CN1078715A - The joint process of methyl naphthol and ethyl naphthol - Google Patents
The joint process of methyl naphthol and ethyl naphthol Download PDFInfo
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- CN1078715A CN1078715A CN 92108433 CN92108433A CN1078715A CN 1078715 A CN1078715 A CN 1078715A CN 92108433 CN92108433 CN 92108433 CN 92108433 A CN92108433 A CN 92108433A CN 1078715 A CN1078715 A CN 1078715A
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Abstract
The present invention relates to the method for a kind of naphthalene through sulfonation, alkali fusion coproduction methyl naphthol and ethyl naphthol, specifically, it is that a kind of naphthalene is after sulfonation, the mixing sodium naphthalene sulfonate that obtains obtains first, second through alkali fusion, distillation and mixes naphthols, separates the novel process that obtains highly purified methyl naphthol and ethyl naphthol respectively through fusion-crystallization again.It has, and energy consumption is low, product purity is high, reduces " three wastes " and the high outstanding advantage of productive rate.
Description
The present invention relates to the technology of naphthalene through sulfonation alkali fusion coproduction methyl naphthol and ethyl naphthol, specifically it is that a kind of refined naphthalene is after sulfonation, neutralization, need not the separating isomerism body, direct alkali fusion, the alkali fusion thing is through acidifying, simple distillation obtains mixing naphthols, will mix naphthols and separate through fusion-crystallization, obtains the novel process of highly purified methyl naphthol and ethyl naphthol respectively.
At present, the sulfonation alkali fusion of synthetic methyl naphthol or ethyl naphthol is produced in the route,
One, methyl naphthol process using low-temperature sulfonation method:
Naphthalene is with vitriol oil sulfonation in the time of 0-40 ℃, can get α-and the mixture of beta-naphthalenesulfonic-acid.Wherein α-Nai Huangsuan accounts for 83-85%, and beta-naphthalenesulfonic-acid accounts for 15-17%, can add magnesium salts in sulfonated products and makes beta-naphthalenesulfonic-acid generate the beta-naphthalenesulfonic-acid magnesium of indissoluble and remove.α-Nai Huangsuan obtains first-naphthols through neutralization, alkali fusion, acidifying and distillation.
Two, ethyl naphthol process using:
Naphthalene sulfonation system beta-naphthalenesulfonic-acid is at first packed naphthalene into that heating makes it fusing in the molten naphthalene pot, when temperature reaches 120-125 ℃, the fused naphthalene is pressed in the good sulfidation pan of preheating, continues to be warming up to 163-165 ℃ again.Under this temperature, in one hour, evenly add the sulfuric acid of preheating then, be incubated a few hours through scale tank, reaction is finished, wherein α-Nai Huangsuan accounts for 10-15%, and beta-naphthalenesulfonic-acid accounts for 85-90%, and beta-naphthalenesulfonic-acid obtains ethyl naphthol through neutralization, alkali fusion, acidifying and distillation.
In order to obtain purer beta-naphthalenesulfonic-acid, need α-Nai Huangsuan is removed through hydrolysis.Therefore sulfonated bodies is depressed in the hydrolyzer.Dilute sulfonated bodies and be warming up to 140-145 ℃ with a spot of water, at this moment, α-Nai Huangsuan is hydrolyzed to naphthalene and sulfuric acid with the speed more faster than beta-naphthalenesulfonic-acid.
There are unreasonable part in above-mentioned traditional sulfonation, alkali fusion operational path, when producing methyl naphthol, remove the beta-naphthalenesulfonic-acid isomer of 15-17%; And when producing ethyl naphthol, to remove the α-Nai Huangsuan isomer of 10-15%, and in this process, wasted the energy, produced a large amount of waste water, spent acid, also lost simultaneously the part refined naphthalene, increased the material unit consumption, made technical process become very complicated simultaneously, equipment corrosion increases greatly.
So, the invention provides the novel method of a kind of naphthalene sulfonation alkali fusion technology coproduction methyl naphthol and ethyl naphthol.
