid chromatographic detection sample; Three, liquid-phase chromatographic analysis is carried out to described standard solution, drawing standard curve; Four, described sample is used liquid-phase chromatographic analysis respectively, intermediate and product in contrast standard curve determination TATB waste water.Described method accurately can detect intermediate related substance phloroglucin, the TETNB and product TATB of trace in TATB waste water, has filled up the defect of prior art.
Description
Technical field
The present invention relates to a kind of method of photoacoustic spectroscopy (TATB) synthetic intermediate and product in liquid chromatogram measuring waste water, specifically, relate to a kind of phloroglucin, 1 adopted in the three kinds of waste water produced in liquid chromatogram measuring TATB production run, 3,5-trimethoxy-2, the method of 4,6-trinitrobenzen (TETNB) and TATB, belongs to chemical analysis field.
Background technology
The chlorinty of photoacoustic spectroscopy (TATB) obviously can affect the thermal stability of TATB, for solving the impact of chlorine impurity in traditional mode of production TATB method, usually adopting with phloroglucin in prior art is raw material, free from chloride TATB is produced through nitrated, alkylation and amination, but production run brings inevitable environmental problem---waste water, described waste water is mainly nitration waste water, alkylation waste water and amination waste water.Set up a kind of practicable analytical plan for without the waste water produced in chlorine TATB production run, analyze the change of intermediate related substance before and after described wastewater treatment, can be the theory significance that the work for the treatment of carrying out described waste water provides very strong.Take phloroglucin as raw material, the structural formula produced without the chemical equation of chlorine TATB, intermediate related substance and product through nitrated, alkylation and amination is as follows:
The first step, nitrated:
The acid mixture of phloroglucin and sulfuric acid and nitric acid is carried out nitration reaction, obtains nitration product 2,4,6-trinitro--1,3,5-benzenetriol (TNPG); Wash nitration product with nitric acid, obtain nitration waste water, the pH value of nitration waste water is much smaller than 1;
Second step, alkylation:
The nitration product TNPG obtained by step one and trimethyl orthoformate (HC (OMe)
3) carry out alkylated reaction, obtain alkylate TETNB; Wash alkylate with ethanol, obtain alkylation waste water;
3rd step, amination:
The alkylate TETNB obtained by step 2 and DMF (DMF) carry out aminating reaction, obtain aminate TATB; Wash aminate with ethanol, obtain amination waste water.
At present, in TATB waste water, the detection method of intermediate its related substances mainly contains ultraviolet spectrophotometry, thin-layered chromatography, dead-stop titration, vapor-phase chromatography and gas chromatography mass spectrometry method etc.Ultraviolet spectrophotometry is more classical method, but sensitivity is not high, because intermediate related substance has extremely close absorption peak in TATB waste water, easily causes interference, analyzes while being unfavorable for polycomponent intermediate.Thin-layered chromatography is highly sensitive, selectivity good, but poor repeatability, and detecting step is loaded down with trivial details.Dead-stop titration agents useful for same toxicity is large, technology is difficult to grasp, and mensuration is organic total amount in TATB waste water, can not distinguish the kind of intermediate related substance in TATB waste water, also not be suitable for the analysis of polycomponent intermediate related substance in TATB waste water.In TATB waste water, the boiling point of intermediate related substance is all higher than 300K, is difficult to gasify in general pillar again, and derivatization treatment afterproduct is difficult to extract from waste water, and therefore vapor-phase chromatography is same with gas chromatography mass spectrometry method inapplicable.
Because TATB kind of waste water is various, matrix is complicated, and the physicochemical property difference of each composition is comparatively large, and especially nitration waste water is highly acid, and pH, much smaller than 1, damages chromatographic mass spectrometry instrument pipeline, unsuitable direct injected.In TATB waste water, intermediate related substance content in waste water is lower, and especially for alkylation waste water and amination waste water, wherein intermediate related substance needs enrichment process; The solvent of alkylation waste water and amination waste water is mainly ethanol, because ethanol all dissolves each other with majority of organic solvent, and cannot by the mode of liquid-liquid extraction to its enrichment; Attempt Solid-Phase Extraction, chromatographic behavior is poor.Described various detection method cannot detect the intermediate related substance of trace in TATB waste water, therefore, does not also have a kind of effective method can detect the intermediate related substance of trace in TATB waste water at present.
Summary of the invention
For the defect that prior art exists, the object of the present invention is to provide a kind of method of TATB synthetic intermediate and product in liquid chromatogram measuring waste water, described waste water take phloroglucin as raw material, produce through nitrated, alkylation and amination and produce without chlorine TATB, described intermediate related substance is phloroglucin and TETNB, and product is TATB.
