CN106984361A - Activated carbon supported cobalt tetraaminophthlocyanine and its application as catalyst in dimethyl disulfide is prepared - Google Patents
Activated carbon supported cobalt tetraaminophthlocyanine and its application as catalyst in dimethyl disulfide is prepared Download PDFInfo
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- CN106984361A CN106984361A CN201710286655.3A CN201710286655A CN106984361A CN 106984361 A CN106984361 A CN 106984361A CN 201710286655 A CN201710286655 A CN 201710286655A CN 106984361 A CN106984361 A CN 106984361A
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- activated carbon
- tetraaminophthlocyanine
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- dimethyl disulfide
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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 cobalt tetraaminophthlocyanine and its application as catalyst in dimethyl disulfide is prepared.The preparation method for the activated carbon supported cobalt tetraaminophthlocyanine that the present invention is provided is：Cobalt tetraaminophthlocyanine is supported on modified activated carbon by chemical graft method, activated carbon supported cobalt tetraaminophthlocyanine is obtained；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 present invention with AC CoTAPc as catalyst during dimethyl disulfide is prepared can and product separate well, and the obtained product yield of specific ionization state CoTAPc catalysis, DMDS purity are all high.Obtained product DMDS yields are up to 87.4%, 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 cobalt tetraaminophthlocyanine and its exist as catalyst
Prepare the application in 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 by 1.25 ︰ 1 of mol ratio, 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.
Metal phthalocyanine and its derivative are similar to the activated centre Porphyrin Molecule structure of Cytochrome P450, are by imines bridge
Key connects the conjugated pi electron macrocyclic ring system that four symmetrical iso-indoles units are constituted, and its chemical property is highly stable, its center gold
Belong to ion can with other molecules occur axial coordination, show excellent catalytic performance, available for catalysis include reduction reaction,
The various organic reactions such as carbonylation, Fischer-Tropsch reactions, ammonia synthesis reaction and oxidation reaction.Research finds four
Amino Cobalt Phthalocyanine effectively can prepare dimethyl disulfide (DMDS) for catalysis oxidation methyl mercaptan salt, but the catalyst is soluble in product
Dimethyl disulfide so that catalyst and product can not be separated well, and product purity is not high, thus requires further improvement.
Based on reaction system be strong alkali solution and course of reaction needs to complete under certain temperature, pressure, and then requires support materials
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 cobalt tetraaminophthlocyanine and its it is used as catalyst
Application in dimethyl disulfide is prepared.The catalyst structure that the present invention is provided is stable, reusable, can effectively be catalyzed
Oxidation methyl mercaptan salt prepares dimethyl disulfide, can well be separated with product, and the production that specific ionization state CoTAPc catalysis is obtained
Product yield, DMDS purity are all high.
To achieve the above object, the technical scheme is that：
Cobalt tetraaminophthlocyanine, is supported on by the preparation method of activated carbon supported cobalt tetraaminophthlocyanine by chemical graft method
On modified activated carbon, activated carbon supported cobalt tetraaminophthlocyanine (AC-CoTAPc) is obtained；The modified activated carbon is pentamethylene bromide
Modified activated carbon.
Further, the cobalt tetraaminophthlocyanine and 1, the mass ratio of pentamethylene bromide modified activated carbon is 0.1：0.5~2.
The cobalt tetraaminophthlocyanine (CoTAPc) can commercially buy acquisition and also be prepared by disclosed method.
Further, cobalt tetraaminophthlocyanine and modified activated carbon are in DMF, K2CO3In the presence of react, obtain activated carbon supported four
Amino Cobalt Phthalocyanine；The modified activated carbon is pentamethylene bromide modified activated carbon.
The DMF can be replaced with benzene, toluene；The K2CO3Na can be used2CO3、NaHCO3Instead of.
