CN109772396A - A kind of metal carbide catalyst and its preparation method and application adding hydrogen coupling reaction for being catalyzed CFC-113a - Google Patents
A kind of metal carbide catalyst and its preparation method and application adding hydrogen coupling reaction for being catalyzed CFC-113a Download PDFInfo
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Abstract
The invention discloses a kind of metal carbide catalyst and its preparation method and application for adding hydrogen coupling reaction for being catalyzed CFC-113a, the metal carbide catalyst is mainly made of at least one of cementite, carbonization nickel, carbonization ruthenium, carbonization palladium, cobalt carbide.When the metal carbide catalyst catalysis CFC-113a adds hydrogen coupling reaction, carried out on fixed-bed reactor, CFC-113a and H2Input material volume ratio be 1:3-5, reaction temperature be 200-400 DEG C, gas space velocity 100-1000h‑1Reaction pressure is normal pressure, CFC-113a reaction raw materials are easy to get and conversion ratio is higher (conversion ratio can reach 90% or more), the selectivity of target product CFC-1316 is higher (selectively can reach 90% or more), and metal carbide catalyst of the invention has higher catalytic stability in gas-phase catalytic hydrogenation coupling dechlorination reaction.
Description
Technical field
The present invention relates to a kind of metal carbide catalyst and its preparations for adding hydrogen coupling reaction for being catalyzed CFC-113a
Methods and applications.
Background technique
One fluorine dichloroethanes (HCFC-141b) is widely used as foaming agent, but the ODP of HCFC-141b is not
Zero, atmospheric ozone layer can still be damaged, therefore Montreal Protocol is included in and is eliminated in the works.Now in the world
Substitute mainly has 1,1,1,3,3- 3-pentafluorobutane (HFC-365mfc), 1,1,1,3,3- pentafluoropropane (HFC-245fa) etc., this
A little compounds do not have destructiveness to ozone layer, but they can still be obviously promoted global warming (GWP is larger), therefore it is only capable of
Substitute as polyurethane foam transitionality uses.Therefore, research and development had not only met zero ozone depletion but also there is the low whole world to become
The compound of warm potentiality is the urgent need of Vehicles Collected from Market, and fluorine hydrogen alkene 1,1, Isosorbide-5-Nitrae, and 4,4- hexafluoro -2- butylene (HFO-
1336mzz) exactly it is able to satisfy current requirement (9) ODP 0, GWP is about.
HFO-1336 preparation method and route are more at present, are most proposed earlier than nineteen fifty-two by Haszeldine R .N, with
2,3- dibromo hexafluorobutenes are raw material, first carry out debromination with zinc powder and obtain 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butine, then through urging
Change hydrogenation and obtains 1,1,1,4,4,4- hexafluoro -2- butylene.
In E.I.Du Pont Company patent CN102015592B, then with 2,2- bis- chloro- 1,1,1- trifluoroethane and copper powder are molten in amide
Agent and 2, in the presence of 2- bipyridyl, in 20~150 DEG C of reactions preparations 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.Honeywell patent
1,1,1,4,4,4- hexafluoro -2- butylene then is prepared using carbon tetrachloride and 3,3,3- trifluoro propene as raw material in CN102884030A；
It is then described in patent CN102892736B and 1,1,1,4,4,4- hexafluoro -2- butylene is prepared with carbon tetrachloride and ethylene reaction；
In patent CN103193586B using hexachlorobutadiene be raw material by fluorination, dechlorination, reduction prepare 1,1,1,4,4,4- hexafluoro-
2- butylene.It is prepared using 1,1,1,4,4,4- hexafluoro butane as raw material through chlorination, alkaline hydrolysis in Ju Hua group patent CN103172489B
1,1,1,4,4,4- hexafluoro -2- butylene.Although above-mentioned route respectively has some superiority, raw material cannot be solved simultaneously and be not easy to obtain,
Target product yield is not high, and the reaction time is longer and is easy to happen side reaction, by-product and the more difficult isolated spy of target product
The problems such as point.
Document [Chemistry Letters, 1991,19 (10): 1825-1826] and patent WO9505353 are reported
Under Cu, Ru or Pd catalysts conditions, it is coupled to obtain CFC-1316 from CFC-113a plus hydrogen, but conversion ratio and selectivity be not high,
And it is tested without catalyst life.E.I.Du Pont Company patent CN103524297A and Sinochem Lantian Co., Ltd.'s patent
In CN103373896B with the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene (CFC-1316) of 2,3- bis- zinc powder organic acid with it is molten
HFO-1336 is obtained in the presence of agent or under the conditions of special catalyst, and has higher yield and stability.This route raw material
It is easy to get, route is short, and by-product and target product separation are easier to.And hydrogen is added to produce to HFO-1336 reaction target from CFC-1316
Object high income, side reaction is few, but from CFC-113a add hydrogen be coupled to obtain CFC-1316 conversion ratio and selectivity it is not high.