The object of the invention is to be achieved through the following technical solutions:
A kind of method of TATB synthetic intermediate and product in liquid chromatogram measuring waste water, wherein, described waste water take phloroglucin as raw material, the nitration waste water, alkylation waste water and the amination waste water that produce without chlorine TATB is produced through nitrated, alkylation and amination, described intermediate related substance is phloroglucin and TETNB, and product is TATB; Described method step is as follows:
Step one, preparing standard solution
Taking phloroglucin, TETNB and TATB tri-kinds of standard substances respectively, is that the acetonitrile of 1:1 and the mixed solution of water are mixed with standard solution by volume ratio;
Step 2, process waste water
(1) nitration waste water is processed
The pH of nitration waste water is adjusted to neutrality, then add extraction into ethyl acetate and go out organic layer liquid, by organic layer liquid dried, the mixed solution adding acetonitrile that volume ratio is 1:1 and water again dissolves, then carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(2) alkylation waste water is processed
Remove the DMF in alkylation waste water and ethanol, drying obtains solid, is that the acetonitrile of 1:1 and the mixed solution enrichment of water are dissolved, regulates pH to neutral by solid volume ratio, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(3) amination waste water is processed
Remove the DMF in amination waste water and ethanol, drying obtains solid; Be that the acetonitrile of 1:1 and the mixed solution enrichment of water are dissolved by solid volume ratio, regulate pH to neutral, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
Wherein, in step (2) and (3), described drying is preferably adopted with the following method: first steaming instrument remove portion ethanol by revolving, then removing remaining DMF and ethanol by oil pump decompression distillation, obtaining solid; Because testing concentration is low, therefore can be that the mixed solution enrichment 5 of the acetonitrile of 1:1 and water is doubly to reach detection line by solid volume ratio;
Step 3, drawing standard curve
The standard solution adopting external standard method obtained to step one carries out liquid-phase chromatographic analysis, analysis condition is as shown in table 1, records the peak area of each reference material mass peak, take peak area as ordinate, concentration is horizontal ordinate drawing standard curve, obtains linear equation and the linearly dependent coefficient of typical curve;
Table 1 liquid-phase chromatographic analysis condition
Intermediate and product in step 4, mensuration TATB waste water
By without chlorine TATB synthetic method, known TATB is only present in amination waste water; TETNB is mainly present in alkylation waste water, also may exist in amination waste water; Phloroglucin is mainly present in nitration waste water, is not precluded within latter two waste water and also has, and just trace exists, if can't detect negligible;
According to often kind of each self-corresponding liquid-phase chromatographic analysis condition of standard solution in table 1, sample step 2 process obtained measures by liquid chromatography respectively, the peak area of wherein phloroglucin, TETNB and TATB can be recorded, directly can draw from step 3 the typical curve obtained according to peak area and check in its content.
For reducing metrical error, after preferably synchronously being processed by standard solution, then carry out step 3 drawing standard curve, concrete disposal route is as follows:
(1) the synchronous process of nitration waste water standard solution
Regulate the pH of phloroglucin standard solution to neutral, then add extraction into ethyl acetate and go out organic layer liquid, by organic layer liquid dried, the mixed solution adding acetonitrile that volume ratio is 1:1 and water again dissolves, then carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(2) the synchronous process of alkylation waste water standard solution
Regulate the pH of phloroglucin standard solution to neutral, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
Regulate the pH of TETNB standard solution to neutral, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(3) the synchronous process of amination waste water standard solution
Regulate the pH of phloroglucin standard solution to neutral, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
Regulate the pH of TETNB standard solution to neutral, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
Regulate the pH of TATB standard solution to neutral, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample.
Standard substance (referencematerial of the present invention, RM) be a kind ofly determined the material or material with one or more enough uniform characteristic value, as " measurer " in analysis to measure industry, in the operative technique level of calibration measurement instrument and device, evaluation Measurement and analysis method, measurement of species or material property value and examination and analyses personnel, and the field such as quality control of product in process of production plays a part indispensable.
External standard method of the present invention is one of conventional method of instrumental analysis, is the one of relative method.Compared with internal standard method, external standard method is not that standard substance is joined in sample, but measures separately under the chromatographic condition identical with sample, and the chromatographic peak area of the chromatographic peak area obtained and tested component is compared the content of trying to achieve tested component.
Beneficial effect
1. the invention provides a kind of method of TATB synthetic intermediate and product in liquid chromatogram measuring waste water, accurately can detect intermediate related substance phloroglucin, the TETNB and product TATB of trace in TATB waste water, fill up the defect of prior art;
2. for reducing metrical error, standard solution and step 2 wastewater treatment drawing standard curve again after adopting same procedure synchronously to process.
Accompanying drawing explanation
Fig. 1 is the canonical plotting of phloroglucin.
Fig. 2 is the liquid chromatogram of phloroglucin standard substance.
Fig. 3 is the canonical plotting of TETNB.
Fig. 4 is the liquid chromatogram of TETNB standard substance.
