CN105523896A - Benzene oxidation method - Google Patents
Benzene oxidation method Download PDFInfo
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- CN105523896A CN105523896A CN201410513857.3A CN201410513857A CN105523896A CN 105523896 A CN105523896 A CN 105523896A CN 201410513857 A CN201410513857 A CN 201410513857A CN 105523896 A CN105523896 A CN 105523896A
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Abstract
The invention discloses a benzene oxidation method. The method comprises the step of enabling a liquid mixture to sequentially flow through a first catalyst bed layer and a second catalyst bed layer under oxidation reaction conditions, wherein the liquid mixture contains benzene, an oxidant and an optional solvent, the first catalyst bed layer and the second catalyst bed layer each is loaded with titanium silicalite molecular sieves, and the superfacial velocity of the liquid mixture flowing through the first catalyst bed layer is lower than that of the liquid mixture flowing through the second catalyst bed layer. According to the method, in a long-time continuous operating process, the single-pass service lives of the titanium silicalite molecular sieves as a catalyst can be effectively prolonged, the regeneration frequency is lowered, the production efficiency of a device is increased, and the operating cost of the device is reduced; and the availability of the oxidant is relatively high. In addition, the method is high in operability, in a practical application process, two reaction zones are arranged in series, and the inner diameter of the reaction zone located at upstream is enabled to be greater than that of the reaction zone located at downstream.
Description
Technical field
The present invention relates to a kind of benzene oxidatoin method.
Background technology
Phenol is large industrial chemicals product important in current organic chemical industry.2000, the world demand amount of phenol, more than 66Mt, was mainly used to prepare dihydroxyphenyl propane, resol and pharmaceutical intermediate etc.In addition, phenol and its derivatives also for painting, in the production of dyestuff, explosive, petroleum additive, wood preservative etc.
The main source of current industrial phenol, except extracting from coal tar or petroleum distillate, all the other are chemical synthesis, and main synthetic method comprises sulfonation method, Raschig-Hooker method, Hydrolysis of Chlorobenzene method, toluene oxidation method, cyclohexane oxidation process and production phenols (also known as cumene process).Except toluene oxidation method, other method is all take benzene as the multistep indirect method of raw material, and not only synthetic route is long, and raw material consumption is large, and environmental pollution is serious, and all there are some problems in reaction conditions, transformation efficiency, product separation etc.For the current prevailing cumene process in countries in the world, although the method advantage is a lot, but its synthetic route is long, intermediate product hydrogen phosphide cumene is easy to blast, and the economic benefit of producing phenol is limited by the change of by product acetone market fluctuation to a great extent.
In recent years, the single step reaction method that benzene hydroxylation directly prepares phenol has attracted the concern of many investigators.Universal along with Green Chemistry idea since last century late nineteen eighties, people set about from the Atom economy and green aspect improving reaction, begin one's study and how to utilize the direct hydroxylation of benzene to prepare phenol.Research mainly concentrates in the selection of oxygenant and corresponding catalyzer, and achieves certain achievement in research, as using HTS as catalyzer, uses H
2o
2oxidation Benzene to phenol, the method mild condition, technological process is simple, and by product H
2o environmental friendliness.
But when being oxidized Benzene to phenol using HTS as catalyst, with the prolongation in reaction times, the catalytic activity of HTS is on a declining curve, causes desirable oxidation selectivity of product obviously to reduce.When react carry out in fixed-bed reactor time, because titanium molecular sieve catalysis activity reduces, need HTS to regenerate in reactor or outside reactor, cause reactor down-time, thus affect production efficiency and improve the running cost of device.
And, when the catalyzer of regeneration puts into operation again, when particularly again putting into operation after reaction in-situ regeneration, the Activity Fluctuation of catalyzer is larger, need could stablize for a long time, cause desirable oxidation selectivity of product to reduce, this not only can reduce the running efficiency of device, but also need later separation purification procedures to adjust operational condition, add the complicacy of operation; Meanwhile, also need to combine the smooth running that operations such as improving temperature of reaction carrys out realization response, but these measures often accelerator activator inactivation.
In addition, in reaction process, the effective rate of utilization of oxygenant also awaits further raising.
Summary of the invention
The object of the invention is to overcome the technical problem that the catalyzer existed in the method for existing titanium molecular sieve catalysis oxidation Benzene to phenol is easy to inactivation, provide a kind of benzene oxidatoin method, the method can one way work-ing life of extending catalyst effectively.
The invention provides a kind of benzene oxidatoin method, under the method is included in oxidation reaction condition, a kind of liquid mixture is made to flow through the first beds and the second beds successively, described liquid mixture contains benzene, at least one oxygenant and optional at least one solvent, described first beds and described second beds are filled with at least one HTS separately, and the superfacial velocity that liquid mixture flows through the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, wherein, v
1<v
2.
According to method of the present invention, even if long-time continuous operates, also catalyst activity can be maintained higher level, obtain higher desirable oxidation selectivity of product, thus effectively extend the one way work-ing life of the HTS as catalyzer, reduce regeneration frequency, improve the production efficiency of device, reduce the running cost of device.
Further, according to method of the present invention, the effective rate of utilization of oxygenant is higher, thus can reduce the running cost of the inventive method further.
In addition, method of the present invention is workable, is beneficial to suitability for industrialized production application.Particularly, in actual application, be arranged in series two reaction zones, and make the internal diameter of the reaction zone being positioned at upstream be greater than the internal diameter of the reaction zone being positioned at downstream.
Embodiment
The invention provides a kind of benzene oxidatoin method, under the method is included in oxidation reaction condition, a kind of liquid mixture is made to flow through the first beds and the second beds successively, described liquid mixture contains benzene, at least one oxygenant and optional at least one solvent, and described first beds and described second beds are filled with at least one HTS separately.
Herein, " at least one " represents one or more; " optionally " represents containing or does not contain.
According to method of the present invention, the superfacial velocity that liquid mixture flows through the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, wherein, v
1<v
2, effectively can delay the deactivation rate of HTS like this, extend the one way work-ing life of HTS.V
2/ v
1be preferably more than 1.5, be more preferably more than 2.V
2/ v
1be preferably less than 15, be more preferably less than 10, more preferably less than 5.Particularly, v
2/ v
1can be 1.5-10, be preferably 2-5.
In the present invention, described superfacial velocity (flow velocity) to refer in the unit time by the area of the mass rate (in kg/s) of the liquid mixture of beds whole process and a certain cross section of beds (with m
2meter) ratio.The quality of the liquid mixture of fixed-bed reactor can will be sent into as " by the mass rate of the liquid mixture of whole beds in the unit time " in unit time.In the present invention, particular requirement be there is no for the superfacial velocity of liquid mixture in the first beds, generally can at 0.001-200kg/ (m
2s) in scope.
Various method can be adopted to regulate the superfacial velocity of described liquid mixture in the first beds and the second beds.Such as, the superfacial velocity of regulates liquid mixture can be carried out by the cross-sectional area of selecting catalyst bed.Particularly, the cross-sectional area of described first beds can be made to be greater than the cross-sectional area of described second beds, thus to make v
1<v
2.Particularly, the internal diameter of described first beds is D
1, the internal diameter of described second beds is D
2, wherein, D
1> D
2.D
1/ D
2be preferably more than 1.5, be more preferably more than 2.D
1/ D
2be preferably less than 15, be more preferably less than 10, more preferably less than 5.Particularly, D
1/ D
2can be 1.5-10, be preferably 2-5.
According to method of the present invention, the residence time of described liquid mixture in the first beds is T
1, the total residence time in beds is T, preferably, and T
1/ T=0.2-0.95, can obtain the catalyzer one way work-ing life extended further like this, can also obtain better reaction effect simultaneously.T
1/ T is preferably more than 0.3, is more preferably more than 0.5, and more preferably more than 0.6.T
1/ T is preferably less than 0.9, is more preferably less than 0.85.Further preferably, T
1/ T=0.5-0.85.
According to method of the present invention, fresh material can be supplemented as the case may be between the first beds and the second beds, when the first beds and/or the second beds are multiple beds, fresh material can be supplemented between the first beds and/or between the second beds in described liquid mixture as the case may be.Such as: between the first beds and the second beds, between the first beds and/or between the second beds, supplement benzene, oxygenant and/or solvent.But, it should be noted that, (namely described liquid mixture flows through whole beds of the first beds, the whole process of the first beds) and the second beds whole beds (namely, the whole process of the second beds), described liquid mixture not included in the fresh material introduced between the first beds, between the second beds and between the first beds and the second beds, previously described superfacial velocity is determined by described liquid mixture, is not subject to the impact whether introducing fresh material.
According to method of the present invention, described first beds and the second beds can contain one or more beds separately.When the first beds and/or the second beds contain multiple beds, can for being connected in series between multiple beds, also can for being connected in parallel, can also be series connection and combination in parallel, such as: multiple beds is divided into many groups, beds often in group for being connected in series and/or being connected in parallel, for being connected in series and/or being connected in parallel between each group.Described first beds and described second beds can be arranged on the different zones of same reactor, also can be arranged in different reactors.
According to method of the present invention, by weight, the amount of the HTS of loading in described first beds is w
1, the amount of the HTS of loading in described second beds is w
2, w
1/ w
2for 0.1-20.W
1/ w
2be preferably more than 0.5, be more preferably more than 1, more preferably more than 2, be further preferably more than 4.W
1/ w
2be preferably less than 15, be more preferably less than 10.Still more preferably, w
1/ w
2for 2-10, as 4-10.When HTS is shaping HTS, w
1and w
2determined by the content of the HTS in shaping HTS.
According to method of the present invention, described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, can use chemical formula xTiO
2siO
2represent.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, x can be 0.0001-0.05, is preferably 0.01-0.03, is more preferably 0.015-0.025.
Described HTS can for the common HTS with various topological framework, such as: described HTS can be selected from the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, and the HTS of other structure (as Ti-ZSM-48) etc. Ti-SBA-15).Described HTS is preferably selected from the HTS of the HTS of MFI structure, the HTS of MEL structure, the HTS of two-dimentional hexagonal structure and BEA structure, is more preferably the HTS of MFI structure.
Described HTS is preferably hollow HTS, can obtain better catalytic effect like this.Described hollow HTS is the HTS of MFI structure, and the crystal grain of this HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
According to method of the present invention, described HTS can be the former powder of HTS, also can be shaping HTS, is preferably shaping HTS.Shaping HTS is generally containing the HTS as activeconstituents and the carrier as binding agent, and wherein, the content of HTS can be conventional selection.Usually, with the total amount of described shaping HTS for benchmark, the content of HTS can be 5-95 % by weight, is preferably 10-95 % by weight, is more preferably 70-90 % by weight; The content of described carrier can be 5-95 % by weight, is preferably 5-90 % by weight, is more preferably 10-30 % by weight.The carrier of described shaping HTS can be conventional selection, as aluminum oxide and/or silicon oxide.The method preparing described shaping HTS is known in the field, no longer describes in detail herein.The granular size of described shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.Usually, the median size of described shaping HTS can be 4-10000 micron, is preferably 5-5000 micron, is more preferably 40-4000 micron, as 100-2000 micron.Described median size is volume average particle size, and laser particle analyzer can be adopted to measure.
According to method of the present invention, described first beds can, for identical, also can be different with the kind of the HTS of loading in described second beds.
One of the present invention preferred embodiment in, the HTS of described first beds filling is hollow HTS, the HTS of described second beds filling is the HTS except hollow HTS, as the HTS (such as titanium-silicon molecular sieve TS-1) of other MFI structure, two dimension the HTS (such as HTS Ti-MCM-41) of hexagonal structure and the HTS (such as HTS Ti-Beta) of BEA structure in one or more, the deactivation rate of HTS can be delayed so further.More preferably, the HTS of described first beds filling is hollow HTS, and the HTS of described second beds filling is titanium-silicon molecular sieve TS-1, the deactivation rate of HTS can not only be delayed so further, extend the one way work-ing life of HTS, and the selectivity for phenol can also be improved further.
In the various reactions adopting HTS as catalyzer (referring generally to the reaction of non-benzene oxidatoin) device, as Ammoximation reaction, in hydroxylating and epoxidation reaction device, usually after plant running for some time, the catalytic activity of catalyzer declines, need to carry out in device or ex-situ regeneration, even if when carry out regenerating also be difficult to obtain satisfied active time, catalyzer is needed to draw off (namely from device, more catalyst changeout), and the catalyzer drawn off (namely, drawing off agent or spent catalyst) current treatment process normally piles up and buries, occupy valuable land resources and inventory space on the one hand, HTS production cost is higher on the other hand, directly pass into disuse and also result in great waste.The present inventor finds in research process, and that in the second beds, loads the reaction unit through regenerating draws off agent, can obtain the phenol selectivity improved further.
Therefore, in another preferred embodiment of the present invention, the HTS of described second beds filling be through regeneration at least one reaction unit draw off agent, described in draw off agent be Ammoximation reaction device draw off agent, hydroxylating draw off agent and epoxidation reaction device draw off agent.Preferably, draw off described in agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off agent.According to this preferred embodiment, the phenol selectivity improved further can be obtained on the one hand, effective recycling of discarded molecular sieve can be realized on the other hand.
This preferred embodiment in, through regeneration the activity drawing off agent according to its source and different.Usually, the activity drawing off agent through regeneration can be the 5-95% of its activity (that is, the activity of fresh dose) when fresh.Preferably, the activity drawing off agent through regeneration can be the 10-90% of its activity when fresh, more preferably the 10-60% of its activity when fresh.When the activity drawing off agent through regeneration is the 10-60% of its activity when fresh, gratifying phenol selectivity can not only be obtained, and the oxygenant effective rate of utilization improved further can be obtained.Under the prerequisite obtaining high oxygenant effective rate of utilization, from the angle taking into account phenol selectivity, the activity drawing off agent through regeneration is the 30-55% of its activity when fresh.The activity of described fresh titanium si molecular sieves is generally more than 95%.
