CN107824225A - The palladium-based catalyst and its application in catalysis unsaturated hydrocarbons hydrogenation halogenation that a kind of ionic liquid promotes - Google Patents
The palladium-based catalyst and its application in catalysis unsaturated hydrocarbons hydrogenation halogenation that a kind of ionic liquid promotes Download PDFInfo
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Abstract
The invention discloses the palladium catalyst that a kind of ionic liquid of porous solid carrier load promotes, the catalyst is prepared as follows：The palladium-containing solution configured, ionic liquid are mixed to get mixed liquor；At 20~60 DEG C, mixed liquor is added drop-wise on porous solid carrier under ul-trasonic irradiation, and impregnated 0.5~6 hour using equi-volume impregnating under ul-trasonic irradiation；Again at 20~60 DEG C, inorganic salt solution is added dropwise toward the porous solid carrier after dipping mixed liquor under ul-trasonic irradiation, and impregnated 1~20 hour under ul-trasonic irradiation；Then it is dried in vacuo at 60~120 DEG C 3~30 hours, both obtains the palladium catalyst that load-type ion liquid promotes, gained catalyst activity component is not easy to distil, and stability is good, long operational time, and catalytic activity is high, and preparation is simple, easy to operate.
Description
Background technology
Polyvinyl chloride (PVC) is important general-purpose plastics.Due to China's richness coal, the energy occurrence characteristics of oil-poor, few gas, electricity
Stone acetylene method prepares the prevailing technology that vinyl chloride is China's Production of PVC.Catalysis used in industrial existing synthesis vinyl chloride thereof
Agent is mercury chloride, because it causes seriously to pollute to environment, and synthesizes in obtained polyvinyl chloride and is limited containing a small amount of mercury
The application of polyvinyl chloride.Therefore, mercuric chleride catalyst will gradually be eliminated, and synthesis vinyl chloride thereof turns under the conditions of catalyst without mercury
The Main way of calcium carbide process PVC Sustainable Development in Future.Catalyst without mercury is mainly using metal chloride as active component, among these
Especially the catalytic activity shown with precious metal chloride is optimal.Gold due to highest catalytic activity be considered as most have it is uncommon
Substitution mercury is hoped to be applied to the catalyst of acetylene hydrochlorination synthesis vinyl chloride thereof.However, Au-based catalyst is because itself is expensive, work
Huge challenge be present in industry.Comparatively, palladium-based catalyst due to its activity it is suitable with Au-based catalyst, while cost is less than golden
Base catalyst, there is good industrial applications prospect.PdCl in palladium-based catalyst2The easy sublimation of active component and cause to urge
The irreversible inactivation of agent.This not only results in catalyst activity reduction, and can cause the loss of precious metal palladium, causes environment
Also the use cost of industrial catalyst can be increased while pollution.
PdCl in palladium-based catalyst2On the one hand the easy sublimation of active component is due to PdCl2Active component is in reaction atmosphere
Lower and acetylene easily forms complex and distilled, still further aspect, weaker with carrier interaction mainly due to it, and from load
Body surface surface current loses.For problem above existing for Pd catalyst, domestic and international research institution is mainly from addition auxiliary agent and support modification
The two aspects are studied.
1) auxiliary agent is added into Pd active components.
Document (Catalysis Communications 83 (2016) 9-13), which is reported in Pd/NFY catalyst, to be added
KCl can improve the stability of catalyst, but at 160 DEG C, V (HCl)/V (C2H2After 10h being reacted under the conditions of)=1.25, Pd-
Still the Pd species for having 37.8% in K/NFY catalyst are lost in.
Chinese patent application (A of CN 101716508) is disclosed using palladium bichloride as active component, and lanthanum chloride is auxiliary agent, former
Material-gas ratio example V (HCl)/V (C2H2)=1.05, the progress acetylene hydrochlorination reactivity worth test at 150 DEG C, analytical reactions tail gas,
The conversion of alkyne of catalyst is 98.2%, although vinyl chloride is selectively higher for the 98%. catalyst stability and activity,
It is that noble-metal-supported mass fraction is higher, so as to cause its cost higher, commercial Application can not be realized.
Chinese patent application (A of CN 103894208) is disclosed using palladium bichloride as active component, and copper is auxiliary agent, acetylene body
Product air speed 20h-1, acetylene hydrochlorination reactivity worth test, analytical reactions tail gas, the acetylene conversion of catalyst are carried out at 150 DEG C
Rate is 60.2%, and vinyl chloride is selectively 98%.Active too low, industrial applications difficulty be present in the catalyst.
Chinese patent application (A of CN 103386315) is disclosed using palladium bichloride as active component, base metal protochloride
One kind in copper, cerium chloride, zinc chloride is auxiliary agent, unstripped gas ratio V (HCl)/V (C2H2)=1.15, second is carried out at 150 DEG C
Alkynes hydrochlorination performance test, analytical reactions tail gas, the acetylene initial conversion of catalyst is 97%, and vinyl chloride is selectively
99%.
Chinese patent application (A of CN 101249451) is disclosed using palladium bichloride as active component, stannous chloride, cerium chloride,
One kind in bismuth chloride is auxiliary agent, unstripped gas ratio V (HCl)/V (C2H2)=1.05, it is anti-that acetylene hydrochlorination is carried out at 160 DEG C
Performance test is answered, analytical reactions tail gas, the conversion of alkyne of catalyst is 96-97%, and vinyl chloride is selectively 99%.
Chinese patent application (A of CN 101514140) is disclosed using palladium bichloride as active component, cesium chloride, cerium chloride, chlorine
Change bismuth, one kind in stannic chloride is auxiliary agent, unstripped gas ratio V (HCl)/V (C2H2)=1.1-1.5, carried out at 140-160 DEG C
Acetylene hydrochlorination reactivity worth is tested, analytical reactions tail gas, and the conversion of alkyne of catalyst is 70-95%, and vinyl chloride is selective
For 96-99%.
Chinese patent application (A of CN 101947465) is disclosed using palladium bichloride as active component, copper, zinc, potassium, barium, nickel,
One kind in bismuth, calcium, lithium is auxiliary agent, unstripped gas ratio V (HCl)/V (C2H2)=1.1, it is anti-that acetylene hydrochlorination is carried out at 180 DEG C
Performance test is answered, analytical reactions tail gas, the conversion of alkyne of reaction 6h catalyst is 70%, and vinyl chloride selectivity is 97-99%.
2) support modification.
Chinese patent application (A of CN 102416323) discloses the modified dipping H of carrier low-kappa number2PdCl4Prepare Pd/
C catalyst, in unstripped gas ratio V (HCl)/V (C2H2Under conditions of)=1.15 acetylene hydrochlorination reactivity worth is carried out in 160 DEG C
Test, analytical reactions tail gas, the acetylene initial conversion of catalyst is 96.48%, and vinyl chloride is selectively 99.28%.This is urged
Although agent initial activity is higher, the problem of catalyst life is short, is still present.
Chinese patent application (A of CN 103506147) is disclosed using porous foam structure as carrier loaded PdCl2It is prepared into
The catalyst arrived, in unstripped gas ratio V (HCl)/V (C2H2Under the conditions of)=1.2 acetylene hydrochlorination reactivity worth is carried out in 185 DEG C
Test, analytical reactions tail gas, the acetylene initial conversion of catalyst is 86.21%, and vinyl chloride is selectively 90.5%.React 6h
Conversion ratio maintains more than 50% afterwards, changes catalyst and life-span shorter problem still be present.
Chinese patent application (A of CN 102357336) is disclosed with HZSM-5, NaZSM-5, zeolite equimolecular sieve as carrier
Load PdCl2The catalyst being prepared, in unstripped gas ratio V (HCl)/V (C2H2Under the conditions of)=1.15 second is carried out in 160 DEG C
Alkynes hydrochlorination performance test, analytical reactions tail gas, the acetylene initial conversion of catalyst is 89.78%, vinyl chloride selection
Property is 98.62%, and it is relatively low to change catalyst activity, is unsatisfactory for industrial requirement.
Chinese patent application (A of CN 103495416) disclose using one kind in CNT, carbon fiber, graphene as
Carrier loaded PdCl2The catalyst being prepared, in unstripped gas ratio V (HCl)/V (C2H2In 180 DEG C of progress under the conditions of)=1.2
Acetylene hydrochlorination reactivity worth is tested, analytical reactions tail gas, and the conversion of alkyne of catalyst is 97.51%, vinyl chloride selectivity
For 99.15%.Although changing, catalyst activity is higher, and content of metal is too high (12-15wt%), and industrial applications are difficult.
Therefore, these methods such as the interaction added between auxiliary agent and support modification processing reinforcement Pd and carrier also are difficult to
The fundamentally losing issue of inhibitory activity component.
Ionic liquid has the advantages that zero vapour pressure is non-volatile, is in a liquid state temperature range is wide, chemically and thermally stability is good,
Also it is reported with certain application in acetylene hydrochlorination reaction.
Chinese patent application (A of CN 101716528) disclose a kind of ion liquid dissolving gold, platinum, palladium, tin, mercury, copper or
The metal chlorides such as rhodium are catalyst system, are reacted applied to acetylene hydrochlorination, but the reaction system belongs to gas liquid reaction system,
The deficiencies of mass-transfer efficiency that reactant and product be present is low, stirring or pneumatic stirring are easily lost in catalyst activity component, it is difficult to
Industrial applications and ionic liquid loaded noble metal catalyst cannot be used for the widely used fixation of current industrial production vinyl chloride
The technique such as bed or fluid bed.
Chinese patent application (A of CN 105001040) discloses Pd prepared by metal nanoparticle/ion liquid system and urged
Agent, in unstripped gas ratio V (HCl)/V (C2H2Under the conditions of)=1.2 acetylene hydrochlorination reactivity worth survey is carried out in 140-220 DEG C
Examination, analytical reactions tail gas, the conversion of alkyne of catalyst is 88%, and vinyl chloride is selectively 99.5%, has no and urges after reaction 15h
Agent inactivates, and changes catalyst and that conversion of alkyne is relatively low still be present.
Pd active components are dispersed in ionic liquid by document report (ACS Catal.2015,5,6724-6731) can be with
Effective catalyzing acetylene hydrochlorination, in unstripped gas ratio V (HCl)/V (C2H2Under the conditions of)=1.2 acetylene hydrogen is carried out in 180 DEG C
Chlorination reaction performance test, analytical reactions tail gas, the acetylene initial conversion of catalyst is 97.3%, and vinyl chloride is selectively
99.5%；But in open reaction system (gas-liquid reaction), 24.6% active component is also found that after reaction 50h
It is lost in.
Chinese patent CN104703953 A disclose a kind of solid supported ionic liquid and metal and are applied to acetylene hydrogen chlorine
Change the method for reaction, selected solid carrier is that specific surface area is more than 0.1m2/ g, pore volume are more than 0.02ml/g solid, institute
The cation of selection ionic liquid is glyoxaline cation, pyridylium or pyrrolidines cation, anion can select
Any anion is selected, selected metal is mainly using Pd as noble metal of representative etc., but evaluation result display reaction 500h
Conversion of alkyne only has 60% or so afterwards.It can be seen that the activity of catalyst is still unsatisfactory for the needs of industrialized production, catalyst inactivation
The reason for open source information in do not refer to.
Although above-mentioned document and patent all report ionic liquid applied in acetylene hydrochlorination reaction, can bring beneficial
Effect.But it will be seen that either ionic liquid still introduces ionic liquid as the gas liquid reaction of solvent in the surface of solids
Body phase does not all completely inhibit the losing issue of Pd active components, and catalyst performance does not obtain the improvement of essence.
Active component is dissolved in ionic liquid, by ionic liquid in work by the present invention using ionic liquid as medium
The salting-out effect of special distribution behavior and inorganic salts on property charcoal, purposefully sinks the ionic liquid dissolved with active component
Product is arrived in the micropore canals of absorbent charcoal carrier.During the course of the reaction, using micropore canals capillary force confinement effect, can be with
The effectively distillation of inhibitory activity component, so as to improve the stability of catalyst, make the use cost of catalyst substantially reduce, have
There is the possibility of very big commercial Application.
The content of the invention
Distilled it is an object of the invention to fundamentally solve palladium catalyst in the reaction of acetylene hydrochlorination synthesis vinyl chloride thereof
A kind of problem of loss, there is provided the acetylene hydrochlorination palladium-based catalyst that stability is good, reactivity is high.
The present invention improves the activity of palladium catalyst, enhancing surely by adding ionic liquid and inorganic salts etc. into palladium catalyst
It is qualitative, reach the effect for not only improving reactivity but also strengthening its stability.The catalyst in production application have load capacity it is low,
The advantages that active high, stability is good, there is good economy and industrial application value.
The present invention proposes a kind of palladium-based catalyst for acetylene hydrochlorination production vinyl chloride, it is characterised in that：The catalysis
The palladium catalyst that the carrier of agent promotes for the ionic liquid of porous solid carrier load, namely the palladium that load-type ion liquid promotes
Catalyst.
The preparation method for the palladium catalyst that described load-type ion liquid promotes is as follows：By the palladium-containing solution configured,
Ionic liquid is mixed to get mixed liquor；At 20~60 DEG C, mixed liquor is added drop-wise to porous solid carrier under ul-trasonic irradiation
On, and impregnated 0.5~8 hour under ul-trasonic irradiation；Again at 20~60 DEG C, under ul-trasonic irradiation toward after impregnating mixed liquor
Porous solid carrier inorganic salt solution is added dropwise, and impregnated 1~20 hour under ul-trasonic irradiation；Then it is true at 60~120 DEG C
Sky is dried 3~30 hours, both obtains the palladium catalyst that load-type ion liquid promotes；The ionic liquid is imidazoles, pyridines
Or pyrrolidines ionic liquid；The palladium-containing solution is the aqueous solution of containing palladium compound；The inorganic salt solution is that sulfur-bearing is inorganic
The aqueous solution of salt；The pore volume of the cumulative volume and the porous solid carrier of the mixed liquor and inorganic salt solution matches.
Porous solid carrier of the present invention be activated carbon, CNT, graphene, alundum (Al2O3), silica,
Titanium dioxide or molecular sieve.
Activated carbon described further is column charcoal or spherical carbon, the mesh of particle diameter 10~100, content of ashes≤12.0wt%,
500~1500m of specific surface area2/g；
Activated carbon described further is preferably cylindricality charcoal or spherical carbon and passes through pickling processes.
The acid solution that pickling processes described further use is the mixing of the one or both of hydrochloric acid solution or salpeter solution
Thing.
Pickling temperature described further is 20~40 DEG C, and pickling time is 0.5~20 hour.
The mass ratio of activated carbon/acid solution described further is 1/ (2~20).
Described CNT is processed into column or spherical, the mesh of particle diameter 10~100, content of ashes≤6.0wt%, compares surface
250~1600m of product2/ g, 0.25~2.5mL/g of pore volume；
Described graphene is processed into column or spherical, the mesh of particle diameter 10~100, content of ashes≤6.0wt%, specific surface area
500~1200m2/ g, 0.2~1.5mL/g of pore volume；
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, 0.2~2.5mL/g of pore volume；
Described silica is processed into column or spherical, the mesh of particle diameter 10~100,50~800m of specific surface area2/ g, pore volume
0.2~2.0mL/g；
Described titanium dioxide processes are into column or spherical, the mesh of particle diameter 10~100,50~800m of specific surface area2/ g, pore volume
0.1~1.2mL/g；
Described molecular sieve is ZSM-5, beta-molecular sieve, γ molecular sieves, 5A molecular sieves, 10X molecular sieves, 13X molecular sieves, is added
Work is into column or spherical, the mesh of particle diameter 10~100,500~1500m of specific surface area2/ g, 0.1~1.2mL/g of pore volume.
Containing palladium compound of the present invention is selected from chlorine palladium acid, ammonium chloropalladate, chlorine palladium acid sodium, the ammonia palladium of dichloro four, chlorine palladium acid
One or more in potassium；
Further, Pd concentration is 0.001~0.05g/ml in described palladium-containing solution；
Ionic liquid cation of the present invention be N- hexyls pyridine, N- butyl-pyridiniums, N- octylpyridiniums, N- butyl-
N- crassitudes, 1- butyl -3- methylimidazoles, 1- propyl group -3- methylimidazoles, 1- ethyl-3-methylimidazoles, 1- hexyls -3-
Methylimidazole, 1- octyl group -3- methylimidazoles, 1- pi-allyl -3- methylimidazoles, 1- butyl -2,3- methylimidazoles；Its anion
For chlorion, bromide ion, hexafluoro-phosphate radical, tetrafluoro phosphate radical, trifluoro methylsulfonimide or tetrafluoroborate, imines root；
Described inorganic salts are mainly selected from the strong inorganic salts of hydrophily.For further, the strong inorganic salts master of hydrophily
Will be selected from the sulfide of alkali metal, the sulfohydrate of alkali metal, the sulphite of alkali metal, alkali metal bisulfites,
(NH4)2S、(NH4)2SO3、NH4HS、NH4HSO3In one or more；
Further, S concentration is 0.01~0.5g/mL in inorganic salt solution of the present invention.
In the catalyst of above-mentioned preparation, specific composition quality content information is as follows：
Described palladium load capacity (opposite carrier quality) is 0.05~1wt%；
Described ionic liquid loaded amount (opposite carrier quality) is 2.5~25wt%；
Described sulphur load capacity (opposite carrier quality) is 0.1~5wt%.
In the preparation method of the present invention, the palladium-containing solution, inorganic salt solution, dosage and the above-mentioned load capacity of ionic liquid
It is corresponding, namely the Theoretical Mass of palladium is 0.05~1wt% of porous solid carrier quality in the mixed liquor；The inorganic salts are molten
The Theoretical Mass of sulphur is 0.1~5wt% of porous solid carrier quality in liquid；The quality of the mixed liquor intermediate ion liquid is more
2.5~25wt% of hole solid carrier quality.
Further, the pore volume of the cumulative volume and the porous solid carrier of the mixed liquor and inorganic salt solution matches,
Refer to the product of the pore volume for taking porous solid carrier and quality, i.e., in porous solid carrier the volume in all ducts and mixed liquor and
The cumulative volume of inorganic salt solution is equal.
The palladium 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 load-type ion liquid
The palladium catalyst of promotion, is passed through unstrpped gas HCl, C2H2, reaction temperature is 100~200 DEG C, 0.1~0.5MPa of reaction pressure,
Acquisition vinyl chloride can be reacted.
Further, the ratio between described amount of gaseous matter n (HCl)/n (C2H2)=1.0~1.2/1.
Described 5~100h of acetylene volume space velocity-1。
The palladium 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 2000h, it is not detected by palladium and is substantially lost in, conversion of alkyne reaches as high as 100%, chloroethene
Alkene selectively reaches as high as 100%.
The characteristics of palladium catalyst that load-type ion liquid of the present invention promotes, is ionic liquid and strongly hydrophilic
Inorganic salts.Active component can be deposited in the carrier micropore of duct by ionic liquid of the present invention, utilize the strong of micropore
The confinement effect of capillary force not easily runs off it to stablize palladium species.Hydrophilic inorganic salt of the present invention can ensure from
Sub- liquid is stable in the presence of in micropore canals in dipping and drying process, particularly in view of for hydrophilic ionic liquid
It may be overflowed in the drying process with moisture from duct.
Load-type ion liquid of the present invention promotes in the preparation method of palladium catalyst, in addition to special ionic liquid
The addition manner and its special role of body and sulfur-containing compound.As background technology is introduced, the support type of reported in literature from
In the method for preparing catalyst that sub- liquid promotes, not referring to ionic liquid is located in the duct of carrier, or positioned at carrier
Outer surface, and customary preparation methods are generally all ionic liquids mixed with the solution of metal-containing compound after, then be impregnated into load
On body, then water or other solvents are removed by dry method.In the drying process, moisture or solvent can be from the holes of carrier
Escaped in road, now also can take ionic liquid and active component out of duct along band, cause ionic liquid and the big portion of active component
Divide and be all distributed in carrier outer surface.This holds during the course of the reaction not only bad for the scattered of ionic liquid and active component
Easily cause the loss of ionic liquid and active component.Preparation method of the present invention is first ionic liquid and containing palladium compound
Load on carrier, sulfur-containing inorganic salt is then added dropwise again.Sulfur-containing inorganic salt of the present invention has the function that to saltout, due to containing
Sulphur inorganic salts are to be added drop-wise to after ionic liquid and containing palladium compound on carrier, and now sulfur-containing inorganic salt is distributed mainly on carrier
Outer surface, and by salting out by the moisture in ionic liquid and containing palladium compound solution in carrier duct from carrier duct
Ionic liquid and containing palladium compound can't be taken out of duct by middle precipitation, this process.In subsequent process of vacuum drying, with
Volatilization in carrier outer surface moisture, sulfur-containing inorganic salt gradually will be also dissolved in ionic liquid, have been eventually formed positioned at load
Ionic liquid in body opening road promotes palladium-sulfur compound.It is high steady that the ionic liquid of this state promotes palladium-sulfur compound to have
It is qualitative.
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 palladium 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 40 mesh, content of ashes 5.0wt%, specific surface area 950m2/ g, hole
Hold 0.8mL/g, and the HCl treatment 0.5h at 20 DEG C by 300ml concentration for 10wt%.110 DEG C dry 20h, standby.Will
50ml H2PdCl4Solution (wherein Pd contents are 0.001g/ml) and 2.5g 1- butyl -3- methylimidazole villaumites mix, 20 DEG C
When mixed liquor is added drop-wise on 100g absorbent charcoal carriers under ul-trasonic irradiation, dip time 6 hours under ul-trasonic irradiation.Again
At 30 DEG C, 10ml Na is added dropwise toward above-mentioned system under ul-trasonic irradiation2S solution (wherein S contents are 0.01g/ml), and
20ml deionized waters, and impregnated 1 hour under ul-trasonic irradiation.Catalyst after dipping is dried in vacuo 3 hours at 120 DEG C, is obtained
To A catalyst, wherein Pd load capacity (opposite carrier quality) is 0.05wt%, and the load capacity (opposite carrier quality) of S elements is
0.1wt%, the load capacity (opposite carrier quality) of ionic liquid is 2.5wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 100
DEG C, pressure 0.1MPa, 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 reacting 2000h, conversion of alkyne 99.2%, vinyl chloride selectivity 99.9%, Pd species flows
Mistake rate is 0.07%.
Embodiment 2
It is carrier to select column CNT, and its particle diameter is 60 mesh, content of ashes 3.0wt%, specific surface area 450m2/ g,
Pore volume 0.62mL/g, and the HCl treatment 20h at 40 DEG C by 300ml concentration for 10wt%.200 DEG C of drying 0.5h are standby.Will
20ml Na2PdCl4Solution (wherein Pd contents are 0.05g/ml) and 25g N- hexyl pyridines bromide mix, in ultrasound at 60 DEG C
Mixed liquor is added drop-wise in 100g carbon nanotube carriers under ripple effect, dip time 6 hours under ul-trasonic irradiation.Again at 40 DEG C
When, toward above-mentioned system dropwise addition 10ml KHS solution (wherein S contents are 0.5g/ml) and 32ml deionizations under ul-trasonic irradiation
Water, and impregnated 20 hours under ul-trasonic irradiation.Catalyst after dipping is dried in vacuo 30 hours at 60 DEG C, obtains B catalyst,
Wherein Pd load capacity (opposite carrier quality) is 1wt%, and the load capacity (opposite carrier quality) of S elements is 5wt%, ionic liquid
Load capacity (opposite carrier quality) be 25wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 200
DEG C, pressure 0.2MPa, n (HCl)/n (C2H2)=1.2/1, acetylene air speed 100h-1.Initial reaction stage, conversion of alkyne are
99.7%, vinyl chloride selectivity 100%；After reaction 2000 hours, conversion of alkyne 99.4%, vinyl chloride selectivity
99.9%, Pd species turnover rate are 0.01%.
Embodiment 3
It is carrier to select column graphene, and its particle diameter is 80 mesh, content of ashes 2.1wt%, specific surface area 650m2/ g, hole
Hold 0.4mL/g.By 10ml (NH4)2PdCl4N- butyl-N- methyl the pyrroles of solution (wherein Pd contents are 0.005g/ml) and 20g
The tetrafluoroborate mixing of alkane is coughed up, mixed liquor is added drop-wise on 100g graphene carriers under ul-trasonic irradiation at 20 DEG C, super
Dip time 4 hours under sound wave effect.Again at 20 DEG C, 10ml (NH is added dropwise toward above-mentioned system under ul-trasonic irradiation4)2S2O3Solution (wherein S contents are 0.01g/ml), and 20ml deionized waters, and impregnated 8 hours under ul-trasonic irradiation.After dipping
Catalyst 90 DEG C be dried in vacuo 9 hours, obtain C catalyst, wherein Pd load capacity (opposite carrier quality) is 0.05wt%,
The load capacity (opposite carrier quality) of S elements is 0.1wt%, and the load capacity (opposite carrier quality) of ionic liquid is 20wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 130
DEG C, pressure 0.3MPa, n (HCl)/n (C2H2)=1.0/1, acetylene air speed 50h-1.Initial reaction stage, conversion of alkyne 99.9%,
Vinyl chloride selectivity 100%；After reaction 2000 hours, conversion of alkyne 99.3%, vinyl chloride selectivity 99.9%, Pd species
Turnover rate is 0.07%.
Embodiment 4
Select column γ-Al2O3For carrier, its particle diameter is 20 mesh, specific surface area 150m2/ g, pore volume 0.7mL/g.By 20ml
Na2PdCl4The tetrafluoroborate mixing of solution (wherein Pd contents are 0.05g/ml) and 25g N- octylpyridiniums, at 25 DEG C
Mixed liquor is added drop-wise to 100g γ-Al under ul-trasonic irradiation2O3On carrier, dip time 4.5 hours under ul-trasonic irradiation.
Again at 25 DEG C, 25ml Na is added dropwise toward above-mentioned system under ul-trasonic irradiation2S2O3Solution (wherein S contents are 0.2g/ml),
And 25ml deionized waters, and impregnated 5 hours under ul-trasonic irradiation.Catalyst after dipping is dried in vacuo 10 hours at 80 DEG C,
D catalyst is obtained, wherein Pd load capacity (opposite carrier quality) is 1.0wt%, and the load capacity (opposite carrier quality) of S elements is
5wt%, the load capacity (opposite carrier quality) of ionic liquid is 25wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 170
DEG C, pressure 0.4MPa, n (HCl)/n (C2H2)=1.15/1, acetylene air speed 5h-1.Initial reaction stage, conversion of alkyne 99.9%,
Vinyl chloride selectivity 100%；After reaction 2000 hours, conversion of alkyne 99.2%, vinyl chloride selectivity 99.9%, Pd species
Turnover rate is 0.03%.
Embodiment 5
Select column TiO2For carrier, its particle diameter is 15 mesh, specific surface area 200m2/ g, pore volume 0.6mL/g.By 20ml's
K2PdCl4The hexafluorophosphate mixing of solution (wherein Pd contents are 0.01g/ml) and 10g 1- hexyl -3- methylimidazoles, 50 DEG C
When mixed liquor is added drop-wise to 100g TiO under ul-trasonic irradiation2On carrier, dip time 4.5 hours under ul-trasonic irradiation.
Again at 50 DEG C, 30ml NaHSO is added dropwise toward above-mentioned system under ul-trasonic irradiation3(wherein S contents are 0.014g/ to solution
Ml), and 10ml deionized waters, and impregnated 5.5 hours under ul-trasonic irradiation.Catalyst after dipping is dried in vacuo 28 at 70 DEG C
Hour, obtain E catalyst, wherein Pd load capacity (opposite carrier quality) is 0.2wt%, load capacity (the opposite carrier matter of S elements
Amount) it is 0.42wt%, the load capacity (opposite carrier quality) of ionic liquid is 10wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 170
DEG C, pressure 0.5MPa, n (HCl)/n (C2H2)=1.2/1, acetylene air speed 100h-1.Initial reaction stage, conversion of alkyne 100%,
Vinyl chloride selectivity 99.9%；After reaction 2000 hours, conversion of alkyne 99.0%, vinyl chloride selectivity 99.9%, Pd things
Kind turnover rate is 0.4%.
Embodiment 6
Select column SiO2For carrier, its particle diameter is 90 mesh, specific surface area 250m2/ g, pore volume 0.85mL/g.By 50ml's
(NH4)2PdCl4The trifluoro sulfonamide mixing of solution (wherein Pd contents are 0.002g/ml) and 6g N- butyl-pyridiniums,
Mixed liquor is added drop-wise to 100g SiO at 30 DEG C under ul-trasonic irradiation2On carrier, dip time 6 is small under ul-trasonic irradiation
When.Again at 30 DEG C, 30ml KHSO is added dropwise toward above-mentioned system under ul-trasonic irradiation3(wherein S contents are 0.01g/ to solution
Ml), and 5ml deionized waters, and impregnated 7 hours under ul-trasonic irradiation.Catalyst after dipping is small in 95 DEG C of vacuum drying 11
When, obtain F catalyst, wherein Pd load capacity (opposite carrier quality) is 0.1wt%, load capacity (the opposite carrier matter of S elements
Amount) it is 0.3wt%, the load capacity (opposite carrier quality) of ionic liquid is 6wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 180
DEG C, pressure 0.2MPa, n (HCl)/n (C2H2)=1.05/1, acetylene air speed 30h-1.Initial reaction stage, conversion of alkyne are
99.9%, vinyl chloride selectivity 99.9%；After reacting 2000h, conversion of alkyne 98.3%, vinyl chloride selectivity 99.9%,
Pd 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 1200m2/ g, hole
Hold 1.0mL/g, and at 25 DEG C by nitric acid treatment 5 hours that 300ml concentration is 10wt%.120 DEG C dry 12h, standby.Will
40ml H2PdCl4Solution (wherein Pd contents are 0.005g/ml) and 10g 1- butyl -2,3- methylimidazoles villaumite mix,
Mixed liquor is added drop-wise on 100g absorbent charcoal carrier under ul-trasonic irradiation at 30 DEG C, the dip time 6 under ul-trasonic irradiation
Hour.Again at 30 DEG C, 50ml Na is added dropwise toward above-mentioned system under ul-trasonic irradiation2SO3(wherein S contents are 0.02g/ to solution
Ml), and 10ml deionized waters, and impregnated 12 hours under ul-trasonic irradiation.Catalyst after dipping is dried in vacuo 9 at 105 DEG C
Hour, obtain G catalyst, wherein Pd load capacity (opposite carrier quality) is 0.2wt%, load capacity (the opposite carrier matter of S elements
Amount) it is 1wt%, the load capacity (opposite carrier quality) of ionic liquid is 10wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 150
DEG C, pressure 0.2MPa, n (HCl)/n (C2H2)=1.1/1, acetylene air speed 30h-1.Initial reaction stage, conversion of alkyne 99.8%,
Vinyl chloride selectivity 99.9%；After reaction 2000 hours, conversion of alkyne 98.9%, vinyl chloride selectivity 99.9%, Pd things
Kind turnover rate is 0.02%.
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 0.9mL/g, and at 35 DEG C by nitric acid treatment 6 hours that 250ml concentration is 15wt%.150 DEG C dry 6h, standby.Will
25ml K2PdCl4Four fluorophosphates of solution (wherein Pd contents are 0.012g/ml) and 15g 1- propyl group -3- methylimidazoles mix
Close, mixed liquor is added drop-wise on 100g absorbent charcoal carrier under ul-trasonic irradiation at 35 DEG C, when being impregnated under ul-trasonic irradiation
Between 6 hours.Again at 35 DEG C, 50ml (NH is added dropwise toward above-mentioned system under ul-trasonic irradiation4)2(wherein S contents are S solution
0.04g/ml), and 15ml deionized waters, and impregnated 15 hours under ul-trasonic irradiation.Catalyst after dipping is in 115 DEG C of vacuum
Dry 7 hours, obtain H catalyst, wherein Pd load capacity (opposite carrier quality) is 0.3wt%, and the load capacity of S elements is (relative
Carrier quality) it is 2wt%, the load capacity (opposite carrier quality) of ionic liquid is 15wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 120
DEG C, pressure 0.2MPa, n (HCl)/n (C2H2)=1.1/1, acetylene air speed 35h-1.Initial reaction stage, conversion of alkyne 99.9%,
Vinyl chloride selectivity 99.9%；After reaction 2000 hours, conversion of alkyne 99.4%, vinyl chloride selectivity 99.9%, Pd things
Kind turnover rate is 0.03%.
Comparative example 1
It is carrier to select column-shaped active carbon, and its particle diameter is 40 mesh, content of ashes 5.0wt%, specific surface area 950m2/ g, hole
Hold 0.8mL/g, and the HCl treatment 3h at 25 DEG C by 300ml concentration for 10wt%.110 DEG C dry 20h, standby.By 30ml
H2PdCl4Solution (wherein Pd contents are 0.01g/ml) and 15g 1- butyl -3- methylimidazole villaumites mix, and add 50ml
Deionized water, mixed liquor is added drop-wise on 100g absorbent charcoal carriers under ul-trasonic irradiation at 30 DEG C, soaked under ul-trasonic irradiation
8 hours stain time.Catalyst after dipping is dried in vacuo 3 hours at 120 DEG C, obtains I catalyst, and wherein Pd load capacity is (relative
Carrier quality) it is 0.3wt%, the load capacity (opposite carrier quality) of ionic liquid is 15wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 160
DEG C, pressure 0.1MPa, n (HCl)/n (C2H2)=1.1/1, acetylene air speed 30h-1.Initial reaction stage, conversion of alkyne 97.8%,
Vinyl chloride selectivity 99.8%；After reaction 200 hours, conversion of alkyne 61.3%, vinyl chloride selectivity 99.7%, Pd species
Turnover rate is 35.7%.
Comparative example 2
It is carrier to select column-shaped active carbon, and its particle diameter is 40 mesh, content of ashes 5.0wt%, specific surface area 950m2/ g, hole
Hold 0.8mL/g, and at 25 DEG C by the HCl treatment 3h that 300ml concentration is 10wt%, 110 DEG C dry 20h, standby.By 30ml
H2PdCl4Solution (wherein Pd contents are 0.01g/ml) and 15g 1- butyl -3- methylimidazole villaumites mix, super at 30 DEG C
Mixed liquor is added drop-wise on 100g absorbent charcoal carriers under sound wave effect, dip time 8 hours under ul-trasonic irradiation.Again at 30 DEG C
When, 50ml NaCl solution (its concentration is 0.01g/ml) is added dropwise toward above-mentioned system under ul-trasonic irradiation, and make in ultrasonic wave
Impregnated 10 hours with lower.Catalyst after dipping is dried in vacuo 6 hours at 110 DEG C, obtains J catalyst, wherein Pd load capacity (phase
To carrier quality) it is 0.3wt%, the load capacity (opposite carrier quality) of ionic liquid is 15wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 160
DEG C, pressure 0.1MPa, n (HCl)/n (C2H2)=1.1/1, acetylene air speed 30h-1.Initial reaction stage, conversion of alkyne 99.1%,
Vinyl chloride selectivity 99.9%；After reaction 200 hours, conversion of alkyne 72.6%, vinyl chloride selectivity 99.6%, Pd species
Turnover rate is 28.9%.
Comparative example 3
It is carrier to select column-shaped active carbon, and its particle diameter is 40 mesh, content of ashes 5.0wt%, specific surface area 950m2/ g, hole
Hold 0.8mL/g, and at 25 DEG C by HCl treatment 3 hours that 300ml concentration is 10wt%.110 DEG C dry 20h, standby.Will
30ml H2PdCl4Solution (wherein Pd contents are 0.01g/ml) and 15g 1- butyl -3- methylimidazole villaumites mix, at 30 DEG C
Mixed liquor is added drop-wise on 100g absorbent charcoal carriers under ul-trasonic irradiation, dip time 8 hours under ul-trasonic irradiation.Exist again
At 30 DEG C, 50ml KSCN solution (wherein S contents are 0.01g/ml) is added dropwise toward above-mentioned system under ul-trasonic irradiation, and super
Impregnated 10 hours under sound wave effect.Catalyst after dipping is dried in vacuo 6 hours at 110 DEG C, obtains K catalyst, wherein Pd is born
Carrying capacity (opposite carrier quality) is 0.3wt%, and the load capacity (opposite carrier quality) of S elements is 0.5wt%, and ionic liquid is born
Carrying capacity (opposite carrier quality) is 15wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 160
DEG C, pressure 0.1MPa, n (HCl)/n (C2H2)=1.1/1, acetylene air speed 30h-1.Initial reaction stage, conversion of alkyne 99.3%,
Vinyl chloride selectivity 99.8%；After reaction 200 hours, conversion of alkyne 77.2%, vinyl chloride selectivity 99.7%, Pd species
Turnover rate is 18.4%.
Comparative example 4
It is carrier to select column-shaped active carbon, and its particle diameter is 40 mesh, content of ashes 5.0wt%, specific surface area 950m2/ g, hole
Hold 0.8mL/g, and at 25 DEG C by HCl treatment 3 hours that 300ml concentration is 10wt%.110 DEG C dry 20h, standby.Will
30ml H2PdCl4Solution (wherein Pd contents are 0.01g/ml), 15g 1- butyl -3- methylimidazole villaumites and 50ml Na2S
Solution (wherein S contents are 0.01g/ml) is mixed, and mixed liquor is added drop-wise into 100g carried by active carbon under ul-trasonic irradiation at 30 DEG C
On body, dip time 8 hours under ul-trasonic irradiation.Catalyst after dipping is dried in vacuo 6 hours at 110 DEG C, obtains L catalysis
Agent, wherein Pd load capacity (opposite carrier quality) are 0.3wt%, and the load capacity (opposite carrier quality) of S elements is 0.5wt%,
The load capacity (opposite carrier quality) of ionic liquid is 15wt%.
This catalyst takes the acetylene hydrochlorination reaction that 2g is applied in fixed bed reactors, is in reaction condition：Temperature 160
DEG C, pressure 0.1MPa, n (HCl)/n (C2H2)=1.1/1, acetylene air speed 30h-1.Initial reaction stage, conversion of alkyne 99.9%,
Vinyl chloride selectivity 99.9%；After reaction 200 hours, conversion of alkyne 97.6%, vinyl chloride selectivity 99.9%, Pd species
Turnover rate is 2.9%.
Claims (10)
1. the palladium catalyst that a kind of load-type ion liquid promotes, it is characterised in that the catalyst is prepared as follows：
The palladium-containing solution configured, ionic liquid are mixed to get mixed liquor；, will be mixed under ul-trasonic irradiation at 20~60 DEG C
Close drop to be added on porous solid carrier, and impregnated 0.5~6 hour under ul-trasonic irradiation；Again at 20~60 DEG C, in ultrasound
Inorganic salt solution is added dropwise in porous solid carrier after the lower mixed liquor toward dipping of ripple effect, and 1~20 is impregnated under ul-trasonic irradiation
Hour；Then be dried in vacuo 3~30 hours at 60~120 DEG C, both load-type ion liquid promotion palladium catalyst；Institute
It is imidazoles, pyridines or pyrrolidines ionic liquid to state ionic liquid；The palladium-containing solution is the aqueous solution of containing palladium compound；
The inorganic salt solution is the aqueous solution of sulfur-containing inorganic salt；The cumulative volume of the mixed liquor and inorganic salt solution with it is described porous solid
The pore volume of body carrier matches.
2. catalyst as claimed in claim 1, it is characterised in that：The Theoretical Mass of palladium carries for porosu solid in the mixed liquor
The 0.05~1% of weight；The Theoretical Mass of sulphur is the 0.1~5% of porous solid carrier quality in the inorganic salt solution；Institute
The quality for stating mixed liquor intermediate ion liquid is the 2.5~25% of porous solid carrier quality.
3. catalyst as claimed in claim 1, it is characterised in that：In described palladium-containing solution Pd concentration be 0.001~
0.05g/mL；S concentration is 0.01~0.5g/mL in described inorganic salt solution.
4. the catalyst as described in one of claims 1 to 3, it is characterised in that：The containing palladium compound is selected from chlorine palladium acid, chlorine palladium
One or more in sour ammonium, chlorine palladium acid sodium, the ammonia palladium of dichloro four, potassium chloropalladate.
5. the catalyst as described in one of claims 1 to 3, it is characterised in that：The ionic liquid cation is N- hexyl pyrroles
Pyridine, N- butyl-pyridiniums, N- octylpyridiniums, N- butyl-N- crassitudes, 1- butyl -3- methylimidazoles, 1- propyl group -3- methyl
Imidazoles, 1- ethyl-3-methylimidazoles, 1- hexyl -3- methylimidazoles, 1- octyl group -3- methylimidazoles, 1- pi-allyl -3- methyl miaows
Azoles, 1- butyl -2,3- methylimidazoles；The ionic liquid anion is chlorion, bromide ion, hexafluoro-phosphate radical, tetrafluoro phosphorus
Acid group, trifluoro methylsulfonimide or tetrafluoroborate, imines root.
6. the catalyst as described in one of claims 1 to 3, it is characterised in that：The sulfur-containing inorganic salt is selected from the sulphur of alkali metal
Compound, the sulfohydrate of alkali metal, the sulphite of alkali metal, the bisulfites of alkali metal, (NH4)2S、(NH4)2SO3、
NH4HS、NH4HSO3In one or more.
7. the catalyst as described in one of claims 1 to 3, it is characterised in that：The porous solid carrier is activated carbon, carbon is received
Mitron, graphene, alundum (Al2O3), silica, titanium dioxide or molecular sieve.
8. catalyst as claimed in claim 7, it is characterised in that：The activated carbon is for cylindricality charcoal or spherical carbon and through overpickling
Processing；The acid that the pickling processes use is the mixture of the one or both of hydrochloric acid solution or salpeter solution；Described pickling
Temperature is 20~40 DEG C, and pickling time is 0.5~20h；The mass ratio of described activated carbon/acid solution is 1/ (2~20).
9. the palladium catalyst that the ionic liquid of porous solid carrier load as claimed in claim 1 promotes is in catalyzing acetylene hydrogen chlorine
The application being combined in the reaction of vinyl chloride.
10. application as claimed in claim 9, it is characterised in that the application detailed process is：In fixed bed reactors, dress
Entering the palladium catalyst that described load-type ion liquid promotes, reaction temperature is 100~200 DEG C, reaction pressure 0.1~
0.5MPa, it is passed through unstrpped gas HCl, C2H2, HCl and C2H2The ratio between amount of material is 1.0~1.2/1, C2H2Volume space velocity 5~
100h-1, you can reaction obtains vinyl chloride.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107498A (en) * | 2015-09-15 | 2015-12-02 | 浙江工业大学 | Method for preparing carbon-loaded gold catalyst and application of catalyst |
| CN105148989A (en) * | 2015-07-28 | 2015-12-16 | 浙江工业大学 | Porous solid material supported ionic liquid-gold catalyst, as well as preparation and application thereof |
-
2017
- 2017-09-29 CN CN201710906036.XA patent/CN107824225B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148989A (en) * | 2015-07-28 | 2015-12-16 | 浙江工业大学 | Porous solid material supported ionic liquid-gold catalyst, as well as preparation and application thereof |
| CN105107498A (en) * | 2015-09-15 | 2015-12-02 | 浙江工业大学 | Method for preparing carbon-loaded gold catalyst and application of catalyst |
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| CN110743616B (en) * | 2019-09-30 | 2022-06-21 | 浙江工业大学 | Environment-friendly acetylene hydrochlorination catalyst and preparation method thereof |
| CN110743613A (en) * | 2019-09-30 | 2020-02-04 | 浙江工业大学 | Supported metal catalyst and preparation method and application thereof |
| CN113210011A (en) * | 2021-04-15 | 2021-08-06 | 沈阳化工大学 | Preparation method and application of catalyst based on sludge-biomass mixed carbon |
| CN115254188A (en) * | 2022-05-07 | 2022-11-01 | 贵州大学 | Method for preparing amphiphilic composite catalyst Pd @ IL/CNT-COOH by one-pot method |
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