CN108658732A - The method for preparing benzenediol - Google Patents

The method for preparing benzenediol Download PDF

Info

Publication number
CN108658732A
CN108658732A CN201710204169.2A CN201710204169A CN108658732A CN 108658732 A CN108658732 A CN 108658732A CN 201710204169 A CN201710204169 A CN 201710204169A CN 108658732 A CN108658732 A CN 108658732A
Authority
CN
China
Prior art keywords
titanium
molecular sieve
solid
sieve
agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710204169.2A
Other languages
Chinese (zh)
Other versions
CN108658732B (en
Inventor
史春风
林民
朱斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201710204169.2A priority Critical patent/CN108658732B/en
Publication of CN108658732A publication Critical patent/CN108658732A/en
Application granted granted Critical
Publication of CN108658732B publication Critical patent/CN108658732B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

This disclosure relates to which a kind of method preparing benzenediol, this method include：Under conditions of oxidation reaction, phenol, oxidant and optional solvent is set to carry out haptoreaction in the presence of a catalyst, then the reaction mixture of gained is separated by solid-liquid separation, the liquid product containing benzenediol is obtained, the catalyst is titanium-silicon molecular sieve catalyst and/or titanium silicoaluminophosphate molecular sieve catalyst；The separation of solid and liquid carries out in solid-liquid separator, and the solid-liquid separator, which has, is separated by solid-liquid separation component.Disclosed method can efficiently isolate the liquid product containing benzenediol from liquid-solid mixture obtained by the reaction, effectively improve the effective rate of utilization of oxidant and the selectivity of benzenediol, while can also obtain higher phenol conversion.

