CN110256207B - Method for extracting cresol and tert-butylated product thereof from coal-based liquid derivative - Google Patents
Method for extracting cresol and tert-butylated product thereof from coal-based liquid derivative Download PDFInfo
- Publication number
- CN110256207B CN110256207B CN201910560862.2A CN201910560862A CN110256207B CN 110256207 B CN110256207 B CN 110256207B CN 201910560862 A CN201910560862 A CN 201910560862A CN 110256207 B CN110256207 B CN 110256207B
- Authority
- CN
- China
- Prior art keywords
- cresol
- tert
- butyl
- mixture
- coal
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for extracting cresol and tert-butylated products thereof from coal-based liquid derivatives, which comprises the steps of taking the coal-based liquid derivatives as raw materials, carrying out alkali washing and rectification to obtain a m-cresol and p-cresol mixture I, adding an acid catalyst and a polar solvent into the mixture I, introducing isobutene to carry out tert-butylated reaction to obtain a mixture II which contains 2, 6-di-tert-butyl-p-cresol, 2-tert-butyl-p-cresol and 6-tert-butyl-m-cresol and does not contain 4, 6-di-tert-butyl-m-cresol; and (3) carrying out vacuum rectification and tert-butyl removal reaction on the mixture II to obtain products 2, 6-di-tert-butyl-p-cresol, p-cresol and m-cresol. The polar solvent is dichloromethane, n-hexane, cyclohexane, toluene, benzene or tetrahydrofuran. The invention adjusts the polarity of the reaction system by adding the polar solvent, changes the intermolecular force among reactants, effectively regulates and controls the distribution of the product, obtains the high-purity cresol product, and reduces the energy consumption by 14.54 percent compared with the prior art.
Description
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to a method for extracting cresol and tert-butyl products thereof from coal-based liquid derivatives.
Background
The phenol compounds generated in the coal chemical industry process are complex in composition, and isomers in the phenol compounds cannot be separated by a traditional method due to small boiling point difference, so that the mixed phenol is limited in use and low in added value.
Because the factors influencing the cresol and isobutylene tert-butylation process in the tert-butylation reaction process and the products generated by the tert-butylation reaction are various, and the generation processes of mono-tert-butyl substitution products and di-tert-butyl substitution products of m-cresol and p-cresol have a mutual competition relationship, the reaction process is complicated, and the cresol tert-butylation process is very difficult to regulate and control. At present, in the alkylation process of m-cresol and p-cresol, most of the di-tert-butyl substitution products of m-cresol and p-cresol are prepared by using acid catalysts. Wherein, 2, 6-di-tert-butyl-p-cresol is directly output as a product, and a di-tert-butyl substitution product 4, 6-di-tert-butyl-m-cresol of m-cresol needs to be subjected to tert-butyl removal treatment to obtain an m-cresol monomer. In the process, the 4, 6-di-tert-butyl-m-cresol can be obtained only through two-step tert-butyl removal reaction, and the process has high energy consumption and is not energy-saving and environment-friendly.
On the basis of the prior art, the application establishes a novel method for extracting cresol and tert-butylated hydroxytoluene products thereof from coal-based liquid derivatives, improves the distribution of reaction products by controlling the tert-butylated reaction in the technological process, and prepares m-cresol, p-cresol and 2, 6-di-tert-butyl-p-cresol products with low energy consumption.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for extracting cresol and tert-butylated products thereof from coal-based liquid derivatives, which is characterized in that the distribution of reaction products is improved by controlling the tert-butylated reaction in the technical process, so that m-cresol, p-cresol and 2, 6-di-tert-butyl-p-cresol products are prepared with low energy consumption, and the defects of the existing tert-butylated reaction process are overcome.
In order to solve the technical problems, the invention provides a method for extracting cresol and tert-butylated products thereof from coal-based liquid derivatives, which comprises the following steps:
(1) taking a coal-based liquid derivative as a raw material, and preparing a m-cresol and p-cresol mixture I through alkali washing and rectification steps;
(2) adding an acid catalyst and a polar solvent into the m-cresol and p-cresol mixture I obtained in the step (1), and carrying out tert-butylation reaction on the m-cresol and p-cresol by using isobutene as a tert-butylation reagent to obtain a mixture II containing 6-tert-butyl-m-cresol, 2-tert-butyl-p-cresol and 2, 6-di-tert-butyl-p-cresol products, wherein the mixture II does not contain 4, 6-di-tert-butyl-m-cresol products;
(3) feeding the mixture obtained in step (2)Adding 10% sodium carbonate solution into II, extracting to obtain upper layer solution III as tert-butylation reaction product and lower layer solution as Na2SO4And (3) rectifying the upper-layer solution III under normal pressure to remove low-boiling-point substances (mainly comprising an isobutylene self-polymer and a solvent), then rectifying under reduced pressure, and gradually collecting fractions at each section to respectively obtain an unreacted m-cresol and p-cresol mixture, 2-tert-butyl-p-cresol, 6-tert-butyl-m-cresol and 2, 6-di-tert-butyl-p-cresol.
In a further improvement, in the step (2), the polar solvent is dichloromethane, n-hexane, cyclohexane, toluene, benzene or tetrahydrofuran.
In a further improvement, in the step (2): the mass of the added acid catalyst is 5 percent of that of the m-cresol and p-cresol mixture I, the volume of the added polar solvent is 50 percent of that of the m-cresol and p-cresol mixture I, the molar ratio of the added isobutene to the m-cresol and p-cresol mixture I is 2.5-3.0:1, and in the reaction process, the isobutene accounts for 0.25-0.36 kg-min in mass space velocity-1Introducing, controlling the reaction temperature at 50-90 ℃, stirring at the speed of 200rmp/min, and reacting for 80-100 min.
Further improved, when the temperature of the atmospheric distillation in the step (3) is raised to 180 ℃, removing low-boiling-point substances, then, changing into vacuum distillation, collecting unreacted m-cresol and p-cresol mixture within the range of 98-104 ℃ under the condition that the pressure is 20mmHg, collecting 2-tert-butyl-p-cresol within the range of 112-.
The purity of the 2, 6-di-tert-butyl-p-cresol obtained in the step (3) is more than or equal to 90%.
In a further improvement, the method also comprises a step (4) of adding an acid catalyst into the 2-tert-butyl-p-cresol and the 6-tert-butyl-m-cresol obtained in the step (3) respectively to carry out a tert-butyl removal reaction so as to obtain p-cresol and m-cresol respectively.
Further improved, the dosage of the acid catalyst in the step (4) is 1% of the mass of the 2-tert-butyl-p-cresol or 6-tert-butyl-m-cresol, the reaction temperature in the tert-butyl removal reaction is 120-140 ℃, the reaction time is 80-100min, and the stirring speed is 200 rmp/min.
The purity of the p-cresol obtained in the step (4) is more than or equal to 85 percent, and the purity of the m-cresol obtained is more than or equal to 85 percent.
Further improvement, the step (1) is specifically as follows: transferring the coal-based liquid derivative into a separating funnel, adding a 10% NaOH solution, shaking for 2-3min, uniformly mixing, standing for 0.5-1.5h until obvious layering occurs, wherein the upper layer is dephenolized oil which does not participate in the reaction, and the lower layer is the sodium phenolate solution; then the sodium phenolate solution is transferred into another separating funnel, and 15% H is added in small amount for multiple times2SO4Measuring the Ph value of the solution by using an acidity meter, stopping adding the solution when the Ph value is 6.00, standing for 0.5-1.5h until obvious layering occurs, and separating the phenolic wastewater in the lower layer to obtain a mixed solution of m-cresol and p-cresol in the upper layer; and adding anhydrous magnesium sulfate into the mixed solution of the m-cresol and the p-cresol, standing for 12 hours, performing suction filtration to obtain an anhydrous mixed solution, rectifying the obtained anhydrous mixed solution, and collecting a fraction section at 185-195 ℃ to obtain a mixture I of the m-cresol and the p-cresol.
The coal-based liquid derivative in the step (1) is coal pyrolysis tar, coal liquefied oil or coal solvent extraction liquid, and the sum of the contents of m-cresol and p-cresol in the m-cresol and p-cresol mixture I obtained in the step (1) is more than or equal to 85%.
After adopting such design, the invention has at least the following advantages:
the method comprises the steps of firstly extracting a mixture of m-cresol and p-cresol from a coal-based liquid derivative, then taking the mixture as a raw material, taking isobutene as a tertiary butylated reagent, adding an acid catalyst, adding a polar solvent of dichloromethane, n-hexane, cyclohexane, toluene, benzene or tetrahydrofuran in the reaction process, changing the intermolecular force among reactants by polar regulation and control of the polar solvent on a reaction system, enabling the selectivity of 6-tertiary butyl m-cresol in a reaction product to be more than 90%, and effectively regulating and controlling the distribution of the product, namely the reaction product comprises unreacted p-cresol and m-cresol, high-purity 2-tertiary butyl p-cresol and 6-tertiary butyl m-cresol, a target product 2, 6-di-tert-butyl p-cresol but does not comprise 4, 6-di-tert-butyl m-cresol. Therefore, the method avoids the problem that in the prior art, after 4, 6-di-tert-butyl-m-cresol is generated through tert-butylation reaction, m-cresol is obtained through secondary tert-butylation removal reaction with high energy consumption.
