CN86100936A

CN86100936A - The production technique of naphthalene

Info

Publication number: CN86100936A
Application number: CN86100936.3A
Authority: CN
Inventors: 拉尔夫·威廉·卡迈克尔; 萨瓦托尔·罗米奥尔多·格雷罗
Original assignee: Individual
Current assignee: Individual
Priority date: 1985-03-04
Filing date: 1986-02-04
Publication date: 1986-09-10
Also published as: CN1003643B; CA1234162A; BE901970A; JPS61200931A

Abstract

The present invention is to be raw material with the thick naphtalene oil of coal deutero-, produces the technological process of the naphthalene ball of colour stable with refined naphthalene.This technology can be removed a large amount of production stages, does not need to wash with sulfuric acid, thereby has avoided handling relevant environmental problem with acid sulfate soil.This technology comprises from the methanol solution of thick naphthalene makes naphthalene crystalization, and prepares refined naphthalene with clay treatment subsequently.

Description

The production technique of naphthalene

The invention relates to from the thick naphtalene oil of coal deutero-and to produce colour stable, the technological process of the refined naphthalene that naphthalene ball is used.

Naphthalene is broad-spectrum primary raw materials in organic chemistry industry.A large amount of naphthalenes is used to produce adjacent naphthalic anhydride, α-and 2-Naphthol and other organic intermediate raw material.(R.S.stobaugh, Hydroc, Processing, 45 volumes, 3 phases, 149 pages, (1966)) are quite a large amount of, and very pure naphthalene is used for producing naphthalene ball.

A kind of method for preparing naphthalene at first is a Doak Tar Oil, and the boiling range of further purifying is 205～235 ℃ a fraction.The coal tar distillate that obtains like this is commonly referred to naphtalene oil.Wherein contain the such heterocycle component of naphthalene, methylnaphthalene, phenolic compound and benzo-thiophene, (people such as G.Gilbert, Ind, Eng, Chem, 53 volumes, 12 phases, 993 pages, 1961) and as the unsaturated compound of indenes and its alkyl derivative and so on.

The content of naphthalene is generally in 75～95% scopes in the naphtalene oil.The quality of naphtalene oil is a feature with the fusing point usually, and fusing point is relevant with the content of naphthalene in the naphtalene oil, in 65～75 ℃ scope.In order to produce the about 79.6 ℃ refined naphthalene of fusing point, the impurity that is included in the naphtalene oil must be removed with the method for physics and chemistry.The degree of purifying depends on the end-use of product naphthalene.Make the naphthalene of Tetra hydro Phthalic anhydride, fusing point is usually between 78～79 ℃.And make the naphthalene of naphthalene ball level, its fusing point is minimum to be 80 ℃, and reveals to put in air and sunlight and should not fade.

In view of the importance of this aromatics, separation and purifying naphthalene are quite attractive problems from coal tar distillate.

The conventional production methods of refined naphthalene is to use sulfuric acid scrubbing naphtalene oil, washs with aqueous sodium hydroxide washes subsequently.But crystalline technology comes into one's own from melts recently.It not only is favourable on productive rate, and not because of handling the environmental problem that sour mud causes.From melts, produce the typical process process of thick naphthalene, in people's such as K.Saxer article, add narration, AIChE meeting, 25-29 day in November, 1979).Is 741 ℃ from content for the 90%(fusing point) naphtalene oil, can produce purity with high yield through six steps and reach 99.7% naphthalene at least.

I.A.Brodie is in Mech.Chem.Eng.Trans.Inst.of Eng Austr 1971:37-44 page or leaf, and having narrated is another technological process of principle with the fusion-crystallization.In this technological process,, also recommend naphtalene oil with high density in order the most advantageously to use crystallization processes.Such crystallization processes, the raw material of handy high density; Otherwise productive rate and efficient all can be adversely affected.

But having only the tar refining factory of minority can produce fusing point is 73 ℃ or higher naphtalene oil, and this content that is equivalent to naphthalene is 87% or higher.Therefore, adopt different process for purification, produce highly purified naphthalene and be only favourable.

In the producing of naphthalene ball level naphthalene, must consider further problem.The naphthalene of making the naphthalene ball level is exposed under air and the sunlight, will keep colour stable at least in the time in two weeks.Therefore, the impurity that also remains in the refined naphthalene after purifying must be lower than certain lower limit.The mechanism of fading also imperfectly understands, and still, it is generally acknowledged, as the unsaturated compound of indenes and phenols component and so on bleaching effect is arranged.

Past had been made a lot of naphthalenes of producing the naphthalene ball level with economic method of making great efforts.Traditional sublimation process has been used to produce the naphthalene of naphthalene ball level, but the cost of this method is very high.Other chemical process is described in (H.G.Frank and G.Collin, coal tar, Springer, 1968) in the document, and these technologies generally also are because cost height (will handle with hydrogen) or because processing condition (the part chlorination or the same Fecl of difficulty ₃Reaction) is not widely adopted.