Description

The method for preparing benzenediol
Technical field
This disclosure relates to a kind of method preparing benzenediol.
Background technology
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 Stabilizer, the antioxidant of material, synthesis ammonia cosolvent, rubber antioxidant, polymerization inhibitor, coating and essence.
In the prior art by by aromatic hydroxy compound (such as phenol) oxygen or oxygen-containing gas, Cu-contained catalyst, and optionally Accelerating agent aoxidize to form benzoquinones, then use reduction reaction to form hydroquinone.
It is existing studies have shown that when oxidation of phenol is directly prepared benzenediol as oxidant using peroxide, if made Use Titanium Sieve Molecular Sieve that can effectively improve the selectivity of the effective rate of utilization and benzenediol of oxidant as catalyst, simultaneously also High phenol conversion can be obtained, but since reaction product needs further separation, constrains the production efficiency of benzenediol.
Invention content
Purpose of this disclosure is to provide a kind of methods preparing benzenediol.This method can be efficiently from obtained by the reaction mixed Close object in isolate the liquid product containing benzenediol, effectively improve the conversion ratio of phenol, the effective rate of utilization of oxidant and The selectivity of benzenediol.
To achieve the goals above, the disclosure provides a kind of method preparing benzenediol, and this method includes：In oxidation reaction Under conditions of, so that phenol, oxidant and optional solvent is carried out haptoreaction in the presence of a catalyst, then by the anti-of gained Answer mixture to be separated by solid-liquid separation, obtain the liquid product containing benzenediol, the catalyst be titanium-silicon molecular sieve catalyst and/ Or titanium silicoaluminophosphate molecular sieve catalyst；
The separation of solid and liquid carries out in solid-liquid separator, and the solid-liquid separator, which has, is separated by solid-liquid separation component, described solid The solid-liquid separator is divided into first area and second area by liquid separating member, and the first area has first area entrance It is exported with first area, the second area is exported with second area；The separation of solid and liquid component makes in reaction mixture The liquid product containing benzenediol be easy by by the residue containing catalyst is difficult to pass through；The reaction mixture is by institute It states first area entrance and enters solid-liquid separator, the liquid product containing benzenediol enters second by being separated by solid-liquid separation component Region is simultaneously obtained by second area outlet collection, and the residue containing catalyst is exported to obtain by first area.
Optionally, the separation of solid and liquid component has through-hole, and the aperture of the through-hole is less than the grain size of the catalyst, excellent Selection of land, the separation of solid and liquid component are selected from porous tubing, porous sieve plate, porous ceramics, ceramic membrane element, stainless steel membrane element At least one of with filter cloth.
Optionally, the solid-liquid separator includes shell, and the tubulose in shell is separated by solid-liquid separation component；It is described solid The both ends of liquid separating member are connect with the housing seal respectively so that the separation of solid and liquid component inside is formed as the firstth area Domain, the space being separated by solid-liquid separation between component and shell are formed as second area；Alternatively, the separation of solid and liquid component inside shape As second area, the space being separated by solid-liquid separation between component and shell is formed as first area.
Optionally, the molar ratio of the oxidant and phenol is (0.1-20)：1, preferably (0.2-10)：1, more preferably (0.5-5)：1；The condition of the oxidation reaction is：Reaction temperature is 0-200 DEG C, pressure 0-3MPa.
Optionally, the oxidant is selected from hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide, cyclohexyl mistake At least one of hydrogen oxide, Peracetic acid and Perpropionic Acid；The solvent be selected from water, the alcohol of C1-C6, C3-C8 ketone and At least one of nitrile of C2-C6；Preferably, the solvent be selected from water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, At least one of isobutanol, acetone, butanone and acetonitrile；It is further preferred that the solvent is water and/or methanol；It is described molten The mass ratio of agent and phenol is (1-100)：1.
Optionally, titanium-silicon molecular sieve catalyst of the titanium-silicon molecular sieve catalyst at least partially Jing Guo activation process, The activation process includes contacting Titanium Sieve Molecular Sieve with the aqueous solution containing acid and selectable peroxide, wherein titanium silicon Molecular sieve in terms of silica, the acid, peroxide, water and Titanium Sieve Molecular Sieve molar ratio be (0.02-15)：(0-10)： (15-100)：1, preferably (0.1-10)：(0.01-5)：(20-80)：1.
Optionally, the acid is at least one in the carboxylic acid selected from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and C1-C5 Kind；The peroxide is in hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide and cyclohexyl hydroperoxide It is at least one；The condition of the activation process includes：Titanium Sieve Molecular Sieve and the aqueous solution containing acid and selectable peroxide The temperature of contact is 0-90 DEG C, and the time is 0.1-48 hours.
Optionally, the activation process makes, on the basis of Titanium Sieve Molecular Sieve, in ultraviolet-visible spectrum, and the process The peak area of absorption peak of the Titanium Sieve Molecular Sieve of activation process between 230-310nm reduces by 2% or more, preferably reduces 2- 30%, 2.5-15% is more preferably reduced, 3-10% is further preferably reduced, still more preferably reduces 3-6%；It is described through making a living The hole for changing the Titanium Sieve Molecular Sieve of processing holds 1% or more reduction, preferably reduces 1-20%, more preferably reduces 1.5-10%, further It is preferred that reducing 2-5%, the Kong Rong is using static determination of nitrogen adsorption.
Optionally, the Titanium Sieve Molecular Sieve at least partly draws off agent, the warp from reaction unit after regeneration The agent that draws off of reaction unit after regeneration is to draw off agent, hydroxyl after regeneration selected from Ammoximation reaction device after regeneration Change reaction unit draw off agent and epoxidation reaction device after regeneration draw off at least one of agent；
Preferably, the Titanium Sieve Molecular Sieve is selected from MFI type Titanium Sieve Molecular Sieve, MEL types Titanium Sieve Molecular Sieve, BEA type titanium silicon Molecular sieve, MWW types Titanium Sieve Molecular Sieve, MOR types Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve of TUN types Titanium Sieve Molecular Sieve and hexagonal structure At least one of.
Optionally, the titanium Si-Al molecular sieve divides for the titanium sial of titanium Si-Al molecular sieve, MEL structures selected from MFI structure Sub- sieve, the titanium Si-Al molecular sieve of BEA structures, the titanium Si-Al molecular sieve of MWW structures, the titanium Si-Al molecular sieve of MOR structures, TUN knot At least one of the titanium Si-Al molecular sieve of the titanium Si-Al molecular sieve of structure and two-dimentional hexagonal structure.
Optionally, the preparation process of the titanium Si-Al molecular sieve includes：
(1) it draws off agent by first to be mixed with beating with organic acid soln, and obtained slurries is subjected to the first heat treatment, separation Obtain the first solid, wherein described first draws off agent as the reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component Agent is drawn off, the condition of first heat treatment is：Temperature is 20-45 DEG C, time 1-30h；
(2) it is carried out at the second heat after mixing first solid, silicon source, titanium source in the presence of aqueous solvent with alkali source It manages, the condition of second heat treatment is：Temperature is 100-200 DEG C, time 0.5-25h；
Alternatively, the preparation process of the titanium Si-Al molecular sieve includes：
A, it draws off agent by second to be mixed with beating with organic acid soln, and obtained slurries is subjected to third heat treatment, separation Obtain the second solid, wherein described second draws off agent as the reaction unit using Si-Al molecular sieve as catalyst activity component Agent is drawn off, the condition of the third heat treatment is：Temperature is 50-150 DEG C, time 0.5-40h；
B, the 4th heat treatment, institute are carried out after mixing second solid, titanium source in the presence of aqueous solvent with alkali source Stating the condition that the 4th is heat-treated is：Temperature is 100-200 DEG C, time 0.5-25h.
Optionally, the described first weight ratio for drawing off agent, titanium source, silicon source, Organic Acid and Base source and water is 100：(0.1- 10)：(0.1-10)：(0.005-50)：(0.5-50)：(20-1000)；
Alternatively, the described second weight ratio for drawing off agent, titanium source, Organic Acid and Base source and water is 100：(0.1-10)： (0.005-50)：(0.5-50)：(20-1000)；
Described first and second draw off agent respectively with SiO2Meter, the organic acid is with H+Meter, when the alkali source contains nitrogen In terms of N, the alkali source not Nitrogen element when with OH-Meter；The concentration of the organic acid soln is more than 0.1mol/L；
The organic acid is selected from least one of aphthenic acids, Peracetic acid and Perpropionic Acid；The alkali source be selected from At least one of ammonia, aliphatic amine, aliphatic hydramine and quaternary ammonium base；Source of aluminium is selected from Aluminum sol, aluminium salt, aluminium hydroxide At least one of with aluminium oxide；The titanium source is inorganic titanium salt and/or organic titanate.
Optionally, the reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component in step (1) is drawn off Agent be the agent of drawing off selected from Ammoximation reaction device, hydroxylating device draw off agent and epoxidation reaction device draw off agent At least one of；Preferably, the Titanium Sieve Molecular Sieve in step (1) is the Titanium Sieve Molecular Sieve of MFI structure, and described first unloads The activity for going out agent is active 50% or less of Titanium Sieve Molecular Sieve when fresh；
Alternatively, the agent that draws off of the reaction unit using Si-Al molecular sieve as catalyst activity component in step a is The synthetic reaction device of hydrogen sulfide and methanol draws off agent；Preferably, the Si-Al molecular sieve in step a is MFI structure Si-Al molecular sieve, the described second activity for drawing off agent is active 50% or less of Si-Al molecular sieve when fresh.
Optionally, in step (2), source of aluminium and alkali source are first mixed to get mixed solution in the presence of aqueous solvent, Then second heat treatment is carried out after again mixing the mixed solution with first solid and titanium source.
Optionally, this method further includes：Before carrying out the reaction, the pH value of reaction system is adjusted to 0.5-5.5, preferably It is adjusted to 1-5, is more preferably adjusted to 1-3.5；And
By the residue cycle containing catalyst exported by the first area in the reaction and from The step of benzenediol being isolated in the liquid product containing benzenediol.
Optionally, this method further includes：According to certain time interval, to feeding flushing liquor in the first area (1) To be rinsed to the separation of solid and liquid component (3), the flushing liquor contains the oxidant, optional phenol and optional molten The time interval of agent, the flushing is 0.5-24 hours, and the duration of the flushing is 5-300 seconds.
Through the above technical solutions, disclosed method can be isolated efficiently from liquid-solid mixture obtained by the reaction Liquid product containing benzenediol effectively improves the effective rate of utilization of oxidant and the selectivity of benzenediol, while can also obtain Obtain higher phenol conversion.In addition, the method stability that the disclosure provides is good, even if long-play, remain able to obtain Higher phenol conversion, oxidant effective rate of utilization and benzenediol selectivity.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is for providing further understanding of the disclosure, and a part for constitution instruction, with following tool Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings：
Fig. 1 is a kind of structural representation of specific implementation mode of the solid-liquid separator used in the method that the disclosure provides Figure；
Fig. 2 is a kind of sectional view of specific implementation mode of the solid-liquid separator used in the method that the disclosure provides；
Fig. 3 is a kind of flow chart of the preferred embodiment for the method that the disclosure provides.
Reference sign
1 first area, 2 second area
3 are separated by solid-liquid separation 4 shell of component
5 heat collector, 6 reactor
7 solid-liquid separators
Specific implementation mode
The specific implementation mode of the disclosure is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched The specific implementation mode stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
In the disclosure, in the absence of explanation to the contrary, the noun of locality used such as " inside and outside " refers to relative to structure Profile it is inner and outer.
The disclosure provides a kind of method preparing benzenediol, and this method includes：Under conditions of oxidation reaction, make phenol, Oxidant and optional solvent carry out haptoreaction in the presence of a catalyst, and the reaction mixture of gained is then carried out solid-liquid Separation, obtains the liquid product containing benzenediol, and the catalyst is that titanium-silicon molecular sieve catalyst and/or titanium Si-Al molecular sieve are urged Agent.
The inventor of the disclosure is by long-term the study found that making using Titanium Sieve Molecular Sieve and/or titanium Si-Al molecular sieve For catalyst, when oxidation of phenol directly to be prepared to benzenediol using peroxide as oxidant, can both make containing phenol and oxygen The liquid mixture of agent is carried out instead by being filled with the bed of molding Titanium Sieve Molecular Sieve and/or titanium silicoaluminophosphate molecular sieve catalyst It answers, directly Titanium Sieve Molecular Sieve and/or titanium Si-Al molecular sieve can also be mixed with phenol and oxidant and reacted, and the latter one On the other hand aspect is easy to during the reaction without using molding Titanium Sieve Molecular Sieve and/or titanium silicoaluminophosphate molecular sieve catalyst Controlling reaction temperature has significant advantage.But directly by Titanium Sieve Molecular Sieve and/or titanium Si-Al molecular sieve and phenol and oxygen Agent hybrid reaction needs detach the reaction mixture obtained after reaction, could be by Titanium Sieve Molecular Sieve and/or titanium sial Molecular sieve is separated with the liquid product containing benzenediol.Therefore, liquid-solid separation efficiency is the important of influence benzenediol production efficiency One of factor.
In the method that the disclosure provides, the separation of solid and liquid carries out in solid-liquid separator, which can be real Existing liquid product is efficiently separated with the residue containing catalyst.Refer to the attached drawing 1, the solid-liquid separator, which has, to be separated by solid-liquid separation The solid-liquid separator is divided into first area 1 and second area 2, the first area 1 by component 3, the separation of solid and liquid component 3 It is exported with first area entrance and first area, there is the second area 2 second area to export (attached to be not shown in figure)；Institute State be separated by solid-liquid separation component 3 so that the liquid product containing benzenediol in reaction mixture be easy by by containing the residual of catalyst Object is stayed to be difficult to pass through.It is so that liquid phase production that described " being easy to pass through ", which refers to the tectonic sieving for being separated by solid-liquid separation component, Object passes through The more the better；It is so that the residual that described " being difficult to pass through ", which refers to the tectonic sieving for being separated by solid-liquid separation component, It is more fewer better that object passes through.As a kind of specific implementation mode, the separation of solid and liquid component can be, for example, porous tubing, porous Sieve plate, porous ceramics, ceramic membrane element, stainless steel membrane element, filter cloth etc..Disclosed method can be efficiently from reacting To liquid-solid mixture in isolate the liquid product containing benzenediol, effectively improve the effective rate of utilization and benzenediol of oxidant Selectivity, while higher phenol conversion can also be obtained.
The reaction mixture enters solid-liquid separator by the first area entrance, in first area 1 and second area 2 Between pressure difference under the action of, be located at first area 1 in reaction mixture in the liquid product containing benzenediol It is obtained at least partially through being separated by solid-liquid separation component 3 into second area 2 and being collected by second area outlet, it is described to contain catalysis The residue of agent will not or will not enter in second area 2 substantially, and be kept in first area 1 and exported by first area It obtains.According to disclosed method, the first area entrance and first area outlet are two different ports.According to this public affairs The method opened, the position relationship between first area 1 and second area 2 are not limited to shown in Fig. 1, as long as first area 1 and second The set-up mode in region 2 can realize above-mentioned function.
According to a kind of specific implementation mode of the disclosure, in order to realize efficiently separating for reaction mixture, the solid-liquid point From component 3 there is through-hole, the aperture of the through-hole to be less than the grain size of the titanium-silicon molecular sieve catalyst.The consolidating with through-hole Liquid separating member 3 can be the common various components with the through-hole that liquid can be made to pass through, it is preferable that the separation of solid and liquid Component 3 is the tubular element that tube wall has through-hole.
The disclosure does not have special limitation to the shape and structure of the solid-liquid separator.Fig. 2 is in disclosed method The sectional view of a kind of specific implementation mode of used solid-liquid separator, as shown in Fig. 2, the solid-liquid separator may include Shell 4, and tubulose in shell 4 are separated by solid-liquid separation component 3, the both ends for being separated by solid-liquid separation component 3 respectively with the shell Body 4 is tightly connected so that be formed as first area 1 inside the separation of solid and liquid component 3, the separation of solid and liquid component 3 and shell Space between 4 is formed as second area 2；Alternatively, being formed as second area 2, the solid-liquid inside the separation of solid and liquid component 3 Space between separating member 3 and shell 4 is formed as first area 1.The quantity for being separated by solid-liquid separation component can be according to anti- It answers the treating capacity of mixture to make appropriate choice, can be one or more.When the quantity for being separated by solid-liquid separation component is one When more than root, it is preferable that the inside for being separated by solid-liquid separation component is formed as first area, the outer wall of adjacent separation of solid and liquid component Between and the space that is separated by solid-liquid separation between component and shell be formed as second area.The internal diameter of the shell can be according to solid-liquid The quantity and outer diameter size and treating capacity of separating member make appropriate choice.The tubulose is separated by solid-liquid separation component can be commercially available It obtains, can also be prepared using common method, it is preferable that it can be ceramic membrane filter that the tubulose, which is separated by solid-liquid separation component, Element.
According to disclosed method, the size of the through-hole on component, first area and the can be separated by solid-liquid separation by adjusting The residence time of pressure difference and reaction mixture in first area between two regions to carry out the degree of separation of solid and liquid Regulation and control.Usually, the pressure difference between first area and second area can be 0.01-3MPa, preferably 0.05-2.5MPa, More preferably 0.1-2MPa.
According to disclosed method, in order to reach ideal reaction effect, the molar ratio of the oxidant and phenol can be with For (0.1-20)：1, preferably (0.2-10)：1, more preferably (0.5-5)：1.
