CN104058936B - A kind of method of separating-purifying paracresol - Google Patents
A kind of method of separating-purifying paracresol Download PDFInfo
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- CN104058936B CN104058936B CN201410280902.5A CN201410280902A CN104058936B CN 104058936 B CN104058936 B CN 104058936B CN 201410280902 A CN201410280902 A CN 201410280902A CN 104058936 B CN104058936 B CN 104058936B
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- paracresol
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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Abstract
A kind of method that the invention discloses separating-purifying paracresol, comprises the following steps: 1) complexation: in reactor, add toluene and chelating agent oxalic acid, heat up and add cresols, insulation reaction, filters, obtains paracresol oxalate complex crude product；2) purification: paracresol oxalate complex crude product is added in purification solvent, filter after stirring, obtain paracresol oxalate complex；3) solving complexation: be added to the water by paracresol oxalate complex, insulation reaction, isolate upper organic phase while hot, lower floor's aqueous phase toluene extracts, and extract is incorporated to upper organic phase；4) distillation: solvent is removed in upper organic phase distillation, obtains paracresol.Compared with the prior art, purification step is added, it is ensured that be finally recovered paracresol purity >=99% obtained.Decrease the consumption of organic solvent, solve complexation approach and use water, and the organic solvent related in separating technology and water can be applied mechanically, and saved cost.
Description
Technical field
The present invention relates to a kind of method separating industry paracresol and metacresol mixture, be specifically related to one
Kind with industry paracresol and metacresol mixture as raw material, it is right to obtain by selecting Separation by Complexation method to purify
The method of cresol.
Background technology
Phenol and methanol carry out the methylation reaction of phenol under solid catalyst effect, and product is mixing first
Phenol, mainly contains orthoresol, paracresol and metacresol, and the xylenol of trace.Sending out of chemical industry
The purity of paracresol is had higher requirement by the exploitation of exhibition and new product.Can be isolated by rectification
Orthoresol, residual mother liquor includes paracresol, metacresol and a small amount of xylenol.Between Yin/paracresol normal
Pressure boiling point difference, less than 1.0 DEG C, is difficult to separate in the way of rectification.Between Mu Qian/the separation side of paracresol
Method includes physical method and the big class of chemical method two.Physical method has azeotropic distillation method, high pressure crystal partition method
And molecular sieve absorption process；Chemical method has the derivative separation such as class chelate partition method, alkylation.Wherein,
Molecular sieve absorption process selects and preparation difficulty due to molecular sieve, and adsorbance is limited, employing the most relatively
Few；Azeotropic distillation method is in the presence of paracresol sodium, and paracresol can azeotrope with water steam, and energy consumption is the biggest；
High pressure crystal partition method needs the pressure of 100～300MPa, the highest to equipment requirements, and investment is too many；Alkyl
Changing partition method and need alkylation and de-alkyl, high vacuum rectification etc., equipment is complex, and investment is relatively big, becomes
This is higher；Class chelate partition method is simple to operate, and raw material is easy to get, and various raw material reusable edible.
CN 1127241A reports, using piperazine or anthalazine as extractant, n-butyl ether, diisopropyl ether or
Isoamyl oxide makees solvent, separating-purifying paracresol from cresols.But, this technique needs to return from water
Receive piperazine and bring the biggest energy consumption, and use the ether solvent of costliness, be difficulty with industrialization.US
Report in 4394526 by inorganic salt (CaBr2、LiBr、MgBr2And MgCl2) selectivity with mix
Paracresol in cresol generates complex and realizes separation and Extraction paracresol from cresols, but, whole
Using substantial amounts of low boiling point organic solvent in individual separating technology, this technique does not possess the preferable market competition
Power.CN 103333052 reports, uses oxalic acid from cresols (metacresol 58.5wt%, paracresol
27.8wt%, 2,4-xylenol 5.7wt%, 2,5-xylenol 4.2wt%, and part orthoresol, benzene
Phenol, ethyl phenol) isolate paracresol.But the method there are disadvantages that:
1) in cresols, paracresol content is less, only 27.8wt%, and Oxalic Acid Method uses limited, it is impossible to
Give play to optimal effect；
2) course of reaction uses volatile low boiling point solvent, such as hexamethylene, petroleum ether, thus increase
The loss of solvent, and the proportion that solvent loss accounts for process costs is maximum；
3) paracresol-oxalate complex is not through purification, directly carries out solving complexation, the paracresol obtained
Quality index is extremely difficult to the requirement of relevant criterion；
4) in complexation process is conciliate in complex reaction, use two kinds of different organic solvents, between solvent, be difficult to reality
Now efficiently separate, thus add the complexity of practical operation.
