CN106631932B - A kind of sulfide oxidation method - Google Patents

A kind of sulfide oxidation method Download PDF

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Publication number
CN106631932B
CN106631932B CN201510725874.8A CN201510725874A CN106631932B CN 106631932 B CN106631932 B CN 106631932B CN 201510725874 A CN201510725874 A CN 201510725874A CN 106631932 B CN106631932 B CN 106631932B
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titanium
molecular sieve
sieve
catalyst bed
modification
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CN106631932A (en
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林民
史春风
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B01J2229/126—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to reduce the pore-mouth size

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of sulfide oxidation methods, it is included under oxidation reaction condition, make containing thioether, the reaction feed of oxidant and optional solvent flows successively through the 1st catalyst bed to the n-th catalyst bed, the integer that n is 2 or more, at least one Titanium Sieve Molecular Sieve is filled in the catalyst bed, this method further includes by the 1st catalyst bed in reaction feed to during the n-th catalyst bed, to the 1st catalyst bed to introducing at least one carrying object between at least a pair of adjacent catalyst bed between the n-th catalyst bed, so that on the basis of the flow direction of reaction feed, this is in adjacent catalyst bed, it is higher than the superficial velocity of the reaction stream in the catalyst bed of upstream positioned at the superficial velocity of reaction stream in the catalyst bed in downstream.In the single trip use service life that Titanium Sieve Molecular Sieve can effectively be extended according to the method for the present invention, the effective rate of utilization and target product selectivity of oxidant are improved, such as sulfoxide selectivity.

Description

A kind of sulfide oxidation method
Technical field
The present invention relates to a kind of sulfide oxidation methods.
Background technique
Sulfoxides are important sulfur-containing compound, if dimethyl sulfoxide (DMSO) is a kind of organic compounds containing sulfur, It is colourless transparent liquid under room temperature, there are the characteristics such as highly polar, high-hygroscopicity, flammable and higher boiling be non-proton.Dimethyl sulfoxide It is dissolved in water, ethyl alcohol, acetone, ether and chloroform, is the strong atent solvent of polarity, is widely used as solvent and reaction reagent.Also, two Methyl sulfoxide has very high selective extraction method ability, can be used as the Extraction solvent that alkane is separated with aromatic hydrocarbon, such as: dimethyl Sulfoxide can be used for the extracting of aromatic hydrocarbons or butadiene, as process solvent and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as poly- The synthetic of urethane and the solvent that reels off raw silk from cocoons, the synthetic as polyamide, fluoroaluminate glasses, polyimides and polysulfones.Meanwhile In medical industry, dimethyl sulfoxide not only can be directly as the raw material and carrier of some drugs, but also can also play anti-inflammatory and stop Bitterly, it the effects of diuresis, calmness, therefore is made an addition in drug frequently as the active component of analgesic drug product.In addition, dimethyl sulfoxide It can be used as capacitor dielectric, antifreezing agent, brake fluid, rare metal extracting agent etc..
Currently, sulfoxide generally uses sulfide oxidation method to be made, according to the difference of oxidant, can be divided into: nitric acid oxidation method, Peroxide oxidation method and Ozonation.Wherein, the major defect of nitric acid oxidation method is equipment seriously corroded, and reaction condition is difficult A large amount of nitrogen oxides can be generated during control, simultaneous reactions, cause environmental pollution；Ozone oxidation rule faces thioether The not high problem of rate.The reaction condition of peroxide oxidation method is mild, environmental pollution is small, can obtain the higher sulfoxide of purity. But in peroxide oxidation method, the price of oxidant is higher, leads to the at high cost of product.
When using peroxide by sulfide oxidation, if using Titanium Sieve Molecular Sieve as catalyst, oxidation can be improved The conversion ratio of agent and the selectivity of desirable oxidation product.But with the extension in reaction time, the catalytic activity meeting of Titanium Sieve Molecular Sieve It is on a declining curve, cause desirable oxidation selectivity of product to be substantially reduced.When reaction carries out in fixed bed reactors, due to titanium Silicon molecular sieve catalytic active reduces, and needs to regenerate Titanium Sieve Molecular Sieve in reactor or outside reactor, leads to reactor It stops work, to influence production efficiency and improve the operating cost of device.
Therefore, for the sulfide oxidation reaction using Titanium Sieve Molecular Sieve as catalyst, how to extend as catalyst Titanium Sieve Molecular Sieve the single trip use service life, reducing regeneration frequency is to improve production efficiency and reduce the key link of operating cost One of.
Summary of the invention
The purpose of the present invention is to provide a kind of sulfide oxidation method, the one way that this method is able to extend Titanium Sieve Molecular Sieve makes Use the service life.
The present invention provides a kind of sulfide oxidation method, this method is included under oxidation reaction condition, makes containing at least one The reaction feed of kind thioether, at least one oxidant and optional at least one solvent flows successively through the 1st catalyst bed to n-th Catalyst bed, the integer that n is 2 or more are filled at least one Titanium Sieve Molecular Sieve in the catalyst bed, and this method is also wrapped It includes in reaction feed through the 1st catalyst bed to during the n-th catalyst bed, to the 1st catalyst bed to the n-th catalyst bed At least one carrying object is introduced between at least a pair of adjacent catalyst bed between layer, so that the flow direction with reaction feed is Benchmark, this is in adjacent catalyst bed, and the superficial velocity of reaction stream is higher than and is located in the catalyst bed in downstream The superficial velocity of reaction stream in the catalyst bed of upstream.
In the single trip use service life that Titanium Sieve Molecular Sieve can effectively be extended according to the method for the present invention, reduce Titanium Sieve Molecular Sieve Regeneration frequency extends the terminal life of Titanium Sieve Molecular Sieve.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of sulfide oxidation method, this method is included under oxidation reaction condition, makes containing at least one The reaction feed of kind thioether, at least one oxidant and optional at least one solvent flows successively through the 1st catalyst bed to n-th Catalyst bed, the integer that n is 2 or more are filled at least one Titanium Sieve Molecular Sieve in the catalyst bed.Herein, " extremely Few one kind " indicates one or more kinds of；" optional " expression " with or without ".
In the present invention, n is the integer between 2 to 50, be preferably selected from 2,3,4,5,6,7,8,9,10,11,12,13,14, 15,16,17,18,19 or 20,2,3,4,5,6,7,8,9 or 10 are more preferably selected from, further preferably selected from 2,3,4 or 5, such as 2。
In the present invention, statement " reaction feed flows successively through the 1st to the n-th catalyst bed " is referred to from the 1st catalyst bed Layer to the n-th catalyst bed successively constitutes the glide path of the reaction feed, but this does not imply that the reaction feed Do not have any alternatively to flow through the 1st to the n-th catalyst bed.In fact, start since entry into the 1st catalyst bed, react into Material (such as its composition or character) can change because sulfide oxidation reaction etc. occurs, and thus lose it as anti- Answer the initial composition or character of raw material.In consideration of it, understanding to meet those skilled in the art to the routine of reaction raw materials, at this In the context of invention, the reaction feed for flowing through each catalyst bed is generally known as reaction mass.Moreover, different flowing through When catalyst bed, which (such as because reacts or introduces new material, such as current-carrying as various factors Body) and change, cause the reaction mass (such as its composition or character) for flowing through different catalysts bed general It is different.The present invention pays close attention to superficial velocity of each reaction mass when flowing through its corresponding catalyst bed.
It according to the method for the present invention, further include passing through the 1st catalyst bed to the n-th catalyst bed phase in reaction feed Between, at least one is introduced to the 1st catalyst bed between at least a pair of adjacent catalyst bed between the n-th catalyst bed Kind carrying object, so that this is to the catalyst bed in adjacent catalyst bed, positioned at downstream on the basis of the flow direction of reaction feed The superficial velocity of reaction stream is higher than the superficial velocity of the reaction stream in the catalyst bed of upstream in layer.
In the present invention, the superficial velocity is (with kg/ (m2S) count) it refers in the unit time through a certain catalyst bed The mass flow (in terms of kg/s) and a certain cross-sectional area of the catalyst bed of the whole reaction mass of layer are (with m2Meter) ratio. For example, the superficial velocity for flowing through the reaction mass of the 1st catalyst bed is v1, refer in the unit time through the 1st catalyst The mass flow (in terms of kg/s) and a certain cross-sectional area of the catalyst bed of the reaction mass of bed whole process are (with m2Meter) ratio Value.Here, " cross-sectional area " is generally referred to as average traversal area for simplifying the angle that the present invention describes.Moreover, So-called " average traversal area " refers to the total catalyst admission space of the catalyst bed (with m3Meter) and the catalyst bed For layer along the ratio of the length (in terms of m) in reaction mass flowing direction, this is obvious to those skilled in the art.For Isometrical catalyst bed, the average traversal area is cross-sectional area.In addition, the present invention is to flowing through each catalyst bed The superficial velocity (absolute value) of reaction mass do not have particular/special requirement, can directly be applicable in it is those of conventionally known in the art, such as The superficial velocity (absolute value) for flowing through the reaction mass of the 1st catalyst bed generally can be in 0.001-200kg/ (m2S) In range, but is not limited thereto.
From making the more excellent angle of the technology of the present invention effect, to the 1st catalyst bed to the n-th catalyst bed it Between at least a pair of adjacent catalyst bed between introduce at least one carrying object so that using the flow direction of reaction feed as base Standard, the superficial velocity of reaction stream is expressed as v in the catalyst bed in downstreamm, anti-in the catalyst bed of upstream The superficial velocity of logistics is answered to be expressed as vm-1, the introduction volume of the carrying object makes vm/vm-1=1.5-15, more preferable vm/vm-1= 2-10, further preferred vm/vm-1=2-5, m are the arbitrary integer in [2, n] section, that is, select 2,3 ..., it is any one in n A integer；Also, as n=2, m=2.For example, in m=2, preferably v2/v1=1.5-15, more preferable v2/v1=2-10, into The preferred v of one step2/v1=2-5.
According to the method for the present invention, the 1st to the n-th catalyst bed can be all set in the same reactor, The differential responses region for constituting the reactor, also can be set individually in n reactor, constitute n different reactors, or Person is set in two or more (up to n-1) reactors in the way of any combination, constitutes multi-reaction-area domain and more The combination of reactor.
According to the method for the present invention, the 1st to the n-th catalyst bed can continuously be connected, and be thus integrally formed formula and urge Agent bed, can also there are separated places with any pair wherein or between multipair adjacent catalyst bed, thus constitute more Segmentation catalyst bed.The separated place can be the inner space of reactor, be can according to need at this time in the inner space The one or more non-catalytic beds (such as the bed being made of inactive filler described below) of middle setting or inner member (example Such as fluid distributor, catalyst bed supporting member, heat exchanger) etc., thus sulfide oxidation of the invention is reacted and is carried out It is more flexible to adjust.
According to the method for the present invention, the 1st to the n-th catalyst bed along the reaction feed glide path successively It is connected in series, constitutes upstream-downstream relationship, wherein the 1st catalyst bed is located at most upstream, the n-th catalyst bed is located at most downstream. Even so, a portion or whole catalyst bed can spatially be arranged side by side, as long as ensure it is described react into Material successively flowing is by wherein.
According to the method for the present invention, the 1st to the n-th catalyst bed can respectively contain one or more catalyst beds Layer.If can be series connection between the multiple catalyst bed, or parallel connection is even containing multiple catalyst beds It connects, can also be series connection and the combination being connected in parallel.For example, when the multiple catalyst bed is divided into multiple groups, every group Interior catalyst bed can be to be connected in series and/or be connected in parallel, and can connect between each group for series connection and/or parallel connection It connects.
According to the method for the present invention, the 1st to the n-th catalyst bed respectively can be fluidized bed, expanded bed, slurry bed system Or the catalyst bed form that fixed bed etc. is conventionally known in the art, but the angle implemented is reacted from convenient for sulfide oxidation of the present invention It sets out, the preferred fixed bed of the 1st to the n-th catalyst bed.
According to the method for the present invention, in the 1st to the n-th catalyst bed, respectively it is filled at least one titanium silicon point Son sieve.Titanium Sieve Molecular Sieve is the general name that titanium atom replaces a kind of zeolite of a part of silicon atom in lattice framework, can use chemistry Formula xTiO2·SiO2It indicates.The content of titanium atom in Titanium Sieve Molecular Sieve is not particularly limited in the present invention, can be this field Conventional selection.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, more preferably 0.015-0.025.
The Titanium Sieve Molecular Sieve can be the common Titanium Sieve Molecular Sieve with various topological structures, such as: the titanium silicon Molecular sieve can be selected from Titanium Sieve Molecular Sieve (such as TS-1), Titanium Sieve Molecular Sieve (such as TS-2), the BEA structure of MEL structure of MFI structure Titanium Sieve Molecular Sieve (such as Ti-Beta), the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, the Titanium Sieve Molecular Sieve of MOR structure Titanium Sieve Molecular Sieve (such as Ti-MCM- of the Titanium Sieve Molecular Sieve (such as Ti-TUN) of (such as Ti-MOR), TUN structure, two-dimentional hexagonal structure 41, Ti-SBA-15) and other structures Titanium Sieve Molecular Sieve (such as Ti-ZSM-48).The Titanium Sieve Molecular Sieve is preferably selected from MFI Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve of MEL structure, the two-dimentional Titanium Sieve Molecular Sieve of hexagonal structure and the titanium silicon of BEA structure of structure Molecular sieve, the more preferably Titanium Sieve Molecular Sieve of MFI structure, such as titanium-silicon molecular sieve TS-1 and/or hollow Titanium Sieve Molecular Sieve.The sky Heart Titanium Sieve Molecular Sieve is the Titanium Sieve Molecular Sieve of MFI structure, and the crystal grain of the Titanium Sieve Molecular Sieve is hollow structure, the sky of the hollow structure The radical length of cavity segment is 5-300 nanometers, and the Titanium Sieve Molecular Sieve is in 25 DEG C, P/P0=0.10, adsorption time is 1 hour Under the conditions of the benzene adsorbance that measures be at least 70 milligrams per grams, the adsorption isotherm of the nitrogen absorption under low temperature of the Titanium Sieve Molecular Sieve and de- There are hysteresis loops between attached thermoisopleth.The hollow Titanium Sieve Molecular Sieve, which is commercially available, (such as to be commercially available from Hunan and builds feldspathization The trade mark of limited liability company be HTS molecular sieve), can also the method according to disclosed in CN1132699C be prepared.
According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the Titanium Sieve Molecular Sieve TS- 1 urface silicon titanium is not less than body phase silicon titanium ratio, can be further improved oxidant effective rate of utilization in this way, and can further prolong The single trip use service life of long Titanium Sieve Molecular Sieve.Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio be 1.2 with On.It is highly preferred that the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5.It is further preferred that the surface Silicon titanium is than being 1.5-4.5 (such as 2.5-4.5) with the ratio of the body phase silicon titanium ratio.It is further preferred that the surface silicon titanium Than being 2-3 with the ratio of the body phase silicon titanium ratio.Molar ratio of the silicon titanium than referring to silica and titanium oxide, the surface silicon Titanium ratio is measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses x-ray fluorescence spectrometry.
According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the Titanium Sieve Molecular Sieve TS- 1 is prepared using method comprising the following steps:
(A) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and optionally supplements water, obtained Dispersion liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:(0.5-8): (5-30): (100- 2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N meter is (in the alkali When source template contains nitrogen, in terms of N；In the alkali source template not Nitrogen element, with OH-Meter)；
(B) optionally, by the dispersion liquid in 15-60 DEG C of standing 6-24h；
(C) dispersion liquid that step (A) obtains or the dispersion liquid that step (B) obtains sequentially are undergone in sealing reaction kettle Stage (1), stage (2) and stage (3) carry out crystallization, and the stage (1) is in 80-150 DEG C of crystallization 6-72 hours (h), stage (2) cooling To after not higher than 70 DEG C and residence time at least 0.5h, the stage (3) is warming up to 120-200 DEG C of crystallization 6-96h again.
In the present invention, " optionally " indicates inessential, it can be understood as " with or without ", " including or not including ".
The alkali source template can be usually used various templates during synthesis of titanium silicon molecular sieve, such as: The alkali source template can be one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine.The quaternary ammonium base It can be various organic level Four ammonium alkali, the aliphatic amine can be various NH3In at least one hydrogen by aliphatic alkyl (such as Alkyl) replace after the compound that is formed, the aliphatic hydramine can be various NH3In at least one hydrogen by the rouge of hydroxyl The compound that fat race group (such as alkyl) is formed after replacing.
Specifically, the alkali source template can be the aliphatic amine and formula of the quaternary ammonium base, Formula II expression that indicate selected from Formulas I One or more of the aliphatic hydramine that III is indicated.
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane Base, R1、R2、R3And R4Specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group or tert-butyl.
R5(NH2)n(Formula II)
In Formula II, n is an integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6 Branched alkyl, specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different Butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6Branched alkylidene, specific example can include but is not limited to methylene, ethylidene, Sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3- C4Branched alkylidene, specific example can include but is not limited to methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.
The specific example of the alkali source template can include but is not limited to: tetramethylammonium hydroxide, tetraethyl hydroxide Ammonium, tetrapropylammonium hydroxide (the various isomers including tetrapropylammonium hydroxide, such as four n-propyl ammonium hydroxide and tetra isopropyl Ammonium hydroxide), tetrabutylammonium hydroxide (the various isomers including tetrabutylammonium hydroxide, such as 4-n-butyl ammonium hydroxide and Four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine One or more of with triethanolamine.Preferably, the alkali source template is tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen Change one or more of ammonium and tetrabutylammonium hydroxide.It is highly preferred that the alkali source template is tetrapropyl hydroxide Ammonium.
The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can Think TiCl4、Ti(SO4)2Or TiOCl2One or more of；The organic titanate can be general formula R7 4TiO4 The compound of expression, wherein R7For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom.
The inorganic silicon source can be silica gel and/or silica solution, preferably silica gel.SiO in the silica solution2Quality hundred Dividing content can be 10% or more, preferably 15% or more, more preferably 20% or more.In preparation according to the preferred embodiment Titanium Sieve Molecular Sieve when, do not use organic silicon source, such as organosilan and organosiloxane.
In the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is preferably 100:(1-6): (8-25): (200-1500), more preferably 100:(2-5): (10-20): (400-1000).
The dispersion liquid that step (A) obtains, which can be sent directly into step (C), carries out crystallization.Preferably, step (A) is obtained Dispersion liquid be sent into step (B) in 15-60 DEG C at a temperature of stand 6-24h.It is walked between step (A) and step (C) Suddenly (B) can significantly improve the urface silicon titanium of the titanium-silicon molecular sieve TS-1 finally prepared, so that the Titanium Sieve Molecular Sieve finally prepared Urface silicon titanium be not less than body phase silicon titanium ratio, the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared can be significantly improved in this way, prolonged Its long single trip use service life, and improve oxidant effective rate of utilization.Generally, by being arranged between step (A) and step (C) Step (B), the urface silicon titanium of the Titanium Sieve Molecular Sieve finally prepared and the ratio of body phase silicon titanium ratio can be in the ranges of 1.2-5 It is interior, preferably in the range of 1.5-4.5 (such as in the range of 2.5-4.5), more preferably in the range of 2-3.The standing is more It is preferred that 20-50 DEG C at a temperature of carry out, as carried out at a temperature of 25-45 DEG C.
In step (B), when being stood, dispersion liquid can be placed in sealing container, open container can also be placed in In stood.Preferably, step (B) carries out in a sealed container, in this way can to avoid during standing into dispersion liquid It is introduced into foreign matter or moieties volatilization in dispersion liquid is caused to be lost.
After the completion of step (B) described standing, directly the dispersion liquid through standing can be sent into reaction kettle and carry out crystallization, It is sent into reaction kettle after dispersion liquid through standing being carried out redisperse and carries out crystallization, be preferably sent into reaction after progress redisperse In kettle, the dispersing uniformity for carrying out the dispersion liquid of crystallization can be further improved in this way.The method of the redisperse can be conventional The combination of one or more of method, such as stirring, ultrasonic treatment and oscillation.The duration of the redisperse is with energy It forms the dispersion liquid through standing subject to uniform dispersion liquid, generally can be 0.1-12h, such as 0.5-2h.The redisperse can To carry out at ambient temperature, as carried out at a temperature of 15-40 DEG C.
In step (C), temperature is adjusted to the heating rate of each phase temperature and rate of temperature fall can use according to specific The type of crystallization device selected, be not particularly limited.In general, raising the temperature to stage (1) crystallization temperature Heating rate can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By stage (1) temperature The rate of temperature fall spent to stage (2) temperature can be for 1-50 DEG C/min, and preferably 2-20 DEG C/min, more preferably 5-10 DEG C/ min.By stage (2) temperature to stage (3) crystallization temperature heating rate can be 1-50 DEG C/min, preferably 2-40 DEG C/ Min, more preferably 5-20 DEG C/min.
In step (C), the crystallization temperature in stage (1) is preferably 110-140 DEG C, more preferably 120-140 DEG C, further excellent It is selected as 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.The temperature in stage (2) is preferably not Higher than 50 DEG C.The residence time in stage (2) is preferably at least 1h, more preferably 1-5h.The stage crystallization temperature of (3) is preferably 140-180 DEG C, more preferably 160-170 DEG C.The crystallization time in stage (3) is preferably 12-20h.
In step (C), in a preferred embodiment, the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3) Degree, can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve of preparation in this way.Preferably, the crystallization temperature in stage (1) compares the stage (3) crystallization temperature is 10-50 DEG C low.It is highly preferred that the crystallization temperature in stage (1) is 20-40 lower than the crystallization temperature in stage (3) ℃.In step (C), in another preferred embodiment, the crystallization time in stage (1) is less than the crystallization time of stage (3), It can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.Preferably, the crystallization time in stage (1) compares the stage (3) the short 5-24h of crystallization time.It is highly preferred that the crystallization time in stage (1) is 6-12h shorter than the crystallization time in stage (3), such as Short 6-8h.In step (C), both preferred embodiments be may be used alone, can also be used in combination, and preferably combination makes With that is, the crystallization temperature and crystallization time in stage (1) and stage (3) meet the requirements of both preferred embodiments simultaneously.
In step (C), in another preferred embodiment, the temperature in stage (2) is not higher than 50 DEG C, and when stopping Between be at least 0.5h, such as 0.5-6h, can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.Preferably, The residence time in stage (2) is at least 1h, such as 1-5h.The preferred embodiment can be with aforementioned two kinds of preferred embodiments Be used separately, can also be applied in combination, preferably be applied in combination, i.e., the crystallization temperature and crystallization time in stage (1) and stage (3) with And the stage (2) temperature and the residence time meet the requirements of above-mentioned three kinds of preferred embodiments simultaneously.
Titanium Sieve Molecular Sieve can be recycled from the mixture that step (C) crystallization obtains using conventional method.It specifically, can be with After the mixture that step (C) crystallization obtains optionally is filtered and washed, solid matter is dried and is roasted, thus Obtain Titanium Sieve Molecular Sieve.The drying and the roasting can carry out under normal conditions.Generally, the drying can be in ring Border temperature (such as 15 DEG C) is to carrying out at a temperature of 200 DEG C.The drying can be under environmental pressure (generally 1 standard atmospheric pressure) It carries out, can also carry out at reduced pressure.The duration of the drying can according to dry temperature and pressure and Dry mode is selected, and is not particularly limited.For example, temperature is preferably 80- when the drying carries out under ambient pressure 150 DEG C, more preferably 100-120 DEG C, dry duration are preferably 0.5-5h, more preferably 1-3h.The roasting can be with 300-800 DEG C at a temperature of carry out, preferably carry out at a temperature of 500-700 DEG C, more preferably 550-650 DEG C at a temperature of Carry out, further preferably 550-600 DEG C at a temperature of carry out.The duration of the roasting can be according to the temperature roasted Degree selection, generally can be 2-12h, preferably 2-5h.The roasting carries out preferably in air atmosphere.
According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is preferably modified Titanium Sieve Molecular Sieve, in this way can be into one Step promotes the catalytic performance of Titanium Sieve Molecular Sieve.The Titanium Sieve Molecular Sieve of the modification refers to the Titanium Sieve Molecular Sieve of experience modification, In contrast, the Titanium Sieve Molecular Sieve for not undergoing modification is unmodified Titanium Sieve Molecular Sieve.The modification includes following Step: by as the Titanium Sieve Molecular Sieve of raw material with containing nitric acid (that is, HNO3) and at least one peroxide modification liquid contact. Titanium Sieve Molecular Sieve as raw material refers to the Titanium Sieve Molecular Sieve of the raw material as modification, can be for without going through the modification The Titanium Sieve Molecular Sieve of processing, or live through the modification but need to carry out the titanium silicon of the modification again Molecular sieve.
Method according to the invention it is possible to which whole Titanium Sieve Molecular Sieve live through above-mentioned modification (that is, Titanium Sieve Molecular Sieve For modified Titanium Sieve Molecular Sieve), or part Titanium Sieve Molecular Sieve lives through above-mentioned modification (that is, Titanium Sieve Molecular Sieve is Modified Titanium Sieve Molecular Sieve and unmodified Titanium Sieve Molecular Sieve).Preferably, on the basis of the total amount of Titanium Sieve Molecular Sieve, at least 50 The Titanium Sieve Molecular Sieve of weight % or more is modified Titanium Sieve Molecular Sieve, and the Titanium Sieve Molecular Sieve of more preferably at least 60 weight % or more is Modified Titanium Sieve Molecular Sieve, such as on the basis of the total amount of the Titanium Sieve Molecular Sieve, the content of the Titanium Sieve Molecular Sieve of the modification It can be 5-95 weight %, preferably 20-90 weight %, more preferably 40-80 weight %.
In the modification, peroxide can be selected from hydrogen peroxide, hydroperoxides and peracid.In the present invention, hydrogen Peroxide refers to that substance obtained from a hydrogen atom in hydrogen peroxide molecule is replaced by organic group, peracid refer to molecule Contain the organic oxacid of-O-O- key in structure.
In the modification, the specific example of the peroxide be can include but is not limited to: hydrogen peroxide, ethylbenzene Hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.It is preferred that Ground, the oxidant are hydrogen peroxide.The hydrogen peroxide can be peroxidating existing in a variety of manners commonly used in the art Hydrogen.
Can be 1 as the Titanium Sieve Molecular Sieve of raw material and the molar ratio of the peroxide in the modification: 0.01-5, preferably 1:0.05-3, more preferably 1:0.1-2.The dosage of the nitric acid can be according to the use of the peroxide Amount is selected.Generally, the molar ratio of the peroxide and the nitric acid can be 1:0.01-50, preferably 1:0.1- 20, more preferably 1:0.2-10, further preferably 1:0.5-5, particularly preferably 1:0.6-3.5, such as 1:0.7-1.2, it is described Titanium Sieve Molecular Sieve is in terms of silica.
In the modification liquid, the concentration of the peroxide and nitric acid respectively can be 0.1-50 weight %.From further The angle for improving the catalytic performance of the Titanium Sieve Molecular Sieve of the modification finally prepared is set out, preferably 0.5-25 weight %.More preferably Ground, in the modification liquid, the concentration of the peroxide and nitric acid is respectively 5-15 weight %.
The solvent of the modification liquid can be the common various solvents that can dissolve nitric acid and the peroxide simultaneously.It is excellent Selection of land, the solvent of the modification liquid are water.
In the modification, as raw material Titanium Sieve Molecular Sieve and modification liquid can 10-350 DEG C at a temperature of into Row contact.From the angle of the catalytic performance for the Titanium Sieve Molecular Sieve for further increasing the modification finally prepared, the contact is excellent It is contacted at a temperature of being selected in 20-300 DEG C.It is highly preferred that it is described contact 50-250 DEG C at a temperature of carry out.It is further excellent Selection of land, it is described contact 60-200 DEG C at a temperature of carry out.It is further preferred that it is described contact 70-150 DEG C at a temperature of It carries out.The duration of the contact can be 1-10h, preferably 3-5h.In the modification, by the titanium as raw material The pressure in container that si molecular sieves are contacted with the modification liquid can be selected according to Contact Temperature, can be environment Pressure, or pressurization.It generally, will be in the container that contacted as the Titanium Sieve Molecular Sieve of raw material with the modification liquid Pressure can be 0-5MPa, and the pressure is gauge pressure.Preferably, under pressure by as the Titanium Sieve Molecular Sieve of raw material with The modification liquid contact.It is highly preferred that in closed container under self-generated pressure by as the Titanium Sieve Molecular Sieve of raw material with it is described Modification liquid contact.
In the modification, as the Titanium Sieve Molecular Sieve of raw material and the exposure level of the modification liquid preferably so that, Using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, modified Titanium Sieve Molecular Sieve 230-310nm it Between the peak area of absorption peak reduce by 2% or more, the hole of modified Titanium Sieve Molecular Sieve, which holds, reduces 1% or more.Modified titanium silicon point The peak area of absorption peak of the son sieve between 230-310nm preferably reduces 2-30%, more preferably reduction 2.5-15%, further excellent Choosing reduces 3-10%, still more preferably reduction 3-6%.The hole of modified Titanium Sieve Molecular Sieve holds preferred reduction 1-20%, more excellent Choosing reduces 1.5-10%, further preferably reduction 2-5%.The Kong Rong is using static determination of nitrogen adsorption.
In using various commercial plants of the Titanium Sieve Molecular Sieve as 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, when being difficult to obtain satisfied activity being regenerated, 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 usually 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.By these draw off after agent (that is, the Titanium Sieve Molecular Sieve drawn off) is regenerated with thioether and oxygen Agent contacts under oxidation reaction condition, still is able to obtain preferable catalytic performance, can especially obtain higher oxidant Effective rate of utilization.Therefore, according to the method for the present invention, at least partly described Titanium Sieve Molecular Sieve is preferably through regenerated with titanium silicon point Son sieve draws off agent as the reaction unit (in addition to sulfide oxidation reaction unit) of catalyst.It is described draw off agent can be for from various Use Titanium Sieve Molecular Sieve as the agent that draws off drawn off in the reaction unit of catalyst, such as can be to unload from oxidation reaction apparatus Out draw off agent.Specifically, it is described draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and Epoxidation reaction device draws off one or more of agent.More specifically, described, to draw off agent can be cyclohexanone amidoxime Change reaction unit draw off agent, phenol hydroxylation reaction unit draws off the drawing off in agent of agent and propylene ring oxidation reaction device It is one or more kinds of.
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.
It is different according to its source through the regenerated activity for drawing off agent.Generally, through the regenerated activity for drawing off agent It can be the 5-95% of activity (that is, activity of fresh Titanium Sieve Molecular Sieve) of Titanium Sieve Molecular Sieve when fresh.Preferably, through again The raw activity for drawing off agent can be active 10-90% of Titanium Sieve Molecular Sieve when fresh, further preferably fresh When active 30-50%, be still more preferably active 35-45% when fresh.The fresh Titanium Sieve Molecular Sieve Activity generally 90% or more, usually 95% or more.
The activity measures by the following method: respectively will be through regenerated agent and the fresh Titanium Sieve Molecular Sieve of drawing off as hexamethylene Ketone oxamidinating reaction catalyst, the condition of the Ammoximation reaction are as follows: 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 by weight 1:7.5:10:7.5:10, at atmosheric pressure In 80 DEG C of reaction 2h.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 the mole-of the cyclohexanone of addition)/addition] × 100%.
According to the method for the present invention, described to draw off the raw material that agent be modified Titanium Sieve Molecular Sieve, it can also be used as not Modified Titanium Sieve Molecular Sieve uses.Preferably, in the modification, the Titanium Sieve Molecular Sieve as raw material draws off agent to be described, The single trip use service life can further be extended in this way, and with it is non-modified draw off agent compared with, the selection of sulfoxide can be significantly improved Property and thioether rate.
According to the method for the present invention, the 1st to the n-th catalyst bed is respectively filled at least one titanium silicon point above-mentioned Son sieve.The type for the Titanium Sieve Molecular Sieve loaded in different catalysts bed can be identical, or different.Also, it is each A kind of Titanium Sieve Molecular Sieve above-mentioned can also be only loaded in a catalyst bed, can also be filled according to the relative scale arbitrarily needed Fill out one or more kinds of Titanium Sieve Molecular Sieve above-mentioned.
According to the method for the present invention, the 1st to the n-th catalyst bed is respectively filled at least one titanium silicon point above-mentioned Son sieve.The type for the Titanium Sieve Molecular Sieve loaded in different catalysts bed can be identical, or different.Also, it is each A kind of Titanium Sieve Molecular Sieve above-mentioned can also be only loaded in a catalyst bed, can also be filled according to the relative scale arbitrarily needed Fill out one or more kinds of Titanium Sieve Molecular Sieve above-mentioned.
Preferably, the Titanium Sieve Molecular Sieve of the 1st catalyst bed filling is hollow Titanium Sieve Molecular Sieve, n-th catalysis The Titanium Sieve Molecular Sieve of agent bed (that is, residual catalyst bed) filling is the Titanium Sieve Molecular Sieve in addition to hollow Titanium Sieve Molecular Sieve, such as Titanium Sieve Molecular Sieve selected from other MFI structures can further delay the deactivation rate of Titanium Sieve Molecular Sieve in this way.It is highly preferred that The Titanium Sieve Molecular Sieve of the 1st catalyst bed filling is hollow Titanium Sieve Molecular Sieve, the titanium silicon of the n-th catalyst bed filling Molecular sieve is titanium-silicon molecular sieve TS-1.The deactivation rate of Titanium Sieve Molecular Sieve can not only further be delayed in this way, extend titanium silicon point The single trip use service life of son sieve, but also can be further improved desirable oxidation selectivity of product.
According to the method for the present invention, Titanium Sieve Molecular Sieve above-mentioned can be Titanium Sieve Molecular Sieve original powder, or molding titanium Si molecular sieves, preferably molding Titanium Sieve Molecular Sieve.Molding Titanium Sieve Molecular Sieve typically contains the Titanium Sieve Molecular Sieve as active constituent With the carrier as binder, wherein the content of Titanium Sieve Molecular Sieve can be conventional selection.Generally, with the molding titanium silicon On the basis of the total amount of molecular sieve, the content of Titanium Sieve Molecular Sieve can be 5-95 weight %, preferably 10-95 weight %, more preferably For 70-90 weight %；The content of the carrier can be 5-95 weight %, preferably 5-90 weight %, more preferably 10-30 weight Measure %.The carrier of the molding Titanium Sieve Molecular Sieve can be conventional selection, such as aluminium oxide and/or silica.Prepare the molding The method of Titanium Sieve Molecular Sieve is it is known in the art, being no longer described in detail herein.The granular size of the molding Titanium Sieve Molecular Sieve It is not particularly limited, can be made appropriate choice according to concrete shape.Generally, the average grain of the molding Titanium Sieve Molecular Sieve Diameter can be 4-10000 microns, preferably 5-5000 microns, more preferably 40-4000 microns, such as 100-2000 microns.It is described Average grain diameter is volume average particle size, can be measured using laser particle analyzer.
According to the method for the present invention, the amount (matter for the Titanium Sieve Molecular Sieve respectively loaded in the 1st to the n-th catalyst bed Amount) it can be identical, or it is different.According to a kind of embodiment, when m takes the arbitrary integer in section [2, n], Wm-1/Wm For 0.1-20, Wm-1/WmPreferably 0.5 or more, more preferably 1 or more, further preferably 2 or more.Here, Wm-1For m-1 The quality of the catalyst loaded in catalyst bed, WmQuality for the catalyst loaded in m catalyst bed.Wm-1/WmIt is excellent 15 are selected as hereinafter, more preferably 10 or less.It is further preferred that Wm-1/WmFor 2-8:1.It is molding titanium silicon in the catalyst When molecular sieve, Wm-1And WmIt is determined by the content of Titanium Sieve Molecular Sieve in the molding Titanium Sieve Molecular Sieve.In addition, each catalyst bed The amount of the catalyst loaded in layer can according to need (such as production capacity) and rationally determine that there is no particular limitation herein.
According to the method for the present invention, the total amount of Titanium Sieve Molecular Sieve is (that is, the titanium loaded in the 1st to the n-th catalyst bed The total amount of si molecular sieves) it can be selected according to the specific treating capacity of system.Generally, the total amount of the catalyst makes sulphur The weight (hourly) space velocity (WHSV) of ether (component as the reaction feed) can be 0.1-100h-1, preferably 2-80h-1, more preferably 10- 50h-1。
According to the method for the present invention, in the 1st to the n-th catalyst bed other than loading the Titanium Sieve Molecular Sieve, Inactive filler can also be further loaded as needed.It can be loaded in whole the 1st to the n-th catalyst beds The inactive filler can also load described nonactive fill out in one or more of described 1st to the n-th catalyst bed Material.Inactive filler is loaded in catalyst bed to be adjusted the amount of catalyst in catalyst bed, thus to anti- The speed answered is adjusted.For some catalyst bed, when loading inactive filler, the inactive filler Content can be 5-95 weight %, for the total amount of the catalyst and inactive filler that load in the catalyst bed. Here, the inactive filler refer to sulfide oxidation reaction without or the not no filler of catalytic activity substantially, this field Through routine it is known that its specific example can include but is not limited to: one or both of quartz sand, ceramic ring and potsherd with On.
According to the present invention, the reaction feed (refers in particular to that the reaction before the 1st catalyst bed will be entered in the present invention Material) contain thioether, oxidant and optional solvent.
The oxidant can for it is common it is various can be by the substance of sulfide oxidation.Preferably, the oxidant was Oxide can be selected from hydrogen peroxide, hydroperoxides and peracid.The specific example of the peroxide may include but unlimited In: hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid And Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide, can further decrease separation costs in this way.The peroxidating Hydrogen can be hydrogen peroxide existing in a variety of manners commonly used in the art.The oxidant can individually a kind of use, can also It is applied in combination with two or more.
The amount for the thioether that the dosage of the oxidant can include according to the reaction feed is selected.Generally, exist In the reaction feed, the molar ratio of the oxidant and the thioether can be 0.1-10:1.In target sulfide oxidation product When for sulfoxide, from the angle for the selectivity for further increasing sulfoxide, the molar ratio of the oxidant and the thioether is preferred For 0.1-2:1, more preferably 0.2-1.5:1, such as 0.5-1.2:1.
According to the method for the present invention, the reaction feed can also further contain solvent, preferably to control reaction Speed.The type of the solvent is not particularly limited in the present invention, and the solvent can be common in sulfide oxidation reaction Various solvents.Preferably, the solvent is water, C1-C10Alcohol, C3-C10Ketone, C2-C10Nitrile and C1-C6Carboxylic acid in extremely Few one kind.Preferably, the solvent is C1-C6Alcohol, C3-C8Ketone and C2-C5One or more of nitrile.More preferably Ground, the solvent be one or both of methanol, ethyl alcohol, acetonitrile, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol and acetone with On.It is further preferred that the solvent is one or more of methanol, acetonitrile, acetone and tert-butyl alcohol.These solvents can With a kind of independent use, can also be used with combination of two or more.
The dosage of the solvent is not particularly limited in the present invention, can be selected according to the amount of thioether and oxidant It selects.Generally, in the reaction feed, the molar ratio of the solvent and the thioether can be 1-100:1, preferably 2- 80:1.
According to the method for the present invention, the thioether can be C2-C16At least one of α-thioether, preferably C3-6α-thioether At least one of.The thioether can be single thioether, or polythiaether, preferably single thioether.These thioethers can be single A kind of only use, can also be used with combination of two or more.Specifically, the thioether can be dimethyl sulfide and/or benzene first Thioether, such as dimethyl sulfide.
According to the method for the present invention, the oxidation reaction condition can be selected according to the set goal oxidation product. Specifically, the oxidation reaction condition in each catalyst bed may be the same or different (preferably identical), respectively can wrap Include: reaction pressure (in terms of gauge pressure) is 0-3MPa, and preferably 0.1-2.5MPa, reaction temperature is 0-120 DEG C, preferably 20-80 DEG C of (example Such as 30-60 DEG C).
According to the method for the present invention, it is reacted, is obtained by the sulfide oxidation carried out in the 1st to the n-th catalyst bed The reaction containing target sulfide oxide (such as sulfoxide) is obtained to discharge.Here, the reaction discharging refers in particular to just leave n-th catalysis Reaction mass after agent bed.
According to the method for the present invention, it optionally includes as needed and isolates the sulfide oxidation from reaction discharging The step of object, acquisition off-gas stream.Here, the off-gas stream can be rendered as without further separation containing not anti- The mixture of reactant, byproduct of reaction and the solvent answered can also become individual unreacted by further separation Reactant, byproduct of reaction and solvent, these can directly as off-gas stream use without any purification at Reason.As separation method, can directly be applicable in this field for this purpose and it is conventional use of those, there is no particular limitation. Moreover, a part that the unreacted reactant and solvent isolated can be used as reaction feed is recycled.
According to the method for the present invention, it by any pair into the 1st to the n-th catalyst bed or multipair adjacent urges Separated place introducing carrying object (as previously described) between agent bed flows through whole catalysis in the separated place downstream to increase Thus the overall circulation of the reaction mass of agent bed can increase accordingly the superficial velocity of each reaction mass, to meet this hair Bright aforementioned regulation.For example, when n is 2, by being introduced to the separated place between the 1st catalyst bed and the 2nd catalyst bed Carrying object, can increase the overall circulation for flowing through the reaction mass of the 2nd catalyst bed, thus increase accordingly the 2nd catalysis The superficial velocity of reaction mass in agent bed, to meet aforementioned regulation of the invention.
There is no particular limitation for introduction volume and incorporation way of the present invention to the carrying object, if its can (1) with from The reaction mass that catalyst bed in the separated place immediately upstream comes out is in the direct downstream in the separated place entering Catalyst bed before, in or after the process, be uniformly mixed, and (2) make each reaction mass superficial velocity meet this The aforementioned regulation of invention.
According to the method for the present invention, the carrying object can be the outflow of solvent, non-active gas and catalyst bed The combination of one or more of object.The effluent of the bed of the catalyst refers to from the 1st catalyst to the n-th catalyst A catalyst bed in bed or the effluent of multiple catalyst beds outflow, the preferably catalyst bed of most downstream Effluent.The effluent of catalyst bed can be used directly as carrying object without isolation, can also isolate target thioether Oxidation product (such as sulfoxide) is used as carrying object afterwards.According to the method for the present invention, the carrying object is more preferably from most downstream Catalyst bed effluent in isolate remaining logistics after target sulfide oxide (such as sulfoxide), such as it is previously described Off-gas stream.
Fluid distributor etc. can be set in the separated place, thus favorably by any mode known in the art In the uniform introducing of carrying object.As needed, before introducing the separated place, the carrying object can by heat exchange (such as Cooling) or pressurization etc. pretreatment.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, used reagent is commercially available reagent, and pressure is gauge pressure.
In following embodiment and comparative example, the content of each ingredient in the reaction solution that is obtained using gas chromatography analysis, Following formula is respectively adopted on the basis of this and calculates thioether rate, oxidant effective rate of utilization and sulfoxide selectivity:
Thioether rate (%)=[(mole of the unreacted thioether of the mole-of the thioether of addition)/sulphur being added The mole of ether] × 100%；
Oxidant effective rate of utilization=[mole for the sulfoxide that reaction generates/(mole-of the oxidant of addition is not anti- The mole for the oxidant answered)] × 100%；
Sulfoxide selectivity=[mole/(the unreacted thioether of the mole-of the thioether of addition for the sulfoxide that reaction generates Mole)] × 100%.
In following embodiment and comparative example, static nitrogen adsorption method and solid ultraviolet-visible diffuse reflectance spectrum method is respectively adopted The Kong Rong and ultraviolet absorption peak of Titanium Sieve Molecular Sieve after before modified are characterized.Wherein, solid ultraviolet-visible diffuse reflectance spectrum (UV-Vis) analysis carries out on SHIMADZU UV-3100 type ultraviolet-visible spectrometer；Static nitrogen is adsorbed on It is carried out on the 2405 type static state n2 absorption apparatus of ASAP of Micromeritics company.
It is related to below through determining Titanium Sieve Molecular Sieve using following methods in the regenerated embodiment and comparative example for drawing off agent The activity of (including regenerative agent and fresh dose):
By Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH3Meter), the hydrogen peroxide of 30 weight % is (with H2O2Meter), the tert-butyl alcohol With cyclohexanone by weight after=1:7.5:10:7.5:10 mixing at atmosheric pressure after 80 DEG C are stirred to react 2 hours, will be anti- It answers object to filter, liquid phase is analyzed with gas-chromatography, be calculated using the following equation the conversion ratio of cyclohexanone and as titanium The activity of si molecular sieves,
The conversion ratio of cyclohexanone=[(the unreacted cyclohexanone mole of the mole-of the cyclohexanone of addition)/it is added The mole of cyclohexanone] × 100%.
In the embodiment and comparative example of the step of preparation Titanium Sieve Molecular Sieve included below, X-ray diffraction analysis exists It is carried out on Siemens D5005 type X-ray diffractometer, with sample and authentic specimen, the five fingers spread out between 2 θ is 22.5 ° -25.0 ° The crystallinity for penetrating the ratio of the sum of diffracted intensity (peak height) of characteristic peak to indicate sample relative to authentic specimen；Fourier transform Infrared spectrum analysis carries out on 8210 type Fourier infrared spectrograph of Nicolet；Silicon titanium is than referring to silica and titanium oxide Molar ratio, urface silicon titanium are surveyed using the ESCALab250 type x-ray photoelectron spectroscopy of Thermo Scientific company Fixed, body phase silicon titanium ratio is measured using Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer.
Embodiment 1-22 is for illustrating method of the invention.
Embodiment 1
Catalyst used in the present embodiment is titanium-silicon molecular sieve TS-1, referring to Zeolites, 1992, Vol.12 943- The preparation of method described in page 950, the specific method is as follows.
(20 DEG C) at room temperature mix 22.5g tetraethyl orthosilicate with 7.0g as the tetrapropylammonium hydroxide of template It closes, and 59.8g distilled water is added, it is molten in normal pressure and 60 DEG C of hydrolysis 1.0h, the hydrolysis for obtaining tetraethyl orthosilicate after being stirred Liquid.With vigorous stirring, it is slowly added into Xiang Suoshu hydrating solution by 1.1g butyl titanate and 5.0g anhydrous isopropyl alcohol institute The solution of composition obtains clear colloid by gained mixture in 75 DEG C of stirring 3h.It is anti-that this colloid is placed in stainless steel sealing It answers in kettle, places 36h in 170 DEG C of at a temperature of constant temperature, obtain the mixture of crystallization product.Obtained mixture is filtered, is received After collecting obtained solid matter water used wash, in 110 DEG C of dry 60min, then in 500 DEG C of roasting 6h, Titanium Sieve Molecular Sieve is obtained TS-1, titanium oxide content are 2.8 weight %.
By Catalyst packing in isometrical fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed Be 2 layers, the catalyst loaded in two catalyst beds it is identical in quality, between two layers of catalyst bed be arranged carrying object enter Mouthful and liquid distributor, liquid distributor be used for the carrying object being sent by carrying object entrance and first catalyst bed Effluent after mixing, is sent into second catalyst bed.
By dimethyl sulfide, as oxidant hydrogen peroxide (in the form of the hydrogen peroxide of 30 weight % provide) and as The methanol of solvent is mixed to form reaction raw materials, and reaction raw materials are sent into fixed bed reactors from bottom and flow through catalyst bed Layer, with Titanium Sieve Molecular Sieve haptoreaction.Wherein, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1:1.1, dimethyl sulfide Molar ratio with methanol is 1:4.Temperature in reactor is 30 DEG C, controls the pressure in fixed bed reactors in reaction process For 0.5MPa, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 20h-1。
The reaction mixture exported from reactor is flashed, gas stream and liquid stream are separated into.Wherein, gas Body logistics condenses dimethyl sulfide by cooling, to recycle dimethyl sulfide；Liquid stream is distilled, and collects first respectively Alcohol, water and dimethyl sulfoxide, dimethyl sulfoxide is exported.The dimethyl sulfide of recycling and methanol are heated to 30 after mixing It DEG C is sent between first catalyst bed and the second catalyst bed as carrying object, the feeding amount of carrying object is so that v2/v1= 2, v1For the superficial velocity of reaction stream in first catalyst bed, v2For the table of reaction stream in second catalyst bed See speed.
The group of the reaction mixture exported from second fixed bed reactors in reaction process using gas-chromatography monitoring At, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity, the reaction listed by table 1 The result that the reaction mixture that reactor exports under time determines is listed in table 1.