According to disclosed method, the oxidant can be peroxide.The peroxide refers in molecular structure Compound containing-O-O- keys can be selected from hydrogen peroxide, hydroperoxides and peracid.The hydroperoxides referred to Substance obtained from a hydrogen atom in oxidation hydrogen molecule is replaced by organic group.The peracid refers to containing in molecular structure There is the organic oxacid of-O-O- keys.The specific example of the peroxide can include but is not limited to：Hydrogen peroxide, tertiary butyl Hydrogen peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant was Hydrogen oxide can further decrease separation costs in this way.The hydrogen peroxide can in a variety of manners be deposited to be commonly used in the art Hydrogen peroxide.From the angle for further increasing safety, according to disclosed method, it is preferable to use with aqueous solution shape Hydrogen peroxide existing for formula.When the hydrogen peroxide provides as an aqueous solution, the concentration of the aqueous hydrogen peroxide solution can Think the normal concentration of this field, such as：20-80 weight %.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can be with It is prepared, can also be commercially available using conventional method, such as：Can be can be commercially available 30 weight % hydrogen peroxide, 50 The hydrogen peroxide of the hydrogen peroxide of weight % or 70 weight %.
According to disclosed method, from the mixability further increased in reaction system between each reactant, strengthens and expand The angle for dissipating and more easily the severe degree of reaction being adjusted is set out, and reaction can be in the presence of a solvent. The type of the solvent is not particularly limited.Usually, the solvent can be selected from the ketone and C2- of water, the alcohol of C1-C6, C3-C8 The nitrile of C6.The specific example of the solvent can include but is not limited to：Water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, Isobutanol, acetone, butanone and acetonitrile.Preferably, the solvent is methanol and/or water.
The dosage of the solvent is not particularly limited, and can be conventional selection.Usually, the mass ratio of solvent and phenol can Think (1-100)：1.Furthermore it is also possible to according to the difference for the form for contacting phenol and oxidant with Titanium Sieve Molecular Sieve, Adjustment appropriate is carried out to the dosage of solvent.
Various methods commonly used in the art may be used to mix each reaction mass.From further increasing mixing The angle of uniformity coefficient is set out, and is preferably first uniformly mixed oxidant with catalyst, then obtained mixture is mixed with phenol. When there are solvent, solvent and oxidant are preferably configured to solution, then mixed with catalyst and phenol.
When the oxidant is hydrogen peroxide and/or hydroperoxides, the pH value of reaction system is generally between 6-7. In order to further increase the effective rate of utilization of the selectivity of benzenediol, the conversion ratio of phenol and oxidant, disclosed method is also May include：Before carrying out the reaction, the pH value of reaction system is adjusted to 0.5-5.5, is preferably adjusted to 1-5, more preferably It is adjusted to 2-4.The method of pH value for adjusting reaction system can be conventional use of for this field, in general, can for Acidic materials are added in reaction system makes pH reduce.Compared with the pH value for not adjusting reaction system, in the identical feelings of remaining condition Under condition, acidic materials are added into reaction system and so that the pH value of reaction system is 0.5-5.5 (preferably 1-5), even if more Haptoreaction at low temperature can also obtain essentially identical phenol conversion, higher oxidant effective rate of utilization and benzene two Phenol selectivity.When the peroxide is peracid, the pH value of reaction system is generally between 3.5-4, but if to reaction Acidic materials are added in system, the pH value of reaction system is adjusted to 1-3.5, remain able to obtain said effect.The pH value Refer in 25 DEG C and the pressure of 1 normal atmosphere, the pH value of measurement.
The type of the acidic materials can be conventional selection, and the disclosure does not have special limitation.Usually, the acidity Substance can be inorganic acid and/or organic acid, it is excellent as one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid and acetic acid It is selected as hydrochloric acid and/or sulfuric acid.Pure acid can be used, the aqueous solution of acid can also be used.The acidic materials and phenol and oxidation The mixing of other components (such as solvent) can carry out in reactor in agent and reaction system, can also outside reactor into Row.The dosage of the acidic materials, which is subject to, enables to the pH value of reaction system to meet previously described requirement.
In order to further increase the selectivity of benzenediol and the conversion ratio of phenol, the titanium-silicon molecular sieve catalyst at least portion Divide to be the titanium-silicon molecular sieve catalyst by activation process.The activation process include by Titanium Sieve Molecular Sieve with containing acid and The aqueous solution of selectable peroxide contacts, wherein Titanium Sieve Molecular Sieve in terms of silica, the acid, peroxide, water and The molar ratio of Titanium Sieve Molecular Sieve can be (0.02-15)：(0-10)：(15-100)：1.By the Titanium Sieve Molecular Sieve of activation process Catalytic performance significantly improve, can effectively improve the selectivity of benzenediol and the conversion ratio of phenol.The acid can be selected from At least one of the carboxylic acid of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and C1-C5.The acid is general in form of an aqueous solutions In the presence of the concentration of aqueous solution is not particularly limited, such as can be 1-60 mass %, preferably 5-30 mass %.The mistake Oxide can be in hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide and cyclohexyl hydroperoxide at least It is a kind of.Preferably, the peroxide is hydrogen peroxide.The hydrogen peroxide can in a variety of manners be deposited to be commonly used in the art Hydrogen peroxide.
Titanium molecular sieve catalysis performance is improved to further increase the selectivity of benzenediol and the conversion of phenol in order to reach The condition of the purpose of rate, the activation process may include：Titanium Sieve Molecular Sieve and the water containing acid and selectable peroxide The temperature of solution contact is 0-90 DEG C, and the time is 0.1-48 hours.In order to promote the mass transfer during catalyst activation treatment, institute It can also includes solvent to state aqueous solution, and the weight ratio of the solvent and Titanium Sieve Molecular Sieve can be (5-30)：1.The solvent can Think at least one of the nitrile selected from the alcohol of C1-C6, the ketone of C3-C8, C2-C6.After the activated processing of Titanium Sieve Molecular Sieve This field may be used to recycle the conventional recycling step of molecular sieve, such as the step of may include filtering, drying, this hair It is bright to repeat no more.
According to a kind of specific implementation mode of the disclosure, the activation process preferably comprise by Titanium Sieve Molecular Sieve with contain The aqueous solution of nitric acid and peroxide contact, wherein Titanium Sieve Molecular Sieve in terms of silica, the nitric acid, peroxide, water with The molar ratio of Titanium Sieve Molecular Sieve can be (0.1-10)：(0.01-5)：(20-80)：1.
The activation process can make, described through making a living in ultraviolet-visible spectrum on the basis of Titanium Sieve Molecular Sieve Changing the peak area of absorption peak of the Titanium Sieve Molecular Sieve of processing between 230-310nm reduces by 2% or more, preferably reduces 2-30%, 2.5-15% is more preferably reduced, 3-10% is further preferably reduced, still more preferably reduces 3-6%；It is described through overactivation at The hole of the Titanium Sieve Molecular Sieve of reason, which holds, reduces 1% or more, preferably reduces 1-20%, more preferably reduces 1.5-10%, further preferably 2-5% is reduced, the Kong Rong is using static determination of nitrogen adsorption.
The content of the Titanium Sieve Molecular Sieve by activation process can be selected according to specific use occasion.It is described Titanium Sieve Molecular Sieve can all Titanium Sieve Molecular Sieve by activation process, can also be partly titanium silicon by activation process point Son sieve.Usually, on the basis of the total amount of the Titanium Sieve Molecular Sieve, the content of the Titanium Sieve Molecular Sieve by activation process can Think 10 weight % or more (such as 10-100 weight %), preferably 50 weight % or more.
Using Titanium Sieve Molecular Sieve as in the various commercial plants of catalyst, as Ammoximation reaction, hydroxylating and In epoxidation reaction device, usually after device runs a period of time, the catalytic activity of catalyst declines, and needs to carry out in device Or ex-situ regeneration, even if when carrying out regeneration and also being difficult to obtain satisfied activity, need to draw off catalyst from device (that is, More catalyst changeout), and the current processing method of the catalyst (that is, drawing off agent or dead catalyst) that draws off is typically to accumulate to bury, On the one hand valuable land resource and inventory space are occupied, another aspect Titanium Sieve Molecular Sieve production cost is higher, directly discarded Without also resulting in great waste.The present inventor has found in the course of the research, if these are drawn off agent (that is, unloading The Titanium Sieve Molecular Sieve gone out) regenerated after contacted under oxidation reaction condition with phenol and oxidant, remain able to obtain it is higher Phenol conversion and benzenediol selectivity, and higher oxidant effective rate of utilization can be obtained, in tandem reaction sequence Phenol conversion and benzenediol are selectively more stable.Therefore, according to disclosed method, at least partly described Titanium Sieve Molecular Sieve The reaction unit using Titanium Sieve Molecular Sieve as catalyst preferably after regeneration draws off agent.It is described that draw off agent can be from each What is drawn off in planting using Titanium Sieve Molecular Sieve as the reaction unit of catalyst draws off agent, such as can be from oxidation reaction apparatus What is drawn off draws off agent.Specifically, it is described draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draws off agent It is one or more in agent with drawing off for epoxidation reaction device.More specifically, described, to draw off agent can be cyclohexanone oxamidinating Reaction unit draw off agent, phenol hydroxylation reaction unit draws off drawing off in agent extremely for agent and propylene ring oxidation reaction device Few one kind.
The regenerated condition of agent progress will be drawn off to be not particularly limited, choosing appropriate can be carried out according to the source for drawing off agent It selects, such as：High-temperature roasting and/or solvent washing.
The activity for drawing off agent after regeneration is different according to its source.Usually, through the regenerated work for drawing off agent Property can be activity (that is, activity of fresh Titanium Sieve Molecular Sieve) of Titanium Sieve Molecular Sieve when fresh 5-95%.Preferably, it passes through The regenerated activity for drawing off agent can be active 10-90% of Titanium Sieve Molecular Sieve when fresh, further preferably new Active 30-50% when fresh.When the activity for drawing off agent after regeneration is its active 10-55% when fresh, no Satisfactory phenol conversion and benzenediol selectivity can be only obtained, and can obtain and further increase having for oxidant Imitate utilization rate.The activity of the fresh Titanium Sieve Molecular Sieve is generally 90% or more, and usually 95% or more.
The activity measures by the following method：It respectively will be through regenerated agent and the fresh Titanium Sieve Molecular Sieve of drawing off as hexamethylene The catalyst of ketone oxamidinating reaction, the condition of the Ammoximation reaction are：Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH3Meter), The hydrogen peroxide of 30 weight % is (with H2O2Meter), the tert-butyl alcohol and cyclohexanone be by weight 1：7.5：10：7.5：10, at atmosheric pressure 2h is reacted in 80 DEG C.Calculate separately using through it is regenerated draw off agent and fresh Titanium Sieve Molecular Sieve as catalyst when cyclohexanone conversion Rate, and using it as through the regenerated activity for drawing off agent and fresh Titanium Sieve Molecular Sieve, wherein the conversion ratio of cyclohexanone= [mole of the cyclohexanone of (mole of the unreacted cyclohexanone of mole-of the cyclohexanone of addition)/addition] × 100%.
When at least partly Titanium Sieve Molecular Sieve draws off agent for reaction unit after regeneration, with the total of the Titanium Sieve Molecular Sieve On the basis of amount, it is preferably 5 weight % or more that reaction unit after regeneration, which draws off the content of agent, can not only be obtained so more preferable Raising oxidant effective rate of utilization effect, and reaction process is more steady easy to control, while can also obtain higher benzene Phenol conversion ratio and benzenediol selectivity.According to disclosed method, even if whole Titanium Sieve Molecular Sieve are through regenerated reaction unit When drawing off agent (that is, the content for drawing off agent through regenerated reaction unit is 100 weight %), remain able to obtain satisfactory benzene Phenol conversion ratio, oxidant effective rate of utilization and benzenediol selectivity.
According to the method for the present invention, the Titanium Sieve Molecular Sieve is one of a part of silicon atom in titanium atom substitution lattice framework The general name of class zeolite can use chemical formula xTiO2·SiO2It indicates.The present invention does not have the content of titanium atom in Titanium Sieve Molecular Sieve It is particularly limited to, can be the conventional selection of this field.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 structures of MEL structures of MFI structure Titanium Sieve Molecular Sieve (such as Ti-Beta), the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structures, the Titanium Sieve Molecular Sieve of MOR structures Titanium Sieve Molecular Sieve (such as Ti-MCM- of the Titanium Sieve Molecular Sieve (such as Ti-TUN) of (such as Ti-MOR), TUN structures, 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 selected from MFI The Titanium Sieve Molecular Sieve of structure, the Titanium Sieve Molecular Sieve of MEL structures, the two-dimentional Titanium Sieve Molecular Sieve of hexagonal structure and the titanium silicon of BEA structures Molecular sieve, the more preferably Titanium Sieve Molecular Sieve of MFI structure, such as non-hollow titanium-silicon molecular sieve TS-1 and/or hollow titanium silicon point Son sieve TS-1.The hollow titanium-silicon molecular sieve TS-1 is the Titanium Sieve Molecular Sieve of MFI structure, and the crystal grain of the Titanium Sieve Molecular Sieve is sky The radical length of core structure, the chamber portion of the hollow-core construction is 5-300 nanometers, and the Titanium Sieve Molecular Sieve is in 25 DEG C, P/P0= 0.10, the benzene adsorbance that adsorption time measures under conditions of being 1 hour is at least 70 milligrams per grams, the low temperature of the Titanium Sieve Molecular Sieve There are hysteresis loops between the adsorption isotherm and desorption isotherm of N2 adsorption.The hollow titanium-silicon molecular sieve TS-1 can be commercially available Obtain (such as commercially available from Hunan Jianchang Petrochemical Co., Ltd the trade mark be HTS molecular sieve), can also basis Method disclosed in CN1132699C is prepared.The Titanium Sieve Molecular Sieve can be Titanium Sieve Molecular Sieve original powder, or at The titanium-silicon molecular sieve catalyst of type.
According to the disclosure conversion ratio of phenol is can effectively improve when the catalyst contains titanium Si-Al molecular sieve.Institute State the general name that titanium Si-Al molecular sieve refers to a kind of zeolite of a part of silicon atom in titanium atom and aluminium atom substitution lattice framework.When When the catalyst contains titanium Si-Al molecular sieve, the titanium Si-Al molecular sieve can be the common titanium with various topological structures Si-Al molecular sieve, such as：The titanium Si-Al molecular sieve can be the titanium Si-Al molecular sieve (such as TS-1) of MFI structure, MEL structures The titanium Si-Al molecular sieve of titanium Si-Al molecular sieve (such as TS-2), the titanium Si-Al molecular sieve (such as Ti-Beta) of BEA structures, MWW structures The titanium Si-Al molecular sieve (such as Ti-MOR) of (such as Ti-MCM-22), MOR structures, titanium Si-Al molecular sieve (such as Ti- of TUN structures TUN), the two-dimentional titanium Si-Al molecular sieve (such as Ti-MCM-41, Ti-SBA-15) of hexagonal structure and the titanium silicoaluminophosphate molecular of other structures It sieves at least one of (such as Ti-ZSM-48).The titanium Si-Al molecular sieve is preferably the titanium Si-Al molecular sieve of MFI structure, MEL knots At least one of the titanium Si-Al molecular sieve of structure and the titanium Si-Al molecular sieve of BEA structures, more preferably the titanium sial of MFI structure point Son sieve.
According to the disclosure, the purpose of the disclosure can be realized using titanium Si-Al molecular sieve as catalyst, but the disclosure Inventor find under study for action, using titanium Si-Al molecular sieve made from ad hoc approach will be particularly conducive to improve phenol conversion Rate.
Therefore, according to a kind of preferred embodiment of the disclosure, the preparation process of the titanium Si-Al molecular sieve includes：
(1) it draws off agent by first to be mixed with beating with organic acid soln, and obtained slurries is subjected to the first heat treatment, separation Obtain the first solid, wherein described first draws off agent as the reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component Agent is drawn off, the condition of first heat treatment is：Temperature is 20-45 DEG C, time 1-30h, preferably 1-24h, more preferably 10-20h；
(2) it is carried out at the second heat after mixing first solid, silicon source, titanium source in the presence of aqueous solvent with alkali source It manages, the condition of second heat treatment is：Temperature is 100-200 DEG C, preferably 120-180 DEG C, more preferably 140-170 DEG C, Time is 0.5-25h, preferably 2-24h, more preferably 5-20h.
In above-mentioned preferred embodiment, the relative crystallinity of first solid obtained after the first heat treatment can Think 70-90%.Agent can be drawn off under specific first heat treatment condition by described first to be processed into specific opposite knot First solid of brilliant degree, then carries out the second heat treatment again, can obtain the good titanium Si-Al molecular sieve of catalytic performance, is used for this public affairs Propylene glycol and the selectivity of propylene glycol can be further increased in the reaction opened.Wherein, the relative crystallinity of the solid is Refer to solid phase for drawing off fresh dose of crystallinity corresponding to agent.
In above-mentioned preferred embodiment, the reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component unloads Go out agent can be from various using Titanium Sieve Molecular Sieve as the device of catalyst activity component in draw off draw off agent, such as can be with Agent is drawn off for what is drawn off from using Titanium Sieve Molecular Sieve as the oxidation reaction apparatus of catalyst activity component.The oxidation reaction can Think each kinds of oxidation reaction, such as the agent that draws off using Titanium Sieve Molecular Sieve as the reaction unit of catalyst activity component can be with For Ammoximation reaction device draw off agent, hydroxylating device draws off drawing off in agent extremely for agent and epoxidation reaction device Few one kind, be specifically as follows cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draws off agent and third Alkene epoxidation reaction device draws off at least one of agent, preferably described to draw off agent to react the catalysis of inactivation under alkaline environment Therefore agent draws off agent for of the invention preferably described first and draws off agent (such as the titanium of inactivation for cyclohexanone oxamidinating reaction unit Silicalite TS-1, powdery, grain size is in 100-500nm).
It is described draw off agent refer to using solvent wash or roast etc. conventional regeneration processes can not be allowed to activation recovering to initially (initial activity refers to that under identical reaction conditions, catalyst is within 1h to the catalyst of inactivation in the case of activity 50% Average activity.Such as in the reaction of practical cyclohexanone oximeization, the initial activity of general catalyst will reach 95% or more).It draws off The activity of agent is different according to its source.Usually, the activity for drawing off agent can be the Titanium Sieve Molecular Sieve when fresh The 5-95% of active (that is, fresh dose activity).Preferably, the described first activity for drawing off agent can be that the Titanium Sieve Molecular Sieve exists When fresh active 50% hereinafter, further preferably described first draw off agent activity can be the Titanium Sieve Molecular Sieve fresh When active 10-40%.Activity of Titanium Sieve Molecular Sieve when fresh is generally 90% or more, and usually 95% or more.
It is described to draw off the decaying catalyst after agent derive from industrial deactivator or be reacted in the lab.When So, from the angle for preparing effect, disclosed method can also use fresh molecular sieve such as Titanium Sieve Molecular Sieve as raw material, only It is method improper for cost control angularly, that the disclosure provides, mainly with the catalysis containing Titanium Sieve Molecular Sieve of inactivation Agent is turned waste into wealth as raw material, to save cost.
In above-mentioned preferred embodiment, the agent that draws off of each device is respectively measured using the reaction of each device, only Ensure, in identical device, under identical reaction condition, the activity for drawing off agent is less than the activity of fresh catalyst, as The present invention's draws off agent.As previously mentioned, in the case of preferred, the activity for drawing off agent is less than active the 50% of fresh catalyst.
In above-mentioned preferred embodiment, by cyclohexanone oxamidinating reaction unit draw off agent for, it is described activity by with Lower method measures：
Take TS-1 molecular sieves (by " and Zeolites, 1992, Vol.12：Prepared by the method described in 943~950 ", TiO2 Mass percentage be 2.1%) be placed in slurry bed reactors of the 100mL with continuous feed and membrane separation device, stirring The mixture of the hydrogen peroxide of water and 30wt% is added under state with the speed of 5.7mL/h, and (volume ratio of water and hydrogen peroxide is 10：9), with the mixture of the speed of 10.5mL/h addition cyclohexanone and the tert-butyl alcohol, (volume ratio of cyclohexanone and the tert-butyl alcohol is 1： 2.5) 36wt% ammonium hydroxide, is added with the speed of 5.7mL/h, above-mentioned three strands of materials stream is while being added, while with corresponding speed Continuous discharge, reaction temperature maintain 80 DEG C, after stable reaction every 1h to product sampling gas chromatography to the group of liquid phase At being analyzed, the conversion ratio of cyclohexanone is calculated using following formula and as the activity of Titanium Sieve Molecular Sieve.Cyclohexanone Conversion ratio=[(mole of the unreacted cyclohexanone of mole-of the cyclohexanone of addition)/mole for the cyclohexanone being added] × 100%.Wherein, using the result of 1h as initial activity.
In above-mentioned preferred embodiment, the Titanium Sieve Molecular Sieve can be the common titanium silicon with various topological structures point Son sieve, such as：The Titanium Sieve Molecular Sieve can be selected from the titanium silicon molecule of the Titanium Sieve Molecular Sieve (such as TS-1) of MFI structure, MEL structures Sieve (such as TS-2), the Titanium Sieve Molecular Sieve (such as Ti-Beta) of BEA structures, the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structures, six The Titanium Sieve Molecular Sieve (such as Ti-MCM-41, Ti-SBA-15) of square structure, the Titanium Sieve Molecular Sieve (such as Ti-MOR) of MOR structures, TUN knots It is one or more in the Titanium Sieve Molecular Sieve (such as Ti-TUN) of structure and the Titanium Sieve Molecular Sieve (such as Ti-ZSM-48) of other structures.It is excellent Selection of land, the Titanium Sieve Molecular Sieve are selected from the titanium silicon of the Titanium Sieve Molecular Sieve of MFI structure, the Titanium Sieve Molecular Sieve of MEL structures and BEA structures It is one or more in molecular sieve.It is highly preferred that the Titanium Sieve Molecular Sieve is the Titanium Sieve Molecular Sieve of MFI structure, such as TS-1 molecules Sieve.
In above-mentioned preferred embodiment, the described first weight ratio for drawing off agent, titanium source, silicon source, Organic Acid and Base source and water can Think 100：(0.1-10)：(0.1-10)：(0.005-50)：(0.5-50)：(20-1000), preferably 100：(0.5-10)： (0.5-10)：(1-15)：(1-20)：(100-800), the more preferably described first weight ratio for drawing off agent and organic acid is 100： (2-8), wherein described first draws off agent with SiO2Meter, the organic acid is with H+Meter, when the alkali source contains nitrogen in terms of N, The alkali source not Nitrogen element when with OH-Meter.
In above-mentioned preferred embodiment, source of aluminium is to be capable of providing the substance of aluminium, and preferably source of aluminium is Aluminum sol, aluminium One or more in salt, aluminium hydroxide and aluminium oxide, Aluminum sol preferred content in terms of aluminium oxide is 10-50 weight %.It is described Aluminium salt can be inorganic aluminate and/or organic aluminium salt, and the organic aluminium salt is preferably the organic aluminium salt of C1-C10, the inorganic aluminum Salt for example can be one or more in aluminum sulfate, sodium metaaluminate, aluminium chloride and aluminum nitrate.
In above-mentioned preferred embodiment, preferred steps (2) can carry out as follows：First source of aluminium and alkali source are existed Mixed solution is mixed to get in the presence of aqueous solvent, after then again mixing the mixed solution with first solid and titanium source Carry out second heat treatment.The activity of titanium Si-Al molecular sieve can so be further increased.
It can also include the step of the recovery product from the material after the heat treatment of step (2) second in above-mentioned preferred embodiment Suddenly, the step of recovery product is conventional method, is familiar with by those skilled in the art, herein and is had no special requirements, usually Refer to the process that product is filtered, washed, dries and roasts.Wherein, described drying process can be at a temperature of between 20-200 DEG C Carry out, described roasting process can between 300-800 DEG C first in nitrogen atmosphere after 0.5-6h in air atmosphere 3-12h into Row.
Alternatively, according to another preferred embodiment of the disclosure, the preparation process of the titanium Si-Al molecular sieve includes：
A, it draws off agent by second to be mixed with beating with organic acid soln, and obtained slurries is subjected to third heat treatment, separation Obtain the second solid, wherein described second draws off agent as the reaction unit using Si-Al molecular sieve as catalyst activity component Agent is drawn off, the condition of the third heat treatment is：Temperature is 50-150 DEG C, time 0.5-40h, preferably 1-24h, more preferably For 10-20h；
B, the 4th heat treatment, institute are carried out after mixing second solid, titanium source in the presence of aqueous solvent with alkali source Stating the condition that the 4th is heat-treated is：Temperature is 100-200 DEG C, and preferably 120-180 DEG C, more preferably 140-170 DEG C, the time is 0.5-25h, preferably 2-24h, more preferably 5-20h.
In above-mentioned preferred embodiment, the relative crystallinity of second solid obtained after third is heat-treated can Think 50-70%.Agent can be drawn off under specific third heat treatment condition by described second to be processed into specific opposite knot Then second solid of brilliant degree carries out the 4th heat treatment, can obtain the good titanium Si-Al molecular sieve of catalytic performance, is used for this public affairs again Propylene glycol and the selectivity of propylene glycol can be further increased in the reaction opened.Wherein, the measurement side of the relative crystallinity Method is as previously described.
In above-mentioned preferred embodiment, being specifically defined as previously mentioned, only Titanium Sieve Molecular Sieve replaces with sial for agent is drawn off Molecular sieve.The agent that draws off of the reaction unit using Si-Al molecular sieve as catalyst activity component can be to use silicon from various Aluminum molecular screen is as the agent that draws off drawn off in the device of catalyst activity component, such as can be from using Si-Al molecular sieve as urging (synthetic reaction device of such as hydrogen sulfide and methanol is drawn off for the agent that draws off drawn off in the synthetic reaction device of agent active component Agent), or what is drawn off from the catalytic cracking reaction device using Si-Al molecular sieve as catalyst activity component draws off agent. It is preferred that described draw off agent to react the catalyst of inactivation under alkaline environment, therefore, preferably described second agent is drawn off for the disclosure For the synthetic reaction device of hydrogen sulfide and methanol draw off agent (as inactivation Si-Al molecular sieve ZSM-5, powdery, grain size is in 100- 500nm)。
As previously mentioned, in the case of preferred, the described second activity for drawing off agent is work of Si-Al molecular sieve when fresh 50% or less property.
In above-mentioned preferred embodiment, by the synthetic reaction device of hydrogen sulfide and methanol draw off agent for, the activity It measures by the following method：
By ZSM-5 molecular sieve (being prepared by method described in embodiment 1 in Chinese patent CN1715185A) at 200 DEG C Tabletting after steam treatment 10h, sieving take 20-40 mesh particles loaded on a diameter of 0.8cm, the pipe reaction pipe that length is 55cm In, catalyst granules bed volume is 2.0cm3.It it is 300 DEG C in the temperature of reaction, the pressure of reaction is 1atm, hydrogen sulfide and first The raw materials components mole ratio of alcohol is 1:2, total gas volume air speed is 700h-1Under conditions of, the catalysis for carrying out synthesizing dimethyl thioether is anti- It answers.Obtained product after gas chromatographic analysis catalysis reaction 3h, according to the conversion ratio of Analysis result calculation methanol and as The activity of Si-Al molecular sieve.The conversion ratio of methanol=[(mole of the unreacted methanol of mole-of the methanol of addition)/add The mole of the methanol entered] × 100%.Wherein, using the result of 1h as initial activity.
In above-mentioned preferred embodiment, the Si-Al molecular sieve can be the common sial with various topological structures point Son sieve, it is preferable that the silicoaluminophosphate molecular is screened from the Si-Al molecular sieve of MFI structure, the Si-Al molecular sieve of FAU structures, MWW structures Si-Al molecular sieve, the Si-Al molecular sieve of MEL structures and at least one of the Si-Al molecular sieve of BEA structures.It is highly preferred that institute It states in the Si-Al molecular sieve, the Si-Al molecular sieve of BEA structures and the Si-Al molecular sieve of MWW structures that Si-Al molecular sieve is MFI structure At least one.
In above-mentioned preferred embodiment, the described second weight ratio for drawing off agent, titanium source, Organic Acid and Base source and water is 100： (0.1-10)：(0.005-50)：(0.5-50)：(20-1000), preferably 100：(0.5-10)：(1-15)：(1-20)：(100- 800), the more preferably described second weight ratio for drawing off agent and organic acid is 100：(2-8), wherein described second draw off agent with SiO2Meter, the organic acid is with H+Meter, when the alkali source contains nitrogen in terms of N, the alkali source not Nitrogen element when with OH-Meter.
In above-mentioned preferred embodiment, preferred steps (b) carry out as follows：By the aqueous solution of alkali source and described the The 4th heat treatment is carried out after two solids and titanium source mixing.
In the preparation preferred embodiment of both the above titanium Si-Al molecular sieve, it is described mashing preferably at normal temperatures and pressures into Row.In the case of specified otherwise, heat treatment is usually to be carried out at autogenous pressures in the case of sealing.
In the preparation preferred embodiment of both the above titanium Si-Al molecular sieve, the organic acid is not required particularly, Can be the organic carboxyl acid of C1-C10, preferably at least one of aphthenic acids, Peracetic acid and Perpropionic Acid.It is preferred that described have The concentration of machine acid solution>0.1mol/L, more preferably >=1mol/L, further preferred 2-15mol/L.In the disclosure, the acid is molten The primary solvent of liquid is water, also can be according to needing that other solvents aids are added.The titanium Si-Al molecular sieve being so prepared is urged Change performance more preferably.
In the preparation preferred embodiment of both the above titanium Si-Al molecular sieve, the titanium source can be organic titanium source (such as Organic titanate) and/or inorganic ti sources (such as inorganic titanium salt).Wherein, inorganic ti sources can be TiCl4、Ti(SO4)2、 TiOCl2, titanium hydroxide, titanium oxide, at least one of nitric acid titanium salt and phosphoric acid titanium salt etc., organic titanium source can be fatty alcohol At least one of titanium and organic titanate.The titanium source is preferably organic titanium source, further preferably organic titanate.It is described It is M that organic titanate, which preferably has structural formula,4TiO4Organic titanate, wherein M be preferably with 1-4 carbon atom alkane Base, and 4 M can be identical or different, the preferably described organic titanate is selected from as isopropyl titanate, metatitanic acid n-propyl, metatitanic acid four At least one of butyl ester and tetraethyl titanate.The specific example of the titanium source can be but be not limited to：TiOCl2, four chlorinations Titanium, titanium sulfate, metatitanic acid orthocarbonate (include the various isomers of metatitanic acid orthocarbonate, such as tetraisopropyl titanate and metatitanic acid four positive third Ester), at least one in butyl titanate (the various isomers of butyl titanate, such as tetra-n-butyl titanate) and tetraethyl titanate Kind.
In the preparation preferred embodiment of both the above titanium Si-Al molecular sieve, the optional range of the type of the alkali source compared with Width can be organic base source and/or inorganic alkali source, wherein inorganic alkali source can be ammonia or cation is alkali metal or alkaline earth The alkali of metal, such as can be sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide, it is described organic Alkali source can be one or more in urea, aliphatic amine, aliphatic hydramine and quaternary ammonium alkali cpd.The quaternary ammonium base can be with For various organic level Four ammonium alkali, the aliphatic amine can be various NH3At least one of hydrogen by aliphatic alkyl (preferably Alkyl) compound that is formed after substitution, the aliphatic hydramine can be various NH3At least one of hydrogen by the fat of hydroxyl The compound formed after fat race alkyl (preferably alkyl) substitution.
Specifically, the quaternary ammonium base can be the quaternary ammonium base as shown in Formula II, and the aliphatic amine can be that formula III indicates Aliphatic amine, the aliphatic hydramine can be as formula IV indicate aliphatic hydramine：
In Formula II, R5、R6、R7And R8Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane Base, such as：R5、R6、R7And R8Can be respectively methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle Butyl.
R9(NH2)nFormula III
In formula III, n is an integer of 1 or 2.When n is 1, R9For C1~C6Alkyl, including C1~C6Straight chained alkyl and C3- C6Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, new Amyl, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R9For C1-C6Alkylidene, including C1~C6Straight-chain alkyl-sub and C3 ~C6Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.More preferably Aliphatic amine compound is one or more in ethamine, n-butylamine, butanediamine and hexamethylene diamine
(HOR10)mNH(3-m)Formula IV
In formula IV, m R10It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-C4 Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is further preferred that the aliphatic alcohol Amine compounds are one or more in monoethanolamine, diethanol amine and triethanolamine.
Most preferably, the alkali source is selected from sodium hydroxide, ammonium hydroxide, ethylenediamine, n-butylamine, butanediamine, hexamethylene diamine, Dan Yi At least one of hydramine, diethanol amine, triethanolamine, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide.Wherein, when described When containing ammonium hydroxide in alkali source, the molar ratio of alkali source is to include molecular forms NH3With ionic species NH4 +Existing ammonia meter.
In the preparation preferred embodiment of both the above titanium Si-Al molecular sieve, the preferably described alkali source is carried in the form of aqueous slkali For the pH of the more preferable aqueous slkali>9.
In the preparation preferred embodiment of both the above titanium Si-Al molecular sieve, the aqueous solvent is essentially water, can also According to addition cosolvent is needed, in embodiment of the disclosure, aqueous solvent is water.
According to disclosed method, the condition of the oxidation reaction is not particularly limited, and can be the conventional choosing of this field It selects.Usually, the condition of the oxidation reaction includes：Temperature can be 0-200 DEG C, preferably 20-180 DEG C；In terms of gauge pressure, pressure Power can be 0-3MPa, preferably 0.1-1.5MPa.
According to disclosed method, the reaction can carry out in common various reaction units, such as：Stir autoclave Reactor or tubular reactor.
According to disclosed method, common various methods may be used to control the temperature in reactor.Such as：It can be with In the periphery setting cooling water jecket of reactor, and the temperature that is detected according to the temperature sensor being arranged in reactor is adjusted The amount for saving cooling water, to control the temperature of reactor within the scope of suitable.
Can also include that punching is sent into the first area according to certain time interval according to disclosed method The step of washing lotion is to be rinsed the separation of solid and liquid component.It can will likely be attached to the solid-liquid point by the flushing It is rinsed from the Titanium Sieve Molecular Sieve on component.
The flushing liquor can be the various liquid substances that can realize above-mentioned function.In the first area of solid-liquid separator When being connected to the reactor for carrying out oxidation reaction, the flushing preferably backwash is (that is, flushing liquor is sent by first area outlet Enter in first area, and be discharged from first area entrance), it is rinsed to which the Titanium Sieve Molecular Sieve being separated by solid-liquid separation on component will be attached to Get off, and sends back in reactor.From ensure the ratio of phenol and oxidant in reaction system will not due to flushing liquor entrance and The angle that big variation occurs is set out, and preferably flushing liquor contains the oxidant, optional phenol and optional solvent, more preferably The ratio in the ratio and previously described reaction raw materials between phenol and oxidant in the flushing liquor is identical.
The time interval of the flushing can make appropriate choice according to the treating capacity of solid-liquid separator, to ensure solid-liquid Separator can be isolated efficiently from reaction mixture subject to the liquid phase containing benzenediol.Usually, the flushing when Between interval can be 0.5-24 hours.The duration rinsed every time is can will be attached to the titanium silicon being separated by solid-liquid separation on component point Son sieve it is whole or it is substantially all rinse subject to.Usually, the duration of the flushing can be 5-300 seconds.
According to disclosed method, the quantity of the solid-liquid separator can be adjusted according to actual needs.By described The residue containing catalyst that first area exports can be recycled in the oxidation reaction, when the separation of solid and liquid When the quantity of device is multiple, it can also be sent by the residue containing catalyst that the first area exports subsequent solid Cycle is in the oxidation reaction after further being detached in liquid/gas separator.Therefore, the method that the disclosure provides may be used also To include：By the residue cycle containing catalyst exported by the first area in the reaction.According to this It is isolated containing benzene in the reaction mixture that the solid-liquid separator that the method for invention uses can be obtained efficiently from oxidation reaction The liquid product of diphenol, the amount of liquid is few therefore excellent according to disclosed method in the obtained residue containing catalyst Residue containing catalyst is directly recycled in the reaction by choosing.
According to disclosed method may be used common various methods by the solid-liquid separator be used to aoxidize The reactor of reaction is connected to, and is separated by solid-liquid separation to which the reaction mixture that oxidation reaction obtains to be sent into solid-liquid separator. For example, the first area entrance of solid-liquid separator can be connected to the outlet end of reactor with pipeline.
Can also include isolating benzenediol from the liquid product containing benzenediol according to disclosed method Step.The method for isolating benzenediol is not particularly limited in the disclosure, can be the conventional selection of this field.Such as it can be with By the way that vacuum fractionation will be carried out containing the liquid product of benzenediol, to obtain benzenediol.
The taking-up for carrying out reaction heat before and after above-mentioned separation of solid and liquid process can also be included according to disclosed method, such as may be used To be connected with heat collector on the channel after the residue containing catalyst is exported to obtain by first area, to take away produced by reaction Heat.
Fig. 3 shows a kind of flow chart of embodiment according to disclosed method.In this embodiment, described anti- It should carry out, the reaction mixture of gained is sent into the first area of solid-liquid separator 7, in the work of pressure difference in reactor 6 Under, at least partly liquid phase in reaction mixture is obtained into after dividing second area (shadow region in figure) of the solid-liquid from device 7 To the liquid product A containing benzenediol, the residue B containing catalyst that first area obtains is sent into heat collector 5, and is changed Thermal medium exchanges heat, and obtains the residue of temperature reduction, and the residue for then reducing the temperature is sent into reactor 6, is followed Ring is used for the reaction.
The invention will be further described with reference to embodiments, but the content being not intended to limit the present invention.
In following embodiment, if not otherwise specified, used reagent is commercially available reagent.
In following embodiment and comparative example, pressure is in terms of gauge pressure.
Hollow Titanium Sieve Molecular Sieve HTS used in following embodiment and comparative example is by Chinese patent CN1301599A explanations Book method described in embodiment 1 is prepared, and grain size is 0.3 μm.
Titanium-silicon molecular sieve TS-1 used in following embodiment be by Journal of Natural Gas Chemistry, 2001,10(4):In 295-307 prepared by method described in the 9-24 rows of page 296, and grain size is 0.3 μm.
Titanium Sieve Molecular Sieve Ti-Beta molecular sieves used in following embodiment be by J.Chem.Soc.Chem.Commun., Prepared by the method described in 1997,677-678, grain size is 0.3 μm.
In following embodiment, be respectively adopted static nitrogen adsorption method and solid ultraviolet-visible diffuse reflectance spectrum method to activity at The Kong Rong and ultraviolet absorption peak of the front and back Titanium Sieve Molecular Sieve of reason are characterized.Wherein, static nitrogen is adsorbed on Micromeritics public affairs It carries out on the 2405 type static state n2 absorption apparatus of ASAP of department, is measured according to ASTM D4222-98 standard methods.It is cold in liquid nitrogen Titanium Sieve Molecular Sieve sample is kept 4h to be de-gassed by nitrogen adsorption in trap at 393K, the vacuum degree of 1.3kPa, is carried out in 77K Nitrogen adsorption.Solid ultraviolet-visible diffuse reflectance spectrum (UV-Vis) is analyzed in SHIMADZU UV-3100 type ultraviolet-visible spectrums It carries out on instrument, is measured under normal temperature and pressure, scanning wavelength range 190nm~800nm.With powder pressing method, after sample calcination process, A certain amount of sample is taken, mortar grinder is put into and arrives<300 mesh, tabletting sample preparation.
In following embodiment and comparative example, reaction product is using its composition of gas chromatographic analysis, and analysis result is using correction Normalization method is quantified.Wherein, the analysis condition of chromatography is：Agilent-6890N type chromatographs, HP-5 capillary chromatographic columns, 0.5 μ L of sample size, 280 DEG C of injector temperature.Column temperature keeps 2min at 100 DEG C, then rises to 200 with the rate of 15 DEG C/min DEG C, and keep 3min.Fid detector, 300 DEG C of detector temperature.Following formula is respectively adopted on this basis to calculate phenol Conversion ratio, the effective rate of utilization of oxidant and the selectivity of benzenediol：
When phenol and oxidant molar ratio≤1, phenol conversion (%)=[(mole-of the phenol of addition is not anti- The mole for the phenol answered)/be added phenol mole] × 100%；
When phenol and oxidant molar ratio ＞ 1, phenol conversion (%)=(mole-unreacted for the middle phenol that feeds intake Phenol mole)/mole for the middle phenol that the feeds intake × mole for the middle phenol that feeds intake/middle oxidant that feeds intake mole × 100%；
Oxidant effective rate of utilization (%)=[mole/(mole of the oxidant of addition for the benzenediol that reaction generates The mole of the oxidant of mole-decomposition of amount-unreacted oxidant)] × 100%；
Benzenediol selectivity (%)=[mole for the benzenediol that reaction generates/(mole-of the phenol of addition is not anti- The mole for the phenol answered)] × 100%.
Embodiment 1-33 is for illustrating disclosed method.
Embodiment 1-33 is carried out using method shown in Fig. 3, uses water as heat transferring medium in heat collector.
Embodiment 1
The hollow Titanium Sieve Molecular Sieve HTS of 50g are placed in 200ml methanol, stirring is in paste-like, then by the catalysis of reaction kettle Agent charge door injects in reaction system.Liquid phase feed inlet valve is opened, inlet valve is opened, phenol, hydrogen peroxide and solvent is sent Enter in the reaction system, is carried out continuously reaction.Wherein, the mass ratio of methanol and phenol is 5：1, mole of phenol and hydrogen peroxide Than being 1：1.1, the feed rate of phenol is 20mL/min, and the temperature in reaction system is 45 DEG C, pressure 0.5MPa, continuously into Row reaction in 100 hours.
It is separated by solid-liquid separation, is obtained containing benzene two by being sent into solid-liquid separator from the reaction mixture exported in reactor The liquid product of phenol and residue (solid content be 83 weight %) containing Titanium Sieve Molecular Sieve, will contain the residual of Titanium Sieve Molecular Sieve Stay object cycle for preparing reaction mass.
Wherein, the solid-liquid separator is formed by ceramic film filtering element and a shell, ceramic in each solid-liquid separator (commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm to film filtering element, membrane tube Internal diameter be 8mm, the outer diameter of membrane tube be 12mm) quantity be 2, the internal diameter of shell is 40mm.The quantity of solid-liquid separator is 60, separator is divided into 6 groups, every group is made of 10 separators, wherein be parallel connection between the separator in same group, often It is series connection between group, when flushing, the ceramic film filtering element in 5 solid-liquid separators in every group is rinsed every time.It will Reaction mixture is sent into the first area inside ceramic film filtering element, in the outer wall and shell by ceramic film filtering element The second area outlet that inner wall is formed, which is collected, obtains the liquid product containing benzenediol.Pressure in first area is 0.8MPa, Pressure in second area is 0.3MPa.
Every 2 hours with flushing liquor (for phenol and hydrogen peroxide and the mixed solution of methanol, ratio between three with The ratio reacted in liquid phase material is identical) flushing in 50 seconds is carried out to the channel on ceramic film filtering element, and obtained after rinsing To mixed liquor be sent into reactor in.
The liquid product containing benzenediol exported from solid-liquid separator is analyzed every 2 hours, calculates phenol Conversion ratio, the effective rate of utilization of oxidant and the selectivity of benzenediol, result when reaction proceeds to 2 hours and 100 is in table 1 In list.
Embodiment 2
Benzenediol is prepared according to the method for embodiment 1, unlike, replace hollow titanium with the titanium-silicon molecular sieve TS-1 of equivalent Si molecular sieves HTS.Reaction result is listed in table 1.
Embodiment 3
Benzenediol is prepared according to the method for embodiment 1, unlike, replace hollow titanium with the Ti-Beta molecular sieves of equivalent Si molecular sieves HTS.Reaction result is listed in table 1.
Embodiment 4
Benzenediol is prepared according to the method for embodiment 1, unlike, hydrochloric acid is sent into reactor by auxiliary agent feed inlet The additive amount of (for the aqueous solution of 25 weight %), hydrochloric acid makes the pH value of the liquid phase material in reactor (be not added with hydrochloric acid for 5.5 When, 6.8) pH value of liquid phase material is.Reaction result is listed in table 1.
Embodiment 5
Benzenediol is prepared according to the method for embodiment 1, unlike, hydrochloric acid is sent into reactor by auxiliary agent feed inlet The additive amount of (for the aqueous solution of 25 weight %), hydrochloric acid makes the pH value of the liquid phase material in reactor (be not added with hydrochloric acid for 4.5 When, 6.8) pH value of liquid phase material is.Reaction result is listed in table 1.
Embodiment 6
Benzenediol is prepared according to the method for embodiment 2, unlike, titanium-silicon molecular sieve TS-1 is before use, first live Change is handled.Concrete operations are：Titanium-silicon molecular sieve TS-1 is added in the mixed aqueous solution containing hydrochloric acid and hydrogen peroxide, is being stirred Mix lower carry out activation process, hydrochloric acid (in terms of HCl) in mixed aqueous solution: hydrogen peroxide: water: TS-1 molecular sieves are (with silica Meter) molar ratio be 10：1：80：1, treatment temperature is 30 DEG C, processing time 20h, recycling is activated later TS-1 points Son sieve.Compared with the titanium-silicon molecular sieve TS-1 of embodiment 2, in the UV-Vis spectrum of the titanium-silicon molecular sieve TS-1 by activation process The peak area of absorption peak between 230-310nm reduces 5.8%, is held by the hole of static determination of nitrogen adsorption and reduces 3.6%.Instead Result is answered to be listed in table 1.
Table 1
Embodiment 1 and embodiment 2 and 3 are compared as can be seen that using hollow Titanium Sieve Molecular Sieve as catalyst energy Enough obtain better catalytic effect.
Embodiment 1 and embodiment 4 and 5 are compared as can be seen that with it is sour by the pH value of reaction system be adjusted to 5.5 with Under, higher benzenediol selectivity can be obtained.
It is used as catalysis after embodiment 6 and embodiment 2 being compared as can be seen that carrying out activation process to Titanium Sieve Molecular Sieve Agent can improve the selectivity of benzenediol and the service life of catalyst.
Embodiment 7-13 measures the activity of Titanium Sieve Molecular Sieve using following methods：
By Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH3Meter), the hydrogen peroxide of 30 weight % is (with H2O2Meter), the tert-butyl alcohol In mass ratio=1 with cyclohexanone：7.5：10：7.5：It will be reacted after 80 DEG C are stirred to react 2h at atmosheric pressure after 10 mixing Object filter, the composition of liquid phase is analyzed with gas chromatography, using following formula calculate cyclohexanone conversion ratio and by its As the activity of Titanium Sieve Molecular Sieve,
The conversion ratio of cyclohexanone=[(mole of the unreacted cyclohexanone of mole-of the cyclohexanone of addition)/it is added Cyclohexanone mole] × 100%.
Embodiment 7
(1) Titanium Sieve Molecular Sieve of activation process is prepared
The raw molecule sieve used is regenerated for the titanium-silicon molecular sieve TS-1 drawn off from cyclohexanone oxamidinating reaction unit Obtained from, activity is 50%, and activity when fresh is 95%, and average grain diameter is 0.6 μm, and regeneration condition is：At 550 DEG C Under 4h is roasted in air atmosphere.
Raw molecule sieve is added in the mixed aqueous solution containing nitric acid and hydrogen peroxide, is carried out at activation under stiring It manages, nitric acid is (with HNO in mixed aqueous solution3Meter): hydrogen peroxide: water: the molar ratio of TS-1 molecular sieves (in terms of silica) is 5：2：60：1, treatment temperature is 30 DEG C, processing time 20h, and recycling later obtains the Titanium Sieve Molecular Sieve TS- by activation process 1.Compared with raw material, the absorption in the UV-Vis spectrum of the titanium-silicon molecular sieve TS-1 by activation process between 230-310nm The peak area at peak reduces 5.3%, is held by the hole of static determination of nitrogen adsorption and reduces 4.8%.
(2) benzenediol is prepared
The above-mentioned titanium-silicon molecular sieve TS-1s by activation process of 50g are placed in 200ml methanol, stirring is in paste-like, so It is injected in reaction system by the catalyst charging hole of reaction kettle afterwards.Open liquid phase feed inlet valve, open inlet valve, by phenol, Hydrogen peroxide and solvent are sent into the reaction system, while opening auxiliary agent inlet valve, and sulfuric acid is sent into reaction system (for 25 weights Measure the aqueous solution of %) it is carried out continuously reaction.Wherein, the mass ratio of methanol and phenol is 5：1, the molar ratio of phenol and hydrogen peroxide It is 1：1.1, the dosage of sulfuric acid so that the pH value of the liquid phase material in reaction system is 3.5, and the feed rate of phenol is 20mL/ Min, the temperature in reaction system is 45 DEG C, and pressure 0.5MPa is carried out continuously reaction in 100 hours.
It is separated by solid-liquid separation, is obtained containing benzene two by being sent into solid-liquid separator from the reaction mixture exported in reactor The liquid product of phenol and residue (solid content be 85 weight %) containing Titanium Sieve Molecular Sieve, will contain the residual of Titanium Sieve Molecular Sieve Stay object cycle for preparing reaction mass.
Wherein, the solid-liquid separator is formed by ceramic film filtering element and a shell, ceramic in each solid-liquid separator (commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm to film filtering element, membrane tube Internal diameter be 8mm, the outer diameter of membrane tube be 12mm) quantity be 5, the internal diameter of shell is 100mm.The quantity of solid-liquid separator is 12, separator is divided into 2 groups, every group is made of 6 separators, wherein be between the separator in same group it is in parallel, every group Between for series connection, when flushing, the ceramic film filtering element in 3 solid-liquid separators in every group is rinsed every time.It will be anti- Mixture is answered to be sent into the first area inside ceramic film filtering element, in the outer wall and shell by ceramic film filtering element The second area outlet that wall is formed, which is collected, obtains the liquid product containing benzenediol.Pressure in first area is 0.8MPa, the Pressure in two regions is 0.5MPa.
Every 1 hour with flushing liquor (for phenol and hydrogen peroxide and the mixed solution of methanol, ratio between three with Ratio in liquid phase material is identical) flushing in 50 seconds carried out to the channel on ceramic film filtering element, and will be obtained after flushing Mixed liquor is sent into reactor.
The liquid product containing benzenediol exported from solid-liquid separator is analyzed every 2 hours, calculates phenol Conversion ratio, the effective rate of utilization of oxidant and the selectivity of benzenediol, result when reaction proceeds to 2 hours and 100 is in table 2 In list.
Embodiment 8
Benzenediol is prepared according to the method for embodiment 7, unlike, in step (2), the dosage of sulfuric acid makes reaction system PH value be 1.Reaction result is listed in table 2.
Embodiment 9
Benzenediol is prepared according to the method for embodiment 7, unlike, in step (2), the molar ratio of phenol and hydrogen peroxide It is 1：0.3, result when reaction proceeds to 2 hours and 100 is listed in table 2.
Embodiment 10
Benzenediol is prepared according to the method for embodiment 7, unlike, in step (2), the molar ratio of phenol and hydrogen peroxide It is 1：0.1, result when reaction proceeds to 2 hours and 100 is listed in table 2.
Embodiment 11
Benzenediol is prepared according to the method for embodiment 7, unlike, used catalyst is the sky by activation process Heart Titanium Sieve Molecular Sieve HTS.Specifically, step (1) is：The raw molecule sieve used is that will be unloaded from phenol hydroxylation reaction unit Obtained from the hollow Titanium Sieve Molecular Sieve HTS gone out is regenerated, activity is 30%, and activity when fresh is 96%, average Grain size is 0.6 μm, and regeneration condition is：4h is roasted in air atmosphere at 570 DEG C.
Raw molecule sieve is added in the mixed aqueous solution containing nitric acid and hydrogen peroxide, is carried out at activation under stiring It manages, nitric acid is (with HNO in mixed aqueous solution3Meter): hydrogen peroxide: water: mole of hollow titanium silicon molecule HTS (in terms of silica) Than being 0.5: 0.5: 50: 1, treatment temperature is 30 DEG C, processing time 20h, and recycling later is obtained by the hollow of activation process Titanium silicon molecule HTS.With raw molecule sieve compared with, in the UV-Vis spectrum of the hollow titanium silicon molecule HTS by activation process The peak area of absorption peak between 230-310nm reduces 5.0%, is held by the hole of static determination of nitrogen adsorption and reduces 3.4%.
Reaction result is listed in table 2.
Embodiment 12
The Titanium Sieve Molecular Sieve used in the present embodiment is the titanium-silicon molecular sieve TS-1 that will be drawn off from propylene oxidation reaction process Obtained from being regenerated, activity is 50%, and activity when fresh is 95%, and average grain diameter is 0.6 μm, regeneration condition For：4h is roasted in air atmosphere at 550 DEG C.
The above-mentioned titanium-silicon molecular sieve TS-1s after regeneration of 50g are placed in 400ml acetone, stirring be in paste-like, then by In the catalyst charging hole injection reaction system of reaction kettle.Liquid phase feed inlet valve is opened, inlet valve is opened, by phenol, tertiary fourth Base hydrogen peroxide and solvent are sent into the reaction system, while opening auxiliary agent inlet valve, and it (is 25 that sulfuric acid is sent into reaction system The aqueous solution of weight %) it is carried out continuously reaction.Wherein, the mass ratio of acetone and phenol is 10：1, phenol and tert-butyl hydroperoxide The molar ratio of hydrogen is 1：5, the dosage of sulfuric acid so that the pH value of the liquid phase material in reaction system is 3.5, the feed rate of phenol For 20mL/min, the temperature in reaction system is 65 DEG C, and pressure 0.5MPa is carried out continuously reaction in 100 hours.
It is separated by solid-liquid separation, is obtained containing benzene two by being sent into solid-liquid separator from the reaction mixture exported in reactor The liquid product of phenol and residue (solid content be 65 weight %) containing Titanium Sieve Molecular Sieve, will contain the residual of Titanium Sieve Molecular Sieve Stay object cycle for preparing reaction mass.
Wherein, the solid-liquid separator is formed by ceramic film filtering element and a shell, ceramic in each solid-liquid separator (commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm to film filtering element, membrane tube Internal diameter be 8mm, the outer diameter of membrane tube be 12mm) quantity be 5, the internal diameter of shell is 100mm.The quantity of solid-liquid separator is 12, separator is divided into 2 groups, every group is made of 6 separators, wherein be between the separator in same group it is in parallel, every group Between for series connection, when flushing, the ceramic film filtering element in 3 solid-liquid separators in every group is rinsed every time.It will be anti- Mixture is answered to be sent into the first area inside ceramic film filtering element, in the outer wall and shell by ceramic film filtering element The second area outlet that wall is formed, which is collected, obtains the liquid product containing benzenediol.Pressure in first area is 1.0MPa, the Pressure in two regions is 0.6MPa.
Every 1 hour with flushing liquor (for phenol and tert-butyl hydroperoxide and the mixed solution of acetone, between three Ratio in ratio and liquid phase material is identical) flushing in 150 seconds is carried out to the channel on ceramic film filtering element, and after rinsing Obtained mixed liquor is sent into reactor.
The liquid product containing benzenediol exported from solid-liquid separator is analyzed every 2 hours, calculates phenol Conversion ratio, the effective rate of utilization of oxidant and the selectivity of benzenediol, result when reaction proceeds to 2 hours and 100 is in table 2 In list.
Embodiment 13
Benzenediol is prepared according to the method for embodiment 12, unlike, catalyst from propylene oxidation reaction process by will unload Regenerative agent obtained from the titanium-silicon molecular sieve TS-1 gone out is regenerated and fresh titanium-silicon molecular sieve TS-1 composition, wherein regeneration The mass ratio of agent and fresh titanium-silicon molecular sieve TS-1 is 2：1.Reaction result is listed in table 2.
Table 2
Embodiment 7-13's as a result, it was confirmed that even if at least partly catalyst come from through it is regenerated draw off agent if can obtain Obtain high phenol conversion, oxidant effective rate of utilization and benzenediol selectivity.
Embodiment 14
(1) Titanium Sieve Molecular Sieve of activation process is prepared
Hollow Titanium Sieve Molecular Sieve HTS is added in the mixed aqueous solution containing nitric acid and hydrogen peroxide, under stiring into Row activation process, nitric acid is (with HNO in mixed aqueous solution3Meter): hydrogen peroxide: water: hollow Titanium Sieve Molecular Sieve HTS is (with titanium dioxide Silicon meter) molar ratio be 6: 5: 20: 1, treatment temperature is 30 DEG C, processing time 20h, later the TS-1 that is activated points of recycling Son sieve.Compared with the hollow Titanium Sieve Molecular Sieve HTS before activation process, the UV- of the hollow Titanium Sieve Molecular Sieve HTS by activation process The peak area of absorption peak in Vis spectrum between 230-310nm reduces 5.0%, is subtracted by the Kong Rong of static determination of nitrogen adsorption Few 3.4%.
(2) benzenediol is prepared
It being placed in 200ml methanol by the hollow Titanium Sieve Molecular Sieve HTS of activation process by 50g is above-mentioned, stirring is in paste-like, Then it is injected in reaction system by the catalyst charging hole of reaction kettle.Liquid phase feed inlet valve is opened, inlet valve is opened, by benzene Phenol, hydrogen peroxide and solvent are sent into the reaction system, while opening auxiliary agent inlet valve, into reaction system be sent into sulfuric acid (for The aqueous solution of 25 weight %) it is carried out continuously reaction.Wherein, the mass ratio of methanol and phenol is 50：1, phenol and hydrogen peroxide Molar ratio is 1：2, the dosage of sulfuric acid so that the pH value of the liquid phase material in reaction system is 3.5, and the feed rate of phenol is 20mL/min, the temperature in reaction system is 45 DEG C, and pressure 0.5MPa is carried out continuously reaction in 100 hours.
It is separated by solid-liquid separation, is obtained containing benzene two by being sent into solid-liquid separator from the reaction mixture exported in reactor The liquid product of phenol and residue (solid content be 85 weight %) containing Titanium Sieve Molecular Sieve, will contain the residual of Titanium Sieve Molecular Sieve Stay object cycle for preparing reaction mass.
Wherein, the solid-liquid separator is formed by ceramic film filtering element and a shell, ceramic in each solid-liquid separator (commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm to film filtering element, membrane tube Internal diameter be 8mm, the outer diameter of membrane tube be 12mm) quantity be 5, the internal diameter of shell is 100mm.The quantity of solid-liquid separator is 12, separator is divided into 2 groups, every group is made of 6 separators, wherein be between the separator in same group it is in parallel, every group Between for series connection, when flushing, the ceramic film filtering element in 3 solid-liquid separators in every group is rinsed every time.It will be anti- Mixture is answered to be sent into the first area inside ceramic film filtering element, in the outer wall and shell by ceramic film filtering element The second area outlet that wall is formed, which is collected, obtains the liquid product containing benzenediol.Pressure in first area is 0.8MPa, the Pressure in two regions is 0.5MPa.
Every 1 hour with flushing liquor (for phenol and hydrogen peroxide and the mixed solution of methanol, ratio between three with Ratio in liquid phase material is identical) flushing in 100 seconds carried out to the channel on ceramic film filtering element, and will be obtained after flushing Mixed liquor is sent into reactor.
The liquid product containing benzenediol exported from solid-liquid separator is analyzed every 2 hours, calculates phenol Conversion ratio, the effective rate of utilization of oxidant and the selectivity of benzenediol, result when reaction proceeds to 2 hours and 100 is in table 3 In list.
Embodiment 15
Benzenediol is prepared according to the method for embodiment 14, unlike, in step (1), the activation process of Titanium Sieve Molecular Sieve Method is：Hollow Titanium Sieve Molecular Sieve HTS is added in the mixed aqueous solution containing hydrochloric acid, carries out activation process under stiring, Nitrohydrochloric acid (in terms of HCl) in aqueous solution: water: the molar ratio of hollow Titanium Sieve Molecular Sieve HTS (in terms of silica) is 0.02: 15: 1, treatment temperature is 50 DEG C, processing time 15h, recycles the hollow Titanium Sieve Molecular Sieve HTS activated later.With activation process Preceding hollow Titanium Sieve Molecular Sieve HTS is compared, by the UV-Vis spectrum of the hollow Titanium Sieve Molecular Sieve HTS of activation process in 230- The peak area of absorption peak between 310nm reduces 7.3%, is held by the hole of static determination of nitrogen adsorption and reduces 6.6%.Reaction result It is listed in table 3.
Embodiment 16
Benzenediol is prepared according to the method for embodiment 14, unlike, in step (1), the activation process of Titanium Sieve Molecular Sieve Method is：Hollow Titanium Sieve Molecular Sieve HTS is added in the mixed aqueous solution containing acetic acid and hydrogen peroxide, is carried out under stiring Activation process, acetic acid is (with CH in mixed aqueous solution3COOH is counted): hydrogen peroxide: water: hollow Titanium Sieve Molecular Sieve HTS is (with titanium dioxide Silicon meter) molar ratio be 12: 8: 100: 1, treatment temperature is 30 DEG C, processing time 20h, recycles the TS-1 that is activated later Molecular sieve.Compared with the hollow Titanium Sieve Molecular Sieve HTS before activation process, hollow Titanium Sieve Molecular Sieve HTS's by activation process The peak area of absorption peak in UV-Vis spectrum between 230-310nm reduces 6.1%, by the Kong Rong of static determination of nitrogen adsorption Reduce 1.7%.Reaction result is listed in table 3.
Table 3
Embodiment 14-16's as a result, it was confirmed that activation process is by Titanium Sieve Molecular Sieve and the water containing nitric acid and peroxide Solution contacts, and when the molar ratio of nitric acid, peroxide, water and Titanium Sieve Molecular Sieve is (0.1-10)：(0.01-5)：(20- 80)：When 1, phenol conversion, oxidant effective rate of utilization and benzenediol selectivity can be further increased.
In following preparation example, X-ray diffraction (XRD) crystalline phase figure of sample is in Siemens D5005 type x-ray diffractometers On be measured.
Preparation example 1
(1) take TS-1 molecular sieves (by " and Zeolites, 1992, Vol.12：It is prepared by the method described in 943~950 ", TiO2Mass percentage be 2.1%) be placed in 100mL band continuous feed and membrane separation device slurry bed reactor in, stirring Mix the mixture (volume ratio of water and hydrogen peroxide that water and the hydrogen peroxide of 30wt% is added in the speed under state with 5.7mL/h It is 10：9), with the mixture of the speed of 10.5mL/h addition cyclohexanone and the tert-butyl alcohol, (volume ratio of cyclohexanone and the tert-butyl alcohol is 1： 2.5) 36wt% ammonium hydroxide, is added with the speed of 5.7mL/h, above-mentioned three strands of materials stream is while being added, while with corresponding speed Continuous discharge, reaction temperature maintain 80 DEG C, after stable reaction every 1h to product sampling gas chromatography to the group of liquid phase At being analyzed, the conversion ratio of cyclohexanone is calculated using following formula and as the activity of Titanium Sieve Molecular Sieve.Cyclohexanone Conversion ratio=[(mole of the unreacted cyclohexanone of mole-of the cyclohexanone of addition)/mole for the cyclohexanone being added] × 100%.The yclohexanone conversion ratio for being for the first time 1h measurement is its initial activity, value 99.5%.Through after a period of time After yclohexanone conversion ratio drops to 50% by initial 99.5%, roasting regeneration mode is used again after isolating catalyst by about 168h Raw (4h is roasted in air atmosphere at 570 DEG C) then proceedes in cyclohexanone oxamidinating reaction, this step to be repeated Suddenly, until the activity after regeneration is less than the 50% of initial activity, the oximes catalyst sample at this moment inactivated is real as this preparation That applies example draws off agent, obtains drawing off agent SH-1 (activity is 40%), SH-2 (activity is 25%), SH-3 successively according to preceding method (activity is 10%).
(2) under room temperature (20 DEG C, similarly hereinafter) normal pressure (0.1MPa, similarly hereinafter), first by the cyclohexanone oximate catalyst SH- of inactivation 1 is mixed with beating with the cycloalkanes aqueous acid of 1mol/L, and then mixed serum is mixed at 45 DEG C, carries out the first heat treatment 12h；By solid (relative crystallinity 71%), silicon source aluminum sulfate, titanium source titanium sulfate and sodium hydrate aqueous solution after separation of solid and liquid Mixed liquor is put into stainless steel after (pH 12) mixing and seals reaction kettle, the second heat treatment 12h is carried out at 170 DEG C, wherein object Expect that quality group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=100：1：1：2：5：250, inactivation Cyclohexanone oximate catalyst is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.It by products therefrom filtering, is washed with water, and in 110 DEG C 120min is dried, then in 550 DEG C of roasting temperature 3h, obtains molecular sieve, XRD crystalline phase figures show to have obtained with MFI knots The titanium Si-Al molecular sieve (TS-A) of structure, grain size are 0.3 μm.
(3) at normal temperatures and pressures, first by the peracetic acid soln of cyclohexanone oximate the catalyst SH-2 and 5mol/L of inactivation It is mixed with beating, then mixed serum is mixed at 20 DEG C, carry out the first heat treatment 20h；By solid (phase after separation of solid and liquid To crystallinity be 89%), silicon source Aluminum sol (content is 20 weight %), titanium source butyl titanate and tetrapropylammonium hydroxide it is water-soluble Mixed liquor is put into stainless steel after liquid (pH 10) mixing and seals reaction kettle, the second heat treatment 20h is carried out at 150 DEG C, wherein Quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=100：2：0.5：8：15：200, The cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.Then it recycles and produces according to the method for step (2) Object, obtains titanium Si-Al molecular sieve, and XRD crystalline phase figures show to have obtained the titanium Si-Al molecular sieve (TS-B) with MFI structure, grain Diameter is 0.3 μm.
(4) at normal temperatures and pressures, by the Perpropionic Acid aqueous solution of cyclohexanone oximate the catalyst SH-3 and 8mol/L of inactivation It is mixed with beating, then mixed serum is mixed at 30 DEG C, carry out the first heat treatment 10h；By solid (phase after separation of solid and liquid To crystallinity be 80%), silicon source aluminium hydroxide, titanium source titanium tetrachloride mixed with ethylenediamine solution (pH 11) after by mixed liquor It is put into stainless steel sealing reaction kettle, the second heat treatment 5h is carried out at 140 DEG C, wherein quality of material group becomes the hexamethylene of inactivation Ketoxime catalyst：Titanium source：Silicon source：Acid：Alkali：Water=100：5：2：5：5：150, the cyclohexanone oximate catalyst of inactivation is with SiO2 Meter, acid is with H+Meter, alkali is in terms of N.Then according to the method recovery product of step (2), titanium Si-Al molecular sieve, XRD crystalline phases are obtained Figure shows to have obtained the titanium Si-Al molecular sieve (TS-C) with MFI structure, and grain size is 0.3 μm.
(5) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, the temperature of the first heat treatment is 60 DEG C, The relative crystallinity of solid is that 65%, XRD crystalline phase figures show to have obtained the titanium Si-Al molecular sieve with MFI structure after separation of solid and liquid (TS-D), grain size is 0.3 μm.
(6) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, the temperature of the first heat treatment is 180 DEG C, the relative crystallinity of solid is that 95%, XRD crystalline phase figures show to have obtained the titanium sial point with MFI structure after separation of solid and liquid Son sieve (TS-E), grain size are 0.3 μm.
(7) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, Perpropionic Acid aqueous solution is replaced with Formic acid, the relative crystallinity of solid is that 60%, XRD crystalline phase figures show to have obtained the titanium sial with MFI structure after separation of solid and liquid Molecular sieve (TS-F), grain size are 0.3 μm.
(8) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, the cyclohexanone oximate catalyst of inactivation： Acid=100：15, the relative crystallinity of solid is that 62%, XRD crystalline phase figures show to have obtained with MFI structure after separation of solid and liquid Titanium Si-Al molecular sieve (TS-G), grain size are 0.3 μm.
(9) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, directly by TS-1 molecular sieves (opposite knot Brilliant degree be 100%), silicon source aluminium hydroxide, titanium source titanium tetrachloride mix with ethylenediamine solution progress second be heat-treated, XRD crystalline substance Phasor shows to have obtained the titanium Si-Al molecular sieve (TS-H) with MFI structure, and grain size is 0.3 μm.
Preparation example 2
(1) by ZSM-5 molecular sieve (being prepared by method described in embodiment 1 in Chinese patent CN1715185A) 200 Tabletting after steam treatment 10h at DEG C, sieving take 20-40 mesh particles anti-for the tubular type of 55cm loaded on a diameter of 0.8cm, length Ying Guanzhong, catalyst granules bed volume are 2.0cm3.It it is 300 DEG C in the temperature of reaction, the pressure of reaction is 1atm, hydrogen sulfide Raw materials components mole ratio with methanol is 1:2, total gas volume air speed is 700h-1Under conditions of, carry out urging for synthesizing dimethyl thioether Change reaction.The product that gas chromatographic analysis catalysis reaction obtains after 3 hours, according to the conversion ratio of Analysis result calculation methanol and is incited somebody to action Its activity as Si-Al molecular sieve.The conversion ratio of methanol=[(mole of the unreacted methanol of mole-of the methanol of addition Amount)/be added methanol mole] × 100%.Wherein, using the result of 1h as initial activity, value 99%.By A period of time about 180h after methanol conversion drops to 50% by initial 99%, is isolated after catalyst with roasting regeneration side Formula regenerates (4h is roasted in air atmosphere at 570 DEG C), then proceedes in the synthetic reaction of hydrogen sulfide and methanol, repeatedly The step for progress, until the activity after regeneration is less than the 50% of initial activity, the catalyst sample at this moment inactivated is as this hair Bright draws off agent, obtains drawing off agent SH-I (activity is 45%), SH-II (activity is 35%), SH- successively according to preceding method III (activity is 15%).
(2) under room temperature (20 DEG C, similarly hereinafter) normal pressure (0.1MPa, similarly hereinafter), first by the catalyst SH-I and 1mol/L of inactivation Cycloalkanes aqueous acid be mixed with beating, then mixed serum is mixed at 50 DEG C, carry out third be heat-treated 12h；Solid-liquid It will mixing after mixing solid (relative crystallinity 70%), titanium source titanium sulfate with sodium hydrate aqueous solution (pH 12) after separation Liquid is put into stainless steel sealing reaction kettle, the 4th heat treatment 12h is carried out at 170 DEG C, wherein quality of material group becomes urging for inactivation Agent：Titanium source：Acid：Alkali：Water=100：1：2：5：250, the catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.By institute It obtains product filtering, be washed with water, and 120min are dried in 110 DEG C, then in 550 DEG C of roasting temperature 3h, obtain molecular sieve, XRD crystalline phase figures show to have obtained the titanium Si-Al molecular sieve (SA-A) with MFI structure, and grain size is 0.3 μm.
(3) at normal temperatures and pressures, first the peracetic acid soln of the catalyst SH-II and 5mol/L of inactivation are mixed with beating, Then mixed serum is mixed at 150 DEG C, carries out third and is heat-treated 20h；By solid (relative crystallinity after separation of solid and liquid For 53%), titanium source butyl titanate mixed with tetrapropylammonium hydroxide solution (pH 10) after mixed liquor is put into stainless steel Reaction kettle is sealed, the 4th heat treatment 20h is carried out at 150 DEG C, wherein quality of material group becomes the catalyst of inactivation：Titanium source：Acid： Alkali：Water=100：2：8：15：200, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.Then it presses According to the method recovery product of step (2), titanium Si-Al molecular sieve is obtained, XRD crystalline phase figures show to have obtained the titanium with MFI structure Si-Al molecular sieve (SA-B), grain size are 0.3 μm.
(4) at normal temperatures and pressures, the Perpropionic Acid aqueous solution of the catalyst SH-III and 8mol/L of inactivation are mixed with beating, Mixed serum is then mixed to processing 10h at 100 DEG C；By solid (relative crystallinity 61%), titanium after separation of solid and liquid Mixed liquor is put into stainless steel after being mixed with ethylenediamine solution (pH 11) and seals reaction kettle by source titanium tetrachloride, at 140 DEG C Hydro-thermal process 5h, wherein quality of material group becomes the catalyst of inactivation：Titanium source：Acid：Alkali：Water=100：5：5：5：150, inactivation Catalyst with SiO2Meter, acid is with H+Meter, alkali is in terms of N.Then according to the method recovery product of step (2), titanium silicoaluminophosphate molecular is obtained Sieve, XRD crystalline phase figures show to have obtained the titanium Si-Al molecular sieve (SA-C) with MFI structure, and grain size is 0.3 μm.
(5) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, the temperature of third heat treatment is 40 DEG C, The relative crystallinity of solid is that 41%, XRD crystalline phase figures show to have obtained the titanium Si-Al molecular sieve with MFI structure after separation of solid and liquid (SA-D), grain size is 0.3 μm.
(6) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, the temperature of third heat treatment is 180 DEG C, the relative crystallinity of solid is that 80%, XRD crystalline phase figures show to have obtained the titanium sial point with MFI structure after separation of solid and liquid Son sieve (SA-E), grain size are 0.5 μm.
(7) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, Perpropionic Acid aqueous solution is replaced with Formic acid, the relative crystallinity of solid is that 38%, XRD crystalline phase figures show to have obtained the titanium sial with MFI structure after separation of solid and liquid Molecular sieve (SA-F), grain size are 0.3 μm.
(8) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, the catalyst of inactivation：Acid=100： 20, the relative crystallinity of solid is that 30%, XRD crystalline phase figures show to have obtained the titanium sial point with MFI structure after separation of solid and liquid Son sieve (SA-G), grain size are 0.3 μm.
(9) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, it is directly that ZSM-5 molecular sieve is (opposite Crystallinity be 100%), titanium source titanium tetrachloride the 4th heat treatment of progress is mixed with ethylenediamine solution, XRD crystalline phase figures show to obtain Titanium Si-Al molecular sieve (SA-H) with MFI structure, grain size are 0.3 μm.
Embodiment 17-32
Benzenediol is prepared according to the method for embodiment 1, unlike, catalyst is replaced with into TS-A, TS-B, TS- respectively C, TS-D, TS-E, TS-F, TS-G, TS-H, SA-A, SA-B, SA-C, SA-D, SA-E, SA-F, SA-G and SA-H, reaction carry out Result when to 2 hours and 100 is listed in table 4.
Embodiment 33
Benzenediol is prepared according to the method for embodiment 1, unlike, with according to the implementation of Chinese patent CN102616805A Titanium Si-Al molecular sieve obtained is catalyst in example 1, and result when reaction proceeds to 2 hours and 100 is listed in table 4.
Table 4
Embodiment 17-33's as a result, it was confirmed that the titanium Si-Al molecular sieve prepared using the preferred method of the disclosure as catalysis Agent can obtain higher phenol conversion, oxidant effective rate of utilization and benzenediol selectivity.
The preferred embodiment of the disclosure is described in detail above in association with attached drawing, still, the disclosure is not limited to above-mentioned reality The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure Monotropic type, these simple variants belong to the protection domain of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the disclosure to it is various can The combination of energy no longer separately illustrates.
In addition, arbitrary combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally Disclosed thought, it should also be regarded as the disclosure of the present invention.

Claims (14)

1. a kind of method preparing benzenediol, which is characterized in that this method includes：Under conditions of oxidation reaction, make phenol, oxygen Agent and optional solvent carry out haptoreaction in the presence of a catalyst, and the reaction mixture of gained is then carried out solid-liquid point From obtaining the liquid product containing benzenediol, the catalyst is that titanium-silicon molecular sieve catalyst and/or titanium Si-Al molecular sieve are catalyzed Agent；
The separation of solid and liquid carries out in solid-liquid separator, and the solid-liquid separator, which has, is separated by solid-liquid separation component (3), the solid-liquid The solid-liquid separator is divided into first area (1) and second area (2) by separating member (3), and the first area (1) has the One area entry and first area outlet, the second area (2) export with second area；The separation of solid and liquid component (3) So that the liquid product containing benzenediol in reaction mixture be easy by by the residue containing catalyst is difficult to pass through；Institute It states reaction mixture and solid-liquid separator is entered by the first area entrance, the liquid product containing benzenediol passes through solid-liquid Separating member (3), which enters second area (2) and collected by second area outlet, to be obtained, and the residue containing catalyst is by the One regional export obtains.
2. according to the method described in claim 1, wherein, the separation of solid and liquid component (3) has through-hole, the aperture of the through-hole Less than the grain size of the catalyst, it is preferable that the separation of solid and liquid component (3) is selected from porous tubing, porous sieve plate, porous pottery At least one of porcelain, ceramic membrane element, stainless steel membrane element and filter cloth.
3. method according to claim 1 or 2, wherein the solid-liquid separator includes shell (4), and is located at shell (4) tubulose in is separated by solid-liquid separation component (3)；The both ends for being separated by solid-liquid separation component (3) are tightly connected with the shell (4) respectively So that be formed as first area (1) inside the separation of solid and liquid component (3), the separations of solid and liquid component (3) and shell (4) it Between space be formed as second area (2)；Alternatively, be formed as second area (2) inside the separation of solid and liquid component (3), it is described The space being separated by solid-liquid separation between component (3) and shell (4) is formed as first area (1).
4. according to the method described in claim 1, wherein, the molar ratio of the oxidant and phenol is (0.1-20)：1, preferably For (0.2-10)：1, more preferably (0.5-5)：1；The condition of the oxidation reaction is：Reaction temperature is 0-200 DEG C, and pressure is 0-3MPa。
5. according to the method described in claim 1, wherein, the oxidant is selected from hydrogen peroxide, tert-butyl hydroperoxide, mistake Aoxidize at least one of isopropylbenzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid；The solvent is selected from water, C1- At least one of the nitrile of the alcohol of C6, the ketone of C3-C8 and C2-C6；Preferably, the solvent is selected from water, methanol, ethyl alcohol, just At least one of propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile；It is further preferred that the solvent is Water and/or methanol；The mass ratio of the solvent and phenol is (1-100)：1.
6. according to the method described in claim 1, wherein, the titanium-silicon molecular sieve catalyst at least partially passes through activation process Titanium-silicon molecular sieve catalyst, the activation process includes by Titanium Sieve Molecular Sieve and the water containing acid and selectable peroxide Solution contacts, wherein Titanium Sieve Molecular Sieve in terms of silica, the acid, peroxide, water and Titanium Sieve Molecular Sieve molar ratio be (0.02-15)：(0-10)：(15-100)：1, preferably (0.1-10)：(0.01-5)：(20-80)：1.
7. according to the method described in claim 6, wherein, the acid for selected from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and At least one of carboxylic acid of C1-C5；The peroxide is selected from hydrogen peroxide, tert-butyl hydroperoxide, peroxidating isopropyl At least one of benzene and cyclohexyl hydroperoxide；The condition of the activation process includes：Titanium Sieve Molecular Sieve with containing acid and can The temperature of the aqueous solution contact of the peroxide selected is 0-90 DEG C, and the time is 0.1-48 hours.
8. according to the method described in claim 6, wherein, the activation process makes, on the basis of Titanium Sieve Molecular Sieve, in purple In outside-visible spectrum, the peak area of absorption peak of the Titanium Sieve Molecular Sieve by activation process between 230-310nm reduces 2% or more, 2-30% is preferably reduced, 2.5-15% is more preferably reduced, 3-10% is further preferably reduced, still more preferably drops Low 3-6%；The hole of the Titanium Sieve Molecular Sieve by activation process, which holds, reduces 1% or more, preferably reduces 1-20%, more preferably subtracts Few 1.5-10% further preferably reduces 2-5%, and the Kong Rong is using static determination of nitrogen adsorption.
9. according to the method described in claim 6, wherein, the Titanium Sieve Molecular Sieve at least partly derives from reaction after regeneration Device draws off agent, and the agent that draws off of the reaction unit after regeneration is unloading selected from Ammoximation reaction device after regeneration Go out agent, hydroxylating device after regeneration draws off drawing off in agent extremely for agent and epoxidation reaction device after regeneration Few one kind；
Preferably, the Titanium Sieve Molecular Sieve is selected from MFI type Titanium Sieve Molecular Sieve, MEL types Titanium Sieve Molecular Sieve, BEA type titanium silicon molecules In the Titanium Sieve Molecular Sieve of sieve, MWW types Titanium Sieve Molecular Sieve, MOR types Titanium Sieve Molecular Sieve, TUN types Titanium Sieve Molecular Sieve and hexagonal structure It is at least one.
10. according to the method described in claim 1, wherein, the titanium Si-Al molecular sieve is the titanium silicoaluminophosphate molecular selected from MFI structure Sieve, the titanium Si-Al molecular sieve of MEL structures, the titanium Si-Al molecular sieve of BEA structures, the titanium Si-Al molecular sieve of MWW structures, MOR structures Titanium Si-Al molecular sieve, TUN structures titanium Si-Al molecular sieve and two-dimentional hexagonal structure at least one of titanium Si-Al molecular sieve.
11. the method according to claim 1 or 10, wherein the preparation process of the titanium Si-Al molecular sieve includes：
(1) it draws off agent by first to be mixed with beating with organic acid soln, and obtained slurries is subjected to the first heat treatment, it is isolated First solid, wherein described first draws off agent drawing off for the reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component Agent, it is described first heat treatment condition be：Temperature is 20-45 DEG C, time 1-30h；
(2) the second heat treatment is carried out after mixing first solid, silicon source, titanium source in the presence of aqueous solvent with alkali source, It is described second heat treatment condition be：Temperature is 100-200 DEG C, time 0.5-25h；
Alternatively, the preparation process of the titanium Si-Al molecular sieve includes：
A, it draws off agent by second to be mixed with beating with organic acid soln, and obtained slurries is subjected to third heat treatment, it is isolated Second solid, wherein described second draws off agent drawing off for the reaction unit using Si-Al molecular sieve as catalyst activity component Agent, the condition that the third is heat-treated are：Temperature is 50-150 DEG C, time 0.5-40h；
B, the 4th heat treatment is carried out after mixing second solid, titanium source in the presence of aqueous solvent with alkali source, described the Four heat treatment condition be：Temperature is 100-200 DEG C, time 0.5-25h.
12. according to the method for claim 11, wherein described first draws off agent, titanium source, silicon source, Organic Acid and Base source and water Weight ratio be 100：(0.1-10)：(0.1-10)：(0.005-50)：(0.5-50)：(20-1000)；
Alternatively, the described second weight ratio for drawing off agent, titanium source, Organic Acid and Base source and water is 100：(0.1-10)：(0.005- 50)：(0.5-50)：(20-1000)；
Described first and second draw off agent respectively with SiO2Meter, the organic acid is with H+Meter, with N when the alkali source contains nitrogen Meter, the alkali source not Nitrogen element when with OH-Meter；The concentration of the organic acid soln is more than 0.1mol/L；
The organic acid is selected from least one of aphthenic acids, Peracetic acid and Perpropionic Acid；The alkali source is selected from ammonia, fat At least one of fat race amine, aliphatic hydramine and quaternary ammonium base；Source of aluminium is selected from Aluminum sol, aluminium salt, aluminium hydroxide and oxygen Change at least one of aluminium；The titanium source is inorganic titanium salt and/or organic titanate.
13. according to the method for claim 11, wherein the work using Titanium Sieve Molecular Sieve as catalyst in step (1) Property component reaction unit draw off agent be selected from Ammoximation reaction device drawing off agent, hydroxylating device draw off agent and Epoxidation reaction device draws off at least one of agent；Preferably, the Titanium Sieve Molecular Sieve in step (1) is MFI structure Titanium Sieve Molecular Sieve, described first draw off agent activity be the Titanium Sieve Molecular Sieve when fresh active 50% or less；It is preferred that Source of aluminium and alkali source in step (2), are first mixed to get mixed solution by ground in the presence of aqueous solvent, then again will be described Mixed solution carries out second heat treatment after being mixed with first solid and titanium source；
Alternatively, the agent that draws off of the reaction unit using Si-Al molecular sieve as catalyst activity component in step a is vulcanization The synthetic reaction device of hydrogen and methanol draws off agent；Preferably, the Si-Al molecular sieve in step a is the sial of MFI structure Molecular sieve, the described second activity for drawing off agent is active 50% or less of Si-Al molecular sieve when fresh.
14. according to the method described in claim 1, wherein, this method further includes：Before carrying out the reaction, the pH of reaction system Value is adjusted to 0.5-5.5, is preferably adjusted to 1-5, is more preferably adjusted to 1-3.5；And
By the residue cycle containing catalyst exported by the first area in the reaction and from described The step of benzenediol is isolated in liquid product containing benzenediol；And
According to certain time interval, to be sent into the first area (1) flushing liquor with to the separation of solid and liquid component (3) into Row rinses, and the flushing liquor contains the oxidant, optional phenol and optional solvent, and the time interval of the flushing is 0.5-24 hours, the duration of the flushing was 5-300 seconds.
CN201710204169.2A 2017-03-30 2017-03-30 Process for preparing benzenediol Active CN108658732B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710204169.2A CN108658732B (en) 2017-03-30 2017-03-30 Process for preparing benzenediol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710204169.2A CN108658732B (en) 2017-03-30 2017-03-30 Process for preparing benzenediol

Publications (2)

Publication Number Publication Date
CN108658732A true CN108658732A (en) 2018-10-16
CN108658732B CN108658732B (en) 2021-11-16

Family

ID=63785683

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710204169.2A Active CN108658732B (en) 2017-03-30 2017-03-30 Process for preparing benzenediol

Country Status (1)

Country Link
CN (1) CN108658732B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112125786A (en) * 2020-09-15 2020-12-25 江西兄弟医药有限公司 Method for synthesizing hydroquinone by phenol hydroxylation

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5493061A (en) * 1994-12-09 1996-02-20 Council Of Scientific & Industrial Research Process for the conversion of phenol to hydroquinone and catechol
CN1268502A (en) * 1999-03-30 2000-10-04 中国石油化工集团公司 Method for hydroxylation of phenol
CN1410406A (en) * 2001-09-29 2003-04-16 中国石油化工股份有限公司 Preparation method of benzenediol
CN101397240A (en) * 2007-09-28 2009-04-01 中国石油化工股份有限公司 Method for preparing p-dihydroxy benzene and pyrocatechol by phenol hydroxylation
CN104003916A (en) * 2013-02-26 2014-08-27 中国石油化工股份有限公司 Dimethyl sulfoxide production method
CN104557450A (en) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 Method for oxidizing cyclohexane
CN104557468A (en) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 Method for phenol hydroxylation
CN106032277A (en) * 2015-03-10 2016-10-19 中国石油化工股份有限公司 Titanium-silicon-aluminum molecular sieve, preparation method and applications thereof, and a cyclic ketone oxidation method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5493061A (en) * 1994-12-09 1996-02-20 Council Of Scientific & Industrial Research Process for the conversion of phenol to hydroquinone and catechol
CN1268502A (en) * 1999-03-30 2000-10-04 中国石油化工集团公司 Method for hydroxylation of phenol
CN1410406A (en) * 2001-09-29 2003-04-16 中国石油化工股份有限公司 Preparation method of benzenediol
CN101397240A (en) * 2007-09-28 2009-04-01 中国石油化工股份有限公司 Method for preparing p-dihydroxy benzene and pyrocatechol by phenol hydroxylation
CN104003916A (en) * 2013-02-26 2014-08-27 中国石油化工股份有限公司 Dimethyl sulfoxide production method
CN104557450A (en) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 Method for oxidizing cyclohexane
CN104557468A (en) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 Method for phenol hydroxylation
CN106032277A (en) * 2015-03-10 2016-10-19 中国石油化工股份有限公司 Titanium-silicon-aluminum molecular sieve, preparation method and applications thereof, and a cyclic ketone oxidation method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112125786A (en) * 2020-09-15 2020-12-25 江西兄弟医药有限公司 Method for synthesizing hydroquinone by phenol hydroxylation

Also Published As

Publication number Publication date
CN108658732B (en) 2021-11-16

Similar Documents

Publication Publication Date Title
CN106032283B (en) Tin Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of cyclic ketones oxidation
CN106032277B (en) Titanium Si-Al molecular sieve and its preparation method and application and a kind of method of cyclic ketones oxidation
CN105728019B (en) A kind of preparation method and application of the ZSM-5 molecular sieve with Jie&#39;s micropore
CN106146262B (en) A method of preparing propylene glycol monomethyl ether
CN103182323B (en) Regeneration method of deactivated titanium-silicon molecular sieve catalyst
CN103182319B (en) Regeneration method of deactivated titanium-silicon molecular sieve
CN108658732A (en) The method for preparing benzenediol
CN111924852A (en) Preparation method of titanium-silicon molecular sieve
CN109110782A (en) A kind of preparation method of SSZ-13 molecular sieve
CN110156571A (en) Propylene method for oxidation
CN104512906B (en) Titanium-silicon molecular sieve and preparation method thereof
CN109593033B (en) Method for oxidizing cyclohexanone
CN110724037B (en) Process for preparing benzenediol
CN110143905A (en) The method for preparing Perpropionic Acid
CN111348984A (en) Method for preparing propylene glycol monomethyl ether and propylene glycol from propylene oxide
CN108658823A (en) The method for preparing Peracetic acid
CN105314649A (en) Tin-silicon molecular sieve, prepration method and application of same
CN110317128A (en) The method for preparing propylene glycol monomethyl ether
CN108658727A (en) Propylene method for oxidation
CN112744825B (en) Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction
CN108658728A (en) Application of the titanium Si-Al molecular sieve in preparing propylene glycol
CN105293517A (en) Titanium-silicon molecular sieve and preparation method and application thereof, and method for direct oxidation of olefin
CN110316739B (en) Vanadium-titanium-silicon molecular sieve, preparation method and application thereof, and phenol hydroxylation method
CN112744838A (en) Titanium-silicon molecular sieve, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction
CN109592694B (en) Titanium-silicon molecular sieve, preparation method and application thereof, and phenol hydroxylation method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant