CN107744836A - A kind of preparation method and applications of load-type ion liquid catalyst - Google Patents
A kind of preparation method and applications of load-type ion liquid catalyst Download PDFInfo
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- CN107744836A CN107744836A CN201710906018.1A CN201710906018A CN107744836A CN 107744836 A CN107744836 A CN 107744836A CN 201710906018 A CN201710906018 A CN 201710906018A CN 107744836 A CN107744836 A CN 107744836A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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Abstract
The invention discloses a kind of ruthenium-based catalyst for acetylene hydrochlorination production vinyl chloride, the ruthenium-based catalyst is prepared using freeze-drying, avoid with the volatilization of moisture in catalyst in conventional vacuum seasoning preparation process and then the active component in catalyst duct is also moved into carrier surface therewith, and then influence the stability of catalyst.The ruthenium-based catalyst has very high stability when producing vinyl chloride for acetylene hydrochlorination, after long-play 8000h, ruthenium is not detected by detector detectability and is lost in, conversion of alkyne reaches as high as 99.8%, and vinyl chloride selectively reaches as high as 100%.
Description
Background technology
Polyvinyl chloride (PVC) is the third-largest general-purpose plastics, is typically obtained by the aggregated reaction of monomer vinyl chloride.Due to me
The energy occurrence characteristics of national wealth coal, oil-poor, few gas, coal base carbide acetylene method prepare the master that vinyl chloride is China's Production of PVC
Stream technique.Industrially, the catalyst used in existing synthesis vinyl chloride thereof is mercury chloride, because it causes seriously to pollute to environment, and
And synthesize in obtained polyvinyl chloride and limit the application of polyvinyl chloride containing a small amount of mercury.Therefore, mercuric chleride catalyst will be by
Gradually it is eliminated, the lower synthesis vinyl chloride thereof of catalyst without mercury effect is the Main way of calcium carbide process PVC Sustainable Development in Future.Mercury-free is urged
For agent mainly using metal chloride as active component, the catalytic activity shown especially with precious metal chloride among these is optimal.
Gold is due to being considered as the catalysis for being most hopeful to substitute mercury to be applied to acetylene hydrochlorination synthesis vinyl chloride thereof with high catalytic activity
Agent.However, Au-based catalyst because itself is expensive, there is huge challenge in industrialization.Comparatively, the reserves of ruthenium are big, valency
Lattice are relatively cheap, are suitable catalyst metals active components.But the shortcomings that load ruthenium catalyst is catalyzing acetylene hydrogen chlorine
Active relatively low, and the RuCl in ruthenium-based catalyst of change3The easy sublimation of active component and cause the irreversible inactivation of catalyst.
This not only results in catalyst activity reduction, and can cause the loss of noble ruthenium, causes also increase while environmental pollution
The use cost of processing industry catalyst.RuCl in ruthenium-based catalyst3On the one hand the easy sublimation of active component is due to RuCl3It is living
Property component under reaction atmosphere and acetylene easily form complex and distil, still further aspect is mutual with carrier mainly due to it
Effect is weaker, and is lost in from carrier surface.
For problem above existing for Ru catalyst, domestic and international research institution is mainly from addition auxiliary agent, support modification, ion
Liquid modifying etc. conducts a research.(1) catalyst performance is improved using the strategy that auxiliary agent is added in ruthenium active component.Document
(RSC Advances 3 (2013) 21062-21068), which is reported in spherical activated charcoal supported ruthenium catalyst (Ru/SAC), adds Co
The activity of catalyst can be improved, but it is 170 DEG C, V (HCl)/V (C that the document, which has only been observed in reaction temperature,2H2)=
1.1/1st, acetylene air speed is 180h-1Under conditions of react 48h result, for commercial Application, the reaction time is far from enough
's.Document (RSC Advances 5 (2015) 37774-37779) has been reported with RuCl3·H2O and KCl is presoma, is prepared for
The Ru catalyst (Ru-K/SAC) that spherical activated charcoal load K is modified, and find that the catalyst has than common Ru/SAC catalyst
Higher activity, it is 170 DEG C, V (HCl)/V (C in reaction temperature2H2)=1.1/1, acetylene air speed are 180h-1Under conditions of can
Realize C2H2Conversion ratio 93.4%.But after the data of the document reach 48h between showing when reacted, conversion ratio has descended to
Less than 90%.Chinese patent (A of CN 103894195) disclose support type Ru-Bi bimetallic catalysts preparation method and its
Application in acetylene hydrochlorination reaction.The catalyst is 180 DEG C, V (HCl)/V (C in reaction temperature2H2)=1.15/1, acetylene
Air speed is 150h-1Under conditions of, acetylene initial conversion is 99%, when the load capacity of ruthenium is that 1%, Ru/Bi mol ratios are 0.5
When, catalyst life 300h.The catalyst life can not meet the requirement of industrial applications.
(2) catalyst performance is improved by support modification.Document (RSC Advances 5 (2015) 86172-86178) is reported
Lead and be prepared for containing-NO using distinct methods2、-NH2, the different groups containing N such as-N-H-N dopped activated carbon；And as carrier,
It is prepared for load ruthenium catalyst.Catalytic activity of the catalyst series in acetylene hydrochlorination reaction is all higher than normal activated carbon
Supported ruthenium catalyst, and Ru/AC-NHN catalyst shows optimal catalytic performance, is 180 DEG C, V (HCl)/V in reaction temperature
(C2H2)=1.15/1, acetylene air speed are 360h-1Under conditions of, after reacting 48h, conversion of alkyne drops to from 93.2%
91.8%.Although catalyst activity reduction is slower, it can not still meet requirement of the industrial production to catalyst stability.
(3) ion liquid modified catalyst performance is used.Document (ACS catalysis 7 (2017) 3510-3520) is reported
Lead and used ion liquid modified activated carbon supported ruthenium as catalyst, there is good catalytic in acetylene hydrochlorination reaction
Energy.It is 170 DEG C, V (HCl)/V (C in reaction temperature when using 0.2%Ru@15%TPPB/AC for catalyst2H2)=1.15/
1st, acetylene air speed is 90h-1Under conditions of, after reacting 400h, conversion of alkyne still can be maintained at 99.3%, but Ru loss
Rate has reached 15%.
Although above-mentioned document and patent all report using addition auxiliary agent, support modification or it is ion liquid modified after load
Type ruthenium catalyst is applied in acetylene hydrochlorination reaction, can bring beneficial effect.However, it is possible to see such catalyst
Larger distance apart from commercial Application still be present in activity or stability.Therefore, answering with more high activity and stability is sought
Supported ruthenium catalyst for acetylene hydrochlorination reaction is significantly.
The content of the invention
It is an object of the invention to fundamentally solve ruthenium catalyst activity in the reaction of acetylene hydrochlorination synthesis vinyl chloride thereof
A kind of problem of component ruthenium sublimation, there is provided the acetylene hydrochlorination ruthenium-based catalyst that stability is good, reactivity is high.
The present invention prepares load-type ion liquid using freeze-drying and promotes ruthenium catalyst, avoids conventional vacuum drying
Load is also moved to therewith with the volatilization of moisture in catalyst and then by the active component in catalyst duct during method preparation
Body surface face, and then influence the stability of catalyst.
The present invention proposes a kind of ruthenium-based catalyst for acetylene hydrochlorination production vinyl chloride, and described ruthenium-based catalyst is
The ionic liquid that porous solid carrier load is prepared using freeze-drying promotes ruthenium catalyst, namely load-type ion liquid to promote
The ruthenium catalyst entered.
The present invention provides the ruthenium catalyst that a kind of described load-type ion liquid promotes, and its preparation method is as follows：It will contain
The ruthenium aqueous solution, ionic liquid mix to obtain mixed liquor；At 20~60 DEG C, the mixed liquor is added drop-wise under ul-trasonic irradiation more
On the solid carrier of hole, and impregnated 0.5~6 hour using equi-volume impregnating under ul-trasonic irradiation；Then will be described porous solid
Body carrier was in -60~-30 DEG C of pre-freezes 6~30 hours；Porous solid carrier is moved into freeze-dryer again, freeze-dryer
Vacuum is 0.08~0.1MPa, and temperature risen into -25~-10 DEG C with 2~5 DEG C/min heating rate, described porous solid
Body carrier maintains 10~20 hours in this temperature；The vacuum for continuing to freeze-dryer is 0.08~0.1MPa, then by institute
State freeze-dryer and temperature is risen to 30~50 DEG C with 2~5 DEG C/min heating rate, and maintain 5~20 hours, both obtained described
The ruthenium catalyst that load-type ion liquid promotes.
Further, the Theoretical Mass of ruthenium is 0.01~2wt% of porous solid carrier quality in the aqueous solution containing ruthenium, excellent
Elect 0.1~1wt% as；The ionic liquid quality is the 1~30wt%, preferably 5~20wt% of porous solid carrier quality.
Porous solid carrier of the present invention is selected from activated carbon, mesoporous carbon, CNT, silica, three oxidations two
One kind in aluminium, titanium dioxide, molecular sieve, metal organic framework compound, covalent organic framework compound, it is preferably activity
Charcoal.
Activated carbon described further is column charcoal or spherical carbon activated carbon, the mesh of particle diameter 10~100, content of ashes≤
12.0wt%, 300~1500m of specific surface area2/g；
Described CNT is processed into column or spherical, the mesh of particle diameter 10~100, content of ashes≤6.0wt%, compares surface
100~1800m of product2/g；
Described graphene is processed into column or spherical, the mesh of particle diameter 10~100, content of ashes≤6.0wt%, specific surface area
200~3000m2/g；
Described alundum (Al2O3) is γ-Al2O3, and column or spherical is processed into, and the mesh of particle diameter 10~100, specific surface area 50
~800m2/g；
Described silica is processed into column or spherical, the mesh of particle diameter 10~100,50~800m of specific surface area2/g；
Described titanium dioxide processes are into column or spherical, the mesh of particle diameter 10~100,50~800m of specific surface area2/g；
Molecular sieve described further is ZSM-5, beta-molecular sieve, γ molecular sieves, 5A molecular sieves, 10X molecular sieves or 13X points
Son sieve.
Metal organic framework compound described further is the MOFs that constructs of nitrogen heterocyclic ring class part, organic carboxyl acid class is matched somebody with somebody
The MOFs that the MOFs or organic carboxyl acid class part that body is constructed are constructed.
Covalent organic framework compound described further is boracic class COFs materials, imines COFs materials or triazine
Class COFs materials.
Further, the aqueous solution containing ruthenium is the aqueous solution containing ruthenium compound, and described is selected from trichlorine containing ruthenium compound
Change ruthenium (III), tribromide ruthenium (III), triiodide ruthenium (III), the sour ammonium of chlordene ruthenium (IV), dichlorophenyl ruthenium (II) dimer, water
Close the sour potassium of pentachloro- ruthenium (III), the sour potassium of hydration pentabromo- chlorine ruthenium (III), three (triphenylphosphine) ruthenous chlorides (II), the ruthenium of trichlorine six
(III) ammonium, pentachloro- nitroso close the sour potassium of ruthenium (III), the ammino ruthenium (III) of one chlorine of dichloride five, five chlorocarbonyls and close ruthenium (III) acid
One or more of any combination in ammonium, triphenylphosphine ruthenic chloride (III), the ammonia two of phosphoric acid four hydration ruthenium (III)；
Ru concentration is 0.001~0.1g/mL, preferably 0.004~0.05g/ml in the described aqueous solution containing ruthenium；
Further, described ionic liquid is one or more in following compounds：
1) glyoxaline ion liquid, it is specific be cation be disubstituted imidazolium cation or trisubstituted imidazoles sun from
Son, the i.e. methylimidazole of 1- alkyl -3,1- alkyl -2,3- methylimidazole or 1- butyl -2- ethyl-3-methylimidazoles, wherein institute
The alkyl stated refers specifically to the alkyl chain of different carbon chain lengths, the alkyl specially from C1 to C16；Specific anion be halogen from
Son, tetrafluoroborate, hexafluoro-phosphate radical, nitrate anion, bisulfate ion, perchlorate, dintrile amine root, acetate, trifluoroacetic acid root,
Phosphate radical or dihydrogen phosphate；
2) quaternary phosphine class ionic liquid, it is specifically tributyl ethyl phosphonium bromide phosphine, tributyl ethylmercury chloride phosphine, tributyl hexyl
Bromide phosphine, tributyl oneself its phosphonium chloride, double (fluoroform sulphonyl) inferior amine salts of oneself its phosphine of tributyl, tributyl ethyl phosphine double (three
Fluoromethane sulphonyl) inferior amine salt, tetrabutyl phosphonium bromide phosphine, tetrabutylphosphonium chloride, triphenyl ethyl phosphonium bromide phosphine, triphenyl ethyl chlorination
Phosphine, tetraphenylphosphonibromide bromide or tetraphenylphosphonium chloride；
3) quaternary ammonium ionic liquid, it is specifically trialkyl methyl ammonium (fluoroform sulphonyl) inferior amine salt or trialkyl methyl
Ammonium chloride, wherein described alkyl is the alkyl chain of different carbon chain lengths, the alkyl specially from C1 to C16；
4) pyrrolidines ionic liquid, it is specifically double (fluoroform sulphonyl) inferior amine salts of N- butyl-N- crassitudes
Or N- Butyl N-methyl pyrrolidines bromides；
5) piperidines ionic liquid, it is specifically double (fluoroform sulphonyl) inferior amine salts of N- butyl-N- methyl piperidines or N-
Butyl N-methyl piperidines bromide；
The present invention is prepared as techniques well known using equi-volume impregnating, that is, the mixed liquor being added dropwise carries with porosu solid
The pore volume of body matches.The maceration extract of dropwise addition is completely into the duct of porous solid carrier.
Therefore, the Theoretical Mass of ruthenium, ionic liquid quality are corresponding with its load capacity in mixed liquor of the present invention：
Described ruthenium load capacity (opposite carrier quality) is 0.01~2wt%；
Described ionic liquid loaded amount (opposite carrier quality) is 1~30wt%.
The ruthenium catalyst that load-type ion liquid prepared by the present invention promotes can be used for acetylene hydrochlorination synthesis vinyl chloride thereof
In reaction.Described acetylene hydrochlorination synthesis vinyl chloride thereof method is as follows：In fixed bed reactors, load the support type ion
Liquid promote ruthenium catalyst, reaction temperature be 100~240 DEG C, 0.1~0.5MPa of reaction pressure, be passed through unstrpped gas HCl,
C2H2, HCl and C2H2The ratio between amount of material is 1.0~1.2/1, you can reaction obtains vinyl chloride.
Described 5~100h of acetylene volume space velocity-1。
The ruthenium catalyst that load-type ion liquid of the present invention promotes has very in the reaction of above-mentioned acetylene hydrochlorination
High stability, after long-play 8000h, ruthenium loss is not detected by detector detectability, conversion of alkyne highest can
Up to 99.8%, vinyl chloride selectively reaches as high as 100%.
Freeze-drying of the present invention prepare load-type ion liquid promotion ruthenium catalyst the characteristics of be it is special
Catalyst made from method has especially excellent catalytic activity and stability.Load-type ion liquid of the present invention promotes
Ruthenium-based catalyst water contained in catalyst in preparation process is first frozen into by ice using freeze-drying, then pass through distillation
Method removes, and this can ensure that the catalyst activity component overwhelming majority is all located in the duct of carrier, avoids common dry legal system
As the volatilization of moisture takes active component out of carrier duct simultaneously and moves to the outer surface of carrier during standby catalyst.It is deposited on
Active component in carrier duct in acetylene hydrochlorination course of reaction can stably in the presence of and not easily run off, ensure that catalysis
The high stability of agent.In addition, dispersion effect of the catalyst activity component prepared using freeze-drying in carrier duct is more
Good, catalyst activity is higher.
Compared with prior art, the present invention has advantages below：
1. under reaction condition, catalyst activity component is not easy to distil, stability is good, long operational time.
2. catalyst activity is high, in relatively low ruthenium load capacity, just there is high reactivity.
3. catalyst preparation is simple, easy to operate.
Embodiment
Illustrate the present invention with instantiation below.It is important to point out that embodiment is served only for what the present invention was carried out
Further illustrate, but it is not intended that limiting the scope of the invention, the present invention are not in any way restricted to this.The neck
The person skilled in the art in domain can make some nonessential modifications and adaptations according to the content of foregoing invention.
Embodiment 1
It is carrier to select column-shaped active carbon, and its particle diameter is 30 mesh, content of ashes 2.5wt%, specific surface area 800m2/ g, hole
Hold 0.6ml/g, and the HCl treatment 3.5h at 25 DEG C by 200ml concentration for 10wt%.110 DEG C dry 10h, standby.Will
25ml RuCl3After the mixing of solution (wherein Ru contents are 0.004g/ml) and 5g 1- butyl -3- methylimidazole villaumites, then add
Enter appropriate amount of deionized water constant volume to 60ml, mixed liquor be added drop-wise on 100g absorbent charcoal carriers under ul-trasonic irradiation at 30 DEG C,
Dip time 5 hours under ul-trasonic irradiation.Then, by said mixture in -40 DEG C of pre-freezes 10 hours；By the mixture of freezing
Moving into freeze-dryer, the vacuum of freeze-dryer is 0.09MPa, and risen to temperature with 4 DEG C/min heating rate-
15 DEG C, the mixture of freezing maintains 15 hours in this temperature；The vacuum for continuing to freeze-dryer is 0.09MPa, then will
Temperature is risen to 40 DEG C by frigorific mixture with 4 DEG C/min heating rate, and is maintained 10 hours, had both been obtained load-type ion liquid and has been promoted
Ruthenium catalyst A, the Ru load capacity entered are 0.1wt%, and ionic liquid loaded amount is 5wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 150
DEG C, pressure 0.1MPa, n (HCl)/n (C2H2)=1.0/1, acetylene air speed 30h-1.Initial reaction stage, conversion of alkyne 99.9%,
Vinyl chloride selectivity 99.9%；After reacting 2000h, conversion of alkyne 99.9%, vinyl chloride selectivity 100%, Ru species flows
Mistake rate is 0%.
Embodiment 2
It is carrier to select column CNT, and its particle diameter is 40 mesh, content of ashes 3.5wt%, specific surface area 200m2/ g,
Pore volume 0.66ml/g.By 50ml ammonium hexachlororuthenate solution (wherein Ru contents are 0.02g/ml) and 20g tributyl bromic ether
After changing phosphine mixing, appropriate amount of deionized water constant volume is added to 66ml, is added drop-wise to mixed liquor under ul-trasonic irradiation at 40 DEG C
In 100g carbon nanotube carriers, dip time 4 hours under ul-trasonic irradiation.Then, by said mixture in -35 DEG C of pre-freezes 14
Hour；The mixture of freezing is moved into freeze-dryer, the vacuum of freeze-dryer is 0.08MPa, and with 3 DEG C/min's
Temperature is risen to -20 DEG C by heating rate, and the mixture of freezing maintains 12 hours in this temperature；Continue to the true of freeze-dryer
Reciprocal of duty cycle is 0.08MPa, then frigorific mixture risen into 35 DEG C by temperature with 3 DEG C/min heating rate, and maintains 15 hours, both
It is 1wt% to obtain ruthenium catalyst B, the Ru load capacity that load-type ion liquid promotes, and ionic liquid loaded amount is 20wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 160
DEG C, pressure 0.2MPa, n (HCl)/n (C2H2)=1.1/1, acetylene air speed 20h-1.Initial reaction stage, conversion of alkyne 99.9%,
Vinyl chloride selectivity 100%；After reaction 2000 hours, conversion of alkyne 99.8%, vinyl chloride selectivity 99.9%, Ru species
Turnover rate is 0.005%.
Embodiment 3
It is carrier to select column graphene, and its particle diameter is 70 mesh, content of ashes 1.5wt%, specific surface area 2630m2/ g, hole
Hold 1.5ml/g.By 10ml pentachloro- ruthenium (III) sour potassium solution (wherein Ru contents are 0.05g/ml) and 15g tetrabutyl chlorination
After phosphine mixing, appropriate amount of deionized water constant volume is added to 150ml, and mixed liquor is added drop-wise to 100g under ul-trasonic irradiation at 20 DEG C
On graphene carrier, dip time 4 hours under ul-trasonic irradiation.Then by said mixture in -50 DEG C of pre-freezes 12 hours；Will
The mixture of freezing is moved into freeze-dryer, and the vacuum of freeze-dryer is 0.1MPa, and with 3 DEG C/min heating rate
Temperature is risen to -25 DEG C, the mixture of freezing maintains 19 hours in this temperature；The vacuum for continuing to freeze-dryer is
0.1MPa, then temperature is risen to 45 DEG C by frigorific mixture with 3 DEG C/min heating rate, and maintain 11 hours, it must both load
Ruthenium catalyst C, the Ru load capacity that type ionic liquid promotes are 0.5wt%, and ionic liquid loaded amount is 15wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 240
DEG C, pressure 0.3MPa, n (HCl)/n (C2H2)=1.0/1, acetylene air speed 50h-1.Initial reaction stage, conversion of alkyne 99.8%,
Vinyl chloride selectivity 100%；After reaction 2000 hours, conversion of alkyne 99.9%, vinyl chloride selectivity 99.9%, Ru species
Turnover rate is 0.007%.
Embodiment 4
Select column γ-Al2O3For carrier, its particle diameter is 25 mesh, specific surface area 550m2/ g, pore volume 0.86ml/g.Will
20ml dichlorophenyl ruthenium (II) dimerization liquid solution (wherein Ru contents are 0.1g/ml) and 30g N- butyl-N- crassitudes
After the mixing of double (fluoroform sulphonyl) inferior amine salts, appropriate amount of deionized water constant volume is added to 86ml, in ul-trasonic irradiation at 25 DEG C
Lower γ-the Al that mixed liquor is added drop-wise to 100g2O3On carrier, dip time 4 hours under ul-trasonic irradiation.Then will be above-mentioned mixed
Compound was in -50 DEG C of pre-freezes 10 hours；The mixture of freezing is moved into freeze-dryer, the vacuum of freeze-dryer is
0.09MPa, and temperature is risen to -25 DEG C with 5 DEG C/min heating rate, the mixture of freezing maintains 17 hours in this temperature；
The vacuum for continuing to freeze-dryer is 0.09MPa, then by frigorific mixture with 5 DEG C/min heating rate by temperature liter
To 50 DEG C, and maintain 10 hours, both the ruthenium catalyst D, the Ru load capacity that promote of load-type ion liquid is 2wt%, ionic liquid
Body load capacity is 30wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 140
DEG C, pressure 0.4MPa, n (HCl)/n (C2H2)=1.2/1, acetylene air speed 60h-1.Initial reaction stage, conversion of alkyne 99.8%,
Vinyl chloride selectivity 100%；After reaction 2000 hours, conversion of alkyne 99.4%, vinyl chloride selectivity 99.9%, Ru species
Turnover rate is 0.02%.
Embodiment 5
Select column TiO2For carrier, its particle diameter is 35 mesh, specific surface area 285.3m2/ g, pore volume 0.82ml/g.By 10ml
Three (triphenylphosphine) ruthenous chloride solution (wherein Ru contents are 0.001g/ml) and 5g N- butyl-N- methyl piperidines double (three
Fluoromethane sulphonyl) after inferior amine salt mixing, appropriate amount of deionized water constant volume is added to 82ml, it will be mixed under ul-trasonic irradiation at 50 DEG C
Close the TiO that drop is added to 100g2On carrier, dip time 5 hours under ul-trasonic irradiation.Then by said mixture -55
DEG C pre-freeze 14 hours；The mixture of freezing is moved into freeze-dryer, the vacuum of freeze-dryer is 0.08MPa, and with 2
DEG C/temperature rises to -10 DEG C by min heating rate, the mixture of freezing maintains 13 hours in this temperature；It is dry to continue to freezing
The vacuum of dry device is 0.08MPa, then frigorific mixture is risen into 30 DEG C by temperature with 2 DEG C/min heating rate, and is maintained
20 hours, it was 0.01wt% both to have obtained ruthenium catalyst E, the Ru load capacity that load-type ion liquid promotes, and ionic liquid loaded amount is
5wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 145
DEG C, pressure 0.5MPa, n (HCl)/n (C2H2)=1.15/1, acetylene air speed 45h-1.Initial reaction stage, conversion of alkyne are
37.2%, vinyl chloride selectivity 99.9%；After reaction 500 hours, conversion of alkyne 35.89%, vinyl chloride selectivity
99.9%, Ru species turnover rate are 0.25%.
Embodiment 6
Select column SiO2For carrier, its particle diameter is 90 mesh, specific surface area 400m2/ g, pore volume 0.97ml/g.By 50ml's
RuN4O10Solution (wherein Ru contents are 0.004g/ml) and 15g 1- propyl group -2,3- methylimidazoles tetrafluoroborate mix
Afterwards, appropriate amount of deionized water constant volume is added to 97ml, and mixed liquor is added drop-wise to at 30 DEG C 100g SiO under ul-trasonic irradiation2
On carrier, dip time 6 hours under ul-trasonic irradiation.Then by said mixture in -40 DEG C of pre-freezes 15 hours；By freezing
Mixture is moved into freeze-dryer, and the vacuum of freeze-dryer is 0.09MPa, and with 4 DEG C/min heating rate by temperature
Degree rises to -25 DEG C, and the mixture of freezing maintains 18 hours in this temperature；The vacuum for continuing to freeze-dryer is
0.09MPa, then temperature is risen to 40 DEG C by frigorific mixture with 4 DEG C/min heating rate, and maintain 15 hours, it must both load
Ruthenium catalyst F, the Ru load capacity that type ionic liquid promotes are 0.2wt%, and ionic liquid loaded amount is 15wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 190
DEG C, pressure 0.2MPa, n (HCl)/n (C2H2)=1.05/1, acetylene air speed 30h-1.Initial reaction stage, conversion of alkyne are
99.8%, vinyl chloride selectivity 100%；After reacting 2000h, conversion of alkyne 99.1%, 99.9%, Ru of vinyl chloride selectivity
Species turnover rate is 0.2%.
Embodiment 7
It is carrier to select column-shaped active carbon, and its particle diameter is 50 mesh, content of ashes 3.0wt%, specific surface area 1000m2/ g,
Pore volume 0.5ml/g, and at 25 DEG C by nitric acid treatment 5 hours that 300ml concentration is 10wt%.110 DEG C dry 12h, standby.Will
After the tetrabutylphosphonium chloride mixing of 10ml triphenylphosphine chlorination ruthenium solution (wherein Ru contents are 0.001g/ml) and 1g, then add
Enter appropriate amount of deionized water constant volume to 50ml, mixed liquor is added drop-wise to at 30 DEG C 100g absorbent charcoal carrier under ul-trasonic irradiation
On, dip time 6 hours under ul-trasonic irradiation.Then by said mixture in -35 DEG C of pre-freezes 14 hours；By the mixing of freezing
Thing is moved into freeze-dryer, and the vacuum of freeze-dryer is 0.08MPa, and with 2 DEG C/min heating rate by temperature liter
To -10 DEG C, the mixture of freezing maintains 10 hours in this temperature；The vacuum for continuing to freeze-dryer is 0.08MPa, then
Temperature is risen to 45 DEG C with 2 DEG C/min heating rate by frigorific mixture, and maintained 15 hours, both obtains load-type ion liquid
Ruthenium catalyst G, the Ru load capacity of promotion are 0.01wt%, and ionic liquid loaded amount is 1wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 110
DEG C, pressure 0.1MPa, n (HCl)/n (C2H2)=1.1/1, acetylene air speed 5h-1.Initial reaction stage, conversion of alkyne 99.8%,
Vinyl chloride selectivity 100%；After reaction 2000 hours, conversion of alkyne 99.27%, vinyl chloride selectivity 99.9%, Ru things
Kind turnover rate is 0.001%.
Embodiment 8
It is carrier to select spherical activated charcoal, and its particle diameter is 10 mesh, content of ashes 1.5wt%, specific surface area 1100m2/ g, hole
Hold 0.6ml/g, and at 35 DEG C by nitric acid treatment 6 hours that 250ml concentration is 15wt%.150 DEG C, 5h is dried, it is standby.Will
20ml Ru (C2H3O2)3After the mixing of solution (wherein Ru contents are 0.1g/ml) and 30g N- Butyl N-methyl pyrrolidines bromide,
Appropriate amount of deionized water constant volume is added to 60ml, mixed liquor is added drop-wise to at 35 DEG C 100g carried by active carbon under ul-trasonic irradiation
On body, dip time 6 hours under ul-trasonic irradiation.Then by said mixture in -55 DEG C of pre-freezes 14 hours；By the mixed of freezing
Compound is moved into freeze-dryer, and the vacuum of freeze-dryer is 0.09MPa, and with 3 DEG C/min heating rate by temperature
- 15 DEG C are risen to, the mixture of freezing maintains 17 hours in this temperature；The vacuum for continuing to freeze-dryer is 0.08MPa,
Temperature is risen to 50 DEG C with 5 DEG C/min heating rate by frigorific mixture again, and maintained 10 hours, both obtains support type ionic liquid
Ruthenium catalyst H, the Ru load capacity that body promotes are 2wt%, and ionic liquid loaded amount is 30wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 200
DEG C, pressure 0.3MPa, n (HCl)/n (C2H2)=1.15/1, acetylene air speed 100h-1.Initial reaction stage, conversion of alkyne are
96.56%, vinyl chloride selectivity 99.9%；After reaction 2000 hours, conversion of alkyne 96.32%, vinyl chloride selectivity
100%, Ru species turnover rate are 0.007%.
Comparative example 1
It is carrier to select column-shaped active carbon, and its particle diameter is 30 mesh, content of ashes 2.5wt%, specific surface area 1000m2/ g, hole
Hold 0.5ml/g, and the HCl treatment 3.5h at 25 DEG C by 200ml concentration for 10wt%.150 DEG C dry 5h, standby.By 25ml
RuCl3After the mixing of solution (wherein Ru contents are 0.004g/ml) and 5g 1- butyl -3- methylimidazole villaumites, add suitable
Deionized water constant volume is measured to 50ml, is added drop-wise on 100g absorbent charcoal carriers at 30 DEG C and impregnates 5 hours.Catalyst after dipping exists
110 DEG C are dried in vacuo 6 hours, obtain I catalyst.Ru load capacity is 0.1wt%, and the load capacity of ionic liquid is 5wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 150
DEG C, pressure 0.1MPa, n (HCl)/n (C2H2)=1.05/1, acetylene air speed 50h-1.Initial reaction stage, conversion of alkyne are
97.3%, vinyl chloride selectivity 99.9%；After reacting 200h, conversion of alkyne 73.7%, 99.9%, Ru of vinyl chloride selectivity
Species turnover rate is 18.2%.
Claims (10)
1. the ruthenium catalyst that a kind of load-type ion liquid promotes, it is characterised in that the ruthenium that the load-type ion liquid promotes is urged
Agent is prepared as follows：The ruthenium aqueous solution will be contained, ionic liquid mixes to obtain mixed liquor；At 20~60 DEG C, make in ultrasonic wave
The mixed liquor is added drop-wise on porous solid carrier with lower, and using equi-volume impregnating dipping 0.5 under ul-trasonic irradiation
~6 hours；Then by the porous solid carrier in -60~-30 DEG C of pre-freezes 6~30 hours；Porous solid carrier is moved into again
In freeze-dryer, the vacuum of freeze-dryer is 0.08~0.1MPa, and with 2~5 DEG C/min heating rate by temperature
- 25~-10 DEG C are risen to, the porous solid carrier maintains 10~20 hours in this temperature；Continue to the true of freeze-dryer
Reciprocal of duty cycle is 0.08~0.1MPa, then the freeze-dryer is risen into 30~50 by temperature with 2~5 DEG C/min heating rate
DEG C, and maintain 5~20 hours, obtain the ruthenium catalyst that the load-type ion liquid promotes.
2. catalyst as claimed in claim 1, it is characterised in that：The Theoretical Mass of ruthenium is porous solid in the aqueous solution containing ruthenium
0.01~2wt% of body carrier quality；The ionic liquid quality is 1~30wt% of porous solid carrier quality.
3. catalyst as claimed in claim 1, it is characterised in that：In the described aqueous solution containing ruthenium Ru concentration be 0.001~
0.1g/mL。
4. the catalyst as described in one of claims 1 to 3, it is characterised in that：The described aqueous solution containing ruthenium is containing ruthenium compound
The aqueous solution, it is described containing ruthenium compound be selected from ruthenium trichloride (III), tribromide ruthenium (III), triiodide ruthenium (III), chlordene ruthenium
(IV) sour ammonium, dichlorophenyl ruthenium (II) dimer, the sour potassium of hydration pentachloro- ruthenium (III), the sour potassium of hydration pentabromo- chlorine ruthenium (III), three (three
Phenylphosphine) ruthenous chloride (II), the ruthenium of trichlorine six (III) ammonium, pentachloro- nitroso close ruthenium (III) sour potassium, the ammino of one chlorine of dichloride five
Ruthenium (III), five chlorocarbonyls close one in the sour ammonium of ruthenium (III), triphenylphosphine ruthenic chloride (III), the ammonia two of phosphoric acid four hydration ruthenium (III)
Kind or several any combination.
5. the catalyst as described in one of claims 1 to 3, it is characterised in that：Described porous solid carrier be selected from activated carbon,
Mesoporous carbon, CNT, silica, aluminum oxide, titanium oxide, molecular sieve, metal organic framework compound, covalent organic framework
One kind in compound.
6. the catalyst as described in one of claims 1 to 3, it is characterised in that：The ionic liquid be glyoxaline ion liquid,
One or more in quaternary phosphine class ionic liquid, quaternary ammonium ionic liquid, pyrrolidines ionic liquid, piperidines ionic liquid.
7. catalyst as claimed in claim 6, it is characterised in that：The cation of the glyoxaline ion liquid is 1- alkyl -3
Methylimidazole, 1- alkyl -2,3- methylimidazole or 1- butyl -2- ethyl-3-methylimidazoles；Described alkyl is C1 to C16
Alkyl；The anion of the glyoxaline ion liquid is halide ion, tetrafluoroborate, hexafluoro-phosphate radical, nitrate anion, sulfuric acid
Hydrogen radical, perchlorate, dintrile amine root, acetate, trifluoroacetic acid root, phosphate radical or dihydrogen phosphate；
The quaternary phosphine class ionic liquid is tributyl ethyl phosphonium bromide phosphine, tributyl ethylmercury chloride phosphine, tributyl hexyl bromide phosphine, three
Butyl oneself its phosphonium chloride, double (fluoroform sulphonyl) inferior amine salts of oneself its phosphine of tributyl, double (the fluoroform sulphurs of tributyl ethyl phosphine
Acyl) inferior amine salt, tetrabutyl phosphonium bromide phosphine, tetrabutylphosphonium chloride, triphenyl ethyl phosphonium bromide phosphine, triphenyl ethyl phosphonium chloride, tetraphenyl
Bromide phosphine or tetraphenylphosphonium chloride；
Described quaternary ammonium ionic liquid is trialkyl methyl ammonium (fluoroform sulphonyl) inferior amine salt or trialkyl methyl ammonium chloride；
Described alkyl is C1 to C16 alkyl；
Described pyrrolidines ionic liquid is double (fluoroform sulphonyl) inferior amine salts of N- butyl-N- crassitudes or N- butyl
N- crassitude bromides；
Described piperidines ionic liquid is double (fluoroform sulphonyl) inferior amine salts of N- butyl-N- methyl piperidines or N- butyl N- first
Phenylpiperidines bromide.
8. the ruthenium catalyst that load-type ion liquid as claimed in claim 1 promotes is in catalyzing acetylene hydrogen chloride synthesis vinyl chloride thereof
Reaction in application.
9. application as claimed in claim 8, it is characterised in that the application detailed process is：In fixed bed reactors, dress
Entering the ruthenium catalyst that the load-type ion liquid promotes, reaction temperature is 100~240 DEG C, 0.1~0.5MPa of reaction pressure,
It is passed through unstrpped gas HCl, C2H2, HCl and C2H2The ratio between amount of material is 1.0~1.2：1, you can reaction obtains vinyl chloride.
10. application as claimed in claim 9, it is characterised in that：Described C2H25~100h of air speed-1。
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| CN108940358A (en) * | 2018-06-25 | 2018-12-07 | 浙江工业大学 | A kind of acid proof basic catalyst and preparation method and application |
| CN111715268A (en) * | 2020-07-26 | 2020-09-29 | 朱丽英 | Catalyst with nitrogen-doped carbon material as carrier and preparation method thereof |
| CN112072120A (en) * | 2020-09-07 | 2020-12-11 | 贵州梅岭电源有限公司 | Hydrophilic/hydrophobic membrane electrode relating to ionic liquid |
| CN112973800A (en) * | 2021-03-01 | 2021-06-18 | 内蒙古大学 | Preparation method and application of nitrogen modified ruthenium-based catalyst |
| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
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| CN116037203A (en) * | 2022-12-30 | 2023-05-02 | 贵州重力科技环保股份有限公司 | Ruthenium catalyst of acetylene hydrochlorination loaded ionic liquid, preparation method and application |
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| CN116037203A (en) * | 2022-12-30 | 2023-05-02 | 贵州重力科技环保股份有限公司 | Ruthenium catalyst of acetylene hydrochlorination loaded ionic liquid, preparation method and application |
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