English Patent 651,514 has been narrated and has been used the silica gel treatment naphthalene.The silica gel of using in this technology will be made sizable upgrading and handle, and wash with water and not be with till the sulfate radical negative ion.Also be not disclosed in the content of indenes in the finished product.

The naphthalene that is derivatized to from oil with clay treatment discloses (hydrocarbon processing, 45 volumes, 3 phases, 149 pages, 1966) by R.B.Stobaugh.But this can not compare with the refining of deutero-naphthalene from coal tar, because contain visibly different impurity from the naphthalene of petroleum derivation.

The difficulty of producing colourless naphthalene from coal tar distillate with inorganic adsorbent is special report (people such as Ж .u. л enuHa, coke and chemistry, 9 phases, 27 pages, 1980) in Russian magazine.Therefore the naphthalene of developing the method manufacturing naphthalene ball level of an economy has been an old task.In other words promptly produce a kind of refined naphthalene, make its contained impurity reach enough low level, satisfy the colour stability of refined naphthalene.

Adopted methyl alcohol to make solvent, the naphthalene crystal that washing crystallizes out from naphtalene oil.English Patent discloses this technology 686, No. 166, but find, washs the crystal of naphthalene several times with methyl alcohol, the fusing point of producing be exposed in air and the sunlight at the naphthalene more than 80 ℃ and also fade.According to previous technology, can not produce a kind of naphthalene of colour stable in this way.(H.G.Franck, G.Collin, coal tar, Springer, 70 pages, 1968; G.Gilbert, Ind.Eng.Chem, 53 volumes, 12 phases, 993 pages, 1961).Equally, previous technology is also pointed out, if refined naphthalene is with the crystalline method, crystallize out from molten mass through limited several steps, or the refined naphthalene of traditional process for refining gained of washing without sulfuric acid and aqueous sodium hydroxide washes, its fusing point the phenomenon of fading also occurs more than 796 ℃.

Found a kind of novel method of production naphthalene ball level naphthalene of very economical surprisingly.In addition, no matter the content of naphthalene all is suitable in the initial naphtalene oil fraction of this novel method.

Have been found that the naphtalene oil that distills out from coal tar distillate is dissolved in the methyl alcohol ratio of naphthalene and methyl alcohol, be preferably in 1: 1 to 1: 3 the scope, preferably go out naphthalene, the naphthalene crystal of fusion gained then with the crystallization from solution of 1 to 3 step, and use clay treatment, just can obtain naphthalene to colour stable.

In a technology of preferentially selecting for use, naphthalene crystallizes out from methanol solution in two steps; Subsequently in about 80～100 ℃ of temperature ranges, 1～10% the carclazyte that is about naphthalene with weight was handled about 30 minutes at least.

Afterclap of the present invention is, it is low to as long as simply use clay treatment that the refined naphthalene that crystallization goes out from methanol solution contains the quantity of phenol and unsaturated compound, just can be with Impurity removal to the bottom line of avoiding fading.The fusing point that obtains with the fusion-crystallization method is 798 ℃ a refined naphthalene on the other hand, though also use clay treatment subsequently, the content of its phenol and indenes is still too high; So that be exposed to air and sunlight following time, color is unsettled.

The technological process of production colour stable naphthalene provided by the invention was made up of following several steps: naphtalene oil is dissolved in generates solution in the methyl alcohol, crystallization naphthalene from solution, to use clay treatment after the fusion of xln naphthalene, generating a kind of fusing point at last minimum is the naphthalene of 80 ℃ colour stable.

The further embodiment of the present invention is, naphthalene with clay treatment after, filter, distillation is produced purity and is about 99% naphthalene.

By common distillation, method of purification derives coal tar naphtalene oil from coal tar.The naphthalene of naphthalene ball level preferably purity is about 99%, and fusing point is minimum to be 80 ℃.

With three example explanation simultaneous tests, the colour stable naphthalene that example 1 and example 2 expressions are produced according to technology of the present invention, and the effect of the four step fusion-crystallization methods that example 3 is listed.Test-results is shown in subordinate list, and as can be seen, example 1 and example 2 are produced the naphthalene of colour stable, and example 3 is molten mass crystallization processes, can not produce the naphthalene of colour stable.

Table

Example 1 example 2 examples 3

From methanol solution from methanol solution from molten mass four

In two the step crystallizations, in two the step crystallizations, the step crystallization, add white

Adding carclazyte adds carclazyte at 88 ℃ and locates at 88 ℃ at 95 ℃ of soil

Handle to handle in 30 minutes and managed 30 minutes in 40 minutes

Naphtalene oil: 69.5 ℃ 61.0 ℃ 73.5 ℃ of fusing points

Naphthalene % 82.5 72.2 90.1

Benzo-thiophene % 2.10 1.75 2.1

Refined naphthalene: 79.6 ℃ 79.4 ℃ 79.8 ℃ of fusing points

Before the clay treatment:

Indenes % 0.02 0.03 0.08

Phenol % does not measure 0.01 0.10

Benzo-thiophene % 0.6 0.75 0.58

Naphthalene % 99.1 98.40 99.2

The naphthalene ball level:

80.10 ℃ 80.05 ℃ 79.9 ℃ of fusing points

Naphthalene % 99.6 99.52 98.80

Colour stability colour stable colour stable color instability

Color APHA 10 13 26

(American Public Health Association (APHA))

Example 1

With fusing point is 69.5 ℃ coal tar naphtalene oil, is dissolved in the methyl alcohol in 60 ℃, then cool to room temperature.Xln in that the first step crystallisation stage forms separates with centrifugal filtration process.The naphthalene dissolution of crystals that the first step is obtained carries out the crystallization second time and further purifies in pure methyl alcohol.The used methyl alcohol of two-step crystallization and the ratio of naphtalene oil are 2: 1 in this example.After subordinate phase crystalline xln is melted, feed in the pressurized vessel, the carclazyte with 5% was handled 1 hour at 85 ℃.After the filtration, distillation is with the naphthalene after the clay treatment, and making a fusing point is 80.1 ℃, and purity is the naphthalene of 99.6% colour stable.

Example 2

Use the lower naphtalene oil of naphthalene content in this example.Adopt same crystallization condition, only contain the phenol of 100ppm in the resulting refreshing naphthalene crystal of the second step crystallization.By the method for general introduction in the example 1, further use clay treatment, subsequently after filtration and distillation, the fusing point that obtains the colour stable naphthalene is 80.05 ℃, the purity of naphthalene is 99.52%.

Example 3

As a comparison, refined naphthalene makes through four steps from molten mass.According to the method that is summarized in the example 1, with this refined naphthalene of clay treatment.But the naphthalene that finally makes is not a colour stable, is exposed in light or the air and can fades.Its fusing point is lower than 80 ℃, and purity is lower than 99%.

When adopting two or more crystallisation step, the methyl alcohol behind the second step crystallization can circulate and be used to dissolve the naphtalene oil of the first step crystallization.

Using centrifuging can the fractional crystallization body.Also can use known other separation method in the coal tar refining technology, as filtering the fractional crystallization body.Though the present invention is only limited to appended claim, the various variations to this technology is made do not depart from the scope of the present invention.

Errata

CPCH856919

Claims

1, a kind of technological process of producing the colour stable naphthalene from coal tar is characterized in that naphthalene is crystallized out from the methanol solution of thick naphthalene, makes refined naphthalene with clay treatment subsequently.

2,, it is characterized in that carrying out crystallization with 1 to 3 step according to the technological process of claim 1.

3, according to the technological process of claim 1, it is characterized in that naphthalene to the ratio of methyl alcohol in 1: 1 to 1: 3 scope.

4, according to the technological process of claim 1, the consumption that it is characterized in that handling the carclazyte of refined naphthalene is about 1% to 10% by weight.

5,, it is characterized in that with the clay treatment refined naphthalene it being in about 82 ℃ to the 100 ℃ scopes of temperature, to carry out according to the technological process of claim 1.

6, a kind of technological process for preparing the colour stable naphthalene is characterized in that this process comprises following several steps:

Naphtalene oil and methyl alcohol wiring solution-forming with coal tar distillate; By in this solution naphthalene crystal being come out,

With the fusion of naphthalene crystal body and;

With clay treatment fused naphthalene crystal body, make that to have fusing point minimum be 80 ℃ colour stable naphthalene.

7, according to the technological process of claim 6, the naphtalene oil that it is characterized in that coal tar distillate in the solution and the ratio of methyl alcohol are about in 1: 1 to 1: 3 the scope.

8,, it is characterized in that wiring solution-forming and crystallization carried out with 1 to 3 step according to the technological process of claim 6.

9, technological process according to Claim 8 is characterized in that handling fused naphthalene crystal with the carclazyte that is about by weight in 1% to 10% scope.

10, according to the technological process of claim 9, it is characterized in that in about 82 ℃ to the 100 ℃ scope of temperature, use clay treatment fused naphthalene crystal body at least three ten minutes.

11,, it is characterized in that filtering the naphthalene after the clay treatment, and the purity of distilling the product naphthalene is at least about 99% according to the technological process of claim 6.

12,, it is characterized in that the naphtalene oil of coal tar distillate is dissolved in the methyl alcohol more than envrionment temperature, and be cooled to envrionment temperature and make its crystallization according to the technological process of claim 6.