As a preferred embodiment, the preparation method of activated carbon supported cobalt tetraaminophthlocyanine：Take dried pentamethylene bromide
Modified activated carbon, adds DMF, K2CO3Through cooling after being reacted with tetramino phthalein mountain valley with clumps of trees and bamboo cobalt, suction filtration obtains 1,5- bis- after washing vacuum drying
Bromo pentane silane modified activated carbon load tetramino phthalein mountain valley with clumps of trees and bamboo cobalt (AC-CoTAPc).
As a preferred embodiment, described DMF, K2CO3Mass ratio with cobalt tetraaminophthlocyanine is 50：0.5~2：0.1.
As a preferred embodiment, the temperature of the reaction is 70~85 DEG C, the time of reaction is 9~15h.
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 (AT-T)；
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 (AC-Br).
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；The dried activated carbon of nitrification is taken to add
DMF, K steam again after2CO3, add under NaH condition of ice bath and react, add 1, pentamethylene bromide reacts at room temperature 1h after 80 DEG C of reactions
24 hours.Through cooling, suction filtration, washing dried 1, the modified activated carbon of pentamethylene bromide.
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 tetramino that a kind of described preparation method is prepared
Cobalt Phthalocyanine.
The structural formula of the activated carbon supported cobalt tetraaminophthlocyanine is：
The activated carbon supported cobalt tetraaminophthlocyanine prepared by above-mentioned preparation method is subjected to X-ray electron spectrum survey
Examination, obtained XPS spectrum figure is shown except containing Elements C, N, O in activated carbon supported cobalt tetraaminophthlocyanine, also containing a small amount of Co members
Element, Co electron energy is 789.1Ev.Because phthalocyanine load capacity is smaller, so high-resolution peak noise is larger, but also can
See peak clearly occur, show that CoTAPc is loaded up.In addition, Br3d electron energy is dropped to by 65.9eV
11.3eV, energy substantially weakens, and is attributed on the 1 ,-Br and the tetramino cobalt phthalein mountain valley with clumps of trees and bamboo of the activated carbon surface that pentamethylene bromide is modified
- NH2Lose HBr and bonding by being condensed, Br3d electron energy substantially reduce further demonstrate that tetramino phthalein mountain valley with clumps of trees and bamboo cobalt into
Work(is loaded on the activated carbon, and is strong chemical action.
The third object of the present invention is that provide a kind of described activated carbon supported cobalt tetraaminophthlocyanine exists as catalyst
Prepare the application in dimethyl disulfide.
Cobalt tetraaminophthlocyanine (CoTAPc), also referred to as tetramino cobalt phthalocyanine, effectively catalysis oxidation sodium methyl mercaptide can be prepared
Dimethyl disulfide (DMDS), but the catalyst is soluble in product dimethyl disulfide so that catalyst and product can not be very
Good separation, product yield and product purity be not high.Activated carbon supported cobalt tetraaminophthlocyanine prepared by the present invention passes through condensation
Lose HBr bondings to load to the cobalt tetraaminophthlocyanine of synthesis on modified activated carbon, obtained AC-CoTAPc is as catalyst
Can and product separate well, and the obtained product yield of specific ionization state CoTAPc catalysis, DMDS purity are all high.This is due to work
Property charcoal (AC) be that the porous carbonaceous material that a kind of pore structure is flourishing, specific surface area is big effectively can adsorb sodium methyl mercaptide in hole
Or surface, effective contact area increase with catalyst, obtained product DMDS yields increase.Activated carbon supported four ammonia
Base Cobalt Phthalocyanine can be repeatedly used as catalyst in dimethyl disulfide is prepared, and reduce production cost；Secondly, activity
The superpower adsorption bleaching of charcoal enables the purity of product to reach 100%.
The present invention also aims to provide a kind of by the use of described activated carbon supported cobalt tetraaminophthlocyanine to be used as catalyst
Under the catalysis of activated carbon supported cobalt tetraaminophthlocyanine oxidation reaction occurs for the method for preparing dimethyl disulfide, methyl mercaptan salt,
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 cobalt tetraaminophthlocyanine is 70~90:0.1~0.7.
