CN113501747A - Reaction and separation composite process for selectively producing cresol from phenol - Google Patents
Reaction and separation composite process for selectively producing cresol from phenol Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 63
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 42
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229930003836 cresol Natural products 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 199
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- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 122
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 64
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- 239000000463 material Substances 0.000 claims description 13
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- 239000007788 liquid Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 125000003717 m-cresyl group Chemical group [H]C1=C([H])C(O*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000000486 o-cresyl group Chemical group [H]C1=C([H])C(O*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 150000001896 cresols Chemical class 0.000 claims 9
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 claims 1
- 230000029936 alkylation Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 150000003739 xylenols Chemical group 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
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- 150000002989 phenols Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
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- 239000006200 vaporizer Substances 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
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- 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
-
- 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
-
- 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
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a reaction and separation composite process for selectively producing cresol from phenol, which comprises the steps of preparing o-cresol, m-cresol and p-cresol from phenol and methanol through a hydrogenation alkylation reaction process, preparing o-cresol products and m-cresol and p-cresol mixtures through a rectification separation process, preparing p-cresol and m-cresol products from the obtained m-cresol and p-cresol mixtures through a gas phase pressure-swing shape-selective adsorption separation process, further obtaining o-cresol, m-cresol and p-cresol mixtures through a liquid phase isomerization reaction process, adding the obtained o-cresol and p-cresol mixtures into the reaction products of hydrogenation and methanol alkylation, and then performing two-tower rectification separation, gas phase pressure-swing shape-selective adsorption separation and liquid phase isomerization reaction. The method for selectively producing m-cresol, p-cresol or o-cresol from phenol is environment-friendly, low in production cost, good in operation stability and high in production efficiency, and has high industrial application value and social and economic benefits.
Description
Technical Field
The invention relates to the technical and chemical production field, in particular to a reaction and separation composite process for selectively producing cresol from phenol.
Background
O-cresol, m-cresol and p-cresol are very important organic chemical intermediates, have numerous downstream products and large market demand, are important raw materials for synthesizing products such as pesticides, dyes, resins, medicines, spices, antioxidants and the like, and have very wide application. At present, the production methods of industrial cresol mainly comprise a toluene sulfonation alkali fusion method, a toluene chlorination hydrolysis method, a phenol methylation method and the like, wherein the toluene sulfonation alkali fusion method and the toluene chlorination hydrolysis method need to use a large amount of acid, alkali, chloride and the like in the production process, and are not beneficial to the development of green chemistry along with the problems of equipment corrosion, environmental pollution and the like.
Therefore, Chinese patent CN101992118A discloses a method for alkylating phenol with methanol, which uses MCM-41 mesoporous molecular sieve as carrier, after loading Fe-V active component, improves the conversion rate of phenol and the selectivity of o-cresol, however, the reaction product is also mixed with a larger amount of 2, 6-xylenol (and trimethylphenol) besides o-cresol; in addition, the reaction product is mainly o-cresol, and the m-cresol product with large market demand and higher added value is low in content. Chinese patent CN1102407A discloses a method for preparing ortho-methylated phenol compounds, which comprises the steps of passing a mixed solution of phenol compounds and methanol through a catalyst bed reactor, catalyzing and carrying out gas-phase reaction under the conditions of temperature of 200-450 ℃, pressure of normal pressure to 0.5MPa and liquid space velocity of 0.1-15 h < -1 >, wherein the reaction product contains a large amount of 2, 6-xylenol (containing more trimethylphenol). Chinese CN103570504A discloses a method for producing cresol by phenol-methanol gas-phase alkylation, wherein phenol and methanol are preheated and then mixed with diluent gas to continuously pass through a catalyst bed layer, and gas-phase reaction is carried out under the reaction conditions of the reaction temperature of 200-500 ℃ and the feeding weight space velocity of 0.5-20 h < -1 >. The total selectivity of various methyl phenols in the reaction product can reach 85%, but the content of intermediate cresol and p-cresol in the product is lower. The phenol alkylation products produced in the above patents are mainly o-cresol and 2, 6-xylenol (with a small amount of trimethylphenol). The invention provides a reaction and separation composite process method for selectively producing m-cresol, p-cresol or o-cresol from phenol, which effectively realizes the selective production of the o-cresol, the p-cresol and the m-cresol by combining a phenol and methanol alkylation technology, a m-cresol and p-cresol shape selective adsorption separation technology and an o-cresol and p-cresol isomerization reaction technology.
On the other hand, o-, m-and p-cresol have wide application and have high requirements on the purity of various phenols in industrial production. The boiling points of m-cresol and p-cresol are very close, 202.2 ℃ and 201.9 ℃ respectively. Therefore, Chinese patent CN107721827B discloses a method for refining m-cresol and p-cresol, which realizes the separation of 2, 6-xylenol, o-cresol and m-cresol and p-cresol by continuously rectifying crude m-cresol and p-cresol for two times, and matching with specific temperature, pressure and reflux ratio. However, it is difficult to achieve separation of m-cresol and p-cresol with extremely close boiling points by such distillation. Chinese patent CN107721827B discloses a method for separating m-cresol and p-cresol, which takes m-cresol and p-cresol obtained by vacuum rectification of crude phenol as raw materials, urea and oxalic acid as complexing agents, and obtains m-cresol and p-cresol with purity of more than 98% by a two-step complexing method and by controlling temperature and reaction time in the processes of complexing and crystallizing. The method for complexing and separating by using urea and the like as complexing agents is a relatively wide separation method, however, the method needs a large amount of solvent, has relatively small treatment capacity on m-cresol and p-cresol mixed raw material liquid, is not beneficial to large-scale production and application while generating serious pollution, and has the advantages of high cost, complex subsequent processing operation process and high energy consumption. The development of a new process for efficiently separating m-cresol and p-cresol to obtain a high purity product is imminent. The gas phase pressure swing shape selective adsorption separation method has the advantages of simple flow, high separation efficiency, renewable shape selective adsorbent, simple and convenient operation condition and the like, and is an economic and environment-friendly separation technical method.
The invention aims to develop a high-efficiency clean process for synthesizing cresol by hydroalkylation of phenol and methanol to replace the existing production process, and adopts a gas-phase pressure-swing shape-selective adsorption separation technology with environment friendliness, simple and convenient operation conditions and high separation efficiency, and combines a liquid-phase isomerization reaction process of o-cresol and p-cresol with environmental protection and low consumption, so that m-cresol, p-cresol or o-cresol can be efficiently and highly selectively produced, the environmental protection and technical problems in the processes of synthesis preparation and separation of cresol can be solved simultaneously, the production process of cresol is greatly optimized, the production efficiency of cresol is obviously improved, and the invention has better innovation and advancement and good industrial application prospect.
Disclosure of Invention
The invention aims to provide a reaction and separation composite process for selectively producing cresol from phenol, which solves the problems of difficult separation of mixed meta-cresol and para-cresol isomers, serious equipment corrosion, large environmental pollution, high energy consumption and material consumption and low production efficiency in the reaction product in the traditional cresol production process.
The above object of the present invention is achieved by the following technical solutions: a reaction and separation composite process for selectively producing cresol from phenol, which takes phenol as a raw material, and comprises the following steps:
step 1, carrying out a hydrogenation alkylation reaction on phenol and methanol to obtain a product containing o-cresol, m-cresol and p-cresol;
step 2, separating the o-cresol, the m-cresol and the p-cresol obtained in the step 1 through multi-tower rectification, firstly separating and extracting the o-cresol, and obtaining the m-cresol and the p-cresol;
step 3, separating the m-cresol and the p-cresol mixture obtained in the step 2 through gas phase pressure swing shape selective adsorption to respectively obtain p-cresol and m-cresol;
and 4, converting the o-cresol and the p-cresol obtained in the step 2 and the step 3 into m-cresol through liquid phase isomerization reaction, thereby obtaining o-cresol, m-cresol and p-cresol mixed cresol, adding the o-cresol, m-cresol and p-cresol mixed cresol of the phenol and methanol alkylation reaction product in the step 1, and then carrying out rectification in the step 2 and gas phase pressure-swing shape-selective adsorption separation in the step 3 to obtain m-cresol, p-cresol or o-cresol products.
Preferably, in step 1After phenol and methanol are preheated, hydrogen is used as a carrier gas to react, and the molar ratio of phenol to methanol is 1.5: 1-10: 1. the pressure is 0.5-5.0MPa, the temperature is 150--1Under the reaction condition of (1) and under the action of solid acid catalyst making hydrogenation alkylation reaction so as to obtain the reaction product containing o-, m-and p-mixed cresol.
Preferably, the solid acid catalyst comprises one of an acidic macroporous twelve-membered ring molecular sieve, a supported phosphoric acid solid acid, a macroporous high-temperature resistant acidic resin and a supported heteropoly acid solid acid, and a hydrogenation activity promoter containing one or more of Mo, Co, Pd and Pt metal elements is added into the solid acid catalyst, and the solid acid catalyst has the hydro-transalkylation reaction performance.
Preferably, in the step 2, the hydroalkylation product containing o-cresol, m-cresol and p-cresol mixture obtained in the step 1 is rectified and separated by a gas-liquid separation tower and two rectifying towers, the gas at the top of the gas-liquid separation tower is pressurized by a compressor and then circulated to the inlet of a hydroalkylation reactor, the water layer is removed from the bottom of the gas-liquid separation tower, and the intermediate oil phase enters the first rectifying tower; pressurizing phenol at the top of the first rectifying tower by using a pump, circulating the phenol to the inlet of the hydroalkylation reactor, and feeding materials at the bottom of the first rectifying tower into a second rectifying tower; the distillate at the top of the second rectifying tower is o-cresol, the material separated from the middle layer of the rectifying tower is m-cresol and p-cresol, and the material at the bottom of the rectifying tower is xylenol.
Preferably, the rectification column comprises one or a combination of two of a bulk packed column, a structured packed column, a sieve tray column or a valve tray column.
Preferably, in the step 3, after the material containing m-cresol and p-cresol obtained in the step 2 is preheated and vaporized, the mixed gas of m-cresol and p-cresol is introduced into an adsorption separation tower unit filled with a shape-selective adsorbent to carry out gas phase pressure swing adsorption separation, and the mixed gas flows out of a tower to be condensed to obtain an m-cresol product; stopping collecting m-cresol product when p-cresol begins to flow out; adopting nitrogen or hydrogen to blow off m-cresol and p-cresol in the adsorbent bed layer of the adsorption separation tower unit, then pumping off through the vacuum adsorbent bed layer, desorbing the p-cresol adsorbed in the holes, and condensing to obtain a p-cresol product.
Preferably, the shape selective adsorbent is a mesoporous ten-membered ring molecular sieve shape selective adsorbent modified by liquid-phase chemical silicon deposition or boron deposition.
Preferably, the operation temperature of the gas phase pressure swing adsorption separation is 205-230 ℃, and the vacuum degree of the gas phase pressure swing desorption is 720-5 mmHg.
In the method, the o-cresol and the p-cresol obtained in the composite process method can be directly used as independent products, and can also be selected as raw materials for the subsequent processing process for increasing the yield of the m-cresol through liquid phase isomerization reaction.
Preferably, in the step 4, the o-cresol and the p-cresol obtained in the step 2 and the step 3 are mixed or are independently used as reaction raw materials and injected into a liquid phase isomerization reaction unit for liquid phase isomerization reaction to obtain an isomerization reaction product, and the liquid phase isomerization reaction product is mixed with o-cresol, m-cresol and p-cresol.
Preferably, the liquid phase isomerization reaction is carried out under the reaction conditions of the reaction pressure of 2.0-8.0MPa, the temperature of 220-420 ℃ and the weight space velocity WHSV of 0.5-8.0h < -1 > and an isomerization catalyst to generate the o-, m-and p-mixed cresol products, and the isomerization catalyst is a solid acid type catalyst and comprises one of strong acid flaky molecular sieves or supported phosphoric acid solid acids.
The invention has the beneficial effects that: the method for selectively producing m-cresol, p-cresol or o-cresol from phenol is environment-friendly, low in production cost, good in operation stability and high in production efficiency; the method not only can convert the phenol raw material into m-cresol, p-cresol or o-cresol without side products, but also can selectively produce the m-cresol, the p-cresol or the o-cresol according to the change of actual market demands, and has higher industrial application value and social and economic benefits.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the invention
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Example 1:
as shown in figure 1, a reaction and separation composite process for selectively producing cresol from phenol, which takes phenol as a raw material, and comprises the following steps:
step 1, phenol and methanol are subjected to a hydrogenation alkylation reaction to prepare a product containing o-cresol, m-cresol and p-cresol. After phenol and methanol are preheated, hydrogen is used as a carrier gas reaction medium (the molar ratio of hydrogen to hydrocarbon is 1: 1-6: 1), and the weight ratio of phenol: the molar ratio of methanol is 1.5: 1-10: 1. the pressure is 0.5-5.0MPa (gauge pressure), the temperature is 150--1Under the reaction condition of (1) and under the action of solid acid catalyst making hydrogenation alkylation reaction so as to obtain the reaction product containing o-, m-and p-mixed cresol. Wherein the reaction product further comprises unreacted converted phenol, dimethylphenol, and trimethylphenol.