Summary of the invention
In view of the defects existing in the prior art with deficiency, the purpose of the present invention is to provide one kind for being catalyzed CFC-113a
Add the metal carbide catalyst and its preparation method and application of hydrogen coupling reaction, the metal carbide catalyst is 1,1,1-
Trifluorotrichloroethane (CFC- 113a) gas-phase catalytic hydrogenation coupling dechlorination reaction obtains having in the reaction of CFC-1316 good
Catalytic performance has higher conversion ratio and target product selectivity.
A kind of metal carbide catalyst adding hydrogen coupling reaction for being catalyzed CFC-113a, it is characterised in that institute
Metal carbide catalyst is stated mainly to be made of at least one of cementite, carbonization nickel, carbonization ruthenium, carbonization palladium, cobalt carbide.
A kind of preparation method adding the metal carbide catalyst of hydrogen coupling reaction for being catalyzed CFC-113a,
It is characterized in that transition metal salt and aqueous solutions of organic acids are ground into viscous liquid with the molar ratio of 1:1-10 in the agate mortar,
Transition metal salt is molysite, nickel salt, ruthenium salt, palladium salt or cobalt salt, and the viscous liquid is then transferred to 100-200 DEG C of constant temperature
Moisture and pre- carbonization are dried and removed in drying box, are transferred in Muffle furnace, in carbon-containing atmosphere and 200-500 DEG C of temperature lower calcination
1-10 hours, obtain the metal carbide catalyst.
A kind of preparation method adding the metal carbide catalyst of hydrogen coupling reaction for being catalyzed CFC-113a,
The gas for being characterized in that the carbon-containing atmosphere is the gaseous mixture of carbonaceous gas and carrier gas, and the carbonaceous gas is CO, CH4、CO2、
At least one of ethane, propane, the carrier gas are N2、H2Or Ar；It is dilute in the gaseous mixture of the carbonaceous gas and carrier gas
The volume content of outgassing is 0-95%；The organic acid is one of oxalic acid, formic acid, propionic acid, citric acid, hydroxyacetic acid or two
Kind or more mixture.
A kind of preparation method adding the metal carbide catalyst of hydrogen coupling reaction for being catalyzed CFC-113a,
It is characterized in that in the preparation process of the metal carbide catalyst also with transition metal salt, organic acid and helping added with auxiliary agent
The quality sum of agent is raw material total amount meter, and the additive amount of auxiliary agent is between 0.05-15 wt %；The auxiliary agent is K salt, Mn salt, Cu
At least one of salt, Zr salt, Cs salt, Ir salt.
A kind of preparation method adding the metal carbide catalyst of hydrogen coupling reaction for being catalyzed CFC-113a,
It is characterized in that in the preparation process of the metal carbide catalyst also added with nitrogenous auxiliary agent, with transition metal salt, organic acid
Quality sum with nitrogenous auxiliary agent is raw material total amount meter, and the additive amount of nitrogenous auxiliary agent is between 0-10wt %；The nitrogenous auxiliary agent
For urea or melamine.
A kind of preparation method adding the metal carbide catalyst of hydrogen coupling reaction for being catalyzed CFC-113a,
Be characterized in that transition metal salt and carbohydrate organic matter with the molar ratio mixed dissolution of 1:0.5-50 in water, transition metal salt is iron
Salt, nickel salt, ruthenium salt, palladium salt or cobalt salt, then dry and remove moisture in 110-130 DEG C of thermostatic drying chamber, then at 160-200 DEG C
Be carbonized 0.5 ~ 5h in advance in thermostatic drying chamber, is finally transferred in Muffle furnace and roasts 1-10 hours under 500-900 DEG C of inert atmosphere,
Obtain the metal carbide catalyst.
A kind of preparation method adding the metal carbide catalyst of hydrogen coupling reaction for being catalyzed CFC-113a,
It is characterized in that the carbohydrate organic matter is at least one of sucrose, glucose, fructose, chitosan；The gas of the inert atmosphere
Body is N2Or Ar.
A kind of preparation method adding the metal carbide catalyst of hydrogen coupling reaction for being catalyzed CFC-113a,
It is characterized in that in the preparation process of the metal carbide catalyst also added with auxiliary agent, with transition metal salt, carbohydrate organic matter
Quality sum with auxiliary agent is raw material total amount meter, and the additive amount of auxiliary agent is between 0.05-15 wt %；The auxiliary agent is K salt, Mn
At least one of salt, Cu salt, Zr salt, Cs salt, Ir salt.
A kind of preparation method adding the metal carbide catalyst of hydrogen coupling reaction for being catalyzed CFC-113a,
It is characterized in that in the preparation process of the metal carbide catalyst also having added with nitrogenous auxiliary agent with transition metal salt, carbohydrate
The quality sum of machine object and nitrogenous auxiliary agent is raw material total amount meter, and the additive amount of nitrogenous auxiliary agent is between 0-10wt %；It is described nitrogenous
Auxiliary agent is urea or melamine.
The metal carbide catalyst adds hydrogen coupling reaction to prepare the application in CFC-1336 in catalysis CFC-113a,
It is characterized in that reaction carries out on fixed-bed reactor, CFC-113a and H2Input material volume ratio be 1:3-5, reaction temperature
It is 200-400 DEG C, gas space velocity 100-1000, reaction pressure is normal pressure.
Compared with the existing technology, the beneficial effect that the present invention obtains is:
The present invention for the first time by metal carbide catalyst be used to be catalyzed CFC-1316 coupling reaction in, be added metal salt assitant and
Nitrogenous auxiliary agent is adulterated by supplied for electronic to catalyst, increases the alkalinity of catalyst.The present invention is with 1,1,1- trifluorotrichloroethane
(CFC- 113a) is that raw material gas-phase catalytic hydrogenation is coupled dechlorination reaction and obtains CFC-1316, reaction raw materials be easy to get and conversion ratio compared with
High (conversion ratio can reach 90% or more), the selectivity of target product CFC-1316 is higher (selectively can reach 90% or more), and
Metal carbide catalyst of the invention has higher catalytic stability (in reality in gas-phase catalytic hydrogenation coupling dechlorination reaction
It applies successive reaction in example and runs 150h, nearly 90%) conversion ratio of CFC- 113a maintains.
Detailed description of the invention
Fig. 1 is the XRD diagram of metal carbide catalyst prepared by embodiment 1.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment one:
It is ground into yellow, viscous liquid in the agate mortar for the Fe(NO3)39H2O of 1:3 and oxalic acid aqueous solution in molar ratio
(concentration of oxalic acid aqueous solution is 30wt%, and the molar ratio of Fe(NO3)39H2O and oxalic acid is 1:3), obtains oxalic acid ferrous solution.Oxalic acid
It after ferrous solution dries and removes moisture at 100 DEG C, is roasted under CO atmosphere in tube furnace, maturing temperature is 500 DEG C, CO volume
Flow 80mL/min, compression molding after the completion of roasting sieve now in 60-100 and obtain metal carbide catalyst (this implementation
Metal carbide catalyst made from example is cementite), the XRD diagram of the metal carbide catalyst is as shown in Figure 1, from Fig. 1
As can be seen that the structure of catalyst shows the crystalline structure of cementite.
It takes the iron-carbonide catalyst of the above-mentioned preparation of 2mL in internal diameter 8mm reaction tube flat-temperature zone, is warming up in a hydrogen atmosphere
Reaction gas CFC- 113a, CFC- 113a and H is passed through after 300 DEG C2Input material volume ratio be 1:6, normal pressure, gas space velocity GHSV takes
800h-1.The conversion ratio of CFC- 113a and the selectivity of CFC-1316 are as shown in table 1.
Embodiment two:
Being ground into viscous liquid in the agate mortar in molar ratio for the ruthenium trichloride of 1:3 and aqueous formic acid, (formic acid is water-soluble
Liquid concentration is 40wt%, and the molar ratio of ruthenium trichloride and formic acid is 1:3), obtain solution A.Solution A dries and removes water at 120 DEG C
After point, in carbon-containing atmosphere and 350 DEG C of roasting temperature 7h in tube furnace, the gas of carbon-containing atmosphere is CH4With mixing for carrier gas
Close gas, CH4Volume flow 20mL/min, carrier gas is nitrogen and volume flow is 40 mL/min, after the completion of roasting tabletting at
Type, 60-100 now sieve i.e. obtain metal carbide catalyst (metal carbide catalyst made from the present embodiment be carbon
Change ruthenium).
Metal carbide catalyst manufactured in the present embodiment adds the process of hydrogen coupling reaction to repeat for being catalyzed CFC- 113a
Embodiment one carries out evaluation response.The conversion ratio of CFC- 113a and the selectivity of CFC-1316 are as shown in table 1.
Embodiment three:
It is ground into viscous liquid (citric acid water in the agate mortar for the cobalt carbonate of 1:3 and aqueous citric acid solution in molar ratio
Solution concentration is 40wt%, and the molar ratio of cobalt carbonate and citric acid is 1:3), then add again 2wt% potassium nitrate re-grind into it is viscous
Thick liquid (is counted, potassium nitrate additive amount is 2wt%) by raw material total amount of cobalt carbonate, citric acid and potassium nitrate, obtains solution B.It is molten
After liquid B dries and removes moisture at 120 DEG C, in carbon-containing atmosphere and 450 DEG C of roasting temperature 1h in tube furnace, carbon-containing atmosphere
Gas is the gaseous mixture of carbonaceous gas and carrier gas, and the carbonaceous gas is CO and CO2Mixed gas, CO and CO2Volume flow is equal
For 20mL/min, carrier gas is nitrogen and flow is 70 mL/min, and compression molding after the completion of roasting sieves now in 60-100
Obtaining metal carbide catalyst, (main component of metal carbide catalyst made from the present embodiment is cobalt carbide, carbonization
Doped with potassium element in cobalt).
Metal carbide catalyst manufactured in the present embodiment adds the process of hydrogen coupling reaction to repeat for being catalyzed CFC- 113a
Embodiment one carries out evaluation response.The conversion ratio of CFC- 113a and the selectivity of CFC-1316 are as shown in table 1.
Example IV:
The nickel nitrate and sucrose mixed dissolution for being in molar ratio 1:2 in water (concentration of aqueous sucrose solution is 30wt%), then add
4wt% urea stirs evenly, and obtains solution C and (counts by raw material total amount of nickel nitrate, sucrose and urea, the additive amount of urea is
4wt%).After solution C dries and removes moisture in 120 DEG C of thermostatic drying chambers, it is carbonized 2h in 160 DEG C of thermostatic drying chambers, then turns in advance
Move to the N in Muffle furnace at 850 DEG C2It is roasted 5 hours under atmosphere, last compression molding, is sieved now in 60-100 and obtain gold
Belonging to carbide catalyst, (main component of metal carbide catalyst made from the present embodiment is carbonization nickel, is carbonized in nickel and adulterates
There is nitrogen).
Metal carbide catalyst manufactured in the present embodiment adds the process of hydrogen coupling reaction to repeat for being catalyzed CFC- 113a
Embodiment one carries out evaluation response.The conversion ratio of CFC- 113a and the selectivity of CFC-1316 are as shown in table 1.
Embodiment five:
The chlorine palladium acid and glucose mixed dissolution for being in molar ratio 1:50 in water (concentration of glucose aqueous solution is 30wt%),
5wt% copper nitrate is added again to stir evenly, and is obtained solution D and (is counted using chlorine palladium acid, glucose and copper nitrate as raw material total amount, copper nitrate
Additive amount is 5wt%).After solution D dries dry removing moisture in 120 DEG C of thermostatic drying chambers, in 190 DEG C of pre- carbon of thermostatic drying chamber
Change 2h, is then transferred in Muffle furnace at 650 DEG C and N2Roasted 20 hours under atmosphere, last compression molding, 60-100 now
Screening i.e. obtain metal carbide catalyst (main component of metal carbide catalyst made from the present embodiment for carbonization palladium,
It is carbonized in palladium doped with copper).
Metal carbide catalyst manufactured in the present embodiment adds the process of hydrogen coupling reaction to repeat for being catalyzed CFC- 113a
Embodiment one carries out evaluation response.The conversion ratio of CFC- 113a and the selectivity of CFC-1316 are as shown in table 1.
1 different metal carbide catalyst of table adds the performance in hydrogen coupling reaction in CFC-113a
| Embodiment | Catalyst | CFC-113a conversion ratio | CFC-1316 selectivity | Evaluation time/h |
| Embodiment one | Cementite | 93% | 84 | 120 |
| Embodiment two | Be carbonized ruthenium | 88% | 95 | 150 |
| Embodiment three | Cobalt carbide | 92% | 89% | 10 |
| Example IV | Be carbonized nickel | 98% | 86% | 10 |
| Embodiment five | Be carbonized palladium | 81% | 93% | 15 |
From table 1 it follows that metal carbide catalyst of the invention be catalyzed CFC-113a add hydrogen coupling reaction when, CFC-
The catalysis with higher of the higher and of the invention metal carbide catalyst of the selectivity of 113a conversion ratio and CFC-1316 is steady
It is qualitative.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a, it is characterised in that the metal carbon
Compound catalyst is mainly made of at least one of cementite, carbonization nickel, carbonization ruthenium, carbonization palladium, cobalt carbide.
2. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a according to claim 1
Preparation method, it is characterised in that transition metal salt and aqueous solutions of organic acids are ground into the agate mortar with the molar ratio of 1:1-10
Viscous liquid, transition metal salt are molysite, nickel salt, ruthenium salt, palladium salt or cobalt salt, are then transferred to the viscous liquid
Moisture and pre- carbonization are dried and removed in 100-200 DEG C of thermostatic drying chamber, are transferred in Muffle furnace, in carbon-containing atmosphere and 200-
500 DEG C temperature lower calcination 1-10 hours, obtain the metal carbide catalyst.
3. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a according to claim 2
Preparation method, it is characterised in that the gas of the carbon-containing atmosphere is the gaseous mixture of carbonaceous gas and carrier gas, the carbonaceous gas
For CO, CH4、CO2, ethane, at least one of propane, the carrier gas is N2、H2Or Ar；The carbonaceous gas and carrier gas
Gaseous mixture in, the volume content of carrier gas is 0-95%；The organic acid is oxalic acid, formic acid, propionic acid, citric acid, hydroxyacetic acid
One or more mixtures of.
4. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a according to claim 2
Preparation method, it is characterised in that in the preparation process of the metal carbide catalyst also be added with auxiliary agent, with transition metal salt,
The quality sum of organic acid and auxiliary agent is raw material total amount meter, and the additive amount of auxiliary agent is between 0.05-15 wt%；The auxiliary agent is K
At least one of salt, Mn salt, Cu salt, Zr salt, Cs salt, Ir salt.
5. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a according to claim 2
Preparation method, it is characterised in that nitrogenous auxiliary agent is added in the preparation process of the metal carbide catalyst, also with transition gold
The quality sum for belonging to salt, organic acid and nitrogenous auxiliary agent is raw material total amount meter, and the additive amount of nitrogenous auxiliary agent is between 0-10wt%；Institute
Stating nitrogenous auxiliary agent is urea or melamine.
6. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a according to claim 1
Preparation method, it is characterised in that transition metal salt and carbohydrate organic matter with the molar ratio mixed dissolution of 1:0.5-50 in water, mistake
Crossing metal salt is molysite, nickel salt, ruthenium salt, palladium salt or cobalt salt, then dries and removes moisture in 110-130 DEG C of thermostatic drying chamber,
Be carbonized 0.5 ~ 5h in advance in 160-200 DEG C of thermostatic drying chamber, is finally transferred in Muffle furnace under 500-900 DEG C of inert atmosphere
Roasting 1-10 hours, obtains the metal carbide catalyst.
7. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a according to claim 6
Preparation method, it is characterised in that the carbohydrate organic matter is at least one of sucrose, glucose, fructose, chitosan；It is described lazy
Property atmosphere gas be N2Or Ar.
8. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a according to claim 6
Preparation method, it is characterised in that in the preparation process of the metal carbide catalyst also be added with auxiliary agent, with transition metal salt,
The quality sum of carbohydrate organic matter and auxiliary agent is raw material total amount meter, and the additive amount of auxiliary agent is between 0.05-15 wt%；The auxiliary agent
For at least one of K salt, Mn salt, Cu salt, Zr salt, Cs salt, Ir salt.
9. a kind of metal carbide catalyst for adding hydrogen coupling reaction for being catalyzed CFC-113a according to claim 6
Preparation method, it is characterised in that nitrogenous auxiliary agent is added in the preparation process of the metal carbide catalyst, also with transition gold
Belong to salt, the quality sum of carbohydrate organic matter and nitrogenous auxiliary agent is raw material total amount meter, the additive amount of nitrogenous auxiliary agent 0-10wt% it
Between；The nitrogenous auxiliary agent is urea or melamine.
10. metal carbide catalyst as described in claim 1 adds hydrogen coupling reaction to prepare CFC- in catalysis CFC-113a
Application in 1336, it is characterised in that reaction carries out on fixed-bed reactor, CFC-113a and H2Input material volume ratio be
1:3-5, reaction temperature are 200-400 DEG C, gas space velocity 100-1000, reaction pressure is normal pressure.
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