CN112574008A - Method for synthesizing 2, 6 di-tert-butylphenol by using environment-friendly heterogeneous catalyst - Google Patents
Method for synthesizing 2, 6 di-tert-butylphenol by using environment-friendly heterogeneous catalyst Download PDFInfo
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- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 24
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 24
- 239000011973 solid acid Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000000110 cooling liquid Substances 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 69
- 239000000047 product Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- ZDWSNKPLZUXBPE-UHFFFAOYSA-N 3,5-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1 ZDWSNKPLZUXBPE-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
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- 239000000543 intermediate Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 specifically Chemical compound 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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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
- C07C37/68—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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- 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
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Abstract
The embodiment of the invention discloses a method for synthesizing 2, 6-di-tert-butylphenol by using an environment-friendly heterogeneous catalyst, which belongs to the technical field of chemical synthesis and comprises the following steps: s1, feeding a reaction raw material, namely tertiary butanol, from a feed inlet at the top end of the first reactor through a feed pump, putting a solid acid catalyst into the first reactor, and performing dehydration reaction to generate an isobutene solution; s2, conveying the reaction liquid from a discharge hole at the top end of the reactor to a cooler for cooling, and conveying the obtained cooling liquid to a primary rectifying tower for rectification; the preparation process is simple, the reaction pressure is stable, the novel heterogeneous catalyst is used for replacing an L acid or aluminum salt homogeneous catalyst in the original production process by introducing a heterogeneous catalyst reaction system, and the process optimization design is performed on the 2, 6 di-tert-butylphenol synthesis reaction unit and the separation unit according to the characteristics of the novel heterogeneous catalyst, so that the aims of simplifying the flow, saving energy and protecting environment are fulfilled, the economic benefit is improved, and the requirement of large-scale industrial green production is met.
Description
Technical Field
The embodiment of the invention relates to the technical field of chemical synthesis, in particular to a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst.
Background
2, 6-di-tert-butylphenol, British name 2DTBP, molecular formula C14H22O, soluble in caustic and common organic solvents such as ethanol, etc. The 2, 6-di-tert-butylphenol is used for preparing hindered phenol antioxidants, rubber anti-aging agents, cresol-formaldehyde resins and plasticizers, can be used as disinfectants in medicine, can be used for preparing surfactants, can be used for preparing various excellent antioxidants and light stabilizers, and can also be used for preparing antioxidants of natural rubber and synthetic plastics, fuel stabilizers, ultraviolet absorbers, pesticides, dye intermediates and the like.
The existing 2, 6-di-tert-butylphenol is widely applied in industry, and various preparation process researches on 2, 6-di-tert-butylphenol are carried out, for example, patent CN1935764A discloses a preparation method of 2, 6-di-tert-butylphenol alkylation liquid, wherein aluminum powder is used as a catalyst to catalyze the reaction of phenol and isobutene, the conversion rate of phenol is more than 85%, the product yield can reach 80%, but the reaction system is a high-pressure reaction, the pressure in the reaction process is unstable, the process operation difficulty coefficient is large, the reaction waste liquid treatment difficulty is large, and the environmental protection cost is high; patent CN 108503513A discloses a preparation method of 2, 6-di-tert-butylphenol, triisobutylaluminum and aluminum trichloride are used as catalysts to catalyze phenol to react with isobutene or isobutylamine, and the yield of the final product can reach 98.5%. The preparation method has mild reaction conditions, high product yield and low possibility of generating byproducts, but the reaction needs to undergo multi-step temperature rise and reduction, the process is complicated, the operation is complex, and simultaneously, the waste water containing metal ions is generated, so that the preparation method has a great pollution effect on the environment; patent CN 102906059B discloses a method for producing 2, 6-di-tert-butylphenol, which takes alumina as a catalyst, and makes phenol and C4 raffinate containing isobutene and 1-butene or 2-butene react under the reaction conditions of 70-130 ℃ and normal pressure, wherein the reaction raw materials are easily available, but the reaction conversion rate is low, the composition of reaction liquid is complex, and the subsequent separation difficulty is large; patent CN 1844071a this patent provides a new process for preparing 2, 6-di-tert-butylphenol with high selectivity by reacting phenols with isobutylene in the presence of triphenoxy aluminum catalyst. The reaction is carried out at high temperature and high pressure, the reaction yield can reach more than 80%, the reaction selectivity is good, but the catalyst is easy to dissolve in the reaction solution, the subsequent treatment cost is high, the metal ion wastewater is easy to generate, and the environmental protection cost is high.
Based on the above, the invention designs a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst, so as to solve the problems.
Disclosure of Invention
The embodiment of the invention provides a method for synthesizing 2, 6-di-tert-butylphenol by using an environment-friendly heterogeneous catalyst, which aims to solve the technical problems in the background art.
The embodiment of the invention provides a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst. In one possible embodiment, the method comprises the following steps:
s1, feeding a reaction raw material, namely tertiary butanol, from a feed inlet at the top end of the first reactor through a feed pump, putting a solid acid catalyst into the first reactor, and performing dehydration reaction to generate an isobutene solution;
s2, conveying the reaction liquid from a discharge hole at the top end of the reactor to a cooler for cooling, conveying the obtained cooling liquid to a first-stage rectifying tower for rectification, discharging the rectified tert-butyl alcohol from the top of the first-stage rectifying tower and refluxing to a first reactor, and discharging water from the bottom of the first-stage rectifying tower into a waste treatment device;
s3, rectifying the rest part in the cooler into a second-stage rectifying tower to obtain high-purity isobutene, introducing the isobutene into a second reactor through a top material outlet of the second-stage rectifying tower under stable pressure by using a discharge pump, and communicating the bottom of the second-stage rectifying tower with a waste liquid treatment device;
s4, heating the second reactor, allowing reaction liquid to enter a third-stage rectifying tower after the reaction liquid exits the second reactor, allowing unreacted reaction raw materials, namely isobutene and phenol, to exit from a discharge port at the top of the third-stage rectifying tower, allowing the unreacted isobutene and phenol to enter a flash tank for separation, allowing the unreacted raw materials in the third-stage rectifying tower to flow back to the second reactor for continuous reaction, and allowing reaction liquid exiting from the bottom of the third-stage rectifying tower to enter a fourth-stage rectifying tower;
and S5, discharging reaction byproducts from the top of the four-stage rectifying tower, and feeding the crude product of the 2, 6 di-tert-butylphenol discharged from the bottom of the four-stage rectifying tower into a five-stage rectifying tower to refine the 2, 6 di-tert-butylphenol.
The embodiment of the invention provides a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst. In a possible embodiment, the catalyst for the dehydration reaction in S1 is a high temperature resistant resin catalyst, and the solid acid catalyst is one of a resin type solid acid catalyst or a silicon-based solid acid catalyst.
The embodiment of the invention provides a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst. In a possible scheme, the first reactor and the second reactor are one of a tower reactor, a tank reactor, a fixed bed reactor or a fluidized bed reactor.
The embodiment of the invention provides a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst. In one possible approach, the amount ratio of phenol to isobutylene species in S4 is 1: (2-3).
The embodiment of the invention provides a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst. In one possible scheme, the tertiary butanol in S1 enters the feed material of the reactor IThe volume space velocity is 0.1-10h-1(ii) a The mass space velocity of the feeding of the isobutene in the S3 into the second reactor is 1-10h-1。
The embodiment of the invention provides a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst. In one possible scheme, the reaction temperature of the reactor I in the S1 is 50-120 ℃, and the reaction pressure is 1-12 bar; the reaction temperature range of the second reactor in the S3 is 40-100 ℃, and the reaction pressure range is 0.1-10 bar.
The embodiment of the invention provides a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst. In one possible embodiment, the flash temperature of the flash tank in S4 is in the range of 0-40 ℃.
The embodiment of the invention provides a method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst. In a possible variant, the operating temperature of the primary rectification column ranges from 20 to 250 ℃, the operating pressure ranges from 0.6 to 1.5bar, and the operating reflux ratio ranges from (1 to 30): 1; the operating temperature range of the secondary rectifying tower is (-20) -120 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-20): 1; the operating temperature range of the three-stage rectifying tower is 0-300 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-20): 1; the operating temperature range of the four-stage rectifying tower is 50-300 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-40): 1; the operating temperature range of the five-stage rectifying tower is (-150) -120 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-25): 1.
based on the scheme, the preparation process is simple, the reaction pressure is stable, the novel heterogeneous catalyst is used for replacing an L acid or aluminum salt homogeneous catalyst in the original production process by introducing a heterogeneous catalyst reaction system, the process optimization design is carried out on the 2, 6 di-tert-butylphenol synthesis reaction unit and the separation unit according to the characteristics of the novel heterogeneous catalyst, the goals of flow simplification, energy conservation and environmental protection are achieved, the economic benefit is improved, and the requirement of large-scale industrial green production is met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a block diagram of a synthesis scheme of the present invention;
FIG. 2 is a schematic diagram of an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "axial," "radial," "circumferential," and the like are used in the indicated orientations and positional relationships based on the drawings for convenience in describing and simplifying the description, but do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the invention.
In the present invention, unless otherwise specifically stated or limited, the terms "mounted," "connected," "fixed," and the like are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally formed; the connection can be mechanical connection, electrical connection or communication connection; either directly or indirectly through intervening media, either internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The technical solution of the present invention will be described in detail below with specific examples. The following several specific embodiments may be combined with each other, and details of the same or similar concepts or processes may not be repeated in some embodiments.
FIG. 1-2 shows a method for synthesizing 2, 6-di-tert-butylphenol by using an environment-friendly heterogeneous catalyst provided by the invention; the method comprises the following steps:
s1, feeding a reaction raw material, namely tertiary butanol, from a feed inlet at the top end of the first reactor through a feed pump, putting a solid acid catalyst into the first reactor, and performing dehydration reaction to generate an isobutene solution;
s2, conveying the reaction liquid from a discharge hole at the top end of the reactor to a cooler for cooling, conveying the obtained cooling liquid to a first-stage rectifying tower for rectification, discharging the rectified tert-butyl alcohol from the top of the first-stage rectifying tower and refluxing to a first reactor, and discharging water from the bottom of the first-stage rectifying tower into a waste treatment device;
s3, rectifying the rest part in the cooler into a second-stage rectifying tower to obtain high-purity isobutene, introducing the isobutene into a second reactor through a top material outlet of the second-stage rectifying tower under stable pressure by using a discharge pump, and communicating the bottom of the second-stage rectifying tower with a waste liquid treatment device;
s4, heating the second reactor, allowing reaction liquid to enter a third-stage rectifying tower after the reaction liquid exits the second reactor, allowing unreacted reaction raw materials, namely isobutene and phenol, to exit from a discharge port at the top of the third-stage rectifying tower, allowing the unreacted isobutene and phenol to enter a flash tank for separation, allowing the unreacted raw materials in the third-stage rectifying tower to flow back to the second reactor for continuous reaction, and allowing reaction liquid exiting from the bottom of the third-stage rectifying tower to enter a fourth-stage rectifying tower;
and S5, discharging reaction byproducts (polymers of mono-tert-butylphenol and isobutene and the like) from the top of the four-stage rectifying tower, and feeding the crude product of the 2, 6-di-tert-butylphenol discharged from the bottom of the four-stage rectifying tower into a five-stage rectifying tower to refine the 2, 6-di-tert-butylphenol.
Through the above, it is found that in the process of synthesizing 2, 6-di-tert-butylphenol by using the environment-friendly heterogeneous catalyst, tert-butyl alcohol can be dehydrated to generate isobutene under the action of the catalyst, isobutene and phenol are subjected to alkylation reaction under the action of the heterogeneous catalyst to generate 2, 6-di-tert-butylphenol, and the product is rectified to generate 2, 6-di-tert-butylphenol, specifically, tert-butyl alcohol serving as a reaction raw material enters from the upper end of a first reactor, and reacts under the catalytic action of the catalyst in the reactor to generate isobutene through dehydration; cooling isobutene liquid through a cooler, introducing the obtained cooling liquid into a first-stage rectifying tower to refine tert-butyl alcohol in the cooling liquid, discharging the tert-butyl alcohol from a discharge hole at the top of the tower, then feeding the cooled cooling liquid into a first-stage reactor again to participate in reaction by using a reflux device, rectifying the cooled gaseous isobutene in a second-stage rectifying tower, discharging the gas at the bottom of the tower, wherein the gas mainly comprises a small amount of tert-butyl alcohol and water, feeding the gas together into the first-stage rectifying tower for treatment, discharging the product isobutene from a discharge hole at the top of the second-stage rectifying tower, feeding the product isobutene and the reaction raw material phenol together from a feed hole of a second-stage reactor, feeding the reaction liquid out of the reactor and then into a third-stage rectifying tower, removing unreacted reaction raw materials from the top of the tower, feeding unreacted isobutene, byproducts and; the reaction liquid led out from the tower bottom enters a four-stage rectifying tower, a small amount of unreacted phenol is removed from the tower top of the four-stage rectifying tower, the product liquid enters a five-stage rectifying tower from the tower bottom, 2-tert-butylphenol is removed from the tower top, and a refined product 2, 6-di-tert-butylphenol is obtained from the tower bottom;
as shown in FIG. 2, the first reactor is preferably a tower reactor, the top of the first reactor is provided with a discharge hole, and the upper part of one side of the tower wall is provided with a feed hole; wherein, the feed inlet is connected with the feed arrangement of tertiary butanol, and the discharge gate connects gradually cooler, isobutene feedstock pump, one-level rectifying column, second grade rectifying column etc. wherein, the one-level rectifying column is got into to cooler discharge gate liquid phase, and the second grade rectifying column is connected to the gaseous phase discharge gate. A discharge hole at the top of the first-stage rectification tower is connected with the first reactor, and a discharge hole at the bottom of the tower is connected with a waste liquid treatment device; the discharge hole at the top of the second-stage rectifying tower is connected with the second reactor, and the discharge hole at the bottom of the tower is connected with the first-stage rectifying tower. The second reactor is preferably a fixed bed reactor and is provided with two feed inlets, the first path is connected with the secondary rectifying tower, and the second path is connected with the phenol feeding device; one path of outlet is connected with the third-stage rectifying tower. The discharge hole at the top of the first-stage rectification tower is connected with the tower reactor, and the discharge hole at the bottom of the first-stage rectification tower is connected with a waste liquid treatment device. A discharge hole at the top of the second-stage rectification tower is connected with an isobutene raw material pump, and the outlet of the raw material pump is connected with the fixed bed reactor; the discharge hole at the bottom of the second-stage rectifying tower is connected with the first-stage rectifying tower. The top of the third-stage rectifying tower is connected with a flash tank, two streams of materials are discharged from the flash tank, the isobutene separated by flash evaporation enters the reactor again for reaction through a first path of discharge port, and a second path of discharge port is connected with a waste liquid treatment device; the discharge hole at the bottom of the third-stage rectifying tower is connected with a fourth-stage rectifying tower. The material outlet of the tower bottom of the four-stage rectifying tower is connected with a byproduct collecting tank, the material outlet of the tower bottom is connected with a five-stage rectifying tower, and the material outlet of the tower bottom of the five-stage rectifying tower is connected with a 2, 6 di-tert-butylphenol product storage tank.
Optionally, the catalyst for the dehydration reaction in S1 is a high temperature resistant resin catalyst, and the solid acid catalyst is one of a resin type solid acid catalyst or a silicon-based solid acid catalyst. It is to be noted that, in this embodiment, the novel solid acid catalyst includes a CD550 type resin catalyst, a CD650 type resin catalyst, a ZGC-111 type resin catalyst, a CS-001 type solid acid catalyst, a CS-N-001 type solid acid catalyst, and the like, wherein the reaction catalyst for preparing isobutylene by dehydrating t-butanol is preferably a CD650 type resin solid acid catalyst; the catalyst for preparing 2, 6 di-tert-butylphenol by reacting phenol with isobutylene is preferably a ZGC-111 type resin catalyst.
The first reactor and the second reactor are preferably one of a tower reactor, a tank reactor, a fixed bed reactor, and a fluidized bed reactor, and the first reactor is preferably a tower reactor, and the second reactor is preferably a fixed bed reactor, in order to further promote the reaction.
More specifically, the quantity ratio of phenol to isobutene in S4 is 1: (2-3), the amount ratio of phenol to isobutylene species is preferably 1: 2.5.
further, the mass space velocity of the tertiary butanol in the S1 fed into the first reactor is 0.1-10h-1(ii) a The mass space velocity of the feeding of the isobutene in the S3 into the second reactor is 1-10h-1(ii) a The preferred mass space velocity of tertiary butanol is 3h-1The feed mass space velocity of isobutene is 2h-1。
Preferably, the reaction temperature of the reactor I in the S1 ranges from 50 ℃ to 120 ℃, and the reaction pressure ranges from 1bar to 12 bar; the reaction temperature range of the second reactor in the S3 is 40-100 ℃, and the reaction pressure range is 0.1-10 bar; the reaction temperature of the first reactor is preferably 130 ℃, the reaction pressure is 5bar, the reaction temperature of the second reactor is 80 ℃, and the reaction pressure is 1.2 bar.
Further, the flash temperature of the flash tank in the S4 ranges from 0 ℃ to 40 ℃; the flash temperature is preferably 20 ℃.
And the operating temperature range of the primary rectifying tower is 20-250 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-30): 1; the operating temperature range of the secondary rectifying tower is (-20) -120 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-20): 1; the operating temperature range of the three-stage rectifying tower is 0-300 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-20): 1; the operating temperature range of the four-stage rectifying tower is 50-300 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-40): 1; the operating temperature range of the five-stage rectifying tower is (-150) -120 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-25): 1; preferably, the tower top temperature of the primary rectifying tower is 222.5 ℃, the tower bottom temperature is 82 ℃, the operating pressure is 1.0bar, and the reflux ratio is 3; the tower top temperature of the secondary rectifying tower is-8 ℃, the tower bottom temperature is 80 ℃, the operating pressure is 1bar, and the reflux ratio is 3; the tower top temperature of the three-stage rectifying tower is 22 ℃, the tower bottom temperature is 250 ℃, the operating pressure is 1bar, and the reflux ratio is 2.8; the tower top temperature of the four-stage rectifying tower is 180 ℃, the tower bottom temperature is 250 ℃, the operating pressure is 0.9bar, and the reflux ratio is 27.8; the tower top temperature of the five-stage rectifying tower is 220 ℃, the tower bottom temperature is 255 ℃, the operation pressure is 0.9bar, and the reflux ratio is 14.
Example one
As shown in the process flow of figure 2, 4kg of CD650 type resin catalyst is laid in a reactor I, tertiary butanol raw material enters the reactor I, the temperature is raised to 100 ℃, reaction liquid obtained through the reaction enters a cooler through the catalytic action, the cooling liquid enters a first-stage filler rectifying tower, the height of the first-stage filler rectifying tower is about 2.5m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is Raschig rings, and the tertiary butanol is led out from the tower top and flows back to the reactor I. The gas in the cooler enters a secondary filler rectifying tower, the height of the secondary filler rectifying tower is about 2m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is Raschig ring, and an isobutene product is discharged from the top of the tower, so that the purity reaches 99.99%; laying ZGC-111 type resin solid acid catalyst of about 5kg in a fixed bed reactor, feeding isobutene and phenol led out from the top of a second-stage filler rectifying tower after mixing and feeding into the fixed bed reactor with the laid catalyst, heating the reactor to 80 ℃ to start reaction, feeding reaction liquid discharged from the reactor into a third-stage filler rectifying tower, wherein the height of the third-stage filler rectifying tower is about 1m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is a Raschig ring, discharging from the top of the rectifying tower after rectification separation, introducing into a flash tank, and feeding isobutene gas phase into a second reactor again after flash separation for reaction. The bottom liquid of the third-level filler rectifying tower enters a fourth-level filler rectifying tower, the height of the fourth-level filler rectifying tower is about 3m, the diameter of the tower is 0.2m, the reflux ratio is 28, and the main fillers are mixed fillers such as Raschig rings, pall rings and the like. The bottom liquid after rectification and separation enters a five-stage packing rectifying tower, the height of the five-stage packing rectifying tower is about 2.5m, the diameter of the tower is 0.2m, the reflux ratio is 14, and main packing is a metal ring saddle and the like. In the reaction, the conversion rate of isobutene reaches more than 95%, the selectivity of 2, 6-di-tert-butylphenol in the product reaches more than 95%, the speed of the 2, 6-di-tert-butylphenol obtained by rectification is 1.836kmol/h, and the purity of the product can reach more than 99.8%.
Example two
As shown in the process flow of figure 2, 4kg of CD650 type resin catalyst is laid in a reactor I, tertiary butanol raw material enters the reactor I, the temperature is raised to 100 ℃, reaction liquid obtained through the reaction enters a cooler through the catalytic action, the cooling liquid enters a first-stage filler rectifying tower, the height of the first-stage filler rectifying tower is about 2.5m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is Raschig rings, and the tertiary butanol is led out from the tower top and flows back to the reactor I. The gas in the cooler enters a secondary filler rectifying tower, the height of the secondary filler rectifying tower is about 2m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is Raschig ring, and an isobutene product is discharged from the top of the tower, so that the purity reaches 99.99%; laying about 5kg of CS-N-001 type solid acid catalyst in a fixed bed reactor, feeding isobutene and phenol led out from the top of a primary filler rectifying tower into the fixed bed reactor with the laid catalyst after mixing, heating the reactor to 90 ℃ to start reaction, feeding reaction liquid discharged from the reactor into a secondary filler rectifying tower, wherein the height of the secondary filler rectifying tower is about 1m, the diameter of the tower is 0.2m, the reflux ratio is 2.8, the main filler is Raschig rings, discharging from the top of the rectifying tower after rectification separation is led into a flash tank, and feeding the isobutene gas phase into a second reactor again after flash separation for reaction. And the tower bottom liquid of the second-level filler rectifying tower enters a third-level filler rectifying tower, the height of the third-level filler rectifying tower is about 3m, the tower diameter is 0.2m, the reflux ratio is 25, and the main fillers are mixed fillers such as Raschig rings, pall rings and the like. The tower bottom liquid after rectification separation enters a four-stage filler rectification tower, the height of the four-stage filler rectification tower is about 2.5m, the diameter of the tower is 0.2m, the reflux ratio is 14, and main fillers are metal ring square saddles and the like. In the reaction, the conversion rate of isobutene reaches more than 85%, the selectivity of 2, 6-di-tert-butylphenol in the product reaches more than 95%, the speed of the 2, 6-di-tert-butylphenol obtained by rectification is 1.81kmol/h, and the purity of the product can reach more than 99.8%.
EXAMPLE III
As shown in the process flow of figure 2, 4kg of CD550 type resin catalyst is laid in a first reactor, tertiary butanol raw material enters the first reactor, reaction liquid obtained through the reaction enters a cooler through the catalysis, the cooling liquid enters a first-stage filler rectifying tower, the height of the first-stage filler rectifying tower is about 2.5m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is a Raschig ring, and the tertiary butanol is led out from the tower top and flows back to the first reactor. The gas in the cooler enters a secondary filler rectifying tower, the height of the secondary filler rectifying tower is about 2m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is Raschig ring, and an isobutene product is discharged from the top of the tower, so that the purity reaches 99.99%; laying about 5kg of CS-001 type resin solid acid catalyst in a fixed bed reactor, feeding isobutene and phenol led out from the top of a primary filler rectifying tower after mixing and feeding into the fixed bed reactor with the laid catalyst, heating the reactor to 80 ℃ to start reaction, feeding reaction liquid discharged from the reactor into a secondary filler rectifying tower, wherein the height of the secondary filler rectifying tower is about 1m, the diameter of the tower is 0.2m, the reflux ratio is 2.6, the main filler is a Raschig ring, discharging from the top of the rectifying tower after rectification separation, guiding into a flash tank, and feeding isobutene gas phase into a second reactor again after flash separation for reaction. And the tower bottom liquid of the second-level filler rectifying tower enters a third-level filler rectifying tower, the height of the third-level filler rectifying tower is about 3m, the tower diameter is 0.2m, the reflux ratio is 26, and the main fillers are mixed fillers such as Raschig rings, pall rings and the like. And the tower bottom liquid after rectification and separation enters a four-stage filler rectification tower, the height of the four-stage filler rectification tower is about 2.5m, the diameter of the tower is 0.2m, the reflux ratio is 7, and main fillers are metal ring square saddles and the like. In the reaction, the conversion rate of isobutene reaches more than 95%, the selectivity of 2, 6-di-tert-butylphenol in the product reaches more than 90%, the speed of the 2, 6-di-tert-butylphenol obtained by rectification is 1.82kmol/h, and the purity of the product can reach more than 99.7%.
Example four
As shown in the process flow of figure 2, 4kg of CD550 type resin catalyst is laid in a first reactor, tertiary butanol raw material enters the first reactor, the temperature is raised to 100 ℃, reaction liquid obtained through the reaction enters a cooler through the catalytic action, the cooling liquid enters a first-stage filler rectifying tower, the height of the first-stage filler rectifying tower is about 2.5m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is Raschig rings, and the tertiary butanol is led out from the tower top and flows back to the first reactor. The gas in the cooler enters a secondary filler rectifying tower, the height of the secondary filler rectifying tower is about 2m, the diameter of the tower is 0.2m, the reflux ratio is 3, the main filler is Raschig ring, and an isobutene product is discharged from the top of the tower, so that the purity reaches 99.99%; laying ZGC-111 type resin solid acid catalyst of about 5kg in a fixed bed reactor, mixing and feeding isobutene and phenol led out from the top of a primary filler rectifying tower into the fixed bed reactor with the laid catalyst, heating the reactor to 90 ℃ to start reaction, feeding reaction liquid discharged from the reactor into a secondary filler rectifying tower, wherein the height of the secondary filler rectifying tower is about 1m, the diameter of the tower is 0.2m, the reflux ratio is 2.5, the main filler is Raschig ring, discharging from the top of the rectifying tower after rectification separation is led into a flash tank, and reacting isobutene gas phase in a second reactor after flash separation. And the tower bottom liquid of the second-level filler rectifying tower enters a third-level filler rectifying tower, the height of the third-level filler rectifying tower is about 3m, the tower diameter is 0.2m, the reflux ratio is 26, and the main fillers are mixed fillers such as Raschig rings, pall rings and the like. And the tower bottom liquid after rectification and separation enters a four-stage filler rectification tower, the height of the four-stage filler rectification tower is about 2.5m, the diameter of the tower is 0.2m, the reflux ratio is 7, and main fillers are metal ring square saddles and the like. In the reaction, the conversion rate of isobutene reaches more than 85%, the selectivity of 2, 6-di-tert-butylphenol in the product reaches more than 90%, the speed of the 2, 6-di-tert-butylphenol obtained by rectification is 1.8kmol/h, and the purity of the product can reach more than 99.7%.
In the present invention, unless otherwise explicitly specified or limited, the first feature "on" or "under" the second feature may be directly contacting the first feature and the second feature or indirectly contacting the first feature and the second feature through an intermediate.
Also, a first feature "on," "above," and "over" a second feature may mean that the first feature is directly above or obliquely above the second feature, or that only the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lower level than the second feature.
In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example" or "some examples," or the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for synthesizing 2, 6 di-tert-butylphenol by using an environment-friendly heterogeneous catalyst is characterized by comprising the following steps:
s1, feeding a reaction raw material, namely tertiary butanol, from a feed inlet at the top end of the first reactor through a feed pump, putting a solid acid catalyst into the first reactor, and performing dehydration reaction to generate an isobutene solution;
s2, conveying the reaction liquid from a discharge hole at the top end of the reactor to a cooler for cooling, conveying the obtained cooling liquid to a first-stage rectifying tower for rectification, discharging the rectified tert-butyl alcohol from the top of the first-stage rectifying tower and refluxing to a first reactor, and discharging water from the bottom of the first-stage rectifying tower into a waste treatment device;
s3, rectifying the rest part in the cooler into a second-stage rectifying tower to obtain high-purity isobutene, introducing the isobutene into a second reactor through a top material outlet of the second-stage rectifying tower under stable pressure by using a discharge pump, and communicating the bottom of the second-stage rectifying tower with a waste liquid treatment device;
s4, heating the second reactor, allowing reaction liquid to enter a third-stage rectifying tower after the reaction liquid exits the second reactor, allowing unreacted reaction raw materials, namely isobutene and phenol, to exit from a discharge port at the top of the third-stage rectifying tower, allowing the unreacted isobutene and phenol to enter a flash tank for separation, allowing the unreacted raw materials in the third-stage rectifying tower to flow back to the second reactor for continuous reaction, and allowing reaction liquid exiting from the bottom of the third-stage rectifying tower to enter a fourth-stage rectifying tower;
and S5, discharging reaction byproducts from the top of the four-stage rectifying tower, and feeding the crude product of the 2, 6 di-tert-butylphenol discharged from the bottom of the four-stage rectifying tower into a five-stage rectifying tower to refine the 2, 6 di-tert-butylphenol.
2. The method for synthesizing 2, 6-di-tert-butylphenol by using the environment-friendly heterogeneous catalyst as claimed in claim 1, wherein the catalyst for the dehydration reaction in S1 is a high temperature resistant resin catalyst, and the solid acid catalyst is one of a resin type solid acid catalyst and a silicon based solid acid catalyst.
3. The method for synthesizing 2, 6 di-tert-butylphenol by using the environment-friendly heterogeneous catalyst as claimed in claim 1, wherein the first reactor and the second reactor are one of a tower reactor, a tank reactor, a fixed bed reactor and a fluidized bed reactor.
4. The method for synthesizing 2, 6 di-tert-butylphenol by using the environment-friendly heterogeneous catalyst as claimed in claim 1, wherein the amount ratio of phenol to isobutylene in S4 is 1: (2-3).
5. The method for synthesizing 2, 6 di-tert-butylphenol by using the environment-friendly heterogeneous catalyst as claimed in claim 1, wherein the mass space velocity of the feed of tert-butanol in S1 into the reactor I is 0.1-10h-1(ii) a The mass space velocity of the feeding of the isobutene in the S3 into the second reactor is 1-10h-1。
6. The method for synthesizing 2, 6 di-tert-butylphenol by using the environment-friendly heterogeneous catalyst as claimed in claim 1, wherein the reaction temperature of the reactor I in S1 is 50-120 ℃, and the reaction pressure is 1-12 bar; the reaction temperature range of the second reactor in the S3 is 40-100 ℃, and the reaction pressure range is 0.1-10 bar.
7. The method for synthesizing 2, 6 di-tert-butylphenol by using the environment-friendly heterogeneous catalyst as claimed in claim 1, wherein the flash temperature of the flash tank in S4 is in the range of 0-40 ℃.
8. The method for synthesizing 2, 6 di-tert-butylphenol by using the environment-friendly heterogeneous catalyst as claimed in claim 1, wherein the operating temperature of the primary rectifying tower is 20-250 ℃, the operating pressure is 0.6-1.5bar, and the operating reflux ratio is (1-30): 1; the operating temperature range of the secondary rectifying tower is (-20) -120 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-20): 1; the operating temperature range of the three-stage rectifying tower is 0-300 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-20): 1; the operating temperature range of the four-stage rectifying tower is 50-300 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-40): 1; the operating temperature range of the five-stage rectifying tower is (-150) -120 ℃, the operating pressure range is 0.6-1.5bar, and the operating reflux ratio is (1-25): 1.
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