CN101412662B - Method for preparing p-dihydroxy benzene - Google Patents
Method for preparing p-dihydroxy benzene Download PDFInfo
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Abstract
The invention relates to a method for preparing hydroquinone (HQ for short), which comprises the following steps: (1) dripping aqueous solution of sodium nitrite into sulphuric acid solution of para-aminophenol to carry out diazotization reaction to obtain dark brown diazonium solution, and using urea, thiourea, thioether, thioalcohol and the like to destroy excessive sodium nitrite; (2) pre-adding dilute sulphuric acid into a reaction kettle, refluxing and dripping the diazonium solution obtained in step (1) to carry out hydrolysis reaction; (3) after extracting hydroquinone from the hydrolyzed solution, using water-phase dilute sulphuric acid in the hydrolysis reaction, and after extracting oil phase and removing solvent, obtaining the crude product of the hydroquinone; and (4) refining the crude product and carrying out post treatment.
Description
Technical field
The invention relates to the Resorcinol preparation method of (being called for short HQ).
Background technology
Resorcinol is important source material, auxiliary agent and the intermediate of rubber, medicine, dyestuff, agricultural chemicals and fine chemistry industry, be mainly used in the preparation filmstrip the black-and-white development agent, produce anthraquinone dye and azoic dyestuff, synthetic gas desulfurization technology catalyzer, make stablizer and antioxidant, the anticoagulant etc. of anti-aging agent, monomer stopper, food and the coating varnish of rubber and plastics.In addition, also extensible other fine chemical product that is processed as of Resorcinol, as MEHQ, 1,4-diamino leuco compound, quinizarin etc.In recent years, the Application Areas of Resorcinol is also being widened gradually.
The synthetic method of Resorcinol is more, kind surplus in the of up to the present existing 10, and that has wherein realized suitability for industrialized production has aniline oxidation style, p-Diisopropylbenzene peroxidation method, phenol-hydrogen peroxide hydroxylation method, a dihydroxyphenyl propane method etc.
Phenol-hydrogen peroxide hydroxylation method: this method is to be raw material with phenol, under catalyst action, with hydroperoxidation, generates Resorcinol and pyrocatechol.Obtain thick Resorcinol through deviating from water, high boiling material, phenol and isolating pyrocatechol, make the Resorcinol product through dissolving, decolouring, recrystallization again.Compare with aniline process and diisopropylbenzene(DIPB) method, phenol hydroxylation method reaction process and lock out operation are simple, so energy consumption is lower, and " three wastes " pollute few.In addition, the pyrocatechol of coproduction also is very important fine chemical product, is the intermediate of vanillin food grade,1000.000000ine mesh, synthetic musk and medicine, agricultural chemicals and dyestuff, also can directly be used as polymerization retarder, oxidation inhibitor etc., and this makes the extremely people favor of phenol hydroxylation technology.
The dihydroxyphenyl propane method: phenol and acetone generate dihydroxyphenyl propane with concentrated hydrochloric acid, H2SO4 or ion-exchange resin catalyzed reaction, under the basic catalyst effect, quantitatively are cracked into phenol and isopropenyl phenol again, and the latter uses hydrogen peroxide oxidation, can obtain Resorcinol and acetone.Phenol and acetone that reaction generates can be recycled.This operational path " three wastes " is few, and the yield height is therefore good in economic efficiency.
Also have a kind of method in addition: p-aminophenol prepares Resorcinol technology through high temperature, highly pressured hydrolysis.
The patent US3 of U.S. Koppers company application, 862, in 247 and GB1,460,655, adopt p-aminophenol and monoammonium sulfate reactant aqueous solution, monoammonium sulfate and p-aminophenol mol ratio are 1.5-4, temperature of reaction 240-280 ℃, react 2-6 hour, yield is up to 72.7% at 58.4-72.7%.
These technology existing problems mainly are: 1. have more tar to generate in the reaction process; 2. Resorcinol product per ton has sulfuric acid (hydrogen) the ammonium black waste water of 15-17 ton, is difficult to recycling treatment; 3. reaction yield about 70%, and thick Resorcinol purity is low, the refining only 55-60% of back total recovery that purifies, raw materials cost height; 4. severe reaction conditions (240 ℃/3Mpa, strongly-acid), equipment corrosion is serious, the difficult choosing of material.
The U.S. Pat 4 of Switzerland Efim Biller application, 270, in 010, adopt expensive methylsulphonic acid, the molar ratio of methylsulphonic acid and p-aminophenol is 1: 1, earlier 240 ℃ of hydrolysis reaction 3 hours, after extracting the Resorcinol of hydrolysis generation, in 240 ℃ of reactions 3 hours, still contain 11.5% unreacted of initial input p-aminophenol amount, transformation efficiency 88.53% this moment in the raffinate water layer again.
The subject matter that this technology exists is: the 1. reaction process cooling that repeatedly heats up, and frequent intensification and cooling, energy consumption is very high; 2. adopting methylsulphonic acid is hydrolyst, reacts under High Temperature High Pressure, and equipment corrosion is serious, the difficult choosing of material; When 3. the raffinate water layer of selective extraction Resorcinol is used further to hydrolysis, extraction agent gas must be promoted only, otherwise can generate the similar thing of Resorcinol, increase the refining difficulty of product.
