CN105523910B - Oxidation method for cyclohexane - Google Patents
Oxidation method for cyclohexane Download PDFInfo
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Abstract
The invention provides an oxidation method for cyclohexane. The method comprises the step of subjecting a liquid mixture containing cyclohexane and an oxidant to passing through catalyst beds under the condition of oxidation reaction, wherein the catalyst beds comprise a first catalyst bed and a second catalyst bed; on the basis of the flow direction of the liquid mixture, the first catalyst bed is located at the upper stream of the second catalyst bed; a titanium-silicon molecular sieve filled in the first catalyst bed is a hollow titanium-silicon molecular sieve; and the titanium-silicon molecular sieve filled in the second catalyst bed is the titanium-silicon molecular sieve different from the hollow titanium-silicon molecular sieve. The method provided by the invention can effectively prolong the single-way service life of the titanium-silicon molecular sieve used as a catalyst, reduce regeneration frequency of the catalyst, improve production efficiency, and enhance operation stability and prolong the total service life of the catalyst at the same time.
Description
Technical field
The present invention relates to a kind of cyclohexane oxidation processes.
Background technology
Cyclohexanone is a kind of important industrial chemicals, is widely used in fiber, synthetic rubber, industrial coating, medicine, agriculture
The industry of medicine, organic solvent.Cyclohexanol is also a kind of important industrial chemicals, for adipic acid processed, plasticizer and detergent etc.,
It is also used for solvent and emulsifying agent.Especially because polyamide industry is developed rapidly, as preparing in the middle of nylon-6 and nylon -66
The demand of the cyclohexanone (alcohol) of body is annual all more than 1,000,000 tons in the whole world.Now, cyclohexanone production process route is main
There are three kinds：Cyclohexane liquid-phase oxidation method, phenol hydrogenation method and part of benzene hydrogenation method, and cyclohexane oxidation process is industrially to produce ring
The main process of hexanone, accounts for more than 90%.But, efficiency is minimum during this production process is also considered as all chemical industry process
One.Cyclohexane oxidation synthesizing cyclohexanone process is one of crucial and bottleneck of restriction caprolactam production.
It is industrial typically to have three kinds of methods using cyclohexane oxidation production cyclohexanone：A kind of is that to use cobalt salt be catalyst
Catalysis oxidation, this method cyclohexane conversion is higher, but causes the easy fouling of reactor due to forming adipic acid cobalt, substantially
It is eliminated.Two is boric acid class catalytic oxidation, and this method capital expenditure is high, and high energy consumption, technique is extremely complex, and operation difficulty is big, and
Easily cause equipment and pipeline Severe blockage.Three is the non-catalyst oxidation for using air direct oxidation, and this method effectively prevent instead
The problem of device fouling is answered, is industrially widely applied, but the complex process, intermediate steps are more, low cyclohexane conversion rate, hexamethylene
Internal circulating load is big, high energy consumption, pollutes also larger, particularly in cyclohexyl hydroperoxide decomposable process, cyclohexanone (alcohol) selectivity
Poor, yield is low.Additionally, a large amount of spent lyes that the process is produced, difficult treatment is still global the difficult problem of environmental protection so far.Cause
This, can be directed to the deficiency of existing process, work out that a kind of cyclohexane conversion is high, and cyclohexanone and cyclohexanol are selectively good, dirty
Dye is small, and environmentally friendly and process is simple new technology is of great practical significance.
A kind of new catalytic oxidation material-HTS (TS-1) is disclosed in USP4410501, it is to hydrocarbon, alcohol, phenol
Deng with good selective oxidation, oxidation of phenol preparing benzenediol, cyclohexanone oxamidinating, epoxidation of propylene are such as applied to
Oneself realizes industrialization.Document (such as J Catal, 1995,157：631~635, Applied Catal A：Gen 2001,211：
1~17 and J Natural Gas Chem 2001,10：295~307) titanium molecular sieve catalysis cyclohexane oxidation is carried out
Research.Generally speaking, reaction condition is gentle, and technical process is simple, environment-friendly.But still generally existing cyclohexane conversion
The low problem of low, effective utilization ratio of hydrogen peroxide, while catalyst is not readily separated so that product and catalyst separation costs are carried
It is high.
During using HTS as catalyst oxidizing ethyle alkyl, common problem is, with prolonging for reaction time
Long, the catalysis activity of HTS can be on a declining curve, causes oxidant conversion ratio, oxidant effective rate of utilization and target oxygen
Change selectivity of product reduction.
And after device operating a period of time, the activity and selectivity of catalyst can be reduced, i.e., catalyst is in operation process
Deactivation phenomenom occurs.Main settling mode is that decaying catalyst is carried out into in-situ regeneration or ex-situ regeneration so that catalyst at present
Activity recovery.Wherein, in-situ regeneration is generally used at a certain temperature mainly for the lighter situation of catalyst inactivation
Solvent and/or oxidant carry out dipping or the flushing of a period of time to decaying catalyst；Ex-situ regeneration loses mainly for catalyst
The more serious situation of degree living, is usually calcined to decaying catalyst.Industrially, it is general using first making through in-situ regeneration
Renewing catalyst activity, when in-situ regeneration cannot recover catalyst activity, then using ex-situ regeneration.
But, when the catalyst through regenerating puts into operation again, when particularly being put into operation again after in-situ regeneration, urge
The activity and selectivity fluctuation of agent is larger, it is necessary to be lot more time to stabilization；It is also desirable to reference to raising reaction temperature etc.
Operate to realize the even running of reaction, but can so further speed up catalyst and inactivate and reduce the selection of desirable oxidation product
Property, subsequent product refining spearation is influenceed, also it is unfavorable for safety in production.
Therefore, accessory substance selectivity is reduced, extends the service life of catalyst, particularly single trip use life-span, so as to drop
The regeneration frequency of low catalyst is still the reaction system urgent need to resolve using HTS as catalyst oxidizing ethyle alkyl
Technical problem.
The content of the invention
Present invention seek to address that being carried as the cyclohexane oxidation above shortcomings of catalyst using HTS
For a kind of cyclohexane oxidation processes, even if the method ensure that continuous run in long period also can be by oxidant conversion ratio and target
Oxidation product selectively stabilization can extend as the single trip use longevity of the HTS of catalyst in higher level
Life.
To realize object defined above, the invention provides a kind of cyclohexane oxidation processes, the method includes：In oxidation reaction bar
Under part, the liquid mixture containing hexamethylene and oxidant is set to flow through beds；The beds are urged including first
Agent bed and the second beds, on the basis of the flow direction of liquid mixture, first beds are located at
The upstream of second beds, the HTS of the first beds filling is hollow HTS,
The hollow HTS is the HTS of MFI structure, and the crystal grain of the HTS is hollow-core construction, the hollow knot
The radical length of the chamber portion of structure is 5-300 nanometers, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is 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 HTS
There is hysteresis loop between line and desorption isotherm；
The HTS of the second beds filling is the HTS different from hollow HTS.
In the present invention, it is to include the first beds and the second catalyst bed by by the catalyst bed designs
Layer, on the basis of the flow direction of liquid mixture, first beds are located at the upper of second beds
Trip, the HTS of the first beds filling is hollow HTS, and the hollow HTS is MFI
The HTS of structure, the crystal grain of the HTS is hollow-core construction, the radical length of the chamber portion of the hollow-core construction
It is 5-300 nanometers, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is that the benzene measured under conditions of 1 hour is inhaled
Attached amount is at least 70 milligrams per grams, is existed between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS
Hysteresis loop；The HTS of the second beds filling is the HTS different from hollow HTS.
Make it possible to effectively extend and the regeneration frequency of catalyst reduced as the single trip use life-span of the HTS of catalyst,
While improve production efficiency, it is possible to increase operation stability, extend the terminal life of catalyst.
Using method of the present invention oxidizing ethyle alkyl, in continuous running for a long time, it is obtained in that relatively stable
Oxidant conversion ratio, desirable oxidation selectivity of product higher.Especially, using the method for the present invention, the selectivity of cyclohexanone
Height, so as to reduce the difficulty of later separation purifying.
The method of the present invention is simple and easy to do, is suitable to large-scale application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of cyclohexane oxidation processes, the method includes：Under oxidation reaction condition, make to contain hexamethylene
The liquid mixture of alkane and oxidant flows through beds；The beds are urged including the first beds and second
Agent bed, on the basis of the flow direction of liquid mixture, first beds are located at second catalyst bed
The upstream of layer, the HTS of the first beds filling is hollow HTS, the hollow titanium silicon molecule
The HTS for MFI structure is sieved, the crystal grain of the HTS is hollow-core construction, the footpath of the chamber portion of the hollow-core construction
It is 5-300 nanometers to length, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is to be measured under conditions of 1 hour
Benzene adsorbance be at least 70 milligrams per grams, the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS it
Between there is hysteresis loop；
The HTS of the second beds filling is the HTS different from hollow HTS.
The method according to the invention, the hollow HTS is commercially available (for example builds feldspar commercially available from Hunan
The trade mark for changing limited company is the molecular sieve of HTS), it is also possible to the method according to disclosed in CN1132699C is prepared.
The method according to the invention, the HTS includes that the HTS of the first bed and the second bed can be with
It is HTS original powder, or shaping HTS, is preferably molded HTS.Shaping HTS one
As contain the HTS as active component and the carrier as binding agent, wherein, the content of HTS can be
Conventional selection.Usually, on the basis of the total amount of the shaping HTS, the content of HTS can be 5-95 weights
Amount %, more preferably preferably 10-95 weight %, 70-95 weight %；The content of the carrier can be 5-95 weight %, excellent
Elect 5-90 weight %, more preferably 5-30 weight % as.The carrier of the shaping HTS can be conventional selection, such as oxygen
Change aluminium and/or silica.The method for preparing the shaping HTS is it is known in the art, no longer describing in detail herein.Institute
The granular size for stating shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.Such as exist
When the shaping HTS is spherical, the average grain diameter of the shaping HTS can be 4-10000 microns, preferably
It is 5-5000 microns, such as 40-2000 microns.The average grain diameter is volume average particle size, can be determined using laser particle analyzer.
The method according to the invention, HTS is the class boiling of a part of silicon atom in titanium atom substitution lattice framework
The general name of stone, can use chemical formula xTiO2·SiO2Represent.The present invention is for the no spy of the content of titanium atom in HTS
Do not limit, can be the conventional selection of this area.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, it is more excellent
Elect 0.015-0.025 as.
HTS described in second bed can be it is common with various topological structures different from hollow titanium silicon
The HTS of molecular sieve, it includes all HTSs except hollow HTS, for example：The HTS
HTS (such as TS-1), the HTS (such as TS-2) of MEL structures, the titanium silicon of BEA structures of MFI structure can be selected from
Molecular sieve (such as Ti-Beta), the HTS (such as Ti-MCM-22) of MWW structures, HTS (such as Ti- of MOR structures
MOR), HTS (such as Ti-MCM-41, Ti- of the HTS (such as Ti-TUN) of TUN structures, two-dimentional hexagonal structure
SBA-15) and other structures HTS (such as Ti-ZSM-48).HTS is preferably selected from described in second bed
The HTS of the HTS, the HTS of MEL structures and BEA structures of MFI structure, more preferably MFI structure
HTS, preferably TS-1.
With the method for the invention it is preferred to when desirable oxidation selectivity of product drops to and meets condition 1, the method is also wrapped
Include and be adjusted step, until desirable oxidation selectivity of product is risen to when meeting condition 2, stop the set-up procedure,
Desirable oxidation selectivity of product S under condition 1, sometime ttWith initial target oxidation product selectivity S0Ratio
Value St/S0It is 0.85≤St/S0<1；
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation product selectivity S0Ratio S '/S0For 0.9≤
S’/S0≤1；
The set-up procedure is to improve the mass content of oxidant in the liquid mixture.
In the method according to the invention, more preferably condition 1, St/S0<0.9。
The method according to the invention, more preferably with oxidant in the amplitude raising liquid mixture in 0.02-5%/day
Mass content.
Method according to the invention it is possible to improve the mass content of oxidant in liquid mixture using various methods.
For example：The addition of oxidant when preparing the liquid mixture can be improved to improve the quality of oxidant in liquid mixture
Content.Oxidant with the form of oxidizing agent solution provide when, can by improve the concentration of oxidant in oxidizing agent solution come
Realize improving the mass content of oxidant in liquid mixture, now the consumption of oxidizing agent solution can keep constant, it is also possible to
Accordingly be adjusted (for example, the consumption of oxidizing agent solution is accordingly reduced, to keep the ratio between hexamethylene and oxidant not
Become), as long as can ensure that the mass content of oxidant in liquid mixture to improve.This mode be particularly well-suited to use with
Oxidizing agent solution form (such as hydrogen peroxide) provides the occasion of oxidant (such as hydrogen peroxide), now can be molten by improving oxidant
The concentration of oxidant (such as hydrogen peroxide) in liquid (such as hydrogen peroxide).The initial concentration of oxidant can in the oxidizing agent solution
Think conventional selection, typically can be 20-70 weight %, preferably 20-50 weight %.
The method according to the invention, the HTS and described second loaded in more preferably described first beds
The weight ratio of the HTS loaded in beds can be 1-20：1, preferably 2-10：1, more preferably 2-
4：1.
The method according to the invention, first beds and the second beds each can containing one or
Multiple beds.When the first beds and/or the second beds contain multiple beds, multiple is urged
Can be to be connected in series between agent bed, or be connected in parallel, can also be to connect and combination in parallel, for example：Will
Multiple beds are divided into multigroup, and beds in every group are string to be connected in series and/or being connected in parallel, between each group
Connection is connected and/or is connected in parallel.First beds and second beds can be arranged on same reaction
The different zones of device, it is also possible to be arranged in different reactors.
The method according to the invention, liquid mixture flows through the apparent speed of the first beds and the second beds
Degree can be identical, or different.Preferably, the superficial velocity that liquid mixture flows through the first beds is v1,
The superficial velocity for flowing through the second beds is v2, wherein, v1＜ v2, so can further extend the list of HTS
Journey service life.It is highly preferred that v2/v1=1.5-10.It is further preferred that v2/v1=2-5.
In the present invention, the superficial velocity refers to the matter by the whole liquid mixture of beds in the unit interval
The area of a certain cross section of amount flow (in terms of kg/s) and beds is (with m2Meter) ratio.Usually, can be by list
The quality of the liquid mixture of feeding fixed bed reactors is used as " by whole beds in the unit interval in the time of position
The mass flow of liquid mixture ".In the present invention, do not have for superficial velocity of the liquid mixture in the first beds
Particular/special requirement, typically can be in 0.001-200kg/ (m2S) in the range of.
Liquid mixture can be adjusted using various methods in the first beds and the second beds
Superficial velocity.For example, the superficial velocity of liquid mixture can be adjusted by the cross-sectional area of selecting catalyst bed.Specifically
Ground, can make the cross-sectional area of first beds more than the cross-sectional area of second beds, so that
Obtain v1＜ v2, it is preferable that v2/v1It is 1.5-10, more preferably causes v2/v1It is 2-5.Determined to urge according to expected superficial velocity
The method of the cross-sectional area of agent bed is known in those skilled in the art, is no longer described in detail herein.
The method according to the invention, when the hollow HTS and described second loaded in first beds
The weight ratio of the HTS loaded in beds is 2-10：When 1, to realize v2/v1=2-5, first catalyst
The internal diameter ratio of the internal diameter of bed and the second beds is 2-5：1.
The method according to the invention, residence time of the liquid mixture in the first beds is T1, in catalyst
Total residence time in bed is T, it is preferable that T1/ T=0.3-0.95.It is highly preferred that T1/ T=0.5-0.85, can so obtain
The HTS single trip use life-span for further extending is obtained, and obtains desirable oxidation selectivity of product higher.
The method according to the invention, the temperature of first beds can be with the temperature of the beds
It is identical or different.Extend from further raising desirable oxidation selectivity of product and further the single trip use life-span of HTS
Angle set out, the temperature of preferably described first beds is higher than the temperature of second beds.More preferably
Ground, the temperature of first beds is higher 5-50 DEG C than the temperature of second beds, preferably 10-20 DEG C.
The method according to the invention, when beds contain the first beds and the second beds, root
Fresh material can be supplemented between the first beds and the second beds according to concrete condition, in the first catalyst bed
When layer and/or the second beds are multiple beds, as the case may be can be between the first beds
And/or second between beds to supplementing fresh cyclohexane in the liquid mixture.For example：In the first beds
And second supplement fresh cyclohexane between beds, between the first beds and/or between the second beds
And optional fresh solvent.However, it is desirable to explanation, liquid mixture when determining superficial velocity refers to flow through first to urge
Whole beds (that is, the whole process of the first beds) and whole beds (that is, second of the second beds of agent bed
The whole process of beds) liquid mixture, be not included between the first beds, between the second beds
And first fresh material introduced between beds and the second beds.
The method according to the invention, the beds can only load HTS, it is also possible to contain titanium silicon point
Son sieve and inactive filler.Load in the beds inactive filler can to beds in HTS amount
It is adjusted, so as to be adjusted to the speed reacted.Contain HTS and inactive filler in the beds
When, the content of inactive filler can be 5-95 weight % in beds.The inactive filler refers to oxidation reaction
Without or the basic filler without catalysis activity, its instantiation can be including but not limited to：Quartz sand, ceramic ring and ceramics are broken
One or more in piece.
Total amount (that is, the HTS in the first beds and the second beds of the HTS
Total amount) can be selected according to the specific treating capacity of system.Usually, with first beds and described second
On the basis of the total amount of the HTS in beds, the weight space velocity of the hexamethylene can be 0.1-20h-1, preferably
It is 0.2-10h-1。
The method according to the invention, the oxidant can be it is conventional it is various can be by the material of cyclohexane oxidation.It is excellent
Selection of land, the oxidant is peroxide.The peroxide refers to the compound containing-O-O- keys in molecular structure, can be with
Selected from hydrogen peroxide, organic peroxide and peracid.The organic peroxide refers to or two in hydrogen peroxide molecule
Individual hydrogen atom replaced by organic group obtained from material.The peracid refers to contain containing the organic of-O-O- keys in molecular structure
Oxygen acid.The instantiation of the peroxide can be included but is not limited to：Hydrogen peroxide, TBHP, peroxidating are different
Propyl benzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide, can so be entered
One step reduction separation costs.The hydrogen peroxide can be the hydrogen peroxide for existing in a variety of manners commonly used in the art.
The method according to the invention, the hydrogen peroxide is typically the aquae hydrogenii dioxidi with mass percentage concentration as 5-70%
The form of solution is added in reaction system, and the aqueous hydrogen peroxide solution of such as technical grade has 27.5%, 30%, 55% and 70%
Deng.
The consumption of the oxidant can be selected according to the amount of hexamethylene.Usually, the hexamethylene and the oxygen
The mol ratio of agent can be 0.1-10：1, preferably 0.2-5：1, more preferably 0.2-2：1.
The method according to the invention, the liquid mixture can contain solvent, it is also possible to do not contain solvent, preferably also contain
There is at least one solvent, can so better control over the speed and severe degree of reaction.Kind of the present invention for the solvent
Class is not particularly limited, and the solvent can either dissolve both hexamethylene and oxidant or promotion mixing, and energy for various
The liquid substance of enough solubilized target oxidation products.Usually, the solvent can be selected from water, C1-C6Alcohol, C3-C8Ketone and C2-
C6Nitrile.The instantiation of the solvent can be included but is not limited to：Water, methyl alcohol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol,
Isobutanol, acetone, butanone and acetonitrile.It is highly preferred that the solvent is acetone and/or butanone.
The present invention is not particularly limited for the consumption of the solvent, can be selected according to the amount of hexamethylene and oxidant
Select.Usually, the solvent and the weight ratio of the hexamethylene can be 0.1-100：1, preferably 0.2-80：1.
The method according to the invention, the oxidation reaction condition can be selected according to the set goal oxidation product.
Specifically, the liquid mixture flows through first beds and the condition of second beds is each wrapped
Include：Temperature can be 0-120 DEG C, preferably 40-100 DEG C；In terms of gauge pressure, pressure can be 0.01-3MPa.
With the method for the invention it is preferred to also include at least one alkaline matter of feeding in the liquid mixture, institute
State the addition of alkaline matter so that the liquid mixture pH value be in 6-9 in the range of, be so obtained in that preferably reaction
Effect.It is highly preferred that the addition of the alkaline matter causes that the pH value of the liquid mixture is in the scope of 6.5-8.5
It is interior, preferably 6.8-8.2.The liquid mixture contacted with HTS pH value more than 6.5 (or being more than 7)
When, if using alkali, further improving the pH value of the liquid mixture, remain able to obtain the effect above.The liquid mixing
The pH value of thing refers in 25 DEG C and the pressure of 1 normal atmosphere, the pH value of the liquid mixture of measure.
Herein, the alkaline matter refers to that the pH value of its aqueous solution is material more than 7.The alkaline matter it is specific
Example can be included but is not limited to：Ammonia (that is, NH3), amine, quaternary ammonium base and M1(OH)n(wherein, M1It is alkali metal or alkaline-earth metal, n
It is and M1Chemical valence identical integer).
Used as the alkaline matter, ammonia can be introduced in the form of liquefied ammonia, it is also possible to introduced in form of an aqueous solutions, may be used also
To introduce in gaseous form.It is not particularly limited as the concentration of the ammonia (that is, ammoniacal liquor) of aqueous solution form, can be selected for conventional
Select, for example 1-36 weight %.
Used as the alkaline matter, amine refers to hydrogen partial on ammonia or is all replaced the material to be formed by alkyl, including one
Level amine, secondary amine and tertiary amine.The amine is specifically as follows material and/or C shown in Formulas I3-C11Heterocyclic amine,
In Formulas I, R1、R2And R3Can be each H or C1-C6Alkyl (such as C1-C6Alkyl), and R1、R2And R3When different
It is H.Herein, C1-C6Alkyl include C1-C6Straight chained alkyl and C3-C6Branched alkyl, its instantiation can include but
It is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, uncle penta
Base, neopentyl and n-hexyl.
The instantiation of amine can be included but is not limited to：Methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, just
Propylamine, di-n-propylamine, Tri-n-Propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butyl
It is amine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, iso-amylamine, two different
Amylamine, triisoamylamine, tertiary amylamine, n-hexylamine and n-octyl amine.
The heterocyclic amine is that have to have the compound of lone pair electrons on nitrogen-atoms and the nitrogen-atoms on finger ring.The heterocycle
Amine for example can be substituted or unsubstituted pyrroles, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, substitution
Or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline,
Substituted or unsubstituted EEDQ, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substitution or not
One or more in substituted isoquinolin and substituted or unsubstituted pyrimidine.
Used as the alkaline matter, quaternary ammonium base is specifically as follows the material shown in Formula II,
In Formula II, R4、R5、R6And R7Can be each C1-C6Alkyl (such as C1-C6Alkyl).The C1-C6Alkyl
Including C1-C6Straight chained alkyl and C3-C6Branched alkyl, its instantiation can include but is not limited to：Methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.
The instantiation of the quaternary ammonium base can be included but is not limited to：TMAH, tetraethyl ammonium hydroxide, four
Propyl group ammonium hydroxide (including four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH are (including four just
Butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl hydrogen-oxygen
Change ammonium.
As the alkaline matter, M1(OH)nIt is the hydroxide or the hydroxide of alkaline-earth metal of alkali metal, for example may be used
Think NaOH, potassium hydroxide, magnesium hydroxide, barium hydroxide and calcium hydroxide.
The method according to the invention, the alkaline matter can be used directly, it is also possible to be configured to the alkaline matter
Used after solution.It is described after can alkaline matter be mixed with oxidant and optionally solvent in feeding fixed bed reactors
Mixing can be carried out outside reactor, it is also possible to carried out in reactor, be not particularly limited.
The method according to the invention, from from the point of view of the technique effect implemented, preferably described alkaline matter is pyridine.
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used according to Zeolites, 1992, Vol.12：
Prepared by the method described in 943-950, its titanium oxide content is 2.5 weight %；
Hollow HTS used is purchased from the hollow titanium that the trade mark of Hunan Jianchang Petrochemical Co., Ltd is HTS
Si molecular sieves, its titanium oxide content is 2.5 weight %.
Ti-MCM-41 HTSs used are the institute in 1994,147-148 in Chem.Commun. according to Corma etc.
Prepared by the method for description, in terms of oxide, the Ti content of the HTS is 3.0 weight %.
Ti-Beta HTSs used are to exist according to Takashi Tatsumi etc.
J.Chem.Soc.Chem.Commun., prepared by the method described in 1997,677-678, in terms of oxide, the titanium silicon point
The Ti content of son sieve is 2.6 weight %.
In following examples and comparative example, the content of each composition in the reaction solution for obtaining is analyzed using gas chromatography,
Below equation is respectively adopted on this basis to calculate oxidant conversion ratio, cyclohexanone selectivity：
Cyclohexane conversion (%)=(participating in the molal quantity of the hexamethylene of the molal quantity/addition of the hexamethylene of reaction) ×
100；
Cyclohexanone selectivity (%)=(molal quantity of the hexamethylene of the molal quantity of the cyclohexanone of reaction generation/reaction consumption)
×100。
In the present invention, in embodiment and comparative example, the preparation method of microspherical catalyst used is as follows：In normal pressure and 60 DEG C of bars
Under part, first organo-silicon compound tetraethyl orthosilicate is added in the TPAOH aqueous solution and is mixed, stirring hydrolysis 5h is obtained
To colloidal solution；Then will be well mixed among HTS or the above-mentioned gained colloidal solution of hollow HTS addition
To slurries, and the wherein quality of HTS or hollow HTS, silanes, TPAOH and water
Than being 100:25:5:250；After above-mentioned slurries are continued to stir 2h, roasting can obtain institute of the present invention after conventional mist projection granulating
The catalyst of microballoon shape.
Embodiment 1-14 is used to illustrate the method for the present invention.
Embodiment 1
Reaction is carried out in two micro fixed-bed reactors being connected in series, wherein, one is loaded in each reactor
Cross section is circular isometrical beds, on the basis of the flow direction of liquid material, positioned at first reaction of upstream
The internal diameter of the first beds in device and the internal diameter of the second beds being located in second reactor in downstream
Ratio is 2：1, shaping hollow titanium si molecular sieves are loaded in the first beds, and (volume average particle size is that 500 μm spherical is urged
Agent, the density of catalyst is 0.70g/cm3), shaping titanium-silicon molecular sieve TS-1 is loaded in the second beds, and (volume is average
Particle diameter is 500 μm of spheric catalyst, and density is 0.76g/cm3), the weight of hollow HTS and titanium-silicon molecular sieve TS-1
Than being 2：1.
Using hexamethylene, as the hydrogen peroxide (in the form of using the hydrogen peroxide of 30 weight % provide) of oxidant and as solvent
Acetone from the bottom feeding of first reactor, by the first beds be loaded on shaping hollow titanium silicon therein
Molecular sieve is contacted；In then continuously entering second reactor from the liquid mixture of first reactor output, by second
Beds be loaded on it is therein shaping titanium-silicon molecular sieve TS-1 contact.
Wherein, hexamethylene and the mol ratio of hydrogen peroxide are 1：2, the pH value in first reactor and second reactor
6.8 are, pH value regulator is ammoniacal liquor (concentration is 25 weight %), and solvent is 15 with the weight ratio of hexamethylene：1；First is urged
Temperature in agent bed and the second beds is controlled as 80 DEG C, 70 DEG C, and first reactor and second react
Pressure in device is respectively 0.5MPa；Total amount with the HTS in the first beds and the second beds is
Benchmark, the weight space velocity of hexamethylene is 5h-1。
The composition of the reactant mixture that continuous monitoring is exported from reactor in course of reaction, in cyclohexanone selectivity StWith
Cyclohexanone selectivity S initially (is measured by sampling) when reaction proceeds to 0.5 hour0Ratio St/S0It is 0.85≤St/S0<When 0.9
(that is, when meeting condition 1), (is only passed through with the mass content that the amplitude in 0.02-5%/day improves hydrogen peroxide in liquid mixture
The concentration of hydrogen peroxide improved in hydrogen peroxide is improved, and the consumption of hydrogen peroxide keeps constant) until cyclohexanone selectivity S ' with it is initial
Cyclohexanone selectivity S0Ratio S '/S0It is 0.9≤S '/S0When≤1 (that is, when meeting condition 2), stop improving oxidant quality
Content.
Continuous operation under these conditions, in running, detects the reactant mixture exported from second reactor
Composition, and calculate cyclohexane conversion, cyclohexanone selectivity, wherein, the reaction time is 2 hours, 360 hours and 720 hours
When result listed in table 1.
Comparative example 1
Using method oxidizing ethyle alkyl same as Example 1, unlike, the shaping titanium silicon in the second beds
Molecular sieve TS-1 is replaced with the hollow HTS of the shaping of equivalent.
Result when reaction time is 2 hours, 360 hours and 720 hours is listed in table 1.
Comparative example 2
Using method oxidizing ethyle alkyl same as Example 1, unlike, the shaping in the first beds is hollow
HTS is replaced with the shaping titanium-silicon molecular sieve TS-1 of equivalent.
Result when reaction time is 2 hours, 360 hours and 720 hours is listed in table 1.
Comparative example 3
Using method oxidizing ethyle alkyl same as Example 1, unlike, the shaping in the first beds is hollow
HTS is replaced with the shaping titanium-silicon molecular sieve TS-1 of equivalent, the shaping titanium-silicon molecular sieve TS-1 in the second beds
Replaced with the hollow HTS of the shaping of equivalent.
Result when reaction time is 2 hours, 360 hours and 720 hours is listed in table 1.
Embodiment 2
Using method oxidizing ethyle alkyl same as Example 1, unlike, the shaping titanium silicon in the second beds
(volume average particle size is 500 μm of spheric catalyst to the shaping HTS Ti-MCM-41 of molecular sieve TS-1 equivalent, close
It is 0.61g/cm to spend3) replace.
Result when reaction time is 2 hours, 360 hours and 720 hours is listed in table 1.
Embodiment 3
Using method oxidizing ethyle alkyl same as Example 1, unlike, the second catalyst in second reactor
(volume average particle size is 500 μm to the shaping HTS Ti-Beta of the shaping titanium-silicon molecular sieve TS-1 equivalent in bed
Spheric catalyst, density is 0.77g/cm3) replace.
Result when reaction time is 2 hours, 360 hours and 720 hours is listed in table 1.
Table 1
The data of embodiment 1 and comparative example 1-3 are compared as can be seen that dividing by hollow HTS and titanium silicon
Son sieve is applied in combination, and when hollow HTS is located at HTS upstream, liquid mixture is flowed through hollow titanium silicon
The apparent speed of molecular sieve makes less than the one way that the apparent speed for flowing through titanium-silicon molecular sieve TS-1 can further extend catalyst
Use the life-span.
Embodiment 4
Reaction is carried out in two micro fixed-bed reactors being connected in series, wherein, one is loaded in each reactor
Cross section is circular isometrical beds, on the basis of the flow direction of liquid material, positioned at first reaction of upstream
The internal diameter of the first beds in device and the internal diameter of the second beds being located in second reactor in downstream
Ratio is 4.4：1, shaping hollow titanium si molecular sieves (same as Example 1), the second catalyst are loaded in the first beds
Shaping titanium-silicon molecular sieve TS-1 (same as Example 1), hollow HTS and titanium-silicon molecular sieve TS-1 are loaded in bed
Weight ratio is 4：1.
Using hexamethylene, as the hydrogen peroxide (in the form of using the hydrogen peroxide of 30 weight % provide) of oxidant and as solvent
Acetone from the bottom feeding of first reactor, by the first beds be loaded on shaping hollow titanium silicon therein
Molecular sieve contact (same as Example 1)；The second reaction is then continuously entered from the liquid mixture of first reactor output
In device, by the second beds be loaded on it is therein shaping titanium-silicon molecular sieve TS-1 (same as Example 1) contact.
Wherein, hexamethylene and the mol ratio of hydrogen peroxide are 1：4, the pH value in first reactor and second reactor
7.2 are, pH value regulator is pyridine solution (concentration is 25 weight %), and solvent is 5 with the weight ratio of hexamethylene：1；By
Temperature in one beds and the second beds is controlled as 60 DEG C, 40 DEG C, first reactor and second
Pressure in reactor is respectively 0.3MPa；With the total of the HTS in the first beds and the second beds
On the basis of amount, the weight space velocity of hexamethylene is 6h-1。
The composition of the reactant mixture that continuous monitoring is exported from reactor in course of reaction, in cyclohexanone selectivity StWith
Cyclohexanone selectivity S initially (is measured by sampling) when reaction proceeds to 0.5 hour0Ratio St/S0It is 0.85≤St/S0<When 0.9
(that is, when meeting condition 1), (is only passed through with the mass content that the amplitude in 0.02-5%/day improves hydrogen peroxide in liquid mixture
The concentration of hydrogen peroxide improved in hydrogen peroxide is improved, and the consumption of hydrogen peroxide keeps constant) until cyclohexanone selectivity S ' with it is initial
Cyclohexanone selectivity S0Ratio S '/S0It is 0.9≤S '/S0When≤1 (that is, when meeting condition 2), stop improving oxidant quality
Content.
Continuous operation under these conditions, in running, detects the reactant mixture exported from second reactor
Composition, and calculate cyclohexane conversion, cyclohexanone selectivity, wherein, the reaction time is 2 hours, 360 hours and 720 hours
When result listed in table 2.
Embodiment 5
Using method oxidizing ethyle alkyl same as Example 4, unlike, the first beds and the second catalyst
Under conditions of the loadings of catalyst are constant in bed, the internal diameter of the first beds of adjustment and the second beds makes
The ratio for obtaining the internal diameter of the internal diameter and the second beds of the first beds is 3.5：1.
Result when reaction time is 2 hours, 360 hours and 720 hours is listed in table 2.
Embodiment 6
Using method oxidizing ethyle alkyl same as Example 4, unlike, the first beds and the second catalyst
Under conditions of the loadings of catalyst are constant in bed, the internal diameter of the first beds of adjustment and the second beds makes
The ratio for obtaining the internal diameter of the internal diameter and the second beds of the first beds is 2：1.
Result when reaction time is 2 hours, 360 hours and 720 hours is listed in table 2.
Embodiment 7
Using method oxidizing ethyle alkyl same as Example 4, unlike, the first beds and the second catalyst
Under conditions of the loadings of catalyst are constant in bed, the internal diameter of the first beds of adjustment and the second beds makes
The ratio for obtaining the internal diameter of the internal diameter and the second beds of the first beds is 1：2.
Result when reaction time is 2 hours, 360 hours and 720 hours is listed in table 2.
Embodiment 8
Using method oxidizing ethyle alkyl same as Example 4, unlike, pH value is 6.
Embodiment 9
Using method oxidizing ethyle alkyl same as Example 4, unlike, pH value regulator is that (concentration is 25 to ammoniacal liquor
Weight %).
Embodiment 10
Using method oxidizing ethyle alkyl same as Example 4, unlike, the first beds and the second catalyst
Temperature in bed is controlled as 60 DEG C, 60 DEG C.
Embodiment 11
Using method oxidizing ethyle alkyl same as Example 4, unlike, the first beds and the second catalyst
Temperature in bed is controlled as 40 DEG C, 60 DEG C.
Embodiment 12
Using method same as Example 4, unlike, do not carry out the set-up procedure.
Embodiment 13
Using method same as Example 1, unlike, pH value regulator is that (concentration is 25 weights to pyridine solution
Amount %).
Embodiment 14
Using method oxidizing ethyle alkyl same as Example 4, unlike, the first beds and the second catalyst
Temperature in bed is controlled as 60 DEG C, 25 DEG C.
Table 2
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
Claims (18)
1. a kind of cyclohexane oxidation processes, the method includes：Under oxidation reaction condition, make the liquid containing hexamethylene and oxidant
Body mixture flows through beds；The beds include the first beds and the second beds, with liquid
On the basis of the flow direction of body mixture, first beds are located at the upstream of second beds, described
The HTS of the first beds filling is hollow HTS, and the hollow HTS is MFI structure
HTS, the crystal grain of the HTS is hollow-core construction, and the radical length of the chamber portion of the hollow-core construction is 5-300
Nanometer, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is that the benzene adsorbance measured under conditions of 1 hour is
, there is hysteresis loop between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS at least 70 milligrams per grams；
The HTS of the second beds filling is the HTS different from hollow HTS.
2. method according to claim 1, wherein, the HTS of the second beds filling is TS-1.
3. method according to claim 1 and 2, wherein, when desirable oxidation selectivity of product drops to and meets condition 1,
The method also includes being adjusted step, until desirable oxidation selectivity of product is risen to when meeting condition 2, stops the adjustment
Step,
Desirable oxidation selectivity of product S under condition 1, sometime ttWith initial target oxidation product selectivity S0Ratio St/
S0It is 0.85≤St/S0<1；
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation product selectivity S0Ratio S '/S0Be 0.9≤S '/
S0≤1；
The set-up procedure is to improve the mass content of oxidant in the liquid mixture.
4. method according to claim 3, wherein, in condition 1, St/S0<0.9。
5. method according to claim 3, wherein, oxygen in the liquid mixture is improved with the amplitude in 0.02-5%/day
The mass content of agent.
6. method according to claim 1 and 2, wherein, the hollow HTS of the first beds filling
The weight ratio of the HTS loaded with second beds is 1-20：1.
7. method according to claim 6, wherein, the hollow HTS of the first beds filling and institute
The weight ratio for stating the HTS of the second beds filling is 2-10：1.
8. method according to claim 1 and 2, wherein, the liquid mixture flows through the apparent of the first beds
Speed is v1, the superficial velocity for flowing through the second beds is v2, v1＜ v2。
9. method according to claim 8, wherein, the liquid mixture flows through the superficial velocity of the first beds
It is v1, the superficial velocity for flowing through the second beds is v2,, v2/v1=1.5-10.
10. method according to claim 1 and 2, wherein, stop of the liquid mixture in the first beds
Time is T1, the total residence time in beds is T.
11. methods according to claim 10, wherein, T1/ T=0.5-0.85.
12. methods according to claim 1 and 2, wherein, the temperature of first beds is urged higher than described second
The temperature of agent bed.
13. methods according to claim 12, wherein, the temperature of first beds is than second catalyst
The temperature of bed is high 5-50 DEG C.
14. methods according to claim 1 and 2, wherein, the liquid mixture is described also containing at least one solvent
Solvent is 0.1-100 with the weight ratio of the hexamethylene：1, the solvent is acetone and/or butanone.
15. methods according to claim 1 and 2, wherein, the oxidant is peroxide.
16. methods according to claim 1 and 2, wherein, hexamethylene is 0.1-10 with the mol ratio of the oxidant：1.
17. methods according to claim 1, wherein, the method also includes to sending at least one in the liquid mixture
Alkaline matter is planted, the feeding amount of the alkaline matter causes that the pH value of the liquid mixture is in the range of 6-9.
18. methods according to claim 1, wherein, the liquid mixture flows through first beds and institute
The condition for stating the second beds each includes：Temperature is 0-120 DEG C；In terms of gauge pressure, pressure is 0.01-3MPa；With described
On the basis of the total amount of the HTS in the first beds and second beds, the weight of the hexamethylene
Air speed is 0.1-20h-1。
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| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN102079695A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclohexane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN102079695A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclohexane |
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