The objective of the invention is to reach in the following manner:
A kind of refined naphthalene is through the method for sulfonation, alkali fusion, acidifying and distillation coproduction methyl naphthol and ethyl naphthol, it is characterized in that refined naphthalene after sulfonation without the separating isomerism body directly with in the alkali and after enter alkali fusion, the alkali fusion thing that alkali fusion obtains enters distillation after acidifying, the mixing naphthols that distillation obtains is sent into the fusion-crystallization separator tank, the cooling rate and the scope of mixing naphthols in the control flume, heat up with certain speed again, the content of methyl naphthol in the effluent of discharge is risen in gradient, then the methyl naphthol of the different melting ranges of step emission; Discharge the ethyl naphthol of different melting ranges then, it is characterized in that:
1) with fused mixing naphthols fast cooling to its fusing point, then,, preferably be cooled to its below fusing point 10 °-25 ℃ with 1 ° of-3 ℃ of control per hour per hour to lower the temperature 0.5-5 ℃;
The mixing naphthols that 2) will solidify is with 1 ° of-5 ℃ of speed per hour, preferably, is warming up to the methyl naphthol fusion again of solidifying with 2 ° of-4 ℃ of speed control per hour, then
3) the fused mixing naphthols of the different melting ranges of step emission;
4) last, discharge is in homothermic purified methyl naphthol or ethyl naphthol.
It is characterized in that: in the described mixing naphthols, the content of methyl naphthol be not less than at least 65% or the no more than at least 35%(content of content of ethyl naphthol).
It is characterized in that: in the described mixing naphthols, the content of content of methyl naphthol no more than at least 35% or ethyl naphthol is not less than 65%(content at least).
It is characterized in that:, preferably be 1 °-2 ℃ fused mixing naphthols fast cooling to its fusing point 0.5 °-5 ℃.
It is characterized in that: fused mixing naphthols was reduced on its fusing point by 1 hour fast at 10 minutes.
It is characterized in that: described constant temperature time is 0.5-8 hour, preferably is 1.5-3 hour.
Advantage of the present invention is tangible, at first the refined naphthalene sulfonation can be carried out under 0-165 ℃ of optional temperature range, isomer need not to separate after the sulfonation, can neutralize and alkali fusion, the alkali fusion thing is after acidifying, can simply distill, to remove low-boiling-point substance and high boiling material, the mixing naphthols that obtains separates by fusion-crystallization, can obtain highly purified methyl naphthol and ethyl naphthol respectively, thereby the energy consumption of greatly reducing and unit consumption have been saved soda acid and have been made process conditions fairly simple, and the generation of " three wastes " also correspondingly reduces greatly; The more important thing is to separate to obtain 〉=the high-grade methyl naphthol and the ethyl naphthol of 99.5% purity, to satisfy the desired quality index of fine chemical product such as medicine, agricultural chemicals, dyestuff by fusion-crystallization.
Below, the present invention will be described in detail by specific embodiment, so that advantage of the present invention is more obvious.
Embodiment 1:
1. naphthalene sulfonation reaction
The fused refined naphthalene is added in the sulfidation pan for 400 kilograms, be warming up to 140 ℃, 343 kilograms of sulfuric acid (97-98%) were evenly added in 20 minutes.Continue to be warming up to 160 ℃, be incubated 2 hours at 160-162 ℃.Content of sampling analysis beta-naphthalenesulfonic-acid (more than 66%) and total acidity (25-27%).
Obtain the beta-naphthalenesulfonic-acid of 80-85% and the α-Nai Huangsuan of 15-20%.In traditional technology, the α-Nai Huangsuan of this 15-20% must be passed through add 30 kg of water,, add 150 kilograms of 40% metabisulfite solutions then, feed water vapor then and drive away the free naphthalene that is hydrolyzed into clean 140-150 ℃ of hydrolysis 1 hour.And method of the present invention need not to carry out said hydrolyzed naphthalene operation, and sulfonated bodies directly is neutralized to Congo red constant indigo plant and drives away SO residual in the sulfonated bodies with S-WAT
2, being cooled to 35-40 ℃, suction strainer with 10% salt solution washing leaching cake, is drained water content≤20%, obtains α-Nai Huangsuan sodium and accounts for the mixture about 576 kilograms (100%) that 15-20% and sodium account for 80-85%.Then
2. alkali fusion:
In alkal melting pan, add 98% caustic soda (sodium chlorate content≤0.05%) 552 kilograms, be heated to 260 ℃, make its fusion.Stir, be warming up to 290 ℃, in 2.5-3 hour, add above-mentioned sodium naphthalene sulfonate salt mixture, till free alkali concentration is 5-6%.Finish, 320-330 ℃ of insulation 1 hour (being full of in the pot anti-oxidation during insulation with water vapor).
Insulation is finished, and the alkali fusion thing is drained in the dilution pot of existing 1800 premium on currency.Stirred 1 hour, and be pressed into the acidifying pot.
3. acid out:
Alkali fusion material is pressed in the acidifying pot, regulates about proportion to 1.16.Pot is interior to be 250 to 300 mmhg through vacuum to vacuum tightness, feeds sulfurous gas acid out (the neutralization pot is supplied with) at 70-80 ℃, is colourless to phenolphthalein.Be warming up to and boil, leave standstill half an hour, layering, lower floor's sodium sulfite solution is emitted; Reheat water is some, is warming up to boiling, for the second time standing demix.With upper strata washing lotion and the sodium sulfite solution merging of standing demix for the first time, be cooled to≤50 ℃, press filtration, filter cake is added in the acidifying pot and (uses for following batch), and filtrate is for neutralization usefulness, and washing lotion is abandoned it.
4. distillation
Layer (thick naphthols) moves in the dehydration pot under the standing demix for the second time, thermal dehydration 2 hours.Go into vacuum still, distillation obtains mixing about 375 kilograms-380 kilograms of naphthols (methyl naphthol accounts for 15-20%, ethyl naphthol accounts for 80-85%).
Following examples 2-5 illustrates the fusion-crystallization separation method of the mixing naphthols of the foregoing description 1.
Embodiment 2
Mixing naphthols (80% second-naphthols with 100 parts of the foregoing descriptions 1; 110 ℃ of 20% first-naphthols fusing point) fusion adds in the crystallization fusion separator tank, with temperature-stable to 115 in the groove ℃, is incubated 1 hour fast.Then, with 1 ℃-5 ℃ cooling rate per hour the temperature in the groove is reduced to 85 ℃, then heat up material in the groove is discharged 15 parts at the material of 85 ℃ of-95 ℃ of thawings with 2-6 ℃ heat-up rate per hour, the material of 95 ℃ of-105 ℃ of thawings is discharged 22 parts, the material of 105 ℃ of-115 ℃ of thawings is discharged 30 parts, and the material that melts more than 115 ℃ all row is 33 parts.(purity second-naphthols 93%; First-naphthols 7%).
Embodiment 3
(first of the second-naphthols 7% of purity 93%-naphthols fusion adds in the crystallization fusion separator tank mixing naphthols that obtains among the embodiment 2 with 100 parts of weight, fast temperature-stable in the groove is incubated 1 hour at 125 ℃.Then, with 1 ℃-5 ℃ cooling rate per hour the temperature in the groove is reduced to 95 ℃, then will discharge 16 parts at the material of 95 ℃ of-105 ℃ of thawings with the material in 2-6 ℃ the heat-up rate thawing vat per hour, the material of 105-115 ℃ of thawing is discharged 18 parts, the material of 115 parts of-120 ℃ of thawings is discharged 26 parts, and the material that melts more than 120 ℃ is all discharged and accounted for 42 parts (second-naphthols purity 99.5% fusing point 〉=121 ℃).
Embodiment 4
85-95 ℃ the molten materials that obtains among the embodiment 2 with 100 parts of weight (second-naphthol content 62%, first-naphthol content 38%) fusion adds in the crystallization fusion separator tank, fast the temperature-stable in the groove is incubated 1 hour at 90 ℃.With 1-5 ℃ cooling rate per hour the temperature in the groove is reduced to 55 ℃ then, then with the material in 2-6 ℃ the heat-up rate fusion tank per hour, 55-70 ℃ of fused material discharged 20 parts, discharge 18 parts at 70 ℃ of-85 ℃ of fused materials, discharge 28 parts at 85 ℃ of-95 ℃ of fused materials, all discharge 34 parts at fused material more than 95 ℃.(second-naphthol content 74%, first-naphthol content 26%).
Embodiment 5
55 ℃ of-70 ℃ of molten materials (be that eutectic first-naphthols contains 61%, second-naphthols contains 38%) among 100 parts of weight embodiment 4 are sent into still pot carry out underpressure distillation, discharge 37 parts at 192-195 ℃ of fraction, (first-naphthol content 88%, second-naphthol content 12%); Discharge 40 parts (first-naphthol content 63%, second-naphthol content 37%) at 195-197 ℃ of fraction; Can discharge 23 parts (first-naphthol content 16%, second-naphthol contents 84%) first, the 3rd section fraction at the fraction more than 197 ℃ and can advance crystallization fusion separation purification respectively again, second section fraction can carry out redistillation.
Following examples 6-10 explanation is the specific embodiment of main products coproduction ethyl naphthol with first-naphthols.
Embodiment 6
1. the sulfonation of naphthalene:
In sulfidation pan, 400 kilograms of refined naphthalenes are added in batches 450 kilograms of sulfuric acid (97-98%) of 0 ℃ ± 5 ℃, keep 5 ℃-10 ℃ two hours, 10 ℃-15 ℃ two hours, 15 ℃-20 ℃ one hour, 20 ℃-25 ℃ one hour, 25 ℃-30 ℃ one hour and 30 ℃-40 ℃ two hours, the sampling analysis α-Nai Huangsuan accounts for 83-85%, and beta-naphthalenesulfonic-acid accounts for 15-17%.In traditional technology, in sulfonated bodies, add sal epsom, remove by filter and make beta-naphthalenesulfonic-acid generate infusible beta-naphthalenesulfonic-acid magnesium salts.And method of the present invention need not to remove isomer, sulfonated bodies directly is neutralized to Congo red constant indigo plant with S-WAT, and residual sulfurous gas in the expeling sulfonated bodies, be cooled to 30 ℃ of-35 ℃ of suction strainers, with 10% salt solution washing leaching cake, drain and obtain the α-Nai Huangsuan naphthalene to water content≤20% and account for 83-85% and sodium 15-17% mixture about 576 kilograms (100%).
Alkali fusion:
In alkal melting pan, add 98% caustic soda (sodium chlorate content≤0.05%) 552 kilograms, be heated to 260 ℃, make its fusion, stir, be warming up to 290 ℃, in 2.5-3 hour, add above-mentioned sodium naphthalene sulfonate salt mixture, till free alkali concentration is 5-6%.Finish, 320-330 ℃ of insulation 1-2 hour (being full of in the pot anti-oxidation during insulation with water vapor).
Insulation is finished, and alkali fusion material is put in the dilution pot of existing 1800 premium on currency.Stirred 1 hour, and be pressed into the acidifying pot.
3. acid out:
Alkali fusion material is pressed in the acidifying pot, regulates than weight about 1.16.The interior pulling vacuum of pot extremely directly reciprocal of duty cycle is 250 to 300 mmhg, feeds sulfurous gas acid out (neutralization pot supply) at 70-80 ℃, and extremely sour phthalein is colourless.Be warming up to and boil, leave standstill half an hour, layering, lower floor's sodium sulfite solution is emitted; Reheat water is some, is warming up to boiling, for the second time standing demix.With upper strata washing lotion and the sulfurous acid pot solution merging of standing demix for the first time, be cooled to≤50 ℃, press filtration, filter cake is added in the acidifying pot, (using for following batch), and filtrate is for neutralization usefulness, and washing lotion is abandoned it.
4. distillation
Layer (thick naphthols) moves in the dehydration pot under the standing demix for the second time, thermal dehydration 2 hours.Go into vacuum still, steamer obtains mixing the about 375-380 kilogram of naphthols (methyl naphthol accounts for 83-85%, ethyl naphthol accounts for 15-17%).
Following examples 7-10 explanation mixes naphthols fusion-crystallization separation method:
Embodiment 7
The mixing naphthols of fused the foregoing descriptions 6 of 100 parts of weight is added in the crystallization fusion separator tank, apace at 10 minutes internal cooling to 82 ℃, then be cooled to 50 ℃ with 0.5-5 ℃ of speed per hour, then be warming up to 64.5 ℃ ± 1 ℃, and discharge 16.6 parts of the thick methyl naphthols (weight) of this melting range with 1-3 ℃ of speed per hour; Then be warming up to 70.5 ℃ ± 1 ℃, and discharge 16.5 parts of the thick methyl naphthols (weight) of this melting range.Be warming up to 80.2 ℃ ± 1 ℃ again, and discharge 19.8 parts of the thick methyl naphthols (weight) of this melting range; Then, be warming up to 86.1 ℃ ± 1 ℃ again, and discharge 14.3 parts of the thick methyl naphthols (weight) of this melting range; At last, 90.9 ℃ ± 1 ℃ constant temperature three hours, and 32.8 parts of (weight) (purity 〉=90% zero pour are 90.9 ℃) of methyl naphthol of discharging this melting range.
Embodiment 8
90.9 ℃ of purity of zero pour 〉=90%(weight with 100 parts of weight of embodiment 7) the thick methyl naphthol of fused is added in the crystallization fusion separator tank, during 30 minutes, be cooled to 92 ℃ apace, then, be cooled to 70 ℃ with 1-5 ℃ of control per hour, then be warming up to 73.9 ℃ ± 1 ℃, and discharge 10 parts of the thick methyl naphthols (weight) of this melting range with 2-4 ℃ speed per hour; Then be warming up to 84.5 ℃ ± 1 ℃ again, and discharge 19 parts of the thick methyl naphthols (weight) of this melting range; Be warming up to 89.4 ℃ ± 1 ℃ again, and discharge 27.5 parts of the thick methyl naphthols (weight) of this melting range, last, material discharges 43.5 parts of (weight) purified methyl naphthols (purity 〉=95% zero pour is 92.1 ℃) 92 ℃ ± 1 ℃ constant temperature two hours.
Embodiment 9
The fused methyl naphthol of the fusing point that obtains among the embodiment 8 with 100 parts of weight 92.1 ℃ (purity 〉=95%) is added in the refinery pit of strap clamp cover, apace at 1 hour internal cooling to 93 ℃, be cooled to 93 ℃ with 2-4 ℃ of control per hour then, be warming up to 80.6 ± 1 ℃ with 1-5 ℃ of control per hour then, and discharge 6.5 parts of the thick methyl naphthols (weight) of this melting range; Then, be warming up to 88.9 ℃ ± 1 ℃ again, and discharge 22 parts of the thick methyl naphthols (weight) of this melting range; Then, be warming up to 92.15 ℃ again, and discharge 27.7 parts of the methyl naphthols (weight) of this melting range, last, material is 93.6 ± 1 ℃ of constant temperature 1 hour, and discharges the refining methyl naphthol (purity 〉=99%, zero pour are 93.65 ℃) of 43.8 parts (weight).
Embodiment 10
With 100 parts of (the methyl naphthol content 63% of 50-65 ℃ melt that obtain among the embodiment 7; Ethyl naphthol content 37%) can repeat the process of embodiment 5, wherein 192-195 ℃ fraction can repeat the process of embodiment 1; Wherein 195-197 ℃ fraction can repeat the process of embodiment 5; Wherein the fraction more than 197 ℃ (methyl naphthol content 85%, ethyl naphthol content 15%) can repeat the process of embodiment 7.
As mentioned above, naphthalene sulfonation of the present invention can be carried out under 0-165 ℃ of optional temperature range, so above-mentioned naphthalene sulfonation condition of the present invention is not subjected to the restriction of embodiment.
Claims (7)
1, a kind of naphthalene is through sulfonation, the technology of alkali fusion coproduction methyl naphthol and ethyl naphthol, comprise 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 and after enter alkali fusion, the alkali fusion thing that alkali fusion obtains enters distillation after acidifying, the mixing naphthols that distillation obtains is sent into the fusion-crystallization separator tank, the cooling rate and the scope of mixing naphthols in the control flume, heat up with certain speed 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; Discharge the ethyl naphthol of different melting ranges then.
2, technology as claimed in claim 1 is characterized in that comprising described methyl naphthol and separating of ethyl naphthol:
1) with fused mixing naphthols fast cooling to its fusing point, then,, preferably be cooled to its below fusing point 10 °-25 ℃ with 1 ° of-3 ℃ of control per hour per hour to lower the temperature 0.5-5 ℃;
The mixing naphthols that 2) will solidify is with 1 ° of-5 ℃ of speed per hour, preferably, is warming up to the methyl naphthol fusion again of solidifying with 2 ° of-4 ℃ of speed control per hour, then
3) the fused mixing naphthols of the different melting ranges of step emission;
4) last, classification is discharged and is in homothermic purified methyl naphthol or ethyl naphthol.
3, technology as claimed in claim 1 or 2 is characterized in that: with fused mixing naphthols fast cooling to its fusing point 0.5 °-5 ℃, preferably be 1 °-2 ℃.
4, technology as claimed in claim 3 is characterized in that: with fused mixing naphthols at 10 minutes to 1 hour fast coolings to its fusing point.
5, technology as claimed in claim 3, its feature also is: described constant temperature time is 0.5-8 hour, preferably is 1.5-3 hour.
6, technology as claimed in claim 1 or 2 is characterized in that: in the described mixing naphthols, the content of methyl naphthol be not less than at least 65% or the no more than at least 35%(content of content of ethyl naphthol).
7, technology as claimed in claim 1 or 2 is characterized in that: in the described mixing naphthols, the content of content of methyl naphthol no more than at least 35% or ethyl naphthol is not less than 65%(content at least).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108433A CN1039902C (en) | 1992-05-21 | 1992-05-21 | Combined process for production of 1-naphthol and beta-naphthol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108433A CN1039902C (en) | 1992-05-21 | 1992-05-21 | Combined process for production of 1-naphthol and beta-naphthol |
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| CN1078715A true CN1078715A (en) | 1993-11-24 |
| CN1039902C CN1039902C (en) | 1998-09-23 |
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| CN92108433A Expired - Fee Related CN1039902C (en) | 1992-05-21 | 1992-05-21 | Combined process for production of 1-naphthol and beta-naphthol |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308299C (en) * | 2003-02-05 | 2007-04-04 | 独立行政法人科学技术振兴机构 | Polycyclic aromatic carbon based solid strong acid |
| CN104447215A (en) * | 2014-10-29 | 2015-03-25 | 绍兴奇彩化工有限公司 | Continuous acidification process for synthesizing 2-naphthol |
| CN104693009A (en) * | 2015-03-04 | 2015-06-10 | 肖刚学 | Method for cooperatively producing 1-naphthol and 2-naphthol from naphthalene sulfonation product by virtue of direct alkali fusion |
| CN106673965A (en) * | 2016-12-21 | 2017-05-17 | 宁夏紫光川庆化工有限公司 | Synthetic process of naphthol |
| 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 |
| CN108821950A (en) * | 2018-05-31 | 2018-11-16 | 山西豪仑科化工有限公司 | A kind of continuous neutralization reaction method of bisnaphthol production |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4237323A (en) * | 1979-06-08 | 1980-12-02 | Aliev Sakhib M O | Method for preparing α-naphthol |
-
1992
- 1992-05-21 CN CN92108433A patent/CN1039902C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308299C (en) * | 2003-02-05 | 2007-04-04 | 独立行政法人科学技术振兴机构 | Polycyclic aromatic carbon based solid strong acid |
| CN104447215A (en) * | 2014-10-29 | 2015-03-25 | 绍兴奇彩化工有限公司 | Continuous acidification process for synthesizing 2-naphthol |
| CN104693009A (en) * | 2015-03-04 | 2015-06-10 | 肖刚学 | Method for cooperatively producing 1-naphthol and 2-naphthol from naphthalene sulfonation product by virtue of direct alkali fusion |
| 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 |
| CN106673965A (en) * | 2016-12-21 | 2017-05-17 | 宁夏紫光川庆化工有限公司 | Synthetic process of naphthol |
| 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 |
| CN108821950A (en) * | 2018-05-31 | 2018-11-16 | 山西豪仑科化工有限公司 | A kind of continuous neutralization reaction method of bisnaphthol production |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN1039902C (en) | 1998-09-23 |
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