CN102850190A - Method for preparing mixed naphthol - Google Patents

Method for preparing mixed naphthol Download PDF

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Publication number
CN102850190A
CN102850190A CN2011101771898A CN201110177189A CN102850190A CN 102850190 A CN102850190 A CN 102850190A CN 2011101771898 A CN2011101771898 A CN 2011101771898A CN 201110177189 A CN201110177189 A CN 201110177189A CN 102850190 A CN102850190 A CN 102850190A
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Prior art keywords
naphthols
isopropyl naphthalene
acid
mixing
reaction
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CN2011101771898A
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Inventor
靳海波
杨索和
何广湘
郭志武
陈倩文
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Beijing Institute of Petrochemical Technology
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Beijing Institute of Petrochemical Technology
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Priority to CN2011101771898A priority Critical patent/CN102850190A/en
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Abstract

The invention discloses a method for preparing mixed naphthol from monoisopropylnaphthalene. The method includes processes including purification and isomerization of monoisopropylnaphthalene, oxidation of monoisopropylnaphthalene under alkaline condition, hydrolysis of oxidation product, and rectification separation. The method can reduce complexity of preparing naphthol by monoisopropylnaphthalene oxidation method, reduce process operation cost and loss, and improve yield and quality of naphthol, and it is a high-efficiency clean high-atom economy naphthol preparation process.

Description

A kind of method of mixing naphthols for preparing
Technical field
The present invention relates to the preparation technology of compound, specifically, relating to by an isopropyl naphthalene (IPN) is raw material, through purification, isomerization, and alkali cleaning, oxidizing reaction, acid hydrolytic reaction, just separation and naphthols rectifying make the mixing naphthols.
Background technology
Naphthols has 1-naphthols, two kinds of isomer of beta naphthal.Wherein beta naphthal claims again ethyl naphthol, 2-Naphthol, is important Organic Chemicals and synthetic intermediate.Not only can be made the dyestuff intermediates such as R acid, butyric acid, G phenol (beta naphthal-6,8-two sulphur phenol) by beta naphthal, also can be used for producing the intermediate 2 of glacial dye naphthols AS, 3-acid and substantive dyestuff sun-proof orchid and ash are purplish red etc.Simultaneously, 2-naphthols also can be made the raw material of oxidation inhibitor, rubber antioxidant fourth and agricultural chemicals and medicine.The 1-naphthols claims again methyl naphthol, naphthyl alcohol, and its purposes is continually developed, and is widely used in the aspects such as medicine, agricultural chemicals, dyestuff, spices manufacturing, chiral catalyst is synthetic, causes market demand constantly to increase, promise well.Its production method is similar to beta naphthal production, is the important isomer during beta naphthal is produced.
The main method of synthetic naphthols has: sulfonated alkali fusion method, isopropyl naphthalene method, hydrolysis method, naphthane method, electrochemical process, hydrogen peroxide method etc.Sulfonated alkali fusion method is the main method of present industry both at home and abroad beta naphthal processed, the technology comparative maturity.This method is take refined naphthalene as raw material, and under vitriol oil effect, sulfonation obtains naphthene sulfonic acid, then uses in the S-WAT and the sodium salt that generates, and obtains sodium naphtholate with the NaOH alkali fusion again, then gets the thick product of naphthols with sulfuric acid acidation.Because the energy consumption of naphthalene process for sulfonation is higher, and produces a large amount of pollutents, be difficult to administer, environment is caused seriously influence.
Hydrolysis method mainly contains two kinds of technology: chloronaphthalene method and naphthylamines method.The chloronaphthalene method is under the condition of High Temperature High Pressure, is chloronaphthalene with the naphthalene chlorination, again at 800 ℃ of lower water flowing steams, under the effect of Catalysts Cu Cl and KCl chloronaphthalene hydrolysis is generated naphthols.The naphthylamines method is that naphthalene is nitrated with nitric acid, reduction obtains naphthalidine, and again take dilute sulphuric acid as medium, hydrolysis obtains the 1-naphthols.The defectives such as it is serious that technical process exists equipment corrosion, and wastewater treatment capacity is large, and technical process is long, and the intermediate naphthylamines is the carcinogens of generally acknowledging, and toxicity is very large.