Embodiment 2
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, the titanium-silicon molecular sieve TS-1 used It is prepared using following methods.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:4:12: 400, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is sealed in beaker using sealed membrane It is stood for 24 hours after mouthful room temperature (being 25 DEG C, similarly hereinafter), followed by magnetic agitation in 35 DEG C of stirring 2h, is allowed to disperse again.It will weigh Dispersion liquid after new dispersion is transferred in sealing reaction kettle, and in 140 DEG C of experience first stage crystallization 6h, then mixture cools down After stopping 2h to 30 DEG C of experience second stage, continue in sealing reaction kettle in 170 DEG C of at a temperature of experience phase III crystallization 12h (wherein, by the heating rate of room temperature to first stage crystallization temperature be 2 DEG C/min, by first stage crystallization temperature to The rate of temperature fall of second stage treatment temperature is 5 DEG C/min, by second stage treatment temperature to the liter of phase III crystallization temperature Warm rate is 10 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly in 110 DEG C of drying 2h, so Afterwards in 550 DEG C of roasting 3h, molecular sieve is obtained.Titanium-silicon molecular sieve TS-1 one prepared by the XRD crystalline phase figure and embodiment 1 of gained sample It causes, what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；In Fourier Transform Infrared Spectroscopy figure, in 960cm-1It is attached Closely there is absorption peak, show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, titanium oxide content is 3.5 weight %, surface Silicon titanium ratio/body phase silicon titanium ratio be 2.58 (embodiment 1 prepare Titanium Sieve Molecular Sieve in, urface silicon titanium/body phase silicon titanium ratio is 1.05)。
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Embodiment 3
Dimethyl sulfide is aoxidized using method same as Example 2, unlike, preparing titanium-silicon molecular sieve TS-1 When, the crystallization temperature of phase III is also 140 DEG C.Titanium Sieve Molecular Sieve prepared by the XRD crystalline phase figure and embodiment 1 of gained sample TS-1 is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Near There is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 4.21, Titanium oxide content is 3.1 weight %.
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Embodiment 4
Dimethyl sulfide is aoxidized using method same as Example 2, unlike, preparing titanium-silicon molecular sieve TS-1 When, the crystallization temperature of first stage is 110 DEG C.Titanium-silicon molecular sieve TS-1 prepared by the XRD crystalline phase figure and embodiment 1 of gained sample Unanimously, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby occur Absorption peak shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.37, oxidation Ti content is 3.2 weight %.
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Embodiment 5
Dimethyl sulfide is aoxidized using method same as Example 2, unlike, prepare titanium-silicon molecular sieve TS-1 When, the crystallization time of first stage is 12h.Titanium-silicon molecular sieve TS-1 one prepared by the XRD crystalline phase figure and embodiment 1 of gained sample It causes, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby inhale Peak is received, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 3.78, titanium oxide Content is 3.4 weight %.
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Embodiment 6
Dimethyl sulfide is aoxidized using method same as Example 2, unlike, prepare titanium-silicon molecular sieve TS-1 When, second stage is to be cooled to 70 DEG C of stop 2h.Titanium Sieve Molecular Sieve TS- prepared by the XRD crystalline phase figure and embodiment 1 of gained sample 1 is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby go out Existing absorption peak, shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.75, oxygen Change Ti content is 3.1 weight %.
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Embodiment 7
Dimethyl sulfide is aoxidized using method same as Example 2, unlike, prepare titanium-silicon molecular sieve TS-1 When, second stage is to be cooled to 30 DEG C of stop 0.2h.Titanium Sieve Molecular Sieve prepared by the XRD crystalline phase figure and embodiment 1 of gained sample TS-1 is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Near There is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.14, Titanium oxide content is 3.1 weight %.
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Embodiment 8
Dimethyl sulfide is aoxidized using method same as Example 2, unlike, prepare titanium-silicon molecular sieve TS-1 When, without second stage.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by embodiment 1, illustrates To be the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absorption peak, shows Titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.08, titanium oxide content 2.5 Weight %.
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Embodiment 9
Dimethyl sulfide is aoxidized using method same as Example 2, unlike, aqueous dispersions are not quiet at room temperature 12h is set, but is sent directly into reaction kettle and carries out crystallization.XRD crystalline phase figure and 1 step of embodiment (1) preparation of gained sample Titanium-silicon molecular sieve TS-1 is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier Transform Infrared Spectroscopy In figure, in 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, titanium oxide content For 3.5 weight %, urface silicon titanium/body phase silicon titanium ratio is 1.18.
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Embodiment 10
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, titanium-silicon molecular sieve TS-1 is being used as Following methods are used to be modified processing before catalyst.
By the titanium-silicon molecular sieve TS-1 of step (1) preparation and contain HNO3(HNO3Mass concentration 10%) and peroxidating be The aqueous solution mixing of hydrogen (mass concentration of hydrogen peroxide is 7.5%), obtained mixture is stirred in closed container at 70 DEG C Reaction 5h is mixed, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, by obtained solid matter in 120 DEG C of dryings To constant weight, modified Titanium Sieve Molecular Sieve is obtained.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide Molar ratio be 1:0.1.Compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 230-310nm reduces 3.5%, is held by the hole of static determination of nitrogen adsorption and reduces 2.6%.By table The result that the reaction mixture that reactor exports under 1 reaction time listed determines is listed in table 1.
Embodiment 11
Dimethyl sulfide is aoxidized using method same as Example 2, unlike, titanium-silicon molecular sieve TS-1 is being used as Following methods are used to be modified processing before catalyst.
By the titanium-silicon molecular sieve TS-1 of preparation and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (peroxide be Change the mass concentration of hydrogen as aqueous solution mixing 7.5%), obtained mixture is stirred to react in closed container at 70 DEG C 5h, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C Weight, obtains modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub You are than being 1:0.1.Compared with raw material Titanium Sieve Molecular Sieve, in 230- in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 310nm reduces 3.4%, is held by the hole of static determination of nitrogen adsorption and reduces 2.7%.It is arranged by table 1 The result that the reaction mixture that reactor exports under reaction time out determines is listed in table 1.
Embodiment 12
Dimethyl sulfide is aoxidized using method same as in Example 10, unlike, in modification, as raw material Be drawn off from phenol hydroxylation reaction unit through regenerated titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 use with The identical method of embodiment 1 preparation, the titanium-silicon molecular sieve TS-1 drawn off 570 DEG C at a temperature of in air atmosphere roast 5h and Regeneration, the activity after regeneration are 35%, 96%) activity when fresh is.Compared with raw material Titanium Sieve Molecular Sieve, obtained modification The peak area of absorption peak in the UV-Vis spectrum of Titanium Sieve Molecular Sieve between 230-310nm reduces 3.3%, by static N2 adsorption The hole of method measurement, which holds, reduces 2.8%.The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines exists It is listed in table 1.
Embodiment 13
Dimethyl sulfide is aoxidized using method identical with embodiment 12, unlike, original will be used as in embodiment 12 Material through the regenerated titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit as catalyst.It is listed by table 1 The result that the reaction mixture that reactor exports under reaction time determines is listed in table 1.
Comparative example 1
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, not in first catalyst bed Carrying object is introduced between second catalyst bed.The reaction mixture that reactor exports under the reaction time listed by table 1 Determining result is listed in table 1.
Table 1
Embodiment 14
The hollow titanium that the present embodiment is HTS as the trade mark for being available from Hunan Jianchang Petrochemical Co., Ltd of catalyst Si molecular sieves, titanium oxide content are 2.5 weight %.
By Catalyst packing in isometrical fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed It is 2 layers, the weight ratio of the loadings of first catalyst bed and second catalyst bed is 2:1.In two layers of catalyst bed Carrying object entrance and liquid distributor be set between layer, carrying object of the liquid distributor for that will be sent by carrying object entrance with The effluent of first catalyst bed after mixing, is sent into second catalyst bed.
By dimethyl sulfide, as oxidant hydrogen peroxide (in the form of the hydrogen peroxide of 40 weight % provide) and as The acetone of solvent is mixed to form reaction raw materials, and reaction raw materials are sent into fixed bed reactors from bottom and flow through catalyst bed Layer, with Titanium Sieve Molecular Sieve haptoreaction.Wherein, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1:0.5, dimethyl sulfide Molar ratio with acetone is 1:6.Temperature in reactor is 35 DEG C, controls the pressure in fixed bed reactors in reaction process For 1.5MPa, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 45h-1。
The reaction mixture exported from reactor is flashed, gas stream and liquid stream are separated into.Gas object Stream condenses dimethyl sulfide by cooling, to recycle dimethyl sulfide；Liquid stream is distilled, and collects water, acetone respectively And dimethyl sulfoxide, dimethyl sulfoxide is exported.After mixing directly (for 25 DEG C) by the dimethyl sulfide of recycling and acetone It is sent between first catalyst bed and the second catalyst bed as carrying object, the feeding amount of carrying object is so that v2/v1=5, v1For the superficial velocity of reaction stream in first catalyst bed, v2For in second catalyst bed reaction stream it is apparent Speed.
The group of the reaction mixture exported from second fixed bed reactors in reaction process using gas-chromatography monitoring At, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity, the reaction listed by table 2 The result that the reaction mixture that reactor exports under time determines is listed in table 2.
Embodiment 15
Dimethyl sulfide is aoxidized using method identical with embodiment 14, unlike, in first catalyst bed With the loadings of second catalyst bed with embodiment 14 under the same conditions, load and adopt in second catalyst bed The titanium-silicon molecular sieve TS-1 prepared with the method for embodiment 1.The reaction mixing that reactor exports under the reaction time listed by table 2 The result that object determines is listed in table 2.
Embodiment 16
Dimethyl sulfide is aoxidized using method identical with embodiment 15, unlike, in first catalyst bed Under conditions of remaining unchanged with the loadings of second catalyst bed, hollow Titanium Sieve Molecular Sieve is adopted before being used as catalyst It is modified processing using the following method；And the titanium silicon point of modification prepared by embodiment 10 is loaded in second catalyst bed Son sieve.
By hollow Titanium Sieve Molecular Sieve and contain HNO3(HNO3Mass concentration be 10%) and hydrogen peroxide (hydrogen peroxide Mass concentration is aqueous solution mixing 5%), obtained mixture is stirred under 120 DEG C of pressure itselfs in closed container anti- 4h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C Weight, obtains modified Titanium Sieve Molecular Sieve.Wherein, hollow Titanium Sieve Molecular Sieve is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub You are than being 1:0.4.Compared with raw material Titanium Sieve Molecular Sieve, in 230- in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 310nm reduces 4.6%, is held by the hole of static determination of nitrogen adsorption and reduces 3.8%.It is arranged by table 2 The result that the reaction mixture that reactor exports under reaction time out determines is listed in table 2.
Table 2
Embodiment 17
Titanium-silicon molecular sieve TS-1 used in the present embodiment is prepared using following methods.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:2:10: 600, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is close using sealed membrane in beaker It is honored as a queen in 40 DEG C of standing 10h, is stirred 0.5h at 25 DEG C followed by magnetic agitation, is allowed to disperse again.It will disperse again Dispersion liquid afterwards is transferred in sealing reaction kettle, and in 130 DEG C of experience first stage crystallization 8h, mixture is then cooled to 50 DEG C After undergoing second stage to stop 5h, continue in sealing reaction kettle in 170 DEG C of at a temperature of experience phase III crystallization 16h (its In, it is 1 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first stage crystallization temperature to second-order The rate of temperature fall of section treatment temperature is 10 DEG C/min, by second stage treatment temperature to the heating rate of phase III crystallization temperature For 20 DEG C/min), then exist without filtering and washing step directly in 120 DEG C of drying 3h after gained crystallization product is taken out 2h is roasted at 580 DEG C, obtains molecular sieve.Titanium-silicon molecular sieve TS-1 one prepared by the XRD crystalline phase figure and embodiment 1 of gained sample It causes, what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；In Fourier Transform Infrared Spectroscopy figure, in 960cm-1It is attached Closely there is absorption peak, show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.25, titanium oxide content is 2.6 weight %.
By Catalyst packing in isometrical fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed It is 2 layers, first catalyst bed loads hollow Titanium Sieve Molecular Sieve (identical as embodiment 14), second catalyst bed filling The weight of the loadings of titanium-silicon molecular sieve TS-1 prepared by embodiment 17, first catalyst bed and second catalyst bed Than for 8:1.Carrying object entrance and liquid distributor are set between two layers of catalyst bed, and liquid distributor is used for will be by carrying The effluent of carrying object and first catalyst bed that fluid inlet is sent into after mixing, is sent into second catalyst bed In.
It is former that dimethyl sulfide, the tert-butyl hydroperoxide as oxidant and the acetonitrile as solvent are mixed to form reaction Reaction raw materials are sent into fixed bed reactors from bottom and flow through catalyst bed by material, with Titanium Sieve Molecular Sieve haptoreaction. Wherein, the molar ratio of dimethyl sulfide and tert-butyl hydroperoxide is 1:1, and the molar ratio of dimethyl sulfide and acetonitrile is 1:8.Instead Answering temperature in device is 50 DEG C, controls the pressure in fixed bed reactors for 2.0MPa in reaction process, dimethyl sulfide Weight (hourly) space velocity (WHSV) is 20h-1。
The reaction mixture exported from reactor is flashed, gas stream and liquid stream are separated into.Wherein, gas Body logistics condenses dimethyl sulfide by cooling, to recycle dimethyl sulfide；Liquid stream is distilled, and collects acetonitrile respectively And dimethyl sulfoxide, dimethyl sulfoxide is exported.The dimethyl sulfide of recycling and acetonitrile are heated to 50 DEG C of works after mixing It is sent between first catalyst bed and the second catalyst bed for carrying object, the feeding amount of carrying object is so that v2/v1=3.5, v1For the superficial velocity of reaction stream in first catalyst bed, v2For in second catalyst bed reaction stream it is apparent Speed.
The group of the reaction mixture exported from second fixed bed reactors in reaction process using gas-chromatography monitoring At, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity, the reaction listed by table 3 The result that the reaction mixture that reactor exports under time determines is listed in table 3.
Embodiment 18
Dimethyl sulfide is aoxidized using method identical with embodiment 17, unlike, first catalyst bed and Second catalyst bed loads the titanium-silicon molecular sieve TS-1 of the preparation of embodiment 16.It is reacted under the reaction time listed by table 3 The result that the reaction mixture of device output determines is listed in table 3.
Embodiment 19
Dimethyl sulfide is aoxidized using method identical with embodiment 17, unlike, first catalyst bed and Second catalyst bed is loaded through regenerated titanium-silicon molecular sieve TS-1 (titanium drawn off from propylene ring oxidation reaction device Silicalite TS-1 using method identical with embodiment 17 prepare, the Titanium Sieve Molecular Sieve drawn off 580 DEG C at a temperature of in sky 3h is roasted in gas atmosphere and is regenerated, and the activity after regeneration is 40%, 95%) activity when fresh is.When the reaction listed by table 3 Between the result that determines of reaction mixture of lower reactor output listed in table 3.
Embodiment 20
Dimethyl sulfide is aoxidized using method identical with embodiment 19, unlike, through regenerated Titanium Sieve Molecular Sieve TS-1 is modified processing before as catalyst, using following methods.
With contain HNO3(HNO3Mass concentration 15%) and hydrogen peroxide be (mass concentration of hydrogen peroxide is 8%) Aqueous solution mixing, is stirred to react 3h at 150 DEG C in closed container for obtained mixture, the temperature of obtained reaction mixture It is cooled to room temperature and is filtered, obtained solid matter is dry to constant weight at 120 DEG C, obtain modified Titanium Sieve Molecular Sieve.Its In, titanium-silicon molecular sieve TS-1 is with SiO2The molar ratio of meter, Titanium Sieve Molecular Sieve and hydrogen peroxide is 1:2.With raw material Titanium Sieve Molecular Sieve It compares, the peak area of the absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification between 230-310nm is reduced 5.3%, held by the hole of static determination of nitrogen adsorption and reduces 4.8%.The reaction that reactor exports under the reaction time listed by table 3 The result that mixture determines is listed in table 3.
Table 3
Embodiment 21
Titanium-silicon molecular sieve TS-1 used in the present embodiment is prepared using following methods.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:5:18: 1000, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is utilized into sealed membrane in beaker In 45 DEG C of standing 8h after sealing；Dispersion liquid through standing is transferred in sealing reaction kettle, in 140 DEG C of experience first stage crystallization 6h continues in sealing reaction kettle after mixture is then cooled to 40 DEG C of experience second stage stop 1h in 160 DEG C of temperature Lower experience phase III crystallization 12h (it is wherein, 5 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by The rate of temperature fall of first stage crystallization temperature to second stage treatment temperature is 5 DEG C/min, by second stage treatment temperature to the The heating rate of three stage crystallization temperatures is 5 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly 110 DEG C of drying 2h are connected to, 3h is then roasted at 550 DEG C, obtain molecular sieve.The XRD crystalline phase figure and embodiment 1 of gained sample are made Standby titanium-silicon molecular sieve TS-1 is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier-transform infrared In spectrogram, in 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, surface silicon Titanium ratio/body phase silicon titanium ratio is 2.71, and titanium oxide content is 4.3 weight %.
By Catalyst packing in isometrical fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed It is 2 layers, first catalyst bed loads hollow Titanium Sieve Molecular Sieve (identical as embodiment 14), second catalyst bed filling The weight of the loadings of titanium-silicon molecular sieve TS-1 prepared by embodiment 21, first catalyst bed and second catalyst bed Than for 4:1.Carrying object entrance and liquid distributor are set between two layers of catalyst bed, and liquid distributor is used for will be by carrying The effluent of carrying object and first catalyst bed that fluid inlet is sent into after mixing, is sent into second catalyst bed In.
It is former that dimethyl sulfide, the cumyl hydroperoxide as oxidant and the acetonitrile as solvent are mixed to form reaction Reaction raw materials are sent into fixed bed reactors from bottom and flow through catalyst bed by material, with Titanium Sieve Molecular Sieve haptoreaction. Wherein, the molar ratio of dimethyl sulfide and cumyl hydroperoxide is 1:1, and the molar ratio of dimethyl sulfide and acetonitrile is 1:6.Instead Answering temperature in device is 60 DEG C, controls the pressure in fixed bed reactors for 1.8MPa in reaction process, dimethyl sulfide Weight (hourly) space velocity (WHSV) is 15h-1。
The reaction mixture exported from reactor is flashed, gas stream and liquid stream are separated into.Wherein, gas Body logistics condenses dimethyl sulfide by cooling, to recycle dimethyl sulfide；Liquid stream is distilled, and collects acetonitrile respectively And dimethyl sulfoxide, dimethyl sulfoxide is exported.After the dimethyl sulfide of recycling and acetonitrile are uniformly mixed and are heated to 60 DEG C It is sent between first catalyst bed and the second catalyst bed as carrying object, the feeding amount of carrying object is so that v2/v1=4, v1For the superficial velocity of reaction stream in first catalyst bed, v2For in second catalyst bed reaction stream it is apparent Speed.
The group of the reaction mixture exported from second fixed bed reactors in reaction process using gas-chromatography monitoring At, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfoxide selectivity, the reaction listed by table 4 The result that the reaction mixture that reactor exports under time determines is listed in table 4.
Embodiment 22
Dimethyl sulfide is aoxidized using method identical with embodiment 21, unlike, in second catalyst bed The Titanium Sieve Molecular Sieve of filling is the Titanium Sieve Molecular Sieve prepared using method same as Example 1.The reaction time listed by table 4 The result that the reaction mixture of lower reactor output determines is listed in table 4.
Table 4
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (61)

1. a kind of sulfide oxidation method, this method are included under oxidation reaction condition, make containing at least one thioether, at least one The reaction feed of oxidant and optional at least one solvent flows successively through the 1st catalyst bed to the n-th catalyst bed, n 2 Above integer, at least one Titanium Sieve Molecular Sieve is filled in the catalyst bed, and this method further includes logical in reaction feed The 1st catalyst bed is crossed to during the n-th catalyst bed, to the 1st catalyst bed at least one between the n-th catalyst bed To at least one carrying object is introduced between adjacent catalyst bed, so that this is to adjacent on the basis of the flow direction of reaction feed Catalyst bed in, in the catalyst bed in downstream the superficial velocity of reaction stream be higher than positioned at upstream catalyst bed The superficial velocity of reaction stream in layer, the carrying object are to be located at most downstream into the n-th catalyst bed from the 1st catalyst bed Catalyst bed effluent in isolate remaining logistics after target sulfide oxide, at least partly Titanium Sieve Molecular Sieve is to change Property Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve of the modification be undergo modification Titanium Sieve Molecular Sieve, the modification packet Including will contact as the Titanium Sieve Molecular Sieve of raw material with the modification liquid being made of nitric acid, hydrogen peroxide and water, in the modification In, it is 1:0.01-5, the hydrogen peroxide and the nitre as the Titanium Sieve Molecular Sieve of raw material and the molar ratio of the hydrogen peroxide The molar ratio of acid is 1:0.01-50, and the Titanium Sieve Molecular Sieve is in terms of silica, in the modification, as raw material Titanium Sieve Molecular Sieve and the modification liquid 10-350 DEG C at a temperature of contacted, the contact is in the container that pressure is 0-5MPa Interior progress, the pressure are gauge pressure, and the duration of the contact is 1-10 hours, and the Titanium Sieve Molecular Sieve is Titanium Sieve Molecular Sieve TS-1 and/or hollow Titanium Sieve Molecular Sieve, the thioether are dimethyl sulfide.
2. according to the method described in claim 1, wherein, the superficial velocity table of reaction stream in the catalyst bed in downstream It is shown as vm, the superficial velocity of reaction stream is expressed as v in the catalyst bed of upstreamm-1, the introduction volume of the carrying object makes Obtain vm/vm-1=1.5-15, m are the arbitrary integer in [2, n] section.
3. according to the method described in claim 2, wherein, the introduction volume of the carrying object makes vm/vm-1=2-10.
4. according to the method described in claim 3, wherein, the introduction volume of the carrying object makes vm/vm-1=2-5.
5. according to the method described in claim 1, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The molar ratio for stating hydrogen peroxide is 1:0.05-3, and the Titanium Sieve Molecular Sieve is in terms of silica.
6. according to the method described in claim 5, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The molar ratio for stating hydrogen peroxide is 1:0.1-2, and the Titanium Sieve Molecular Sieve is in terms of silica.
7. according to the method described in claim 1, wherein, in the modification, the hydrogen peroxide and the nitric acid Molar ratio is 1:0.1-20.
8. according to the method described in claim 7, wherein, in the modification, the hydrogen peroxide and the nitric acid Molar ratio is 1:0.2-10.
9. according to the method described in claim 8, wherein, in the modification, the hydrogen peroxide and the nitric acid Molar ratio is 1:0.5-5.
10. according to the method described in claim 9, wherein, in the modification, the hydrogen peroxide and the nitric acid Molar ratio is 1:0.6-3.5.
11. according to the method described in claim 1, wherein, in the modification liquid, the concentration of the hydrogen peroxide and nitric acid is respectively For 0.1-50 weight %.
12. according to the method for claim 11, wherein in the modification liquid, the concentration of the hydrogen peroxide and nitric acid is each From for 0.5-25 weight %.
13. according to the method for claim 12, wherein in the modification liquid, the concentration of the hydrogen peroxide and nitric acid is each From for 5-15 weight %.
14. according to the method described in claim 1, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material State modification liquid 20-300 DEG C at a temperature of contacted.
15. according to the method for claim 14, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 50-250 DEG C at a temperature of contacted.
16. according to the method for claim 15, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 60-200 DEG C at a temperature of contacted.
17. according to the method described in claim 1, wherein, the duration of the contact is 3-5 hours.
18. according to the method described in claim 1, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The exposure level for stating modification liquid makes, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, modified The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduces by 2% or more；The Kong Rong of modified Titanium Sieve Molecular Sieve subtracts Few 1% or more, the Kong Rong are using static determination of nitrogen adsorption.
19. according to the method for claim 18, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 2-30%.
20. according to the method for claim 19, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 2.5-15%.
21. according to the method for claim 20, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 3-10%.
22. according to the method for claim 21, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 3-6%.
23. according to the method described in claim 1, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The exposure level for stating modification liquid makes, and the hole of modified Titanium Sieve Molecular Sieve, which holds, reduces 1-20%.
24. according to the method for claim 23, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, and the hole of modified Titanium Sieve Molecular Sieve, which holds, reduces 1.5-10%.
25. according to the method for claim 24, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, and the hole of modified Titanium Sieve Molecular Sieve, which holds, reduces 2-5%.
26. method described in any one of -25 according to claim 1, wherein at least partly Titanium Sieve Molecular Sieve is from least A kind of reaction unit draws off agent, it is described draw off agent be Ammoximation reaction device draw off agent, hydroxylating device is drawn off Agent and epoxidation reaction device draw off agent.
27. according to the method described in claim 1, wherein, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the titanium The urface silicon titanium of silicalite TS-1 is not less than body phase silicon titanium ratio, mole of the silicon titanium than referring to silica and titanium oxide Than the urface silicon titanium is measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses x ray fluorescence spectrometry Measurement.
28. according to the method for claim 27, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is More than 1.2.
29. according to the method for claim 28, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5。
30. according to the method for claim 29, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5。
31. according to claim 1 with the method described in any one of 27-30, wherein at least partly Titanium Sieve Molecular Sieve is titanium silicon Molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 are prepared using method comprising the following steps:
(A) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and optionally supplements water, dispersed Liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:(0.5-8): (5-30): (100- 2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N meter；
(B) optionally, by the dispersion liquid 15-60 DEG C standing 6-24 hours；
(C) dispersion liquid that step (A) obtains or the dispersion liquid that step (B) obtains sequentially are undergone into the stage in sealing reaction kettle (1), stage (2) and stage (3) carry out crystallization, the stage (1) 80-150 DEG C crystallization 6-72 hours, the stage (2) is cooled to not high In 70 DEG C and the residence time is at least 0.5 hour, and the stage (3) is warming up to 120-200 DEG C, then crystallization 6-96 hours.
32. according to the method for claim 31, wherein the stage, (1) was in 110-140 DEG C of crystallization.
33. according to the method for claim 32, wherein the stage, (1) was in 120-140 DEG C of crystallization.
34. according to the method for claim 33, wherein the stage, (1) was in 130-140 DEG C of crystallization.
35. according to the method for claim 31, wherein crystallization 6-8 hours stage (1).
36. according to the method for claim 31, wherein the residence time in stage (2) is 1-5 hours.
37. according to the method for claim 31, wherein the stage (3) is warming up to 140-180 DEG C.
38. according to the method for claim 37, wherein the stage (3) is warming up to 160-170 DEG C.
39. according to the method for claim 31, wherein the stage (3) crystallization 12-20 hours again.
40. according to the method for claim 31, wherein stage (1) and stage (3) meet one of the following conditions or two Person:
Condition 1: the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3)；
Condition 2: the crystallization time in stage (1) is less than the crystallization time of stage (3).
41. according to the method for claim 40, wherein condition 1: crystallization temperature of the crystallization temperature in stage (1) than the stage (3) Spend low 10-50 DEG C.
42. according to the method for claim 41, wherein condition 1: crystallization temperature of the crystallization temperature in stage (1) than the stage (3) Spend low 20-40 DEG C.
43. according to the method for claim 40, wherein condition 2: the crystallization time in stage (1) than the stage (3) crystallization when Between it is 5-24 hours short.
44. according to the method for claim 43, wherein condition 2: the crystallization time in stage (1) than the stage (3) crystallization when Between it is 6-12 hours short.
45. according to the method for claim 31, wherein the stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
46. according to the method for claim 31, wherein the titanium source is inorganic titanium salt and/or organic titanate；The alkali Source template is one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine.
47. according to the method for claim 46, wherein the alkali source template is quaternary ammonium base.
48. according to the method for claim 47, wherein the alkali source template is tetrapropylammonium hydroxide.
49. according to the method for claim 46, wherein the inorganic titanium salt is TiCl4、Ti(SO4)2And TiOCl2In one Kind is two or more；The organic titanate is selected from general formula R7 4TiO4The compound of expression, R7Selected from 2-4 carbon atom Alkyl.
50. according to the method described in claim 1, wherein, the Titanium Sieve Molecular Sieve of the 1st catalyst bed filling is hollow titanium The Titanium Sieve Molecular Sieve of si molecular sieves, the n-th catalyst bed filling is titanium-silicon molecular sieve TS-1.
51. according to claim 1, method described in any one of 3-25 and 50, wherein Wm-1/WmFor 0.1-20, Wm-1It is The quality of the catalyst loaded in m-1 catalyst bed, WmQuality for the catalyst loaded in m catalyst bed, m are Arbitrary integer in [2, n] section.
52. method according to claim 51, wherein Wm-1/WmFor 2-8:1.
53. method described in any one of -25 and 50 according to claim 1, wherein the oxidant rubs with the thioether You are than being 0.1-10:1.
54. method according to claim 53, wherein the molar ratio of the oxidant and the thioether is 0.1-2:1.
55. method according to claim 54, wherein the molar ratio of the oxidant and the thioether is 0.2-1.5:1.
56. method described in any one of -25 and 50 according to claim 1, wherein the oxidant is selected from peroxide.
57. method according to claim 56, wherein the oxidant is selected from hydrogen peroxide, tert-butyl hydroperoxide, second Benzene hydrogen peroxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
58. method described in any one of -25 according to claim 1, wherein the oxidation reaction condition includes: that temperature is 0-120℃；Pressure is 0-3MPa, and the pressure is gauge pressure.
59. method according to claim 58, wherein temperature is 20-80 DEG C.
60. method according to claim 59, wherein temperature is 30-60 DEG C.
61. method according to claim 58, wherein pressure 0.1-2.5MPa.
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