Fig. 5 is the canonical plotting of TATB.
Fig. 6 is the liquid chromatogram of TATB standard substance.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
Take phloroglucin as raw material, the structural formula produced without the chemical equation of chlorine TATB, intermediate related substance and product through nitrated, alkylation and amination is as follows:
The first step, nitrated:
By phloroglucin 1kg and sulfuric acid 10L, and the acid mixture 2.4L of sulfuric acid and nitric acid (wherein, sulfuric acid 1L, nitric acid 1.4L) carries out nitration reaction, and obtain nitration product 2,4,6-trinitro--1,3,5-benzenetriol (TNPG), yield is 98%; With the nitric acid washing nitration product twice of 3mol/L, obtain nitration waste water, the pH value of nitration waste water is much smaller than 1;
Second step, alkylation:
The nitration product TNPG2kg obtained by step one and trimethyl orthoformate (HC (OMe)
3) 10L carries out alkylated reaction, obtain alkylate TETNB, yield is 85%; Wash alkylate with ethanol, obtain alkylation waste water;
3rd step, amination:
The alkylate TETNB1.5kg obtained by step 2 and DMF (DMF) 6L carries out aminating reaction, and obtain aminate TATB, yield is 97%; Wash aminate with ethanol, obtain amination waste water.
A kind of method of TATB synthetic intermediate and product in liquid chromatogram measuring waste water, wherein, described waste water is the present embodiment take phloroglucin as raw material, the nitration waste water, alkylation waste water and the amination waste water that produce without chlorine TATB is produced through nitrated, alkylation and amination, described intermediate related substance is phloroglucin and TETNB, and product is TATB; Described method step is as follows:
Step one, preparing standard solution
Accurately take phloroglucin, TETNB and TATB standard substance 5mg respectively, accurately extremely ± 0.0001g, be the standard solution that the acetonitrile of 1:1 and the mixed solution of water are mixed with variable concentrations gradient by volume ratio respectively, wherein, the concentration of phloroglucin standard solution is respectively 0.1 μ g/mL, 0.5 μ g/mL and 1 μ g/mL, the concentration of TETNB standard solution is respectively 0.1 μ g/mL, 1 μ g/mL, 10 μ g/m, 30 μ g/mL and 100 μ g/mL, and the concentration of TATB standard solution is respectively 1 μ g/mL, 2.5 μ g/mL, 5 μ g/mL and 15 μ g/mL.
Step 2, process waste water and the corresponding standard solution of synchronous process
(1) nitration waste water and the corresponding standard solution of synchronous process is processed
Get nitration waste water 1mL, adding 1.95mL ammonia neutralization to the pH value of solution is 6 ~ 7, then in solution, 3mL extraction into ethyl acetate is added, abundant vortex stirring is even, centrifugal 5min, centrifugal complete after taking-up organic layer liquid wherein, dry up with hair dryer, adding 1mL volume ratio is afterwards that the acetonitrile of 1:1 and the mixed solution of water dissolve again, then carries out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collects filtrate and is used as liquid chromatographic detection sample;
The pH value of phloroglucin standard solution is adjusted to 6 ~ 7, then extraction into ethyl acetate is added, abundant vortex stirring is even, centrifugal 5min, centrifugal complete after taking-up organic layer liquid wherein, dry up with hair dryer, adding volume ratio is afterwards that the acetonitrile of 1:1 and the mixed solution of water dissolve again, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm again, collect filtrate and be used as liquid chromatographic detection sample;
(2) alkylation waste water and the corresponding standard solution of synchronous process is processed
Get alkylation waste water 20mL, first steaming instrument remove portion ethanol by revolving, then removing remaining DMF and ethanol by oil pump decompression distillation, obtaining solid; The volume ratio of solid 4mL is the acetonitrile of 1:1 and the mixed solution enrichment 5 times dissolving of water, adjust ph to 6 ~ 7, then carries out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collects filtrate and is used as liquid chromatographic detection sample;
The pH value of phloroglucin standard solution is adjusted to 6 ~ 7, carries out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
The pH value of TETNB standard solution is adjusted to 6 ~ 7, carries out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(3) amination waste water and the corresponding standard solution of synchronous process is processed
Get amination waste water 20mL, first steaming instrument remove portion ethanol by revolving, then removing remaining DMF and ethanol by oil pump decompression distillation, obtaining solid; The volume ratio of solid 4mL is the acetonitrile of 1:1 and the mixed solution enrichment 5 times dissolving of water, adjust ph to 6 ~ 7, then carries out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collects filtrate and is used as liquid chromatographic detection sample;
The pH value of phloroglucin standard solution is adjusted to 6 ~ 7, carries out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
The pH value of TETNB standard solution is adjusted to 6 ~ 7, carries out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
The pH value of TATB standard solution is adjusted to 6 ~ 7, carries out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
Step 3, drawing standard curve
Standard solution after adopting external standard method synchronously to process step 2 carries out liquid-phase chromatographic analysis, analysis condition is as shown in table 1, record the peak area of each reference material mass peak, take peak area as ordinate, concentration is horizontal ordinate drawing standard curve, and obtain linear equation and the linearly dependent coefficient of typical curve, measurement result is shown in Fig. 1 ~ 6 and table 2, wherein, Fig. 2,4 and 6 maximum peak be the peak of standard substance;
Table 2 typical curve and linearly dependent coefficient
| Standard solution | Phloroglucin | TETNB | TATB |
| Typical curve | y＝834.61x+56.21 | y＝192.12x－36.198 | y＝113.1x－9.7308 |
| Linearly dependent coefficient | r＝0.9979 | r＝0.9999 | r＝0.9982 |
Intermediate and product in step 4, mensuration TATB waste water
By without chlorine TATB synthetic method, known TATB is only present in amination waste water, TETNB is mainly present in alkylation waste water, also may exist in amination filtrate, phloroglucin is mainly present in nitration waste water, be not precluded within latter two waste water and also have, just trace exists, if can't detect negligible.
According to often kind of each self-corresponding liquid-phase chromatographic analysis condition of standard solution in table 1, after liquid chromatograph is stable, wastewater sample step 2 process obtained measures by liquid chromatography respectively, record the peak area of phloroglucin in wastewater sample, TETNB and TATB, directly record the content of phloroglucin, TETNB and TATB from typical curve according to peak area, result is as shown in table 3.
Table 3 wastewater sample measurement result
Claims (3)
1. the method for TATB synthetic intermediate and product in liquid chromatogram measuring waste water, is characterized in that: described method step is as follows:
Step one, preparing standard solution
Taking phloroglucin, TETNB and TATB tri-kinds of standard substances respectively, is that the acetonitrile of 1:1 and the mixed solution of water are mixed with standard solution by volume ratio;
Step 2, process waste water
(1) nitration waste water is processed
The pH of nitration waste water is adjusted to neutrality, then add extraction into ethyl acetate and go out organic layer liquid, by organic layer liquid dried, the mixed solution adding acetonitrile that volume ratio is 1:1 and water again dissolves, then carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(2) alkylation waste water is processed
Remove the DMF in alkylation waste water and ethanol, drying obtains solid, is that the acetonitrile of 1:1 and the mixed solution enrichment of water are dissolved, regulates pH to neutral by solid volume ratio, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(3) amination waste water is processed
Remove the DMF in amination waste water and ethanol, drying obtains solid; Be that the acetonitrile of 1:1 and the mixed solution enrichment of water are dissolved by solid volume ratio, regulate pH to neutral, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
Step 3, drawing standard curve
After standard solution being carried out the synchronous process identical with process waste water, external standard method is adopted to carry out liquid-phase chromatographic analysis to described standard solution, analysis condition is as shown in table 1, record the peak area of each reference material mass peak, take peak area as ordinate, concentration is horizontal ordinate drawing standard curve, obtains linear equation and the linearly dependent coefficient of typical curve;
Table 1 liquid-phase chromatographic analysis condition
Intermediate and product in step 4, mensuration TATB waste water
According to often kind of each self-corresponding liquid-phase chromatographic analysis condition of standard solution in table 1, sample step 2 process obtained measures by liquid chromatography respectively, the peak area of wherein phloroglucin, TETNB and TATB can be recorded, directly can draw from step 3 the typical curve obtained according to peak area and check in its content.
2. the method for TATB synthetic intermediate and product in a kind of liquid chromatogram measuring waste water according to claim 1, it is characterized in that: in (2) and (3) of step 2, described drying is adopted with the following method: first steam instrument remove portion ethanol by revolving, then remove remaining DMF and ethanol by oil pump decompression distillation, obtain solid.
3. the method for TATB synthetic intermediate and product in a kind of liquid chromatogram measuring waste water according to claim 1 and 2, is characterized in that: described standard solution synchronously processes as follows:
(1) the synchronous process of nitration waste water standard solution
Regulate the pH of phloroglucin standard solution to neutral, then add extraction into ethyl acetate and go out organic layer liquid, by organic layer liquid dried, the mixed solution adding acetonitrile that volume ratio is 1:1 and water again dissolves, then carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(2) the synchronous process of alkylation waste water standard solution
Regulate the pH of the standard solution of phloroglucin, TETNB to neutral respectively, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample;
(3) the synchronous process of amination waste water standard solution
Regulate the pH of the standard solution of phloroglucin, TETNB and TATB to neutral respectively, carry out filtering with microporous membrane with the filter membrane that aperture is 0.45pm, collect filtrate and be used as liquid chromatographic detection sample.
Priority Applications (1)
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