CN106984362A - Activated carbon supported Tetrasulphated phthalcyanine cobalt and its application as catalyst in dimethyl disulfide is prepared - Google Patents
Activated carbon supported Tetrasulphated phthalcyanine cobalt and its application as catalyst in dimethyl disulfide is prepared Download PDFInfo
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- CN106984362A CN106984362A CN201710286780.4A CN201710286780A CN106984362A CN 106984362 A CN106984362 A CN 106984362A CN 201710286780 A CN201710286780 A CN 201710286780A CN 106984362 A CN106984362 A CN 106984362A
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- activated carbon
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- tetrasulphated phthalcyanine
- dimethyl disulfide
- tetrasulphated
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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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
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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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 Tetrasulphated phthalcyanine cobalt and its application as catalyst in dimethyl disulfide is prepared.The preparation method for the activated carbon supported Tetrasulphated phthalcyanine cobalt that the present invention is provided is：Four sulfonic acid chloride Cobalt Phthalocyanines are supported on modified activated carbon by chemical graft method, activated carbon supported Tetrasulphated phthalcyanine cobalt (AC CoPcS) is obtained；The modified activated carbon is ethylenediamine modified activated carbon.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 present invention with AC CoPcS as catalyst during dimethyl disulfide is prepared can and product separate well, and the obtained product yield of specific ionization state CoPcS catalysis, DMDS purity are all high.Obtained product DMDS yields are up to 86.8%, and the purity of product can reach 100%.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of activated carbon supported Tetrasulphated phthalcyanine cobalt and its be used as catalyst
Application in dimethyl disulfide is prepared.
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.
In recent years, metal phthalocyanine and its derivative are widely used in catalysis due to its special property and novel function
Field of material technology.The research report that metal phthalocyanine is used for oxidation reaction as catalyst is numerous, wherein studying most commonly used
It is Tetrasulphated phthalcyanine (iron, copper, manganese, cobalt, nickel).There are some researches show degree of association of the Phthalocyanine in reaction medium is to it
Catalytic performance has large effect, and it is easily formed dimer even polymer as catalyst in the solution so that metal phthalein
The active site of the big plane axial coordination of cyanines is reduced, so as to cause catalytic efficiency to reduce.In order to reduce Phthalocyanine shape in the solution
Into dimer or polymer, its catalytic activity is improved, seeks appropriate approach and solves this problem into the focus of research.
Therefore develop it is a kind of in certain temperature, pressure and alkaline-resisting, pressure-resistant, resistant to elevated temperatures metal phthalocyanine loaded material as urging
Agent has important industry meaning to the industrial production of dimethyl disulfide.
The content of the invention
In view of this, it is an object of the invention to provide a kind of activated carbon supported Tetrasulphated phthalcyanine cobalt and its conduct catalysis
Application of the agent in dimethyl disulfide is prepared.The catalyst structure that the present invention is provided is stable, reusable, can effectively urge
Change oxidation methyl mercaptan salt and prepare dimethyl disulfide, can well be separated with product, and the production that specific ionization state CoPcS catalysis is obtained
Product yield, DMDS purity are all high.
To achieve the above object, the technical scheme is that：
The preparation method of activated carbon supported Tetrasulphated phthalcyanine cobalt, is born four sulfonic acid chloride Cobalt Phthalocyanines by chemical graft method
It is loaded on modified activated carbon, obtains activated carbon supported Tetrasulphated phthalcyanine cobalt (AC-CoPcS)；The modified activated carbon is ethylenediamine
Modified activated carbon.
Further, the mass ratio of the Tetrasulphated phthalcyanine cobalt and ethylenediamine modified activated carbon is 0.1：0.5~3.5.
