CN114295773B - On-line testing equipment and method for acidity of oxidation liquid or alkalinity of circulating working liquid in process of preparing hydrogen peroxide by anthraquinone method - Google Patents
On-line testing equipment and method for acidity of oxidation liquid or alkalinity of circulating working liquid in process of preparing hydrogen peroxide by anthraquinone method Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 238000012360 testing method Methods 0.000 title claims abstract description 25
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 11
- 238000004448 titration Methods 0.000 claims abstract description 72
- 238000005070 sampling Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003918 potentiometric titration Methods 0.000 claims abstract description 22
- 239000012224 working solution Substances 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 39
- 238000004140 cleaning Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000011010 flushing procedure Methods 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000010998 test method Methods 0.000 claims 9
- 238000004458 analytical method Methods 0.000 abstract description 33
- 238000000605 extraction Methods 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 5
- 238000010926 purge Methods 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000012530 fluid Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MKNQNPYGAQGARI-UHFFFAOYSA-N 4-(bromomethyl)phenol Chemical compound OC1=CC=C(CBr)C=C1 MKNQNPYGAQGARI-UHFFFAOYSA-N 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to an on-line testing device and method for acidity of an oxidation liquid or alkalinity of a circulating working liquid in an anthraquinone method hydrogen peroxide preparation process, comprising an automatic quantitative sampling system and an automatic titration system, wherein the automatic quantitative sampling system comprises a six-way valve, a quantitative ring, a three-way valve and a steady flow valve, and the automatic titration system comprises a potentiometric titration cell, an electrode and quantitative titration equipment; the six-way valve, the three-way valve and the steady flow valve are sequentially connected; the quantitative ring is connected with a six-way valve; the automatic sampling system is connected with the potentiometric titration system. The invention can realize on-line automatic sampling, titration and result analysis; adopting inert gas to continuously purge the six-way valve group, isolating the six-way valve group from air and preventing the air from entering the process system; the method has the advantages that extraction operation is not needed, the emulsification phenomenon of mixing the working solution and the pure water is avoided, the analysis speed is high, the time required from sampling to analysis is less than or equal to 15 minutes, and the detection hysteresis is greatly reduced.
Description
Technical Field
The invention relates to online testing of acidity of an oxidation liquid and alkalinity of a circulating working liquid in an anthraquinone method hydrogen peroxide process, in particular to online testing equipment and method of acidity of the oxidation liquid or alkalinity of the circulating working liquid in an anthraquinone method hydrogen peroxide process.
Background
Hydrogen peroxide is a green oxidant, and most of the hydrogen peroxide in the world is produced by the anthraquinone process. In the technology of producing hydrogen peroxide by anthraquinone method, working solution circulates in the system according to the sequence of hydrogenation, oxidation, extraction and post-treatment. In the traditional anthraquinone method hydrogen peroxide production technology, the post-treatment process adopts an alkali treatment process, so that the hydrogenated liquid and the circulating working liquid are alkalescent, and the alkalinity index of the circulating working liquid is<4mg/L (in K) 2 CO 3 Counting, the same as below); in order to prevent the hydrogen peroxide from being decomposed severely in alkaline environment, a certain amount of phosphoric acid is added into the hydrogenated liquid before the oxidation process to ensure the oxidation liquid and the raffinateThe liquid shows weak acidity, and the index of the acidity of the oxidation liquid is 3-6 mg/L (H 3 PO 4 Meter, the same applies below).
