CN107552076A - One kind tool nanocomposite carrier catalysts for gas phase fluorination and preparation method thereof - Google Patents
One kind tool nanocomposite carrier catalysts for gas phase fluorination and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to one kind tool nanocomposite carrier catalysts for gas phase fluorination and preparation method thereof, nanocrystalline metal fluoride carrier is included in the fluorination catalyst；The nanocrystalline metal fluoride carrier is selected from nanocrystalline Al F3, nanocrystalline M gF2, nanocrystalline ZrF2With nanocrystalline CaF2In at least two.The nanocrystalline metal fluoride is prepared by sol-gal process and ultrasonic method combination.Described tool nanocomposite carrier catalysts for gas phase fluorination is prepared by co-precipitation preparation method.The advantages that catalysts for gas phase fluorination specific surface area prepared by the present invention is big, catalytic activity is high, stability is good, it is suitable for fluorine chlorine substitution gas phase fluorination, is especially suitable for the preparation of the refrigerants such as R125, R134a.
Description
Technical field
The present invention relates to a kind of fluorination catalyst and preparation method thereof, and in particular to a kind of for halogenated hydrocarbons and hydrogen fluoride
Tool nanocomposite carrier catalysts for gas phase fluorination of gas phase fluorination and preparation method thereof.
Background technology
In fluorine chemical field, because hydrogen fluorohydrocarbon (HFCs) ODP (ODP) is 0, global warming potential
Value (GWP) is smaller, and refrigeration performance is similar to fluorochlorohydrocarbon (CFCs), is CFCs ideal substitute, is widely used in large-scale business
Industry refrigerant, foaming agent, extinguishing chemical etc..At present, market mainstream environment friendly refrigerating fluid (R125, R134a, R1234yf) product
Key production technology thereof is gas phase fluorination catalytic reaction process, and catalysts for gas phase fluorination is the core in the process route, and gas phase
Fluorination catalyst mainly uses chromium base solid catalyst.The catalytic activity and stability of chromium base solid catalyst and the ratio of catalyst
All there is substantial connection for surface area, hole parameter, crystallite dimension, crystal formation etc..
At present, in chromium base solid catalyst field, prior art is typically all using adding metal promoter, surfactant etc.
Means regulate and control the pore structure of catalyst and hole parameter, micropore ratio or acid-base property, so as to improve the activity of catalyst, and it is relevant
Metallic compound crystal formation urges gas phase fluorination the correlative study of the influence of catalytic performance less and not deep enough, relevant nanocrystalline gold
It is then less to belong to correlative study of the compound to catalysts for gas phase fluorination catalytic performance.As Chinese patent CN 101214449A are disclosed
A kind of fluorination catalyst and preparation method thereof, in the patent adds aluminum fluoride, although it is brilliant for γ and β to refer to aluminum fluoride
Type, but the patent does not refer to the preparation of the aluminum fluoride with specific crystal formation structure.The tradition preparation of nanocrystalline metal fluoride
Method is agglutinating nature yeast, but the crystallization, aging and drying and other steps in this method are required to the long period, are unfavorable for work
Industry metaplasia is produced.As Chinese patent CN105597795A discloses the preparation method of a kind of nanometer of Naluminum fluoride base catalyst, use is molten
Glue-gel method prepares nanocrystalline aluminum fluoride, and crystallization and ageing time are added together in the patent also exists more than 30h, drying time
More than 24h.
The content of the invention
Taken for the nanocrystalline metal fluoride for preparing of deficiency of the prior art, and conventional gel-sol method
The problems such as long, one aspect of the present invention provide a kind of new tool nanocomposite carrier catalysts for gas phase fluorination and its preparation side
Method, on the other hand provide a kind of preparation technology of time-consuming shorter nanocrystalline metal fluoride.
To achieve the above object, the concrete scheme that the present invention uses is as follows：
One aspect of the present invention provides a kind of tool nanocomposite carrier catalysts for gas phase fluorination, the nanocomposite carrier
In include nanocrystalline metal fluoride；The nanocrystalline metal fluoride is selected from nanocrystalline Al F3, nanocrystalline M gF2, it is nanocrystalline
ZrF2With nanocrystalline CaF2In at least two.
In embodiments of the present invention, the nanocrystalline metal fluoride is selected from nanocrystalline Al F3, nanocrystalline M gF2, nanometer
Brilliant ZrF2With nanocrystalline CaF2In two or three.
In some embodiments, the nanocomposite carrier includes two kinds of nanocrystalline metal fluorides, such as：Receive
The brilliant MgF of rice2With nanocrystalline Al F3。
In other embodiments, the nanocomposite carrier includes three kinds of nanocrystalline metal fluorides, such as：
Nanocrystalline M gF2, nanocrystalline Al F3With nanocrystalline ZrF2；Nanocrystalline M gF2, nanocrystalline Al F3With nanocrystalline CaF2。
The nanocrystalline metal fluoride included in nanocomposite carrier provided by the invention is not limited to arrange in the present invention
The nanocrystalline metal fluoride combinations of act, the present invention is can also be used for comprising other combinations within the scope of the present invention, such as：Receive
The brilliant AlF of rice3With nanocrystalline ZrF2；Nanocrystalline Al F3With nanocrystalline CaF2；Nanocrystalline M gF2With nanocrystalline CaF2；Nanocrystalline M gF2With
Nanocrystalline ZrF2；Nanocrystalline M gF2, nanocrystalline CaF2With nanocrystalline ZrF2；Etc..
In embodiments of the present invention, the nanocrystalline Al F3For the one or more in α, β, γ crystalline structure.It is preferred that
, the nanocrystalline Al F3For two kinds in α, β, γ crystalline structure.
In some embodiments, the nanocrystalline Al F3For α and the nanocrystalline Al F of beta crystal structure3Mixture, α is brilliant
The mass ratio of type and beta crystal is 1~80:20~99.Preferably, the mass ratio of alpha-crystal form and beta crystal is 40~60:40~60, example
Such as：40:60、50:50、60:40, etc..
In other embodiments, the nanocrystalline Al F3For the nanocrystalline Al F of β and γ crystalline structures3Mixture, β
The mass ratio of crystal formation and γ crystal formations is 1~80:20~99.Preferably, the mass ratio of beta crystal and γ crystal formations is 40~60:40~
60, such as：40:60、50:50、60:40, etc..
Also in some embodiments, the nanocrystalline Al F3For the nanocrystalline Al F of α and γ crystalline structures3Mixture, α
The mass ratio of crystal formation and γ crystal formations is 1~80:20~99.Preferably, the mass ratio of alpha-crystal form and γ crystal formations is 40~60:40~
60, such as：40:60、50:50、60:40, etc..
In embodiments of the present invention, the nanocrystalline Al F3Specific surface area be 132~215m2/ g, such as：132m2/
g、139m2/g、158m2/g、163m2/g、181m2/g、196m2/g、198m2/g、201m2/g、206m2/ g or 215m2/g。
In embodiments of the present invention, the nanocrystalline Al F3Size controlling in 15~45nm.Preferably, the nanometer
Brilliant AlF3Size controlling in 21~36nm, such as：21nm, 22nm, 23nm, 25nm, 28nm, 32nm, 33nm or 36nm.
In embodiments of the present invention, the nanocrystalline M gF2For tetragonal structure structure.
In embodiments of the present invention, the nanocrystalline M gF2Specific surface area be 150~210m2/g.Preferably, it is described
Nanocrystalline M gF2Specific surface area be 170~190m2/ g, such as：170m2/g、172m2/g、174m2/g、177m2/g、180m2/g
Or 188m2/g。
In embodiments of the present invention, the nanocrystalline M gF2Size controlling in 21~35nm, such as：22nm、24nm、
26nm, 28nm, 30nm, 32nm or 34nm.
In embodiments of the present invention, the nanocrystalline CaF2For cubic structure.
In embodiments of the present invention, the nanocrystalline CaF2Specific surface area be 101~137m2/g.Preferably, it is described
Nanocrystalline CaF2Specific surface area be 110~130m2/ g, such as：113m2/g、115m2/g、120m2/g、125m2/ g or 130m2/
g。
In embodiments of the present invention, the nanocrystalline CaF2Size controlling in 33~50nm, such as：35nm、41nm、
45nm or 50nm.
In embodiments of the present invention, the nanocrystalline ZrF2For one kind in tetragonal structure and monoclinic form structure or two
Kind.
In embodiments of the present invention, the nanocrystalline ZrF2Specific surface area be 110~150m2/g.Preferably, it is described
Nanocrystalline ZrF2Specific surface area be 125~145m2/ g is for example：125m2/g、129m2/g、138m2/ g or 145m2/g。
In embodiments of the present invention, the nanocrystalline ZrF2Size controlling in 28~45nm.Preferably, the nanometer
Brilliant ZrF2Size controlling in 30~40nm for example：32nm, 34nm, 36nm, 38nm or 40nm.
Another aspect of the present invention provides a kind of preparation side of above-mentioned tool nanocomposite carrier catalysts for gas phase fluorination
Method, comprise the following steps：
1) prepared by chromium based compound
Chromic salts and other metal salts are dissolved in water to obtain mixing salt solution, ammonification water sedimentation, aging, filters, washs, do
Dry, roasting, crushing obtains chromium based compound powder；
2) prepared by catalyst precursor
Chromium based compound powder obtained by step 1) and nanocrystalline metal fluoride and graphite are mixed, compression molding obtains
To catalyst precursor；
Wherein, the nanocrystalline metal fluoride is AlF3、MgF2、ZrF2And CaF2In at least two；
3) prepared by fluorination catalyst
The catalyst precursor that step 2) obtains is fluorinated in inert gas and HF mixed gas, obtains fluorination catalyst
Agent.
In the preparation method of chromium based compound of the present invention, the Cr salt is selected from chromic nitrate, chromium chloride, chromium sulfate, chrome alum；Institute
Stating other metals in other metal salts can need to be selected according to catalyst formulation, all to strengthen catalyst activity
Metal can serve as selecting object.Technical scheme for convenience of explanation, some citings are provided herein, but be not limited to
This.
In embodiments of the present invention, other described metal salts are selected from Co salt, Ni salt, Cu salt, Zn salt, Fe salt, Mg salt, In
At least one of salt, Al salt and La salt.Wherein, the Co salt is selected from cobalt nitrate, cobalt chloride；The Ni salt selects nickel chloride, nitric acid
Nickel；The Cu salt is selected from copper chloride, copper nitrate；The Zn salt is selected from zinc chloride, zinc nitrate；The Fe salt is selected from iron chloride；Institute
State Mg salt and be selected from magnesium carbonate, magnesium bicarbonate, magnesium nitrate, magnesium chloride, magnesium sulfate；The In salt is selected from indium nitrate, inidum chloride, sulfuric acid
Indium；The Al salt is selected from aluminum nitrate, aluminium chloride, aluminium isopropoxide；The La salt is selected from lanthanum chloride, lanthanum nitrate.
In some embodiments, other described metal salts are four kinds of Al salt, In salt, Ni salt and La salt, such as AlCl3、
InCl3、NiCl2And LaCl3。
In the preparation method of chromium based compound of the present invention, the pH value of the ammonification water mixed precipitation is 9~13, such as：9、
10th, 11,12 or 13.
In the preparation method of chromium based compound of the present invention, the temperature of the drying is 90~120 DEG C, such as：90℃、100
DEG C, 110 DEG C or 120 DEG C；The time of the drying is 6~12h.In some embodiments, the dry time is 6~10h examples
Such as：6h, 7h, 8h, 9h or 10h.
In the preparation method of chromium based compound of the present invention, the roasting is carried out in inert gas, the roasting
Temperature is 300~400 DEG C.Preferably, the temperature of the roasting is 300~350 DEG C.
In the preparation method of catalyst precursor of the present invention, the chromium based compound powder, nanocrystalline metal fluoride, stone
The mass ratio of ink is 70~98:1~20:1~10.Preferably, the chromium based compound powder, nanocrystalline metal fluoride, stone
The mass ratio of ink is 80~95:5~15:1~5.
In some embodiments, the chromium based compound powder, nanocrystalline metal fluoride, the mass ratio of graphite are
85:10:5；In other embodiments, the chromium based compound powder, nanocrystalline metal fluoride, the mass ratio of graphite are
88:10:2；In other embodiments, the chromium based compound powder, nanocrystalline metal fluoride, graphite quality ratio are
93:5:2。
In the preparation process of fluorination catalyst of the present invention, the fluorination of catalyst precursor is the mixing in inert gas and HF
Carried out under gas, fluorination temperature is 250~400 DEG C.Preferably, it is 310~350 DEG C to be fluorinated temperature, such as：310℃、320
DEG C, 330 DEG C, 340 DEG C or 350 DEG C.
In the preparation process of fluorination catalyst of the present invention, the fluorination time control is in 8~40h.Preferably, the fluorination
Time control in 10~40h, such as：10h, 15h, 18h, 20h, 24h, 25h, 28h, 30h, 35h or 40h.
Further, the present invention also provides a kind of preparation method of above-mentioned nanocrystalline metal fluoride, passes through sol-gel
It is prepared by method and ultrasonic method combination.Ultrasonic wave using playing the role of for the use of following three：First, ultrasound accelerates dissolution of raw material
And increase its solubility, the balance of dissolution-crystallization is promoted, shortens crystallization induction period, so as to shorten crystallization time；Second, super
Crystallization, aging are carried out under sound so that reaction solution intermediate ion, proton, the motion of nucleus rule oriented and speed are accelerated, and can speed up crystalline substance
Body grows, so as to effectively shorten crystal growth time；Third, ultrasound causes crystal seed to quickly generate while rapid dispersion, i.e.,
Nucleus is just quickly dispersed in growth process in reaction solution, so that nucleus quantity increase in reaction solution, and gained nanoparticle
Footpath is smaller more homogeneous, i.e. ultrasonic wave is advantageous to that synthesizing high specific surface area, crystallinity is homogeneous, the fluorination of nanocrystalline metal of uniform particle diameter
Thing.
Specifically, the preparation method of the nanocrystalline metal fluoride comprises the following steps：
Metal salt stirring and dissolving and is flowed back in solvent, the fluorination reagent aqueous solution is then added dropwise under ultrasonic agitation state
Reacted, obtain lyosol through crystallization, aging, dry, obtain solid gel, be then calcined and nanocrystalline metal fluorination is made
Thing；
Wherein, the metal salt is selected from any of Mg salt, Al salt, Ca salt and Zr salt.
The Mg salt is selected from magnesium carbonate, magnesium bicarbonate, magnesium nitrate, magnesium chloride, magnesium sulfate；The Al salt be selected from aluminum nitrate,
Aluminium chloride, aluminium isopropoxide；The Ca salt is selected from calcium chloride, calcium nitrate；The Zr salt selects zirconium chloride, zirconium nitrate, basic zirconium chloride.
In the preparation method of nanocrystalline metal fluoride of the present invention, the solvent of dissolved metal salt is water, methanol, ethanol, different
At least one of propyl alcohol and isobutanol.In some embodiments, the solvent is water, methanol, ethanol, isopropanol and isobutyl
Any of alcohol；In other embodiments, the solvent is the mixing of water and methanol, ethanol, isopropanol or isobutanol
Thing, such as：Water and ethanol, water and methanol, water and isopropanol, water and isobutanol.
In the preparation method of nanocrystalline metal fluoride of the present invention, the fluorination reagent is ammonium fluoride, hydrogen fluoride, the tetrabutyl
At least one of ammonium fluoride (TBAF) and hydrogen fluoride pyridine.Preferably, the fluorination reagent is ammonium fluoride, hydrogen fluoride, four fourths
One or both of base ammonium fluoride (TBAF) and hydrogen fluoride pyridine.
In some embodiments, the fluorination reagent is ammonium fluoride；In some embodiments, the fluorination reagent is
Hydrogen fluoride；In other embodiments, the fluorination reagent is TBAF；Also in some embodiments, the fluorination reagent
For hydrogen fluoride pyridine.
In the preparation method of nanocrystalline metal fluoride of the present invention, the selection of supersonic frequency has important shadow to crystal growth
Ring, supersonic frequency is too small, then does not have the effect for promoting and strengthening crystal growth；Supersonic frequency is excessive, then smashes crystal, destroys
Crystal growth.In embodiments of the present invention, supersonic frequency is controlled in 40~80KHz, the typical but non-limit of the supersonic frequency
Property example processed has：40KHz, 45KHz, 50KHz, 55KHz, 60KHz, 65KHz, 75KHz or 80KHz.The ultrasonic time control
10~30min after adding the fluorination reagent aqueous solution to be added dropwise.
In the preparation method of nanocrystalline metal fluoride of the present invention, the metal salt in solvent stirring and dissolving and flow back
Temperature is 20~160 DEG C；Preferably, reflux temperature control is at 60~160 DEG C, the reflux temperature it is typical but unrestricted
Property example has：60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C or 160 DEG C.The return time is 0~2h；Preferably, during backflow
Between be 0.5~2h, the typical case of the return time but non-limiting examples have 0.5h, 1.0h, 1.5h or 2.0h.
In the preparation method of nanocrystalline metal fluoride of the present invention, the fluorination reagent aqueous solution is added dropwise into metal salt solution
Time control is in 1~90min.Preferably, time for adding control is in 2~80min；It is furthermore preferred that time for adding control 3~
70min；Particularly preferred, time for adding is controlled in 5~60min.
In the preparation method of nanocrystalline metal fluoride of the present invention, the temperature that the fluorination reagent aqueous solution is added dropwise and is reacted
Spend for 20~160 DEG C；Preferably, reaction temperature control is at 60~160 DEG C, the reaction temperature it is typical but non-limiting
Example has：60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C or 160 DEG C.
In the preparation method of nanocrystalline metal fluoride of the present invention, described crystallization, aging temperature are 20~160 DEG C, institute
Stating crystallization, the typical case of aging temperature but non-limiting examples has：60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C or 160 DEG C.It is described
Crystallization, total aging time are 8~12h, and the crystallization, the typical case of total aging time but non-limiting examples have：8h、9h、10h、
11h or 12h.
In the preparation method of nanocrystalline metal fluoride of the present invention, the drying temperature of the lyosol is 100~130
DEG C, the typical but non-limiting examples of the drying temperature have：100 DEG C, 110 DEG C, 120 DEG C, 125 DEG C or 130 DEG C；The liquid
6~12h of drying time of colloidal sol, the typical but non-limiting examples of the drying time have：6h, 7h, 8h, 9h, 10h, 11h or
12h。
In the preparation method of nanocrystalline metal fluoride of the present invention, lyosol obtains solid gel, solid after drying
The temperature that gel is calcined is 350~550 DEG C, and the typical but non-limiting examples of the sintering temperature have：350℃、380
DEG C, 400 DEG C, 420 DEG C, 450 DEG C, 500 DEG C or 550 DEG C；The roasting time is 3~8h, and the drying time is typical but non-limit
Property example processed has：3h, 4h, 5h, 6h, 7h or 8h.
It is anti-that tool nanocomposite carrier catalysts for gas phase fluorination provided by the invention is suitable for fluorine chlorine substitution gas phase fluorination
Should, it is especially suitable for R125 and R134a preparation.
The water used in embodiments of the present invention is deionized water.
Heretofore described " inert gas " refers to the gas for not participating in reaction during roasting and fluorination, such as
Nitrogen, argon gas etc..
Drying of the present invention, refer to borrow energy to make material reclaimed water or solvent gasify, and take away generated steam
Process.Drying mode is drying drying used by some embodiments of the present invention.It should be pointed out that same effect can be reached
Drying means also include but is not limited to drying, vacuum drying, freeze-drying, pneumatic conveying drying, etc..
Term " washing " of the present invention, refers to by certain effect to weaken or eliminate between impurity and material
Interaction, makes the combination of impurity and material be changed into the combination of impurity and solvent, impurity is departed from material.The present invention
Some embodiments in refer to the process of be rinsed material to pH ≈ 7 with water, ethanol.
Terminology used in the present invention " filtering " represent gravity or other external force effect under by medium by fluid with it is non-
The operation of fluid separation, the medium includes but is not limited to filter paper, gauze, filter core, pellicle, filter screen etc., in theory, containing more
The material of pore structure can turn into the medium of filtering；The equipment of filtering includes but is not limited to vacuum or decompressor, pressurization dress
Put, centrifugal device etc..
Unless explicitly stated otherwise in contrast, otherwise, all scopes that the present invention quotes include end value.For example, " roasting
Temperature is 350~550 DEG C ", the span for representing temperature during roasting is 350 DEG C≤T≤550 DEG C.
Terminology used in the present invention "one" or " one kind " describes key element and component described herein.So do only
It is for convenience, and to provide general meaning to the scope of the present invention.This description should be read to include one or extremely
It is few one, and the odd number also includes plural number, unless it is obvious that it is meant otherwise.
Numeral in the present invention is approximation, no matter whether uses the wording such as " about " or " about ".The numerical value of numeral has
It is possible that the difference such as 1%, 2%, 5%, 7%, 8%, 10%.It is any to have whenever a numeral with N values is disclosed
The numeral that N+/- 1%, N+/- 2%, N+/- 3%, N+/- 5%, N+/- 7%, N+/- 8% or N+/- 10% are worth can be by clearly public
Open, wherein " +/- " refers to add deduct, and the scope between N-10% to N+10% is also disclosed.
Unless otherwise defined, the otherwise implication of all scientific and technical terminologies used herein and common skill of the art
As art personnel are generally understood that.Although similar or equivalent method and material also can use with approach described herein and material
In the implementation or test of embodiment of the present invention, but suitable method and material is described below.What is be mentioned above is all
Publication, patent application, patent and other bibliography are incorporated herein in a manner of being cited in full text, except non-quoted physical segment
Fall.If conflict occurs, it is defined by this specification and its included definition.In addition, material, method and embodiment are only exemplary
, it is no intended to limited.
The beneficial effects of the present invention are：
1) present invention first prepares the nanocrystalline metal fluoride for being made and possessing high-specific surface area, then introduces the fluoride
In catalyst, the drastically decline for first introducing specific surface area during metal oxide is fluorinated as metal fluoride again is avoided,
So as to improve the activity of catalyst；
2) at least two different nanocrystalline metal fluorides are included in nanocomposite carrier of the invention, passes through difference
Interaction between the carrier of crystal formation, the overall carbon accumulation resisting ability for improving catalysts for gas phase fluorination, so as to improve the longevity of catalyst
Life；
3) carry out preparing nanocrystalline metal fluoride by sol-gel process and ultrasonic method combination, considerably reduce crystalline substance
Change the time, so as to reduce the preparation time of nanocrystalline metal fluoride, be advantageous to industrialized production；
4) fluorination catalyst provided by the invention is applied to synthesis R134a gas phase fluorinations.The catalyst has high ratio
Area and nanocrystalline so that not only activity is high for the catalyst, and shows good carbon accumulation resisting ability, steady so as to improve catalyst
Qualitative, after catalyst successive reaction 1150h, raw material R133a conversion ratio stills remain in 30% or so.
Brief description of the drawings
Fig. 1：The life diagram for the fluorination catalyst that comparative example 1 and embodiment 5 provide
Embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to the following side of being preferable to carry out
Formula.It should be pointed out that for those skilled in the art on the basis of this innovation and creation design, some deformations for making and
Improve, protection scope of the present invention is belonged to, in order to further describe the present invention, below in conjunction with the accompanying drawings with for specific embodiment
It is bright.
The preparation of the nanocrystalline metal fluoride of embodiment 1
10g metal salts are dissolved in 200mL solvents, reflow treatment 2h under heating stirring, then maintained at this temperature, Yu Chao
The aqueous solution that fluorination reagent is added dropwise under the ultrasonic agitation state that acoustic frequency is 40~80KHz is reacted, and time for adding 5~
60min, then crystallization, aging 12h obtain lyosol, then lyosol are consolidated in 110 DEG C of dry 10h at such a temperature
Body gel, finally it is calcined 6h at 350~550 DEG C and nanocrystalline metal fluoride is made.Different metal salt, organic solvent, fluorination examination
Obtained nanocrystalline metal fluorided structure performance is shown in Table 1 under agent, sintering temperature.
The structural parameters of obtained nanocrystalline metal fluoride under the conditions of the differential responses of table 1
The preparation of the chromium based compound of embodiment 2
Weigh 50g CrCl3·6H2O、2.83g AlCl3、0.33g InCl3、0.63g NiCl2、0.10g LaCl3Dissolving
In 900mL deionized waters, mixed salt solution is mixed to pH value of solution=10, filtering washing with ammoniacal liquor and obtains sample, sample is thrown
Roaster is transferred to after entering the dry 6h of 110 DEG C of baking oven, in N2320 DEG C of high-temperature roasting 3h in atmosphere, the sample comminution sieving after roasting,
Unformed chromium based compound powder is obtained, it is standby.
Embodiment 3
85% unformed chromium based compound powder, 10% nanocrystalline metal fluoride, 5% graphite mixed pressuring plate are molded
Nanocomposite carrier catalysts for gas phase fluorination presoma, the precursor is fitted into reactor, is passed through nitrogen and AHF mixing
Gas is fluorinated 24h at 350 DEG C, obtains having nanocomposite carrier catalysts for gas phase fluorination.
Wherein, the nanocrystalline metal fluoride is made up of nanocrystalline magnesium fluoride and nanocrystalline aluminum fluoride, its corresponding matter
Amount is than being 45:55.Nanocrystalline magnesium fluoride is nanocrystalline for the tetragonal structure obtained under the experiment condition of numbering 11 in the table 1 of embodiment 1
Magnesium fluoride；Nanocrystalline aluminum fluoride is the α and the nanocrystalline fluorine of beta crystal that are obtained in the table 1 of embodiment 1 under the experiment condition of numbering 5 and 10
Change the mixture of aluminium, both mass ratioes are 40:60.
Embodiment 4
93% unformed chromium based compound powder, 5% nanocrystalline metal fluoride, 2% graphite mixed pressuring plate are molded
Nanocomposite carrier catalysts for gas phase fluorination presoma, the precursor is fitted into reactor, is passed through nitrogen and AHF mixing
Gas is fluorinated 30h at 320 DEG C, obtains having nanocomposite carrier catalysts for gas phase fluorination.
Wherein, the nanocrystalline metal fluoride is made up of nanocrystalline magnesium fluoride and nanocrystalline aluminum fluoride, its corresponding matter
Amount is than being 55:45, nanocrystalline magnesium fluoride is nanocrystalline for the tetragonal structure obtained under the experiment condition of numbering 12 in the table 1 of embodiment 1
Magnesium fluoride, nanocrystalline aluminum fluoride are α the and γ crystal type nano crystalline substance fluorine that is obtained in the table 1 of embodiment 1 under the experiment condition of numbering 2 and 3
Change the mixture of aluminium, both mass ratioes are 50:50.
Embodiment 5
88% unformed chromium based compound powder, 10% nanocrystalline metal fluoride, 2% graphite mixed pressuring plate are molded
Nanocomposite carrier catalysts for gas phase fluorination presoma, the precursor is fitted into reactor, is passed through nitrogen and AHF mixing
Gas is fluorinated 40h at 320 DEG C, obtains having nanocomposite carrier catalysts for gas phase fluorination.
Wherein, the nanocrystalline metal fluoride is by nanocrystalline magnesium fluoride, nanocrystalline aluminum fluoride, nanocrystalline zirconium fluoride group
Into its corresponding mass ratio is 40:45:15.Nanocrystalline magnesium fluoride is obtains under the experiment condition of numbering 11 in the table 1 of embodiment 1
The nanocrystalline magnesium fluoride of tetragonal structure；Nanocrystalline aluminum fluoride is the β that is obtained in the table 1 of embodiment 1 under the experiment condition of numbering 3 and 10
With the mixture of γ crystal type nano crystalline substance aluminum fluorides, both mass ratioes are 50:50；Nanocrystalline zirconium fluoride is in the table 1 of embodiment 1
The nanocrystalline zirconium fluoride of monoclinic form obtained under the experiment condition of numbering 14.
Embodiment 6
80% unformed chromium based compound powder, 15% nanocrystalline metal fluoride, 5% graphite mixed pressuring plate are molded
Nanocomposite carrier catalysts for gas phase fluorination presoma, the precursor is fitted into reactor, is passed through nitrogen and AHF mixing
Gas is fluorinated 30h at 350 DEG C, obtains having nanocomposite carrier catalysts for gas phase fluorination.
Wherein, the nanocrystalline metal fluoride is made up of nanocrystalline magnesium fluoride, nanocrystalline aluminum fluoride, nano calcium fluoride,
Its corresponding mass ratio is 45:35:20.Nanocrystalline magnesium fluoride for obtained in the table 1 of embodiment 1 under the experiment condition of numbering 12 four
The nanocrystalline magnesium fluoride of prismatic crystal type；Nanocrystalline aluminum fluoride is the β and γ that are obtained in the table 1 of embodiment 1 under the experiment condition of numbering 3 and 10
The mixture of crystal type nano crystalline substance aluminum fluoride, both mass ratioes are 50:50；Nanocrystalline calcirm-fluoride is to be numbered in the table 1 of embodiment 1
The cubic crystal type nano crystalline substance calcirm-fluoride obtained under 15 experiment conditions.
Comparative example 1
Catalysts for gas phase fluorination forerunner is made in 98% unformed chromium based compound powder, the shaping of 2% graphite mixed pressuring plate
Body, the precursor is fitted into reactor, the mixed gas for being passed through nitrogen and AHF is fluorinated 40h at 320 DEG C, obtains having nanometer
Brilliant complex carrier catalysts for gas phase fluorination.
The performance evaluation of embodiment 7
The fluorination catalyst for respectively providing comparative example 1, embodiment 3~6 is used for the evaluation experimental for synthesizing R134a, evaluation
Condition is as follows：Load 100mL fluorination catalysts in self-control fixed bed, reaction temperature control is 310~350 DEG C.Lead in reactor
Enter R133a and HF, R133a flow is 36g/h, and HF flows are 75g/h.R133a and HF enters reactor reaction after mixing,
Product gas is scrubbed, alkali cleaning carries out gas chromatographic analysis again after removing HCl and HF.R133a conversion ratio and R134a selectivity
It is shown in Table 2.
The fluorination catalyst that comparative example 1 and embodiment 5 are provided carries out life test, and test result is shown in accompanying drawing 1.
Evaluation experimental result and catalyst performance of the fluorination catalyst of table 2 to synthesis R134a
From the data in table 2, after adding nanocrystalline metal fluoride complex carrier, the fluorination catalyst of preparation is being urged
When changing preparation R134a, raw material R133a conversion ratio significantly improves, and the selection of target product also accordingly improves, and accessory substance product
Selectivity be greatly lowered, show that fluorination catalyst provided by the invention catalytic of living is higher.
Fig. 1 test results are shown, after successive reaction 1150h, catalyst still keeps greater activity and stability, R133a
Conversion ratio still remain in 30% or so, show that catalyst provided by the invention has the longer life-span, can for a long time
It is interior to keep higher catalytic activity.
Claims (10)
1. one kind tool nanocomposite carrier catalysts for gas phase fluorination, it is characterised in that included in the nanocomposite carrier
There is nanocrystalline metal fluoride；The nanocrystalline metal fluoride is selected from nanocrystalline Al F3, nanocrystalline M gF2, nanocrystalline ZrF2With
Nanocrystalline CaF2In at least two.
2. tool nanocomposite carrier catalysts for gas phase fluorination according to claim 1, it is characterised in that described nanocrystalline
AlF3For one or more in α, β, γ crystalline structure；The nanocrystalline M gF2For tetragonal structure structure；The nanocrystalline CaF2For
Cubic structure；The nanocrystalline ZrF2For one or both of tetragonal structure and monoclinic form structure.
3. a kind of preparation method of tool nanocomposite carrier catalysts for gas phase fluorination as claimed in claim 1 or 2, its feature
It is, comprises the following steps：
1) prepared by chromium based compound
Chromic salts and other metal salts are dissolved in water to obtain mixing salt solution, ammonification water sedimentation, aging, filters, washs, dry,
Roasting, crushing obtain chromium based compound powder；
2) prepared by catalyst precursor
Chromium based compound powder obtained by step 1) and nanocrystalline metal fluoride and graphite are mixed, compression molding is urged
Agent presoma；
Wherein, the nanocrystalline metal fluoride is nanocrystalline Al F3, nanocrystalline M gF2, nanocrystalline ZrF2With nanocrystalline CaF2In
At least two；
3) prepared by fluorination catalyst
The catalyst precursor that step 2) obtains is fluorinated in inert gas and HF mixed gas, obtains fluorination catalyst.
4. the preparation method of tool nanocomposite carrier catalysts for gas phase fluorination according to claim 3, it is characterised in that
Chromium based compound powder, nanocrystalline metal fluoride, the mass ratio of graphite are 70~98 in the step 2):1~20:1~10.
5. tool nanocomposite carrier catalysts for gas phase fluorination according to claim 1, it is characterised in that described nanocrystalline
The preparation method of metal fluoride includes：Metal salt stirring and dissolving and is flowed back in solvent, then under ultrasonic agitation state
The fluorination reagent aqueous solution is added dropwise to be reacted, obtains lyosol through crystallization, aging, is dried to obtain solid gel, is then calcined
Nanocrystalline metal fluoride is made；Wherein, the metal salt is selected from any of Mg salt, Al salt, Ca salt and Zr salt.
6. the preparation method of nanocrystalline metal fluoride according to claim 5, it is characterised in that described solvent is
At least one of water, methanol, ethanol, isopropanol and isobutanol；Fluorination reagent is ammonium fluoride, hydrogen fluoride, tetrabutyl ammonium fluoride
At least one of with hydrogen fluoride pyridine.
7. the preparation method of nanocrystalline metal fluoride according to claim 5, it is characterised in that described reflux temperature
For 20~160 DEG C, 0.5~2h of return time；Described supersonic frequency is 40~80KHz, and ultrasonic time is controlled in completion of dropwise addition
10~30min afterwards.
8. the preparation method of nanocrystalline metal fluoride according to claim 5, it is characterised in that described dropwise addition fluorination
The time for adding of the reagent aqueous solution is 1~90min, and it is 20~160 DEG C that fluorination reagent, which is added dropwise, and carries out reaction temperature；Described crystalline substance
Change, aging temperature are 20~160 DEG C, and crystallization, total aging time are 8~12h.
9. the preparation method of nanocrystalline metal fluoride according to claim 5, it is characterised in that the lyosol
Drying temperature is 100~130 DEG C, 6~12h of drying time；Described sintering temperature be 350~550 DEG C, roasting time be 3~
8h。
10. the application of tool nanocomposite carrier catalysts for gas phase fluorination as claimed in claim 1 or 2, it is characterised in that institute
Fluorination catalyst is stated to be used in fluorine chlorine substitution gas phase fluorination.
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| CN109806858A (en) * | 2019-02-18 | 2019-05-28 | 南通宝凯化工有限公司 | A kind of preparation method of catalysts for gas phase fluorination |
| CN110653004A (en) * | 2019-09-05 | 2020-01-07 | 上海化工研究院有限公司 | Catalyst for trapping and catalyzing VOCs degradation and preparation method and application thereof |
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