As a preferred embodiment, the mass ratio of the methyl mercaptan salt and activated carbon supported cobalt tetraaminophthlocyanine is 80~90:0.2
~0.7.
As a preferred embodiment, the mass ratio of the methyl mercaptan salt and activated carbon supported cobalt tetraaminophthlocyanine is 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%~98.1%, is 81 in the mass ratio of methyl mercaptan salt and catalyst：One way turns when 0.2
Rate reaches 98.1%, and once through yield is up to 87.4%.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 0.9MPa.
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, the system by methyl mercaptan salt,
Activated carbon supported cobalt tetraaminophthlocyanine, oxygen and aqueous medium composition.
Further, the methyl mercaptan salt includes sodium methyl mercaptide and methyl mercaptan potassium.
Further, the activated carbon supported cobalt tetraaminophthlocyanine is 1, pentamethylene bromide modified activated carbon load tetramino phthalein
Cyanines cobalt.
Activated carbon supported cobalt tetraaminophthlocyanine is used as catalyst energy in the system for preparing dimethyl disulfide, the system
Enough effective catalysis oxidation methyl mercaptan salt prepares dimethyl disulfide, reusable, and can well be separated with product, obtains
Product dimethyl disulfide yield is up to 87.4%, and purity can reach 100%.
The beneficial effects of the present invention are：
1) present invention is provided a kind of activated carbon supported cobalt tetraaminophthlocyanine and its can be applied in preparation as catalyst
In dimethyl disulfide, raw material sodium methyl mercaptide is strong alkali solution, and catalytic reaction need to be completed under certain temperature, pressure.Pass through
Cobalt tetraaminophthlocyanine is supported on the catalyst structure stabilization that activated carbon is obtained, reusable, Neng Goushi by chemical graft mode
Alkaline-resisting, pressure-resistant, high temperature resistant and effective catalysis oxidation sodium methyl mercaptide prepares dimethyl disulfide in present reaction system.
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 cobalt tetraaminophthlocyanine of the invention loses HBr bondings by the cobalt tetraaminophthlocyanine of synthesis by being condensed
Load on modified activated carbon, obtained AC-CoTAPc as catalyst during dimethyl disulfide is prepared can and
Product is separated well, and the obtained product yield of specific ionization state CoTAPc catalysis, DMDS purity are all high.This is due to activated carbon
(AC) be a kind of pore structure is flourishing, specific surface area is big porous carbonaceous material can effectively by sodium methyl mercaptide absorption in hole or
Surface, effective contact area increase with catalyst, obtained product DMDS yields are up to 87.4%, and secondly, activated carbon is superpower
Adsorption bleaching enable the purity of product to reach 100%.
4) activated carbon supported cobalt tetraaminophthlocyanine is made in the system for preparing dimethyl disulfide that the present invention is provided, the system
For catalyst can effectively catalysis oxidation methyl mercaptan salt prepare dimethyl disulfide, it is reusable, and can and product it is good
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 that corresponding product DMDS shows free state CoTAPc (a) respectively with AC-CoTAPc (b) catalysis oxidations sodium methyl mercaptide
It is intended to.
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-CoTAPc of embodiment 1 preparation
The preparation of 1.1,5- 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 obtains 1, the modified activated carbon 2.03g of pentamethylene bromide after drying.
2. the preparation of activated carbon supported cobalt tetraaminophthlocyanine (AC-CoTAPc)
Dried 1 is weighed, the modified activated carbon 1g of pentamethylene bromide is added steam again after in 100mL round-bottomed flasks
DMF50mL, K2CO31.0g, the cobalt tetraaminophthlocyanine for accurately weighing the above-mentioned synthesis of 0.1g reacts 12 hours in 80 DEG C.Through cooling,
Suction filtration, obtains 1, pentamethylene bromide modified activated carbon load cobalt tetraaminophthlocyanine 0.98g after washing vacuum drying.
The AC-CoTAPc of embodiment 2 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-CoTAPc and add in reactor, tighten bolt on reactor, close charging aperture valve and discharging
Mouth valve.Control cabinet power supply is opened, regulation control cabinet temperature button to required temperature adjusts temperature in rotating speed, cooling water control kettle
Degree.Treat that temperature reaches setting value, open oxygen valve regulation pressure and start recording reaction time to needed for reacting.After reaction terminates
First closing control case power supply, the valve closed during oxygen channel closes oxygen pressure reducing valve, opens atmospheric valve and treats that gas is drained
Discharging opening valve is opened afterwards obtains 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 0.1gAC-CoTAPc 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 89.7%, and the once through yield of dimethyl disulfide reaches that 38.7%, 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 0.5gAC-CoTAPc 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 94.2%, and the once through yield of dimethyl disulfide reaches that 78.6%, 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 0.2gAC-CoTAPc 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 98.1%, and the once through yield of dimethyl disulfide reaches that 87.4%, product purity is 100%.
Embodiment 6 free state CoTAPc and AC-CoTAPc 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 cobalt tetraaminophthlocyanine 160ppm and activated carbon supported cobalt tetraaminophthlocyanine
0.2g.(a) substantially can be found that free state cobalt tetraaminophthlocyanine is dissolved completely in product DMDS with (b) contrast in Fig. 2, and
Upper oil phase is clearly separated for faint yellow i.e. product (DMDS) using activated carbon supported tetramino catalyst oil phase product and solution.
By following table it can be seen that it is 87.4% to obtain product yield as catalyst with activated carbon supported cobalt tetraaminophthlocyanine, and DMDS is pure
Spend for 100%, product yield that specific ionization state CoTAPc catalysis is obtained, DMDS purity are all high.This is due to that activated carbon (AC) is
The porous carbonaceous material that a kind of pore structure is flourishing, specific surface area is big effectively can adsorb sodium methyl mercaptide on hole or surface,
With effective contact area increase of catalyst, obtained product (DMDS) yield increase.Secondly, the superpower adsorption bleaching of activated carbon
Performance enables the purity of product to reach 100%.
The performance comparison of two kinds of catalyst
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 cobalt tetraaminophthlocyanine, it is characterised in that by chemical graft method by tetramino phthalein
Cyanines cobalt is supported on modified activated carbon, obtains activated carbon supported cobalt tetraaminophthlocyanine；The modified activated carbon is pentamethylene bromide
Modified activated carbon.
2. preparation method according to claim 1, it is characterised in that the cobalt tetraaminophthlocyanine and 1, pentamethylene bromide changes
Property activated carbon mass ratio be 0.1：0.5~2.
3. preparation method according to claim 1, it is characterised in that cobalt tetraaminophthlocyanine and modified activated carbon DMF,
K2CO3In the presence of react, obtain activated carbon supported cobalt tetraaminophthlocyanine；The modified activated carbon is that pentamethylene bromide is modified work
Property charcoal.
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 cobalt tetraaminophthlocyanine that the preparation method described in claim any one of 1-4 is prepared.
6. the answering in dimethyl disulfide is prepared as catalyst of the activated carbon supported cobalt tetraaminophthlocyanine described in claim 5
With.
7. it is used as the side of catalyst preparation dimethyl disulfide by the use of the activated carbon supported cobalt tetraaminophthlocyanine described in claim 5
Method, it is characterised in that under the catalysis of activated carbon supported cobalt tetraaminophthlocyanine oxidation reaction occurs for methyl mercaptan salt, obtains dimethyl two
Thioether.
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 cobalt tetraaminophthlocyanine
Mass ratio be 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 four
Amino Cobalt Phthalocyanine, 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 cobalt tetraaminophthlocyanine is 1,5- bis-
Bromo pentane silane modified activated carbon loads cobalt tetraaminophthlocyanine.
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| CN108084069A (en) * | 2017-11-14 | 2018-05-29 | 广东省石油与精细化工研究院 | A kind of method that mercaptan aqueous phase oxidation prepares disulfide |
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