CN1079952A - The production technique of cresols - Google Patents
The production technique of cresols Download PDFInfo
- Publication number
- CN1079952A CN1079952A CN 93106095 CN93106095A CN1079952A CN 1079952 A CN1079952 A CN 1079952A CN 93106095 CN93106095 CN 93106095 CN 93106095 A CN93106095 A CN 93106095A CN 1079952 A CN1079952 A CN 1079952A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- technology
- hydroxide
- reaction
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of technology of producing cresols is disclosed, comprise the following steps: (a) thus with oxygen or oxygen-containing gas flower hydrocarbon being carried out oxidation obtains containing the uncle of flower hydrocarbon and the oxidation product solution of Bai hydroperoxide; (b) make resulting oxidation product solution and organic quaternary ammonium salt and alkali reaction in the step (a), or with the organic quaternization of hydroxide, thereby reduce the content of uncle's hydroperoxide; (c) reaction mixture in the step (b) is decomposed in the presence of catalyzer; (d) make the decomposition of the mixture in the step (c) carry out hydrogenation, thereby obtain cresols.
Description
The present invention relates to produce the technology of cresols.
As the production technique of cresols, a kind of technology that is widely known by the people is to come the oxidation Cymene with oxygen, and the tertiary hydrogen peroxide breakdown of Cymene becomes required cresols and acetone then.
But in this technology, a kind of uncle's hydroperoxide that have the Cymene of oxidation methyl can form with above-mentioned tertiary hydrogen superoxide as a kind of by product when oxidation.These uncle's hydroperoxide can be transformed into isopropyl-phenol and formaldehyde by its decomposition.This formaldehyde can form a kind of resin with the cresols condensation that is generated, thereby makes that the productive rate of cresols reduces in this technology.
In order to address this problem, someone proposes a kind of technology, the decomposition of uncle's hydroperoxide is stopped halfway to suppress the formation of formaldehyde, thereby the productive rate of avoiding causing owing to this by product reduces, making remaining uncle's hydroperoxide hydrogenation become alkylbenzene then (for example can be referring to JP-A 52-57130, JP-B 59-8246, JP-B1-49248).
Yet, in this technology still some uncle hydroperoxide decomposition.Therefore, side reaction to a certain degree will inevitably take place, so this technology always has the loss of cresols productive rate between by product formaldehyde and primary product cresols.
In order to prevent the generation of formaldehyde, someone has proposed a kind of technology, wherein makes the reaction of the mixture of resulting uncle of oxidation and Bai hydroperoxide and a kind of alkali and a kind of organic quaternary ammonium salt so that only make uncle's hydroperoxide decomposition (referring to for example JP-A 63-35558).This technology is included in the production of cresols and does not generate the formaldehyde by product, so can avoid the reduction of the cresols productive rate that the generation owing to formaldehyde causes; But, in this technology, do not effectively utilize uncle's hydroperoxide, therefore can not think that from the angle that improves the cresols productive rate this technology is gratifying.
In this case, the present inventor has furtherd investigate the production technique of cresols.The result, they have found a kind of novel process that comprises the following step: the solution that makes the oxidation products that contains Cymene uncle and Bai hydroperoxide that obtains through oxygen or oxygen-containing gas oxidation by Cymene before decomposing with a kind of organic quaternary ammonium salt and a kind of alkali reaction, or with a kind of organic quaternary ammonium hydroxide reaction, thereby make uncle's hydroperoxide decomposition, and make the tertiary hydrogen superoxide keep not decomposing simultaneously, thereby only reduce the content of uncle's hydroperoxide; This reaction mixture is decomposed, thereby obtain cresols by the tertiary hydrogen superoxide; Make this decomposition of the mixture carry out hydrogenation.
This technology can prevent aforesaid any when commonly using in the technology common observed uncle hydroperoxide decomposition because the reduction of the cresols productive rate that generation formaldehyde causes, also can optionally reclaim with form, thereby improve the productive rate of cresols uncle's degradation production of hydroperoxide and other by product as the Cymene of raw material.
