CN107029793A - Activated carbon supported metal complex and its application as catalyst in dimethyl disulfide is prepared - Google Patents
Activated carbon supported metal complex and its application as catalyst in dimethyl disulfide is prepared Download PDFInfo
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- CN107029793A CN107029793A CN201710286591.7A CN201710286591A CN107029793A CN 107029793 A CN107029793 A CN 107029793A CN 201710286591 A CN201710286591 A CN 201710286591A CN 107029793 A CN107029793 A CN 107029793A
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention belongs to chemical field, and in particular to a kind of activated carbon supported metal complex and its application as catalyst in dimethyl disulfide is prepared.Activated carbon supported CoL (the Cl that the present invention is provided2) preparation method of (CoL) metal complex is：By chemical graft method by CoL (Cl2) (CoL) metal complex is supported on modified activated carbon, obtains activated carbon supported CoL (Cl2) (CoL) metal complex；The modified activated carbon is 1,5 dibromo pentane modified activated carbons.The catalyst structure is stable, reusable, can realize in reaction system alkaline-resisting, pressure-resistant, high temperature resistant and effective catalysis oxidation methyl mercaptan salt prepares dimethyl disulfide.The catalyst of the present invention can well be separated during dimethyl disulfide is prepared with product, and specific ionization state CoL (Cl2) (CoL) metal complex catalyzed obtained product purity height.Obtained product DMDS yields are up to 76.7%, and the purity of product can reach 100%.
Description
Technical field
The invention belongs to chemical field, it is related to a kind of activated carbon supported metal complex and its is preparing two as catalyst
Application in methyl disulfide, specially activated carbon supported CoL (Cl2) (CoL) metal complex and its as catalyst system
Application in standby dimethyl disulfide.
Background technology
Dimethyl disulfide (DMDS) turns into important industrial chemicals because of its extensive purposes, and economic value is quite high, has
Good market prospects.But, because its produce synthesis condition more harshness, raw material stench, have a severe toxicity, and raw material is difficult acquisition,
Many restrictions cause the producer of domestic production now less.
Dimethyl disulfide synthetic method mainly has：Methanol vulcanization method, methyl mercaptan vulcanization method, methyl mercaptan oxidizing process, sulfuric acid
Diformazan ester process.
1. dimethyl sulfate ester process
Dimethyl sulfate ester process is first to prepare sodium disulfide using sulphur and vulcanized sodium as raw material, then sodium disulfide and sulfuric acid
Dimethyl ester carries out methylation reaction and produces dimethyl disulfide, and key reaction formula is as follows：
Na2S+S→Na2S2
(CH3)2SO4+Na2S2→CH3SSCH3+Na2SO4
The advantage of this method is that raw material is easy to get, and reaction condition is gentle, process route relative maturity, research both at home and abroad compared with
Many, current China produces dimethyl disulfide based on the method.However, there is also certain defect, raw material sulphuric acid two for this method
Methyl esters belongs to toxic articles, once occurring accident, the harm to life and environment is extremely serious, and consumption of raw materials quota is higher.
2. methyl mercaptan oxidizing process
Methyl mercaptan oxidizing process is to aoxidize to be dehydrated to produce dimethyl disulfide with oxygen reaction by raw material of methyl mercaptan, mainly
Reaction equation is：
Main technique is：Air and methyl mercaptan are passed through reactor using mol ratio as 1.25: 1, the bar existed in catalyst
Temperature of reaction system is 0~200 DEG C under part, and pressure is 0.1~1.1MPa, and product is obtained after the processes such as supercooling, separation, alkali cleaning
To product.The yield of dimethyl disulfide is 74%~81%, and the conversion ratio of methyl mercaptan is 86%~96%.This method is only in state
Outer to have a small amount of report, domestic temporarily without correlative study report, technology path is also immature, need to further research and develop.
3. methanol vulcanizes method
Methanol vulcanization method is that, using methanol, hydrogen sulfide and sulphur as waste dimethyl disulfide, dominating process route has
Two kinds of one-stage process and two-phase method.One-stage process is that one-time reaction is made two under certain condition for material benzenemethanol, hydrogen sulfide and sulphur
Methyl disulfide, reaction equation is：
CH3OH+H2S+S→CH3SSCH3+H2O
The method methanol conversion is 51.5%, and its Main By product is methyl sulfide and carbon disulfide.Two-phase method be methanol and
Hydrogen sulfide first reacts obtained methyl mercaptan, and dimethyl disulfide is made with reaction of Salmon-Saxl again in methyl mercaptan, and reaction equation is：
CH3OH+H2S→CH3SH+H2O
2CH3SH+S→CH3SSCH3+H2S
Two-phase method methanol conversion per pass is 32%, and product is that dimethyl sulfide, Main By product are carbon disulfide, first sulphur
Alcohol and diformazan polysulfide.Accessory substance can be used in reaction inner loop, and the three wastes are not produced substantially.Have the disadvantage：The route
Technique is relative complex, and technical equipment requires higher, and state's interior energy reaches the factory of the technical requirements and few, need further to change
Enter.
4. methyl mercaptan vulcanizes method
Methyl mercaptan vulcanization method is to produce dimethyl disulfide using methyl mercaptan and sulphur as raw material directly reaction, and main reaction formula is：
2CH3SH+S→CH3SSCH3+H2S
This method is divided into the progress of two steps, and the first step is carried out in stirred reactor, and feedstock is than methyl mercaptan (mol): sulphur
(mol)=4: 1, temperature is 40 DEG C, and pressure is 0.55MPa, using A21 macroreticular resins as catalyst, dimethyl disulfide
Yield is 80%, and catalyst is made using second triamine, and its yield is 78.5%, and accessory substance is dimethyl polythiaether.Product is through over cure
Change to enter after hydrogen abjection step and second step reaction is carried out in jacketed pipe type reactor, the high income of dimethyl disulfide reaches
98.5%.Simple using methyl mercaptan vulcanization method route process CIMS, reaction condition is gentle, and technology is relatively low with equipment requirement, is adapted to
Domestic industry level.Shortcoming：Raw material methyl mercaptan is difficult to obtain, and is gaseous state under normal temperature, normal pressure, and foul smelling, domestic at present raw
The factory for producing methyl mercaptan is less, thus limits the popularization of the technique.
Methyl mercaptan salt oxidizing process is, using methyl mercaptan salt as raw material, diformazan to be prepared with oxygen reaction under catalyst existence condition
Base disulfide, the method avoids the pollution to environment in numerous and diverse process conditions and production process, but to catalyst performance requirement
It is higher.
Azacrown ether containing is the class artificial ligand that the part oxygen atom on nitrogen-atoms substitution crown ether cycle is obtained.Existing many is ground
Study carefully and show, because the nitrogen-atoms of introducing has relative soft base property so that such part is to transition metal, heavy metal, alkali gold
Category, alkaline-earth metal plasma have special complexing, and it can not only occur mating reaction with positively charged ion, also can
It is complexed with negatively charged anion.And di mon mating compound in its ring system because, containing two nitrogen-atoms, causing it to mistake
The selectivity and stability for crossing metal ion and heavy metal ion are more excellent.Free state di mon mating compound is used for being catalyzed
Oxidation methyl mercaptan salt prepares dimethyl disulfide, and catalyst is soluble in product dimethyl disulfide so that catalyst and product are not
It can well separate, product purity is not high, thus require further improvement.Based on reaction system is strong alkali solution and reacts
Journey needs to complete under certain temperature, pressure, and then requires that support materials are alkaline-resisting, pressure-resistant, high temperature resistant.
Therefore develop one kind in certain temperature, pressure and alkaline-resisting, pressure-resistant, resistant to elevated temperatures support materials as catalyst to two
The industrial production of methyl disulfide has important industry meaning.
The content of the invention
In view of this, it is an object of the invention to provide a kind of activated carbon supported CoL (Cl2) (CoL) metal complex and
Its application as catalyst in dimethyl disulfide is prepared.The catalyst structure that the present invention is provided is stable, reusable,
Effectively dimethyl disulfide can be prepared for catalysis oxidation methyl mercaptan salt, can well be separated with product, and specific ionization state CoL
(Cl2) (CoL) metal complex catalyzed obtained product purity height.
To achieve the above object, the technical scheme is that：
Activated carbon supported CoL (Cl2) (CoL) metal complex preparation method, by chemical graft method by CoL (Cl2)
(CoL) metal complex is supported on modified activated carbon, obtains activated carbon supported CoL (Cl2) (CoL) metal complex；It is described to change
Property activated carbon be pentamethylene bromide modified activated carbon.
Further, the CoL (Cl2) mass ratio of (CoL) metal complex and pentamethylene bromide modified activated carbon is
0.1：0.5~2.
As a preferred embodiment, described DMF, K2CO3With CoL (Cl2) (CoL) metal complex mass ratio be 50：0.5~
3：0.1.
Further, modified activated carbon is added into CoL (Cl2) in (CoL) metal complex aqueous solution, in DMF, K2CO3Deposit
In lower reaction, activated carbon supported CoL (Cl are obtained2) (CoL) metal complex；The modified activated carbon is modified for pentamethylene bromide
Activated carbon.
The DMF can be replaced with benzene, toluene；The K2CO3Na can be used2CO3、NaHCO3Instead of.
As a preferred embodiment, the temperature of reaction is 70~85 DEG C, the time of reaction is 9~15h.
Activated carbon supported CoL (the Cl2) (CoL) metal complex can commercially buy acquisition also by published
Method is prepared.
A kind of specific activated carbon supported CoL (Cl2) (CoL) metal complex preparation method：By pentamethylene bromide
Modified activated carbon adds CoL (Cl2) in (CoL) metal complex aqueous solution, add DMF, K2CO3Reacted 12 hours at 80 DEG C.It is cold
But to room temperature, suction filtration, with DMF and deionized water wash respectively three times it is vacuum dried after 1, pentamethylene bromide modified activated carbon
Load C oL (Cl2) (CoL) metal complex.
Further, described 1, the preparation method of pentamethylene bromide modified activated carbon comprises the following steps：
1) it is washed with deionized after activated carbon is immersed in aqueous solution of nitric acid to neutrality, nitric acid treatment is obtained after drying
Activated carbon；
2) take step 1) processing after activated carbon add DMF, K2CO3With NaH reactions, 1 is added, pentamethylene bromide reacts,
Obtain pentamethylene bromide modified activated carbon.
A kind of specific preparation method of pentamethylene bromide modified activated carbon：Weigh dried active carbon powder (AC)
24h is impregnated with the concentrated nitric acid aqueous solution, is then washed with deionized water to neutrality, in 60 DEG C of drying in oven, vacuum is put into afterwards and is done
In 105 DEG C of vacuum drying in dry case, the activated carbon (AC-T) of nitric acid treatment is obtained, it is standby.
Take and nitrify DMF, K that dried activated carbon is added steam again after2CO3, add under NaH condition of ice bath and react, add 1,
Pentamethylene bromide reacts at room temperature 1h and reacted 24 hours after 80 DEG C.Through cooling, suction filtration washs dried 1, pentamethylene bromide changes
Activated carbon after property.
As a preferred embodiment, step 1) described in the volume ratio of nitric acid in aqueous solution of nitric acid and aqueous medium be 1:2.
As a preferred embodiment, step 1) in be immersed in temperature in aqueous solution of nitric acid be 50~70 DEG C.
As a preferred embodiment, step 2) in activated carbon and K2CO3Mass ratio be 1：1~2.
As a preferred embodiment, step 2) described in DMF, K2CO3Mass ratio with NaH is 50：1~3：1~3.
As a preferred embodiment, step 2) in activated carbon and 1, the mass ratio of pentamethylene bromide is 10：1~3.
The second object of the present invention is to provide the activated carbon supported CoL that a kind of described preparation method is prepared
(Cl2) (CoL) metal complex.
Activated carbon supported CoL (the Cl2) structural formula of (CoL) metal complex is：
Activated carbon supported CoL (the Cl that will be prepared by above-mentioned preparation method2) (CoL) metal complex carry out X penetrate
Line electron spectrum is tested, and obtained XPS spectrum figure is shown except containing Elements C, N, O, Br in composite, also containing a small amount of Co members
Element, it will be seen that load C oL (Cl2) after (CoL) metal complex, the Co peaks that composite catalyst is occurred in that, Co electron energy is
784.3eV.Due to CoL (Cl2) (CoL) metal complex load capacity is smaller, so high-resolution peak noise is larger, but
It can see peak clearly occur, show CoL (Cl2) (CoL) metal complex loads up.Br3d electron energy by
65.9eV drops to 11.3eV, and energy substantially weakens, and is attributed to 1 ,-the Br for the activated carbon surface that pentamethylene bromide is modified is with coordinating
- NH on thing L loses HBr and bonding by being condensed, and Br3d electron energy, which is substantially reduced, further demonstrates that CoL (Cl2) (CoL) gold
Metal complex is successfully loaded on the activated carbon, and is strong chemical action.
The third object of the present invention is to provide a kind of described activated carbon supported CoL (Cl2) (CoL) metal complex work
The application for being catalyst in dimethyl disulfide is prepared.
CoL(Cl2) (CoL) metal complex in catalysis oxidation sodium methyl mercaptide prepares dimethyl disulfide (DMDS), its
Product dimethyl disulfide is soluble in as catalyst so that catalyst and product can not be separated well, product yield and production
Product purity is not high.CoL(Cl2) (CoL) metal complex be compund of aza crown ether have the knot similar to crown compound
Structure feature, the oxygen heteroatom of ordered arrangement is conducive to the formation and stably of Oxygen adduct, improves oxygen carrying capability.In addition, by changing
Method is modified its structure, and introducing methoxyl group, hydroxyl, halogen in aza-crown ether ring waits lone pair electrons center function
Key, both can be for adjusting the cavity size of crown ether by these specific three-dimensional effects of function base and electronic effect, and having to join
With the coordination to metal ion.Strengthen the stability of complex.Based on this, the present invention passes through introducing 1, pentamethylene bromide and its cobalt
Complex CoL, has synthesized 1, the cobalt metal compounding CoL of pentamethylene bromide modification, and is loaded on the activated carbon, is prepared into
Activated carbon supported four oxygen diaza crown ether cobalt metal compound new function catalysis material.
Activated carbon supported CoL (Cl prepared by the present invention2) (CoL) metal complex as catalyst can and product it is good
Separation, and specific ionization state CoL (Cl2) (CoL) metal complex catalyzed obtained product DMDS purity is high, purity can reach
100%.Activated carbon supported CoL (the Cl2) (CoL) metal complex can be more in dimethyl disulfide is prepared as catalyst
It is secondary to reuse, reduce production cost.
The present invention also aims to provide a kind of utilization described activated carbon supported CoL (Cl2) (CoL) metal complex
As the method for catalyst preparation dimethyl disulfide, methyl mercaptan salt is in activated carbon supported CoL (Cl2) (CoL) metal complex
Catalysis under occur oxidation reaction, obtain dimethyl disulfide.
Further, the methyl mercaptan salt includes sodium methyl mercaptide and methyl mercaptan potassium.
Raw material sodium methyl mercaptide and methyl mercaptan potassium are strong alkali solution, and catalytic reaction need to be completed under certain temperature, pressure.It is logical
Cross chemical graft mode by catalyst be supported on the catalyst that activated carbon obtains can realize in reaction system it is alkaline-resisting, pressure-resistant,
High temperature resistant.
As a preferred embodiment, the methyl mercaptan salt selects sodium methyl mercaptide.
Dimethyl disulfide (DMDS) its reaction equation is produced using sodium methyl mercaptide oxidizing process as follows：
4CH3SNa+O2+2H2O→2CH3SSCH3+4NaOH
Further, the methyl mercaptan salt and activated carbon supported CoL (Cl2) (CoL) metal complex mass ratio for 70~
90:0.1~0.7.
As a preferred embodiment, the methyl mercaptan salt and activated carbon supported CoL (Cl2) (CoL) metal complex mass ratio
For 80~90:0.1~0.5.
As a preferred embodiment, the methyl mercaptan salt and activated carbon supported CoL (Cl2) (CoL) metal complex mass ratio
For 81：0.2.
In the case of other conditions identical, catalyst amount is within the scope of the invention with the increase of catalyst amount
The conversion per pass of methyl mercaptan salt, 90%~97.3%, is 81 in the mass ratio of methyl mercaptan salt and catalyst：One way turns when 0.2
Rate reaches 97.3%, and once through yield is up to 76.7%.But dropped on the contrary with the increase DMDS once through yields of catalyst amount
It is low, accelerate with the increase reaction rate of catalyst amount, but it is not meant to that the yield of product can increase, because excessive urges
Agent can hinder the material in course of reaction to transmit on the contrary.The change of catalyst amount has no effect on product DMDS purity and pure
Degree reaches 100%.In line with economic appropriate principle, the optimum quality ratio of raw material and the catalyst is 81 in the reaction：0.2.
Further, the temperature for occurring oxidation reaction is 50~80 DEG C；The time of oxidation reaction is 45~90min；Oxidation is anti-
The oxygen pressure answered is 0.5~1.0MPa.
As a preferred embodiment, the temperature for occurring oxidation reaction is 65 DEG C；The time of oxidation reaction is 60min；Oxidation reaction
Oxygen pressure be 0.7MPa.
The present invention also aims to provide a kind of process units for preparing dimethyl disulfide, including it is reactor, high-purity
Oxygen unit, temperature controller and rotating speed controller；The high purity oxygen gas device is connected by pipeline with reactor top, described
Pipeline is additionally provided with oxygen pressure reducing valve and oxygen gauge；Stirring and heater are provided with the reactor, passes through temperature
Controller and rotating speed controller control rotating speed and temperature in reactor；Charging aperture, discharging are additionally provided with the top of the reactor
Mouth, exhaust outlet and cooling water circulation pipeline.
The present invention also aims to provide a kind of system for preparing dimethyl disulfide, the system by methyl mercaptan salt,
Activated carbon supported CoL (Cl2) (CoL) metal complex, oxygen and aqueous medium composition.
Further, the methyl mercaptan salt includes sodium methyl mercaptide and methyl mercaptan potassium.
Further, the activated carbon supported CoL (Cl2) (CoL) metal complex be pentamethylene bromide modified activated carbon
Load C oL (Cl2) (CoL) metal complex.
Activated carbon supported CoL (Cl in the system for preparing dimethyl disulfide, the system2) (CoL) metal complex
As catalyst can effectively catalysis oxidation methyl mercaptan salt prepare dimethyl disulfide, it is reusable, and can and product it is fine
Separation, obtained product dimethyl disulfide conversion per pass reaches 97.3%, and once through yield is up to 76.7%, purity energy
Enough reach 100%.
The beneficial effects of the present invention are：
1) a kind of activated carbon supported CoL (Cl that the present invention is provided2) (CoL) metal complex and its can as catalyst
Apply in dimethyl disulfide is prepared, raw material sodium methyl mercaptide is strong alkali solution, and catalytic reaction need to be under certain temperature, pressure
Complete.By chemical graft mode by CoL (Cl2) to be supported on the catalyst structure that activated carbon obtains steady for (CoL) metal complex
It is fixed, it is reusable, alkaline-resisting, pressure-resistant, high temperature resistant and effective catalysis oxidation sodium methyl mercaptide system in reaction system can be realized
Standby dimethyl disulfide.
2) the characteristics of being based on activated carbon structure and excellent honest and clean wide material sources price, is conducive to urging the industry of agent as support materials
Metaplasia is produced, and plays a part of adsorption bleaching to product.
3) present invention is by introducing pentamethylene bromide and CoL (Cl2) (CoL) metal complex L, synthesize 1,5- dibromos
CoL (the Cl of pentane modification2) (CoL) metal complex, and loaded on the activated carbon, it has been prepared into activated carbon supported CoL
(Cl2) (CoL) metal complex this new function catalysis material, it is common crown ether metal complex as industrial production diformazan
Catalyst during base disulfide has established certain theoretical foundation.Activated carbon supported CoL (Cl2) (CoL) metal complex
Can well it be separated with product during dimethyl disulfide is prepared as catalyst, and specific ionization state CoL (Cl2)(CoL)
Metal complex catalyzed obtained product DMDS purity is high.
4) activated carbon supported CoL (Cl in the system for preparing dimethyl disulfide that the present invention is provided, the system2)(CoL)
Metal complex as catalyst can effectively catalysis oxidation methyl mercaptan salt prepare dimethyl disulfide, it is reusable, and energy
Separated well with product, obtained product dimethyl disulfide yield is up to 76.7%, and purity can reach 100%.
Brief description of the drawings
Fig. 1 is the process units schematic flow diagram of dimethyl disulfide；1- high purity oxygen gas devices, 2- oxygen pressure reducing valves, 3-
Oxygen gauge, 4- reactors, 5- valves, 6- temperature controllers, 7- rotating speed controllers.
Fig. 2 is free state CoL (Cl2) (CoL) (a) and activated carbon supported CoL (Cl2) (CoL) (b) catalysis oxidation methyl mercaptan
Sodium distinguishes corresponding product DMDS schematic diagrames.
Embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.Unreceipted tool in preferred embodiment
The experimental method of concrete conditions in the establishment of a specific crime, generally according to normal condition, illustrated embodiment is to preferably be said to present disclosure
It is bright, but be not that present disclosure is only limitted to illustrated embodiment.So those skilled in the art are according to foregoing invention
Content carries out nonessential modifications and adaptations to embodiment, still falls within protection scope of the present invention.
The catalyst activity charcoal load C oL (Cl of embodiment 12) (CoL) metal complex preparation
1.CoL(Cl2) (CoL) metal complex synthesis
Weigh 0.1317g (0.5mmol) ligand Ls and 0.2379g CoCl2.6H2O (1mmol) is dissolved in 20mL water, in room
Uniform stirring 2h under the conditions of temperature, it is observed that after solution colour gradually becomes light blue, continuing to stir 2h.Obtain CoL (Cl2)
(CoL) the metal complex aqueous solution.
The preparation of 2.1,5- dibromo pentanes modified activated carbon (AC-Br)
Dried 10g active carbon powders (AC) are weighed with concentrated nitric acid aqueous solution V (HNO3):V(H2O)=1:2 in 60 DEG C
24h is impregnated in 250mL beakers, is then washed with deionized water to neutrality, in 60 DEG C of drying in oven, vacuum drying chamber is put into afterwards
In in 105 DEG C vacuum drying, obtain the activated carbon (AC-T) of nitric acid treatment, it is standby.
The accurate dried activated carbon 2.0g of nitrification that weighs is in 100mL round-bottomed flasks, the DMF50mL added steam again after,
K2CO32.0g, adds and 8h is reacted under 2gNaH condition of ice bath, adds 2.0g 1, it is anti-after 80 DEG C that pentamethylene bromide reacts at room temperature 1h
Answer 24 hours.Through cooling, suction filtration, washing dried 1, the modified activated carbon 2.03g of pentamethylene bromide.
3. activated carbon supported CoL (Cl2) (CoL) metal complex preparation
The activated carbon 1g for taking dried pentamethylene bromide modified is added to CoL (Cl2) (CoL) metal complex water
Solution, the DMF50mL, K added steam again after2CO31.0g reacts 12 hours in 80 DEG C.Be cooled to room temperature, suction filtration, with DMF and
Deionized water wash respectively three times it is vacuum dried after activated carbon supported CoL (Cl2) (CoL) metal complex 0.912g.
Activated carbon supported CoL (the Cl of embodiment 22) (CoL) metal complex is used as catalyst preparation dimethyl disulfide
Device and method
Prepare the process units of dimethyl disulfide, including reactor 4, high purity oxygen gas device 1, temperature controller 6 and turn
Fast controller 7；The high purity oxygen gas device 1 is connected by pipeline with the top of reactor 4, and the pipeline is additionally provided with oxygen decompression
Valve 2 and oxygen gauge 3；Stirring and heater are provided with the reactor 4, is controlled by temperature controller 6 and rotating speed
Instrument 7 controls rotating speed and temperature in reactor；The top of reactor 4 is additionally provided with charging aperture, discharging opening, exhaust outlet and cooling
Water circulating pipe.Cooling water circulation pipeline adjusts temperature in reactor by recirculated cooling water.The process units signal stream
Journey figure is as shown in Figure 1.
The method that dimethyl disulfide is prepared using the process units for preparing dimethyl disulfide：Weigh sodium methyl mercaptide solution
Pour into reactor, weigh activated carbon supported CoL (Cl2) (CoL) metal complex add reactor in, tighten spiral shell on reactor
Bolt, closes charging aperture valve and discharging opening valve.Control cabinet power supply is opened, regulation control cabinet temperature button to required temperature is adjusted
Save rotating speed, cooling water control temperature in the kettle.Treat that temperature reaches setting value, pressure needed for opening oxygen valve regulation to reaction simultaneously starts
Recording reacting time.Reaction first closing control case power supply, the valve closed during oxygen channel after terminating, close oxygen decompression
Valve, opening atmospheric valve opens discharging opening valve after gas is drained and obtains product.Product is separated, by filtering, extracting
To dimethyl disulfide.
The method that embodiment 3 prepares dimethyl disulfide
Take 400mL sodium methyl mercaptides solution (mass fraction of sodium methyl mercaptide is 18%) and the activated carbon supported CoL (Cl of 0.1g2)
(CoL) oxidation reaction 80min occurs in the reaction unit that oxygen pressure is 0.6MPa, temperature is 55 DEG C for metal complex, obtains
Dimethyl disulfide.The conversion per pass of sodium methyl mercaptide reaches 89.4%, the once through yield of dimethyl disulfide reaches 42.6%,
Product purity is 100%.
The method that embodiment 4 prepares dimethyl disulfide
Take 500mL sodium methyl mercaptides solution (mass fraction of sodium methyl mercaptide is 18%) and the activated carbon supported CoL (Cl of 0.5g2)
(CoL) oxidation reaction 50min occurs in the reaction unit that oxygen pressure is 1.0MPa, temperature is 75 DEG C for metal complex, obtains
Dimethyl disulfide.The conversion per pass of sodium methyl mercaptide reaches 93.6%, the once through yield of dimethyl disulfide reaches 72.3%,
Product purity is 100%.
The method that embodiment 5 prepares dimethyl disulfide
Take 450mL sodium methyl mercaptides solution (mass fraction of sodium methyl mercaptide is 18%) and the activated carbon supported CoL (Cl of 0.2g2)
(CoL) oxidation reaction 60min occurs in the reaction unit that oxygen pressure is 0.7MPa, temperature is 65 DEG C for metal complex, obtains
Dimethyl disulfide.The conversion per pass of sodium methyl mercaptide reaches 97.3%, the once through yield of dimethyl disulfide reaches 76.7%,
Product purity is 100%.
Free state CoL (the Cl of embodiment 62) (CoL) metal complex and activated carbon supported CoL (Cl2) (CoL) metal combination
Thing catalytic performance is contrasted
450g sodium methyl mercaptides solution (sodium methyl mercaptide content 18%), rotating speed 600r/min, pressure is 0.7MPa, reaction time
60min, 65 DEG C of reaction temperature, catalyst amount is respectively CoL (Cl2) (CoL) metal complex 160ppm and activated carbon supported
CoL(Cl2) (CoL) metal complex 0.2g.(a) substantially can be found that the oxygen diaza of free state four hat with (b) contrast in Fig. 2
Ether cobalt metal compounding (CoL (Cl2) (CoL)) be dissolved completely in product DMDS, and use activated carbon supported four oxygen diaza
Crown ether cobalt metal compounding (AC-CoL (Cl2) (CoL)) obtain oil phase product as catalyst and solution is clearly separated, upper strata oil
It is mutually faint yellow i.e. product (DMDS).By following table it can be seen that with (AC-CoL (Cl2) (CoL)) and as catalyst obtain product receive
Rate is 76.7%, with respect to free state CoL (Cl2) the obtained product yield of (CoL) catalyst declines, but obtained product DMDS is pure
Spend for 100%.This is likely to be activated carbon supported CoL (Cl2) (CoL) catalyst is by Co metals and the oxygen phenodiazine of complex four
Miscellaneous crown ether (L) is obtained with certain stability by complexing, and activated carbon changes crown ether as the introducing of support materials
The stability of ring, makes its crown ether cyclic structure be changed under the conditions of reaction under high pressure, thus cause it is activated carbon supported after urge
Agent catalytic activity is reduced.
The performance comparison of two kinds of catalyst of table
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to skill of the invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (13)
1. activated carbon supported CoL (Cl2) (CoL) metal complex preparation method, it is characterised in that pass through chemical graft method
By CoL (Cl2) (CoL) metal complex is supported on modified activated carbon, obtains activated carbon supported CoL (Cl2) (CoL) metal combination
Thing；The modified activated carbon is pentamethylene bromide modified activated carbon.
2. preparation method according to claim 1, it is characterised in that the CoL (Cl2) (CoL) metal complex and 1,5-
The mass ratio of dibromo pentane modified activated carbon is 0.1：0.5~2.
3. preparation method according to claim 1, it is characterised in that modified activated carbon is added into CoL (Cl2) (CoL) metal
In the complex aqueous solution, in DMF, K2CO3In the presence of react, obtain activated carbon supported CoL (Cl2) (CoL) metal complex；Institute
Modified activated carbon is stated for pentamethylene bromide modified activated carbon.
4. preparation method according to claim 1, it is characterised in that described 1, the preparation of pentamethylene bromide modified activated carbon
Method comprises the following steps：
1) it is washed with deionized after activated carbon is immersed in aqueous solution of nitric acid to neutrality, the activity of nitric acid treatment is obtained after drying
Charcoal；
2) take step 1) processing after activated carbon add DMF, K2CO3With NaH reactions, 1 is added, pentamethylene bromide reaction obtains 1,
Pentamethylene bromide modified activated carbon.
5. the activated carbon supported CoL (Cl that the preparation method described in claim any one of 1-4 is prepared2) (CoL) metal combination
Thing.
6. the activated carbon supported CoL (Cl described in claim 52) (CoL) metal complex as catalyst preparing dimethyl two
Application in thioether.
7. utilize the activated carbon supported CoL (Cl described in claim 52) (CoL) metal complex is used as catalyst preparation dimethyl
The method of disulfide, it is characterised in that methyl mercaptan salt is in activated carbon supported CoL (Cl2) catalysis of (CoL) metal complex issues
Raw oxidation reaction, obtains dimethyl disulfide.
8. method according to claim 7, it is characterised in that the methyl mercaptan salt includes sodium methyl mercaptide and methyl mercaptan potassium.
9. method according to claim 7, it is characterised in that the methyl mercaptan salt and activated carbon supported CoL (Cl2)(CoL)
The mass ratio of metal complex is 70~90:0.1~0.7.
10. method according to claim 7, it is characterised in that the temperature for occurring oxidation reaction is 50~80 DEG C；Oxidation is anti-
The time answered is 45~90min；The oxygen pressure of oxidation reaction is 0.5~1.0MPa.
11. a kind of system for preparing dimethyl disulfide, it is characterised in that the system is by methyl mercaptan salt, activated carbon supported CoL
(Cl2) (CoL) metal complex, oxygen and aqueous medium composition.
12. system according to claim 11, it is characterised in that the methyl mercaptan salt includes sodium methyl mercaptide and methyl mercaptan
Potassium.
13. system according to claim 11, it is characterised in that the activated carbon supported CoL (Cl2) (CoL) metal combination
Thing is pentamethylene bromide modified activated carbon load C oL (Cl2) (CoL) metal complex.
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| Title |
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| VICTOR N. NEMYKIN等: ""Preparation, characterization, and catalytic activity of synthetic carbon-supported (phthalocyaninato)cobalt-containing complexes in dodecane-1-thiol oxidation reaction"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 李红琦等: ""冠醚过渡金属配合物的制备"", 《无机化学》 * |
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