The tetraline method is first the naphthalene shortening to be converted into naphthane; Be Tetralone an intermediate of Sertraline with oxygen with its liquid phase catalytic oxidation again, dehydrogenation generates the 1-naphthols again.The reaction conditions of this method harshness causes high cost, and catalyst material is expensive, lacks competitiveness.In a word, traditional synthetic method is polystep reaction, just can generate naphthols through long technological process, has produced multiple intermediate, causes the utilization ratio of atom lower; Because the selectivity of reaction is generally relatively poor, so certainly lead to a large amount of refuses, cause cost higher simultaneously, pollutant emission is many, and it is large to process the pollution technical difficulty, environment is caused have a strong impact on.
Direct catalysis synthesis process: process for catalytic synthesis has powerful industrialization potentiality as new green synthesis process.Its basic thought is just for problems such as naphthol synthesis process are complicated, the blowdown intractability is large, directly from the source namely by naphthalene under the effect of catalyzer and oxygenant, an one-step hydroxylation reaction is synthetic naphthols directly, simplifies reactions steps, reduce reaction intermediate, improve atom utilization.But the method industrialization also has a very long segment distance.
The isopropyl naphthalene method is take naphthalene as raw material, and under the effect of alkylating reagent, (β-IPN), make β-IPNHP with molecular oxygen oxidation again, last acid decomposition obtains beta naphthal and acetone to make β-isopropyl naphthalene through the catalysis isopropylation.Because the technology of isopropyl naphthalene method is complicated, but but has large-scale, the advantage such as efficient, cleaning, atom utilization are high, pollution-free.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, and a kind of efficient, cleaning, high, the free of contamination method of mixing naphthols for preparing of atom utilization are provided.
The object of the invention can be achieved by the following measures: the method comprises that (acid hydrolytic reaction, just separation and naphthols rectifying make the mixing naphthols to raw material one isopropyl naphthalene for the purification of IPN, isomerization, alkali cleaning, oxidizing reaction;
Purification refers to remove impurity a small amount of in the isopropyl naphthalene;
Isomerization refers to the conversion between α-an isopropyl naphthalene and β-an isopropyl naphthalene;
Alkali cleaning refers to adopt the acidic substance in the alkali liquid washing one isopropyl naphthalene raw material;
Oxidizing reaction refers to adopt molecular oxygen oxidation one isopropyl naphthalene under the condition of alkalescence;
Acid hydrolytic reaction refers to that the hydrogen peroxide isopropyl naphthalene is decomposed into naphthols and acetone under acidic conditions.
A described isopropyl naphthalene isomerization is reacted under an acidic catalyst condition, and alkylating reagent is propylene, 2-butylene, and an acidic catalyst is Lewis acid or H type zeolite catalyst, preferred AlCl 3, the HM h-mordenite, HY Hydrogen Y zeolite catalyzer, isomerisation temperature is at 120-350 ℃, preferred 180-270 ℃.
Described mixing naphthols purpose product is two kinds of 1-naphthols and beta naphthals, and both ratios are between the 1:6-1:1, preferred 1:5-1:2.。
A described isopropyl naphthalene alkali cleaning, the oxidation under alkaline condition, alkaline condition is NaOH, Na 2The C aqueous solution, concentration range are 0.5%-3.5%, preferred 1.5%-2.5%;
Oxidizing reaction temperature is preferably 90-100 ℃ at 80-110 ℃; The ratio of an isopropyl naphthalene molar weight is at 20-60 in the molar weight of reacting used oxygen-containing gas and the charging, preferred 40-50; The volumetric concentration of oxygen can be 5~100%, is preferably 15~50%; Promotor is stearic acid, and initiator is hydrogen peroxide, isobutyric aldehyde or hydrogen peroxide isopropyl naphthalene.
Described acid hydrolytic reaction is mineral acid, and is preferred: hydrochloric acid, sulfuric acid, perchloric acid, and catalyst concn 0.5-1.5%, solvent are dodecane, acetonitrile, acetic acid, methyl alcohol, temperature of reaction is 20-50 ℃.
Be that profit two is separated described just the separation; Rectifying separation purpose product mixing naphthols.
Isomerization reaction is in stirred reactor or in the fixed-bed reactor, and temperature is at 120-350 ℃, preferred 180-270 ℃.Can promote the alpha-alkyl naphthalene to transform to β-alkylnaphthalene.
One isopropyl naphthalene carries out oxidizing reaction under alkaline condition, oxidation is that the oxygen-containing gas that contains molecular oxygen is implemented; Oxygen-containing gas passes into reactor bottom by inlet pipe and joins in the catalyst system, and even bubbling under the condition of high-speed stirring is beneficial to oxygen and fully contacts with reactant.
The present invention relates to reactor and can adopt intermittence, semicontinuous, continuous mode production, but preferably adopt semicontinuous or continuous mode.
The present invention compared with prior art has following advantage: the present invention is that the technological process pollutent is few, wastewater discharge is few, can prepare two kinds of 1-naphthols and beta naphthals, and the ratio that process can the modulation product, to adapt to the demand in market, process can satisfy the needs of producing the high quality naphthols simultaneously.
Description of drawings
Fig. 1 is preparation mixing naphthols process flow sheet of the present invention.
Embodiment
The below enumerates 3 embodiment, the present invention is further specified, but the present invention is not only limited to these embodiment.
According to the present invention, mix naphthols by an isopropyl naphthalene through process preparations such as isomerization, oxidizing reaction, acid decomposition, rectifying.
Embodiment 1-1
Take an isopropyl naphthalene (IPN) as raw material, β-IPN/ α-IPN=7:3 wherein, at 500 ℃, the HM mordenite catalyst of activation 2-3h, isomerization reaction 3h under 270 ℃, 1MPa, β-IPN/ α-IPN=8:2 can modulation β position and the ratio of α position, is conducive to the ratio of modulation product.Its mixture after alkali cleaning, is entered oxidation reactor, 100 ℃ of temperature of reaction, the 1.5%NaOH aqueous solution is under the catalyzer, and take isobutyric aldehyde as initiator, air is oxygenant, the content of IPNHP obviously rises in the product, and behind the 10h, the selectivity of hydrogen peroxide isopropyl naphthalene has surpassed 60%., IPNHP content reaches 13.4%.Product after its oxidation directly enters decomposition reactor, under normal temperature, normal pressure with HClO 4Be catalyzer, AcOH is solvent, reaction 1.5h, and the productive rate that mixes naphthols is 93%, wherein beta naphthal accounts for 67.1%, 1-naphthols and accounts for 22.6%.It mixes naphthols and goes out 1-naphthols and beta naphthal through sepn process is separable.
Embodiment 1-2: change oxidising process catalyzer and reaction conditions
Take an isopropyl naphthalene (IPN) as raw material, β-IPN/ α-IPN=7:3 wherein, at 500 ℃, the HM mordenite catalyst of activation 2-3h, isomerization reaction 3h under 270 ℃, 1MPa, β-IPN/ α-IPN=8:2 can modulation β position and the ratio of α position, is conducive to the ratio of modulation product.Its mixture after alkali cleaning, is entered oxidation reactor, and 90 ℃ of temperature of reaction, the 0.5%NaOH aqueous solution is under the catalyzer, with H 2O 2Be initiator, air is oxygenant, and what IPNHP(cries in the product) content obviously rise, behind the 15h, the selectivity of hydrogen peroxide isopropyl naphthalene has surpassed 56%., IPNHP content reaches 12.1%.Product after its oxidation directly enters decomposition reactor, under normal temperature, normal pressure with HClO 4Be catalyzer, AcOH is solvent, reaction 1.5h, and the productive rate that mixes naphthols is 90%, wherein beta naphthal accounts for 65.5%, 1-naphthols and accounts for 21.6%.It mixes naphthols and goes out 1-naphthols and beta naphthal through sepn process is separable.
Embodiment 1-3: the catalysts and solvents that changes acid hydrolytic reaction
Take an isopropyl naphthalene (IPN) as raw material, β-IPN/ α-IPN=7:3 wherein, at 500 ℃, the HM mordenite catalyst of activation 2-3h, isomerization reaction 3h under 270 ℃, 1MPa, β-IPN/ α-IPN=8:2 can modulation β position and the ratio of α position, is conducive to the ratio of modulation product.Its mixture after alkali cleaning, is entered oxidation reactor, and 100 ℃ of temperature of reaction, the 1.5%NaOH aqueous solution is under the catalyzer, with H 2O 2Be initiator, air is oxygenant, and the content of IPNHP obviously rises in the product, and behind the 15h, the selectivity of hydrogen peroxide isopropyl naphthalene has surpassed 56%., IPNHP content reaches 12.1%.Product after its oxidation directly enters hydrolysis reactor, and take HCl as catalyzer, methyl alcohol is solvent under normal temperature, normal pressure, reaction 3.5h, and the productive rate that mixes naphthols is 65%, wherein beta naphthal accounts for 65.0%, 1-naphthols and accounts for 20.3%.It mixes naphthols and goes out 1-naphthols and beta naphthal through sepn process is separable.
Embodiment 2-1
Take an isopropyl naphthalene (IPN) as raw material, β-IPN/ α-IPN=7:3 wherein, at 500 ℃, the HY zeolite catalyst of activation 2-3h, isomerization reaction 3h under 300 ℃, 1MPa, β-IPN/ α-IPN=8:2 can modulation β position and the ratio of α position, is conducive to the ratio of modulation product.Its mixture after alkali cleaning, is entered oxidation reactor, at 100 ℃ of temperature of reaction, 1.5%Na 2CO 3The aqueous solution is under the catalyzer, and take isobutyric aldehyde as initiator, air is oxygenant, and the content of IPNHP obviously rises in the product, and behind the 10h, the selectivity of hydrogen peroxide isopropyl naphthalene has surpassed 75%., IPNHP content reaches 15.4%.Product after its oxidation directly enters hydrolysis reactor, under normal temperature, normal pressure with HClO 4Be catalyzer, AcOH is solvent, reaction 1.5h, and the productive rate that mixes naphthols is 93%, wherein beta naphthal accounts for 67.1%, 1-naphthols and accounts for 22.6%.It mixes naphthols and goes out 1-naphthols and beta naphthal through sepn process is separable.
Embodiment 2-2: change initiator
Take an isopropyl naphthalene (IPN) as raw material, β-IPN/ α-IPN=7:3 wherein, at 500 ℃, the HY zeolite catalyst of activation 2-3h, isomerization reaction 3h under 300 ℃, 1MPa, β-IPN/ α-IPN=8:2 can modulation β position and the ratio of α position, is conducive to the ratio of modulation product.Its mixture after alkali cleaning, is entered oxidation reactor, at 100 ℃ of temperature of reaction, 1.5%Na 2CO 3The aqueous solution is under the catalyzer, and take the hydrogen peroxide isopropyl naphthalene as initiator, air is oxygenant, and the content of IPNHP obviously rises in the product, and behind the 10h, the selectivity of hydrogen peroxide isopropyl naphthalene has surpassed 75%., IPNHP content reaches 15.4%.Product after its oxidation directly enters decomposition reactor, under normal temperature, normal pressure with HClO 4Be catalyzer, AcOH is solvent, reaction 1.5h, and the productive rate that mixes naphthols is 93%, wherein beta naphthal accounts for 67.1%, 1-naphthols and accounts for 22.6%.It mixes naphthols and goes out 1-naphthols and beta naphthal through sepn process is separable.
Embodiment 3-1
Take an isopropyl naphthalene (IPN) as raw material, β-IPN/ α-IPN=7:3 wherein is under the AlCl3 catalyzer, isomerization reaction 3h under 180 ℃, normal pressure, β-IPN/ α-IPN=8.5:1.5 can modulation β position and the ratio of α position, is conducive to the ratio of modulation product.Its mixture after alkali cleaning, is entered oxidation reactor, 100 ℃ of temperature of reaction, the 1.5%NaOH aqueous solution is under the catalyzer, and take isobutyric aldehyde as initiator, air is oxygenant, the content of IPNHP obviously rises in the product, and behind the 10h, the selectivity of hydrogen peroxide isopropyl naphthalene has surpassed 75%., IPNHP content reaches 16.0%.Product after its oxidation directly enters decomposition reactor, under normal temperature, normal pressure with HClO 4Be catalyzer, AcOH is solvent, reaction 1.5h, and the productive rate that mixes naphthols is 93%, wherein beta naphthal accounts for 68.%, 1-naphthols and accounts for 22.5%.It mixes naphthols and goes out 1-naphthols and beta naphthal through sepn process is separable.
Embodiment 3-2: the content (oxygen, 100% content) that changes oxygen-containing gas
Take an isopropyl naphthalene (IPN) as raw material, β-IPN/ α-IPN=7:3 wherein is under the AlCl3 catalyzer, isomerization reaction 3h under 180 ℃, normal pressure, β-IPN/ α-IPN=8.5:1.5 can modulation β position and the ratio of α position, is conducive to the ratio of modulation product.Its mixture after alkali cleaning, is entered oxidation reactor, 100 ℃ of temperature of reaction, the 1.5%NaOH aqueous solution is under the catalyzer, and take isobutyric aldehyde as initiator, oxygen is oxygenant, the content of IPNHP obviously rises in the product, and behind the 10h, the selectivity of hydrogen peroxide isopropyl naphthalene has surpassed 75%., IPNHP content reaches 16.0%.Product after its oxidation directly enters decomposition reactor, under normal temperature, normal pressure with HClO 4Be catalyzer, AcOH is solvent, reaction 1.5h, and the productive rate that mixes naphthols is 93%, wherein the 1-naphthols accounts for 68.%, 1-naphthols and accounts for 22.5%.It mixes naphthols and goes out 1-naphthols and beta naphthal through sepn process is separable.

Claims (10)

1. one kind prepares the method for mixing naphthols, it is characterized in that: the method comprises purification, the isomerization of raw material one isopropyl naphthalene, alkali cleaning, oxidizing reaction, and acid hydrolytic reaction, just separation and naphthols rectifying make the mixing naphthols;
Purification refers to remove impurity a small amount of in the isopropyl naphthalene;
Isomerization refers to the conversion between α-an isopropyl naphthalene and β-an isopropyl naphthalene;
Alkali cleaning refers to adopt the acidic substance in the alkali liquid washing one isopropyl naphthalene raw material;
Oxidizing reaction refers to adopt molecular oxygen oxidation one isopropyl naphthalene under the condition of alkalescence;
Acid hydrolytic reaction refers to that the hydrogen peroxide isopropyl naphthalene is decomposed into naphthols and acetone under acidic conditions.
2. the method for mixing naphthols for preparing according to claim 1, it is characterized in that: a described isopropyl naphthalene isomerization is reacted under an acidic catalyst condition, alkylating reagent is propylene, 2-butylene, an acidic catalyst is Lewis acid or H type zeolite catalyst, and isomerisation temperature is at 120-350 ℃.
3. the method for mixing naphthols for preparing according to claim 1 and 2, it is characterized in that: a described isopropyl naphthalene isomerization is reacted under an acidic catalyst condition, and alkylating reagent is propylene, 2-butylene, and an acidic catalyst is AlCl 3, HM h-mordenite or HY Hydrogen Y zeolite catalyzer, isomerisation temperature is at 180-270 ℃.
4. the method for mixing naphthols for preparing according to claim 1 is characterized in that: described mixing naphthols purpose product is two kinds of 1-naphthols and beta naphthals, and both ratios are between the 1:6-1:1.
5. according to claim 1 or the 4 described methods of mixing naphthols that prepare, it is characterized in that: described mixing naphthols purpose product is two kinds of 1-naphthols and beta naphthals, and both ratios are 1:5-1:2.
6. the method for mixing naphthols for preparing according to claim 1 is characterized in that: a described isopropyl naphthalene alkali cleaning, and oxidation under alkaline condition, alkaline condition is NaOH, Na 2CO 3The aqueous solution, concentration range are 0.5%-3.5%; Oxidizing reaction temperature is 80-110 ℃; The ratio of an isopropyl naphthalene molar weight is at 20-60 in the molar weight of reacting used oxygen-containing gas and the charging; The volumetric concentration of oxygen is 5~100%; Promotor is stearic acid, and initiator is hydrogen peroxide, isobutyric aldehyde or hydrogen peroxide isopropyl naphthalene.
7. according to claim 1 or the 6 described methods of mixing naphthols that prepare, it is characterized in that: a described isopropyl naphthalene alkali cleaning, oxidation under alkaline condition, alkaline condition is NaOH, Na 2CO 3The aqueous solution, concentration range are 1.5%-2.5%; Oxidizing reaction temperature is 90-100 ℃; The ratio of an isopropyl naphthalene molar weight is at 40-50 in the molar weight of reacting used oxygen-containing gas and the charging; The volumetric concentration of oxygen is 15~50%.
8. the method for mixing naphthols for preparing according to claim 1, it is characterized in that: described acid hydrolytic reaction is mineral acid, and catalyst concn 0.5-1.5%, solvent are dodecane, acetonitrile, acetic acid, methyl alcohol, and temperature of reaction is 20-50 ℃.
9. according to claim 1 or the 8 described methods of mixing naphthols that prepare, it is characterized in that: described acid hydrolytic reaction is hydrochloric acid, sulfuric acid, perchloric acid.
10. the method for mixing naphthols for preparing according to claim 1 is characterized in that: be that profit two is separated described just the separation; Rectifying separation purpose product mixing naphthols.
CN2011101771898A 2011-06-28 2011-06-28 Method for preparing mixed naphthol Pending CN102850190A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1496227A (en) * 1974-04-22 1977-12-30 Kureha Chemical Ind Co Ltd Method for the production of beta-naphthol
CN101781172A (en) * 2010-01-04 2010-07-21 曲靖众一精细化工股份有限公司 Novel process for efficiently and continuously synthesizing 2-naphthol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1496227A (en) * 1974-04-22 1977-12-30 Kureha Chemical Ind Co Ltd Method for the production of beta-naphthol
CN101781172A (en) * 2010-01-04 2010-07-21 曲靖众一精细化工股份有限公司 Novel process for efficiently and continuously synthesizing 2-naphthol

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
洪仲苓主编: "《化工有机原料深加工》", 30 June 1997, article ""5.5.3.23 2-萘酚"", pages: 654-655 *
洪仲苓主编: "《化工有机原料深加工》", 30 June 1997, 化学工业出版社 *
魏文德主编: "《有机化工原料大全 第三卷》", 31 August 1990, 化学工业出版社 *

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Application publication date: 20130102