Press among the clear 53-2433 of open patent of KCC's application in Mitsui east, adopts p-aminophenol and hydrogenchloride and hydrogen bromide according to hydrolysis in 1: 2 respectively, 230 ℃ of hydrolysis temperatures, hydrolysis time 7 hours; When hydrogenchloride was hydrolyst, the transformation efficiency of p-aminophenol was 75.0%, and the selectivity of Resorcinol is 45.3%; When hydrogen bromide was hydrolyst, the transformation efficiency of p-aminophenol was 80.1%, and the selectivity of Resorcinol is 50.7%.The spy of the said firm application opens among the clear 53-12824, adopts p-aminophenol and hydrogenchloride and hydrogen bromide in 1: 1 ratio hydrolysis respectively, and hydrolysis temperature is 250 ℃, hydrolysis time 6 hours; The yield of Resorcinol is respectively 90.1% and 93.7%.
This technology weak point is: 1. have more tar to generate in the reaction process; 2. react on up to carrying out under 250 ℃ the strong acidic condition, condition is very harsh, 3. can find from the contrast of two patents of above-mentioned Mitsui east pressure company, during hydrolysis the ratio of p-aminophenol and hydrogen halide to the influence of hydrolysis yield much smaller than the influence of hydrolysis temperature to yield; Especially in the time of more than 240 ℃, the hydrolysis yield obviously improves, but can find by consulting of handbook of corrosion, there is a weight break point in acid to corrosion of metal between 230-240 ℃, most of metals are more than 240 ℃, corrosion is aggravation rapidly, thereby equipment corrosion is serious, is difficult to select the suitable device material.
Summary of the invention
The objective of the invention is: a kind of novel method of utilizing the hydrolysis of p-aminophenol process diazotization to prepare Resorcinol is provided.
The objective of the invention is to realize with following technical proposal:
The reaction equation that p-aminophenol diazotization hydrolysis reaction prepares Resorcinol is:
Diazotization reaction
Hydrolysis reaction
Concrete preparation and process for refining process are:
(1) under stirring and cooling off, in the sulphuric acid soln of p-aminophenol, drip sodium nitrite in aqueous solution and carry out diazotization reaction, obtain Vandyke brown diazonium liquid.Destroy excessive Sodium Nitrite with urea, thiocarbamide, thioether, mercaptan etc.;
(2) the pre-dilute sulphuric acid that adds in reactor, refluxing drips the diazonium liquid that (1) step obtains down, and reaction is hydrolyzed.This reaction both can be intermittently also can serialization;
(3) hydrolyzed solution is after extracting Resorcinol, and water dilute sulphuric acid cover is used for hydrolysis reaction, obtains the Resorcinol crude product after the extraction oil phase is sloughed solvent;
(4) can obtain the pure product of white needles Resorcinol behind the Resorcinol crude product refining, we have adopted following three kinds of methods, all reach satisfied effect: the one, and the Resorcinol crude product is through activated carbon decolorizing repeatedly, repeatedly water crystallization obtains the pure product of Resorcinol.General decolouring adds the crystalline operation and needs more than twice at least.The 2nd, elder generation distills the Resorcinol crude product and obtains near-white or flaxen Resorcinol under high vacuum, adopt activated carbon decolorizing, water crystallization once can obtain white crystals again.The 3rd, directly adopt the nitrogen heating sublimation to separate and can obtain the pure product of Resorcinol.
In the above-mentioned steps (1), the sulphuric acid soln weight percent concentration is 5～50%, preferred 10～30%, best 12～20%; The molar ratio of contained sulfuric acid amount is 1: 1.5 to 1: 2.5 in p-aminophenol amount and the aqueous sulfuric acid, preferred 1: 1.8 to 1: 2.2, and best 1: 1.9 to 1: 2.1; The molar ratio of p-aminophenol amount and Sodium Nitrite amount is 1: 0.9 to 1: 2, preferred 1: 1 to 1: 1.3, and best 1: 1.02 to 1: 1.1.Temperature of reaction is-15～15 ℃, preferred-10～5 ℃, and best-5～0 ℃.
Described Sodium Nitrite can directly divide some batches of addings, also can be made into the aqueous solution and drip.The concentration of sodium nitrite in aqueous solution should guarantee can dissolve fully under the envrionment temperature at least, also can suitably be lower than this concentration;
Reaction finishes, and adds urea, thiocarbamide, thioether, mercaptan etc. to destroy excessive Sodium Nitrite.Above-mentioned admixture both can use separately, also can two or morely use together.Preferred urea and/or thiocarbamide, the amount of adding is being advisable by the excessive Sodium Nitrite of completely destroy.
In the above-mentioned steps (2), hydrolysis is 5～75% with vitriolic concentration, preferred 15～55%, best 25～35%; P-aminophenol amount and hydrolysis are 1: 1 to 1: 24 with the mol ratio of sulfuric acid amount in the aqueous sulfuric acid, preferred 1: 5 to 1: 18, and best 1: 9 to 1: 12; Temperature of reaction is 95～115 ℃, preferred 100～110 ℃, and best 102～108 ℃.
Hydrolysis reaction both can intermittently also can serialization.Diazonium liquid and hydrolysis sulfuric acid both can drip by a certain percentage simultaneously, also can add part or all of hydrolysis sulfuric acid in advance in reactor;
In general, rhythmic reaction can partly or entirely join the hydrolysis aqueous sulfuric acid in the hydrolysis kettle.If continuous reaction, hydrolysis sulfuric acid partly adds hydrolysis kettle, and part is added dropwise in the hydrolysis kettle with diazonium liquid simultaneously in proportion.
In the above-mentioned steps (3), hydrolyzed solution extracts after being cooled to room temperature, this process of cooling both can be cooled off with recirculated cooling water, after also can in corrosion-resistant heat exchanger, carrying out heat exchange with the raffinate spent acid that extracts Resorcinol, be cooled to room temperature with recirculated cooling water again, this raffinate spent acid cover is used for hydrolysis reaction, so can make full use of heat energy, reduces energy expenditure.
Resorcinol in the hydrolyzed solution is extracted, and is hydrolyzed solution and extraction agent adverse current to be carried out the serialization extraction treatment by extraction plant obtain extracting oil phase and raffinate water.Described extraction plant is every sieve formula extraction tower, also can be plural serial stage extraction whizzer.
Hydrolyzed solution extraction solvent for use can be ether, alcohol, ester, ketone or halogenated hydrocarbon.Ethers is as ether, propyl ether, butyl ether; Alcohols is as butanols, amylalcohol, hexanol, octanol and butyleneglycol etc.; The ester class is as vinyl acetic monomer, propyl acetate, acetic acid (just) butyl ester, tributyl phosphate, trioctyl phosphate etc.; Ketone is as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl tertbutyl ketone etc.; Halogenated hydrocarbon is as methylene dichloride, chloroform, ethylene dichloride, trieline, trichloropropane, Benzene Chloride, dichlorobenzene etc.; Preferred n-butyl acetate, methyl iso-butyl ketone (MIBK), dichlorobenzene etc.
Described extraction oil phase mainly contains Resorcinol and extraction agent.The main sulfur acid of described raffinate water, sodium pyrosulfate, water and do not extract Resorcinol completely on a small quantity.
Both removing of extraction agent can also can be reduced pressure by normal pressure in the extraction oil phase.For making solvent removal complete, when normal pressure precipitation latter temperature rises to 120 ℃, can progressively be with negative pressure also to be stabilized in gradually about 0.09Mpa, both made feed temperature be no more than 150 ℃, make solvent removal complete again simultaneously.
In the above-mentioned steps (3), before with hydrolyzed solution cooling extraction, can also carry out processed to hydrolyzed solution earlier,, can in follow-up extracting operation, reduce the consumption of extraction agent like this to reduce the water content of hydrolyzed solution.It is that hydrolyzed solution is carried out air distillation or underpressure distillation processing that hydrolyzed solution is carried out processed.When hydrolyzed solution was carried out air distillation, pressure was environmental stress, and temperature is to carry out under 100～115 ℃ the condition.During the air distillation concentrating hydrolysate, be equivalent to hydrolysis reaction and still carrying out, therefore can suitably shorten hydrolysis time; When hydrolyzed solution being carried out the underpressure distillation processing, at pressure is that 0.070～0.095Mpa and temperature of charge are to carry out under 50～100 ℃ of conditions, during the underpressure distillation concentrating hydrolysate, can after finishing, hydrolysis progressively reduce pressure, utilize the temperature of hydrolyzed solution itself, the decompression back overflows water vapor to reduce the boiling point of water, makes full use of the heat of hydrolyzed solution self.
In the above-mentioned steps (4), the refining of thick Resorcinol can adopt three kinds of methods:
First kind of process for purification is repeatedly decolouring, crystallization process repeatedly.Take off in the thick Resorcinol of most solvent and add an amount of water, active carbon for decolorization, zinc powder (or iron powder) respectively, be warming up to 80-85 ℃ of little backflow, drip 30% dilute sulphuric acid, 0.5-1hr again refluxes, filtered while hot is removed gac, filter cake with about 90 ℃ hot wash once, crystallization is lowered the temperature, separated out to filtrate naturally.Suction filtration obtains faint yellow Resorcinol, contains to wet about 10%, and primary crystallization Resorcinol yield is 80%; The Resorcinol that primary crystallization obtains repeats above-mentioned decolouring, crystallization operation 1-2 time, till the Resorcinol that obtains (ash) white, needle-shaped crystals; Mother liquor extracts Resorcinol after concentrating, and precipitation obtains the Resorcinol crude product, re-refines to obtain the pure product of Resorcinol.
The consumption of the used gac of decolorization is 1～20% of a Resorcinol crude product amount, preferred 2～15%, best 4～10%; The consumption of zinc powder is 0.1～15% of a Resorcinol crude product amount, preferred 0.5～10%, best 1～5%; Vitriolic concentration is 10～60%, preferred 15～50%, best 20～40%; The vitriolic consumption is 5～45% of a Resorcinol crude product amount, preferred 10～30%, best 15～25%; Bleaching temperature is in 80～90 ℃ of little backflows or total reflux.
Second kind of process for purification adds once decolouring, crystallization process for distillation.Resorcinol crude product behind the precipitation carries out molecular distillation earlier, distillatory vacuum tightness is 1～5mmHg, when the liquid temperature reaches 170 ℃, discharging is very fast, continues slow heat temperature raising, makes normal discharging, 250 ℃ of the whole Wen Keda of still liquid, the Resorcinol that obtains of distillation is faint yellow or near-white, operates according to decolouring and crystalline step in the process for purification one, and the crystallization of once decolouring can obtain appearance white, Resorcinol finished product that content is qualified.
The third process for purification is a nitrogen heating sublimation method.With join behind the Resorcinol crude product porphyrize behind the precipitation middle and lower part have one deck core (in the sublimer of the dividing plate of aperture＜0.1mm), feed temperature from the sublimer bottom and be 150～170 ℃ hot nitrogen, with Resorcinol in 140～160 ℃ of distillations.By controlling the temperature of follow-up each condensation collector, Resorcinol is separated out in first receptor in 80～100 ℃, and yellow impurities is not separated out at 80～100 ℃, in second and third susceptor, can collect yellow impurities after being cooled to room temperature, thereby separate the pure product of white Resorcinol that obtain.The Resorcinol that this method obtains need not activated carbon decolorizing, crystallization, and the distillation yield is about 92%.
The present invention has following good result: no tar generates in (1) diazotization reaction of the present invention and the hydrolysis reaction.Hydrolyzed solution extracts can overlap after Resorcinol also concentrates and is used for hydrolysis reaction, concentrates the water jacket that steams and is used for diazotization reaction, realizes hydrolysis spent acid, wastewater zero discharge; Because spent acid is repeatedly applied mechanically the posthydrolysis yield and descended, need further to concentrate and to apply mechanically once more behind the desalination and do not influence yield.(2) hydrolysis reaction can carry out in serialization in present method, improves production capacity; (3) the inventive method is a kind of industrialized process for preparing, adopt the distillation crystallization method can obtain high-quality Resorcinol, content can reach more than 99.5%, and the hydrolysis yield is about 90%, the aftertreatment yield can reach 85% in p-aminophenol Resorcinol total recovery more than 95%.
Embodiment
Embodiment 1:
The Resorcinol preparation method carries out according to the following steps:
Diazotization reaction: in the 1000L reactor, add 15% sulfuric acid 408Kg (0.625Kmol), industrial goods 98% p-aminophenol 27.8Kg (0.25Kmol), stirring is cooled to-5～0 ℃, drip 40% sodium nitrite in aqueous solution 48Kg (0.275Kmol), dropping time 30-45min, drip Bi Baowen 0.5hr, add 1.5Kg urea, stir 15min, emit when not obvious when nitrogen, add 1.5Kg thiocarbamide restir 15min.Dropping, insulation and charge temperature all remain on-5～5 ℃, obtain Vandyke brown diazonium liquid 470-480Kg, in 0 ℃ of preservation.
Hydrolysis reaction: in the 2000L reactor, add 30% sulfuric acid 1000Kg, be heated to 106-108 ℃ of backflow, above-mentioned diazonium liquid is incubated in about 0 ℃ down and drips, drip 1-2hr, in the 102-104 ℃ of insulation 3-4hr that refluxes, cooling obtains light brown hydrolyzed solution 1460Kg, divides the extraction hydrolyzed solution four times with methyl iso-butyl ketone (MIBK) 300Kg, obtain red-brown extraction oil reservoir 315-320Kg, the extraction oil reservoir contains Resorcinol about 7%; Raffinate water layer 1450Kg contains Resorcinol 0.1-0.2%, and sulfuric acid content is 23-25%.Getting raffinate water layer 200Kg is extracted to Resorcinol content at twice with methyl iso-butyl ketone (MIBK) (MIBK) 50Kg and overlaps below 0.05% and be used for diazotization reaction; The about 250Kg of 1250Kg dilute sulphuric acid normal pressure dehydration is concentrated into 30% in addition, and cover is used for hydrolysis reaction.
Aftertreatment:
(1) repeatedly decolouring, crystallization process repeatedly: Resorcinol oil reservoir precipitation to liquid temperature under the vacuum of 0.075～0.095Mpa that extraction obtains reaches 100 ℃, and the solvent methyl iso-butyl ketone (MIBK) is taken off to the greatest extent fully.Cooling slightly, add entry 40Kg, GH-81 gac 1Kg, zinc powder (or iron powder) 0.6Kg, be warming up to 80-85 ℃ of little backflow, drip 30% sulfuric acid 3.5Kg, 0.5-1hr again refluxes, filtered while hot is removed gac (adding the 0.16Kg Sodium Pyrosulfite in the filtrate Receiving bin in advance), and filter cake washs once with about 90 ℃ hot water 30Kg, and crystallization is lowered the temperature, separated out to filtrate naturally.Suction filtration obtains the about 22Kg of faint yellow Resorcinol, contains to wet about 10%, and the primary crystallization yield is 80%; Filtration obtains red-brown mother liquor 70Kg, contain Resorcinol 6-7%, primary crystallization Resorcinol wet basis 22Kg, add water 35Kg, gac 1Kg, zinc powder (or iron powder) 0.6Kg, the same operation temperature rising reflux decolouring, filtered while hot, mother liquor nature decrease temperature crystalline, suction filtration obtains the pure product 10Kg of needle-like (ash) white crystals Resorcinol, and mother liquor is concentrated to concentrate and reclaimed Resorcinol.
(2) distillation adds decolouring, crystallization process: a collection of or many batches of laminated and washing deacidifications of (is example with four batches) extraction oil, adopt 1%NaHCO
3The washing oil reservoir takes off to the greatest extent in vacuum precipitation to the solvent of 0.075-0.095Mpa to pH=5-6 about solution 120Kg.After the liquid temperature reached 100 ℃, changing the decompression precipitation device was water distilling apparatus, vacuum tightness 1-5mmHg, and when the liquid temperature reached 170 ℃, discharging was very fast, continued slow heat temperature raising and made normal discharging, warm about 250 ℃ eventually of still liquid.The Resorcinol that distills out adds entry 160Kg, GH-101 gac 4Kg, zinc powder 2.4Kg, be warming up to 80-85 ℃ of little backflow, drip 30% sulfuric acid 14Kg, 0.5-1hr again refluxes, filtered while hot is removed gac, filter cake washs once with about 90 ℃ hot water 120Kg, and crystallization is lowered the temperature, separated out to filtrate naturally.Suction filtration obtains the about 100Kg of faint yellow Resorcinol, contains to wet about 10%, and one time water crystallization can obtain white, needle-shaped crystals, and refining yield is 90%; Filter mother liquor 280Kg, contain Resorcinol 5～7%, mother liquor extracts Resorcinol with 120Kg methyl iso-butyl ketone (MIBK) (MIBK), adds decolouring, crystallization method by above-mentioned distillation behind the precipitation and handles and obtain Resorcinol again.
(3) nitrogen heating sublimation method.The Resorcinol crude product 28Kg (content 90%) that precipitation is obtained is ground into fine particle, join the middle and lower part have one deck core (in the sublimer of the dividing plate of aperture＜0.1mm), from the sublimer bottom with 150～200m
3/ hr feeding temperature is 150～170 ℃ a hot nitrogen, and Resorcinol is distilled out in 140～160 ℃.By controlling the temperature of follow-up each condensation collector, Resorcinol is separated out in first receptor in 80～100 ℃, and the yellow impurities para benzoquinone is not separated out at 80～100 ℃.In second and third susceptor, can collect yellow para benzoquinone 1.6Kg after being cooled to room temperature, obtain the about 23Kg of the pure product of white Resorcinol.The Resorcinol that this method obtains need not activated carbon decolorizing, crystallization, and the distillation yield is about 92%.
Embodiment 2 to embodiment 7:
The preparation method is with embodiment 1, and difference is: diazotization reaction sulfuric acid concentration difference.
| The embodiment sequence number | Diazotization | Acid is formed at the bottom of the hydrolysis | Hydrolyzed solution | |||
| Acidity % | Sulfuric acid Kg | Water Kg | Weight Kg | HQ％ | Yield % | |
| 2 | 10 | 300 | 700 | 1402 | 1.79 | 91.26 |
| 3 | 13 | 300 | 700 | 1476.4 | 1.73 | 92.88 |
| 4 | 17 | 150 | 350 | 987.3 | 2.56 | 91.91 |
| 5 | 22.5 | 300 | 700 | 1338.1 | 1.75 | 85.15 |
| 6 | 22.5 | 150 | 350 | 845.4 | 2.76 | 85.75 |
| 7 | 30 | 150 | 350 | 850.6 | 2.71 | 83.38 |
Diazotization acidity is brought up to more than 30% by 10%, the deepening that darkens of diazonium liquid and hydrolyzed solution, and diazonium salt is easily separated out and is caused unsafe factor under the low temperature.
Embodiment 8 to embodiment 12:
The preparation method is with embodiment 1, and difference is, acid proportioning at the bottom of the change hydrolysis.Sulfuric acid/water in the end acid (kg/kg) is formed and to be respectively 1. 300/700; 2. 300/450; 3. 150/350; 4. 300/450; 5. 300/300.
| The embodiment sequence number | Acid is formed at the bottom of the hydrolysis | Hydrolyzed solution | |||
| Sulfuric acid Kg | Water Kg | Weight Kg | HQ％ | Yield % | |
| 8 | 300 | 700 | 1476.4 | 1.73 | 92.88 |
| 9 | 300 | 450 | 1228.4 | 2.09 | 93.36 |
| 10 | 150 | 350 | 987.3 | 2.56 | 91.91 |
| 11 | 300 | 450 | 1224.4 | 2.18 | 92.06 |
| 12 | 300 | 300 | 1075.5 | 2.08 | 81.35 |
When acid concentration was 30-40% at the bottom of the hydrolysis, the variation that end acid is formed was little to the influence of yield, and the oil reservoir yield is more than 90%; End acid concentration brings up to 50%, and yield obviously descends.
Embodiment 13 to embodiment 23:
The preparation method is with embodiment 1, and difference is that investigation hydrolysis raffinate is applied mechanically the influence to the hydrolysis yield.
| The embodiment sequence number | End acid is formed | Hydrolyzed solution | The extraction oil reservoir | The raffinate water layer | Number of times is applied mechanically in acid | |||||||
| Sulfuric acid Kg | HQ content % | Weight Kg | HQ content % | HQ yield % | Weight Kg | HQ content % | HQ yield % | Weight Kg | HQ content % | HQ yield % | ||
| 13 | 2000 | 0 | 2945. 8 | 1.9 | 100 | 637 .3 | 7.2 4 | 83. 89 | 2587 5.4 | 0.1 5 | 7.8 | |
| 14 | 2272. 8 | 0.1 9 | 3191. 3 | 1.5 5 | 82. 14 | 634 .4 | 7.6 8 | 88. 58 | 3134. 6 | 0.1 6 | 9.1 | 1 |
| 15 | 2152. 5 | 0.0 8 | 3080. 1 | 1.6 7 | 90. 39 | 643 .3 | 7.3 8 | 86. 32 | 3025. 1 | 0.0 4 | 2.2 | 2 |
| 16 | 2011. 8 | 0.0 48 | 2962. 5 | 1.9 9 | 105 | 642 .5 | 7.4 6 | 87. 15 | 2853. 9 | 0.0 37 | 1.9 | 3 |
| 17 | 2195. 1 | 0.0 69 | 3151. 6 | 1.4 9 | 82. 62 | 639 .1 | 7.4 4 | 86. 45 | 3078. 4 | 0.0 8 | 4.4 8 | 4 |
| 18 | 2489. 4 | 0.0 1 | 3407. 1 | 1.5 3 | 94. 32 | 639 .5 | 7.3 2 | 85. 11 | 3336. 7 | 0..3 9 | 23. 66 | 5 |
| 19 | 2001. 7 | 0.0 48 | 2932. 2 | 1.6 5 | 86. 22 | 646 2 | 7.6 4 | 89. 79 | 2835. 7 | 0.1 8 | 9.2 8 | 6 |
| 20 | 2000 | 0.0 21 | 2953. 4 | 1.6 1 | 85. 69 | 645 .6 | 7.0 2 | 82. 40 | 2880. 4 | 0.0 7 | 3.6 6 | 7 |
| 21 | 2742. 3 | 0.3 2 | 3674. 9 | 1.5 4 | 86. 94 | 639 .7 | 7.5 2 | 87. 46 | 3592. 8 | 0.2 0 | 13. 06 | 8 |
| 22 | 2388. 0 | 0.0 76 | 3313. 7 | 1.4 3 | 82. 86 | 651 .3 | 6.8 6 | 81. 23 | 3251. 5 | 0.2 7 | 15. 96 | 9 |
| 23 | 2000 | 0.1 1 | 2940. 8 | 1.6 2 | 82. 25 | 655 .2 | 6.9 0 | 82. 20 | 2872. 6 | 0.0 4 | 2.1 | 11 |
| On average | 88. 95 | 85. 25 | 8.1 7 |
By the situation of applying mechanically as can be known, apply mechanically 8 batches when above,, the hydrolysis yield is exerted an influence because the concentration of sodium pyrosulfate progressively improves in the reclaim(ed) sulfuric acid when 30% spent acid.
Embodiment 24 to embodiment 27:
The effect of extracting of more different extraction agents extracts the hydrolyzed solution 612Kg that contains Resorcinol 2% with following solvents 200Kg respectively, and the result is as follows.
| The embodiment sequence number | Extraction agent | The extraction oil reservoir | The raffinate water layer | Extraction yield % | HQ balance ratio % | ||||
| Weight Kg | HQ content % | HQ weight Kg | Weight Kg | HQ content % | HQ weight Kg | ||||
| 24 | N-butyl acetate | 210.0 | 5.12 | 10.75 | 581.7 | 0.23 | 1.34 | 88.92 | ?100.8 |
| 25 | Mibk | 209.4 | 5.61 | 11.75 | 582.4 | 0.06 | 0.35 | 97.11 | ?100.8 |
| 26 | Propyl carbinol | 281.0 | 3.93 | 11.04 | 521.7 | 0.15 | 0.78 | 93.40 | ?98.5 |
| 27 | N-butyl ether | 212.3 | 5.04 | 10.7 | 586.8 | 0.26 | 1.53 | 87.4 | ?99.9 |
Test-results shows that the effect of extracting of mibk is best, contains big water gaging in the oil reservoir although the propyl carbinol extraction efficiency than n-butyl acetate height, extracts, and follow-up precipitation prepares that the pure product difficulty of Resorcinol is big, yield is low.Embodiment 28 to embodiment 31: the refining employing of thick Resorcinol is activated carbon decolorizing, crystalline method repeatedly repeatedly.
The Resorcinol solution that embodiment 28 extraction obtains carries out precipitation by the described method of embodiment 1 post-treating method (1), and the thick Resorcinol behind the precipitation is through activated carbon decolorizing, water crystallization, and the Resorcinol that obtains is no crystal formation faint yellow solid.Because activated carbon dosage is big, the HQ yield is lower.Embodiment 29-31 repeats the aforesaid operations step once again, and the Resorcinol that obtains is the near-white crystal.Because water and activated carbon dosage are big, operation steps is many, and the HQ yield is lower.
| Lot number | Oil reservoir | Precipitation | Secondary decolourization, crystallization | ||||||
| The surplus Kg of still | Methyl iso-butyl ketone (MIBK) Kg | Gac Kg | The HQ solid | Mother liquor | |||||
| Weight Kg | HQ％ | Weight Kg | Yield % | Weight Kg | HQ content % | ||||
| 28 | 821.79 | 6.98 | 151.9 | 754.95 | 5.73 | 28.60 | 49.9 | 220.3 8 | 8.26 |
| 29-1 | 279.32 | 7.26 | 59.48 | 262.78 | 1.03 | 72.08 | 8.35 | ||
| 29-2 | 0.53 | 11.63 | 57.3 | 42.29 | 4.5 | ||||
| 30-1 | 618.1 | 7.64 | 118.48 | 541.92 | 2.5 | 93.56 | 5.47 | ||
| 30-2 | 1.5 | 27.39 | 58 | 78.57 | 6.08 | ||||
| 31-1 | 315.27 | 7.51 | 67.83 | 300.55 | 1.14 | 66.8 | 8.5 | ||
| 31-2 | 0.85 | 12.06 | 50.9 | 30.97 | 5.23 | ||||
Embodiment 32 to embodiment 34:
The refining employing distillation of thick Resorcinol adds once decolouring, crystalline method.The Resorcinol solution that obtains of extraction carries out the Resorcinol HQ yield about 90% that negative pressure precipitation, molecular distillation, activated carbon decolorizing, crystallization obtain by the described method of embodiment 1 post-treating method (2), is needle-like white or light yellow crystallization.
| Embodiment | Extraction liquid | Distillation | The HQ crystal | Mother liquor | ||||||
| Weight Kg | HQ content % | Overhead product Kg | The residual Kg of still | Weight Kg | HQ content % | Yield % | Weight Kg | HQ content % | HQ yield % | |
| 32 | 898.9 | 6.82 | 62.53 | 2.43 | 55.9 | 99.59 | 90.81 | 132.61 | 3.07 | 6.64 |
| 33 | 993.7 | 6.59 | 60.78 | 2.53 | 58.02 | 99.62 | 88.26 | 137.68 | 3.23 | 6.8 |
| 34 | 1039.3 | 6.41 | 70.09 | 2.82 | 59.92 | 99.48 | 89.52 | 147.62 | 3.39 | 7.51 |
Embodiment 35 to embodiment 37:
The refining employing nitrogen heating sublimation method of thick Resorcinol.The Resorcinol solution that extraction obtains obtains thick Resorcinol by the described method precipitation of embodiment 1 post-treating method (3), become powdery yellow or brown solid through spraying hot nitrogen drying, put into the hot nitrogen heating of using 130-160 ℃ in the sublimer again, the segmentation condensation obtains white, needle-shaped crystals Resorcinol solid and faint yellow para benzoquinone solid respectively.
| Embodiment | Extraction liquid | Distillation | The HQ crystal | Yellow impurities (para benzoquinone) | ||||
| Weight Kg | HQ content % | Tail gas absorption of K g | The residual Kg of still | Weight Kg | Content % | Yield % | Weight Kg | |
| 35 | 1821 | 6.68 | 2.4 | 5.7 | 115.6 | 99.86 | 94.87 | 3.2 |
| 36 | 1994 | 6.93 | 2.8 | 6.1 | 132.0 | 99.79 | 95.32 | 4.9 |
| 37 | 2187 | 6.56 | 3.5 | 5.9 | 136.4 | 99.88 | 94.93 | 6.7 |
The foregoing description only is that the part of carrying out in order clearly the present invention to be described is given an example, and is not limitation of the invention.To those of ordinary skill in the art, in the variation of being done on the basis that does not change flesh and blood of the present invention or change and still to be among protection scope of the present invention.
Claims (4)
1. one kind prepares the method for Resorcinol by p-aminophenol diazotization hydrolysis reaction, it is characterized in that, comprises the following steps:
(1) under stirring and cooling off, in the sulphuric acid soln of p-aminophenol, drip sodium nitrite in aqueous solution and carry out diazotization reaction, obtain Vandyke brown diazonium liquid, destroy excessive Sodium Nitrite with urea, thiocarbamide, thioether, mercaptan;
Described sulphuric acid soln weight percent concentration is 5～50%, the molar ratio of contained sulfuric acid amount is 1: 1.5～2.5 in p-aminophenol amount and the aqueous sulfuric acid, the molar ratio of p-aminophenol amount and Sodium Nitrite amount is 1: 0.9～2, and temperature of reaction is-15～15 ℃; Described urea, thiocarbamide, thioether, mercaptan use separately, or severally use together, and used amount needs can the excessive Sodium Nitrite of completely destroy;
(2) the pre-dilute sulphuric acid that adds in reactor, refluxing drips the diazonium liquid that (1) step obtains down, and reaction is hydrolyzed;
The concentration of described dilute sulphuric acid is 5～75%, in the described diazonium liquid in p-aminophenol amount and the dilute sulphuric acid mol ratio of sulfuric acid amount be 1: 1～24, temperature of reaction is 95～115 ℃;
(3) hydrolyzed solution is cooled to room temperature, and after extracting Resorcinol, water dilute sulphuric acid cover is used for hydrolysis reaction, obtains the Resorcinol crude product after the extraction oil phase is sloughed solvent;
Described extraction is hydrolyzed solution and extraction agent adverse current to be carried out the serialization extraction treatment by extraction plant obtain extracting oil phase and raffinate water;
Described extraction oil phase mainly contains Resorcinol and extraction agent, the main sulfur acid of described raffinate water, sodium pyrosulfate, water and do not extract Resorcinol completely on a small quantity;
(4) Resorcinol crude product refining, aftertreatment;
In the described step (3), removing when adopting normal pressure precipitation latter temperature to rise to 120 ℃ of extraction agent progressively is with negative pressure and is stabilized in 0.09Mpa gradually, makes feed temperature be no more than 150 ℃;
In the described step (4), adopt the nitrogen heating sublimation to separate the pure product of Resorcinol that obtain.
2. according to the method for preparing Resorcinol of claim 1, it is characterized in that, in the described step (3), before with hydrolyzed solution cooling extraction, hydrolyzed solution is carried out processed, so that in follow-up extracting operation, reduce the consumption of extraction agent.
3. according to the method for preparing Resorcinol of claim 2, it is characterized in that in the described step (3), when hydrolyzed solution being carried out the air distillation dehydration, pressure is environmental stress, temperature is 100～115 ℃, suitably shortens hydrolysis time.
4. according to the method for preparing Resorcinol of claim 2, it is characterized in that, in the described step (3), when hydrolyzed solution being carried out the underpressure distillation processing, at pressure is that 0.070～0.095Mpa and temperature of charge are to carry out under 50～100 ℃ of conditions, and this step is progressively decompression after hydrolysis finishes, and utilizes the temperature of hydrolyzed solution itself, the decompression back reduces the boiling point of water, and water vapor is overflowed.
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| CN101735019B (en) * | 2009-12-31 | 2012-09-26 | 浙江龙盛化工研究有限公司 | Process for producing resorcinol by continuously hydrolyzing m-phenylenediamine |
| CN102503777B (en) * | 2011-10-20 | 2014-10-29 | 江苏瑞祥化工有限公司 | Post-treatment method of hydroquinone prepared by diazotization and hydrolysis of paraaminophenol |
| CN102731267B (en) * | 2012-06-27 | 2015-04-01 | 江苏扬农化工集团有限公司 | Continuous process method for preparing hydroquinone |
| CN102746122A (en) * | 2012-07-19 | 2012-10-24 | 江苏扬农化工集团有限公司 | Hydrolysis process for hydroquinone |
| CN102826961A (en) * | 2012-08-14 | 2012-12-19 | 江苏扬农化工集团有限公司 | Cycling treatment method for waste acid produced in production of hydroquinone |
| CN103483401B (en) * | 2013-09-24 | 2016-08-10 | 南京工业大学 | Method for separating hydroquinone from alpha-arbutin fermentation liquor |
| CN104744217A (en) * | 2013-12-27 | 2015-07-01 | 江苏扬农化工集团有限公司 | Hydroquinone synthesis method |
| CN104147808B (en) * | 2014-07-29 | 2016-05-04 | 华南理工大学 | A kind of dephenolize extractant and application thereof |
| CN115974654A (en) * | 2020-06-12 | 2023-04-18 | 内蒙古盛唐国际蒙医药研究院有限公司 | Resorcinol preparation method |
| CN112225642B (en) * | 2020-10-19 | 2023-06-20 | 内蒙古盛唐国际蒙医药研究院有限公司 | Method for preparing resorcinol by micro-channel reaction |
| CN114591146A (en) * | 2020-12-03 | 2022-06-07 | 中国科学院大连化学物理研究所 | Method for preparing hydroquinone from p-aminophenol |
| CN112794792A (en) * | 2021-04-14 | 2021-05-14 | 维思普新材料（苏州）有限公司 | Preparation method of tetramethyl bisphenol A |
| CN114163310A (en) * | 2021-12-16 | 2022-03-11 | 北京石油化工学院 | Method for separating and purifying benzenediol isomer |
| CN115612402B (en) * | 2022-11-05 | 2023-10-24 | 郑州瑞特高温陶瓷有限公司 | Graphite high-temperature anticorrosive paint and preparation method thereof |
| CN116023237A (en) * | 2022-12-08 | 2023-04-28 | 复旦大学 | Continuous preparation method of hydroquinone in water phase |
| CN116969815B (en) * | 2023-09-25 | 2023-11-24 | 山东富宇石化有限公司 | Hydroquinone purifying and dehydrating method |
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