That is to say, the invention provides a kind of technology of producing cresols, comprise the following steps: (a) with oxygen or oxygen-containing gas oxidation Cymene, thereby obtain containing the uncle of Cymene and the oxidation product solution of Bai hydroperoxide; (b) make resulting oxidation product solution and a kind of organic quaternary ammonium salt and alkali reaction in the step (a), or react with a kind of organic quaternary ammonium hydroxide thing, thus the content of minimizing uncle hydroperoxide; (c) reaction mixture in the step (b) is decomposed in the presence of catalyzer; (d) make the decomposition of the mixture in the step (c) carry out hydrogenation, thereby obtain needed cresols.
To narrate below with oxygen or oxygen-containing gas p-cymene and carry out the step of oxidation with the oxidation product solution that obtains containing Cymene uncle and Bai hydroperoxide.
Employed raw material Cymene can be various forms in this step, for example ortho position Cymene, a position Cymene and contraposition Cymene.The compound of these forms can use separately or also can use by any ratio intermingling.
This step can adopt general liquid-phase oxidation to realize, realizes by Cymene and oxygen or oxygen-containing gas such as air are contacted usually.
Oxidation is usually at normal pressure or add to depress and carry out.The pressure of oxygen or oxygen-containing gas is usually in the 0-20 kg/cm
2(gauge pressure) scope.
In this step, can allow alkali to be present in the reactive system jointly.The example of alkali has alkali-metal carbonate, as yellow soda ash and salt of wormwood; The oxyhydroxide of alkaline-earth metal is as magnesium hydroxide and calcium hydroxide; The carbonate of alkaline-earth metal is as lime carbonate; Amine is as pyridine, piperidines and triethylamine; And ammonia.As if possible, these alkali can use with the solution form.
Initiator can be added in the reactive system in this step.The example of initiator has azo-compound, as 2,2 '-Diisopropyl azodicarboxylate, and superoxide, as the hydroperoxide of benzoyl peroxide and Cymene.The amount ranges of initiator is generally the 0.01-5% of Cymene weight.
Temperature of reaction is generally 30-200 ℃, better is 80-150 ℃.
The ratio of uncle hydroperoxide and the tertiary hydrogen superoxide that is generated is usually scope (primary/uncle of 5-30/95-70; The two summation is 100).
After finishing, reaction obtains a kind of oxidation product solution.If necessary, this solution can be carried out again common aftertreatment as separating with separating funnel or filtering.This oxidation product solution can be used for next procedure without special aftertreatment; But, under the situation without alkali in this step, the aqueous solution of the oxidation product solution that is generated available alkaline matter such as alkali-metal oxyhydroxide, alkali-metal carbonate, the oxyhydroxide of alkaline-earth metal or carbonate of alkaline-earth metal etc. before being used for next step washs.
Below narration is made solution and the organic quaternary ammonium salt and the alkali of resulting oxidation products in the top step, or react with organic quaternary ammonium hydroxide, thus the step of minimizing uncle hydroperoxide content.
The example that can be used for the organic quaternary ammonium salt of this reaction is the compound of following general formula:
R in the formula
1And R
2Can be C independently
1-C
24Alkyl or aralkyl, both all can be by the optional replacement of at least one substituting group; R
3And R
4Can be C independently
1-C
10Alkyl; X is the negatively charged ion residue; Compound with following general formula:
R in the formula
5Be the optional C that replaces
1-C
24Alkyl; R
6Be hydrogen atom or C
1-C
2Alkyl; The definition of X is the same.
In described in the above two kinds of compounds, the example of negatively charged ion residue is a halogen atom, as chlorine, bromine and iodine; And sour residue, as H
2PO
4, CH
3COO, CH
3OSO
3, C
2H
5OSO
3, ClO
4And HSO
4
As the aralkyl of the optional replacement in the compound [1], its example has phenmethyl, 1-styroyl and 2-styroyl, and all these groups can be substituted by any way.