In industrial production, the acidity of the oxidation liquid and the alkalinity of the circulating working liquid need to be manually analyzed every 1 hour, the analysis method is an acid-base titration method, and the method is described as follows by taking the acidity of the oxidation liquid as an example: a worker manually takes a certain amount of oxidizing liquid at a gas-liquid separator in the on-site oxidation process; taking 100mL of oxidation liquid by using a measuring cylinder, shaking and extracting in a pear-shaped separating funnel by using 20mL of pure water, putting the lower water phase into a triangular flask, and repeatedly extracting for 5 times; 1-2 drops of an acid indicator (methyl red-methylene blue mixed indicator) are dropwise added into the water phase, and 0.01mol/L sodium hydroxide aqueous solution is used for titration, wherein the disappearance of mauve is used as a titration end point; the amount of sodium hydroxide consumed is converted to the acidity of the oxidizing liquid. The alkalinity analysis of the circulating working solution is the same as the above steps, the on-site sampling position is that after the clay bed is post-treated, the titration solution is hydrochloric acid solution with the concentration of 0.01mol/L, the indicator is an alkaline indicator (bromocresol green-methyl red mixed indicator), and the green color at the titration end point is changed into wine red.
The current acidity and alkalinity analysis methods have the following drawbacks: the manual field sampling, the manual shaking extraction and the manual titration are needed, the detection is needed once every 1 hour, and the workload is high; the error of manual operation is larger and the repeatability is poorer; the sampling and analysis processes are longer, the time is longer, the detection result is lagged, and certain difficulty is brought to process adjustment.
In order to realize the detection of the pH of the water phase, an online extraction column is added in Chinese patent CN112875651A, a stirring kettle is added in Chinese patent CN112897471A, the circulating working solution is quantitatively taken out online, neutral distilled water is used for extraction, and a pH meter is used for detecting the pH of the water phase, so that the use effect is good. However, the method needs quantitative sampling of circulating working solution and pure water, automatic extraction or stirring, automatic quantitative separation of oil phase and water phase, and automatic cleaning of an extraction column and a stirring kettle; the whole set of system needs two-phase extraction operation, and in practical application, the working solution and pure water are easy to generate an emulsified phase, so that the two-phase accurate separation is difficult to realize; when automatic sampling, the condition that the sampling valve entrains air to the production device is extremely easy to appear, has the potential safety hazard.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides an on-line testing device for acidity of an oxidation liquid or alkalinity of a circulating working liquid in a hydrogen peroxide preparation process by an anthraquinone method, which comprises an automatic quantitative sampling system and an automatic titration system, wherein the automatic quantitative sampling system comprises a six-way valve, a quantitative ring, a three-way valve and a steady flow valve, and the automatic titration system comprises a potentiometric titration tank, an electrode and quantitative titration equipment; the six-way valve, the three-way valve and the steady flow valve are sequentially connected; the quantitative ring is connected with a six-way valve; the automatic quantitative sampling system is connected with the potentiometric titration system.
Further, the automatic titration system further comprises a cleaning tank and a soaking tank, wherein liquid discharge pipelines are arranged at the bottoms of the potentiometric titration tank, the cleaning tank and the soaking tank, electromagnetic valves are arranged on the liquid discharge pipelines, and after analysis is finished, the electromagnetic valves are opened to lead out waste liquid in the tank to a sewage system of the production device.
Further, the potentiometric titration cell is provided with a stirring device, the stirring device is preferably a magnetic stirrer, and the start and stop of stirring and the rotating speed are controlled by an automatic control system; the flow stabilizing valve is of a pressure reducing valve or a needle valve; the volume of the quantitative ring is 1-200 mL, preferably 10-100 mL.
Furthermore, the quantitative titration equipment realizes automatic quantitative titration by controlling the rotation speed of a pump head of the peristaltic pump.
The second aspect of the invention provides a method for testing the acidity of an oxidation liquid or the alkalinity of a circulating working liquid in an anthraquinone process hydrogen peroxide preparation process on line, which comprises the following steps:
(1) Sampling: the oxidation liquid or the circulating working liquid in the process pipeline enters the quantitative ring through the six-way valve, and the quantitative ring is fully filled and then returns to the process pipeline through the six-way valve;
(2) And (3) sample injection: the inert gas sweeps the quantitative ring to enable the oxidation liquid or the circulating working liquid to enter the potentiometric titration tank through the three-way valve and the steady flow valve in sequence;
(3) Titration: dripping a titration reagent into the potentiometric titration cell by adopting quantitative titration equipment, automatically judging a titration end point according to the change of potential, stopping titration and recording the dosage of the titration reagent;
(4) And (3) result processing: and calculating the acidity of the oxidation liquid or the alkalinity of the circulating working liquid according to the dosage of the titration reagent.