The purity of the 2, 6-di-tert-butyl-p-cresol in the product obtained by the tertiary butylation reaction is more than or equal to 90 percent and can be directly output as a product, and the 2-tert-butyl-p-cresol and the 6-tert-butyl-m-cresol are respectively subjected to the tertiary butyl removal reaction to obtain p-cresol and m-cresol products, wherein the purity is more than 85 percent.
The boiling point of the added polar solvent is lower, the solvent can be removed by utilizing a conventional rectification mode, the step of collecting 4, 6-di-tert-butyl-m-cresol fraction is reduced in the step of vacuum rectification, and the process cost for separating and preparing cresol and cresol tert-butylated products is further reduced.
Drawings
The foregoing is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description.
FIG. 1 is a GC-MS detection spectrum of a mixture II in the method for extracting cresol and tert-butylated products thereof from coal-based liquid derivatives.
FIG. 2 is a GC-MS detection spectrum of a mixture II in a method for extracting cresol and tert-butylated products thereof from coal-based liquid derivatives in the prior art.
Detailed Description
The following examples are intended to illustrate the invention in detail and should not be construed as limiting the scope of the invention, except to the extent that the amounts are by weight. The coal-based liquid derivative comprises liquid products prepared by taking coal as a raw material through various methods, including coal pyrolysis tar, coal liquefied oil, coal solvent extraction liquid and the like. The following examples illustrate the method of extracting cresol and cresol tertiary butylated products from coal pyrolysis tar, and the technical scheme of the present application is described in detail.
Example 1:
1080kg of a mixture I of m-cresol and p-cresol with the content of 89.10 wt% obtained by performing alkali washing and rectification on coal pyrolysis tar, 54kg of concentrated sulfuric acid catalyst and 691.97kg of dichloromethane polar solvent are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 60 ℃, and then 1500kg of isobutene is added according to the airspeed of 0.31 kg/min-1Introducing into the reaction kettle, after about 90min, maintaining the reaction temperature at 60 + -2 deg.C for 90min to obtain a mixture II.
After the reaction is finished, adding 10% sodium carbonate solution into the mixture II, layering the mixture, wherein the upper layer solution III is a tert-butylation reaction product, and the lower layer solution is Na2SO4Removing the lower layer solution, rectifying the upper layer solution III under normal pressure to remove low boiling point substances such as solvent, and then rectifying under reduced pressure to gradually collect the fractions, thereby respectively obtaining 234.79kg of m-cresol and p-cresol mixture with the purity of 90.51%, 222.28kg of 2-tert-butyl-p-cresol with the purity of 91.56%, 475.19kg of 6-tert-butyl-m-cresol with the purity of 89.33% and 789.30kg of 2, 6-di-tert-butyl-p-cresol with the purity of 90.52%.
Then 222.28kg of 2-tert-butyl-p-cresol and 2.22kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 120 ℃, and the temperature is maintained for 90 min; the residue was subjected to rectification under reduced pressure to obtain 133.37kg of p-cresol with a purity of 89.46%.
475.19kg of 6-tert-butyl m-cresol and 4.75kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is increased to 120 ℃, and the temperature is maintained for 90 min; the residue was subjected to rectification under reduced pressure to obtain 281.18kg of m-cresol with a purity of 88.35%.
Example 2:
1080kg of a mixture I of m-cresol and p-cresol with the content of 89.10 wt% obtained by performing alkali washing and rectification on coal pyrolysis tar, 54kg of concentrated sulfuric acid catalyst and 344.68kg of n-hexane polar solvent are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 60 ℃, and then 1500kg of isobutene is added according to the airspeed of 0.31 kg/min-1Introducing into the reaction kettle, and maintaining the reaction temperature during about 90minKeeping the system at 60 +/-2 ℃ and reacting for 90min to obtain a mixture II.
