CN106748629A - A kind of method of the iodine heptafluoro-propane of direct method gas phase catalytic synthesis 2 - Google Patents
A kind of method of the iodine heptafluoro-propane of direct method gas phase catalytic synthesis 2 Download PDFInfo
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- CN106748629A CN106748629A CN201611025272.2A CN201611025272A CN106748629A CN 106748629 A CN106748629 A CN 106748629A CN 201611025272 A CN201611025272 A CN 201611025272A CN 106748629 A CN106748629 A CN 106748629A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/158—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of halogenated hydrocarbons
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Abstract
The invention discloses a kind of method of the iodine heptafluoro-propane of direct method gas phase catalytic synthesis 2, belong to organic chemical synthesis field.The method is with 2 hydrogen heptafluoro-propane (C3HF7) and I2It is raw material, the iodine heptafluoro-propane (C of gas phase catalytic synthesis 2 under catalyst action3F7I), with activated carbon, expanded graphite, activated alumina, 3A molecular sieves, porous fluorinated aluminium or porous fluorinated magnesium as carrier, used as catalyst activity component, rare-earth salts is used as accelerator for one or two alkali metal or alkali salt for the catalyst.Advantages of nontoxic raw materials of the present invention, cheap, process is simple, mild condition, flow is short, it is easy to control, and is adapted to large-scale industrial production and environmentally safe, environmental protection.
Description
Technical field
The invention belongs to organic chemical synthesis field, and in particular to one kind is with 2- hydrogen heptafluoro-propanes (C3HF7) and I2It is original
Material, by means of direct method gas phase catalytic synthesis C under catalyst action3F7The preparation method of I,
Background technology
C3F7I is production perfluoroalkyl iodides (CF3(C2F4)n, abbreviation RFI, is that a hydrogen-like atom is replaced completely by fluorine atom
Single iodo perfluoro hydride compounds) crucial telogen, may not only be applied to prepare medical agricultural chemicals key intermediate and synthesize fluorine-containing essence
Thin chemicals, is alternatively arranged as the working media of photodissociation iodine laser in addition.In recent years, because fluorine-containing surfactant, fabric are whole
Reason agent and downstream fluoride-containing PMMA demand growth are swift and violent, telogen C3F7The market demand of I is powerful, but the country is also not
There is C3F7The large-scale industrialization production technology of I, therefore try to explore to prepare full-fluorine alkyl iodide typical case's telogen
C3F7The new synthesis of I has great importance for the application for promoting the material.
The industrial method for preparing 2- iodine heptafluoro-propanes mainly has hexafluoropropene method, tetrafluoroethene method and seven fluorine different at present
Potassium butyrate method, double seven fluorine isopropyl mercury methods and the iodo- perfluor -2- butylene methods of 2-, the equation of its synthetic reaction such as (1.1)~
(1.5) shown in.Wherein hexafluoropropene method is to synthesize C in the world3F7I most common methods, are also major part company production at present
C3F7The method that I is used, the method is with iodine pentafluoride (IF5), iodine (I2) and hexafluoropropene (C3F6) it is raw material, in metal
24h is reacted at 150 DEG C under the spontaneous pressure of autoclave under aluminium or silver iodide catalyst action, C can be made3F7I yields reach 99%,
The method is simple to operate, mild condition, but the cost of raw material is higher in the method, and IF5With very strong toxicity and corrosivity,
Just gradually be cancelled (Murphy PM.,Baldwin CS.,Buck RC.Syntheses utilizing n-
perfluoroalkyl iodides[RFI,CnF2n+1-I]2000-2010[J].J.Fluorine Chem.,2012,138:3-
23.).For the shortcoming that the method is present, Scientific Research Workers have carried out a series of improvement, and such as use ICl, HF replaces in the method
IF5, with BF3It is catalyst, yield can be made to improve to 94%, but the method is still present expensive starting materials and the problem being not easy to obtain.Four
PVF method synthesizes C3F7I is also a kind of relatively common synthetic method, and the method is with tetrafluoroethene (C2F4) and CF3I
(CF3I) it is raw material, lewis acid catalyst is added under nitrogen protection, synthesizes the 1- iodine heptafluoro-propanes that mass fraction is 95%,
Then by cooling catalyst is to -196 DEG C and adds C3F6, it is warming up to 80 DEG C of fluorine third of insulation reaction 36h isomerization generation 2- iodine seven
Alkane, selectivity up to 98%.Although the method side reaction is few, C2F4It is explosive material, security is poor；When simultaneous isomerization reacts
Between long, severe reaction conditions.Therefore also larger (Petrov V A, the Krespan C G.Addition of of difficulty are industrialized
some unreactive fluoroalkanes to tetrafluoroethylene.:Direct catalytic
synthesis of F-butene-2[J].J.Fluorine Chem.,2000,102(1-2):199-204.).Three kinds of sides afterwards
Method all uses the organic coordination compound of metal as raw material, generally existing expensive starting materials and the problems such as be not easy to obtain.Therefore, one is found
Simple to operate, mild condition, environment amenable inexpensive C3F7The synthetic line of I is that pendulum is being engaged in fluorine chemistry scientific worker
Challenge in front.