Described activity measures by the following method: will draw off through regeneration the catalyzer that agent and fresh dose are used as cyclohexanone oxamidinating reaction respectively, the condition of this Ammoximation reaction is: catalyzer (in HTS), 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure in 80 DEG C of reaction 2h.Calculate with the transformation efficiency drawing off pimelinketone when agent and fresh dose are catalyzer through regeneration respectively, and it can be used as the activity drawing off agent and fresh dose through regeneration, wherein, transformation efficiency=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100% of pimelinketone.
This preferred embodiment in, the HTS of loading in described second beds can be all through regeneration draw off agent, also can partly for through regeneration draw off agent.Preferably, the HTS of loading in described second beds is all draw off agent through what regenerate.
This preferred embodiment in, described first beds filling HTS be fresh titanium si molecular sieves, be preferably fresh hollow HTS.In the present invention, fresh titanium si molecular sieves is with to draw off agent relative, refer to that the HTS prepared (is generally except carrying out activation treatment before use and carries out roasting, to remove the material or group that remain in the preparation process of HTS), do not live through the HTS of other physical chemistry treating processes outward.
According to method of the present invention, beds only can load HTS, also can contain HTS and inactive filler.In beds, load inactive filler to adjust the amount of HTS in beds, thus the speed of reaction is regulated.When beds contains HTS and inactive filler, in beds, the content of inactive filler can be 5-95 % by weight.Described inactive filler refers to the filler not having or substantially do not have catalytic activity to oxidizing reaction, and its specific examples can include but not limited to: one or more in quartz sand, ceramic ring and potsherd.
According to method of the present invention, HTS is as catalyzer, and its consumption is as the criterion can realize catalysis.If weigh the consumption of catalyzer from the weight hourly space velocity angle of benzene, usually, the weight hourly space velocity of benzene can be 0.01-20h
-1, be preferably 5-15h
-1.In the present invention, weight hourly space velocity with the total amount of HTS in whole beds for benchmark.
According to method of the present invention, described oxygenant can be common various can by the material of benzene oxidatoin.Method of the present invention is specially adapted to the occasion carrying out Oxybenzene using superoxide as oxygenant, can significantly improve the effective rate of utilization of superoxide like this.Described superoxide refers to the compound containing-O-O-key in molecular structure, can be selected from hydrogen peroxide, organo-peroxide and peracid.Described organo-peroxide refers to that one or two hydrogen atom in hydrogen peroxide molecule is replaced by organic group and the material obtained.Described peracid refers to the organic oxacid containing-O-O-key in molecular structure.In the present invention, the specific examples of described oxygenant can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can reduce separation costs further like this.
The hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.From the angle improved further according to the security of method of the present invention, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.According to method of the present invention, when described hydrogen peroxide provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
The consumption of described oxygenant can be conventional selection, is not particularly limited.Usually, the mol ratio of benzene and oxygenant can be more than 0.1, is preferably more than 0.2; The mol ratio of benzene and oxygenant can be less than 50.From the optionally angle improved further for phenol, the mol ratio of benzene and oxygenant is preferably less than 25, is more preferably less than 10, and more preferably less than 5, further preferably less than 2.
According to method of the present invention, described liquid mixture contains or not containing solvent, preferably containing solvent, like this by the content of solvent in regulates liquid mixture, can adjust, make reaction more steady to the speed of reaction.Described solvent can either dissolve benzene and oxygenant or mixing both promoting for various, again can the liquid substance of solubilized target oxidation products.Usually, described solvent can be selected from C
1-C
6alcohol, C
3-C
8ketone and C
2-C
6nitrile.The specific examples of described solvent can include but not limited to: methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.
The consumption of described solvent can carry out appropriate selection according to the consumption of benzene and oxygenant.Usually, the mol ratio of solvent and benzene can be 0.1-100:1, is preferably 0.2-80:1, is more preferably 1-50:1, more preferably 5-20:1.
According to method of the present invention, from the angle improving reaction effect further, also comprise and send at least one alkaline matter in described liquid mixture, the feeding amount of described alkaline matter makes the pH value of described liquid mixture be in the scope of 6.5-9, as being in the scope of 7-8.5.Described alkaline matter refer to the pH value of its aqueous solution be greater than 7 material.The specific examples of described alkaline matter can include but not limited to: ammonia (that is, NH
3), amine, quaternary ammonium hydroxide and M
1(OH)
n(wherein, M
1for basic metal or alkaline-earth metal, as sodium, potassium, magnesium or calcium; N is and M
1the identical integer of valency).The pH value of described liquid mixture refers at 25 DEG C and 1 standard atmosphere pressure, the pH value of this liquid mixture of mensuration.
Described alkaline matter can directly use, and uses after also described alkaline matter can being mixed with solution.Can will send in fixed-bed reactor after alkaline matter and oxygenant and optional solvent, described mixing can be carried out outside reactor, also can carry out in reactor, be not particularly limited.
According to method of the present invention, described oxidation reaction condition can be selected according to the set goal oxidation products.Usually, the temperature of described first beds and the second beds can be 20-150 DEG C separately, is preferably 30-120 DEG C, is more preferably 40-100 DEG C.Pressure in fixed-bed reactor can be 0-5MPa, and be preferably 0.1-3.5MPa, be more preferably 0.5-2.5MPa, described pressure is in gauge pressure.According to method of the present invention, the reaction conditions of described first beds and described second beds can be the same or different.From the angle of operation terseness, described first beds is identical with the reaction conditions of described second beds.From the one way work-ing life and the oxygenant effective rate of utilization that improve HTS further, and the angle improving phenol selectivity is further set out, more described second catalyst bed floor height 5-30 DEG C (as 10-20 DEG C) of temperature of described first beds.
Can also comprise according to method of the present invention and the reaction mixture exported from fixed-bed reactor is separated, to obtain desirable oxidation product (as phenol) and unreacted reactant.The method being carried out being separated by reaction mixture can be selected for the routine of this area, is not particularly limited.Isolated unreacted reactant can recycle.
According to method of the present invention, effectively can extend the one way work-ing life of the HTS as catalyzer, make device can steady running within the longer time, reduce running cost; Further, method of the present invention has higher selectivity for phenol.
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In following examples and comparative example, agents useful for same is commercially available analytical reagent, and pressure is gauge pressure, and HTS used is fresh titanium si molecular sieves if not otherwise specified.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used according to Zeolites, the method preparation described in 1992, Vol.12:943-950, its titanium oxide content is 2.5 % by weight; Hollow HTS used is be the hollow HTS of HTS purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd, and its titanium oxide content is 2.5 % by weight; HTS Ti-MCM-41 used is that prepared by the method described in 1994,147-148, its titanium oxide content is 3 % by weight according to Corma etc. at Chem.Commun.; HTS Ti-Beta used is that prepared by the method described in 1997,677-678, its titanium oxide content is 2.6 % by weight according to TakashiTatsumi etc. at J.Chem.Soc.Chem.Commun..
In following examples and comparative example, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate benzene transformation efficiency, oxygenant effective rate of utilization and phenol selectivity on this basis respectively.
X
benzene=[(m
o benzene-m
benzene)/m
o benzene] × 100% (formula I)
In formula I, X
benzenerepresent benzene transformation efficiency;
M
o benzenerepresent the quality of the benzene added;
M
benzenerepresent the quality of unreacted benzene.
S
phenol=[n
phenol/ (n
o benzene-n
benzene)] × 100% (formula II)
In formula II, S
phenolrepresent phenol selectivity;
N
o benzenerepresent the molar weight of the benzene added;
N
benzenerepresent the molar weight of unreacted benzene;
N
phenolrepresent the molar weight of the phenol that reaction generates.
U
oxygenant=[n
phenol/ (n
o oxygenant-n
oxygenant)] × 100% (formula III)
In formula III, U
oxygenantrepresent oxygenant effective rate of utilization;
N
o oxygenantrepresent the molar weight of the oxygenant added;
N
oxygenantrepresent the molar weight of unreacted oxygenant;
N
phenolrepresent the molar weight of the phenol that reaction generates.
Following examples 9 and 10 adopt following methods to measure the activity of catalyzer:
By catalyzer, 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone in mass ratio=1:7.5:10:7.5:10 mixing after at atmosheric pressure after 80 DEG C of stirring reaction 2h, reactant is filtered, analyze with the composition of vapor-phase chromatography to the liquid phase obtained, adopt the transformation efficiency of following formulae discovery pimelinketone and it can be used as the activity of this catalyzer
The transformation efficiency (%) of pimelinketone=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100%.
Embodiment 1-18 is for illustration of method of the present invention.
Embodiment 1
Following six kinds of catalyzer are related in embodiment 1-7.
C1: shaping hollow HTS, volume average particle size is 600 microns, and with the total amount of shaping hollow HTS for benchmark, the content of hollow HTS is 75 % by weight, and the content as the silicon oxide of binding agent is 25 % by weight, and density is 0.68g/cm
3.
C2: shaping titanium-silicon molecular sieve TS-1, volume average particle size is 600 microns, and with the total amount of shaping titanium-silicon molecular sieve TS-1 for benchmark, the content of titanium-silicon molecular sieve TS-1 is 75 % by weight, and the content as the silicon oxide of binding agent is 25 % by weight, and density is 0.73g/cm
3.
C3: catalyzer C1 being used as cyclohexanone oxamidinating reaction unit, draw off from reaction unit after running for some time, what obtain draws off agent at the temperature of 550 DEG C, roasting 5 hours in air atmosphere, the regenerator obtained is as catalyzer C3, and its activity is 45% (activity of C1 is 96%).
C4: catalyzer C2 being used as cyclohexanone oxamidinating reaction unit, draw off from reaction unit after running for some time, what obtain draws off agent at the temperature of 550 DEG C, roasting 5 hours in air atmosphere, the regenerator obtained is as catalyzer C4, and its activity is 45% (activity of C2 is 95%).
C5: shaping HTS Ti-MCM-41, volume average particle size is 600 microns, and with the total amount of shaping HTS Ti-MCM-41 for benchmark, the content of HTS Ti-MCM-41 is 75 % by weight, content as the silicon oxide of binding agent is 25 % by weight, and density is 0.61g/cm
3.
C6: shaping HTS Ti-Beta, volume average particle size is 600 microns, and with the total amount of shaping HTS Ti-Beta for benchmark, the content of HTS Ti-Beta is 75 % by weight, content as the silicon oxide of binding agent is 25 % by weight, and density is 0.69g/cm
3.
Embodiment 1
The present embodiment adopts reducing fixed-bed reactor, and wherein, reducing fixed-bed reactor have the beds of two different inner diameters, is the internal diameter zone of transition of taper between two beds, wherein not loading catalyst.With liquid mixture flow direction in the reactor for benchmark, the beds being positioned at upstream is called the first beds, the beds being positioned at downstream is called the second beds.The ratio of the internal diameter of the first beds and the second beds is 2:1.
Loading catalyst C1 in first beds, loading catalyst C2 in the second beds, wherein, the weight ratio of C1 and C2 is 4:1.
By benzene, hydrogen peroxide (providing using the form of the hydrogen peroxide of 30 % by weight) and the methanol mixed as solvent, form liquid mixture.In liquid mixture, add ammoniacal liquor (concentration is 25 % by weight), the pH value of liquid mixture is adjusted to 8 by 5.1.Described liquid mixture is sent into fixed-bed reactor from bottom, and flows through the first beds and the second beds successively, carry out oxidizing reaction.Wherein, in liquid mixture, the mol ratio of benzene and hydrogen peroxide is 1:2.5, and the mol ratio of benzene and methyl alcohol is 1:10.The weight hourly space velocity (with the total amount of the HTS in the first beds and the second beds for benchmark, lower same) of benzene is 10h
-1.Temperature in first beds and the second beds all controlled to be 45 DEG C, the pressure-controlling in fixed-bed reactor is 1.8MPa.
React continuously, monitor the composition of the effluent flowed out from fixed-bed reactor in reaction process, and calculate benzene transformation efficiency, oxygenant effective rate of utilization and phenol selectivity.The result of reacting 2 hours and 520 hours is listed in Table 1.
Embodiment 2
Adopt the method Oxybenzene identical with embodiment 1, unlike, under the condition that the loadings of the first beds and the second beds is constant, equal loading catalyst C1 in the first beds and the second beds.The result of reacting 2 hours and 300 hours is listed in Table 1.
Embodiment 3
Adopt the method Oxybenzene identical with embodiment 1, unlike, under the condition that the loadings of the first beds and the second beds is constant, equal loading catalyst C2 in the first beds and the second beds.The result of reacting 2 hours and 260 hours is listed in Table 1.
Comparative example 1
Adopt the method Oxybenzene identical with embodiment 3, unlike, under the condition that the kind of the loadings of catalyzer is all constant in the first beds and the second beds, the fixed-bed reactor used are isometrical fixed-bed reactor, and the internal diameter of two beds in reactor is all identical with the internal diameter of the first beds in embodiment 3.The result of reacting 2 hours and 120 hours is listed in Table 1.
Comparative example 2
Adopt the method Oxybenzene identical with embodiment 3, unlike, under the condition that the kind of the loadings of catalyzer is all constant in the first beds and the second beds, the fixed-bed reactor used are reducing fixed-bed reactor, and the first beds and the ratio of the internal diameter of the second beds are 1:2 (internal diameter of the second beds is identical with embodiment 3).The result of reacting 2 hours and 100 hours is listed in Table 1.
Embodiment 4
Adopt the method Oxybenzene identical with embodiment 1, unlike, under the condition that the loadings of catalyzer C1 and catalyzer C2 is constant, loading catalyst C2 in the first beds, the second beds loading catalyst C1.The result of reacting 2 hours and 200 hours is listed in Table 1.
Embodiment 5
Adopt the method Oxybenzene identical with embodiment 1, unlike, under the condition that the loadings of the first beds and the second beds is constant, loading catalyst C2 in the first beds, loading catalyst C1 in the second beds.The result of reacting 2 hours and 180 hours is listed in Table 1.
Embodiment 6
Adopt the method Oxybenzene identical with embodiment 1, unlike, under the condition that catalyzer total filling amount is constant, make the weight ratio of C1 and C2 be 1:1.The result of reacting 2 hours and 360 hours is listed in Table 1.
Embodiment 7
Adopt the method Oxybenzene identical with embodiment 1, unlike, under the condition that catalyzer total filling amount is constant, make the weight ratio of C1 and C2 be 1:2.The result of reacting 2 hours and 330 hours is listed in Table 1.
Embodiment 8
Adopt the method Oxybenzene identical with embodiment 1, unlike, do not use ammoniacal liquor (that is, not regulating the pH value of liquid mixture).The result of reacting 2 hours and 460 hours is listed in Table 1.
Embodiment 9
Adopt the method Oxybenzene identical with embodiment 1, unlike, the catalyzer C3 of catalyzer C2 equivalent replaces.The result of reacting 2 hours and 540 hours is listed in Table 1.
Embodiment 10
Adopt the method Oxybenzene identical with embodiment 1, unlike, the catalyzer C4 of catalyzer C2 equivalent replaces.The result of reacting 2 hours and 540 hours is listed in Table 1.
Embodiment 11
Adopt the method Oxybenzene identical with embodiment 1, unlike, the catalyzer C5 of catalyzer C2 equivalent replaces.The result of reacting 2 hours and 440 hours is listed in Table 1.
Embodiment 12
Adopt the method Oxybenzene identical with embodiment 1, unlike, the catalyzer C6 of catalyzer C2 equivalent replaces.The result of reacting 2 hours and 460 hours is listed in Table 1.
Table 1
The result of table 1 confirms, adopts method of the present invention can extend the one way work-ing life of the HTS as catalyzer, reduces the regeneration frequency of catalyzer.
Embodiment 13-16 relates to following two kinds of catalyzer.
C7: (for volume average particle size is the spherical catalyst of 400 μm, density is 0.65g/cm to shaping hollow HTS
3), this catalyzer contains the hollow HTS of 90 % by weight and the silicon oxide of 10 % by weight.
C8: (for volume average particle size is the spherical catalyst of 400 μm, density is 0.70g/cm to shaping titanium-silicon molecular sieve TS-1
3), this catalyzer contains the titanium-silicon molecular sieve TS-1 of 90 % by weight and the silicon oxide of 10 % by weight.
Embodiment 13
The present embodiment adopts reducing fixed-bed reactor, and wherein, reducing fixed-bed reactor have the beds of two different inner diameters, is the internal diameter zone of transition of taper between two beds, wherein not loading catalyst.With liquid mixture flow direction in the reactor for benchmark, the beds being positioned at upstream is called the first beds, the beds being positioned at downstream is called the second beds.The ratio of the internal diameter of the first beds and the second beds is 4:1.
Loading catalyst C7 in first beds, loading catalyst C8 in the second beds, wherein, the weight ratio of C7 and C8 is 10:1.
By benzene, hydrogen peroxide (providing using the form of the hydrogen peroxide of 40 % by weight) with mix as the acetone of solvent, form liquid mixture.Described liquid mixture is sent into fixed-bed reactor from bottom, and flows through the first beds and the second beds successively, carry out oxidizing reaction.Wherein, in liquid mixture, the mol ratio of benzene and hydrogen peroxide is 2:1, and the mol ratio of benzene and acetone is 1:5.The weight hourly space velocity of benzene is 5h
-1.Temperature in first beds and the second beds all controlled to be 60 DEG C, the pressure in fixed-bed reactor all controls as 2.5MPa.
React continuously, monitor the composition of the effluent flowed out from fixed-bed reactor in reaction process, and calculate benzene transformation efficiency, oxygenant effective rate of utilization and phenol selectivity.The result of reacting 2 hours and 520 hours is listed in table 2.
Embodiment 14
Adopt the method Oxybenzene identical with embodiment 13, unlike, the temperature of the first beds is 60 DEG C, and the temperature of the second beds is 40 DEG C.
The result of reacting 2 hours and 550 hours is listed in table 2.
Embodiment 15
Adopt the method Oxybenzene identical with embodiment 13, unlike, the temperature of the first beds is 40 DEG C, and the temperature of the second beds is 60 DEG C.
The result of reacting 2 hours and 480 hours is listed in table 2.
Embodiment 16
Adopt the method Oxybenzene identical with embodiment 13, unlike, under the condition that the total filling amount of catalyzer is constant, make the weight ratio of C7 and C8 be 20:1.
The result of reacting 2 hours and 460 hours is listed in table 2.
Table 2
Embodiment 17 and embodiment 18 relate to following two kinds of catalyzer.
C9: (for volume average particle size is the spherical catalyst of 800 μm, density is 0.69g/cm to shaping hollow HTS
3), this catalyzer contains the hollow HTS of 85 % by weight and the silicon oxide of 15 % by weight.
C10: (for volume average particle size is the spherical catalyst of 800 μm, density is 0.77g/cm to shaping titanium-silicon molecular sieve TS-1
3), this catalyzer contains the titanium-silicon molecular sieve TS-1 of 85 % by weight and the silicon oxide of 15 % by weight.
Embodiment 17
The present embodiment adopts reducing fixed-bed reactor, and wherein, reducing fixed-bed reactor have the beds of two different inner diameters, is the internal diameter zone of transition of taper between two beds, wherein not loading catalyst.With liquid mixture flow direction in the reactor for benchmark, the beds being positioned at upstream is called the first beds, the beds being positioned at downstream is called the second beds.The ratio of the internal diameter of the first beds and the second beds is 5:1.
Loading catalyst C9 in first beds, loading catalyst C10 in the second beds, wherein, the weight ratio of C9 and C10 is 10:1.
Benzene, tertbutyl peroxide and the acetonitrile as solvent are mixed, forms liquid mixture.Described liquid mixture is sent fixed-bed reactor from bottom, and flows through the first beds and the second beds successively, carry out oxidizing reaction.Wherein, in liquid mixture, the mol ratio of benzene and tertbutyl peroxide is 1:5, and the mol ratio of benzene and acetonitrile is 1:20.The weight hourly space velocity of benzene is 15h
-1.Temperature in first beds and the second beds all controlled to be 95 DEG C, the pressure-controlling in fixed-bed reactor is 1.5MPa.
React continuously, monitor the composition of the effluent flowed out from fixed-bed reactor in reaction process, and calculate benzene transformation efficiency, oxygenant effective rate of utilization and phenol selectivity.The result of reacting 2 hours and 500 hours is listed in table 3.
Embodiment 18
Adopt the method Oxybenzene identical with embodiment 17, unlike, the temperature of the first beds is 95 DEG C, and the temperature of the second beds is 75 DEG C.
React continuously, monitor the composition of the effluent flowed out from fixed-bed reactor in reaction process, and calculate benzene transformation efficiency, oxygenant effective rate of utilization and phenol selectivity.The result of reacting 2 hours and 520 hours is listed in table 3.
Table 3
Claims (13)
1. a benzene oxidatoin method, under the method is included in oxidation reaction condition, a kind of liquid mixture is made to flow through the first beds and the second beds successively, described liquid mixture contains benzene, at least one oxygenant and optional at least one solvent, described first beds and described second beds are filled with at least one HTS separately, and the superfacial velocity that liquid mixture flows through the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, wherein, v
1<v
2.
2. method according to claim 1, wherein, the HTS of loading in the HTS of loading in described first beds and described second beds is identical or different.
3. method according to claim 2, wherein, the HTS of loading in described first beds is hollow HTS, the crystal grain of described hollow HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
4. method according to claim 3, wherein, the HTS of loading in described second beds is titanium-silicon molecular sieve TS-1.
5. according to the method in claim 1-4 described in any one, wherein, at least part of HTS of loading in described second beds be through regeneration at least one reaction unit draw off agent, described in draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off agent.
6. the amount of the HTS of according to the method in claim 1-4 described in any one, wherein, by weight, loading in described first beds is w
1, the amount of the HTS of loading in described second beds is w
2, w
1/ w
2for 0.1-20, be preferably 2-10.
7. method according to claim 1, wherein, the residence time of described liquid mixture in described beds is T, and the residence time in described first beds is T
1, T
1/ T=0.2-0.95; Preferably, T
1/ T=0.5-0.85.
8. method according to claim 1, wherein, the temperature of described first beds is compared with the temperature height 5-30 DEG C of the second beds.
9. method according to claim 1, wherein, the method also comprises sends at least one alkaline matter in described liquid mixture, and the feeding amount of described alkaline matter makes the pH value of described liquid mixture be in the scope of 6.5-9.
10. according to the method in claim 1-4 and 7-9 described in any one, wherein, v
2/ v
1=1.5-10; Preferably, v
2/ v
1=2-5.
11. methods according to claim 1, wherein, the mol ratio of benzene and described oxygenant is 0.1-50:1.
12. according to the method in claim 1-4,7-9 and 11 described in any one, and wherein, described oxygenant is superoxide.
13. according to the method in claim 1-4,7-9 and 11 described in any one, in the scope of each comfortable 20-150 of temperature DEG C of described first beds and described second beds; In gauge pressure, the pressure in reactor is in the scope of 0-5MPa; The weight hourly space velocity of benzene is 0.01-20h
-1.
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