After the reaction is finished, adding 10% sodium carbonate solution into the mixture II, layering the mixture, wherein the upper layer solution III is a tert-butylation reaction product, and the lower layer solution is Na2SO4Removing the lower layer solution, rectifying the upper layer solution III under normal pressure to remove low boiling point substances such as solvent, and then rectifying under reduced pressure to gradually collect fractions, thereby respectively obtaining 567.56kg of m-cresol and p-cresol mixture with purity of 89.61%, 400.57kg of 2-tert-butyl-p-cresol with purity of 88.56%, 335.46kg of 6-tert-butyl-m-cresol with purity of 87.37% and 470.93kg of 2, 6-di-tert-butyl-p-cresol with purity of 90.03%.
400.57kg of 2-tert-butyl-p-cresol and 4.00kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 130 ℃, and the temperature is maintained for 90 min; the residue was subjected to rectification under reduced pressure to obtain 239.86kg of p-cresol with a purity of 90.07%.
335.46kg of 6-tert-butyl metacresol and 3.35kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 130 ℃, and the temperature is maintained for 90 min; the residue was subjected to rectification under reduced pressure to obtain 198.50kg of m-cresol with a purity of 89.77%.
Example 3:
1080kg of a mixture I of m-cresol and p-cresol with the content of 89.10 wt% obtained by performing alkali washing and rectification on coal pyrolysis tar, 54kg of concentrated sulfuric acid catalyst and 406.83kg of cyclohexane polar solvent are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 60 ℃, and then 1500kg of isobutene is added according to the airspeed of 0.31 kg/min-1Introducing into the reaction kettle, after about 90min, maintaining the reaction temperature at 60 + -2 deg.C for 100min to obtain a mixture II.
After the reaction is finished, adding 10% sodium carbonate solution into the mixture II, layering the mixture, wherein the upper layer solution III is a tert-butylation reaction product, and the lower layer solution is Na2SO4Removing lower layer solution, rectifying upper layer solution III under normal pressure to remove low boiling point substances such as solvent, rectifying under reduced pressure, and gradually collecting fractions to obtain intermediate solution with purity of 89.54%,487.03kg of p-cresol mixture, 74.47kg of 2-tert-butyl-p-cresol with a purity of 90.11%, 384.42kg of 6-tert-butyl-m-cresol with a purity of 89.72% and 542.51kg of 2, 6-di-tert-butyl-p-cresol with a purity of 91.05%.
Putting 74.47kg of 2-tert-butyl-p-cresol and 0.74kg of concentrated sulfuric acid into a reaction kettle, starting stirring at the stirring speed of 200rmp/min, heating to 120 ℃, and maintaining the temperature for 100 min; the residue was subjected to rectification under reduced pressure to obtain 44.59kg of p-cresol with a purity of 88.31%.
384.42kg of 6-tert-butyl m-cresol and 3.84kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is increased to 120 ℃, and the temperature is maintained for 100 min; the residue was subjected to rectification under reduced pressure to obtain 227.47kg of m-cresol with a purity of 87.96%.
Example 4:
1080kg of a mixture I of m-cresol and p-cresol with the content of 89.10 wt% obtained by performing alkali washing and rectification on coal pyrolysis tar, 54kg of concentrated sulfuric acid catalyst and 433.46kg of toluene polar solvent are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 60 ℃, and then 1500kg of isobutene is added according to the airspeed of 0.31 kg/min-1Introducing into the reaction kettle, after about 90min, maintaining the reaction temperature at 60 + -2 deg.C for 90min to obtain a mixture II.
After the reaction is finished, adding 10% sodium carbonate solution into the mixture II, layering the mixture, wherein the upper layer solution III is a tert-butylation reaction product, and the lower layer solution is Na2SO4Removing the lower layer solution, rectifying the upper layer solution III under normal pressure to remove low boiling point substances such as solvent, and then rectifying under reduced pressure to gradually collect fractions, thereby respectively obtaining 396.31kg of m-cresol and p-cresol mixture with the purity of 90.77%, 118.46kg of 2-tert-butyl-p-cresol with the purity of 89.87%, 419.51kg of 6-tert-butyl-m-cresol with the purity of 88.19% and 632.38kg of 2, 6-di-tert-butyl-p-cresol with the purity of 92.45%.
118.46kg of 2-tert-butyl-p-cresol and 1.18kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is increased to 120 ℃, and the temperature is maintained for 90 min; the residue was subjected to rectification under reduced pressure to obtain 70.93kg of p-cresol with a purity of 89.58%.
419.51kg of 6-tert-butyl metacresol and 4.19kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is increased to 120 ℃, and the temperature is maintained for 90 min; the residue was subjected to rectification under reduced pressure to obtain 248.23kg of m-cresol with a purity of 89.65%.
Example 5:
1080kg of a mixture I of m-cresol and p-cresol with the content of 89.10 wt% obtained by performing alkali washing and rectification on coal pyrolysis tar, 54kg of concentrated sulfuric acid catalyst and 459.57kg of benzene polar solvent are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 60 ℃, and then 1500kg of isobutene is added according to the airspeed of 0.31 kg/min-1Introducing into the reaction kettle, keeping the reaction temperature at 60 +/-2 ℃ for 90min during about 80min after the introduction, and obtaining a mixture II.
After the reaction is finished, adding 10% sodium carbonate solution into the mixture II, layering the mixture, wherein the upper layer solution III is a tert-butylation reaction product, and the lower layer solution is Na2SO4Removing the lower layer solution, rectifying the upper layer solution III under normal pressure to remove low boiling point substances such as solvent, and then rectifying under reduced pressure to gradually collect the fractions, thereby respectively obtaining 309.27kg of m-cresol and p-cresol mixture with the purity of 89.73%, 176.98kg of 2-tert-butyl-p-cresol with the purity of 89.75%, 439.27kg of 6-tert-butyl-m-cresol with the purity of 87.09% and 715.49kg of 2, 6-di-tert-butyl-p-cresol with the purity of 90.81%.
176.98kg of 2-tert-butyl-p-cresol and 1.77kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is increased to 120 ℃, and the temperature is maintained for 80 min; the residue was subjected to rectification under reduced pressure to obtain 105.98kg of p-cresol with a purity of 87.85%.
439.27kg of 6-tert-butyl metacresol and 4.39kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is increased to 120 ℃, and the temperature is maintained for 80 min; the residue was subjected to rectification under reduced pressure to obtain 259.92kg of m-cresol with a purity of 89.48%.
Example 6:
1080kg of m-cresol and p-cresol with the content of 89.10 wt% obtained by performing alkali washing and rectification on coal pyrolysis tarPutting the material I, 54kg of concentrated sulfuric acid catalyst and 464.80kg of tetrahydrofuran polar solvent into a reaction kettle, starting stirring at the stirring speed of 200rmp/min, heating to 70 ℃, and then adding 1500kg of isobutene at the airspeed of 0.31 kg-min-1Introducing into the reaction kettle, after about 90min, maintaining the reaction temperature at 60 + -2 deg.C for 100min to obtain a mixture II.
After the reaction is finished, adding 10% sodium carbonate solution into the mixture II, layering the mixture, wherein the upper layer solution III is a tert-butylation reaction product, and the lower layer solution is Na2SO4Removing the lower layer solution, rectifying the upper layer solution III under normal pressure to remove low boiling point substances such as solvent, and then rectifying under reduced pressure to gradually collect the fractions, thereby respectively obtaining 422.42kg of m-cresol and p-cresol mixture with the purity of 90.09%, 252.52kg of 2-tert-butyl-p-cresol with the purity of 90.38%, 597.37kg of 6-tert-butyl-m-cresol with the purity of 89.79% and 159.35kg of 2, 6-di-tert-butyl-p-cresol with the purity of 90.51%.
252.52kg of 2-tert-butyl-p-cresol and 2.52kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 140 ℃, and the temperature is maintained for 80 min; the residue was subjected to rectification under reduced pressure to obtain 151.21kg of p-cresol with a purity of 88.29%.
597.37kg of 6-tert-butyl metacresol and 5.97kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 140 ℃, and the temperature is maintained for 80 min; the residue was subjected to rectification under reduced pressure to obtain 353.47kg of m-cresol with a purity of 88.93%.
Comparative example 1:
1080kg of mixed m-p-cresol with the content of 89.10 wt% obtained by performing alkali washing and rectification on coal pyrolysis oil and 54kg of concentrated sulfuric acid catalyst are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is raised to 60 ℃, and then 1500kg of isobutene is added according to the airspeed of 0.31 kg/min-1And (3) introducing the mixture into a reaction kettle, keeping the reaction temperature at 60 +/-2 ℃ during about 90min, and keeping the system to react for 90min to obtain a mixture II.
After the reaction is finished, adding 10% sodium carbonate solution into the mixture II, layering the mixture, wherein the upper layer solution III is a tert-butylation reaction productThe layer solution is Na2SO4Removing the lower layer solution, rectifying the upper layer solution III under normal pressure to remove low boiling point substances such as solvent, and then rectifying under reduced pressure to gradually collect fractions, thereby respectively obtaining 31.16kg of 6-tert-butyl-m-cresol with the purity of 85.21%, 1070.85kg of 2, 6-di-tert-butyl-p-cresol with the purity of 88.52%, and 1015.41kg of 4, 6-di-tert-butyl-m-cresol with the purity of 89.34%.
Wherein the collection temperature of the fraction of the 4, 6-di-tert-butyl-m-cresol is 164-170 ℃.
Putting 31.16kg of 6-tert-butyl-p-cresol and 0.31kg of concentrated sulfuric acid into a reaction kettle, starting stirring at the stirring speed of 200rmp/min, heating to 120 ℃, and maintaining the temperature for 90 min; the residue was subjected to rectification under reduced pressure to obtain 18.56kg of m-cresol with a purity of 92.46%.
1015.41kg of 4, 6-di-tert-butyl-m-cresol and 10.15kg of concentrated sulfuric acid are put into a reaction kettle, stirring is started, the stirring speed is 200rmp/min, the temperature is increased to 120 ℃, and the temperature is maintained for 90 min; the residue was subjected to rectification under reduced pressure to obtain 600.83kg of m-cresol with a purity of 91.35%.
Detection examples
The mixture II in the example 1 and the comparative example 1 is diluted by absolute ethyl alcohol and then subjected to GC-MS detection, a chromatographic column is an HP-5MS capillary column, the specification is 30m × 0.25.25 mu m × 0.25.25 mm, and the detection conditions are as follows (1), the chromatographic conditions comprise the injection port temperature of 250 ℃, the pressure of 34.5kPa, constant-current operation, the split ratio of 100:1, the chromatographic column pressure of 34.5KPa, the flow rate of 0.8ml/min, the average linear velocity of 37cm/min, the column temperature of 40 ℃, the initial temperature of 100 ℃ at the rate of 2 ℃/min, the temperature of 200 ℃ at the rate of 10 ℃/min, 10min of carrier gas is helium, the injection amount is 1 mu L, (2) the mass spectrum conditions comprise that an ionization source is an EI source, the electron energy is 70eV, and the mass scanning range is 10-400 AMU.
As shown in the accompanying FIGS. 1 and 2, the GC-MS chart of the mixture II obtained in example 1 is shown in the chart of FIG. 1, and the GC-MS chart of the mixture II obtained in comparative example 1 is shown in the chart of FIG. 2, and it is clear from the comparison of the two charts that the tertiary butylation reaction of comparative example 1 mainly contains 2, 6-di-T-butyl-P-cresol (BHT) and 4, 6-di-T-butyl-M-cresol (DMC), while the tertiary butylation reaction of example 1 mainly contains 2, 6-di-T-butyl-P-cresol (BHT) and 2-T-butyl-P-cresol (2-T-P) and 6-T-butyl-M-cresol (6-T-M) and does not contain 4, 6-di-T-butyl-M-cresol (DMC), so that it can be obtained by adding a polar solvent during the tertiary butyl reaction, the method can well regulate and control the polarity of a reaction system, change intermolecular force among reactants, achieve the technical effect of effectively regulating and controlling product distribution, and avoid the problem that after 4, 6-di-tert-butyl-m-cresol is generated through a tert-butylation reaction in the prior art, an m-cresol product is obtained through a secondary tert-butylation removal reaction with high energy consumption.
In addition, compared with the conventional process, the optimized process has the advantage that the overall energy consumption in the solvent removal, rectification and tert-butyl removal reaction processes is reduced by 14.54%. The method for extracting the cresol and the tert-butylated hydroxytoluene products from the coal-based liquid derivatives saves energy consumption and reduces cost.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention in any way, and it will be apparent to those skilled in the art that the above description of the present invention can be applied to various modifications, equivalent variations or modifications without departing from the spirit and scope of the present invention.
Claims (9)
1. A method for extracting cresol and tert-butylated hydroxytoluene products from coal-based liquid derivatives is characterized by comprising the following steps:
(1) taking a coal-based liquid derivative as a raw material, and preparing a m-cresol and p-cresol mixture I through alkali washing and rectification steps;
(2) adding a concentrated sulfuric acid catalyst and a solvent into the m-cresol and p-cresol mixture I obtained in the step (1), and carrying out tert-butylation reaction on the m-cresol and p-cresol by using isobutene as a tert-butylation reagent to obtain a mixture II containing 6-tert-butyl-m-cresol, 2-tert-butyl-p-cresol and 2, 6-di-tert-butyl-p-cresol products, wherein the mixture II does not contain 4, 6-di-tert-butyl-m-cresol products; wherein the solvent is dichloromethane, n-hexane, cyclohexane, toluene, benzene or tetrahydrofuran;
(3) and (3) adding a sodium carbonate solution into the mixture II obtained in the step (2), extracting to obtain an upper layer solution III, rectifying the upper layer solution III at normal pressure to remove low-boiling-point substances, then rectifying under reduced pressure, and gradually collecting fractions to respectively obtain an unreacted m-cresol and p-cresol mixture, 2-tert-butyl-p-cresol, 6-tert-butyl-m-cresol and 2, 6-di-tert-butyl-p-cresol.
2. The method for extracting cresol and its tert-butylated products from coal-based liquid derivatives according to claim 1, wherein in the step (2): the mass of the added concentrated sulfuric acid catalyst is 5% of the mass of the m-cresol and p-cresol mixture I, the volume of the added solvent is 50% of the volume of the m-cresol and p-cresol mixture I, the molar ratio of the added isobutene to the m-cresol and p-cresol mixture I is 2.5-3.0:1, and in the reaction process, the isobutene accounts for 0.25-0.36 kg/min in mass space velocity-1Introducing, controlling the reaction temperature at 50-90 ℃, stirring at the speed of 200rmp/min, and reacting for 80-100 min.
3. The method for extracting cresol and its tert-butylated hydroxytoluene product as claimed in claim 2, wherein the temperature of atmospheric distillation in step (3) is increased to 180 ℃, low boilers are removed, and vacuum distillation is used instead, and the unreacted m-cresol and p-cresol mixture is collected at 98-104 ℃ under 20mmHg, 2-tert-butyl-p-cresol is collected at 118 ℃ of 112-.
4. The method for extracting the cresol and the tertiary butylated product thereof from the coal-based liquid derivative according to claim 3, wherein the purity of the 2, 6-di-tert-butyl-p-cresol obtained in the step (3) is not less than 90%.
5. The method for extracting cresol and its tert-butylated products from coal-based liquid derivatives according to any one of claims 1 to 4, further comprising a step (4) of adding concentrated sulfuric acid catalyst to the 2-tert-butyl-p-cresol and 6-tert-butyl-m-cresol obtained in the step (3) respectively to perform a tert-butyl removal reaction to obtain p-cresol and m-cresol respectively.
6. The method for extracting cresol and its tert-butylated product from coal-based liquid derivative as claimed in claim 5, wherein the amount of concentrated sulfuric acid catalyst used in step (4) is 1% of the mass of 2-tert-butyl-p-cresol or 6-tert-butyl-m-cresol, the reaction temperature in the tert-butyl removal reaction is 120-140 ℃, the reaction time is 80-100min, and the stirring rate is 200 rmp/min.
7. The method for extracting the cresol and the tertiary butylated product thereof in the coal-based liquid derivative according to claim 6, wherein the purity of the p-cresol obtained in the step (4) is more than or equal to 85%, and the purity of the m-cresol obtained in the step (4) is more than or equal to 85%.
8. The method for extracting cresol and its tert-butylated products from coal-based liquid derivatives according to claim 1, wherein the step (1) is specifically: transferring the coal-based liquid derivative into a separating funnel, adding NaOH solution, shaking for 2-3min, standing for 0.5-1.5h after uniform mixing till obvious layering occurs, and taking the lower layer solution, namely the sodium phenolate solution; then transferring the sodium phenolate solution into another separating funnel, and adding H for a plurality of times in small amount2SO4Stopping the solution until the Ph value is 6.00, standing for 0.5-1.5h until obvious layering occurs, and separating out the phenol-containing wastewater at the lower layer to obtain a mixed solution of m-cresol and p-cresol at the upper layer; and adding anhydrous magnesium sulfate into the mixed solution of the m-cresol and the p-cresol, standing for 12 hours, performing suction filtration to obtain an anhydrous mixed solution, rectifying the obtained anhydrous mixed solution, and collecting a fraction section at 185-195 ℃ to obtain a mixture I of the m-cresol and the p-cresol.
9. The method for extracting cresol and its tert-butylated forms of cresol from coal-based liquid derivatives according to claim 8, wherein the coal-based liquid derivatives in step (1) are coal pyrolysis tar, coal liquefied oil or coal solvent extraction liquid, and the sum of the contents of m-cresol and p-cresol in the mixture of m-cresol and p-cresol obtained in step (1) is greater than or equal to 85%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910560862.2A CN110256207B (en) | 2019-06-26 | 2019-06-26 | Method for extracting cresol and tert-butylated product thereof from coal-based liquid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910560862.2A CN110256207B (en) | 2019-06-26 | 2019-06-26 | Method for extracting cresol and tert-butylated product thereof from coal-based liquid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110256207A CN110256207A (en) | 2019-09-20 |
| CN110256207B true CN110256207B (en) | 2020-07-10 |
Family
ID=67921798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910560862.2A Active CN110256207B (en) | 2019-06-26 | 2019-06-26 | Method for extracting cresol and tert-butylated product thereof from coal-based liquid derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110256207B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110759816B (en) * | 2019-11-15 | 2022-11-18 | 陕西煤业化工集团神木天元化工有限公司 | Method for removing pyridine base in mixed phenol |
| CN113801077B (en) * | 2021-09-16 | 2023-04-21 | 杭州泽邦科技有限公司 | Method for rapidly removing BHT antioxidant |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100447121C (en) * | 2006-07-15 | 2008-12-31 | 孟祥儒 | Production process of antioxidant 2,6-di-tert-butyl-4-methy phenol |
| CN103212438B (en) * | 2013-05-02 | 2014-12-10 | 天津北洋国精科技有限责任公司 | Catalyst for alkylation separation of m-cresol and p-cresol and separation method |
| CN103333052B (en) * | 2013-07-25 | 2015-07-29 | 北京旭阳化工技术研究院有限公司 | Between a kind of separation industries to mixture cresol to prepare the method for pure p-cresol and pure meta-cresol |
| CN106810422A (en) * | 2017-01-16 | 2017-06-09 | 河北工业大学 | A kind of method that liquid-phase alkylation method separates M-and P-cresols |
-
2019
- 2019-06-26 CN CN201910560862.2A patent/CN110256207B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110256207A (en) | 2019-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110256207B (en) | Method for extracting cresol and tert-butylated product thereof from coal-based liquid derivative | |
| CN110372512B (en) | Separation and purification process of dimethyl carbonate | |
| CN101054340A (en) | Method of separating and purifying o/p-dihydroxy benzene prepared by phenol hydroxylation | |
| CN108586207A (en) | A kind of separating technology extracting 2,4- xylenols and 2,5- xylenols from crude phenols | |
| CN106588589A (en) | Purification method for polyoxymethylene dimethyl ether(PODE) | |
| CN113563173B (en) | Preparation method of citral | |
| CN107556172B (en) | Process method for producing ethylene glycol mono-tert-butyl ether | |
| CN102531834A (en) | System and process for recovering waste liquid in 1, 4-butanediol production process | |
| CN102399122B (en) | Method for preparing cyclopentadiene and methyl cyclopentadiene | |
| CN106278854B (en) | A kind of preparation method by α-isophorone isomery β-isophorone | |
| CN101643379A (en) | Preparation method of high-purity 1,3-pentadiene | |
| CN109704937A (en) | Furfural and the method for secondary low-boiling-point substance continuous rectification purification | |
| CN1868992A (en) | Alkylphenol coproduction technology | |
| CN105218307A (en) | Octyl alconyl produce in light constituent residual night aldehydes add hydrogen retrieval separation method | |
| CN109988055A (en) | A kind of preparation method of high-purity cyclopentadiene and methyl cyclopentadiene | |
| CN114105802A (en) | Method for controlling metal ions and chromaticity in preparation process of N-ethylformamide | |
| CN112047857B (en) | Preparation method of 6-aminocapronitrile | |
| CN1803743A (en) | Tripropylene glycol synthesis method | |
| CN114230442A (en) | Method for reducing isopropyl phenol in reaction system for preparing bisphenol A | |
| CN112174997B (en) | Device and method for preparing high-purity gamma-chloropropyltrichlorosilane | |
| CN111378467A (en) | Method for treating cyclohexane oxidation by-products | |
| CN101585748B (en) | Method for extracting methyl cyclopentadiene from hydrogenation heavy components of gasoline | |
| CN114685362B (en) | Separation method of 2-methylpyridine | |
| CN111072519B (en) | Preparation method of cyanoethyl ester | |
| CN111662160A (en) | Method for improving productivity of cyclohexanol dehydrogenation device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |