CN110922340A - Synthetic method of phenylhydrazine - Google Patents
Synthetic method of phenylhydrazine Download PDFInfo
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- CN110922340A CN110922340A CN201911381637.9A CN201911381637A CN110922340A CN 110922340 A CN110922340 A CN 110922340A CN 201911381637 A CN201911381637 A CN 201911381637A CN 110922340 A CN110922340 A CN 110922340A
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- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229940067157 phenylhydrazine Drugs 0.000 title claims abstract description 53
- 238000010189 synthetic method Methods 0.000 title description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 126
- 239000000243 solution Substances 0.000 claims abstract description 100
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000007788 liquid Substances 0.000 claims abstract description 66
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 42
- 238000006722 reduction reaction Methods 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012954 diazonium Substances 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 29
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- NPNNLGXEAGTSRN-UHFFFAOYSA-N 9-bromo-10-(10-bromoanthracen-9-yl)anthracene Chemical compound C12=CC=CC=C2C(Br)=C(C=CC=C2)C2=C1C1=C(C=CC=C2)C2=C(Br)C2=CC=CC=C12 NPNNLGXEAGTSRN-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 238000005070 sampling Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 239000012085 test solution Substances 0.000 claims description 11
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 7
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 abstract description 4
- 239000000413 hydrolysate Substances 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000008399 tap water Substances 0.000 abstract description 2
- 235000020679 tap water Nutrition 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000003916 acid precipitation Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- ZDPYEHLCFKFDKO-UHFFFAOYSA-N 2-phenyl-1H-pyridazine-3,6-diol Chemical compound C1(=CC=CC=C1)N1NC(=CC=C1O)O ZDPYEHLCFKFDKO-UHFFFAOYSA-N 0.000 description 1
- PCCSBWNGDMYFCW-UHFFFAOYSA-N 5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)-1,3-oxazolidine-2,4-dione Chemical compound O=C1C(C)(C=2C=CC(OC=3C=CC=CC=3)=CC=2)OC(=O)N1NC1=CC=CC=C1 PCCSBWNGDMYFCW-UHFFFAOYSA-N 0.000 description 1
- 239000005772 Famoxadone Substances 0.000 description 1
- 239000005774 Fenamidone Substances 0.000 description 1
- AVKHCKXGKPAGEI-UHFFFAOYSA-N Phenicarbazide Chemical compound NC(=O)NNC1=CC=CC=C1 AVKHCKXGKPAGEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- -1 aromatic hydrazine compounds Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- LMVPQMGRYSRMIW-KRWDZBQOSA-N fenamidone Chemical compound O=C([C@@](C)(N=C1SC)C=2C=CC=CC=2)N1NC1=CC=CC=C1 LMVPQMGRYSRMIW-KRWDZBQOSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JOVOSQBPPZZESK-UHFFFAOYSA-N phenylhydrazine hydrochloride Chemical compound Cl.NNC1=CC=CC=C1 JOVOSQBPPZZESK-UHFFFAOYSA-N 0.000 description 1
- 229940038531 phenylhydrazine hydrochloride Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- CXJSOEPQXUCJSA-UHFFFAOYSA-N pyridaphenthion Chemical compound N1=C(OP(=S)(OCC)OCC)C=CC(=O)N1C1=CC=CC=C1 CXJSOEPQXUCJSA-UHFFFAOYSA-N 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing phenylhydrazine, which adopts aniline, hydrochloric acid, sodium nitrite, water, ammonium bisulfite solution, 98 percent sulfuric acid, liquid caustic soda and caustic soda flakes as main raw materials, wherein the aniline, the hydrochloric acid, the sodium nitrite and tap water are converged by a metering pump through a flowmeter respectively, and then undergo diazotization reaction through a tubular reactor (a Miger reactor) at a high speed to obtain a diazonium salt solution. And (3) enabling the diazonium salt solution after the reaction through the pipeline to flow into a reduction tank to perform cold reduction reaction with the ammonium bisulfite solution, and heating to raise the temperature to perform hot reduction reaction. Adding concentrated sulfuric acid into the reducing solution, and heating for hydrolysis. And (3) carrying out filter pressing operation after the hydrolysate is cooled, adding liquid alkali into the solid crystal obtained by filtering for dissolving, and then adding caustic soda flakes for neutralizing. And (4) performing filter pressing to remove salt, standing and layering the filtrate, wherein the oil phase is the finished product of the phenylhydrazine.
Description
Technical Field
The invention relates to a synthetic method of aromatic hydrazine compounds, in particular to a synthetic method of phenylhydrazine.
Background
Phenylhydrazine of the formula C6H8N2The structural formula is as follows:
。
phenylhydrazine is an important fine chemical intermediate and has wide application in life, is used for synthesizing 1-phenyl semicarbazide which is an intermediate of triazophos as an organic phosphorus pesticide and 1-phenyl-3, 6-dihydroxypyridazine which is an intermediate of pyridaphenthion in pesticide production, is also an intermediate of famoxadone and fenamidone which are new bactericide varieties, and is used as an organic synthesis raw material, an intermediate of industries such as dye, medicine and the like and an analysis reagent, so that the synthesis of phenylhydrazine plays an important role in industrial production. The industrial process of synthesizing phenylhydrazine at present mainly adopts aniline through diazotization, reduction and acid precipitation to obtain phenylhydrazine hydrochloride, and then the phenylhydrazine is obtained through neutralization. Stannous chloride is mostly adopted in the prior reduction process, so that the harm to personnel and environment is inevitable; the acidity of waste liquid generated by acid precipitation is high, and the Chemical Oxygen Demand (COD) is high; the salt waste water generated in the neutralization process is large in quantity and difficult in biochemical treatment, the industrial production cost of the phenylhydrazine is increased, and the market development of phenylhydrazine products is limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the phenylhydrazine synthesis method which has the advantages of simple process, less pollution, less waste, environmental protection and low cost.
In order to solve the technical problems, the invention provides a method for synthesizing phenylhydrazine, which adopts aniline, hydrochloric acid, sodium nitrite, water, ammonium bisulfite solution, 98% sulfuric acid, liquid caustic soda and caustic soda flakes as main raw materials, wherein the mass ratio of the raw materials is aniline: hydrochloric acid: sodium nitrite aqueous solution: water: ammonium bisulfite solution: 98% concentrated sulfuric acid: sodium hydroxide =1: (2.5-4.5): (0.5-2.5): (3-5): (5-5.5): (1.1-1.3): (2.5-4.0).
Preferably, the mass ratio of the raw materials is aniline: hydrochloric acid: sodium nitrite aqueous solution: water: ammonium bisulfite solution: 98% concentrated sulfuric acid: sodium hydroxide =1: 3.5: 1.5: 4: 5.2: 1.2:3.2.
The aniline, the hydrochloric acid, the sodium nitrite and the tap water are converged by a metering pump through a flowmeter respectively, and then pass through a tubular reactor (a Miger reactor) at a high speed to carry out diazotization reaction, so as to obtain a diazonium solution. And (3) enabling the diazonium salt solution after the reaction through the pipeline to flow into a reduction tank to perform cold reduction reaction with the ammonium bisulfite solution, and heating to raise the temperature to perform hot reduction reaction. Adding concentrated sulfuric acid into the reducing solution, and heating for hydrolysis. And (3) carrying out filter pressing operation after the hydrolysate is cooled, adding liquid alkali into the solid crystal obtained by filtering for dissolving, and then adding caustic soda flakes for neutralizing. And (4) performing filter pressing to remove salt, standing and layering the filtrate, wherein the oil phase is the finished product of the phenylhydrazine. The method comprises the following specific steps:
the method comprises the following steps: diazotization, turning on switches of each metering pump, turning on a water inlet valve and a water outlet valve of a water flow meter, flushing dirt in a pipeline, sequentially and slowly turning on a feed valve and a discharge valve of a hydrochloric acid, aniline and sodium nitrite solution flow meter, carrying out diazotization reaction through a tubular reactor at the speed of 2m/s, immediately checking an end point and adjusting when a diazonium solution flows out from a reaction pipeline, stabilizing a rotor of the flow meter as soon as possible, ensuring the end point to be normal, and strictly controlling the temperature of the diazotization reaction to be 50-80 ℃, the pH value to be 0.5-4.5 and the end point to be bluish in the reaction process to obtain the diazonium solution. And after the diazotization reaction is finished, closing a flow meter switch and stopping the metering pump.
Step two: and (3) reducing, namely adding an ammonium bisulfite solution with the content of 60-65% g/ml into a reduction tank, cooling to 5-10 ℃, allowing the diazonium solution after the pipeline reaction in the step one to flow into the reduction tank for reduction reaction, performing cold reduction for 30-60 minutes in the reduction tank, opening a steam valve, heating to 60-80 ℃, timing for reaction for 1 hour, and obtaining a reduction solution.
Step three: and (3) acidolysis, namely adding 98% concentrated sulfuric acid into the reducing solution obtained in the step two, heating to 90-110 ℃, reacting for 2 hours in a timing manner, and cooling to 20 ℃ to obtain acidolysis solution.
Step four: and (3) filtering 1, cooling the acidolysis solution obtained in the third step, and then filtering to obtain phenylhydrazine sulfate solid crystals.
And fifthly, dissociating, namely adding 32% liquid caustic soda into the solid crystals of phenylhydrazine sulfate in the fourth step for dissolving, then adding caustic soda flakes for neutralization, and preserving heat at 40-50 ℃ for 1h to obtain a neutralized liquid.
Step six: and 2, filtering the neutralized liquid obtained in the fifth step to remove sodium salt, and transferring the filtrate to a liquid separation tank.
Step seven: layering, namely standing the filtrate in the liquid separation tank in the sixth step for 30min, and then quickly and slowly separating out the lower-layer alkaline water, wherein the upper-layer oil phase is the finished phenylhydrazine product.
Preferably, in step one, the end point microscopic blue color is measured by placing a small amount of starch-KI solution on a test plate and adding a drop of saturated FeSO4Dipping a small amount of diazonium salt solution on a fine plastic rod, adding the solution into a starch-KI test solution on a test board, observing that the color is changed into slight blue, namely the end point is reached, and if the color is too light or colorless, the solution is NaNO2The insufficient end point is not reached, and the excessive depth is NaNO2In excess.
Preferably, the diazonium salt obtained in step one should be a yellow clear liquid or a creamy yellow liquid, without reddening.
Preferably, in the fourth step, the filtered solid crystal is sampled and detected, and if the phenylhydrazine sulfate content is more than 70%, the next step is carried out, and if the phenylhydrazine sulfate content is not more than 70%, the filtering is continued.
Preferably, in step four, the filtrate collected in the filtrate tank after filtration is used for producing the pyrazolone series product.
Preferably, in the fifth step, the upper layer liquid in the neutralized liquid is sampled and detected, if the phenylhydrazine content is more than 92%, the next step is carried out, and if the phenylhydrazine content is less than 92%, a certain amount of caustic soda flakes are added, and the sampling and detection are carried out again.
Preferably, in step seven, the lower alkaline aqueous layer contains excess liquid alkali and can be reused.
Aiming at the problems of large harm to personnel and environment, large acidity of waste liquid generated by acid precipitation, high Chemical Oxygen Demand (COD), large amount of salt waste water generated in the neutralization process, difficult biochemical treatment, high production cost and the like caused by adopting a highly toxic reducing agent in the prior art, the invention provides the phenylhydrazine synthesis method which has the advantages of simple process, small pollution, less waste, environmental protection and low cost.
The method for synthesizing phenylhydrazine has the advantages that: the reducing agent adopts an ammonium bisulfite solution, so that the toxicity is low, and the harm to personnel and environment is small; the acid precipitation filtrate is used for producing pyrazolone series products and other industrial production, and salt wastewater is not generated in the neutralization process, so that the generated waste is less; the Chemical Oxygen Demand (COD) of the wastewater produced in the production process is low, the biochemical treatment is simple, the environment is protected, the production cost is low, and the filtrate and the layered alkaline water can be recycled from the attached drawing, so that the environment is protected, and the production cost is low.
Drawings
FIG. 1 is a schematic diagram of the process for the synthesis of phenylhydrazine.
Detailed Description
Example 1: a synthetic method of phenylhydrazine adopts aniline, hydrochloric acid, sodium nitrite, water, ammonium bisulfite solution, 98 percent sulfuric acid, liquid caustic soda and caustic soda flakes as main raw materials, and comprises the following steps:
the method comprises the following steps: diazotization, turning on the switches of all metering pumps, turning on a water inlet valve and a water outlet valve of a water flow meter, flushing dirt in a pipeline, sequentially and slowly turning on a feed valve and a discharge valve of a hydrochloric acid, aniline and sodium nitrite solution flow meter, and carrying out diazotization reaction through a tubular reactor at the speed of 2m/s, wherein the mass ratio of aniline: hydrochloric acid: sodium nitrite: water =1: 2.5: 0.5: and 3, when the diazonium salt solution flows out from the reaction pipeline, immediately checking the end point, adjusting, stabilizing the rotor of the flowmeter as soon as possible, ensuring the normal end point, and strictly controlling the temperature of the diazotization reaction at 50 ℃, the pH value at 0.5 and the microscopic blue color at the end point in the reaction process to obtain the diazonium salt solution. The resulting diazonium salt should be a yellow clear liquid or a creamy yellow liquid, without reddening. And after the diazotization reaction is finished, closing a flow meter switch and stopping the metering pump.
The final point of microscopic blue color test method comprises placing a small amount of starch-KI test solution on a test board, adding a drop of saturated FeSO4Dipping a small amount of diazonium salt solution on a fine plastic rod, adding the solution into a starch-KI test solution on a test board, observing that the color is changed into slight blue, namely the end point is reached, and if the color is too light or colorless, the solution is NaNO2The insufficient end point is not reached, and the excessive depth is NaNO2In excess.
Step two: reducing, namely adding an ammonium bisulfite solution with the content of 63% g/ml into a reduction tank, cooling to 5 ℃, and adding aniline according to the mass ratio: ammonium bisulfite solution =1: and 5, flowing the diazonium salt solution subjected to the pipeline reaction in the step one into a reduction tank for reduction reaction, performing cold reduction in the reduction tank for 30 minutes, opening a steam valve, heating to 60 ℃, and reacting for 1 hour in a timing manner to obtain a reduction solution.
Step three: and (2) acid hydrolysis, namely adding 98% concentrated sulfuric acid into the reducing solution obtained in the step two, wherein the mass ratio of aniline: sulfuric acid =1: 1.1, heating to 90 ℃, reacting for 2 hours in a timing manner, and cooling to 20 ℃ to obtain acidolysis solution.
Step four: and (3) filtering 1, cooling the acidolysis solution obtained in the third step, and then filtering to obtain phenylhydrazine sulfate solid crystals. And sampling and detecting the filtered solid crystal, entering the next step if the phenylhydrazine sulfate content is more than 70%, and continuing filtering if the phenylhydrazine sulfate content is not higher than 70%. And (3) the filtrate collected in the filtrate tank after filtration is used for producing pyrazolone series products.
Step five, dissociating, namely adding 32% liquid caustic soda into the solid crystals of phenylhydrazine sulfate in the step four for dissolving, and then adding caustic soda flakes for neutralizing, wherein the mass ratio of aniline: NaOH =1:2.5, and the temperature is kept at 40 ℃ for 1h to obtain a neutralized liquid. And (3) sampling and detecting the supernatant liquid in the neutralization solution, entering the next step if the phenylhydrazine content is more than 92%, adding a certain amount of caustic soda flakes if the phenylhydrazine content is less than 92%, and standing again for sampling and detecting.
Step six: and 2, filtering the neutralized liquid obtained in the fifth step to remove sodium salt, and transferring the filtrate to a liquid separation tank.
Step seven: layering, namely standing the filtrate in the liquid separation tank in the sixth step for 30min, and then quickly and slowly separating out the lower-layer alkaline water, wherein the upper-layer oil phase is the finished phenylhydrazine product, and the lower-layer alkaline water layer contains excessive liquid alkali and can be recycled for continuous use.
The content of phenylhydrazine is 93.1 percent by taking, and the calculation yield is up to 81.3 percent.
Example 2: a synthetic method of phenylhydrazine adopts aniline, hydrochloric acid, sodium nitrite, water, ammonium bisulfite solution, 98 percent sulfuric acid, liquid caustic soda and caustic soda flakes as main raw materials, and comprises the following steps:
the method comprises the following steps: diazotization, turning on the switches of all metering pumps, turning on a water inlet valve and a water outlet valve of a water flow meter, flushing dirt in a pipeline, sequentially and slowly turning on a feed valve and a discharge valve of a hydrochloric acid, aniline and sodium nitrite solution flow meter, and carrying out diazotization reaction through a tubular reactor at the speed of 2m/s, wherein the mass ratio of aniline: hydrochloric acid: sodium nitrite: water =1: 3.5: 1.5: and 4, when the diazonium salt solution flows out from the reaction pipeline, immediately checking the end point, adjusting, stabilizing the rotor of the flowmeter as soon as possible, ensuring the normal end point, and strictly controlling the temperature of the diazotization reaction at 65 ℃, the pH value at 2.5 and the microscopic blue color at the end point in the reaction process to obtain the diazonium salt solution. The resulting diazonium salt should be a yellow clear liquid or a creamy yellow liquid, without reddening. And after the diazotization reaction is finished, closing a flow meter switch and stopping the metering pump.
The final point of microscopic blue color test method comprises placing a small amount of starch-KI test solution on a test board, adding a drop of saturated FeSO4Dipping a small amount of diazonium salt solution on a fine plastic rod, adding the solution into a starch-KI test solution on a test board, observing that the color is changed into slight blue, namely the end point is reached, and if the color is too light or colorless, the solution is NaNO2The insufficient end point is not reached, and the excessive depth is NaNO2In excess.
Step two: reducing, namely adding an ammonium bisulfite solution with the content of 60 percent g/ml into a reduction tank, cooling to 8 ℃, and adding aniline according to the mass ratio: ammonium bisulfite solution =1: and 5.2, flowing the diazonium salt solution subjected to the pipeline reaction in the step one into a reduction tank for reduction reaction, cooling and reducing for 45 minutes in the reduction tank, opening a steam valve, heating to 70 ℃, timing and reacting for 1 hour to obtain the reduction solution.
Step three: and (2) acid hydrolysis, namely adding 98% concentrated sulfuric acid into the reducing solution obtained in the step two, wherein the mass ratio of aniline: sulfuric acid =1: 1.2, heating to 100 ℃, reacting for 2 hours in a timing manner, and cooling to 20 ℃ to obtain acidolysis solution.
Step four: and (3) filtering 1, cooling the acidolysis solution obtained in the third step, and then filtering to obtain phenylhydrazine sulfate solid crystals. And sampling and detecting the filtered solid crystal, entering the next step if the phenylhydrazine sulfate content is more than 70%, and continuing filtering if the phenylhydrazine sulfate content is not higher than 70%. And (3) the filtrate collected in the filtrate tank after filtration is used for producing pyrazolone series products.
Step five, dissociating, namely adding 32% liquid caustic soda into the solid crystals of phenylhydrazine sulfate in the step four for dissolving, and then adding caustic soda flakes for neutralizing, wherein the mass ratio of aniline: NaOH =1:3.2, and the temperature is kept at 45 ℃ for 1h to obtain a neutralized liquid. And (3) sampling and detecting the supernatant liquid in the neutralization solution, entering the next step if the phenylhydrazine content is more than 92%, adding a certain amount of caustic soda flakes if the phenylhydrazine content is less than 92%, and standing again for sampling and detecting.
Step six: and 2, filtering the neutralized liquid obtained in the fifth step to remove sodium salt, and transferring the filtrate to a liquid separation tank.
Step seven: layering, namely standing the filtrate in the liquid separation tank in the sixth step for 30min, and then quickly and slowly separating out the lower-layer alkaline water, wherein the upper-layer oil phase is the finished phenylhydrazine product, and the lower-layer alkaline water layer contains excessive liquid alkali and can be recycled for continuous use.
The content of phenylhydrazine is 94.6 percent by taking, and the calculation yield is as high as 84 percent.
Example 3: a synthetic method of phenylhydrazine adopts aniline, hydrochloric acid, sodium nitrite, water, ammonium bisulfite solution, 98 percent sulfuric acid, liquid caustic soda and caustic soda flakes as main raw materials, and comprises the following steps:
the method comprises the following steps: diazotization, turning on the switches of all metering pumps, turning on a water inlet valve and a water outlet valve of a water flow meter, flushing dirt in a pipeline, sequentially and slowly turning on a feed valve and a discharge valve of a hydrochloric acid, aniline and sodium nitrite solution flow meter, and carrying out diazotization reaction through a tubular reactor at the speed of 2m/s, wherein the mass ratio of aniline: hydrochloric acid: sodium nitrite: water =1: 4.5: 2.5: and 5, when the diazonium salt solution flows out from the reaction pipeline, immediately checking the end point, adjusting, stabilizing the rotor of the flow meter as soon as possible, ensuring the normal end point, and strictly controlling the temperature of the diazotization reaction at 75 ℃, the pH value at 4 and the microscopic blue color at the end point in the reaction process to obtain the diazonium salt solution. The resulting diazonium salt should be a yellow clear liquid or a creamy yellow liquid, without reddening. And after the diazotization reaction is finished, closing a flow meter switch and stopping the metering pump.
The final point of microscopic blue color test method comprises placing a small amount of starch-KI test solution on a test board, adding a drop of saturated FeSO4Dipping a small amount of diazonium salt solution on a fine plastic rod, adding the solution into a starch-KI test solution on a test board, observing that the color is changed into slight blue, namely the end point is reached, and if the color is too light or colorless, the solution is NaNO2The insufficient end point is not reached, and the excessive depth is NaNO2In excess.
Step two: reducing, namely adding an ammonium bisulfite solution with the content of 63% g/ml into a reduction tank, cooling to 5 ℃, and adding aniline according to the mass ratio: ammonium bisulfite solution =1: 5.5, flowing the diazonium salt solution after the pipeline reaction in the step one into a reduction tank for reduction reaction, cooling and reducing for 50 minutes in the reduction tank, opening a steam valve, heating to 75 ℃, timing and reacting for 1 hour to obtain the reduction solution.
Step three: and (2) acid hydrolysis, namely adding 98% concentrated sulfuric acid into the reducing solution obtained in the step two, wherein the mass ratio of aniline: sulfuric acid =1: 1.3, heating to 110 ℃, reacting for 2 hours in a timing manner, and cooling to 20 ℃ to obtain acidolysis solution.
Step four: and (3) filtering 1, cooling the acidolysis solution obtained in the third step, and then filtering to obtain phenylhydrazine sulfate solid crystals. And sampling and detecting the filtered solid crystal, entering the next step if the phenylhydrazine sulfate content is more than 70%, and continuing filtering if the phenylhydrazine sulfate content is not higher than 70%. And (3) the filtrate collected in the filtrate tank after filtration is used for producing pyrazolone series products.
Step five, dissociating, namely adding 32% liquid caustic soda into the solid crystals of phenylhydrazine sulfate in the step four for dissolving, and then adding caustic soda flakes for neutralizing, wherein the mass ratio of aniline: NaOH =1:4.0, and the temperature is kept at 48 ℃ for 1h to obtain a neutralized liquid. And (3) sampling and detecting the supernatant liquid in the neutralization solution, entering the next step if the phenylhydrazine content is more than 92%, adding a certain amount of caustic soda flakes if the phenylhydrazine content is less than 92%, and standing again for sampling and detecting.
Step six: and 2, filtering the neutralized liquid obtained in the fifth step to remove sodium salt, and transferring the filtrate to a liquid separation tank.
Step seven: layering, namely standing the filtrate in the liquid separation tank in the sixth step for 30min, and then quickly and slowly separating out the lower-layer alkaline water, wherein the upper-layer oil phase is the finished phenylhydrazine product, and the lower-layer alkaline water layer contains excessive liquid alkali and can be recycled for continuous use.
The content of phenylhydrazine is 92.9 percent, and the calculation yield is as high as 81.9 percent.
Example 4: a synthetic method of phenylhydrazine adopts aniline, hydrochloric acid, sodium nitrite, water, ammonium bisulfite solution, 98 percent sulfuric acid, liquid caustic soda and caustic soda flakes as main raw materials, and comprises the following steps:
the method comprises the following steps: diazotization, turning on the switches of all metering pumps, turning on a water inlet valve and a water outlet valve of a water flow meter, flushing dirt in a pipeline, sequentially and slowly turning on a feed valve and a discharge valve of a hydrochloric acid, aniline and sodium nitrite solution flow meter, and carrying out diazotization reaction through a tubular reactor at the speed of 2m/s, wherein the mass ratio of aniline: hydrochloric acid: sodium nitrite: water =1: 4.5: 2.5: and 5, when the diazonium salt solution flows out from the reaction pipeline, immediately checking the end point, adjusting, stabilizing the rotor of the flow meter as soon as possible, ensuring the normal end point, and strictly controlling the temperature of the diazotization reaction at 80 ℃, the pH value at 4.5 and the microscopic blue color at the end point in the reaction process to obtain the diazonium salt solution. The resulting diazonium salt should be a yellow clear liquid or a creamy yellow liquid, without reddening. And after the diazotization reaction is finished, closing a flow meter switch and stopping the metering pump.
The final point of microscopic blue color test method comprises placing a small amount of starch-KI test solution on a test board, adding a drop of saturated FeSO4Dipping a small amount of diazonium salt solution on a fine plastic rod, adding the solution into a starch-KI test solution on a test board, observing that the color is changed into slight blue, namely the end point is reached, and if the color is too light or colorless, the solution is NaNO2The insufficient end point is not reached, and the excessive depth is NaNO2In excess.
Step two: reducing, namely adding an ammonium bisulfite solution with the content of 65 percent g/ml into a reduction tank, cooling to 10 ℃, and adding aniline according to the mass ratio: ammonium bisulfite solution =1: 5.5, flowing the diazonium salt solution after the pipeline reaction in the step one into a reduction tank for reduction reaction, cooling and reducing for 60 minutes in the reduction tank, opening a steam valve, heating to 80 ℃, timing and reacting for 1 hour to obtain the reduction solution.
Step three: and (2) acid hydrolysis, namely adding 98% concentrated sulfuric acid into the reducing solution obtained in the step two, wherein the mass ratio of aniline: sulfuric acid =1: 1.3, heating to 110 ℃, reacting for 2 hours in a timing manner, and cooling to 20 ℃ to obtain acidolysis solution.
Step four: and (3) filtering 1, cooling the acidolysis solution obtained in the third step, and then filtering to obtain phenylhydrazine sulfate solid crystals. And sampling and detecting the filtered solid crystal, entering the next step if the phenylhydrazine sulfate content is more than 70%, and continuing filtering if the phenylhydrazine sulfate content is not higher than 70%. And (3) the filtrate collected in the filtrate tank after filtration is used for producing pyrazolone series products.
Step five, dissociating, namely adding 32% liquid caustic soda into the solid crystals of phenylhydrazine sulfate in the step four for dissolving, and then adding caustic soda flakes for neutralizing, wherein the mass ratio of aniline: NaOH =1:4.0, and the temperature is kept at 50 ℃ for 1h to obtain a neutralized liquid. And (3) sampling and detecting the supernatant liquid in the neutralization solution, entering the next step if the phenylhydrazine content is more than 92%, adding a certain amount of caustic soda flakes if the phenylhydrazine content is less than 92%, and standing again for sampling and detecting.
Step six: and 2, filtering the neutralized liquid obtained in the fifth step to remove sodium salt, and transferring the filtrate to a liquid separation tank.
Step seven: layering, namely standing the filtrate in the liquid separation tank in the sixth step for 30min, and then quickly and slowly separating out the lower-layer alkaline water, wherein the upper-layer oil phase is the finished phenylhydrazine product, and the lower-layer alkaline water layer contains excessive liquid alkali and can be recycled for continuous use.
The content of phenylhydrazine is 92.5 percent, and the calculation yield is up to 82.9 percent.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (9)
1. The method for synthesizing phenylhydrazine is characterized in that aniline, hydrochloric acid, sodium nitrite, water, ammonium bisulfite solution, 98% sulfuric acid, liquid caustic soda and caustic soda flakes are used as main raw materials, and the mass ratio of the raw materials is that aniline: hydrochloric acid: sodium nitrite aqueous solution: water: ammonium bisulfite solution: 98% concentrated sulfuric acid: sodium hydroxide =1: (2.5-4.5): (0.5-2.5): (3-5): (5-5.5): (1.1-1.3): (2.5-4.0).
2. The method for synthesizing phenylhydrazine according to claim 1, wherein the mass ratio of the raw materials is aniline: hydrochloric acid: sodium nitrite aqueous solution: water: ammonium bisulfite solution: 98% concentrated sulfuric acid: sodium hydroxide =1: 3.5: 1.5: 4: 5.2: 1.2:3.2.
3. The method for synthesizing phenylhydrazine is characterized by comprising the following steps:
the method comprises the following steps: diazotization, namely adding water, hydrochloric acid, aniline and sodium nitrite aqueous solution into a pipeline of a tubular reactor in sequence through a flowmeter to carry out diazotization reaction, controlling the reaction temperature to be 50-80 ℃, the pH value to be 0.5-4.5 and the end point to be bluish to obtain a diazonium salt solution;
step two: reducing, namely adding an ammonium bisulfite solution with the content of 60-65% g/ml into a reduction tank, cooling to 5-10 ℃, allowing a diazonium salt solution obtained after the pipeline reaction in the step I to flow into the reduction tank through a funnel for reduction reaction, performing cold reduction in the reduction tank for 30-60 minutes, opening a steam valve, heating to 60-80 ℃, timing for reaction for 1 hour, and obtaining a reduction solution;
step three: acid hydrolysis, namely adding 98% concentrated sulfuric acid into the reducing solution obtained in the step two, heating to 90-110 ℃, reacting for 2 hours in a timing manner, and cooling to 20 ℃ to obtain acid hydrolysis solution;
step four: filtering 1, namely cooling the acidolysis solution obtained in the third step, and then filtering to obtain phenylhydrazine sulfate solid crystals;
step five, dissociating, namely adding 32% liquid caustic soda into the phenylhydrazine sulfate solid crystal in the step four for dissolving, then adding caustic soda flakes for neutralizing, and preserving heat at 40-50 ℃ for 1h to obtain a neutralized solution;
step six: filtering 2, filtering the neutralized liquid in the fifth step to remove sodium salt, and transferring the filtrate to a liquid separation tank;
step seven: layering, namely standing the filtrate in the liquid separation tank in the sixth step for 30min, and then quickly and slowly separating out the lower-layer alkaline water, wherein the upper-layer oil phase is the finished phenylhydrazine product.
4. The method for synthesizing phenylhydrazine according to claim 3, wherein in step one, the end point microscopic blue color is measured by placing a small amount of starch-KI test solution on a test plate and adding a drop of saturated solutionFeSO4Dipping a small amount of diazonium salt solution on a fine plastic rod, adding the solution into a starch-KI test solution on a test board, observing that the color is changed into slight blue, namely the end point is reached, and if the color is too light or colorless, the solution is NaNO2The insufficient end point is not reached, and the excessive depth is NaNO2In excess.
5. The method for synthesizing phenylhydrazine according to claim 3, wherein the diazonium salt obtained in step one is a yellow clear liquid or a creamy yellow liquid, and does not become red.
6. The method for synthesizing phenylhydrazine according to claim 1, wherein in step four, the filtered solid crystals are sampled and detected, and if the phenylhydrazine sulfate content is above 70%, the next step is performed, and if the phenylhydrazine sulfate content is not above 70%, the filtering is continued.
7. The method for synthesizing phenylhydrazine according to claim 1, wherein in step four, the filtrate collected in the filtrate tank after filtration is used for producing pyrazolone series products.
8. The method for synthesizing phenylhydrazine according to claim 1, wherein in step five, the upper layer liquid in the neutralized liquid is sampled and detected, if the phenylhydrazine content is more than 92%, the next step is performed, and if the phenylhydrazine content is less than 92%, the caustic soda flakes are added, and the sampling and detection are performed again by standing.
9. The method for synthesizing phenylhydrazine according to claim 1, wherein in step seven, the lower alkaline water layer contains excess liquid alkali and can be reused.
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