The solid acid catalyst used for the alkylation reaction of the phenol and the methanol is an acidic macroporous dodecacyclic molecular sieve or a supported phosphoric acid solid acid or a macroporous high-temperature-resistant acidic resin or a supported heteropoly acid solid acid, and one or more hydrogenation activity promoters containing Mo, Co, Pd and Pt metal elements are added into the solid acid catalyst, and the solid acid catalyst has the reaction performance of the transalkylation of the hydrogen.
And 2, separating the o-cresol, the m-cresol and the p-cresol obtained in the step 1 through multi-tower rectification, firstly separating and extracting the o-cresol, and obtaining the m-cresol and the p-cresol.
In the step 2, the hydroalkylation product containing o-cresol, m-cresol and p-cresol mixture obtained in the step 1 is rectified and separated by a gas-liquid separation tower and two rectifying towers, the gas (hydrogen) at the top of the gas-liquid separation tower is pressurized by a compressor and then circulates to the inlet of a hydroalkylation reactor, the water layer is removed from the bottom of the tower, and the intermediate oil phase enters the first rectifying tower; pressurizing phenol at the top of the first rectifying tower by using a pump, circulating the phenol to the inlet of the hydroalkylation reactor, and feeding materials at the bottom of the first rectifying tower into a second rectifying tower; the distillate at the top of the second rectifying tower is o-cresol, the material separated from the middle layer of the rectifying tower is m-cresol and p-cresol, a small amount of tower bottom material is xylenol (containing trace amount of trimethylphenol), and the xylenol is circularly fed into the inlet of the hydroalkylation reactor to generate cresol through the hydroalkylation transfer reaction.
The two rectifying towers for separating cresol, o-cresol, m/p-mixed cresol and xylenol from the reaction product of the hydrogenation alkylation reaction adopt one or the combination of two of a bulk packed tower, a regular packed tower, a sieve plate tower or a floating valve plate tower.
And 3, respectively separating the m-cresol and the p-cresol mixture obtained in the step 2 by gas phase pressure swing shape selective adsorption to obtain p-cresol and m-cresol.
Preheating and vaporizing the material containing m-cresol and p-cresol obtained in the step 2, and introducing the mixed gas of m-cresol and p-cresol into an adsorption separation tower unit filled with a shape selective adsorbent to perform gas phase pressure swing adsorption separation (wherein the operation temperature of the gas phase pressure swing adsorption separation is 205-230 ℃, and the vacuum degree of the gas phase pressure swing desorption is 720-5 mmHg).
In the process, the cresol is firstly discharged from a tower and condensed to obtain a high-purity m-cresol product; stopping collecting m-cresol product when p-cresol begins to flow out; adopting nitrogen or hydrogen to blow off m-cresol and p-cresol in the adsorbent bed layer of the adsorption separation tower unit (blowing off the mixture of m-cresol and p-cresol to circularly return to the tower inlet for separation again), then carrying out extraction and desorption on the p-cresol adsorbed in the holes through the vacuum adsorbent bed layer, and condensing to obtain a high-purity p-cresol product.
Wherein the shape selective adsorbent is a mesopore ten-membered ring molecular sieve shape selective adsorbent modified by liquid phase chemical silicon deposition or boron deposition.
The o-cresol and p-cresol obtained in the composite process method can be directly used as separate products, and can also be selected as raw materials for the subsequent processing process of increasing the yield of the m-cresol through isomerization reaction.
And 4, further carrying out liquid phase isomerization reaction on the o-cresol and the p-cresol obtained in the step 2 and the step 3 to convert the o-cresol and the p-cresol into m-cresol so as to obtain o-cresol, m-cresol and p-cresol mixed cresol, adding the o-cresol, m-cresol and p-cresol mixed cresol which is the reaction product of phenol and methanol in the step 1 into the o-cresol, m-cresol and p-cresol mixed cresol, and then carrying out rectification in the step 2 and the gas phase pressure-variable shape-selective adsorption separation method in the step 3 to obtain an m-cresol, p-cresol or o-cresol product, wherein the purity of the m-cresol, p-cresol or o-cresol product is more than 99%.
In step 4, the o-cresol and the p-cresol obtained in step 2 and step 3 are mixed or are independently used as reaction raw materials and injected into a liquid phase isomerization reaction unit to carry out a liquid phase isomerization reaction process, so as to obtain an isomerization reaction product, wherein the liquid phase isomerization reaction product comprises o-cresol, m-cresol and p-cresol.
The liquid phase isomerization reaction is carried out at the reaction pressure of 2.0-8.0MPa (gauge pressure), the temperature of 220-420 ℃ and the weight space velocity WHSV of 0.5-8.0h-1Under the reaction condition of (3) and under the action of isomerization catalyst to make isomerization reaction to obtain o-, m-and p-mixed cresol product. Wherein the isomerization catalyst is a solid acid catalyst and adopts one of a strongly acidic flaky molecular sieve or a supported phosphoric acid solid acid.
Example 2:
mixing a mixture of 1: the phenol and the methanol of 1 are taken as reaction raw materials and are fully mixed, and then are sent into a preheater through a mass metering pump, the temperature of the preheater is set to be 250 ℃, and the mixture enters an alkylation reaction unit after being fully preheated. The alkylation reaction unit is pre-filled with a Mo modified MCM-49 molecular sieve, the molecular sieve is molded to prepare 1.5-3MM clover type catalyst particles, and the molecular sieve is prepared by mixing hydrogen: the molar ratio of phenol is 4: 1. the reaction pressure is 1.0MPa, the reaction temperature is 430 ℃, and the weight space velocity WHSV is 1.0h-1The alkylation reaction is carried out under the reaction condition of (1), and after gas-liquid separation and condensation of reaction products, the selectivity of a mixture of o-cresol, m-cresol and p-cresol in the product composition is more than 95%.
Example 3:
the mixture of o-cresol, m-cresol and p-cresol of example 2 was pumped into a vaporizer by a mass metering pump, the temperature of the vaporizer was set at 210 ℃, and then the vaporized m-cresol and p-cresol gases were passed into a shape selective adsorption separation unit. The adsorption separation unit is pre-filled with a ZSM-5 molecular sieve deposited by polyamino siloxane as a shape selective adsorbent, the temperature of the adsorption separation unit is set to 215 ℃, and a product after condensation is collected and marked as m-cresol at a product outlet of the shape selective adsorption separation unit, wherein the purity of the m-cresol is more than 99%. Then, firstly, adopting a nitrogen blowing-off method for blowing-off for 1 hour, then adopting a vacuum pumping-off method, wherein the vacuum degree of pressure swing desorption is 720-50mmHg, and collecting a product from the beginning of pumping-off to the end of pumping-off at a product outlet of the shape-selective adsorption unit to obtain the product, namely the p-cresol, wherein the purity of the p-cresol is more than 99%.
Example 4:
the o-cresol collected in example 1 and the p-cresol collected in example 3 were mixed and then fed into a preheater by a mass metering pump, the temperature of the preheater was set at 250 ℃, and the mixture was fully preheated and then fed into an isomerization reaction unit. Strongly acidic flaky molecular sieves are filled in the isomerization reaction unit in advance to serve as isomerization catalysts, the molecular sieves are prepared into 1.5-3MM clover type catalyst particles after being molded, isomerization reaction is carried out under the reaction conditions that the reaction pressure is 3.0MPa, the reaction temperature is 350 ℃, and the weight space velocity WHSV is 1.8h < -1 >, and the selectivity of a mixture of o-cresol, m-cresol and p-cresol in the composition of a reaction product is larger than 96% after gas-liquid separation and condensation.
Claims (10)
1. A reaction and separation composite process for selectively producing cresol from phenol is characterized in that phenol is used as a raw material, and the composite process method comprises the following steps:
step 1, phenol and methanol are subjected to a hydrogenation reaction to prepare a mixed cresol product containing o, m and p;
step 2, separating the o-cresol, the m-cresol and the p-cresol obtained in the step 1 through multi-tower rectification, firstly separating and extracting the o-cresol, and obtaining the m-cresol and the p-cresol;
step 3, separating the m-cresol and the p-cresol mixture obtained in the step 2 through gas phase pressure swing shape selective adsorption to respectively obtain p-cresol and m-cresol;
and 4, converting the o-cresol and the p-cresol obtained in the step 2 and the step 3 into m-cresol through liquid phase isomerization reaction, thereby obtaining o-cresol, m-cresol and p-cresol mixed cresol, adding the o-cresol, m-cresol and p-cresol mixed cresol of the phenol and methanol alkylation reaction product in the step 1, and then carrying out rectification in the step 2 and gas phase pressure-swing shape-selective adsorption separation in the step 3 to obtain m-cresol, p-cresol or o-cresol products.
2. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 1, characterized in that: after the phenol and the methanol are preheated in the step 1, hydrogen is used as a carrier gas to react, and the molar ratio of the phenol to the methanol is 1.5: 1-10: 1. the pressure is 0.5-5.0MPa, the temperature is 150--1Under the reaction condition of (1) and under the action of solid acid catalyst making hydrogenation alkylation reaction so as to obtain the reaction product containing o-, m-and p-mixed cresol.
3. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 2, characterized in that: the solid acid catalyst comprises one of an acidic macroporous dodecacyclic molecular sieve, a supported phosphoric acid solid acid, a macroporous high-temperature-resistant acidic resin and a supported heteropoly acid solid acid, and a hydrogenation activity cocatalyst containing one or more metal elements of Mo, Co, Pd and Pt is added into the used solid acid catalyst, and the solid acid catalyst has the reaction performance of hydroalkylation transfer.
4. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 1, characterized in that: step 2, rectifying and separating the hydroalkylation product containing o-cresol, m-cresol and p-cresol mixture obtained in the step 1 through a gas-liquid separation tower and two rectifying towers, pressurizing the gas at the top of the gas-liquid separation tower through a compressor, circulating the gas to the inlet of a hydroalkylation reactor, removing a water layer from the bottom of the gas-liquid separation tower, and allowing an intermediate oil phase to enter a first rectifying tower; pressurizing phenol at the top of the first rectifying tower by using a pump, circulating the phenol to the inlet of the hydroalkylation reactor, and feeding materials at the bottom of the first rectifying tower into a second rectifying tower; the distillate at the top of the second rectifying tower is o-cresol, the material separated from the middle layer of the rectifying tower is m-cresol and p-cresol, and the material at the bottom of the rectifying tower is xylenol.
5. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 4, wherein: the rectifying tower comprises one or the combination of two of a bulk packed tower, a regular packed tower, a sieve plate tower or a floating valve plate tower.
6. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 1, characterized in that: preheating and vaporizing the material containing m-cresol and p-cresol obtained in the step 2, introducing the mixed gas of m-cresol and p-cresol into an adsorption separation tower unit filled with a shape-selective adsorbent to perform gas phase pressure swing adsorption separation, and firstly, flowing out of a tower to be condensed to obtain an m-cresol product; stopping collecting m-cresol product when p-cresol begins to flow out; adopting nitrogen or hydrogen to blow off m-cresol and p-cresol in the adsorbent bed layer of the adsorption separation tower unit, then pumping off the adsorbent bed layer through vacuum, desorbing the p-cresol adsorbed in the holes, and condensing to obtain a p-cresol product.
7. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 6, wherein: the shape-selective adsorbent is a mesopore ten-membered ring molecular sieve shape-selective adsorbent modified by liquid-phase chemical silicon deposition or boron deposition.
8. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 6, wherein: the operation temperature of the gas phase pressure swing adsorption separation is 205-230 ℃, and the vacuum degree of the gas phase pressure swing desorption is 720-5 mmHg.
9. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 1, characterized in that: and 4, mixing the o-cresol and the p-cresol obtained in the step 2 and the step 3 or independently using the o-cresol and the p-cresol as reaction raw materials, injecting the mixture into a liquid phase isomerization reaction unit to carry out liquid phase isomerization reaction to obtain an isomerization reaction product, wherein the liquid phase isomerization reaction product comprises o-cresol, m-cresol and p-cresol.
10. The integrated reaction and separation process for the selective production of cresols from phenol according to claim 1, characterized in that: the liquid phase isomerization reaction is carried out at the reaction pressure of 2.0-8.0MPa, the temperature of 220-420 ℃ and the weight space velocity WHSV of 0.5-8.0h-1Under the reaction condition of (1) and an isomerization catalyst, carrying out isomerization reaction to generate o-, m-and p-mixed cresol products, wherein the isomerization catalyst is a solid acid type catalyst and contains one of strong acid flaky molecular sieves or supported phosphoric acid solid acids.
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| CN114570053B (en) * | 2022-03-22 | 2024-04-16 | 山西永东化工股份有限公司 | Method for separating and purifying o-, m-and p-cresol of coal tar |
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