Further, the preparation method comprises the following steps：
1) take Tetrasulphated phthalcyanine cobalt to be dissolved in DMF, add SOCl2Reaction, obtains four modified sulfonic acid chloride Cobalt Phthalocyanines molten
Liquid；
2) ethylenediamine modified activated carbon is added in above-mentioned four modified sulfonic acid chloride phthalocyanine cobalt liquors and reacted, obtain activated carbon
Load Tetrasulphated phthalcyanine cobalt (AC-CoPcS).
The DMF can be replaced with benzene, toluene；The SOCl2It can be replaced with benzene sulfonyl chloride, sulfonic acid chloride.
As a preferred embodiment, step 1) described DMF, SOCl2Mass ratio with Tetrasulphated phthalcyanine cobalt is 80-120：3~
10：0.1.
As a preferred embodiment, step 1) in the temperature of reaction be 70~85 DEG C, time of reaction is 20~26h.
As a preferred embodiment, step 2) in the temperature of reaction be 40~50 DEG C, time of reaction is 10~15h.
The Tetrasulphated phthalcyanine cobalt (AC-CoPcS) can commercially buy acquisition and is also prepared into by disclosed method
Arrive.
A kind of specific preparation method of activated carbon supported Tetrasulphated phthalcyanine cobalt：Tetrasulphated phthalcyanine cobalt is taken to be dissolved in DMF
In, add SOCl220~26h is reacted at 70~85 DEG C, the remaining unreacted SOCl of 50 DEG C of vacuum distillations is cooled to2, obtain modified
Four sulfonic acid chloride phthalocyanine cobalt liquors；Ethylenediamine modified activated carbon is added 40 in above-mentioned four modified sulfonic acid chloride phthalocyanine cobalt liquors
10~15h is reacted at~50 DEG C, taking-up is cooled to room temperature.CoPcS and CoPc (SO2Cl)4All be highly soluble in water therefore, spend from
Sub- water can remove remaining unreacted phthalocyanine derivates, be put into 60 DEG C of dryings in baking oven, produce ethylenediamine modified activated carbon
Load Tetrasulphated phthalcyanine cobalt (AC-CoPcS).
Further, the preparation method of the ethylenediamine 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 (AT-T)；
2) take step 1) processing after activated carbon add SOCl2React to obtain chloride activated carbon；Chloride activated carbon is added
Enter into the DMF solution of ethylenediamine reaction, obtain ethylenediamine modified activated carbon (AC-E).
A kind of specific preparation method of ethylenediamine modified activated carbon：Weigh dried active carbon powder (AC) and use dense nitre
Aqueous acid impregnates 24h, is then washed with deionized water to neutrality, in 60 DEG C of drying in oven, is put into afterwards in vacuum drying chamber
In 105 DEG C of vacuum drying, the activated carbon (AC-T) of nitric acid treatment is obtained, it is standby.The dried activated carbon of nitrification is taken to add SOCl2In
Back flow reaction 12h at 80 DEG C, reaction is warming up to 130 DEG C after terminating and is evaporated remaining unreacted SOCl2, it is cooled to room temperature and obtains acyl chlorides
Change activated carbon；Chloride activated carbon is added to 50 DEG C of reaction 8h in the DMF solution of ethylenediamine, room temperature is cooled to, spends respectively
Ionized water, DMF and absolute ethyl alcohol remove remaining unreacted EDA, and in 60 DEG C of drying in oven, vacuum drying chamber is put into afterwards
In in 105 DEG C vacuum drying, obtain ethylenediamine modification activated carbon fiber (AC-E).
As a preferred embodiment, in the preparation method of ethylenediamine modified activated carbon, step 1) described in aqueous solution of nitric acid
The volume ratio of nitric acid and aqueous medium is 1:2.
As a preferred embodiment, in the preparation method of ethylenediamine modified activated carbon, step 1) in be immersed in aqueous solution of nitric acid
Temperature be 50~70 DEG C.
As a preferred embodiment, in the preparation method of ethylenediamine modified activated carbon, step 2) in activated carbon and SOCl2Quality
Than for 2：3-10.
