CN108246277A

CN108246277A - One kind efficiently synthesizes trifluoroiodomethane method

Info

Publication number: CN108246277A
Application number: CN201810235825.XA
Authority: CN
Inventors: 赵毅; 赵趫; 王天源; 计燕秋; 张琳; 石琳; 刘颖
Original assignee: Dalian Kelide Optoelectronic Material Co Ltd
Current assignee: Dalian Kelide Optoelectronic Material Co Ltd
Priority date: 2018-03-21
Filing date: 2018-03-21
Publication date: 2018-07-06
Anticipated expiration: 2038-03-21
Also published as: CN108246277B

Abstract

The invention discloses one kind to efficiently synthesize trifluoroiodomethane method, by CF₃COOH steam and iodine vapor, under catalyst action, reaction generation trifluoroiodomethane；The catalyst is using activated carbon or graphene as carrier loaded 1~10wt%KNO₃With 2~7wt%RbNO₃Catalyst；Then NaOH solution, silica gel and molecular sieve are passed sequentially through to effectively remove CF₃Thus impurity and moisture in I efficiently collect high-purity C F₃I products.The method has that reaction rate is fast, selectivity is good, yield is high, reactant utilization rate is high, energy saving, is expected to realization industrialized production, meets the current market demand.

Description

One kind efficiently synthesizes trifluoroiodomethane method

Technical field

The present invention relates to one kind to efficiently synthesize trifluoroiodomethane method.

Background technology

Trifluoroiodomethane (CF₃I greenhouse effects) are dived value (GWP) ＜ 5, and ozone depletion value (ODP) of diving is 0, is combined State is classified as the major components of the 3rd generation environmental protection refrigerant.Other than it can be used as new gas extinguishing chemical and refrigerant, in fluorine-containing centre Other fields such as body, conductor etching, foaming agent also have wide practical use.

CF₃I document reports CF₃I synthesis technologies are numerous, and main method has：

(1) perfluorocarboxylic acid salt pyrolysismethod：With CF₃COM (M=Ag, Na, K, Hg, Pb, Ba) and iodine (I₂) it is raw material, in strong pole Property solvent in heat resolve prepare CF₃I, this is also to be suggested the synthetic method with industrialization and practical value earliest, (J.Am.Chem.Soc.1950(72)：584-587.3806-7 J.Chem.Soc., 1951 (2)：584-587.).Wherein with silver The pyrolysis yield of salt is higher but expensive.The discoveries such as Paskovich, sodium salt or sylvite flow back in dimethylformamide (DMF) Under, CF can be improved₃I yields are to 70% or so, (J.Org.Chem., 1967,32 (3)：833-835.).Xu Huatang etc. is with ring fourth It is solvent that sulfone, which substitutes DMF, obtains CF₃The yield of I is 80% or so, (chemical reagent, 1989,11 (2)：123.).

(2) fluoroform iodide process：Japan Patent JP52068110 is reported with fluoroform (CF₃) and I H₂It is living for raw material Property charcoal carrying alkali metal or alkaline-earth metal be catalyst preparation CF₃I.Catalyst shows preferable catalytic activity, due to reaction Temperature is high, and catalyst carbon deposition is serious, and the service life is shorter, and the high polymer generated increases and recycles unreacted I₂Difficulty.

(3) it is proposed in French Patent (FRP) FR2794456 with pentafluoroethane (C₂F₅) and I H₂For the synthetic route of raw material, the technique With the catalyst system and catalyzing similar with fluoroform iodide process, unstripped gas is catalyzed by activated carbon supported alkali or alkaline earth metal Agent bed can obtain CF₃I。

In conclusion existing preparation CF₃There are expensive raw material prices, of high cost for the method for I, and reaction dissolvent consumption is big, production The a series of problems such as object yield is low, poor selectivity, raw material availability are low.Therefore, find one it is easy to operate, high selectivity CF₃I synthetic routes are most important.

Invention content

To solve the above-mentioned problems, the purpose of the present invention is to provide a kind of synthesis easy to operate, selectivity of product is high CF₃The method of I.In order to achieve the above object, the invention is realized by the following technical scheme：

One kind efficiently synthesizes CF₃The method of I, CF₃COOH steam and iodine vapor, under catalyst action, reaction generation trifluoro Iodomethane；

The catalyst is using activated carbon or graphene as carrier loaded 1~10wt%KNO₃With 2~7wt%RbNO₃Urge Agent；CF₃The molar ratio of COOH steam and iodine vapor is 1：1~2：1；Reaction temperature is 450-550 DEG C；Reaction time is 10- 15min；CF₃The flow of COOH steam is 10-20mL/min.

Catalyst is synthesized KNO₃And RbNO₃It is dissolved in water, adds in activated carbon or graphene thereto, be ultrasonically treated 30min is stood overnight；Filtering, 5h is dried by Solid separate at 100 DEG C, then 500 DEG C of calcinings under high pure nitrogen atmosphere Catalyst is made in 2h.KNO₃And RbNO₃It is 3-8g/500ml with water consumption ratio.

Further, in the above-mentioned technical solutions, obtained trifluoroiodomethane is passed through the first collector, the second receipts successively Storage, caustic treater, drier and absorber remove impurity and moisture content；It is heated outside first collector using recirculated water；Alkali cleaning The lye of tank is NaOH solution；Drier in drier is silica gel；Adsorbent in absorber is molecular sieve.

Further, in the above-mentioned technical solutions, the temperature of level-one collector outer circulation water is 70-80 DEG C；In caustic treater A concentration of 0.1-5% of NaOH solution；Adsorbent is 5A molecular sieves in absorber.

Further, in the above-mentioned technical solutions, trifluoroiodomethane is received using cold-trap.

Further, in the above-mentioned technical solutions, the temperature for collecting trifluoroiodomethane cold-trap is -70 DEG C.

Further, in the above-mentioned technical solutions, CF₃COOH steam is to be vaporized to generate by the vaporizer that temperature is 100 DEG C； Iodine vapor is generated by the iodine evaporator that temperature is 200 DEG C.

Further, in the above-mentioned technical solutions, trifluoroiodomethane method is efficiently synthesized, reaction unit includes reactor, The reactor inlet connects CF₃COOH vaporizers and iodine evaporator；The reactor outlet is sequentially connected the first collector, Two collectors, caustic treater, drier, absorber, cold-trap.

It is provided by the present invention to efficiently synthesize CF₃I methods are using activated carbon or graphene as carrier loaded 1~10wt% KNO₃With 2~7wt%RbNO₃As catalyst, make CF₃COOH steam and iodine vapor chemically react in high-temperature reactor And generate CF₃Then I passes sequentially through NaOH solution, silica gel and molecular sieve to effectively remove CF₃Impurity and moisture in I, thus The CF of synthesis₃The yield of I is up to 90%, since catalyst selects matters, and processing step reasonable design, can not only accelerate Reaction rate improves yield, energy saving so as to improve the utilization rate of reactant, is expected to realize industrialized production, so as to Meet the current market demand.

Description of the drawings

Fig. 1 is the flow chart provided by the invention for efficiently synthesizing trifluoroiodomethane method.

Case is embodied

Embodiment 1

1st, synthetic catalyst：By 3.0g KNO₃With 5g RbNO₃It is dissolved in 500mL water, adds in 100g activity thereto Charcoal is ultrasonically treated 30min, stands overnight；Filtering, dries 5h, then in high pure nitrogen atmosphere by Solid separate at 100 DEG C Lower 500 DEG C of calcinings 2h, is made catalyst.

2nd, CF is synthesized₃I

(1)CF₃COOH steam and iodine vapor in molar ratio 1：1 enters 500 DEG C of reactors, is catalyzed in reactor equipped with 100g Agent controls CF₃The flow of COOH steam is 20mL/min, CF₃The reaction time of COOH and iodine generates CF for 10min₃I。

(2) make above-mentioned CF₃I gases are passed through the first collector, the second collector, caustic treater, drier and absorber successively, Remove H₂O、CO₂, the impurity such as HF.It is recycled outside level-one collector using 80 DEG C of water；Lye in caustic treater is 0.5%NaOH Solution；Drier in drier is silica gel；Adsorbent in absorber is 5A molecular sieves.Finally by -70 DEG C of cold-trap pair CF₃I solution is received, CF₃The yield of I is 84.6%.

Embodiment 2

1st, synthetic catalyst：By 7.0g KNO₃With 0.7g RbNO₃It is dissolved in 500mL water, adds in 100g graphite thereto Alkene is ultrasonically treated 30min, stands overnight；Filtering, dries 5h, then in high pure nitrogen atmosphere by Solid separate at 100 DEG C Lower 500 DEG C of calcinings 2h, is made catalyst.

2nd, CF is synthesized₃I

(1)CF₃COOH steam and iodine vapor in molar ratio 2：1 enters 550 DEG C of reactors, is catalyzed in reactor equipped with 100g Agent controls CF₃The flow of COOH steam is 20mL/min, CF₃The reaction time of COOH and iodine generates CF for 10min₃I。

(2) make above-mentioned CF₃I gases are passed through the first collector, the second collector, caustic treater, drier and absorber successively, Remove H₂O、CO₂, the impurity such as HF.It is recycled outside level-one collector using 80 DEG C of water；Lye in caustic treater is 0.5%NaOH Solution；Drier in drier is silica gel；Adsorbent in absorber is 5A molecular sieves.Finally by -70 DEG C of cold-trap pair CF₃I solution is received, CF₃The yield of I is 90.7%.

Claims

1. one kind efficiently synthesizes trifluoroiodomethane method, it is characterised in that：

CF₃COOH steam and iodine vapor, under catalyst action, reaction generation trifluoroiodomethane；

The catalyst is using activated carbon or graphene as carrier loaded 1~10wt%KNO₃With 2~7wt%RbNO₃Catalysis Agent；CF₃The molar ratio of COOH steam and iodine vapor is 1：1~2：1；Reaction temperature is 450-550 DEG C；Reaction time is 10- 15min；CF₃The flow of COOH steam is 10-20mL/min.

2. trifluoroiodomethane method is efficiently synthesized according to claim 1, it is characterised in that：By obtained trifluoroiodomethane according to It is secondary to be passed through the first collector, the second collector, caustic treater, drier and absorber, remove impurity and moisture content；Outside first collector It is heated using recirculated water；The lye of caustic treater is NaOH solution；Drier in drier is silica gel；Suction in absorber Attached dose is molecular sieve.

3. according to claim 2 efficiently synthesize trifluoroiodomethane method, it is characterised in that：Level-one collector outer circulation water Temperature be 70-80 DEG C；A concentration of 0.1-5% of NaOH solution in caustic treater；Adsorbent is 5A molecular sieves in absorber.

4. trifluoroiodomethane method is efficiently synthesized according to claim 2, it is characterised in that：Using cold-trap to trifluoroiodomethane It is received.

5. according to claim 4 efficiently synthesize trifluoroiodomethane method, it is characterised in that：Collect trifluoroiodomethane cold-trap Temperature be -70 DEG C.

6. efficiently synthesize trifluoroiodomethane method according to Claims 1 to 5 any one, it is characterised in that：CF₃COOH Steam is to be vaporized to generate by the vaporizer that temperature is 100 DEG C；Iodine vapor is generated by the iodine evaporator that temperature is 200 DEG C.

7. according to claim 6 efficiently synthesize trifluoroiodomethane method, it is characterised in that：Reaction unit includes reaction Device, the reactor inlet connect CF₃COOH vaporizers and iodine evaporator；The reactor outlet is sequentially connected the first collection Device, the second collector, caustic treater, drier, absorber, cold-trap.