The representative instance of compound [1] and [2] has: tetramethylammonium chloride, tetraethylammonium chloride, chlorination four positive third ammoniums, chlorination four positive fourth ammoniums, the zephiran chloride trimethyl ammonium, benzyltriethylammonium chloride, chlorination stearyl trimethyl ammonium, trimethyl octadecyl ammonium chloride, Trimethyllaurylammonium chloride, chlorination trimethylammonium cetyltrimethyl ammonium, Varisoft TA 100, chlorination two hexadecyl Dimethyl Ammonium, chlorination three decyl ammonium methyls, the chlorination neighbour, between, to the methoxy-benzyl triethyl ammonium, the chlorination neighbour, between, to the phenoxy benzyl triethyl ammonium, trimethyl lauryl ammonium chloride, chlorination trimethylammonium decyl ammonium, tricaprylylmethylammchloride chloride, chlorination N-butyl-pyridinium, chlorination N-lauryl pyridine, chlorination N-lauroyl picoline, chlorination triethyl propyl ammonium, chlorination diethyl propyl group hexadecyldimethyl benzyl ammonium, the chlorination neighbour, between, the p-chlorobenzyl triethyl ammonium, methyl chloride ethyl propyl hexadecyldimethyl benzyl ammonium, chlorination diethyl butyl benzyl ammonium, methyl chloride diethyl hexadecyldimethyl benzyl ammonium, chlorination dimethyl ethyl hexadecyldimethyl benzyl ammonium, chlorination tripropyl hexadecyldimethyl benzyl ammonium, tonsilon dipropyl hexadecyldimethyl benzyl ammonium, chlorination diethyl dibenzyl ammonium, chlorination dimethyl lauryl hexadecyldimethyl benzyl ammonium, chlorination dimethyl stearyl hexadecyldimethyl benzyl ammonium, chlorination dimethyl octyl group hexadecyldimethyl benzyl ammonium, chlorination dimethyl nutmeg base hexadecyldimethyl benzyl ammonium, and corresponding to these muriatic bromides, iodide, perchlorate, dihydrogen phosphate, hydrosulfate, methyl-sulfate and ethyl sulfate.These compounds can use separately, or intermingling uses.The consumption of these compounds calculates usually at the 0.001-1 mole by every mole of uncle's hydroperoxide, more fortunately the scope of 0.001-0.5 mole.
The example of the alkali that can use together with organic quaternary ammonium salt is the oxyhydroxide of alkali-metal oxyhydroxide and alkaline-earth metal, for example sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, hydrated barta, magnesium hydroxide and strontium hydroxide.The consumption of alkali calculates usually at the 0.1-20 mole by every mole of uncle's hydroperoxide, more fortunately the scope of 0.5-10 mole.
In above-mentioned reaction, use under the situation of the organic quaternary ammonium of hydroxide, can use the compound of following general formula:
R in the formula
7And R
8Be C independently
1-C
24Alkyl or aralkyl, the both can be by the optional replacement of at least one substituting group; R
9And R
10Be C independently
1-C
10Alkyl; Or the compound of following general formula:
R in the formula
11Be the optional C that replaces
1-C
24Alkyl; R
12Be hydrogen atom or C
1-C
2Alkyl.
As the optional aralkyl that replaces in the compound [3], its example has phenmethyl, 1-styroyl and 2-styroyl, and all these groups can be substituted by any way.
The representative instance of compound [3] and [4] has: tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxide four positive third ammoniums, hydroxide four positive fourth ammoniums, the hydroxide benzyltrimethylammon.um, hydroxide benzyl triethyl ammonium ammonium, hydroxide stearyl trimethyl ammonium, hydroxide trimethylammonium octadecyl ammonium, hydroxide lauryl trimethyl ammonium, hydroxide trimethylammonium cetyltrimethyl ammonium, hydroxide distearyl Dimethyl Ammonium, hydroxide two hexadecyl Dimethyl Ammonium, hydroxide three decyl ammonium methyls, hydroxide neighbour, between, to the methoxy-benzyl triethyl ammonium, hydroxide neighbour, between, to the phenoxy benzyl triethyl ammonium, hydroxide trimethyldodecane base ammonium, hydroxide trimethylammonium decyl ammonium, the hydroxide tricaprylmethylammonium, hydroxide N-butyl-pyridinium, hydroxide N-lauryl pyridine, hydroxide N-lauroyl picoline, hydroxide triethyl propyl ammonium, hydroxide diethyl propyl group hexadecyldimethyl benzyl ammonium, hydroxide neighbour, between, the p-chlorobenzyl triethyl ammonium, hydroxide methylethyl propyl group hexadecyldimethyl benzyl ammonium, hydroxide diethyl butyl benzyl ammonium, hydroxide methyl diethyl hexadecyldimethyl benzyl ammonium, hydroxide dimethyl ethyl hexadecyldimethyl benzyl ammonium, hydroxide tripropyl hexadecyldimethyl benzyl ammonium, hydroxide ethyl dipropyl hexadecyldimethyl benzyl ammonium, hydroxide diethyl dibenzyl ammonium, hydroxide dimethyl lauryl hexadecyldimethyl benzyl ammonium, hydroxide dimethyl stearyl hexadecyldimethyl benzyl ammonium, hydroxide dimethyl octyl group hexadecyldimethyl benzyl ammonium, hydroxide dimethyl nutmeg base hexadecyldimethyl benzyl ammonium.These oxyhydroxide can use separately or intermingling uses.The consumption of these oxyhydroxide calculates common scope at the 0.001-5 mole by every mole of uncle's hydroperoxide.
Under the situation of using the organic quaternary ammonium of hydroxide, better be to be used in combination with alkali simultaneously, because do the consumption that can reduce the organic quaternary ammonium of hydroxide like this.In this case, the consumption of the organic quaternary ammonium of hydroxide calculates common scope at the 0.001-1 mole by every mole of uncle's hydroperoxide, better is the 0.001-0.5 mole.The consumption of the organic quaternary ammonium of hydroxide calculates usually in the scope of 0.1-5 mole by every mole of uncle's hydroperoxide under without the situation of alkali, better is the 0.3-3 mole.
The example of the alkali that can use with the organic quaternary ammonium of hydroxide has alkali metal hydroxide and alkaline earth metal hydroxides, for example sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, hydrated barta, magnesium hydroxide and strontium hydroxide.The consumption of alkali calculates common scope at the 0.1-20 mole by every mole of uncle's hydroperoxide, better is the 0.5-10 mole.
In this step, reaction is usually at polar solvent, as carrying out under water, methyl alcohol or the ethanol existence.Better make water.
Temperature of reaction better is 70-110 ℃ usually 30-150 ℃ scope.
Adopt this selectivity decomposition method, can optionally decompose uncle's hydroperoxide,, help obtaining required cresols so in decomposition step subsequently, can not generate the formaldehyde by product.Therefore, owing to the possibility that the side reaction between cresols that is generated and the formaldehyde reduces the cresols productive rate, be non-existent in this technology.In addition, the tertiary hydrogen peroxide breakdown becomes cresols afterwards by making the further hydrogenation of reaction mixture, can make degradation production and other by product of uncle's hydroperoxide change into the raw material Cymene that can recycle, feasible Cymene gained cresols gain in yield from being consumed.
Although this decomposition reaction is optionally, yet the tertiary hydrogen superoxide also can be reacted with uncle's hydroperoxide.But the speed of reaction of tertiary hydrogen superoxide is more much lower than uncle's hydroperoxide, and the decomposition productive rate of tertiary hydrogen superoxide carries out hydrogenation after can resolving into cresols by it, is reclaimed with the form of Cymene; Therefore, be higher than from the ultimate yield of the Cymene gained cresols that consumed and adopt the getable productive rate of any traditional technology.But from the economic point of view, the tertiary hydrogen peroxide breakdown is disadvantageous to being higher than desired degree.From an economic point of view, promptly from this technology through one-pass cresols productive rate and energy efficiency, usually, advantageously decompose in such a way, promptly the weight ratio of uncle's hydroperoxide and tertiary hydrogen superoxide reduces to usually and is not more than 1/25(W/W), better be not more than 1/50(W/W), better be not more than 1/100(W/W), this just can reduce the by product that generation can cause productive rate to reduce in step subsequently, and should be controlled at 20% or littler as the transformation efficiency of the tertiary hydrogen superoxide of cresols precursor, better be 10% or littler, be more preferably 5% or littler.
Be adjusted to above-mentioned numerical value by consumption and temperature of reaction, just can reach these decomposition result concentration, organic quaternary ammonium salt or its oxyhydroxide of alkali.