As a preferred embodiment, in the preparation method of ethylenediamine modified activated carbon, step 2) described in SOCl2, ethylenediamine with
DMF mass ratio is 3-10：3-8：100.
The second object of the present invention is to provide the activated carbon supported tetrasulfonic acid that a kind of described preparation method is prepared
Base Cobalt Phthalocyanine.
The structural formula of the activated carbon supported Tetrasulphated phthalcyanine cobalt is：
The activated carbon supported Tetrasulphated phthalcyanine cobalt prepared by above-mentioned preparation method is subjected to X-ray electron spectrum
Test, obtained XPS spectrum figure is shown in activated carbon supported Tetrasulphated phthalcyanine cobalt except containing Elements C, N, O, also containing a small amount of
Co elements, Co electron energy is 789.1Ev.Because phthalocyanine load capacity is smaller, so high-resolution peak noise is larger, still
It can be seen that clearly there is peak, show that CoPcS is loaded up.Cl2p electron energy is dropped to by 205.9eV
198.3eV, energy dropoff is attributed to the-NH2 and the tetrasulfonic acid base cobalt phthalein mountain valley with clumps of trees and bamboo of the activated carbon surface of ethylenediamine modification-SO2Cl leads to
Cross condensation and lose HCl and bonding, the reduction combination of Cl2p electron energy can be changed, and further demonstrate that tetrasulfonic acid Ji Taiqing
Cobalt 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 Tetrasulphated phthalcyanine cobalt as catalyst
Application in dimethyl disulfide is prepared.
Tetrasulphated phthalcyanine cobalt (CoPcS), during catalysis oxidation sodium methyl mercaptide prepares dimethyl disulfide (DMDS)
It is soluble in product dimethyl disulfide so that catalyst and product can not be separated well, product yield and product purity are not
It is high.Activated carbon supported Tetrasulphated phthalcyanine cobalt prepared by the present invention is by way of chemical graft by the tetrasulfonic acid Ji Taiqing of synthesis
Cobalt is loaded on modified activated carbon, and obtained AC-CoPcS can well be separated as catalyst with product, and specific ionization
It is all high that state CoPcS is catalyzed obtained product yield, DMDS purity.This be due to activated carbon (AC) be a kind of pore structure it is flourishing,
The big porous carbonaceous material of specific surface area can be effectively by sodium methyl mercaptide absorption on hole or surface, with effectively contacting for catalyst
Area increase, obtained product DMDS yields increase.The activated carbon supported Tetrasulphated phthalcyanine cobalt is being prepared as catalyst
It can be repeatedly used in dimethyl disulfide, reduce production cost；Secondly, the superpower adsorption bleaching of activated carbon causes production
The purity of product can reach 100%.
The present invention also aims to provide a kind of by the use of described activated carbon supported Tetrasulphated phthalcyanine cobalt to be used as catalysis
The method that agent prepares dimethyl disulfide, it is anti-that oxidation occurs under the catalysis of activated carbon supported Tetrasulphated phthalcyanine cobalt for methyl mercaptan salt
Should, 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 mass ratio of the methyl mercaptan salt and activated carbon supported Tetrasulphated phthalcyanine cobalt is 70~90:0.1~
0.9。
As a preferred embodiment, the mass ratio of the methyl mercaptan salt and activated carbon supported Tetrasulphated phthalcyanine cobalt is 80~90:
0.3~0.9.
As a preferred embodiment, the mass ratio of the methyl mercaptan salt and activated carbon supported Tetrasulphated phthalcyanine cobalt is 81:0.4.
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, 92.2%~98.4%, is 81 in the mass ratio of methyl mercaptan salt and catalyst：One way when 0.4
Conversion ratio reaches 98.4%.But reduced on the contrary with the increase DMDS once through yields of catalyst amount, with catalyst amount
Increase reaction rate to accelerate, but be not meant to that the yield of product can increase, because excessive catalyst can hinder reaction on the contrary
During material transmission.The change of catalyst amount has no effect on product DMDS purity and purity reaches 100%.In line with warp
Help appropriate principle, the optimum quality ratio of raw material and the catalyst is 81 in the reaction：0.4.
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 0.9MPa.
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, it is characterised in that the system
It is made up of methyl mercaptan salt, activated carbon supported Tetrasulphated phthalcyanine cobalt, oxygen and aqueous medium.
Further, the methyl mercaptan salt includes sodium methyl mercaptide and methyl mercaptan potassium.
Further, the activated carbon supported Tetrasulphated phthalcyanine cobalt is that ethylenediamine modified activated carbon loads Tetrasulphated phthalcyanine
Cobalt.
Activated carbon supported Tetrasulphated phthalcyanine cobalt is used as catalyst in the system for preparing dimethyl disulfide, the system
Can effectively catalysis oxidation methyl mercaptan salt prepare dimethyl disulfide, it is reusable, and can and product separate well, obtain
Product dimethyl disulfide yield up to 86.8%, purity can reach 100%.
The beneficial effects of the present invention are：
1) present invention is provided a kind of activated carbon supported Tetrasulphated phthalcyanine cobalt and its can be applied in system as catalyst
In standby dimethyl disulfide, raw material sodium methyl mercaptide is strong alkali solution, and catalytic reaction need to be completed under certain temperature, pressure.It is logical
Cross chemical graft mode and Tetrasulphated phthalcyanine cobalt is supported on the catalyst structure stabilization that activated carbon is obtained, reusable, energy
Enough realize alkaline-resisting in reaction system, pressure-resistant, high temperature resistant and effective catalysis oxidation sodium methyl mercaptide prepares 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) activated carbon supported Tetrasulphated phthalcyanine cobalt of the invention by way of chemical graft by the tetrasulfonic acid base of synthesis
Phthalein mountain valley with clumps of trees and bamboo cobalt is loaded on modified activated carbon, and obtained AC-CoPcS can well be separated as catalyst with product, and ratio
It is all high that free state CoPcS is catalyzed obtained product yield, DMDS purity.This is due to that activated carbon (AC) is a kind of pore structure hair
Reach, the porous carbonaceous material that specific surface area is big effectively can adsorb sodium methyl mercaptide on hole or surface, effective with catalyst
Contact area increase, obtained product DMDS yields are up to 86.8%.Secondly, the superpower adsorption bleaching of activated carbon causes product
Purity can reach 100%.
4) activated carbon supported Tetrasulphated phthalcyanine cobalt in the system for preparing dimethyl disulfide that the present invention is provided, the system
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 yield is up to 87.4%, 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 CoPcS (a) and the difference corresponding product DMDS signals of AC-CoPcS (b) catalysis oxidations sodium methyl mercaptide
Figure.
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 AC-CoPcS of embodiment 1 preparation
1. the preparation of ethylenediamine modified activated carbon (AC-E)
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.
It is accurate to weigh dried activated carbon (AC-T) 2.0g of nitrification, add 5mL SOCl2, in back flow reaction at 80 DEG C
12h, reaction is warming up to 130 DEG C after terminating and is evaporated remaining unreacted SOCl2, it is cooled to room temperature and obtains chloride activated carbon.By 5mL
Ethylenediamine (EDA) is dissolved in 100mLDMF, in the AC for adding above-mentioned chloride, 50 DEG C of reaction 8h, is cooled to room temperature, is spent respectively
Ionized water, DMF and absolute ethyl alcohol remove remaining unreacted EDA, and in 60 DEG C of drying in oven, vacuum drying chamber is put into afterwards
In in 105 DEG C vacuum drying, obtain ethylenediamine modification activated carbon fiber (AC-E).
2. the preparation of activated carbon supported tetrasulfonic acid base phthalein mountain valley with clumps of trees and bamboo cobalt (AC-CoPcS)
It is accurate to weigh in 0.1g CoPcS dissolvings 100mLDMF, add 5mL SOCl2, 24h is reacted at 75 DEG C, is cooled to 50
The remaining unreacted SOCl of DEG C vacuum distillation2, produce four modified sulfonic acid chloride cobalt phthalocyanine (CoPc (SO2Cl)4) solution for standby.
AC-E after 2g is dried in vacuo adds above-mentioned CoPc (SO2Cl)4In solution, 12h is reacted at 45 DEG C, taking-up is cooled to room temperature.
CoPcS and CoPc (SO2Cl)4All it is highly soluble in water therefore, remaining unreacted phthalocyanine derivates can be gone with deionized water
Remove, be put into 60 DEG C of dryings in baking oven, produce AC-CoPcS.
Embodiment 2AC-CoPcS 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 AC-CoPcS and add in reactor, tighten bolt on reactor, close charging aperture valve and discharging opening
Valve.Control cabinet power supply is opened, regulation control cabinet temperature button to required temperature adjusts rotating speed, cooling water control temperature in the kettle.
Treat that temperature reaches setting value, open oxygen valve regulation pressure and start recording reaction time to needed for reacting.Reaction is first after terminating
Closing control case power supply, the valve closed during oxygen channel closes oxygen pressure reducing valve, opens atmospheric valve after gas is drained
Open discharging opening valve and obtain product.Product is separated, by filtering, dimethyl disulfide being obtained by extraction.
The method that embodiment 3 prepares dimethyl disulfide
400mL sodium methyl mercaptides solution (mass fraction of sodium methyl mercaptide is 18%) and 0.1g AC-CoPcS are taken in oxygen pressure
It is strong be 0.6MPa, occur oxidation reaction 80min in the reaction unit that temperature is 55 DEG C, obtain dimethyl disulfide.Sodium methyl mercaptide
Conversion per pass reaches 93.8%, and the once through yield of dimethyl disulfide reaches that 66.2%, product purity is 100%.
The method that embodiment 4 prepares dimethyl disulfide
500mL sodium methyl mercaptides solution (mass fraction of sodium methyl mercaptide is 18%) and 0.7g AC-CoPcS are taken in oxygen pressure
It is strong be 1.0MPa, occur oxidation reaction 50min in the reaction unit that temperature is 75 DEG C, obtain dimethyl disulfide.Sodium methyl mercaptide
Conversion per pass reaches 97.1%, and the once through yield of dimethyl disulfide reaches that 69.3%, product purity is 100%.
The method that embodiment 5 prepares dimethyl disulfide
450mL sodium methyl mercaptides solution (mass fraction of sodium methyl mercaptide is 18%) and 0.4g AC-CoPcS are taken in oxygen pressure
It is strong be 0.9MPa, occur oxidation reaction 60min in the reaction unit that temperature is 65 DEG C, obtain dimethyl disulfide.Sodium methyl mercaptide
Conversion per pass reaches 98.7%, and the once through yield of dimethyl disulfide reaches that 86.8%, product purity is 100%.
Embodiment 6 free state CoPcS and AC-CoPcS catalytic performance is contrasted
450g sodium methyl mercaptides solution (sodium methyl mercaptide content 18%), rotating speed 600r/min, pressure is 0.9MPa, reaction time
60min, 65 DEG C of reaction temperature, catalyst amount is respectively CoPcS 160ppm and AC-CoPcS0.4g.In Fig. 2 (a) and (b)
Contrast substantially can be found that free state CoPcS catalyst is dissolved completely in product DMDS, and uses AC-CoPcS catalyst oils
Phase product and solution are clearly separated upper oil phase for faint yellow i.e. product (DMDS).By following table it can be seen that with activated carbon supported four
It is 86.8% that sulfonic group phthalein mountain valley with clumps of trees and bamboo cobalt (AC-CoPcS) obtains product yield as catalyst, and DMDS purity is 100% specific ionization
It is all high that state CoPcS is catalyzed obtained product yield, DMDS purity.It is identical with the conclusion that chapter 2 is drawn.This is equally because living
Property charcoal (AC) unique chemical property and stereochemical structure, can be effectively by methyl mercaptan as support materials surface large area pore structure
Sodium absorption is on hole or surface, effective contact area increase with catalyst, obtained product (DMDS) yield increase.Its
Secondary, the superpower adsorption bleaching characteristic of activated carbon enables the purity of product to reach 100%.
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. the preparation method of activated carbon supported Tetrasulphated phthalcyanine cobalt, it is characterised in that by chemical graft method by four sulphonyl
Chlorine Cobalt Phthalocyanine is supported on modified activated carbon, obtains activated carbon supported Tetrasulphated phthalcyanine cobalt (AC-CoPcS)；The modified active
Charcoal is ethylenediamine modified activated carbon.
2. preparation method according to claim 1, it is characterised in that the Tetrasulphated phthalcyanine cobalt is modified with ethylenediamine and lived
Property charcoal mass ratio be 0.1：0.5~3.5.
3. preparation method according to claim 1, it is characterised in that the preparation method comprises the following steps：
1) take Tetrasulphated phthalcyanine cobalt to be dissolved in DMF, add SOCl2Reaction, obtains four modified sulfonic acid chloride phthalocyanine cobalt liquors；
2) ethylenediamine modified activated carbon is added in above-mentioned four modified sulfonic acid chloride phthalocyanine cobalt liquors and reacted, obtain activated carbon supported
Tetrasulphated phthalcyanine cobalt (AC-CoPcS).
4. preparation method according to claim 1, it is characterised in that the preparation method bag of the ethylenediamine modified activated carbon
Include 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 (AT-T)；
2) take step 1) processing after activated carbon add SOCl2React to obtain chloride activated carbon；Chloride activated carbon is added to second
Reacted in the DMF solution of diamines, obtain ethylenediamine modified activated carbon (AC-E).
5. the activated carbon supported Tetrasulphated phthalcyanine cobalt that the preparation method described in claim any one of 1-4 is prepared.
6. the activated carbon supported Tetrasulphated phthalcyanine cobalt described in claim 5 is as catalyst in dimethyl disulfide is prepared
Using.
7. it is used as catalyst preparation dimethyl disulfide by the use of the activated carbon supported Tetrasulphated phthalcyanine cobalt described in claim 5
Method, it is characterised in that under the catalysis of activated carbon supported Tetrasulphated phthalcyanine cobalt oxidation reaction occurs for methyl mercaptan salt, obtains diformazan
Base 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 Tetrasulphated phthalcyanine
The mass ratio of cobalt is 70~90:0.1~0.9.
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 four
Sulfonic phthalocyanin cobalt, 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 Tetrasulphated phthalcyanine cobalt is second two
Amine modified activated carbon loads Tetrasulphated phthalcyanine cobalt.
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| CN110170315A (en) * | 2019-04-15 | 2019-08-27 | 绍兴文理学院元培学院 | A kind of fiber base aeroge adsorbent and its application in absorption dyeing waste-water |
| CN111370712A (en) * | 2020-02-24 | 2020-07-03 | 中南大学 | Preparation method of high-activity electrochemical oxygen reduction catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110170315A (en) * | 2019-04-15 | 2019-08-27 | 绍兴文理学院元培学院 | A kind of fiber base aeroge adsorbent and its application in absorption dyeing waste-water |
| CN110170315B (en) * | 2019-04-15 | 2021-12-31 | 绍兴文理学院元培学院 | Fiber-based aerogel adsorbent and application thereof in adsorption of dyeing wastewater |
| CN111370712A (en) * | 2020-02-24 | 2020-07-03 | 中南大学 | Preparation method of high-activity electrochemical oxygen reduction catalyst |
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