CN106831355A - A kind of method for mixing the alkylation of M-and P-cresols high pressure fixed bed - Google Patents
A kind of method for mixing the alkylation of M-and P-cresols high pressure fixed bed Download PDFInfo
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- CN106831355A CN106831355A CN201710027396.2A CN201710027396A CN106831355A CN 106831355 A CN106831355 A CN 106831355A CN 201710027396 A CN201710027396 A CN 201710027396A CN 106831355 A CN106831355 A CN 106831355A
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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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
Abstract
The present invention is a kind of method for mixing the alkylation of M-and P-cresols high pressure fixed bed.The method is comprised the following steps：Alkylating agent is pressurized liquefied, then with mixed phenol together injecting reactor in, keep fixed bed reactors pressure be 1.7 ~ 4.2MPa, temperature be 50 ~ 110 DEG C, air speed be 0.1 ~ 5h‑1Lower reaction, obtains the autohemagglutination product of isobutene, single tert-butyl group product of M-and P-cresols and the dual-tert-butyl product of M-and P-cresols.Wherein, reactor is fixed bed reactors；Alkylating agent is isobutene and auxiliary agent, and the volume of auxiliary agent is the 70 ~ 90% of alkylating agent cumulative volume；Mol ratio isobutene：Mixed phenol=0.5 ~ 3：1.Invention increases the utilization ratio of raw material, the conversion ratio of this kind of method metacresol can reach 94.22%, and the conversion ratio of paracresol can reach 89.46%.
Description
Technical field
Separated and its technical field the present invention relates to mix M-and P-cresols, specifically using a kind of isobutene mixed liquor
In M-and P-cresols high pressure fixed bed alkylated reaction is mixed, effective controlling reaction temperature makes the carrying out of reaction high-efficiency and continuous.
Background technology
Alkylation process separates M-and P-cresols because integrated cost is low, and the advantage of good product quality is increasingly subject to each section
The attention of department is ground, and is mixed M-and P-cresols and isobutene alkylated reaction and is obtained the autohemagglutination product of isobutene, M-and P-cresols
The dual-tert-butyl product of single tert-butyl group product, M-and P-cresols, is that mixed in M-and P-cresols alkylation separating technology is important
Process, but such experiment domestic at present exists only in laboratory stage, and based on batch tank reactor, treating capacity is small,
Reaction is incomplete, it is impossible to realize industrialization.And with the development of the industries such as medicine, plastics, the production of domestic high-purity M-and P-cresols
It is difficult to meet the demand in market at all, therefore, it is possible to simple and direct, safety, the tert-butyl group that economic method obtains M-and P-cresols is produced
Thing is significant for isolated high-purity M-and P-cresols.
Chinese patent CN103212438A discloses new catalyst and the separation side that a kind of alkylation methods separates M-and P-cresols
Method, in the presence of novel strong acids catalyst, there is alkyl substitution reaction generation in cresols with methyl tertiary butyl ether(MTBE) for the invention
The di-t-butyl product of M-and P-cresols, but the reaction need to carry out 7~9h under conditions of atmospheric agitation, and reaction efficiency is extremely low, and
Catalyst need to introduce hexamethylene extraction, and processing step is complicated, is unfavorable for environmental protection, and the alkylating agent of the technique is methyl- tert fourth in addition
Base ether, although can generate methyl alcohol after self-polymeric reaction, but alkylation reaction will not occur in the presence of strong acid catalyst, and price is slightly
Height, is unfavorable for controlling cost.
Chinese patent CN101863742A discloses a kind of separation method of new M-and P-cresols, and the invention is urged in strong acid
In the presence of agent, make first between the mixture of M-and P-cresols and isobutene reaction generation 2- Butylated Hydroxytoluenes and the 6- tert-butyl groups
Phenol, but the invention needs 1~2h of reaction in reactor at reaction conditions, although and the reaction time shortens many but program
Equally exist treating capacity small, it is impossible to continuous production, it is impossible to industrialized defect, alkylating agent selects high-purity isobutene, valency in addition
Lattice are expensive, and a large amount of autohemagglutinations of meeting in the presence of strong acid catalyst, and quantity of heat production is big, is unfavorable for operation.
Chinese patent CN104496759A discloses the method that a kind of alkylation of fixed bed separates M-and P-cresols, the invention with
The mixed solution and isobutene gas of M-and P-cresols are that raw material uses immobilized acidic ion liquid for catalyst is sent out in fixed bed
Raw alkylated reaction.Although the invention uses fixed bed reactors, reaction can be carried out continuously, due to using vapour-liquid reaction
Two-phase is insufficient contact, and residence time of the isobutene in mixed phenol liquid is too short, in order to ensure that the two can sufficiently be contacted, just
The air speed of reaction must be reduced, can substantially reduce production efficiency, the alkylating agent of the reaction is high-purity isobutene, valency in addition
Lattice are expensive, are unfavorable for controlling cost.
Deficiency for more than, the present invention uses a kind of method of M-and P-cresols high pressure fixed bed alkylated reaction, the skill
Isobutene mixed liquor is used in art as the alkylating agent of the reaction.
The content of the invention
It is an object of the invention to be directed in current mixing M-and P-cresols alkylated reaction, alkylated reaction overlong time,
Raw material availability is not high, is unfavorable for the defect of the later separation of product, using one kind mixing M-and P-cresols high pressure fixed bed alkyl
The method for changing reaction, the technology uses isobutene mixed liquor as the alkylating agent of the reaction.The alkylating agent can overcome instead
Should in due under the condition of high voltage with the presence of strong acid catalyst isobutene can a large amount of autohemagglutinations, the danger of device temperature runaway can be caused,
So as to ensure that this programme can smoothly drive, and reaction conversion ratio can be enable to reach more than 90%.
The technical scheme is that：
A kind of method for mixing the alkylation of M-and P-cresols high pressure fixed bed, comprises the following steps：
By alkylating agent be forced into 1.7~4.2MPa liquefaction, then with mixed phenol together injecting reactor in, keep fixed bed
The pressure of reactor is 1.7~4.2MPa, and temperature is 50~110 DEG C, is 0.1~5h in air speed-1Lower reaction, obtains isobutene
Single tert-butyl group product and the dual-tert-butyl product of M-and P-cresols of autohemagglutination product, M-and P-cresols.
Wherein, reactor is fixed bed reactors；Alkylating agent is isobutene and auxiliary agent, and the volume of auxiliary agent is alkylating agent
The 70~90% of cumulative volume；Mol ratio isobutene：Mixed phenol=0.5~3：1.
Used catalyst is the type ion exchange resin of Amberlyst 15.
Described mixed phenol is specially paracresol and metacresol, and wherein paracresol mass content is 10~90%.
Described auxiliary agent is one or more in propane, butane and iso-butane.
Beneficial effects of the present invention are
(1) it is reactive liquid solution that the technology realizes mixing M-and P-cresols alkylated reaction, isobutene is completely dissolved
In M-and P-cresols is mixed, the two can be allowed more fully to contact, so that increase the utilization ratio of raw material, first between this kind of method
The conversion ratio of phenol can reach 94.22%, and the conversion ratio of paracresol can reach 89.46%, relative to existing mixing M-and P-cresols
The conversion ratio of atmospheric fixed bed alkylated reaction M-and P-cresols has great lifting；
(2) it is reactive liquid solution that the technology realizes mixing M-and P-cresols alkylated reaction, can be fully contacted raw material, is made up
Raw material is the insufficient contact shortcoming of gas liquid reaction, and this technology can make the air speed reach 5h-1And can guarantee that conversion ratio higher, phase
1h is up to compared with gas liquid reaction air speed-1Have and significantly lifted, so as to substantially increase the treating capacity of reactor.
(3) isobutene in alkylating agent, the polymer of a part of autohemagglutination generation isobutene is the extraordinary alkyl of quality
Carburetion, a part with cresols reaction generation cresols tert-butyl group product, can gasify under unreacted isobutene normal temperature and pressure with
Auxiliary agent is together collected and recycled, and can accomplish the utilization completely of raw material；
(4) not only any reaction in itself to the auxiliary agent in the alkylating agent there is no under conditions of high pressure strong acid catalyst,
Do not reacted with mixed phenol simultaneously, simple is dissolved in mixed phenol, when normal temperature and pressure is recovered, it can the rapid gas from product
Change so as to take away the heat that reaction is produced, it is thus possible to ensure that stable reaction continues efficiently to carry out；
(5) under the condition of high voltage that strong acid catalyst is present, isobutene is reduced with the well-mixed auxiliary agent of isobutene
Concentration, making the reaction condition of isobutene self-polymeric reaction becomes harsh such that it is able to effectively reduce the hair of isobutene self-polymeric reaction
It is raw, its autohemagglutination product is only accounted for 5% or so of whole alkylation reaction product；After the reduction of self-polymeric reaction can be substantially reduced simultaneously
The energy consumption of continuous separation product, reduces the running cost of whole separating technology；
(6) auxiliary agent is not involved in any reaction while itself not occurring to gasify rapidly under any reaction, normal temperature and pressure, and
Take away substantial amounts of heat, it is thus possible to accomplish that the heat for preventing a large amount of self-polymeric reactions from generating makes the purpose of device temperature runaway.
(7) auxiliary agent is not involved in any reaction while itself not occurring to gasify rapidly under any reaction, normal temperature and pressure, because
This auxiliary agent can be recycled and reused, and isobutene content in the alkylating agent is only 10~30%, thus it is same amount of should
For the more high-purity isobutene of alkylating agent, cost savings percent 70~90%.
Brief description of the drawings
Fig. 1 is a kind of method figure for mixing the alkylation of M-and P-cresols high pressure fixed bed；
The mixed phenol feed pump 8- fixed bed reactors of 1,2,3,4- flowmeter 5- blenders 6- alkylation liquid feed pumps 7-
The product collecting pipe 11,12- stop valves of 9- counterbalance valves 10
Specific embodiment
The method that the present invention is provided is further described below by the embodiment of laboratory scale, but not therefore
And limit the present invention.
The method of mixing M-and P-cresols high pressure fixed bed alkylation of the invention, is described as follows as shown in Figure 1：
Each gas pressurized to 1.7~4.2MPa is liquefied respectively, according to catalyst useful load in the reactor, alkene phenol rubs
That ratio 0.5~3：1, the 0.1~5h of volume content 70~90% and air speed of auxiliary agent in alkylating agent-1, by formula：
Wherein V is catalyst volume, and τ is air speed, and a is alkene phenol mol ratio, and b is the volume fraction shared by isobutene, M1And ρ1
It is the molal weight and density of isobutene, M2And ρ2It is the molal weight and density of cresols, V1It is the volume flow of isobutene, V2
Be mixing M-and P-cresols volume flow, calculate the volume flow of each liquid and the volume flow of mixed phenol and adjust flowmeter 1,
2nd, 3,4 parameter, makes alkylating agent each component be sufficiently mixed in blender 5, while fixed bed reactors are heated to 50~
110 DEG C, isobutene mixed liquor and mixed phenol are injected in fixed bed reactors 8 simultaneously by pump 6,7 respectively afterwards, and adjust back pressure
The aperture of valve 9 makes reactor pressure maintain 1.7~4.2MPa, while open valve 12 and collecting unreacted isobutene and helping
Agent, opens the sampling analysis of valve 11 after stable reaction, wherein 10 is collection of products tank.
I.e.：
By alkylating agent be forced into 1.7~4.2MPa liquefaction, then with mixed phenol together injecting reactor in, keep fixed bed
The pressure of reactor is 1.7~4.2MPa, and temperature is 50~110 DEG C, is 0.1~5h in air speed-1Lower reaction, obtains isobutene
Single tert-butyl group product and the dual-tert-butyl product of M-and P-cresols of autohemagglutination product, M-and P-cresols.
Wherein, reactor is fixed bed reactors；Alkylating agent is isobutene and auxiliary agent, and the volume of auxiliary agent is alkylating agent
The 70~90% of cumulative volume；Mol ratio isobutene：Mixed phenol=0.5~3：1.
Used catalyst is the type ion exchange resin of Amberlyst 15.
Described mixed phenol is specially paracresol and metacresol, and wherein paracresol mass content is 10~90%.
Described auxiliary agent is one or more in propane, butane and iso-butane.
, with volume percent, the content of other materials is with quality for alkylating agent content in following embodiment
Percentage meter.
Specially：
Embodiment one：
Alkylating agent is constituted：The isobutene content 30% of butane volume content 70%；
Fixed bed reactors operating pressure：1.7MPa；
Fixed bed reactors operation temperature：50℃
Air speed：0.1h-1
Mol ratio isobutene: mixed phenol=0.5: 1
Paracresol mass fraction：10%
In internal diameter 25mm, the middle filling 100ml catalyst of the single hop fixed bed reactors of 400mm high；
The first step：The determination of each flow
Because it is 0.1h to use fixed bed reactors air speed-1, catalytic amount is 100ml, according to formula
Wherein V is catalyst volume, and τ is air speed, and a is alkene phenol mol ratio, and b is the volume fraction shared by isobutene, M1And ρ1
It is the molal weight and density of isobutene, M2And ρ2It is the molal weight and density of cresols, V1It is the volume flow of isobutene, V2
To mix the volume flow of M-and P-cresols；(following examples are same)
The flow of mixed phenol be can be calculated for 4.27ml/h, isobutene flow 1.72ml/h, butane flow is 4.01ml/h, different
Butane and propane flow are 0；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while isobutene and auxiliary agent difference is pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and be analyzed with GC-MS, as a result showing, paracresol accounts for 2.52%, and metacresol accounts for 19.96%, 4- Butylated Hydroxytoluenes and accounts for
4.13%, 6- tert-butyl-m-cresol account for 36.77%, BHT and account for 1.30%, and 4,6- di-t-butyl metacresols account for 14.83%, isobutene
Autopolymer accounts for 20.49%, and it is 57.15% to calculate paracresol conversion ratio, and metacresol conversion ratio is 61.20%.
Embodiment two：
Alkylating agent is constituted：The isobutene content 20% of butane content 80%
Fixed bed reactors operating pressure：4.2MPa
Fixed bed reactors operation temperature：70℃
Air speed：4.2h-1
Alkene phenol mol ratio：2：1
Paracresol mass fraction：50%
Reactor used and loaded catalyst is with embodiment one
The first step：The determination of each flow
Because it is 4.2h to use fixed bed reactors air speed-1, catalytic amount is 100ml, by the formula meter in example one
Calculation can mix the flow of phenol for 46.33ml/h, isobutene flow 74.73ml/h, and butane flow is 298.94ml/h, iso-butane and
Propane flow is 0；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while making isobutene and auxiliary agent difference pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and be analyzed with GC-MS, as a result showing, paracresol accounts for 2.37%, and metacresol accounts for 1.61%, 4- Butylated Hydroxytoluenes and accounts for
22.70%, 6- tert-butyl-m-cresol account for 16.41%, BHT and account for 16.76%, and 4,6- di-t-butyl metacresols account for 31.46%, isobutyl
Alkene autopolymer accounts for 8.24%, and it is 89.46% to calculate paracresol conversion ratio, and metacresol conversion ratio is 94.22%.
Embodiment three：
Alkylating agent is constituted：The isobutene content 10% of butane content 90%
Fixed bed reactors reaction pressure：4.2MPa
Fixed bed reactors operation temperature：110℃
Air speed：5h-1
Alkene phenol mol ratio：3：1
Paracresol mass fraction：90%
Reactor used and loaded catalyst is with embodiment one
The first step：The determination of each flow
Because it is 5h to use fixed bed reactors air speed-1, catalytic amount is 100ml, is calculated by the formula in example one
The flow of phenol can be mixed for 19.85ml/h, isobutene flow 48.02ml/h, butane flow is 432.13ml/h, iso-butane and third
Alkane flow is 0；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while making isobutene and auxiliary agent difference pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and shown with result, paracresol accounts for 16.51%, and metacresol accounts for 1.65%, 4- Butylated Hydroxytoluenes and accounts for the tertiary fourths of 45.45%, 6-
Base metacresol accounts for 5.18%, BHT and accounts for 22.04%, and 4,6- di-t-butyl metacresols account for 2.60%, and isobutene autopolymer is accounted for
6.57%, it is 71.16% to calculate paracresol conversion ratio, and metacresol conversion ratio is 73.98%.
Example IV：
Alkylating agent is constituted：The isobutene content 20% of propane content 80%
Fixed bed reactors operating pressure：3.5MPa
Fixed bed reactors operation temperature：70℃
Air speed：3.5h-1
Alkene phenol mol ratio：2：1
Paracresol mass fraction：50%
Reactor used and loaded catalyst is with embodiment one
The first step：The determination of each flow
Because it is 3.5h to use fixed bed reactors air speed-1, catalytic amount is 100ml, by the formula meter in example one
Calculation can mix the flow of phenol for 38.61ml/h, isobutene flow 62.28ml/h, and propane flow is 249.11ml/h, iso-butane and
Butane flow is 0；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while making isobutene and auxiliary agent difference pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and be analyzed with GC-MS, as a result showing, paracresol accounts for 3.41%, and metacresol accounts for 2.65%, 4- Butylated Hydroxytoluenes and accounts for
34.51%, 6- tert-butyl-m-cresol account for 29.58%, BHT and account for 7.32%, and 4,6- di-t-butyl metacresols account for 17.22%, isobutyl
Alkene autopolymer accounts for 5.31%, and it is 88.53% to calculate paracresol conversion ratio, and metacresol conversion ratio is 91.33%.
Embodiment five：
Alkylating agent is constituted：The isobutene content 20% of iso-butane content 80%
Fixed bed reactors operating pressure：2MPa
Fixed bed reactors operation temperature：70℃
Air speed：2h-1
Alkene phenol mol ratio：2：1
Paracresol mass fraction：50%
Reactor used and loaded catalyst is with embodiment one
The first step：The determination of each flow
Because it is 2h to use fixed bed reactors air speed-1, catalytic amount is 100ml, is calculated by the formula in example one
The flow of phenol can be mixed for 22.06ml/h, isobutene flow 35.59ml/h, iso-butane flow is 142.35ml/h, butane and third
Alkane flow is 0；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while making isobutene and auxiliary agent difference pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and be analyzed with GC-MS, as a result showing, paracresol accounts for 3.33%, and metacresol accounts for 1.65%, 4- Butylated Hydroxytoluenes and accounts for
24.83%, 6- tert-butyl-m-cresol account for 24.83%, BHT and account for 8.30%, and 4,6- di-t-butyl metacresols account for 20.41%, isobutyl
Alkene autopolymer accounts for 16.65%, and it is 85.98% to calculate paracresol conversion ratio, and metacresol conversion ratio is 94.11%.
Embodiment six：
Alkylating agent is constituted：The isobutene content 20% of 40% propane content of butane content 40%
Fixed bed reactors operating pressure：3.5MPa
Fixed bed reactors operation temperature：70℃
Air speed：2.5h-1
Alkene phenol mol ratio：2：1
Paracresol mass fraction：50%
Reactor used and loaded catalyst is with embodiment one
The first step：The determination of each flow
Because it is 2.5h to use fixed bed reactors air speed-1, catalytic amount is 100ml, by the formula meter in example one
The flow that calculation can mix phenol is 27.58ml/h, and isobutene flow 44.48ml/h, butane flow is 88.97ml/h, propane flow
It is 88.97ml/h, iso-butane flow is 0；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while making isobutene and auxiliary agent difference pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and be analyzed with GC-MS, as a result showing, paracresol accounts for 2.79%, and metacresol accounts for 2.01%, 4- Butylated Hydroxytoluenes and accounts for
16.70%, 6- tert-butyl-m-cresol account for 17.44%, BHT and account for 21.68%, and 4,6- di-t-butyl metacresols account for 24.23%, isobutyl
Alkene autopolymer accounts for 15.15%, and it is 88.58% to calculate paracresol conversion ratio, and metacresol conversion ratio is 92.08%.
Embodiment seven：
Alkylating agent is constituted：The isobutene content 20% of 40% propane content of iso-butane content 40%
Fixed bed reactors operating pressure：3MPa
Fixed bed reactors operation temperature：60℃
Air speed：4.5h-1
Alkene phenol mol ratio：2：1
Paracresol mass fraction：50%
Reactor used and loaded catalyst is with embodiment one
The first step：The determination of each flow
Because it is 4.5h to use fixed bed reactors air speed-1, catalytic amount is 100ml, by the formula meter in example one
The flow that calculation can mix phenol is 49.64ml/h, and isobutene flow 80.07ml/h, butane flow is 160.14ml/h, propane flow
It is 160.15ml/h, iso-butane flow is 0；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while making isobutene and auxiliary agent difference pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and be analyzed with GC-MS, as a result showing, paracresol accounts for 4.34%, and metacresol accounts for 2.04%, 4- Butylated Hydroxytoluenes and accounts for
24.34%, 6- tert-butyl-m-cresol account for 23.87%, BHT and account for 9.16%, and 4,6- di-t-butyl metacresols account for 22.37%, isobutyl
Alkene autopolymer accounts for 13.88%, and it is 82.55% to calculate paracresol conversion ratio, and metacresol conversion ratio is 92.90%.
Embodiment eight：
Alkylating agent is constituted：The isobutene content 20% of 40% iso-butane content of butane content 40%
Fixed bed reactors operating pressure：1.7MPa
Fixed bed reactors operation temperature：60℃
Air speed：3.2h-1
Alkene phenol mol ratio：2：1
Paracresol mass fraction：50%
Reactor used and loaded catalyst is with embodiment one
The first step：The determination of each flow
Because it is 3.2h to use fixed bed reactors air speed-1, catalytic amount is 100ml, by the formula meter in example one
The flow that calculation can mix phenol is 35.30ml/h, and isobutene flow 56.94ml/h, butane flow is 113.88ml/h, isobutane stream
It is 113.88ml/h to measure, and propane flow is 0；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while making isobutene and auxiliary agent difference pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and be analyzed with GC-MS, as a result showing, paracresol accounts for 6.38%, and metacresol accounts for 3.10%, 4- Butylated Hydroxytoluenes and accounts for
23.37%, 6- tert-butyl-m-cresol account for 23.09%, BHT and account for 10.70%, and 4,6- di-t-butyl metacresols account for 28.57%, isobutyl
Alkene autopolymer accounts for 4.79%, and it is 76.39% to calculate paracresol conversion ratio, and metacresol conversion ratio is 90.41%.
Embodiment nine：
Alkylating agent is constituted：The isobutene content 20% of 40% iso-butane content of butane content, 20% propane content 20%
Fixed bed reactors operating pressure：3.8MPa
Fixed bed reactors operation temperature：65℃
Air speed：4h-1
Alkene phenol mol ratio：2：1
Paracresol mass fraction：50%
Reactor used and loaded catalyst is with embodiment one
The first step：The determination of each flow
Because it is 4h to use fixed bed reactors air speed-1, catalytic amount is 100ml, is calculated by the formula in example one
The flow of phenol can be mixed for 44.13ml/h, isobutene flow 71.17ml/h, butane flow is 142.36ml/h, iso-butane flow
It is 71.17ml/h, propane flow is 71.17ml/h；
Second step：Alkylated reaction
Each flow meter parameter is adjusted according to above-mentioned result of calculation, while making isobutene and auxiliary agent difference pressurized liquefied and abundant
Mixing, together injects in the reactor for having reached operation temperature together with mixed phenol, maintains above operating parameter, and reaction takes after a period of time
Sample, and be analyzed with GC-MS, as a result showing, paracresol accounts for 9.92%, and metacresol accounts for 8.24%, 4- Butylated Hydroxytoluenes and accounts for
24.73%, 6- tert-butyl-m-cresol account for 25.90%, BHT and account for 11.66%, and 4,6- di-t-butyl metacresols account for 12.98%, isobutyl
Alkene autopolymer accounts for 6.57%, and it is 68.93% to calculate paracresol conversion ratio, and metacresol conversion ratio is 73.98%.
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. it is a kind of to mix the method that M-and P-cresols high pressure fixed bed is alkylated, it is characterized by the method is comprised the following steps：
By alkylating agent be forced into 1.7 ~ 4.2MPa liquefaction, then with mixed phenol together injecting reactor in, keep fixed bed reaction
The pressure of device is 1.7 ~ 4.2MPa, and temperature is 50 ~ 110 DEG C, is 0.1 ~ 5h in air speed-1Lower reaction, the autohemagglutination for obtaining isobutene is produced
Single tert-butyl group product and the dual-tert-butyl product of M-and P-cresols of thing, M-and P-cresols；
Wherein, reactor is fixed bed reactors；Alkylating agent is isobutene and auxiliary agent, and the volume of auxiliary agent is alkylating agent totality
Long-pending 70-90%；Mol ratio isobutene：Mixed phenol=0.5 ~ 3：1.
2. the method that mixing M-and P-cresols high pressure fixed bed as claimed in claim 1 is alkylated, it is characterized by used catalyst
It is the type ion exchange resin of Amberlyst 15.
3. the method that mixing M-and P-cresols high pressure fixed bed as claimed in claim 1 is alkylated, it is characterized by described mixed phenol
Specially paracresol and metacresol, wherein paracresol mass content are 10 ~ 90%.
4. the method that mixing M-and P-cresols high pressure fixed bed as claimed in claim 1 is alkylated, it is characterized by described auxiliary agent
It is one or more in propane, butane and iso-butane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079690A (en) * | 2020-08-24 | 2020-12-15 | 西安石油大学 | Alkylation reaction device and method for 2,4/2, 5-xylenol |
| CN112694389A (en) * | 2020-12-25 | 2021-04-23 | 南京晶典抗氧化技术研究院有限公司 | Synthesis method for synthesizing 2,6 di-tert-butyltoluene through heterogeneous catalysis |
| CN113248349A (en) * | 2021-06-16 | 2021-08-13 | 南京元素科技有限公司 | Device for alkylation continuous reaction of m-cresol and/or p-cresol |
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| GB1427876A (en) * | 1973-07-03 | 1976-03-10 | Union Rheinische Braunkohlen | Process for the production of o-sec-butyl-phenol |
| CN101863742A (en) * | 2010-06-07 | 2010-10-20 | 吴鸿宾 | Separation method of m-cresol and p-cresol mixture |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1427876A (en) * | 1973-07-03 | 1976-03-10 | Union Rheinische Braunkohlen | Process for the production of o-sec-butyl-phenol |
| CN101863742A (en) * | 2010-06-07 | 2010-10-20 | 吴鸿宾 | Separation method of m-cresol and p-cresol mixture |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079690A (en) * | 2020-08-24 | 2020-12-15 | 西安石油大学 | Alkylation reaction device and method for 2,4/2, 5-xylenol |
| CN112079690B (en) * | 2020-08-24 | 2023-03-10 | 西安石油大学 | Alkylation reaction device and method for 2,4/2, 5-xylenol |
| CN112694389A (en) * | 2020-12-25 | 2021-04-23 | 南京晶典抗氧化技术研究院有限公司 | Synthesis method for synthesizing 2,6 di-tert-butyltoluene through heterogeneous catalysis |
| CN113248349A (en) * | 2021-06-16 | 2021-08-13 | 南京元素科技有限公司 | Device for alkylation continuous reaction of m-cresol and/or p-cresol |
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