In this step, reaction mixture can be carried out such as liquid-phase chromatographic analysis checking the weight ratio of uncle's hydroperoxide and tertiary hydrogen superoxide, this is also feasible may determine the terminal point that reacts.
After reaction finishes, for example can make reaction mixture sat and separate with separating funnel, then washing, and then be used for subsequently step.
Below narration is made that resulting reaction mixture carries out step of decomposition in the abovementioned steps in the presence of catalyzer.
The example that can be used for the catalyzer in this step is an acidic catalyst, sulphur and Burmah catalyzer.The specific examples of an acidic catalyst has mineral acid; For example sulfuric acid, hydrochloric acid, perchloric acid, SO
2And SO
3; Organic acid, for example Phenylsulfonic acid, tosic acid, cresol sulfonic acid and Mono Chloro Acetic Acid; Solid acid, for example silica-alumina, aluminum oxide and acidic ion exchange resin; Heteropolyacid, for example tungstosilicic acid, tungstophosphoric acid and phospho-molybdic acid.The Burmah catalyzer is meant a kind of catalyzer of following general formula:
M is Ni, Pd or Fe(II in the formula); Ph is a phenyl, and it randomly can be replaced by at least one substituting group; N is an integer in 1,2 or 3; Z is the formal charge of this title complex, is selected from 0 ,-1 and-2.The example of Burmah catalyzer has two (dithio benzil) nickel, two (dithio benzil) palladium and two (dithio benzil) iron (II).Catalyzer is sulfuric acid and cresol sulfonic acid preferably.Although catalyst consumption can be decided according to its kind, be generally about 0.0001-1% scope of reaction mixture weight to be processed.
Temperature of reaction is usually 30-150 ℃ scope.
In this step, the mixture after handling like this can carry out such as liquid-phase chromatographic analysis to check the degree of decomposition of hydroperoxide.
After reaction finished, reaction mixture need not to carry out special aftertreatment, perhaps if necessary, can use in step subsequently after through the aftertreatment such as filtering and neutralizing.Perhaps, in step subsequently, use after the acetone that this reaction mixture also can generate removing.
Below narration is made resulting decomposition mixture in the abovementioned steps carry out the step of hydrogenation.
This step can adopt general shortening to realize, usually by at normal pressure or add to depress in the presence of catalyzer and introduce hydrogen and realize.The pressure of hydrogen is usually in the 0-100 kg/cm
2(gauge pressure) scope.
The example of spendable catalyzer is that those are by metal, as the material of Pd, Cr, Cu, Pt, Ni, Ru, Rh or Re composition in this step.These catalyzer also can use with the form that is stated from the carrier, and carrier for example has gac, titanium dioxide, zirconium dioxide, silicon oxide-magnesium oxide, aluminum oxide, aluminum oxide-magnesium oxide or acidic ion exchange resin.Better those that form by Pd or Cu-Cr.Be more preferably Pd/C, Pd/ aluminum oxide, Pd/TiO
2, Cu-Cr/C, Cu-Cr/TiO
2With the Pd/ acidic ion exchange resin.Catalyst consumption is generally the 0.001-20% of decomposition of the mixture weight to be processed.
In this step, if necessary, can allow any other catalyzer to be present in the reactive system jointly.The catalyzer that uses in the example of such catalyzer and the decomposition step is identical.Decomposition of the mixture need not to remove catalyzer used in this decomposition step and just can use same as before.
Temperature of reaction is usually 0-250 ℃ of scope, more fortunately 20-250 ℃ of scope.
After reaction finishes, remove catalyzer, provide cresols, Cymene and acetone, if necessary, can distill then by neutralization and separate and purifying with filtration method.
The by product that is generated by the decomposition of uncle's hydroperoxide selectivity in abovementioned steps can change into the flower hydrocarbon that looses and reclaim with unreacted Cymene part then, and both all recycle as raw material in technology of the present invention.
The technology of the present invention and any traditional technology that comprise abovementioned steps are all very inequality, its difference is to avoid the reduction of the cresols productive rate that the reaction owing to cresols and by product formaldehyde causes, and the by product that the Cymene oxidation is generated can be reclaimed effectively with the form of Cymene, thereby with the resulting productivity ratio of any traditional technology, the cresols productive rate that obtains from the Cymene that is consumed all increases.