Summary of the invention
The technical problem to be solved be to provide a kind of by/mixture of paracresol is through once
Property separate, obtain pure paracresol, and be capable of the separation paracresol circulating Separation by Complexation and mix with metacresol
The method of compound.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of separation paracresol and a first
The method of phenol mixture, the steps include:
1) complexation: add toluene and chelating agent oxalic acid in reactor, be warming up to 60～70 DEG C, adds mixed
Close cresol, insulation reaction 1～3h, filter, obtain filtrate and the paracresol-oxalate complex of white fine particulate
Crystal crude product；
The addition of described toluene is 2.1 ± 0.2 times of cresols quality, and described oxalic acid addition is
In cresols 1.0 ± 0.1 times of paracresol mole；
2) purification: by step 1) in paracresol-oxalate complex crystal crude product join in purification solvent,
Stirring 1 ± 0.5h, filters, obtains paracresol-oxalate complex sterling；
3) complexation is solved: by step 2) paracresol-oxalate complex sterling of gained is added to the water, heats up
To 40～80 DEG C, insulation reaction 1.5 ± 0.5h, (40～80 DEG C) isolate upper organic phase, lower floor while hot
Aqueous phase toluene extracts, and extract is incorporated to upper organic phase；
4) distillation: by step 3) upper organic phase distillation remove solvent, obtain paracresol, the first distilled out
Benzene is applied to step 1) or step 3) in；
5) reclaim chelating agent: by step 3) in lower floor's aqueous phase distill to obtain oxalic acid, be applied to step 1),
Water is back to step 3) in.
Step 1) in, described cresols comprises paracresol, metacresol and 2,6-xylenol, its group
Become: paracresol 10～90wt.%, metacresol 10～90wt.%, 2,6-xylenols 0～5wt.%.
Step 1) in, described chelating agent oxalic acid is anhydrous oxalic acid or two oxalic acid hydrates.
In step 2) in, purification solvent is the mixture of toluene-methanol, and wherein the volume content of methanol is
1%～20%, preferably 2%～10%.
Step 2) in, during filtration, the temperature of purification solvent is 0～24 DEG C, preferably 0～5 DEG C.
Step 2) in, the quality of purification solvent is 1～4 times of paracresol-oxalate complex crude product quality, excellent
Elect 1～2 times as.
Step 3) in, solve in complex reaction 1～5 times that consumption is paracresol-oxalate complex quality of water,
It is preferably 1～3 times.
Step 3) in, the temperature solving complex reaction is preferably 45～55 DEG C.
Technical scheme disclosed in the present application has the advantage that relative to previous separation method, the present invention
Add purification step, provide guarantee for the high-purity of complexation-crystallization method separation product paracresol and arrange
Execute.And the present invention adopts in solving complexation approach and uses water as solvent, greatly reduces process costs.
Circulation Separation by Complexation method is a kind of environmentally friendly green separation method, uses in Separation by Complexation technique
Toluene and the equal recycled of water, omnidistance separating technology does not has the discharge of the three wastes.
It addition, the content of paracresol is 71.3wt% in the cresols of present invention use, example table
Bright, compared to previous separation method, the present invention achieves more preferable separating effect.
Additionally, this method can at utmost be extracted isolates paracresol, so that first between in surplus stock
Phenol is fully enriched with, and weight/mass percentage composition increases to 82.0～84.6% from 28.2%, can be as first between separation and Extraction
The raw material of phenol.