Further, the inert gas is nitrogen; the titration reagent is a solution of titration solute dissolved in titration solvent, and the concentration of the titration reagent is 0.001-0.1 mol/L.
Further, the titration solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and ethylene glycol; when the acidity of the oxidation liquid is detected, the titrant is sodium hydroxide or potassium hydroxide; when the alkalinity of the circulating working solution is detected, the titrant is HCl or HNO 3 。
Further, the method further comprises the preparation of an electrode before titration: taking out the electrode soaked in the soaking tank, placing the electrode in a cleaning tank, sequentially flushing with a titration reagent and a flushing reagent, and placing the electrode in a potentiometric titration tank; cleaning of the electrode after titration: the electrode is placed in a cleaning tank, the electrode is cleaned by adopting a flushing reagent, a titration solvent and cleaning water in sequence, and then the electrode is placed in a soaking tank.
Further, the bottoms of the potentiometric titration tank, the cleaning tank and the soaking tank are provided with liquid discharge pipelines, electromagnetic valves are arranged on the liquid discharge pipelines, and after analysis is finished, the electromagnetic valves are opened to lead out waste liquid in the tank to a sewage system of the production device.
Furthermore, a peristaltic pump is adopted to spray the flushing reagent, the titration reagent and the cleaning water, the electrode is cleaned, and the starting and stopping and the rotating speed of the peristaltic pump are controlled by an automatic control system; the positions of the electrodes among the titration tank, the cleaning tank and the soaking tank are switched and controlled by an automatic control system.
Further, cleaning water is arranged in the soaking tank, and the cleaning water is an HCl aqueous solution with pH=4-6; the flushing reagent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, toluene, pseudocumene, mesitylene, C9 heavy aromatic hydrocarbon, C10 heavy aromatic hydrocarbon, dichloroethane and chloroform.
Further, the six-way valve is provided with six pipe orifices, and the pipe orifice A is connected with a nitrogen pipeline; the pipe orifice B is connected with the blow-down pipe through a three-way valve, and is connected with the potentiometric titration tank through a three-way valve and a steady flow valve; the pipe orifice C and the pipe orifice F are connected with a quantitative ring; the working fluid is introduced into the orifice D through the pipeline and then returns from the orifice E to the process pipe.
The sampling and sample injection switching of the automatic titration system is realized by rotating a handle of a six-way valve through an automatic control system, and the specific process of sampling and sample injection is as follows:
sampling: nitrogen enters the six-way valve from the pipe orifice A, is directly discharged from the pipe orifice B, and is discharged through the three-way valve; the oxidation liquid or the circulating working liquid enters the six-way valve from the pipe orifice D, enters the quantitative ring through the pipe orifice C, and returns to the process pipeline through the pipe orifice F and the pipe orifice E;
sample introduction: the nitrogen enters a potentiometric titration tank through a pipe orifice A and a pipe orifice F of a six-way valve, and the oxidation liquid or the circulating working liquid in the purging quantitative ring enters a potentiometric titration tank through a pipe orifice C, a pipe orifice B, a three-way valve and a flow stabilizing valve; the oxidizing liquid or the circulating working liquid in the process pipeline is introduced into the pipe orifice D through the pipeline and then directly returns to the process pipeline from the pipe orifice E.
In the result processing state of the automatic potentiometric titration system, the formulas for calculating the acidity of the oxidizing liquid and the alkalinity of the working liquid are as follows.
Detecting the acidity of the oxidation liquid:
wherein: a: acidity of oxidation solution, mg/L; c 1 : alkaline titration reagent concentration, mol/L; v (V) 1 : alkaline titration reagent dosage, mL; m is M p : the relative molecular mass of phosphoric acid; v (V) 0 : ring volume, mL, was quantified.
When the alkalinity of the circulating working solution is detected:
wherein: b: circulating working fluid alkaliDegree, mg/L; c 2 : acid titration reagent concentration, mol/L; v (V) 2 : dosage of acid titration reagent, mL; m is M k : the relative molecular mass of potassium carbonate; v (V) 0 : ring volume, mL, was quantified.
The invention has the beneficial effects that:
(1) automatic sampling, titration and result analysis are realized, and labor can be saved;
(2) the potentiometric titration has high accuracy and good repeatability of analysis results;
(3) the extraction operation is not needed, the emulsification phenomenon of mixing the working solution and the pure water is avoided, the analysis speed is high, the time required from sampling to analysis is less than or equal to 15 minutes, and the detection hysteresis is greatly reduced;
(4) the six-way valve is adopted for automatic quantitative sampling, working solution continuously flows in the six-way valve, sampling has no hysteresis, and the quantitative ring is adopted for determining the sampling volume, so that the problem of fluctuation of the sampling quantity caused by process pressure fluctuation is solved;
(5) the six-way valve group is subjected to continuous nitrogen purging replacement, is isolated from air, prevents the air from entering the process system, and avoids the formation of explosive mixed gas between the air and heavy aromatic hydrocarbon steam in the working solution;
(6) the six-way valve group is provided with the flow stabilizing valve, so that the sampling process can be stabilized, and liquid splashing is prevented.
Drawings
FIG. 1 is a schematic diagram of an automatic quantitative sampling system during sampling.
FIG. 2 is a schematic diagram of an automatic quantitative sampling system during sample injection.
Reference numerals illustrate: 1 is a six-way valve, 2 is a three-way valve, 3 is a steady flow valve, 1-1 is a pipe orifice A,1-2 is a pipe orifice B,1-3 is a pipe orifice C,1-4 is a pipe orifice D,1-5 is a pipe orifice E,1-6 is a pipe orifice F,1-7 is a handle, and 1-8 is a dosing ring.
Detailed Description
Embodiments of the present invention will be further described with reference to examples.
The deviation in the embodiment of the invention is defined as follows:
deviation= (online analysis result-manual analysis result)/manual analysis result×100%.
Example 1
Some 20 ten thousand tons/year (27.5% meter, the same applies below) hydrogen peroxide production device is provided with the equipment and the acidity of the oxidation liquid is tested. The used steady flow valve is a pressure reducing valve, the volume of the quantitative ring is 10mL, the flushing reagent is ethanol, the titration solvent is ethanol, the titration solute is sodium hydroxide, the concentration of the titration reagent is 0.01mol/L, and the cleaning water is HCl aqueous solution with pH=4. Samples were taken at 1 hour intervals (10-15 min) and compared with manual analysis performed simultaneously (40-60 min), the results of which are shown in Table 1.
Table 1 results of on-line testing of the acidity of the resulting oxidizing solutions were compared with results of manual analysis.
Example 2
The device for producing hydrogen peroxide of 20 ten thousand tons/year is provided with the equipment and used for testing the acidity of the oxidation liquid. The flow stabilizing valve is a needle valve, the volume of the quantitative ring is 20mL, the flushing reagent is C9 heavy aromatic hydrocarbon, the titration solvent is methanol, the titration solute is sodium hydroxide, the concentration of the titration reagent is 0.001mol/L, and the flushing water is HCl aqueous solution with pH=4.5. Samples were taken at 1 hour intervals (10-15 min) and compared with manual analysis performed simultaneously (40-60 min), the results of which are shown in Table 2.
Table 2 results of on-line testing of the acidity of the resulting oxidizing solutions were compared with results of manual analysis.
Example 3
The device for producing hydrogen peroxide of 20 ten thousand tons/year is provided with the equipment and used for testing the acidity of the oxidation liquid. The steady flow valve is a needle valve, the volume of the quantitative ring is 50mL, the flushing reagent is pseudocumene, the titration solvent is a mixture of ethanol and n-propanol, the titration solute is potassium hydroxide, the concentration of the titration reagent is 0.01mol/L, and the cleaning water is HCl aqueous solution with pH=5. Samples were taken at 1 hour intervals (10-15 min) and compared with manual analysis performed simultaneously (40-60 min), the results of which are shown in Table 3.
Table 3 results of on-line testing of the acidity of the resulting oxidizing solutions were compared with results of manual analysis.
Example 4
The device for producing hydrogen peroxide of 20 ten thousand tons/year is provided with the equipment and used for testing the acidity of the oxidation liquid. The steady flow valve is a needle valve, the volume of the quantitative ring is 50mL, the flushing reagent is methanol, the titration solvent is n-propanol, the titration solute is potassium hydroxide, the concentration of the titration reagent is 0.005mol/L, and the cleaning water is HCl aqueous solution with pH=6. Samples were taken at 1 hour intervals (10-15 min) and compared with manual analysis performed simultaneously (40-60 min), the results of which are shown in Table 4.
Table 4 results of on-line testing of the acidity of the resulting oxidizing solutions were compared with results of manual analysis.
Example 5
And a hydrogen peroxide production device of 20 ten thousand tons/year is provided with the equipment and is used for testing the alkalinity of the working fluid of the industrial cycle. The used steady flow valve is a needle valve, the quantitative ring volume is 40mL, the flushing reagent is C10 heavy aromatic hydrocarbon, the titration solvent is isopropanol, the titration solute is HCl, the concentration of the titration reagent is 0.01mol/L, and the cleaning water is an HCl aqueous solution with pH=4. Samples were taken at 1 hour intervals (10-15 min) and compared with manual analysis performed simultaneously (40-60 min), the results of which are shown in Table 5.
Table 5 on-line testing the alkalinity results of the resulting circulating working fluid compared to the results of manual analysis.
Example 6
Some 20 ten thousand tons/yearAnd the hydrogen peroxide production device is provided with the equipment and is used for testing the alkalinity of the working fluid in the industrial cycle. The flow stabilizing valve is a needle valve, the volume of the quantitative ring is 100mL, the flushing reagent is mesitylene, the titration solvent is glycol, and the titration solute is HNO 3 The concentration of the titrating agent was 0.05mol/L, and the washing water was aqueous HCl with pH=4.5. Samples were taken at 1 hour intervals (10-15 min) and compared with manual analysis performed simultaneously (40-60 min), the results of which are shown in Table 6.
Table 6 on-line testing the alkalinity results of the resulting circulating working fluid compared to the results of manual analysis.
Example 7
And a hydrogen peroxide production device of 20 ten thousand tons/year is provided with the equipment and is used for testing the alkalinity of the working fluid of the industrial cycle. The steady flow valve is a needle valve, the volume of the quantitative ring is 60mL, the flushing reagent is dichloroethane, the titration solvent is n-butanol, the titration solute is HCl, the concentration of the titration reagent is 0.1mol/L, and the cleaning water is an HCl aqueous solution with pH=5. Samples were taken at 1 hour intervals (10-15 min) and compared with manual analysis performed simultaneously (40-60 min), the results of which are shown in Table 7.
Table 7 results of on-line testing the alkalinity of the resulting circulating working fluid were compared with results of manual analysis.
Example 8
And a hydrogen peroxide production device of 20 ten thousand tons/year is provided with the equipment and is used for testing the alkalinity of the working fluid of the industrial cycle. The steady flow valve is a needle valve, the volume of the quantitative ring is 20mL, the flushing reagent is toluene, the titration solvent is isobutanol, the titration solute is HCl, the concentration of the titration reagent is 0.01mol/L, and the cleaning water is an HCl aqueous solution with pH=6. Samples were taken at 1 hour intervals (10-15 min) and compared with manual analysis performed simultaneously (40-60 min), the results of which are shown in Table 8.
Table 8 results of on-line testing the alkalinity of the resulting circulating working fluid were compared with results of manual analysis.
From the above examples, it can be seen that the present invention has a difference of 3% from the results of manual titration in practical use, and can replace manual titration analysis.
Claims (9)
1. The method for testing the acidity of an oxidation liquid or the alkalinity of a circulating working liquid in the hydrogen peroxide preparation process by an anthraquinone method comprises the steps of adopting online testing equipment, wherein the online testing equipment comprises an automatic quantitative sampling system and an automatic titration system, the automatic quantitative sampling system comprises a six-way valve, a quantitative ring, a three-way valve and a steady flow valve, and the automatic titration system comprises a potentiometric titration tank, an electrode and quantitative titration equipment;
the six-way valve, the three-way valve and the steady flow valve are sequentially connected; the quantitative ring is connected with a six-way valve; the automatic quantitative sampling system is connected with the potentiometric titration system;
the test method comprises the following steps:
(1) Sampling: the oxidation liquid or the circulating working liquid in the process pipeline enters the quantitative ring through the six-way valve, and the quantitative ring is fully filled and then returns to the process pipeline through the six-way valve;
(2) And (3) sample injection: the inert gas sweeps the quantitative ring to enable the oxidation liquid or the circulating working liquid to enter the potentiometric titration tank through the three-way valve and the steady flow valve in sequence;
(3) Titration: dripping a titration reagent into the potentiometric titration cell by adopting quantitative titration equipment, automatically judging a titration end point according to the change of potential, stopping titration and recording the dosage of the titration reagent;
(4) And (3) result processing: calculating the acidity of the oxidizing solution or the alkalinity of the circulating working solution according to the dosage of the titration reagent;
the titration reagent is a solution of a titration solute dissolved in a titration solvent; the titration solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and ethylene glycol.
2. The test method according to claim 1, wherein the automatic titration system further comprises a cleaning tank and a soaking tank, wherein a liquid draining pipeline is arranged at the bottoms of the potentiometric titration tank, the cleaning tank and the soaking tank, and an electromagnetic valve is arranged on the liquid draining pipeline.
3. The test method according to claim 1, wherein the potentiometric titration cell has a stirring device; the flow stabilizing valve is of a pressure reducing valve or a needle valve; the volume of the quantitative ring is 1-200 mL.
4. The test method according to claim 3, wherein the stirring device is a magnetic stirrer, and the volume of the quantitative ring is 10-100 mL.
5. The test method according to claim 1, wherein the quantitative titration apparatus realizes automatic quantitative titration by controlling the rotation speed of the pump head of the peristaltic pump.
6. The test method of claim 1, the inert gas being nitrogen; the concentration of the titration reagent is 0.001-0.1 mol/L.
7. The test method of claim 1, wherein the titrant is sodium hydroxide or potassium hydroxide when detecting the acidity of the oxidizing solution; when the alkalinity of the circulating working solution is detected, the titrant is HCl or HNO 3 。
8. The test method of claim 2, further comprising preparing an electrode prior to titration: taking out the electrode soaked in the soaking tank, placing the electrode in a cleaning tank, sequentially flushing with a titration reagent and a flushing reagent, and placing the electrode in a potentiometric titration tank;
cleaning of the electrode after titration: the electrode is placed in a cleaning tank, the electrode is cleaned by adopting a flushing reagent, a titration solvent and cleaning water in sequence, and then the electrode is placed in a soaking tank.
9. The test method according to claim 8, wherein the soaking tank is provided with cleaning water, and the cleaning water is an HCl aqueous solution with ph=4-6;
the flushing reagent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, toluene, pseudocumene, mesitylene, C9 heavy aromatic hydrocarbon, C10 heavy aromatic hydrocarbon, dichloroethane and chloroform.
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