The content of the invention
To overcome the deficiencies in the prior art, the present invention is using 2- hydrogen heptafluoro-propanes (C3F7) and I H2It is raw material, in catalyst
Under effect, using direct method gas phase catalytic synthesis C3F7I (specific reaction equation is as described below), to reach advantages of nontoxic raw materials, work
Skill is simple, the effect of mild condition, building-up process safety.
7C3F7H+3I2→6C3F7I+7HF+3C
The invention provides a kind of direct method gas phase catalytic synthesis C3F7The method of I, specifically includes following steps：
(1) preparation of catalyst：Selection activated carbon, expanded graphite, activated alumina, 3A molecular sieves, porous fluorinated aluminium or
Porous fluorinated magnesium carries out acid treatment as catalyst carrier to above-mentioned carrier, i.e., in 2mol/lHCl solution soak 12~
24h, with after deionized water drip washing to neutrality in drying box in 120 DEG C of 6~12h of drying；Choose one or two alkali metal salts
Or alkali salt is used as catalyst activity component, rare-earth salts is chosen as accelerator, gas phase catalysis is prepared using infusion process and is closed
Into C3F7Catalyst needed for I, will said catalyst carrier impregnated in the aqueous solution containing catalyst activity component and accelerator
In 6~12h；Then dried after vacuum distillation, finally in N2Calcined in sintering furnace in atmosphere and catalyst is obtained.
The mass ratio of the active component and carrier is 10%~20%, and the quality of affiliated accelerator is the 0 of active component
~0.5%.
(2) gas phase catalytic synthesis 2- iodine heptafluoro-propane：Fill the catalyst of step (1) preparation in the reactor first, and
Heating response device temperature is to 500~700 DEG C；Then unstripped gas C is controlled by mass flow controller3F7H and a small amount of O2Stream
Amount, and the form for passing through bubbling is 190~220 DEG C of iodine tanks into heating-up temperature, and reactor is entered after mixing with iodine steam, in order to
Prevent formed I2Steam blocking pipeline, is incubated using heating tape to pipeline；Last raw material is urged in the reactor
Change reaction and obtain the mix products containing unstripped gas, iodine vapor and target product 2- iodine heptafluoro-propanes.
The unstripped gas C3F7The flow of H is 60~120mL/min, O2Flow be 3.2~6.3mL/min, the raw material
Gas C3F7H and O2Volume ratio be 95:5.
(3) mix products post processing：Raw material I is carried out first with iodine collecting tank2Recovery；Then gas out is carried out
Alkali cleaning, removes the HF in mixed gas；Then the gas after alkali cleaning is carried out except water process by the drier equipped with calcium chloride；Most
To be collected into afterwards and contain 2- iodine heptafluoro-propane, unstripped gas C3F7The crude product of H is added in rectifying column, using two-phase contact process
Middle crude product each component volatility difference realizes the separation of each component in crude product, so as to obtain target product 2- iodine heptafluoro-propanes.
Further, in the preparation of step (1) catalyst, the anion of the rare-earth salts is halide ion, nitrate anion
Ion, carbonate ions, sulfate ion or acetate ion, cation are lanthanum ion, cerium ion, neodymium ion or samarium ion.
Further, in the preparation of step (1) catalyst, the alkali metal salt, the anion of alkali salt are halogen
Plain ion, nitrate ion, carbonate ions, sulfate ion or acetate ion；The cation of the alkali metal salt be potassium from
Son, rubidium ion or cesium ion, the cation of the alkali salt is magnesium ion or strontium ion.
Compared with prior art, the present invention has following technique effect：
(1) direct method that the invention is provided prepares 2- iodine heptafluoro-propane methods and overcomes conventional method raw material universal expensive and not
The shortcoming being easy to get, the raw material environmental protection for being used and price is relatively cheap, while catalyst does not occur instead with reaction medium
Should, good stability.
(2) the direct method gas phase catalytic synthesis that the present invention is provided prepare 2- iodine heptafluoro-propane methods process is simples, can be continuous
Operation, mild condition, building-up process safety, it is adaptable to industrialized production.
(3) present invention provide direct method gas phase catalytic synthesis 2- iodine heptafluoro-propane method target products selectivity compared with
Height, the complete unstrpped gas of unreacted can be recycled.
Specific embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiments.
Embodiment 1
Catalyst is prepared first：30mL activated carbons (12.6g) are measured with graduated cylinder soak 12h in 2mol/L HCl solutions,
With deionized water drip washing 6h is dried to neutrality and in drying box in 120 DEG C；Weigh 2.52g potassium fluorides and be dissolved in 30mL distilled water
In, dry 12h with Rotary Evaporators vacuum distillation and in 120 DEG C of drying box after above-mentioned absorbent charcoal carrier is impregnated into wherein 6h
Afterwards in N in 600 DEG C of sintering furnaces2Calcined in atmosphere.Then catalytic reaction is carried out：Above-mentioned catalyst is fitted into reactor
Heating response device temperature controls unstripped gas C to 600 DEG C by mass flow controller3F7H and O2Flow be respectively 100mL/
Min and 5.3mL/min, and by the form of bubbling into the I that heating-up temperature is 190 DEG C2Tank, enters anti-after mixing with iodine steam
Answering device carries out catalytic reaction.Finally to containing target product C3F7The mixture of I is post-processed：Carried out first with iodine collecting tank
Raw material I2Recovery；Then gas out carries out alkali cleaning, removes the HF in mixed gas；Then the gas after alkali cleaning is by dress
The drier for having calcium chloride is carried out except water process；Finally contain C by what is be collected into3F7I, raw material C3F7The crude product of H and accessory substance etc.
It is added in rectifying column, the separation of each component in crude product is realized using crude product each component volatility difference in two-phase contact process,
So as to obtain target product C3F7I。
Embodiment 2
Catalyst is prepared first：The porous fluorinated aluminium of 30mL (36.2g) is measured with graduated cylinder to be soaked with 2mol/L HCl solutions
24h, 12h is dried with deionized water drip washing to neutrality and in drying box in 120 DEG C；Weigh 3.62g rubidium nitrates and be dissolved in 30mL
In distilled water, Rotary Evaporators vacuum distillation and the drying at 120 DEG C will be used after above-mentioned many sky aluminum fluoride carrier impregnation wherein 12h
Dried in case after 12h in 600 DEG C of sintering furnaces in N2Calcined in atmosphere.Then catalytic reaction is carried out：By above-mentioned catalyst
Heating response device temperature controls unstripped gas C to 500 DEG C by mass flow controller in being fitted into reactor3F7H and O2Flow
Respectively 60mL/min and 3.2mL/min, and by the form of bubbling into the I that heating-up temperature is 200 DEG C2Tank, with iodine steam
After mixing catalytic reaction is carried out into reactor.Finally to containing target product C3F7The mixture of I is post-processed：First with
Iodine collecting tank carries out raw material I2Recovery；Then gas out carries out alkali cleaning, removes the HF in mixed gas；Then after alkali cleaning
Gas carried out except water process by the drier equipped with calcium chloride；Finally contain C by what is be collected into3F7I, raw material C3F7H and pair
The crude product of product etc. is added in rectifying column, is realized using crude product each component volatility difference in two-phase contact process each in crude product
The separation of component, so as to obtain target product C3F7I。
Embodiment 3
Catalyst is prepared first：30mL expanded graphites (9.8g) are soaked into 18h with 2mol/L HCl solutions, deionization is used
Water wash dries 8h to neutrality and in drying box in 120 DEG C；It is 1 to weigh 1.47g mass ratioes:1 potassium fluoride and rubidium nitrate
Mixture is dissolved in 30mL distilled water, will above-mentioned expanded graphite impregnate wherein 8h after with Rotary Evaporators vacuum distillation and
Dried in 120 DEG C of drying box after 12h in 600 DEG C of sintering furnaces in N2Calcined in atmosphere.Then catalytic reaction is carried out：Will
Above-mentioned catalyst be fitted into reactor in heating response device temperature to 700 DEG C, unstripped gas C is controlled by mass flow controller3F7H
And O2Flow be respectively 80mL/min and 4.2mL/min, and by the form of bubbling into the I that heating-up temperature is 220 DEG C2Tank,
After mixing with iodine steam catalytic reaction is carried out into reactor.Finally to containing target product C3F7The mixture of I is located after carrying out
Reason：Raw material I is carried out first with iodine collecting tank2Recovery；Then gas out carries out alkali cleaning, removes the HF in mixed gas；
Then the gas after alkali cleaning is carried out except water process by the drier equipped with calcium chloride；Finally contain C by what is be collected into3F7I, original
Material C3F7The crude product of H and accessory substance etc. is added in rectifying column, using crude product each component volatility difference reality in two-phase contact process
The separation of each component in existing crude product, so as to obtain target product C3F7I。
Embodiment 4
Catalyst is prepared first：30mL activated carbons (12.6g) are measured with graduated cylinder soak 12h in 2mol/L HCl solutions,
With deionized water drip washing 6h is dried to neutrality and in drying box in 120 DEG C；Weigh 2.52g potassium fluorides and 0.013g cerous nitrates are molten
Solution uses Rotary Evaporators vacuum distillation and at 120 DEG C in 30mL distilled water after above-mentioned absorbent charcoal carrier is impregnated into wherein 6h
Dried in drying box after 12h in 700 DEG C of sintering furnaces in N2Calcined in atmosphere.Then catalytic reaction is carried out：Urged above-mentioned
Agent be fitted into reactor in heating response device temperature to 600 DEG C, unstripped gas C is controlled by mass flow controller3F7H and O2's
Flow is respectively 120mL/min and 6.3mL/min, and by the form of bubbling into the I that heating-up temperature is 210 DEG C2Tank, with iodine
After steam catalytic reaction is carried out into reactor.Finally to containing target product C3F7The mixture of I is post-processed：First
Raw material I is carried out using iodine collecting tank2Recovery；Then gas out carries out alkali cleaning, removes the HF in mixed gas；Then alkali
Gas after washing is carried out except water process by the drier equipped with calcium chloride；Finally contain C by what is be collected into3F7I, raw material C3F7H
Crude product with accessory substance etc. is added in rectifying column, and crude product is realized using crude product each component volatility difference in two-phase contact process
The separation of middle each component, so as to obtain target product C3F7I。
The experimental result of the catalytic reaction of the present invention of table 1
Claims (3)
1. a kind of method of direct method gas phase catalytic synthesis 2- iodine heptafluoro-propanes, it is characterised in that the method comprises the following steps：
(1) preparation of catalyst：Selection activated carbon, expanded graphite, activated alumina, 3A molecular sieves, porous fluorinated aluminium or porous
Magnesium fluoride carries out acid treatment as catalyst carrier to above-mentioned carrier, i.e., 12~24h is soaked in 2mol/lHCl solution, uses
In 120 DEG C of 6~12h of drying in drying box after deionized water drip washing to neutrality；Choose one or two alkali metal salts or alkaline earth
Slaine chooses rare-earth salts as accelerator as catalyst activity component, said catalyst carrier impregnated in and contain catalysis
6~12h in the aqueous solution of agent active component and accelerator；Then dried after vacuum distillation, finally in N2In sintering furnace in atmosphere
Middle calcining is obtained catalyst；
The mass ratio of the active component and carrier is 10%~20%, the quality of affiliated accelerator for active component 0~
0.5%；
(2) gas phase catalytic synthesis 2- iodine heptafluoro-propane：Fill the catalyst of step (1) preparation in the reactor first, and heat
Temperature of reactor is to 500~700 DEG C；Then unstripped gas C is controlled by mass flow controller3F7H and a small amount of O2Flow,
And the form by bubbling enters heating-up temperature for 190~220 DEG C of iodine tanks, and reactor is entered after mixing with iodine steam；It is last former
Material carries out catalytic reaction and obtains the mixing product containing unstripped gas, iodine vapor and target product 2- iodine heptafluoro-propanes in the reactor
Thing；
The unstripped gas C3F7The flow of H is 60~120mL/min, O2Flow be 3.2~6.3mL/min, the unstripped gas
C3F7H and O2Volume ratio be 95:5；
(3) mix products post processing：Raw material I is carried out first with iodine collecting tank2Recovery；Then alkali cleaning is carried out to gas out,
Remove the HF in mixed gas；Then the gas after alkali cleaning is carried out except water process by the drier equipped with calcium chloride；Finally will
What is be collected into contains 2- iodine heptafluoro-propane, unstripped gas C3F7The crude product of H is added in rectifying column, using thick in two-phase contact process
Product each component volatility difference realizes the separation of each component in crude product, so as to obtain target product 2- iodine heptafluoro-propanes.
2. a kind of method of direct method gas phase catalytic synthesis 2- iodine heptafluoro-propanes as claimed in claim 1, it is characterised in that：
In the preparation of step (1) catalyst, the anion of the rare-earth salts is halide ion, nitrate ion, carbonate ions, sulfate radical
Ion or acetate ion, cation are lanthanum ion, cerium ion, neodymium ion or samarium ion.
3. a kind of method of direct method gas phase catalytic synthesis 2- iodine heptafluoro-propanes as claimed in claim 1, it is characterised in that：
In the preparation of step (1) catalyst, the alkali metal salt, the anion of alkali salt are halide ion, nitrate ion, carbon
Acid ion, sulfate ion or acetate ion；The cation of the alkali metal salt is potassium ion, rubidium ion or cesium ion, institute
The cation for stating alkali salt is magnesium ion or strontium ion.
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Cited By (2)
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| CN115181004A (en) * | 2022-09-09 | 2022-10-14 | 天津绿菱气体有限公司 | Preparation method of trifluoroiodomethane |
| CN116854572A (en) * | 2023-08-30 | 2023-10-10 | 哲弗智能系统（上海）有限公司 | Preparation method of perfluoro hexanone |
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