Technology of the present invention both can also can realize with continuous processing with the interruption method.
Can obtain cresols with high yield according to technology of the present invention, its method is to carry out oxidation with oxygen or oxygen-containing gas p-cymene, then with organic quaternary ammonium salt and alkali, or handle with the organic quaternary ammonium of hydroxide, thereby reduce the content of uncle's hydroperoxide, and this reaction mixture is decomposed, and hydrogenation then, thus prevented to cause side reaction that any productive rate reduces and the by product that reclaims the Cymene form effectively.Technology of the present invention has an additional advantage, and promptly the cresols that is generated can be easily and separation of by-products.
The present invention will further specify by following example, but these examples are not to be used for limiting the scope of the invention.
Use following abbreviation noun in each example, the various structures of corresponding compound are as follows:
Example 1
I. in a reaction vessel that agitator, gas blow pipe, thermometer and condenser be housed, put into raw material Cymene (5045 weight parts; Form: Cymene, 98.3%; 3HPO, 1.10%; 1HPO, 0.032%; CAL, 0.122%; CUL, 0.007%; CUA, 0.0540%; CLF, 0.007%), wherein contain Cymene hydroperoxide (1.13%) as reaction initiator.Reaction obtain after finishing 5116 weight part oxidation products solvents (form: the Umbrella flower with, 86.2%; 3HPO, 9.28%; 1HPO, 1.68%; CAL, 0.620%; CUL, 0.073%; CUA, 0.125%; CLF, 0.006%).
II. resulting oxidation product solution (500 weight part) in this example I part is put into a reaction vessel, to wherein adding benzyltriethylammonium chloride (0.507 weight part) and 8% aqueous sodium hydroxide solution (49.5 weight part), this mixture stirred 2.5 hours at 80 ℃.This mixture is left standstill, and remove the organic phase that wherein water obtains 498 weight parts with separating funnel and (form: Cymene, 86.3%; 3HPO, 9.22%; 1HPO, 0.005%; CAL, 0.953%; CUL, 0.114%; CUA, 1.69%; CLF, 0.001%).The weight ratio of 1HP O and 3HPO is 1/1844 in the organic phase, transformation efficiency: 1HPO is 99.7%, and 3HPO is 0.972%.
In a reaction vessel that the organic phase (488 weight part) that generated of a part is housed, add entry (50.0 weight part), stir this mixtures washing 1 hour at 80 ℃.This mixture is left standstill, and remove wherein water with separating funnel, the organic phase that obtains after the washing of 487 weight parts (is formed: Cymene, 86.4%; 3HPO, 9.36%; 1HPO, 0.007%; CAL, 0.964%; CUL, 0.130%; CUA, 1.67%; CLF, 0.001%).
With the resulting washing organic phase of a part (477 weight part) decompression (10-20 mmhg) condensations down under 70 ℃, reclaim Cymene (the Cymene content of 391 weight parts as overhead product, 98.7%), and obtain 83.9 weight parts and (form: the flower hydrocarbon that looses, 30.5% as the cohesion oil of bottoms; 3HPO, 51.9%; 1HPO, 0.710%; CAL, 5.46%; CUL, 0.620%; CUA, 9.17%; CLF does not find).
III. resulting enriched oil (20.0 weight part) in this example II part is joined in the mixture of sulfuric acid (0.00803 weight part) under stirring and acetone (2.01 weight part) that refluxes.After interpolation finishes, this mixture was kept 15 minutes at 65 ℃, provided 21.7 weight part decomposition of the mixture and (form: Cymene, 28.4%; 3HPO does not find; 1HPO does not find; CAL, 0.417%; CUL, 1.57%; CUA, 7.31%; CLF, 30.0%; DMST, 3.00%; Other, 29.3%).The transformation efficiency of 3HPO is 100%, and the productive rate of CLF was 96.6%(before acid is decomposed from 3HPO).Overall yield from oxidation step to this step cresols is 58.8%.
IV. in an autoclave of making by stainless steel, put into decomposition of the mixture (15.0 weight part), 5% palladium-titanium deoxide catalyst (0.300 weight part) and acidic ion exchange resin (Rohm that this example III part obtains; Haas company; Commodity are called Amberlyst 15; 0.294 weight part).With the hydrogen gauge pressure is 5 kg/cm
2Hydrogen introduce and wherein to carry out hydrogenation reaction, carried out 2 hours at 40 ℃ earlier, carried out 1 hour at 75 ℃ then.After reaction finishes, remove by filter catalyzer, and adding aqueous sodium hydroxide solution neutralization reaction mixture equals till 7 up to the pH of water layer value.Make reaction mixture sat, and remove wherein water, provide 15.0 weight part reaction mixtures and (form: Cymene, 42.8% with separating funnel; 3HPO does not find; 1HPO does not find; ; CAL, 0.0730%; CUL, 0.161%; CUA does not find; CLF, 30.7%; DMST, 0.363%; Other, 25.9%).The cresols overall yield is that 78.2%(calculates from the Cymene that is consumed).
The transformation efficiency of by product in this reduction step (CAL+DMST+CUA+CUL) is 95.0%, the productive rate of Cymene is that 126.1%(calculates from the by product (CAL+DMST+CUA+CUL) before the hydrogenation), the cresols rate of recovery is the amount of 102.3%(for cresols before the hydrogenation).
Example 2-5
Press the same quadrat method described in the example 1 II part, with resulting oxidation mixture (being hydroperoxide mixture) in organic quaternary ammonium salt or its hydroxide treatment example 1 I part, but its condition is as shown in table 1.The results are shown in Table 1.
Resulting reaction mixture washes with water and is concentrated in the step in front, and then, each step is subsequently undertaken by the same quadrat method described in example 1 the III-IV part, obtains required cresols and Cymene with high yield thus.
Example 6-15
By the same quadrat method described in the example 1 IV part resulting decomposition mixture in example 1 the I-III part is carried out hydrogenation reaction, but its parts are as shown in table 2.The results are shown in table 2.
1-5 explains as follows in the table 2:
* 1: the total conversion rate of by product in the hydrogenation (CAL, DMST, CUA and CUL).
[A]＝CAL+DMST+CUA+CUL
[A]
Transform=(before the hydrogenation behind the amount-hydrogenation of [A] amount of [A])/(amount of [A] before the hydrogenation) * 100
* 2: the productive rate of CYM in the hydrogenation.
CYM
Productive rate=(mole number of CYM behind mole number-hydrogenation of the preceding CYM of hydrogenation)/(mole number of [A] before the hydrogenation) * 100
* 3: the rate of recovery of CLF in the hydrogenation.
CLF
Reclaim=(amount of CLF behind the hydrogenation)/(amount of CLF before the hydrogenation) * 100
* 4: decomposition of the mixture neutralizes before the hydrogenation.
* 5: acidic ion exchange resin.
In addition, the Wt%=weight % in the table 2.
Claims (18)
1, a kind of technology of producing cresols comprises the following steps:
(a) thus carrying out oxidation with oxygen or oxygen-containing gas p-cymene obtains containing the uncle of Cymene and the oxidation product solution of Bai hydroperoxide;
(b) make resulting oxidation product solution and organic quaternary ammonium salt and alkali reaction in the step (a), or with the organic quaternization of hydroxide, thereby reduce the content of uncle's hydroperoxide;
(c) reaction mixture in the step (b) is decomposed in the presence of catalyzer; With
(d) make the decomposition of the mixture in the step (c) carry out hydrogenation, thereby obtain cresols.
2, according to the technology of claim 1, wherein the reaction in the step (b) is carried out by this way, and the weight ratio of feasible uncle's hydroperoxide that are left and tertiary hydrogen superoxide reduces to and is not more than 1/25(W/W).
3, according to the technology of claim 2, the transformation efficiency of tertiary hydrogen superoxide is 20% or littler in the step (b).
4, according to the technology of claim 1, wherein the reaction in the step (b) is carried out with organic quaternary ammonium salt and alkali.
5, according to the technology of claim 2, wherein the reaction in the step (b) is carried out with organic quaternary ammonium salt and alkali.
6, according to the technology of claim 3, wherein the reaction in the step (b) is carried out with organic quaternary ammonium salt and alkali.
7, according to the technology of claim 1, wherein the reaction in the step (b) is carried out with organic quaternary ammonium of hydroxide and alkali.
8, according to the technology of claim 2, wherein the reaction in the step (b) is carried out with organic quaternary ammonium of hydroxide and alkali.
9, according to the technology of claim 3, wherein the reaction in the step (b) is carried out with organic quaternary ammonium of hydroxide and alkali.
10, according to the technology of claim 1, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
11, according to the technology of claim 2, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
12, according to the technology of claim 3, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
13, according to the technology of claim 4, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
14, according to the technology of claim 5, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
15, according to the technology of claim 6, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
16, according to the technology of claim 7, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
17, according to the technology of claim 8, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
18, according to the technology of claim 9, wherein the hydrogenation in the step (d) carries out with Pd catalyzer or Cu-Cr catalyzer.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP134861/92 | 1992-05-27 | ||
| JP13486192 | 1992-05-27 | ||
| JP17422292 | 1992-07-01 | ||
| JP174222/92 | 1992-07-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1079952A true CN1079952A (en) | 1993-12-29 |
| CN1043881C CN1043881C (en) | 1999-06-30 |
Family
ID=26468841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93106095 Expired - Fee Related CN1043881C (en) | 1992-05-27 | 1993-05-24 | Process for production of cresols |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1043881C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114105845A (en) * | 2021-11-16 | 2022-03-01 | 浙江新和成股份有限公司 | Selective decomposition method of cymene oxidation product and application thereof |
-
1993
- 1993-05-24 CN CN 93106095 patent/CN1043881C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114105845A (en) * | 2021-11-16 | 2022-03-01 | 浙江新和成股份有限公司 | Selective decomposition method of cymene oxidation product and application thereof |
| CN114105845B (en) * | 2021-11-16 | 2023-09-01 | 浙江新和成股份有限公司 | Selective decomposition method of cymene oxidation product and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1043881C (en) | 1999-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1280280C (en) | Process for continuous production of olefinic oxide | |
| JP6935399B2 (en) | Method for producing isopropyl alcohol | |
| CN1139916A (en) | Process for the preparation of alkylene glycols | |
| CN1206394A (en) | Process for producing 1,1,1,3,3-pentafluoropropane | |
| CN1816540A (en) | Process for the preparation of propylene carbonate | |
| KR101619399B1 (en) | Preparation method of 1,4-cyclohexanedimethanol | |
| EP2374789A1 (en) | Method for producing beta-alkoxypropionamide | |
| CN1408743A (en) | Process for preparing epoxy resin | |
| CN105330832B (en) | A kind of synthetic method of epoxy radicals end-blocking butanol polyoxyethylene poly-oxygen propylene aether | |
| CN1397536A (en) | Process for prodn. of alpha-olefine | |
| EP3173403B1 (en) | Method for preparing n,n'-bis(2-cyanoethyl)-1,2-ethylenediamine by using cation exchange resin as catalyst | |
| CN1756786A (en) | Process for production of a carboxylic acid/diol mixture suitable for use in polyester production | |
| CN1290809C (en) | Method of high yield cyclohexyl hydroperoxide decomposition | |
| JP4918336B2 (en) | Method for producing alkylene oxide adduct | |
| CN1894180A (en) | Ecology-friendly bromo-benzene synthesizing method | |
| CN112321434A (en) | Preparation method of salicylate green synthesis process | |
| CN1043881C (en) | Process for production of cresols | |
| CN112457175B (en) | Method for preparing 1, 3-dibenzyloxy-2-acetone | |
| US9518035B2 (en) | Method for preparing glycidol using glycerol and glycidol obtained thereby | |
| JP2010143890A (en) | Method for producing epoxy compound | |
| CN1566064A (en) | Process for preparing azelaic acid by oleic acid phase transfer catalytic oxidation | |
| CN1277960A (en) | Method for preparing retinene, and intermediates for prepn. of retinene | |
| CN1040316C (en) | Process for production of cresols | |
| CN1787985A (en) | Process of removing organic halogen-containing compounds | |
| CN1129699A (en) | Process for producing L-ascorbic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |