CN107029793B - Activated carbon supported metal complex and its application in dimethyl disulfide is being prepared as catalyst - Google Patents
Activated carbon supported metal complex and its application in dimethyl disulfide is being prepared as catalyst Download PDFInfo
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- CN107029793B CN107029793B CN201710286591.7A CN201710286591A CN107029793B CN 107029793 B CN107029793 B CN 107029793B CN 201710286591 A CN201710286591 A CN 201710286591A CN 107029793 B CN107029793 B CN 107029793B
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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 fields, and in particular to a kind of activated carbon supported metal complex and its prepare the application in dimethyl disulfide as catalyst.Activated carbon supported CoL (Cl provided by the invention2) (CoL) metal complex the preparation method comprises the following steps: by chemical graft method by CoL (Cl2) (CoL) metal complex is supported on modified activated carbon, obtain activated carbon supported CoL (Cl2) (CoL) metal complex；The modified activated carbon is pentamethylene bromide modified activated carbon.The catalyst structure is stablized, reusable, can be realized alkaline-resisting, the pressure-resistant, high temperature resistant in reaction system and effective catalysis oxidation methyl mercaptan salt prepares dimethyl disulfide.Catalyst of the invention can separate well during preparing dimethyl disulfide with product, and specific ionization state CoL (Cl2) (CoL) metal complex catalyzed obtained product purity height.For obtained product DMDS yield up to 76.7%, 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 as catalyst in preparation two
Application in methyl disulfide, specially activated carbon supported CoL (Cl2) (CoL) metal complex and its made as catalyst
Application in standby dimethyl disulfide.
Background technique
Dimethyl disulfide (DMDS) becomes 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 severe toxicity, and raw material is not easy to obtain,
Many restrictions cause the producer of domestic production now less.
Dimethyl disulfide synthetic method mainly has: methanol vulcanization, methyl mercaptan vulcanization, methyl mercaptan oxidizing process, sulfuric acid
Diformazan ester process.
1. dimethyl sulfate method
Dimethyl sulfate method 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 advantages of this method is that raw material is easy to get, and reaction condition is mild, process route relative maturity, both at home and abroad research compared with
More, China produces dimethyl disulfide based on the method at present.However, this method also suffers from certain drawbacks, raw material sulphuric acid two
Methyl esters belongs to toxic articles, once accident occurs, extremely serious to the harm of life and environment, and consumption of raw materials quota is higher.
2. methyl mercaptan oxidizing process
Methyl mercaptan oxidizing process is to react oxidation dehydration as raw material with oxygen using methyl mercaptan to produce dimethyl disulfide, mainly
Reaction equation are as follows:
Main technique are as follows: air and methyl mercaptan are passed through reactor with molar ratio for 1.25: 1, the item existing for catalyst
Temperature of reaction system is 0~200 DEG C under part, and pressure is 0.1~1.1MPa, and product obtains 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
There is a small amount of report outside, it is domestic temporarily to report that technology path is also immature, further research and develop without correlative study.
3. methanol vulcanization
Methanol vulcanization is using methanol, hydrogen sulfide and sulphur as waste dimethyl disulfide, and dominating process route has
One-stage process and two kinds of 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 are as follows:
CH3OH+H2S+S→CH3SSCH3+H2O
The method methanol conversion is 51.5%, and Main By product is methyl sulfide and carbon disulfide.Two-phase method be methanol and
Hydrogen sulfide, which first reacts, is made methyl mercaptan, and dimethyl disulfide, reaction equation is made in methyl mercaptan with reaction of Salmon-Saxl again are as follows:
CH3OH+H2S→CH3SH+H2O
2CH3SH+S→CH3SSCH3+H2S
Two-phase method methanol conversion per pass is 32%, and product is dimethyl sulfide, Main By product is carbon disulfide, first sulphur
Alcohol and diformazan polysulfide.By-product can be recycled inside reaction, not generate the three wastes substantially.The disadvantage is that: the route
Technique is relative complex, and technical equipment is more demanding, and the domestic factory that can reach the technical requirements is simultaneously few, need further to change
Into.
4. methyl mercaptan vulcanization
Methyl mercaptan vulcanization is directly to react to produce dimethyl disulfide as raw material using methyl mercaptan and sulphur, main reaction formula are as follows:
2CH3SH+S→CH3SSCH3+H2S
This method is divided into the progress of two steps, and the first step carries out in stirred reactor, and feedstock is than methyl mercaptan (mol): sulphur
(mol)=4: 1, temperature is 40 DEG C, pressure 0.55MPa, using A21 macroreticular resin as catalyst, dimethyl disulfide
Yield is 80%, makees catalyst, yield 78.5% using second triamine, by-product is dimethyl polythiaether.Product is through over cure
It is up to after changing hydrogen abjection step into progress second step reaction, the yield of dimethyl disulfide in jacketed pipe type reactor
98.5%.Simple using methyl mercaptan vulcanization route process CIMS, reaction condition is mild, and technology is lower with equipment requirement, is suitble to
Domestic industry is horizontal.Disadvantage: raw material methyl mercaptan is not easy to obtain, and is gaseous state under room temperature, normal pressure, and foul smelling, the current country are raw
The factory for producing methyl mercaptan is less, thus limits the popularization of the technique.
Methyl mercaptan salt oxidizing process is reacted with oxygen prepare diformazan in the presence of a catalyst using methyl mercaptan salt as raw material
Base disulfide, the method avoid the pollution in many and diverse process conditions and production process to environment, but to catalyst performance requirement
It is higher.
Azacrown ether containing is a kind of artificial ligand that nitrogen-atoms replaces the part oxygen atom on crown ether cycle to obtain.There are many grind
Study carefully and show that the nitrogen-atoms due to introducing has opposite soft base property, so that such ligand is to transition metal, heavy metal, alkali gold
Category, alkaline-earth metal plasma have special complexing, and mating reaction can not only occurs with positively charged ion in it, also can
It is complexed with negatively charged anion.And di mon mating compound in its ring system because, containing there are two nitrogen-atoms, causing it to mistake
Selectivity and the stability for crossing metal ion and heavy metal ion are more excellent.Free state di mon mating compound is used to be 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 separate well, product purity is not high, thus requires further improvement.It is strong alkali solution based on reaction system and reacted
Journey needs are completed under certain temperature, pressure, and then require that support materials are alkaline-resisting, pressure-resistant, high temperature resistant.
Therefore develop one kind in certain temperature, pressure and support materials alkaline-resisting, pressure-resistant, resistant to high temperature as catalyst to two
The industrial production of methyl disulfide has important industry meaning.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of activated carbon supported CoL (Cl2) (CoL) metal complex and
It is preparing the application in dimethyl disulfide as catalyst.Catalyst structure provided by the invention is stablized, reusable,
Effectively dimethyl disulfide can be prepared for catalysis oxidation methyl mercaptan salt, can be separated well with product, and specific ionization state CoL
(Cl2) (CoL) metal complex catalyzed obtained product purity height.
To achieve the above object, the technical solution of the present invention is as follows:
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 active carbon be pentamethylene bromide modified activated carbon.
Further, the CoL (Cl2) (CoL) metal complex and the mass ratio of pentamethylene bromide modified activated carbon be
0.1:0.5~2.
As a preference, described DMF, K2CO3With CoL (Cl2) (CoL) metal complex mass ratio be 50:0.5~
3:0.1.
Further, CoL (Cl is added in modified activated carbon2) in (CoL) metal complex aqueous solution, in DMF, K2CO3Deposit
In lower reaction, activated carbon supported CoL (Cl is obtained2) (CoL) metal complex；The modified activated carbon is modified for pentamethylene bromide
Active carbon.
The DMF can be replaced with benzene, toluene；The K2CO3Na can be used2CO3、NaHCO3Instead of.
As a preference, 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 buy on the market acquisition also by published
Method is prepared.
A kind of specific activated carbon supported CoL (Cl2) (CoL) metal complex preparation method: by pentamethylene bromide
CoL (Cl is added in modified activated carbon2) in (CoL) metal complex aqueous solution, DMF, K is added2CO3It is reacted 12 hours at 80 DEG C.It is cold
But to room temperature, filter, with DMF and deionized water wash respectively it is vacuum dried three times 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 the following steps are included:
1) it is washed with deionized after active carbon being immersed in aqueous solution of nitric acid to neutrality, obtains nitric acid treatment after dry
Active carbon；
2) step 1) is taken treated that DMF, K is added in active carbon2CO3It being reacted with NaH, adds 1, pentamethylene bromide reacts,
Obtain pentamethylene bromide modified activated carbon.
A kind of specific preparation method of pentamethylene bromide modified activated carbon: the active carbon powder (AC) after weighing drying
For 24 hours with concentrated nitric acid aqueous solution dipping, it is then washed with deionized water to neutrality, in 60 DEG C of drying in oven, it is dry to be put into vacuum later
It is dried in vacuo in dry case in 105 DEG C, obtains the active carbon (AC-T) of nitric acid treatment, it is spare.
DMF, K steam again after is added in active carbon after taking nitrification dry2CO3, it is added under NaH condition of ice bath and reacts, be added 1,
Pentamethylene bromide reacts 24 hours after reacting at room temperature 1h in 80 DEG C.It through cooling, filters, 1 after washing is dry, pentamethylene bromide changes
Active carbon after property.
As a preference, the volume ratio of nitric acid and aqueous medium in aqueous solution of nitric acid described in step 1) is 1:2.
As a preference, the temperature being immersed in aqueous solution of nitric acid in step 1) is 50~70 DEG C.
As a preference, active carbon and K in step 2)2CO3Mass ratio be 1:1~2.
As a preference, DMF, K described in step 2)2CO3Mass ratio with NaH is 50:1~3:1~3.
As a preference, active carbon and 1 in step 2), 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 preparation method described in one kind is prepared
(Cl2) (CoL) metal complex.
Activated carbon supported CoL (the Cl2) (CoL) metal complex structural formula are as follows:
Activated carbon supported CoL (the Cl that will be prepared by above-mentioned preparation method2) (CoL) metal complex carry out X penetrate
The test of line electron spectrum, obtained XPS spectrum figure are shown in composite material in addition to containing Elements C, N, O, Br, also containing a small amount of Co member
Element, it will be seen that load C oL (Cl2) after (CoL) metal complex, the peak Co that composite catalyst occurs, the electron energy of Co 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.The electron energy of Br3d by
65.9eV drops to 11.3eV, and energy obviously weakens, and is attributed to 1 ,-Br and the cooperation of the modified activated carbon surface of pentamethylene bromide
- NH on object L loses HBr bonding by condensation, and the electron energy of Br3d, which substantially reduces, further demonstrates that CoL (Cl2) (CoL) gold
Metal complex successfully loads on the activated carbon, and is strong chemical action.
The third object of the present invention is to provide activated carbon supported CoL (Cl described in one kind2) (CoL) metal complex work
The application in dimethyl disulfide is being prepared for catalyst.
CoL(Cl2) (CoL) metal complex prepared in dimethyl disulfide (DMDS) in catalysis oxidation sodium methyl mercaptide,
It is soluble in product dimethyl disulfide as catalyst, prevent catalyst and product be from separating well, product yield and production
Product purity is not high.CoL(Cl2) (CoL) metal complex be compund of aza crown ether have knot similar with crown compound
Structure feature, the oxygen heteroatom of ordered arrangement are conducive to the formation and stabilization of Oxygen adduct, improve oxygen carrying capability.In addition, passing through
Method modifies its structure, introduces methoxyl group, hydroxyl, halogen in aza-crown ether ring and waits lone pair electrons center function
Key both can be used to adjust the cavity size of crown ether, having can join by these specific three-dimensional effects of function base and electronic effect
With the coordination to metal ion.Enhance 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 has been 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 preparing dimethyl disulfide as catalyst
Secondary reuse, reduces production cost.
Activated carbon supported CoL (the Cl is utilized the object of the invention is also to provide a kind of2) (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 oxidation reaction occurs, 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 catalysis reaction need to be completed under certain temperature, pressure.It is logical
Cross chemical graft mode by catalyst be supported on the catalyst that active carbon obtains can be realized in reaction system it is alkaline-resisting, pressure-resistant,
High temperature resistant.
As a preference, the methyl mercaptan salt selects sodium methyl mercaptide.
It is as follows that dimethyl disulfide (DMDS) its reaction equation is produced using sodium methyl mercaptide oxidizing process:
4CH3SNa+O2+2H2O→2CH3SSCH3+4NaOH
Further, the methyl mercaptan salt and activated carbon supported CoL (Cl2) (CoL) metal complex mass ratio be 70~
90:0.1~0.7.
As a preference, the methyl mercaptan salt and activated carbon supported CoL (Cl2) (CoL) metal complex mass ratio
For 80~90:0.1~0.5.
As a preference, the methyl mercaptan salt and activated carbon supported CoL (Cl2) (CoL) metal complex mass ratio
For 81:0.2.
If other conditions are the same, catalyst amount is within the scope of the invention with the increase of catalyst amount
The conversion per pass of methyl mercaptan salt is 90%~97.3%, and when the mass ratio of methyl mercaptan salt and catalyst is 81:0.2, one way turns
Rate reaches 97.3%, and one-way yield is up to 76.7%.But as the increase DMDS one-way yield of catalyst amount drops instead
It is low, as the increase reaction rate of catalyst amount is accelerated, but it is not meant to that the yield of product will increase, because excessive urge
Agent can hinder the substance in reaction process to transmit instead.The change of catalyst amount has no effect on the purity of product DMDS and pure
Degree reaches 100%.In line with economic appropriate principle, the optimum quality ratio of raw material and the catalyst is 81:0.2 in the reaction.
Further, the temperature that oxidation reaction occurs 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 preference, the temperature that oxidation reaction occurs is 65 DEG C；The time of oxidation reaction is 60min；Oxidation reaction
Oxygen pressure be 0.7MPa.
The object of the invention is also to provide a kind of process units for preparing dimethyl disulfide, including it is reaction kettle, high-purity
Oxygen unit, temperature controller and revolving speed controller；The high purity oxygen gas device is described by connecting at the top of pipeline and reaction kettle
Pipeline is additionally provided with oxygen pressure reducing valve and oxygen gauge；It is provided with stirring and heating device in the reaction kettle, passes through temperature
Controller and revolving speed controller control revolving speed and temperature in reaction kettle；Feed inlet, discharging are additionally provided at the top of the reaction kettle
Mouth, exhaust outlet and cooling water circulating pipe.
The object of the invention is also 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.
The system for preparing dimethyl disulfide, activated carbon supported CoL (Cl in 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 one-way 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 provided by the invention2) (CoL) metal complex and its can as catalyst
It applies in preparing dimethyl disulfide, raw material sodium methyl mercaptide is strong alkali solution, and catalysis reaction need to be under certain temperature, pressure
It completes.By chemical graft mode by CoL (Cl2) to be supported on the catalyst structure that active carbon obtains steady for (CoL) metal complex
It is fixed, it is reusable, it can be realized alkaline-resisting, pressure-resistant, high temperature resistant and effective catalysis oxidation sodium methyl mercaptide system in reaction system
Standby dimethyl disulfide.
2) based on activated carbon structure and the excellent honest and clean feature of price from a wealth of sources, be conducive to urge the industry of agent as support materials
Metaplasia produces, and plays the role of adsorption bleaching to product.
3) present invention is by introducing pentamethylene bromide and CoL (Cl2) (CoL) metal complex L, synthesize 1,5- dibromo
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 basis.Activated carbon supported CoL (Cl2) (CoL) metal complex
It can be separated well with product during preparing dimethyl disulfide as catalyst, and specific ionization state CoL (Cl2)(CoL)
Metal complex catalyzed obtained product DMDS purity is high.
4) system provided by the invention for preparing dimethyl disulfide, activated carbon supported CoL (Cl in the system2)(CoL)
Metal complex as catalyst can effectively catalysis oxidation methyl mercaptan salt prepare dimethyl disulfide, it is reusable, and energy
It is separated well with product, for obtained product dimethyl disulfide yield up to 76.7%, purity can reach 100%.
Detailed description of the invention
Fig. 1 is the process units schematic flow diagram of dimethyl disulfide；1- high purity oxygen gas device, 2- oxygen pressure reducing valve, 3-
Oxygen gauge, 4- reaction kettle, 5- valve, 6- temperature controller, 7- revolving speed controller.
Fig. 2 is free state CoL (Cl2) (CoL) (a) and activated carbon supported CoL (Cl2) (CoL) (b) catalysis oxidation methyl mercaptan
Sodium respectively corresponds product DMDS schematic diagram.
Specific embodiment
Hereinafter reference will be made to the drawings, and the preferred embodiment of the present invention is described in detail.Tool is not specified in preferred embodiment
The experimental method of concrete conditions in the establishment of a specific crime, usually according to normal condition, illustrated embodiment are to preferably say to the contents of the present invention
It is bright, but be not that the contents of the present invention are 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.
1 catalyst activity charcoal load C oL (Cl of embodiment2) (CoL) metal complex preparation
1.CoL(Cl2) (CoL) metal complex synthesis
Weigh 0.1317g (0.5mmol) ligand L and 0.2379g CoCl2.6H2O (1mmol) is dissolved in 20mL water, in room
Uniform stirring 2h under the conditions of temperature, it can be observed that continuing to stir 2h after solution colour gradually becomes light blue.Obtain CoL (Cl2)
(CoL) metal complex aqueous solution.
The preparation of 2.1,5- dibromo pentane modified activated carbon (AC-Br)
10g active carbon powder (AC) concentrated nitric acid aqueous solution V (HNO after weighing drying3):V(H2O)=1:2 in 60 DEG C
It impregnates for 24 hours, is then washed with deionized water to neutrality in 250mL beaker, in 60 DEG C of drying in oven, be put into vacuum oven later
In in 105 DEG C be dried in vacuo, obtain the active carbon (AC-T) of nitric acid treatment, it is spare.
The DMF50mL steam again after is added in 100mL round-bottomed flask in active carbon 2.0g after accurately weighing nitrification drying,
K2CO32.0g is added under 2gNaH condition of ice bath and reacts 8h, addition 2.0g 1, anti-in 80 DEG C after pentamethylene bromide room temperature reaction 1h
It answers 24 hours.It through cooling, filters, 1 after washing is dry, the modified active carbon 2.03g of pentamethylene bromide.
3. activated carbon supported CoL (Cl2) (CoL) metal complex preparation
The modified active carbon 1g of pentamethylene bromide after taking drying is added to CoL (Cl2) (CoL) metal complex water
Solution adds DMF50mL, K steam again after2CO31.0g reacts 12 hours in 80 DEG C.Be cooled to room temperature, filter, with DMF and
Deionized water wash respectively it is vacuum dried three times after activated carbon supported CoL (Cl2) (CoL) metal complex 0.912g.
Activated carbon supported CoL (the Cl of embodiment 22) (CoL) metal complex is as catalyst preparation dimethyl disulfide
Device and method
It prepares the process units of dimethyl disulfide, including reaction kettle 4, high purity oxygen gas device 1, temperature controller 6 and turns
Fast controller 7；For the high purity oxygen gas device 1 by connecting at the top of pipeline and reaction kettle 4, the pipeline is additionally provided with oxygen decompression
Valve 2 and oxygen gauge 3；It is provided with stirring and heating device in the reaction kettle 4, is controlled by temperature controller 6 and revolving speed
Instrument 7 controls revolving speed and temperature in reaction kettle；Feed inlet, discharge port, exhaust outlet and cooling are additionally provided at the top of the reaction kettle 4
Water circulating pipe.Cooling water circulating pipe adjusts temperature in reaction kettle by recirculated cooling water.The process units signal stream
Journey figure is as shown in Figure 1.
It utilizes the method that the process units for preparing dimethyl disulfide prepares dimethyl disulfide: weighing sodium methyl mercaptide solution
It pours into reaction kettle, weighs activated carbon supported CoL (Cl2) (CoL) metal complex be added reaction kettle in, tighten spiral shell on reaction kettle
Bolt closes feed inlet valve and discharge port valve.Control cabinet power supply is opened, control cabinet temperature button is adjusted to required temperature, adjusts
Save revolving speed, cooling water control temperature in the kettle.Setting value is reached to temperature, open pressure needed for oxygen valve is adjusted to reaction and is started
Recording reacting time.Control cabinet power supply is first closed after reaction, closes the valve during oxygen channel, closes oxygen decompression
Valve, opening blow valve open discharge port valve after gas drains and obtain product.Product is separated, by filtering, extracting
To dimethyl disulfide.
The method that embodiment 3 prepares dimethyl disulfide
Take 400mL sodium methyl mercaptide 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 one-way yield of dimethyl disulfide reaches 42.6%,
Product purity is 100%.
The method that embodiment 4 prepares dimethyl disulfide
Take 500mL sodium methyl mercaptide 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 one-way yield of dimethyl disulfide reaches 72.3%,
Product purity is 100%.
The method that embodiment 5 prepares dimethyl disulfide
Take 450mL sodium methyl mercaptide 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 one-way yield of dimethyl disulfide reaches 76.7%,
Product purity is 100%.
6 free state CoL (Cl of embodiment2) (CoL) metal complex and activated carbon supported CoL (Cl2) (CoL) metal combination
The comparison of object catalytic performance
450g sodium methyl mercaptide solution (sodium methyl mercaptide content 18%), revolving speed 600r/min, pressure 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) and (b) comparison is obviously it can be found that four oxygen diaza of free state hat 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)) as catalyst obtain oily phase product and solution is clearly separated, upper layer oil
It is product (DMDS) that phase, which is faint yellow,.By following table it can be seen that with (AC-CoL (Cl2) (CoL)) catalyst is used as to obtain product receipts
Rate is 76.7%, opposite free state CoL (Cl2) product yield decline that (CoL) catalyst obtains, but obtained product DMDS is pure
Degree is 100%.This is likely to be activated carbon supported CoL (Cl2) (CoL) catalyst is by four oxygen phenodiazine of Co metal and complex
Miscellaneous crown ether (L) obtains the stability for having certain by complexing, and active carbon changes crown ether as the introducing of support materials
The stability of ring makes its crown ether cyclic structure change under the conditions of reaction under high pressure, so as to cause urging after activated carbon supported
Agent catalytic activity reduces.
The performance comparison of two kinds of catalyst of table
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (12)
1. activated carbon supported CoL (Cl2) (CoL) metal complex preparation method, which is characterized in that pass through chemical graft method
By CoL (Cl2) (CoL) metal complex is supported on modified activated carbon, obtain activated carbon supported CoL (Cl2) (CoL) metal combination
Object；The modified activated carbon is pentamethylene bromide modified activated carbon；CoL (the Cl2) L in (CoL) metal complex is
Four oxygen diaza crown ethers.
2. preparation method according to claim 1, which is characterized 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, which is characterized in that CoL (Cl is added in modified activated carbon2) (CoL) metal
In complex aqueous solution, in DMF, K2CO3In the presence of react, obtain activated carbon supported CoL (Cl2) (CoL) metal complex；Institute
Stating modified activated carbon is pentamethylene bromide modified activated carbon.
4. preparation method according to claim 1, which is characterized in that described 1, the preparation of pentamethylene bromide modified activated carbon
Method the following steps are included:
1) it is washed with deionized after active carbon being immersed in aqueous solution of nitric acid to neutrality, the activity of nitric acid treatment is obtained after dry
Charcoal；
2) step 1) is taken treated that DMF, K is added in active carbon2CO3It is reacted with NaH, adds 1, pentamethylene bromide reaction obtains 1,
Pentamethylene bromide modified activated carbon.
5. the activated carbon supported CoL (Cl that the described in any item preparation methods of claim 1-4 are prepared2) (CoL) metal combination
Object.
6. activated carbon supported CoL (Cl described in claim 52) (CoL) metal complex as catalyst preparing dimethyl two
Application in thioether.
7. utilizing activated carbon supported CoL (Cl described in claim 52) (CoL) metal complex is as catalyst preparation dimethyl
The method of disulfide, which is characterized 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. the method according to the description of claim 7 is characterized in that the methyl mercaptan salt includes sodium methyl mercaptide and methyl mercaptan potassium.
9. the method according to the description of claim 7 is characterized 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. the method according to the description of claim 7 is characterized in that the temperature that oxidation reaction occurs 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, which is characterized in that the system is as described in methyl mercaptan salt, claim 5
Activated carbon supported CoL (Cl2) (CoL) metal complex, oxygen and aqueous medium composition.
12. system according to claim 11, which is characterized in that the methyl mercaptan salt includes sodium methyl mercaptide and methyl mercaptan
Potassium.
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Non-Patent Citations (2)
| Title |
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| "Preparation, characterization, and catalytic activity of synthetic carbon-supported (phthalocyaninato)cobalt-containing complexes in dodecane-1-thiol oxidation reaction";Victor N. Nemykin等;《Journal of Molecular Catalysis A: Chemical》;20060906;第264卷;第103-109页 * |
| "冠醚过渡金属配合物的制备";李红琦等;《无机化学》;19860630(第2期);第108-111页 * |
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