CN105523898B - A kind of method of oxidation of phenol - Google Patents
A kind of method of oxidation of phenol Download PDFInfo
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- CN105523898B CN105523898B CN201410512801.6A CN201410512801A CN105523898B CN 105523898 B CN105523898 B CN 105523898B CN 201410512801 A CN201410512801 A CN 201410512801A CN 105523898 B CN105523898 B CN 105523898B
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Abstract
一种苯酚氧化的方法，是在苯酚氧化的条件下使包括苯酚和氧化剂在内的物料在固定床上与以钛硅分子筛为活性组分的催化剂进行接触，其特征在于所说的固定床有至少串联的第一催化剂床层和第二催化剂床层，所述液体混合物依次流过第一催化剂床层和第二催化剂床层，液体混合物流过第一催化剂床层的表观速度小于流过第二催化剂床层的表观速度。该方法可以在反应接触过程中维持催化剂的活性以及氧化剂总的转化率和目的产物选择性，使总的催化剂单程运行时间延长，同时延缓催化剂失活，提高催化剂总寿命。A kind of method for phenol oxidation is to make materials including phenol and oxidant contact with a catalyst using titanium silicon molecular sieve as active component on a fixed bed under the condition of phenol oxidation, and it is characterized in that said fixed bed has at least The first catalyst bed and the second catalyst bed are connected in series, the liquid mixture flows through the first catalyst bed and the second catalyst bed in sequence, and the superficial velocity of the liquid mixture flowing through the first catalyst bed is lower than that through the second catalyst bed. The superficial velocity of the two catalyst beds. The method can maintain the activity of the catalyst, the total conversion rate of the oxidant and the selectivity of the target product during the reaction contact process, prolong the total catalyst single-pass operation time, delay the deactivation of the catalyst, and improve the total life of the catalyst.
Description
Technical field
The present invention relates to a kind of methods of oxidation of phenol.
Background technique
Hydroquinone and catechol are two kinds of important industrial chemicals and chemical intermediate, and tool has been widely used.It is adjacent
It is anti-oxidant that benzenediol can be used as rubber curing agent, electroplating additive, skin anticorrosion and bactericidal agent, hair dye, photographic developer, color picture
Agent, fur dyeing color developing agent, paint and the anti-peeling agent of varnish.Hydroquinone is mainly used for developer, anthraquinone dye, azo dye
Material, stabilizer, the antioxidant for synthesizing ammonia cosolvent, rubber antioxidant, polymerization inhibitor, coating and essence.
In the prior art by by aromatic hydroxy compound (such as phenol) use oxygen or oxygen-containing gas, Cu-contained catalyst, and optionally
Promotor aoxidize to form benzoquinones, use reduction reaction then to form hydroquinone.But this method can not be prepared into simultaneously
To benzoquinones and benzenediol.
Last century early eighties, Italian Taramasso disclose a kind of referred to as titanium silicon point in USP4410501
The new catalytic oxidation material of son sieve (TS-1), it has good selective oxidation to hydrocarbon, alcohol, phenol etc.
(EP0230949, USP4480135, USP4396783).
Use Titanium Sieve Molecular Sieve that can obtain hydroquinone and catechol simultaneously as catalyst.But this preparation
The leeway that method phenol conversion, the selectivity of purpose product benzenediol and catalyst life etc. are still improved.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of prior art, the conversion ratio and purpose product benzenediol of oxidant are maintained
Selectivity extends oxidation of phenol parallel-adder settle-out time and provides a kind of reaction method of oxidation of phenol in higher level.