Detailed description of the invention
Embodiment 1
With the self-produced cresols of the Chemical Group that circles in the air as raw material, including paracresol 71.3wt%, a first
Phenol 28.2wt%, 2,6-dimethyl cresol 0.5wt%.First, in glass there-necked flask, toluene and grass are added
Acid (Anhui anhydrous oxalic acid company limited), oxalic acid addition is paracresol mole in raw material cresols
1.0 times, the addition of toluene is 2.1 times of cresols quality, is heated to 70 DEG C, adds cresols,
Add insulation reaction 2h, be cooled to 5 DEG C, crystallize 1h.Solid-liquid separation, solid is paracresol-oxalic acid complexation
Thing crude product, filtrate is the toluene solution of enrichment metacresol.Paracresol-oxalate complex crude product is joined first
In benzene-methanol, wherein the volume content of methanol is 4%, and the consumption of mixed solvent is paracresol-oxalate complex
1 times of crude product quality, 5 DEG C of stirring 1h, solid-liquid separation, solid is paracresol-oxalic acid that purity is more than 99%
Complex sterling.Paracresol-oxalate complex sterling being added to the water, the addition of water is paracresol-grass
2.6 times of acid complex quality, are warming up to 50 DEG C, hydrolyze 1h, isolate upper organic phase, lower floor while hot
Aqueous phase toluene extracts, and extract is incorporated to upper organic phase.Organic facies is evaporated off solvent toluene, obtains pure paracresol,
Recovered solvent toluene is applied in the hydrolysis of next round.Aqueous phase distillation remove water, obtain without pasture and water
Acid is applied to the complex reaction of next round.
Paracresol extraction efficiency, paracresol purity, the composition analysis of cresols the results are shown in Table 1
Embodiment 2
Anhydrous oxalic acid, with embodiment 1, is only replaced with two oxalic acid hydrates, adds two water by experimental provision and operation
The mole closing oxalic acid is constant.
Embodiment 3
Purification step, with embodiment 1, is only changed into: purification solvent is toluene-methanol by experimental provision and operation
Mixture.Wherein the content of methanol is 2%, and purification solvent consumption is paracresol-oxalate complex crude product
1.5 times, filtration temperature is 0 DEG C.
Embodiment 4
Purification step, with embodiment 1, is only changed into: purification solvent is toluene-methanol by experimental provision and operation
Mixture.Wherein the content of methanol is 2%, and purification solvent consumption is the 2 of paracresol-oxalate complex crude product
Times, filtration temperature is 5 DEG C.
Embodiment 5
Purification step, with embodiment 1, is only changed into: purification solvent is toluene-methanol by experimental provision and operation
Mixture.Wherein the content of methanol is 3%, and purification solvent consumption is the 2 of paracresol-oxalate complex crude product
Times, filtration temperature is 3 DEG C.
Embodiment 6
Experimental provision and operation with embodiment 1, only by solve complexation approach change into: the consumption of water be paracresol-
2 times of oxalate complex sterling quality, hydrolysising reacting temperature is 45 DEG C.
Embodiment 7
Experimental provision and operation with embodiment 1, only by solve complexation approach change into: the consumption of water be paracresol-
3 times of oxalate complex sterling quality, hydrolysising reacting temperature is 50 DEG C.
Embodiment 8
Experimental provision and operation are with embodiment 1, only by step 1) mesoxalic acid use recovery oxalic acid.
Embodiment 9
Experimental provision and operation with embodiment 1, only by step 1) in toluene use reclaim toluene.
Embodiment 10
Experimental provision and operation with embodiment 1, only by step 3) in water use recycle-water.
Table 1
| Embodiment | Paracresol extraction efficiency | Paracresol purity | M-and P-cresols ratio in complexation mother solution |
| Embodiment 1 | 92.7% | 99.4% | 82.9%:15.6% |
| Embodiment 2 | 90.5% | 99.5% | 80.1%:16.3% |
| Embodiment 3 | 91.5% | 99.3% | 82.9%:15.6% |
| Embodiment 4 | 87.6% | 99.4% | 82.9%:15.6% |
| Embodiment 5 | 87.5% | 99.5% | 82.9%:15.6% |
| Embodiment 6 | 92.0% | 99.3% | 82.9%:15.6% |
| Embodiment 7 | 93.2% | 99.3% | 82.9%:15.6% |
| Embodiment 8 | 92.5% | 99.3% | 82.5%:15.8% |
| Embodiment 9 | 92.6% | 99.2% | 82.3%:16.2% |
| Embodiment 10 | 92.9% | 99.4% | 82.9%:15.6% |
Present invention achieves following effect:
1. this method adds purification step, and the purity of isolated product paracresol is 99.1～99.5%.
Meet the index request of Japanese Industrial Standards JIS K8306-2013.
2. chelating agent uses cheap oxalic acid or two oxalic acid hydrates, reduces process costs.
3. the chelating agent oxalic acid, the solvent toluene that reclaim in this method all can be recycled, and reduce three waste discharge.
4. the by-product that this method obtains, can be as the raw material of separation and Extraction metacresol rich in metacresol.
Claims (5)
1. a method for separating-purifying paracresol, comprises the following steps:
1) complexation: add toluene and chelating agent oxalic acid in reactor, be warming up to 60 ~ 70 DEG C, adds the cresols of purification to be separated, insulation reaction 1 ~ 3h, filters, obtain filtrate and paracresol-oxalate complex crude product；
The addition of described toluene is 2.1 ± 0.2 times of cresols quality, described oxalic acid addition is paracresol mole in cresols 1.0 ± 0.1 times；
2) purification: the paracresol in step 1)-oxalate complex crude product is added in purification solvent, stir 1 ± 0.5h, filter, obtain paracresol-oxalate complex；
Described purification solvent is the mixture of toluene and methanol, and wherein the volume content of methanol is 1% ~ 20%；
3) solve complexation: by step 2) paracresol-oxalate complex be added to the water, be warming up to 40 ~ 80 DEG C, insulation reaction 1.5 ± 0.5h, under the conditions of 40 ~ 80 DEG C, isolate upper organic phase, lower floor's aqueous phase with toluene extract, extract is incorporated to upper organic phase；
4) distillation: the upper organic phase of step 3) is distilled and removes solvent, obtain paracresol；
Step 1) in, the cresols of described purification to be separated, consisting of: paracresol 10 ~ 90wt.%, metacresol 10 ~ 90wt.%, 2,6-xylenol 0 ~ 5wt.%；
In step 1), described chelating agent oxalic acid is anhydrous oxalic acid or two oxalic acid hydrates；
Being distilled by the lower floor's aqueous phase obtained in step 3), gained oxalic acid is applied to step 1), and gained water is back in step 3)；The toluene obtained in step 4) still-process is applied in step 1) or step 3).
The method of a kind of separating-purifying paracresol the most according to claim 1, it is characterised in that: step 2) in, in described filter process, purification solution temperature is 0 ~ 24 DEG C.
The method of a kind of separating-purifying paracresol the most according to claim 1, it is characterised in that: step 2) in, the quality of described purification solvent is 1 ~ 4 times of paracresol-oxalate complex crude product quality.
The method of a kind of separating-purifying paracresol the most according to claim 1, it is characterised in that: in step 3), described solve in complex reaction 1 ~ 5 times that quality is paracresol-oxalate complex quality of water.
The method of a kind of separating-purifying paracresol the most according to claim 1, it is characterised in that: in step 3), the described temperature solving complex reaction is 50 ± 5 DEG C.
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| CN103333052A (en) * | 2013-07-25 | 2013-10-02 | 北京旭阳化工技术研究院有限公司 | Method for preparing pure p-cresol and pure m-cresol by separating industrial mixed p-cresol and m-cresol |
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| CN103333052A (en) * | 2013-07-25 | 2013-10-02 | 北京旭阳化工技术研究院有限公司 | Method for preparing pure p-cresol and pure m-cresol by separating industrial mixed p-cresol and m-cresol |
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| 对甲酚与间甲酚的分离;邓国才等;《天津化工》;19951231(第4期);第12-15页 * |
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