CN1208297C - Preparation method of joint production of alpha maphthol and beta naphthol - Google Patents
Preparation method of joint production of alpha maphthol and beta naphthol Download PDFInfo
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- CN1208297C CN1208297C CN 03132363 CN03132363A CN1208297C CN 1208297 C CN1208297 C CN 1208297C CN 03132363 CN03132363 CN 03132363 CN 03132363 A CN03132363 A CN 03132363A CN 1208297 C CN1208297 C CN 1208297C
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Abstract
The present invention discloses a preparation method for joint production of methyl naphthol and ethyl naphthol, which comprises the following steps: naphthalene is sulfonated by concentrated sulfuric acid at low temperature, and filtered to obtain alpha-naphthalenesulfonic acid and acidic mother liquid; the acidic mother liquid is dripped in molten naphthalene and through high-temperature sulfonation, hydrolysis and blowing naphthalene to obtain high-purity beta-naphthalenesulfonic acid solution; alpha-naphthalenesulfonic acid and beta-naphthalenesulfonic acid solution are respectively neutralized, melted with alkali and acidified to obtain high-purity methyl naphthol and ethyl naphthol; beta-naphthalenesulfonic acid is simultaneously removed by being dissolved in sulfuric acid. With the method, methyl naphthol and ethyl naphthol with the content>=99% can be obtained once with no need of further purification; waste acid after low-temperature sulfonation is directly used for synthesizing beta-naphthalenesulfonic acid, and a small amount of alpha-naphthalenesulfonic acid is removed by hydrolysis and blowing naphthalene to greatly raise the total yield and lighten three waste pressure. The method has the advantages of high efficiency, low consumption, large universality and easy industrialization.
Description
One, technical field
The present invention relates to the preparation method of a kind of coproduction methyl naphthol and ethyl naphthol, specifically, be by naphthalene is generated α-Nai Huangsuan with concentrated acid sulfonation at low temperatures, produced simultaneously β-isomer is stayed in the acid mother liquor, be used for high temperature sulfonation production high purity beta-naphthalenesulfonic-acid, α, beta-naphthalenesulfonic-acid obtain the preparation method of high purity first, ethyl naphthol separately respectively through alkali fusion.
Two, background technology
Naphthyl alcohol is commonly called as methyl naphthol, present intermediate mainly as the agricultural chemicals SevinCarbaryl, also can be used as the intermediate of some medicines and fine chemical product, its industrial production adopts mainly that naphthalene is nitrated, reduction, hydrolysis method, owing to produce β-nitro-naphthalene of about 4% nitrated the time, common product content about 96%, thereby to obtain 99.5% high purity methyl naphthol, and need to adopt the nitro-naphthalene Crystallization Separation to purify or the product Crystallization Separation, step is long, the cost height, the three wastes are many.
The also useful low-temperature sulfonation alkali fusion of methyl naphthol is produced, and removes because the isomer that produces need separate, and about about 40% so product yield is low, three wastes discharge amount is big.
2-Naphthol is commonly called as ethyl naphthol, is widely used as dyestuff, Pigment Intermediates, and it is produced and mainly utilizes the production of high temperature sulfonation alkali fusion, and the alpha-isomer that produces in the sulfonation process separates by hydrolysis, recovery naphthalene.Mature production technology has realized scale operation.
Patent ZL92108433.1 adopts coproduction to produce methyl naphthol, ethyl naphthol.The main points of its technology be with naphthalene under 0～165 ℃ of any chosen temperature with concentrated acid sulfonation after, through neutralization, alkali fusion, acidifying and distilation steps, it is characterized in that naphthalene after sulfonation without the separating isomerism body, directly with in the alkali with after enter alkali fusion, the alkali fusion thing that obtains behind the alkali fusion enters distillation after acidifying, the mixing naphthols that distillation obtains is sent into the fusion-crystallization separator tank, make with 0.5～5 ℃ of speed per hour and to mix naphthols in the groove and reduce to 50 ℃ from 125 ℃, be warming up to 125 ℃ from 50 ℃ with 1～5 ℃ of speed per hour again, the concentration gradients of methyl naphthol in the effluent of discharge is risen, the methyl naphthol of the different melting ranges of step emission discharges the ethyl naphthol of different melting ranges then.The desirable highly purified methyl naphthol of this patent, ethyl naphthol will be by with mixing prod perfectly crystallization processes repeatedly; And an income rate of high purity methyl naphthol, ethyl naphthol is low, and (based on income rate of high purity methyl naphthol among the embodiment of methyl naphthol only is 6.25% of thick naphthols total amount, based on an income rate of ethyl naphthol among the embodiment of ethyl naphthol only for thick naphthols total amount 6.25%) rest part must be aided with rectifying separation, complex operation, energy consumption height; And can purified in the mixings naphthols ratio of first, ethyl naphthol be restricted: the content of requirement methyl naphthol is not less than 65% or the content no more than 35% of ethyl naphthol at least during main product methyl naphthol coproduction ethyl naphthol; Require the content of ethyl naphthol to be not less than 65% or the content no more than 35% of methyl naphthol at least during main product ethyl naphthol coproduction methyl naphthol.
Three, summary of the invention
1. goal of the invention: the purpose of this invention is to provide a kind of preparation method, α-Nai Huangsuan, beta-naphthalenesulfonic-acid by separating high-purity, obtain high purity first, ethyl naphthol through alkali fusion, acidifying respectively, realize coproduction, solve complex operation in the general joint process, problem that the three wastes are big simultaneously.
2. technical scheme: technical scheme of the present invention is as follows:
(A) vitriol oil is joined in the sulfidation pan, controlled temperature is 10～80 ℃, and refined naphthalene is added in batches, and the mass ratio of the vitriol oil and refined naphthalene is 1: 1～10: 1, insulation reaction 2～10 hours, and filtering separation obtains α-Nai Huangsuan and acid mother liquor respectively;
(B) to be neutralized to the pH value with sodium sulfite solution when temperature is 80～110 ℃ be 6～8 to isolated α-Nai Huangsuan, filter down at 5～50 ℃, obtain aqueous α-Nai Huangsuan sodium, in alkal melting pan, add and caustic soda, be warming up to 280～350 ℃, add α-Nai Huangsuan sodium is 5～10% until free alkali concentration in batches, be incubated 30～60 minutes, then the alkali fusion thing is added to the water, stirred 30～60 minutes, shift in the acidifying pot, being neutralized to the pH value with sulfurous gas is 6～8, be warming up to boiling-layering, lower floor is a sodium sulfite solution, and the upper strata is the crude product methyl naphthol, the crude product methyl naphthol is added in the dehydration pot, thermal dehydration 1～4 hour joins vacuum still, distill methyl naphthol;
(C) acid mother liquor in the step (A) is added drop-wise in the fused naphthalene, the mass ratio of acid mother liquor and naphthalene 1: 2～10: 1, controlled temperature are 110～150 ℃, are warming up to 150～170 ℃ then, and insulation reaction obtained beta-naphthalenesulfonic-acid solution in 2～4 hours;
(D) beta-naphthalenesulfonic-acid solution thin up obtains the beta-naphthalenesulfonic-acid aqueous solution, the beta-naphthalenesulfonic-acid aqueous solution is blown naphthalene with water vapour reclaim naphthalene under 130～150 ℃, controlled temperature is at 90～110 ℃ then, being neutralized to the pH value with sodium sulfite solution is 6～8, under 5～50 ℃, filter and obtain aqueous sodium, in alkal melting pan, add caustic soda, be warming up to 280～350 ℃, add sodium is 5～10% until free alkali concentration in batches, be incubated 30～60 minutes, then the alkali fusion thing be added to the water, stirred 30～60 minutes, shift in the acidifying pot, being neutralized to the pH value with sulfurous gas is 6～8, is warming up to boiling, layering, lower floor is a sodium sulfite solution, the upper strata is the crude product ethyl naphthol, the crude product ethyl naphthol is added in the dehydration pot thermal dehydration 1～4 hour, join vacuum still, distill ethyl naphthol.
The controlled temperature that the middle vitriol oil of above-mentioned step (A) joins sulfidation pan is 50～60 ℃.Step (B) and (D) in in the sodium sulfite solution with the time temperature be 95～100 ℃.Step (B) and (D) in filtration temperature be controlled at 10～20 ℃, adopt the suction filtration mode.
Step (B) and (D) in free alkali concn be 5～6% o'clock, no longer add α-Nai Huangsuan sodium and sodium.Controlled temperature was 120～130 ℃ when acid mother liquor was added drop-wise in the fused naphthalene in the step (C).Step (B) and (D) in dewatering time in the dehydration pot be 2～3 hours.
The mass ratio of the vitriol oil and refined naphthalene is 1: 1～3: 1 in the step (A).The mass ratio of acid mother liquor and naphthalene is 1: 0.5～1: 1.5 in the step (D).
3. beneficial effect:
The present invention compared with prior art, its remarkable advantage is:
(1) nitrated, the reduction of the naphthalene that adopts of traditional methyl naphthol production, hydrolysis method can not once obtain 99.5% high purity methyl naphthol, need to adopt the nitro-naphthalene Crystallization Separation to purify or the product Crystallization Separation, and step is long, the cost height, and the three wastes are many.Adopt the present invention can once obtain the methyl naphthol of content 〉=99%, do not need again through being further purified.
(2) the low-temperature sulfonation alkali fusion is produced methyl naphthol, removes because the isomer that produces need separate, and about about 40% so product yield is low, three wastes discharge amount is big; Adopt the present invention because the spent acid behind the low-temperature sulfonation is directly used in the synthetic of beta-naphthalenesulfonic-acid, a small amount of α-Nai Huangsuan in the spent acid by hydrolysis, blow naphthalene and remove, thereby total recovery improves (about 76%) greatly, three wastes pressure alleviates greatly.
(3) adopt coproduction to produce methyl naphthol, ethyl naphthol among the ZL92108433.1, because its purification procedures is long, and the ratio of first, ethyl naphthol is restricted in the energy purified mixing naphthols, adopt when of the present invention owing to when sulfonation, α-Nai Huangsuan is separated when sulfonation finishes efficiently with beta-naphthalenesulfonic-acid, carry out alkali fusion, acidifying respectively, disposable highly purified methyl naphthol, the ethyl naphthol of obtaining respectively.Thereby do not had the repeatedly trouble of purifying, be not subjected to the restriction of first, ethyl naphthol ratio yet.
Four, description of drawings
Preparation technology's schema of coproduction methyl naphthol and ethyl naphthol
Five, specific embodiment
Further specify the present invention by the following examples.
Embodiment 1:
One, low-temperature sulfonation reaction
Vitriol oil 200Kg is added in the low-temperature sulfonation pot, and controlled temperature evenly adds the 100Kg refined naphthalene at 50～60 ℃, and insulation reaction is 3 hours under uniform temp, at 5 ℃ of following suction filtrations, obtains acidiferous α-Nai Huangsuan filter cake 150Kg and the about 150Kg of acid mother liquor.
Two, high temperature sulfonation reaction
The 140Kg refined naphthalene is added in the high temperature sulfidation pan, and controlled temperature is at 120～130 ℃, drips the about 150Kg of acid mother liquor in ", low-temperature sulfonation reaction ", and being warming up to 160 ℃ of insulation reaction 3 hours must beta-naphthalenesulfonic-acid solution.
Three, the high purity methyl naphthol is produced
1, neutralization
150Kg naphthene sulfonic acid controlled temperature in will " one, low-temperature sulfonation reaction " is more than 95 ℃, and being neutralized to pH value with sodium sulfite solution is 6～8, is cooled to 20 ℃ of following suction filtrations, must water content is about 20% α-Nai Huangsuan sodium 150Kg.
2, alkali fusion
In alkal melting pan, add 98% caustic soda 48Kg, be warming up to 320 ℃, add α-Nai Huangsuan sodium, in batches till free alkali concentration is 5～6%, finish, be incubated 60～90 minutes, insulation finishes, the alkali fusion thing is joined in the dilution water, stirred 40 minutes, be pressed in the acidifying pot.
3, acidifying
Alkali fusion material is pressed in the acidifying pot, and it is 6～8 that the sulfurous gas neutralization that produces with neutralizing is acidified to the pH value, is warming up to boiling, layering, and lower floor's sodium sulfite solution is emitted and is used for and α-Nai Huangsuan, and the upper strata is the crude product methyl naphthol.
4, distillation
The crude product methyl naphthol is added in the dehydration pot, and thermal dehydration 2 hours adds vacuum still, and distillation obtains the about 70Kg of methyl naphthol of content 〉=99%.
Four, the high purity ethyl naphthol is produced
1, hydrolysis
150 ℃ of hydrolysis of beta-naphthalenesulfonic-acid solution in will " two, high temperature sulfonation reaction " one hour the beta-naphthalenesulfonic-acid hydrating solution.
2, blow naphthalene
The beta-naphthalenesulfonic-acid hydrating solution is blown naphthalene with steam under 130～150 ℃, reclaim naphthalene 30Kg, during solution enters and operation.
3, neutralization
Controlled temperature is at 100 ℃, and being neutralized to the pH value with sodium sulfite solution is 6～8, is cooled to 20 ℃ of following suction filtrations, water content is about 20% α-Nai Huangsuan sodium 250Kg.
4, alkali fusion
In alkal melting pan, add 98% caustic soda 80Kg, be warming up to 320 ℃, add sodium, in batches till free alkali concentration is 5～6%, finish, be incubated 30～60 minutes, insulation finishes, the alkali fusion thing is added in the dilution water, stirred 40 minutes, be pressed in the acidifying pot.
5, acidifying
Alkali fusion material is pressed in the acidifying pot, and it is 6～8 that the sulfurous gas neutralization that produces with neutralizing is acidified to the pH value, is warming up to boiling, layering, and lower floor's sodium sulfite solution is emitted and is used for and beta-naphthalenesulfonic-acid, and the upper strata is the crude product ethyl naphthol
6, distillation
The crude product ethyl naphthol is added in the dehydration pot, and thermal dehydration 2 hours adds vacuum still, and distillation obtains the about 110Kg of ethyl naphthol of content 〉=99%.
Embodiment 2:
One, low-temperature sulfonation reaction
The vitriol oil (96～98%) 150Kg is added in the low-temperature sulfonation pot, and controlled temperature evenly adds the 100Kg refined naphthalene at 70～80 ℃, and insulation reaction is 5 hours under uniform temp, at 5 ℃ of following suction filtrations, obtains containing wet α-Nai Huangsuan 150Kg and the about 100Kg of acid mother liquor.
Two, high temperature sulfonation reaction
The 70Kg refined naphthalene is added in the high temperature sulfidation pan, and controlled temperature is at 120～130 ℃, drips the about 100Kg of acid mother liquor in ", low-temperature sulfonation reaction ", and being warming up to 160 ℃ of insulation reaction 4 hours must beta-naphthalenesulfonic-acid solution.
Three, the high purity methyl naphthol is produced
1, neutralization
150Kg naphthene sulfonic acid controlled temperature in will " one, low-temperature sulfonation reaction " is more than 95 ℃, and being neutralized to pH value with sodium sulfite solution is 6～8, is cooled to 20 ℃ of following suction filtrations, must water content is about 20% α-Nai Huangsuan sodium 150Kg.
2, alkali fusion
In alkal melting pan, add 98% caustic soda 48Kg, be warming up to 320 ℃, add α-Nai Huangsuan sodium, in batches till free alkali concentration is 5～6%, finish, be incubated 30～60 minutes, insulation finishes, the alkali fusion thing is joined in the dilution water, stirred 40 minutes, be pressed in the acidifying pot.
3, acidifying
Alkali fusion material is pressed in the acidifying pot, and it is 6～8 that the sulfurous gas neutralization that produces with neutralizing is acidified to the pH value, and be warming up to boiling one and boil, layering, lower floor's sodium sulfite solution is emitted and is used for and α-Nai Huangsuan, and the upper strata is the crude product methyl naphthol.
4, distillation
The crude product methyl naphthol is added in the dehydration pot, and thermal dehydration 2 hours adds vacuum still, and distillation obtains the about 70Kg of methyl naphthol of content 〉=99%.
Four, the high purity ethyl naphthol is produced
1, hydrolysis
150 ℃ of hydrolysis of beta-naphthalenesulfonic-acid solution in will " two, high temperature sulfonation reaction " one hour the beta-naphthalenesulfonic-acid hydrating solution.
2, blow naphthalene
The beta-naphthalenesulfonic-acid hydrating solution is blown naphthalene reclaim naphthalene 20Kg under 130～150 ℃, during solution enters and operation.
3, neutralization
Controlled temperature is at 100 ℃, and being neutralized to the pH value with sodium sulfite solution is 6～8, is cooled to 20 ℃ of following suction filtrations, water content is α-Nai Huangsuan sodium 125～130Kg of about 20%.
4, alkali fusion
In alkal melting pan, add 98% caustic soda 40Kg, be warming up to 320 ℃, add sodium, in batches till free alkali concentration is 5～6%, finish, be incubated 30～60 minutes, insulation finishes, the alkali fusion thing is added in the dilution water, stirred 40 minutes, be pressed in the acidifying pot.
5, acidifying
Alkali fusion material is pressed in the acidifying pot, and it is 6～8 that the sulfurous gas neutralization that produces with neutralizing is acidified to the pH value, and be warming up to boiling one and boil, layering, lower floor's sodium sulfite solution is emitted and is used for and beta-naphthalenesulfonic-acid, and the upper strata is the crude product ethyl naphthol
6, distillation
The crude product ethyl naphthol is added in the dehydration pot, and thermal dehydration 2 hours adds vacuum still, and distillation obtains the about 55Kg of ethyl naphthol of content 〉=99%.
Embodiment 3:
One, low-temperature sulfonation reaction
The vitriol oil (96～98%) 800Kg is added in the low-temperature sulfonation pot, and controlled temperature evenly adds the 100Kg refined naphthalene at 20～25 ℃, and insulation reaction is 2 hours under uniform temp, at 5 ℃ of following suction filtrations, obtains containing wet α-Nai Huangsuan 180Kg and the about 720Kg of acid mother liquor.
Two, high temperature sulfonation reaction
The 650Kg refined naphthalene is added in the high temperature sulfidation pan, and controlled temperature is at 120～130 ℃, drips the about 720Kg of acid mother liquor in ", low-temperature sulfonation reaction ", and being warming up to 160 ℃ of insulation reaction 2.5 hours must beta-naphthalenesulfonic-acid solution.
Three, the high purity methyl naphthol is produced
1, neutralization
180Kg naphthene sulfonic acid controlled temperature in will " one, low-temperature sulfonation reaction " is more than 95 ℃, and being neutralized to pH value with sodium sulfite solution is 6～8, is cooled to 20 ℃ of following suction filtrations, must water content is about 20% α-Nai Huangsuan sodium 180Kg.
2, alkali fusion
In alkal melting pan, add 98% caustic soda 58Kg, be warming up to 320 ℃, add α-Nai Huangsuan sodium, in batches till free alkali concentration is 5～6%, finish, be incubated 30～60 minutes, insulation finishes, the alkali fusion thing is joined in the dilution water, stirred 40 minutes, be pressed in the acidifying pot.
3, acidifying
Alkali fusion material is pressed in the acidifying pot, and it is 6～8 that the sulfurous gas neutralization that produces with neutralizing is acidified to the pH value, and be warming up to boiling one and boil, layering, lower floor's sodium sulfite solution is emitted and is used for and α-Nai Huangsuan, and the upper strata is the crude product methyl naphthol.
4, distillation
The crude product methyl naphthol is added in the dehydration pot, and thermal dehydration 2 hours adds vacuum still, and distillation obtains the about 85Kg of methyl naphthol of content 〉=99%.
Four, the high purity ethyl naphthol is produced
1, hydrolysis
150 ℃ of hydrolysis of beta-naphthalenesulfonic-acid solution in will " two, high temperature sulfonation reaction " one hour the beta-naphthalenesulfonic-acid hydrating solution.
2, blow naphthalene
The beta-naphthalenesulfonic-acid hydrating solution is blown naphthalene reclaim naphthalene 25Kg under 130～150 ℃, during solution enters and operation.
3, neutralization
Controlled temperature is at 100 ℃, and being neutralized to the pH value with sodium sulfite solution is 6～8, is cooled to 20 ℃ of following suction filtrations, water content is about 20% the about 1250Kg of α-Nai Huangsuan sodium.
4, alkali fusion
In alkal melting pan, add 98% caustic soda 400Kg, be warming up to 320 ℃, add sodium, in batches till free alkali concentration is 5～6%, finish, be incubated 30～60 minutes, insulation finishes, the alkali fusion thing is added in the dilution water, stirred 40 minutes, be pressed in the acidifying pot.
5, acidifying
Alkali fusion material is pressed in the acidifying pot, and it is 6～8 that the sulfurous gas neutralization that produces with neutralizing is acidified to the pH value, and be warming up to boiling one and boil, layering, lower floor's sodium sulfite solution is emitted and is used for and beta-naphthalenesulfonic-acid, and the upper strata is the crude product ethyl naphthol
6, distillation
The crude product ethyl naphthol is added in the dehydration pot, and thermal dehydration 2 hours adds vacuum still, and distillation obtains the about 560Kg of ethyl naphthol of content 〉=99%.
Embodiment 4:
One, low-temperature sulfonation reaction
The vitriol oil (96～98%) 500Kg is added in the low-temperature sulfonation pot, and controlled temperature evenly adds the 100Kg refined naphthalene at 40～50 ℃, and insulation reaction is 5 hours under uniform temp, at 5 ℃ of following suction filtrations, obtains containing wet α-Nai Huangsuan 160Kg and the about 440Kg of acid mother liquor.
Two, high temperature sulfonation reaction
The 460Kg refined naphthalene is added in the high temperature sulfidation pan, and controlled temperature is at 120～130 ℃, drips the about 440Kg of acid mother liquor in ", low-temperature sulfonation reaction ", and being warming up to 160 ℃ of insulation reaction 3 hours must beta-naphthalenesulfonic-acid solution.
Three, the high purity methyl naphthol is produced
1, neutralization
160Kg naphthene sulfonic acid controlled temperature in will " one, low-temperature sulfonation reaction " is more than 95 ℃, and being neutralized to pH value with sodium sulfite solution is 6～8, is cooled to 20 ℃ of following suction filtrations, must water content is about 20% α-Nai Huangsuan sodium 160Kg.
2, alkali fusion
In alkal melting pan, add 98% caustic soda 48Kg, be warming up to 320 ℃, add α-Nai Huangsuan sodium, in batches till free alkali concentration is 5～6%, finish, be incubated 30～60 minutes, insulation finishes, the alkali fusion thing is joined in the dilution water, stirred 40 minutes, be pressed in the acidifying pot.
3, acidifying
Alkali fusion material is pressed in the acidifying pot, and it is 6～8 that the sulfurous gas neutralization that produces with neutralizing is acidified to the pH value, and be warming up to boiling one and boil, layering, lower floor's sodium sulfite solution is emitted and is used for and α-Nai Huangsuan, and the upper strata is the crude product methyl naphthol.
4, distillation
The crude product methyl naphthol is added in the dehydration pot, and thermal dehydration 2 hours adds vacuum still, and distillation obtains the about 75Kg of methyl naphthol of content 〉=99%.
Four, the high purity ethyl naphthol is produced
1, hydrolysis
150 ℃ of hydrolysis of beta-naphthalenesulfonic-acid solution in will " two, high temperature sulfonation reaction " one hour the beta-naphthalenesulfonic-acid hydrating solution.
2, blow naphthalene
The beta-naphthalenesulfonic-acid hydrating solution is blown naphthalene reclaim naphthalene 35Kg under 130～150 ℃, during solution enters and operation.
3, neutralization
Controlled temperature is at 100 ℃, and being neutralized to the pH value with sodium sulfite solution is 6～8, is cooled to 20 ℃ of following suction filtrations, water content is about 20% the about 860Kg of α-Nai Huangsuan sodium.
4, alkali fusion
In alkal melting pan, add 98% caustic soda 280Kg, be warming up to 320 ℃, add sodium, in batches till free alkali concentration is 5～6%, finish, be incubated 30～60 minutes, insulation finishes, the alkali fusion thing is added in the dilution water, stirred 40 minutes, be pressed in the acidifying pot.
5, acidifying
Alkali fusion material is pressed in the acidifying pot, and it is 6～8 that the sulfurous gas neutralization that produces with neutralizing is acidified to the pH value, and be warming up to boiling one and boil, layering, lower floor's sodium sulfite solution is emitted and is used for and beta-naphthalenesulfonic-acid, and the upper strata is the crude product ethyl naphthol
6, distillation
The crude product ethyl naphthol is added in the dehydration pot, and thermal dehydration 2 hours adds vacuum still, and distillation obtains the about 390Kg of ethyl naphthol of content 〉=99%.
Embodiment 5: substantially the same manner as Example 1, different is that in the vitriol oil 200Kg adding low-temperature sulfonation pot, controlled temperature evenly adds the 200Kg refined naphthalene at 70～80 ℃.
Embodiment 6: substantially the same manner as Example 1, different is, with in the sodium sulfite solution and the time temperature be 100～110 ℃.
Claims (9)
1. the preparation method of coproduction methyl naphthol and ethyl naphthol, its feature is made up of the following step:
(A) vitriol oil is joined in the sulfidation pan, controlled temperature is 10～80 ℃, and refined naphthalene is added in batches, and the mass ratio of the vitriol oil and refined naphthalene is 1: 1～10: 1, insulation reaction 2～10 hours, and filtering separation obtains α-Nai Huangsuan and acid mother liquor respectively;
(B) to be neutralized to the pH value with sodium sulfite solution when temperature is 80～110 ℃ be 6～8 to isolated α-Nai Huangsuan, filter down at 5～50 ℃, obtain aqueous α-Nai Huangsuan sodium, in alkal melting pan, add caustic soda, be warming up to 280～350 ℃, add α-Nai Huangsuan sodium is 5～10% until free alkali concentration in batches, be incubated 30～60 minutes, then the alkali fusion thing is added to the water, stirred 30～60 minutes, shift in the acidifying pot, being neutralized to the pH value with sulfurous gas is 6～8, be warming up to boiling-layering, lower floor is a sodium sulfite solution, and the upper strata is the crude product methyl naphthol, the crude product methyl naphthol is added in the dehydration pot, thermal dehydration 1～4 hour joins vacuum still, distill methyl naphthol;
(C) acid mother liquor in the step (A) is added drop-wise in the fused naphthalene, the mass ratio of acid mother liquor and naphthalene 1: 2～10: 1, controlled temperature are 110～150 ℃, are warming up to 150～170 ℃ then, and insulation reaction obtained beta-naphthalenesulfonic-acid solution in 2～4 hours;
(D) beta-naphthalenesulfonic-acid solution thin up obtains the beta-naphthalenesulfonic-acid aqueous solution, the beta-naphthalenesulfonic-acid aqueous solution is blown naphthalene with water vapour reclaim naphthalene under 130～150 ℃, controlled temperature is at 90～110 ℃ then, being neutralized to the pH value with sodium sulfite solution is 6～8, under 5～50 ℃, filter and obtain aqueous sodium, in alkal melting pan, add caustic soda, be warming up to 280～350 ℃, add sodium is 5～10% until free alkali concentration in batches, be incubated 30～60 minutes, then the alkali fusion thing be added to the water, stirred 30～60 minutes, shift in the acidifying pot, being neutralized to the pH value with sulfurous gas is 6～8, is warming up to boiling, layering, lower floor is a sodium sulfite solution, the upper strata is the crude product ethyl naphthol, the crude product ethyl naphthol is added in the dehydration pot thermal dehydration 1～4 hour, join vacuum still, distill ethyl naphthol.
2. method according to claim 1 is characterized in that the controlled temperature that the middle vitriol oil of step (A) joins sulfidation pan is 50～60 ℃.
3. method according to claim 1, it is characterized in that step (B) and (D) in in the sodium sulfite solution with the time temperature be 95～100 ℃.
4. method according to claim 1, it is characterized in that step (B) and (D) in filtration temperature be controlled at 10～20 ℃, adopt the suction filtration mode.
5. method according to claim 1, it is characterized in that step (B) and (D) in free alkali concn be 5～6% o'clock, no longer add α-Nai Huangsuan sodium and sodium.
6. method according to claim 1, controlled temperature is 120～130 ℃ when it is characterized in that acid mother liquor is added drop-wise in the fused naphthalene in the step (C).
7. method according to claim 1, it is characterized in that step (B) and (D) in dewatering time in the dehydration pot be 2～3 hours.
8. method according to claim 1 is characterized in that the mass ratio of the middle vitriol oil of step (A) and naphthalene is 1: 1～3: 1.
9. method according to claim 1 is characterized in that the mass ratio of middle acid mother liquor of step (C) and naphthalene is 1: 0.5～1: 1.5.
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| CN 03132363 Expired - Fee Related CN1208297C (en) | 2003-08-18 | 2003-08-18 | Preparation method of joint production of alpha maphthol and beta naphthol |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781172B (en) * | 2010-01-04 | 2012-12-12 | 曲靖众一精细化工股份有限公司 | Novel process for efficiently and continuously synthesizing 2-naphthol |
| CN102351660A (en) * | 2011-08-05 | 2012-02-15 | 山东菜央子盐场 | Method for improving p-cresol production rate and p-cresol product purity |
| CN104628608B (en) * | 2015-02-16 | 2016-11-16 | 曲靖众一合成化工有限公司 | A kind of tower negative pressure continuous noble gas air stripping blows naphthalene method and device thereof |
| CN104693009B (en) * | 2015-03-04 | 2016-08-24 | 肖刚学 | Naphthalene sulfonated products direct alkali fusion coproduction 1-naphthols and the method for beta naphthal |
| CN106187835A (en) * | 2016-07-14 | 2016-12-07 | 江苏扬农化工集团有限公司 | 2,3 dihydroxy naphthlene 1,6 disulfonic acid chemical intermediate synthetic methods |
| CN108002984B (en) * | 2017-09-14 | 2021-02-19 | 重庆紫光化工股份有限公司 | Production system and method for continuously preparing (alpha, beta) sodium naphthol from naphthalene |
| CN108530271A (en) * | 2018-05-31 | 2018-09-14 | 山西豪仑科化工有限公司 | A kind of naphthalene method of sulfonating of coproduction 1- naphthols and beta naphthal |
| CN111217680A (en) * | 2020-02-14 | 2020-06-02 | 乌海时联环保科技有限责任公司 | Method for preventing naphthol from discoloring |
| CN112961034B (en) * | 2021-02-23 | 2023-07-25 | 上海东庚化工技术有限公司 | Clean naphthol production process taking sulfur trioxide as raw material |
| CN112979427B (en) * | 2021-02-23 | 2023-07-25 | 上海东庚化工技术有限公司 | Process for synthesizing naphthol through sulfur trioxide indirect sulfonation reaction |
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