The method of oxidation of phenol provided by the invention is to make the liquid containing phenol and oxidant under conditions of oxidation of phenol
Body mixture is contacted with the catalyst that Titanium Sieve Molecular Sieve is active component on a fixed bed, it is characterised in that described fixation
Bed has at least concatenated first catalyst bed and the second catalyst bed, the liquid mixture to flow successively through the first catalyst
Bed and the second catalyst bed, the superficial velocity that liquid mixture flows through the first catalyst bed is v1, flow through the second catalysis
The superficial velocity of agent bed is v2, v1< v2；The Titanium Sieve Molecular Sieve loaded in the first catalyst bed, crystal grain are hollow knot
Structure, the radical length of the chamber portion of the hollow structure are 5-300 nanometers, and in 25 DEG C, P/P0=0.10, adsorption time 1
The benzene adsorbance measured under conditions of hour is at least 70 milligrams per grams, the adsorption isotherm of the nitrogen absorption under low temperature of the Titanium Sieve Molecular Sieve
There are hysteresis loops between line and desorption isotherm.
Using method of the invention, the activity of catalyst and oxidant can be maintained total in reaction contact process
Conversion ratio and purpose product selectivity, extends total catalyst one way runing time, while delaying catalyst inactivation, raising
Catalyst entire life.Process of the present invention is simple and easy to control, is conducive to industrialized production and application.
Specific embodiment
The present invention provides a kind of method of oxidation of phenol, this method is included under oxidation reaction condition, makes containing phenol
The first catalyst bed and the second catalyst bed, first catalyst bed are flowed successively through with the liquid mixture of oxidant
At least one Titanium Sieve Molecular Sieve is respectively filled with second catalyst bed.
In the present invention, "at least one" indicates one or more (such as two or more).
According to the method for the present invention, it is v that liquid mixture, which flows through the superficial velocity of the first catalyst bed,1, flow through second
The superficial velocity of catalyst bed is v2, wherein v1<v2.It is preferred that v2/v1For 1.1-10, more preferable v2/v1For 1.2-8.The present invention
In, the superficial velocity refers in the unit time through the mass flow of the liquid mixture of place catalyst bed (with m3/s
Meter) with the cross-sectional area of the catalyst bed (with m2Meter) ratio.Liquid mixture apparent speed in the first catalyst bed
Degree generally can be in the range of 0.01-100m/s.
The liquid mixture can be adjusted using various methods in the first catalyst bed and the second catalyst bed
In superficial velocity.For example, the apparent linear velocity of liquid mixture can be adjusted by the cross-sectional area of selecting catalyst bed
Degree.Specifically, the cross-sectional area of first catalyst bed can be made to be greater than the cross-sectional area of second catalyst bed,
So that v1<v2, it is preferable that v2/v1For 1.1-10, more preferably make v2/v1For 1.2-8.At this point, the liquid mixture
It can be identical by the mass flow of the first catalyst bed and the second catalyst bed, or it is different, as long as can be really
Guarantor's liquid mixture flows through the first catalyst bed and the superficial velocity of the second catalyst bed can satisfy previously described want
It asks.The method that the cross-sectional area of catalyst bed is determined according to expected superficial velocity is that those skilled in the art institute is public
Know, is no longer described in detail herein.For example, it is also possible to adjust the lines of expression of liquid mixture by the height of selecting catalyst bed
Speed.Specifically, the height of first catalyst bed can be made to be less than the height of second catalyst bed, to make
Obtain v1<v2.At this point, the liquid mixture can be by the mass flow of the first catalyst bed and the second catalyst bed
It is identical, or it is different, as long as can ensure that liquid mixture flows through the table of the first catalyst bed and the second catalyst bed
Seeing speed can satisfy previously described requirement.The side of the height of catalyst bed is determined according to expected superficial velocity
Method be it is known in those skilled in the art, be also no longer described in detail herein.And particularly, those skilled in the art can be combined with
Liquid mixture is adjusted above by the cross-sectional area of selecting catalyst bed and by the height of selecting catalyst bed
Superficial linear vilocity adjusts the superficial linear vilocity of liquid mixture by the draw ratio of catalyst bed.Draw ratio refers to herein
The ratio of the diameter of the height and cross section of catalyst bed (is the area of cross section if catalyst bed cross section is non-circular
It is converted into the circular respective diameters of homalographic).Specifically, the draw ratio of first catalyst bed can be made to be less than described
The draw ratio of second catalyst bed, so that v1<v2.At this point, the liquid mixture passes through the first catalyst bed and the
The mass flow of two catalyst beds can be identical, or it is different, as long as can ensure that liquid mixture flows through first and urges
The superficial velocity of agent bed and the second catalyst bed can satisfy previously described requirement.According to expected apparent speed
It is known in those skilled in the art for spending the method that determines the draw ratio of catalyst bed, is also no longer described in detail herein.
According to the method for the present invention, as described above, wherein the first catalyst bed and the second catalyst bed in operational process
The mass flow of layer may be the same or different.Preferably, the first catalyst bed and the second catalyst bed in operational process
The mass flow of layer is identical.Herein in the mass flow of the first catalyst bed and the second catalyst bed identical finger unit time
The quality of material total amount for flowing through the first catalyst bed is identical with the quality of material total amount of the second catalyst bed is flowed through, that is, flows through
The material of first catalyst bed all flows through the second catalyst bed, and flows through the material whole source of the second catalyst bed
In the material for flowing through the first catalyst bed.
According to the method for the present invention, first catalyst bed and the second catalyst bed respectively can containing one or
Multiple catalyst beds.It is multiple to urge when the first catalyst bed and/or the second catalyst bed contain multiple catalyst beds
Between agent bed can for be connected in series, or be connected in parallel, can also for series connection with combination in parallel, such as: by
Multiple catalyst beds are divided into multiple groups, and the catalyst bed in every group is to be connected in series and/or be connected in parallel, and are string between each group
Connection is connected and/or is connected in parallel.First catalyst bed and second catalyst bed can be set in same reaction
The different zones of device also can be set in different reactors.
Titanium Sieve Molecular Sieve is the general name that titanium atom replaces a kind of zeolite of a part of silicon atom in lattice framework, can use change
Formula xTiO2·SiO2It indicates.The content of titanium atom in Titanium Sieve Molecular Sieve is not particularly limited in the present invention, can be ability
The conventional selection in domain.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, more preferably 0.015-0.025.
The Titanium Sieve Molecular Sieve can be the common Titanium Sieve Molecular Sieve with various topological structures, such as: the titanium silicon
Molecular sieve can be selected from Titanium Sieve Molecular Sieve (such as TS-1), Titanium Sieve Molecular Sieve (such as TS-2), the BEA structure of MEL structure of MFI structure
Titanium Sieve Molecular Sieve (such as Ti-Beta), the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, the Titanium Sieve Molecular Sieve of MOR structure
Titanium Sieve Molecular Sieve (such as Ti-MCM- of the Titanium Sieve Molecular Sieve (such as Ti-TUN) of (such as Ti-MOR), TUN structure, two-dimentional hexagonal structure
41, Ti-SBA-15) and other structures Titanium Sieve Molecular Sieve (such as Ti-ZSM-48).The Titanium Sieve Molecular Sieve is preferably MFI knot
The Titanium Sieve Molecular Sieve of the Titanium Sieve Molecular Sieve of structure, the Titanium Sieve Molecular Sieve of MEL structure and BEA structure, more preferably the titanium silicon of MFI structure
Molecular sieve.
In the first catalyst bed, the Titanium Sieve Molecular Sieve of filling, crystal grain is hollow structure, the cavity portion of the hollow structure
The radical length divided is 5-300 nanometers, and the Titanium Sieve Molecular Sieve is in 25 DEG C, P/P0=0.10, the condition that adsorption time is 1 hour
Under the benzene adsorbance that measures be at least 70 milligrams per grams, adsorption isotherm and desorption of the nitrogen absorption under low temperature of the Titanium Sieve Molecular Sieve etc.
There are hysteresis loops between warm line.It is preferred that MFI structure.The hollow Titanium Sieve Molecular Sieve, which is commercially available, (such as is commercially available from China
The trade mark of petrochemical industry Hunan Jianchang Petrochemical Co., Ltd is the molecular sieve of HTS), it can also be according to disclosed in CN1132699C
Method is prepared.
The Titanium Sieve Molecular Sieve loaded in second catalyst bed and the titanium silicon molecule loaded in the first catalyst bed
Sieve can be the same or different, preferably different, i.e., preferably different from the Titanium Sieve Molecular Sieve of hollow Titanium Sieve Molecular Sieve, such as
TS-1。
According to the method for the present invention, the Titanium Sieve Molecular Sieve can be Titanium Sieve Molecular Sieve original powder, or molding titanium silicon
Molecular sieve.
It is loaded in the amount for the Titanium Sieve Molecular Sieve loaded in first catalyst bed and second catalyst bed
The amount of Titanium Sieve Molecular Sieve can be identical, or different.Generally, the titanium silicon loaded in first catalyst bed point
The amount of son sieve is w1, the amount for the Titanium Sieve Molecular Sieve loaded in second catalyst bed is w2, w1/w2For 0.1-20, preferably
0.2-10.When Titanium Sieve Molecular Sieve is molding Titanium Sieve Molecular Sieve, w1And w2By containing for the Titanium Sieve Molecular Sieve in molding Titanium Sieve Molecular Sieve
Amount determines.
The total amount of the Titanium Sieve Molecular Sieve is (that is, the Titanium Sieve Molecular Sieve in the first catalyst bed and the second catalyst bed
Total amount) can be selected according to the specific treating capacity of system.Generally, with first catalyst bed and described second
On the basis of the total amount of Titanium Sieve Molecular Sieve in catalyst bed, the weight space velocity of the phenol can be 0.1-20h-1, preferably
0.2-10h-1。
According to the method for the present invention, it respectively can only be filled in first catalyst bed and second catalyst bed
Titanium Sieve Molecular Sieve is filled out, Titanium Sieve Molecular Sieve and inactive filler can also be contained.Inactive filler energy is loaded in catalyst bed
It is enough that the amount of Titanium Sieve Molecular Sieve in catalyst bed is adjusted, so that the speed to reaction is adjusted.It is urged described first
It is non-live in catalyst bed when agent bed and second catalyst bed respectively contain Titanium Sieve Molecular Sieve and inactive filler
The content of property filler can be 5-95 weight %.The inactive filler refers to no to oxidation reaction or basic without catalysis work
The filler of property, specific example can include but is not limited to: one of quartz sand, ceramic ring and potsherd are a variety of.
According to the method for the present invention, the oxidant can for it is common it is various can be by the substance of oxidation of phenol.It is preferred that
Ground, the oxidant are peroxide.The peroxide refers to the compound for containing-O-O- key in molecular structure, Ke Yixuan
From hydrogen peroxide, organic peroxide and peracid.The organic peroxide refers to one or two of hydrogen peroxide molecule
Substance obtained from hydrogen atom is replaced by organic group.The peracid refers to the organic oxygen-containing for containing-O-O- key in molecular structure
Acid.The specific example of the peroxide can include but is not limited to: hydrogen peroxide, tert-butyl hydroperoxide, peroxidating isopropyl
Benzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide, in this way can be into one
Step reduces separation costs.The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.
The dosage of the oxidant can be selected according to the amount of phenol, generally, the phenol and the oxidant
Molar ratio can be 0.1-10:1, preferably 0.2-5:1.The condition of the oxidation of phenol are as follows: 0-120 DEG C of temperature, pressure
0.01-5MPa, preferable temperature is 20-100 DEG C, reaction pressure 0.1-3MPa.Wherein, first catalyst bed and described
The reaction temperature of second catalyst bed can be the same or different.In the preferred embodiment of the present invention, described first
The temperature of catalyst bed is higher than described 5-30 DEG C of second catalyst bed, so can get better purpose product selectivity and
The single pass life of catalyst further decreases the difficulty of product later separation purifying.
According to the method for the present invention, the liquid mixture can contain solvent, can also not contain solvent, preferably described
Liquid mixture also contains at least one solvent, can preferably control the speed and severe degree of reaction in this way.The present invention couple
It is not particularly limited in the type of the solvent, the solvent can be common various solvents in oxidation of phenol reaction.It is preferred that
Ground, the solvent are water, C1-C10Alcohol, C3-C10Ketone, C2-C10Nitrile and C1-C6At least one of carboxylic acid.Preferably,
The solvent is C1-C6Alcohol, C3-C8Ketone and C2-C5One or more of nitrile.It is highly preferred that the solvent is
One or more of water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol and acetone.Further preferably
Ground, the solvent are one or more of water, methanol, acetone and tert-butyl alcohol.Generally, the solvent and phenol rub
You are than being 1-100:1, preferred molar ratio 2-80:1.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, pressure is in terms of gauge pressure.
In following embodiment and comparative example, hollow Titanium Sieve Molecular Sieve used is according to public in Chinese patent CN1132699C
The method preparation opened, through analyzing, which is MFI structure, and titanium oxide content is 2.5 weight %, the titanium silicon point
There are hysteresis loop between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of son sieve, crystal grain is hollow crystal grain and cavity portion
The radical length divided is 15-180 nanometers；The Titanium Sieve Molecular Sieve sample is at 25 DEG C, P/P0=0.10, adsorption time is 1 hour
Under the conditions of the benzene adsorbance that measures be 78 milligrams per grams, titanium oxide content is 2.5 weight %.
Titanium-silicon molecular sieve TS-1 used is by Journal of Natural Gas Chemistry, 2001,10 (4):
In 295-307 prepared by method described in the 9-24 row of page 296, and titanium oxide content is 2.5 weight %.
It forms hollow Titanium Sieve Molecular Sieve and contains hollow Titanium Sieve Molecular Sieve and the silica as oxidant, to form hollow titanium
On the basis of the total amount of si molecular sieves, the content of hollow Titanium Sieve Molecular Sieve is 75 weight %, and the content of silica is 25 weight %.
Molding titanium-silicon molecular sieve TS-1 contains titanium-silicon molecular sieve TS-1 and the silica as binder, to form titanium silicon point
On the basis of the total amount of son sieve TS-1, the content of titanium-silicon molecular sieve TS-1 is 75 weight %, and the content of silica is 25 weight %.
In embodiment and comparative example, agents useful for same is ommercially available AR, and hydrogen peroxide is mass concentration 30%
Aqueous hydrogen peroxide solution.
In comparative example and embodiment:
Embodiment 1
It reacts and is carried out in the micro fixed-bed reactor being connected in series at two, wherein load one in each reactor
Cross section is circular isometrical catalyst bed, first reaction on the basis of the flow direction of liquid material, positioned at upstream
The internal diameter of the first catalyst bed in device and the internal diameter of the second catalyst bed in second reactor for being located at downstream
Ratio is 2:1, filling molding hollow titanium si molecular sieves in the first catalyst bed, filling molding titanium silicon in the second catalyst bed
The weight ratio of molecular sieve TS-1, hollow Titanium Sieve Molecular Sieve and titanium-silicon molecular sieve TS-1 is 2:1.
By phenol, as the hydrogen peroxide (in the form of the hydrogen peroxide of 30 weight % provide) of oxidant and as solvent
Methanol is sent into from the bottom of first reactor, by the first catalyst bed with be loaded on molding hollow titanium silicon therein and divide
Son sieve contact；The liquid mixture exported from first reactor then continuously enters in second reactor, urges by second
Agent bed with be loaded on molding titanium-silicon molecular sieve TS-1 therein and contact, the first catalyst bed and second in operational process
The mass flow of catalyst bed is identical.
Wherein, the molar ratio of phenol and oxidant is 4:1, and the weight ratio of solvent and phenol is 15:1；By the first catalyst
Temperature in bed and the second catalyst bed is controlled as 70 DEG C, the pressure in first reactor and second reactor
Respectively 1.8MPa；On the basis of the total amount of the Titanium Sieve Molecular Sieve in the first catalyst bed and the second catalyst bed, phenol
Weight space velocity be 2h-1, superficial velocity of the liquid mixture in first reactor is 0.1m/s.
Continuous operation under the above conditions in operational process, detects the reaction mixture exported from second reactor
Composition, and calculate oxidant conversion ratio, oxidant effective rate of utilization, benzenediol selectivity.Wherein, the reaction time be 1 hour,
Result at 120 hours and 240 hours is listed in table 1.
Embodiment 2
Using method oxidation of phenol same as Example 1, the difference is that, adjust the first catalyst bed and the second catalysis
The reaction temperature of catalyst in agent bed, so that the reaction temperature of the first catalyst bed is 70 DEG C, the second catalyst bed
Reaction temperature is 55 DEG C.
Result when reaction time is 1 hour, 120 hours and 240 hours is listed in table 2.
Embodiment 3
Using method same as Example 1, the difference is that, it adjusts in the first catalyst bed and the second catalyst bed
The reaction temperature of catalyst, so that the reaction temperature of the first catalyst bed is 55 DEG C, the reaction temperature of the second catalyst bed
It is 70 DEG C.
Result when reaction time is 1 hour, 120 hours and 240 hours is listed in table 2.
Comparative example 1
It reacts and is carried out in the micro fixed-bed reactor being connected in series at two, wherein load one in each reactor
Cross section is circular isometrical catalyst bed, first reaction on the basis of the flow direction of liquid material, positioned at upstream
The internal diameter of the first catalyst bed in device and the internal diameter of the second catalyst bed in second reactor for being located at downstream
Ratio is 1:1, filling molding hollow titanium si molecular sieves in the first catalyst bed, filling molding titanium silicon in the second catalyst bed
The weight ratio of molecular sieve TS-1, hollow Titanium Sieve Molecular Sieve and titanium-silicon molecular sieve TS-1 is 2:1.
By phenol, as the hydrogen peroxide (in the form of the hydrogen peroxide of 30 weight % provide) of oxidant and as solvent
Methanol is sent into from the bottom of first reactor, by the first catalyst bed with be loaded on molding hollow titanium silicon therein and divide
Son sieve contact；The liquid mixture exported from first reactor then continuously enters in second reactor, passes through the second catalysis
Agent bed with be loaded on molding titanium-silicon molecular sieve TS-1 therein and contact.
Wherein, the molar ratio of phenol and oxidant is 4:1, and the weight ratio of solvent and phenol is 15:1；By the first catalyst
Temperature in bed and the second catalyst bed is controlled as 70 DEG C, the pressure in first reactor and second reactor
Respectively 1.8MPa；On the basis of the total amount of the Titanium Sieve Molecular Sieve in the first catalyst bed and the second catalyst bed, phenol
Weight space velocity be 2h-1, the superficial velocity of liquid mixture in a second reactor is 0.1m/s.
Result when reaction time is 1 hour, 80 hours and 120 is listed in table 1.
Comparative example 2
It reacts and is carried out in the micro fixed-bed reactor being connected in series at two, wherein load one in each reactor
Cross section is circular isometrical catalyst bed, first reaction on the basis of the flow direction of liquid material, positioned at upstream
The internal diameter of the first catalyst bed in device and the internal diameter of the second catalyst bed in second reactor for being located at downstream
Ratio is 1:2, filling molding hollow titanium si molecular sieves in the first catalyst bed, filling molding titanium silicon in the second catalyst bed
The weight ratio of molecular sieve TS-1, hollow Titanium Sieve Molecular Sieve and titanium-silicon molecular sieve TS-1 is 0.5:1.
By phenol, as the hydrogen peroxide (in the form of the hydrogen peroxide of 30 weight % provide) of oxidant and as solvent
Methanol is sent into from the bottom of first reactor, by the first catalyst bed with be loaded on molding hollow titanium silicon therein and divide
Son sieve contact；The liquid mixture exported from first reactor then continuously enters in second reactor, passes through the second catalysis
Agent bed with be loaded on molding titanium-silicon molecular sieve TS-1 therein and contact.
Wherein, the molar ratio of phenol and oxidant is 4:1, and the weight ratio of solvent and phenol is 15:1；By the first catalyst
Temperature in bed and the second catalyst bed is controlled as 70 DEG C, the pressure in first reactor and second reactor
Respectively 1.8MPa；On the basis of the total amount of the Titanium Sieve Molecular Sieve in the first catalyst bed and the second catalyst bed, phenol
Weight space velocity be 2h-1, superficial velocity of the liquid mixture in first reactor is 0.5m/s.
Result when reaction time is 1 hour, 80 hours and 120 is listed in table 1.
Table 1
Embodiment 4
The hollow Titanium Sieve Molecular Sieve of molding used in the present embodiment contains hollow Titanium Sieve Molecular Sieve and the oxygen as binder
SiClx, on the basis of the total amount for forming hollow Titanium Sieve Molecular Sieve, the content of hollow Titanium Sieve Molecular Sieve is 85 weight %, silica
Content is 15 weight %.
The molding titanium-silicon molecular sieve TS-1 of use contains titanium-silicon molecular sieve TS-1 and the silica as binder, with molding
On the basis of the total amount of titanium-silicon molecular sieve TS-1, the content of titanium-silicon molecular sieve TS-1 is 85 weight %, and the content of silica is 15 weights
Measure %.
It reacts and is carried out in the micro fixed-bed reactor being connected in series at two, wherein load one in each reactor
Cross section is circular isometrical catalyst bed, first reaction on the basis of the flow direction of liquid material, positioned at upstream
The internal diameter of the first catalyst bed in device and the internal diameter of the second catalyst bed in second reactor for being located at downstream
Ratio is 5:1, filling molding hollow titanium si molecular sieves in the first catalyst bed, filling molding titanium silicon in the second catalyst bed
The weight ratio of molecular sieve TS-1, hollow Titanium Sieve Molecular Sieve and titanium-silicon molecular sieve TS-1 is 10:1.
By phenol, as the hydrogen peroxide (in the form of the hydrogen peroxide of 30 weight % provide) of oxidant and as solvent
Acetone is sent into from the bottom of first reactor, by the first catalyst bed with be loaded on molding hollow titanium silicon therein and divide
Son sieve contact；The liquid mixture exported from first reactor then continuously enters in second reactor, passes through the second catalysis
Agent bed with be loaded on molding titanium-silicon molecular sieve TS-1 therein and contact, the first catalyst bed and second is urged in operational process
The mass flow of agent bed is identical.
Wherein, the molar ratio of phenol and oxidant is 3:1, and the weight ratio of solvent and phenol is 10:1；By the first catalyst
Temperature in bed and the second catalyst bed is controlled as 90 DEG C, the pressure in first reactor and second reactor
Respectively 0.5MPa；On the basis of the total amount of the Titanium Sieve Molecular Sieve in the first catalyst bed and the second catalyst bed, phenol
Weight space velocity be 6h-1, superficial velocity of the liquid mixture in first reactor is 0.5m/s.
Continuous operation under the above conditions in operational process, detects the reaction mixture exported from second reactor
Composition, and calculate oxidant conversion ratio, oxidant effective rate of utilization, benzenediol selectivity, wherein the reaction time be 1 hour,
120 hours and result when 240 are listed in table 2.
Embodiment 5
Using method same as Example 4, the difference is that, it is catalyzed in the first catalyst bed and the second catalyst bed
Under conditions of the loadings of agent are constant, the internal diameter of the first catalyst bed and the second catalyst bed is adjusted, so that the first catalysis
The ratio of the internal diameter of the internal diameter of agent bed and the second catalyst bed is 2:1.
Result when reaction time is 1 hour, 120 hours and 240 is listed in table 2.
Embodiment 6
Using method same as Example 4, the difference is that, it is catalyzed in the first catalyst bed and the second catalyst bed
Under conditions of the loadings of agent are constant, the internal diameter of the first catalyst bed and the second catalyst bed is adjusted, so that the first catalysis
The ratio of the internal diameter of the internal diameter of agent bed and the second catalyst bed is 15:1.
Result when reaction time is 1 hour, 120 hours and 240 is listed in table 2.
Embodiment 7
Using method same as Example 4, the difference is that, it is catalyzed in the first catalyst bed and the second catalyst bed
Under conditions of the loadings of agent are constant, the internal diameter of the first catalyst bed and the second catalyst bed is adjusted, so that the first catalysis
The ratio of the internal diameter of the internal diameter of agent bed and the second catalyst bed is 3:2.
Result when reaction time is 1 hour, 120 hours and 240 is listed in table 2.
Embodiment 8
Using method same as Example 4, the difference is that, it adjusts in the first catalyst bed and the second catalyst bed
The reaction temperature of catalyst, so that the reaction temperature of the first catalyst bed is 90 DEG C, the reaction temperature of the second catalyst bed
It is 70 DEG C.
Result when reaction time is 1 hour, 120 hours and 240 is listed in table 2.
Embodiment 9
Using method same as Example 4, the difference is that, it adjusts in the first catalyst bed and the second catalyst bed
The reaction temperature of catalyst, so that the reaction temperature of the first catalyst bed is 70 DEG C, the reaction temperature of the second catalyst bed
It is 90 DEG C.
Result when reaction time is 1 hour, 120 hours and 240 is listed in table 2.
Embodiment 10
Using method same as Example 4, the difference is that, it adjusts in the first catalyst bed and the second catalyst bed
The reaction temperature of catalyst, so that the reaction temperature of the first catalyst bed is 90 DEG C, the reaction temperature of the second catalyst bed
It is 100 DEG C.
Result when reaction time is 1 hour, 120 hours and 240 is listed in table 2.
Table 2
From embodiment and comparative example it can be seen that production method of the invention maintains oxidant effective rate of utilization and purpose to produce
Object selectivity delays catalyst inactivation in higher range, extends total runing time, and then improves catalyst
Entire life.
Claims (9)
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| CN201410512801.6A CN105523898B (en) | 2014-09-29 | 2014-09-29 | A kind of method of oxidation of phenol |
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| CN201410512801.6A CN105523898B (en) | 2014-09-29 | 2014-09-29 | A kind of method of oxidation of phenol |
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| US5493061A (en) * | 1994-12-09 | 1996-02-20 | Council Of Scientific & Industrial Research | Process for the conversion of phenol to hydroquinone and catechol |
| US5808167A (en) * | 1996-08-20 | 1998-09-15 | Solutia Inc. | Selective introduction of active sites for hydroxylation of benzene |
| EP0962439A1 (en) * | 1998-05-29 | 1999-12-08 | Ube Industries, Ltd. | Process and apparatus for producing dihydric phenolic compound |
| CN102757301A (en) * | 2011-04-29 | 2012-10-31 | 中国石油化工股份有限公司 | Method for oxidizing phenol |
| CN102850188A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Method for simultaneously producing hydroquinone and catechol |
| CN104341274A (en) * | 2013-07-31 | 2015-02-11 | 中国石油化工股份有限公司 | Method for simultaneously producing dihydroxybenzene and benzoquinone |
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| CN1132699C (en) * | 1999-12-24 | 2003-12-31 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
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| GB2116974A (en) * | 1982-03-19 | 1983-10-05 | Anic Spa | Process for hydroxylating aromatic hydrocarbons |
| US5493061A (en) * | 1994-12-09 | 1996-02-20 | Council Of Scientific & Industrial Research | Process for the conversion of phenol to hydroquinone and catechol |
| US5808167A (en) * | 1996-08-20 | 1998-09-15 | Solutia Inc. | Selective introduction of active sites for hydroxylation of benzene |
| EP0962439A1 (en) * | 1998-05-29 | 1999-12-08 | Ube Industries, Ltd. | Process and apparatus for producing dihydric phenolic compound |
| CN102757301A (en) * | 2011-04-29 | 2012-10-31 | 中国石油化工股份有限公司 | Method for oxidizing phenol |
| CN102850188A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Method for simultaneously producing hydroquinone and catechol |
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