CN107552006A - A kind of porosu solid loaded metal matrix ionic liquid of enrichment HCl gases - Google Patents
A kind of porosu solid loaded metal matrix ionic liquid of enrichment HCl gases Download PDFInfo
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- CN107552006A CN107552006A CN201710906657.8A CN201710906657A CN107552006A CN 107552006 A CN107552006 A CN 107552006A CN 201710906657 A CN201710906657 A CN 201710906657A CN 107552006 A CN107552006 A CN 107552006A
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Abstract
The invention discloses a kind of porosu solid loaded metal matrix ionic liquid of enrichment HCl gases, it is mainly used in HCl/C2H2HCl gases are enriched with gaseous mixture or acetylene hydrochlorination synthesis vinyl chloride thereof industrial tail gas；Or in HCl/C2H2HCl gases and catalyzing acetylene hydrochlorination are enriched with mixed material gas.The porosu solid loaded metal matrix ionic liquid is made up of porous solid carrier and the active component being supported on porous solid carrier, and the active component is Metal Substrate ionic liquid, and the Metal Substrate ionic liquid is the compound of ionic liquid and metal chloride.The compound ionic liquid that the present invention uses has excellent selective absorption performance to HCl, and HCl adsorption rate reaches as high as 99.5%, by adsorption and enrichment HCl gases of the present invention, and parses the HCl gas purity height obtained after desorption and reaches as high as 99.99%.
Description
Technical field
The present invention relates to gas be enriched with field, and in particular to a kind of porosu solid loaded metal matrix of enrichment HCl gases from
Sub- liquid.
Background technology
In preparing chloroethylene by acetylene hydrochlorination industry, the mixed air containing HCl, such as HCl/C be present2H2Mixed air, chloroethene
Alkene industrial tail gas etc., it is a problem that HCl gases are isolated in these mixed airs.Industrially, for vinyl chloride industrial tail gas
In HCl generally uses alkali lye carry out absorption removal, although this method is simple, HCl be converted into the low chlorate of added value and
It can not recycle, and add the discharge of waste liquid.
Adsorption method of separation is a kind of conventional method that valuable gas is separated and recovered from mixed air, and this method is to rely on
Selective absorption of the sorbing material to specific gas simultaneously realizes absorption and desorption and regeneration as temperature and pressure changes, wherein inhaling
Enclosure material is crucial.
The most frequently used sorbing material is molecular sieve.Chinese patent CN106794443A discloses a kind of novel carbon molecular sieve
(CMS) it is gas absorption separation material, the material includes is with mean pore size scopeExtremelyMicropore carbon
Change vinylidene chloride copolymer.These materials are separable to be included (such as) propane/propylene, methane/nitrogen and ethane/ethylene
The ability of admixture of gas.Chinese patent CN106799202A disclose it is a kind of for gas separation adsorbent of molecular sieve and its
Preparation method.It has RHO molecular sieve configurations, and its chemical composition mol ratio is X2O3：mYO2：nM2O, wherein X be triad,
Y is quadrivalent element, M is univalent element or monovalent cation.This kind of molecular sieve uses to be adjusted by crown ether, alkali, water, silicon source and silicon source
The Primogel being made into, is synthesized through hydro-thermal method.Compared with Li exchanges the conventional molecular sieve of X-type molecular sieve isopreference absorption nitrogen,
The molecular sieve quadrivalent element Y contents are higher, influenceed by corrosion of vapor effect smaller；Compared with traditional RHO molecular sieves, this point
Son sieve can in nitrogen oxygen separating preferential a large amount of absorption nitrogens, oxygen argon separation in preferentially a large amount of adsorption of oxygen.Applied to air
During separation process, the molecular sieve has high stability and high separability energy simultaneously, thus can ensure PSA separation air events
Production efficiency.
Metal-organic framework material also has preferable gas absorption separating effect.For example, Chinese patent
It is adsorbent that CN106807330A, which discloses a kind of metal-organic framework material (MOFs), and the material is by metal ion, organic
The part porous structure material that ligand complex is formed in a solvent.The MOFs materials can be used for the shorter quick transformation of cycle period
Adsorption separation process, the disposal ability of unit volume device is significantly increased, suitable for the separation of atm number admixture of gas
Purification is with concentrating the purification process such as purification.But the patent is not known the use range of such sorbing material, it is more undeclared to containing
The adsorbing separation effect of HCl mixed air.Chinese patent CN106699817A discloses a kind of system of metal-organic framework material
Preparation Method and its application.Including cabaltous nitrate hexahydrate and 5- (4- (5- tetrazole radicals) phenyl) M-phthalic acid 1) are added into N, N- bis-
The in the mixed solvent of NMF and water obtains mixed liquor after stirring；2) mixed liquor is placed in closed autoclave
In, it is heated to 100~110 DEG C and is incubated, is then cooled to room temperature and obtains reaction product；3) reaction product being filtrated to get, is obtained
To red bulk crystals, 4) red bulk crystals are exchanged with methanol, then heating in vacuum 5~7 hours at 220 DEG C, are produced
To metal-organic framework material.The metal-organic framework material is used for CO and CO2Mix in gas to CO2Selective absorption point
From.Chinese patent CN105944680A discloses a kind of metal-organic framework material for adsorbing separation propylene and propine, this
It is a kind of anion-containing metal-organic framework materials adsorbent, the adsorbent is a kind of aperture in the adjustable height of 0.4-1.2nm
Spend orderly micropore class hybrid inorganic-organic materials.Pore volume is in 0.1-1.2cm3/ g is adjustable.Substantial amounts of anion active site and its
The space arrangement of high-sequential makes it show the performance of excellent absorption propine.So as to very high propine selectivity and suction
Attached capacity, it is the potential propylene of tool and propine separating and purifying technology.
Ionic liquid can also be used for gas absorption separation.Chinese patent CN104277880A discloses one kind and utilizes ionic liquid
The method of body absorption and separation lighter hydrocarbons from dry gas or industrial tail gas.It is molten with the mixing of ionic liquid or ionic liquid and molecular solvent
Agent contacts, absorption obtains the absorbing liquid containing lighter hydrocarbons, then is obtained gently through Desorption separation as absorbent with dry gas or industrial tail gas
Hydrocarbon；Described lighter hydrocarbons are the alkane or alkene for mainly containing C2~C4.Described absorbent have very high lighter hydrocarbons solubility and
Separation selectivity, it is possible to achieve lighter hydrocarbons efficiently separate recovery, and comprehensive recovery reaches as high as 98.5%.
In HCl/C2H2HCl is adsorbed in the mixed airs containing HCl such as mixed air, acetylene hydrochlorination synthesis vinyl chloride thereof industrial tail gas,
And then be enriched with or separated and recovered, it is significantly.But so far there is not yet report is for the mixing containing HCl
There is the sorbing material of high-selectivity adsorption effect in gas to HCl.
In addition, in the reaction that gas containing HCl participates in, excessive HCl is generally required to improve another more valuable reaction
The conversion ratio of thing, such as C2H2In being reacted with HCl hydrogen chlorides synthesis vinyl chloride thereof, HCl/C2H2Mol ratio is typically greater than 1.If
Hydrogen chloride and HCl/C in acetylene reaction environment can be improved2H2Mol ratio, can also equally reach acetylene and hydrogen chloride mixing is former
Expect the reaction effect that HCl is excessive in gas.At present, also there is not yet the open report of the technical field.
The content of the invention
The present invention provides a kind of material of absorption/enrichment HCl gases, and is applied to HCl/C2H2Mixed air, acetylene hydrogen
HCl is adsorbed in chlorination synthesis vinyl chloride thereof industrial tail gas, and then is isolated recovery；Or applied to HCl/C2H2Blended stock gas
Middle enrichment HCl simultaneously carries out efficient acetylene hydrochlorination reaction.
The present invention includes following technical scheme：
The present invention provides a kind of material of absorption/enrichment HCl gases, i.e., porosu solid loaded metal matrix ionic liquid is in richness
Collect the application in HCl gases；The porosu solid loaded metal matrix ionic liquid is by porous solid carrier and is supported on porous solid
Active component composition on body carrier,
The porous solid carrier is selected from activated carbon, mesoporous carbon, CNT, silica, aluminum oxide, titanium oxide, molecule
One kind in sieve, metal organic framework compound, covalent organic framework compound, preferably activated carbon；The active component is
Metal Substrate ionic liquid, the Metal Substrate ionic liquid are the compound of ionic liquid and metal chloride；Described ionic liquid
Body is imidazoles, pyridines, quaternary phosphines class or pyrrolidines ionic liquid；
Further, the cation of the ionic liquid 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- methylimidazole, 1- butyl -
3- methylimidazoles, tributyl-methyl phosphonium phosphine, tributyl ethyl phosphine, tetrabutyl phosphine, tributyl hexyl phosphine, tributyl octyl group phosphine, three fourths
Base decyl phosphine, tributyl dodecyl phosphine, tributyl myristyl phosphine, triphenyl ethyl phosphine, triphenyl butyl phosphine, triphenyl first
Base phosphine, triphenyl propyl group phosphine, triphenyl amyl group phosphine, triphenyl acetonyl phosphine, triphenylbenzylphosphonium phosphine, triphenyl (3- bromopropyls)
Phosphine, triphenyl bromomethyl phosphine, triphenylmethoxy phosphine, triphenyl ethoxycarbonylmethyl group phosphine, triphenyl (3- bromopropyls) phosphine, triphen
Base vinyl phosphonic, tetraphenyl phosphine；The anion of the ionic liquid is chlorion, bromide ion, trifluoro methylsulfonimide or imines
Root；
Described metal chloride is chlorauride, palladium bichloride, ruthenic chloride, platinum chloride, copper chloride, aluminium chloride, inidum chloride, chlorine
Change the one or more in mercury, bismuth chloride, iron chloride, manganese chloride, barium chloride, calcium chloride, preferably chlorauride, palladium bichloride, chlorine
Change ruthenium, copper chloride, aluminium chloride, inidum chloride, iron chloride, barium chloride.
Further, the present invention provides a kind of preparation method of described porosu solid loaded metal matrix ionic liquid, step
It is as follows：(1) ionic liquid and metal chloride are heated into 3~20h at 80~200 DEG C respectively；By the ionic liquid after heating and
Metal chloride is well mixed, and is heated to 60~200 DEG C of 0.5~6h of stirring, until obtaining transparent clear liquid, stopping adds for melting
Heat, Metal Substrate ionic liquid is prepared into, is transferred in closed container and is sealed；Total matter based on gained Metal Substrate ionic liquid
Amount, the quality dosage of metal chloride accounts for the 0.01~10% of gross mass, remaining as ionic liquid；
(2) first by porosu solid in 60~120 DEG C of 3~20h of vacuum drying treatment；By step (1) prepare Metal Substrate from
Sub- liquid is dissolved in solvent, then by dissolved with the molten of Metal Substrate ionic liquid at 0~100 DEG C and under ul-trasonic irradiation
Agent is added drop-wise in porous solid carrier dropwise, impregnates 1~12h after being well mixed under ul-trasonic irradiation；Then 100~200
DEG C 12~24h of heating in vacuum, produces the porosu solid loaded metal matrix ionic liquid.
Further, the mass ratio of described Metal Substrate ionic liquid and porosu solid is 0.05~0.5：1.
Described porosu solid has at least 50m2/ g BET specific surface area, it is however preferred to have at least 300m2/ g BET ratios
Surface area；With at least 0.2mL/g pore volume, it is however preferred to have at least 0.35mL/g pore volume.
Further, described solvent is water, fatty alcohol, acetonitrile, hydrochloric acid, toluene, benzene, acetone, hexamethylene, DMF, NMP, king
Water, organic chloroazotic acid, nitrobenzene, tetrahydrofuran, propanethiol, thiocarbamide, chloromethane, carbon disulfide or hydrogen peroxide.
Further, the mass ratio of the solvent and Metal Substrate ionic liquid is recommended as 0.5~5：1.
Specifically, the preparation method of porosu solid loaded metal matrix ionic liquid of the present invention preferably by it is following operate into
OK：(1) ionic liquid and metal chloride are heated into 7~18h at 95~170 DEG C respectively；By the ionic liquid and gold after heating
Belonging to chloride to be well mixed, be heated to 70~170 DEG C of 2~6h of stirring, until obtaining transparent clear liquid, stopping is heated for melting,
Metal Substrate ionic liquid is prepared into, is transferred in closed container and is sealed；Based on the gross mass of gained Metal Substrate ionic liquid,
The quality dosage of metal chloride accounts for the 1~6.5% of gross mass, remaining as ionic liquid；
(2) first by porosu solid in 60~120 DEG C of 3~18h of vacuum drying treatment；By step (1) prepare Metal Substrate from
Sub- liquid is dissolved in solvent, then by dissolved with the molten of Metal Substrate ionic liquid at 20~55 DEG C and under ul-trasonic irradiation
Agent is added drop-wise in porous solid carrier dropwise, impregnates 2~5h after being well mixed under ul-trasonic irradiation；Then at 100~190 DEG C
12~20h of heating in vacuum, produce the porosu solid loaded metal matrix ionic liquid.
Further, porosu solid loaded metal matrix ionic liquid of the present invention can be applied to HCl/C2H2Gaseous mixture or
Acetylene hydrochlorination synthesis vinyl chloride thereof industrial tail gas is enriched with HCl；Or applied to HCl/C2H2HCl is enriched with mixed material gas and is urged
Change acetylene hydrochlorination reaction.
Porosu solid loaded metal matrix ionic liquid of the present invention can be applied to HCl/C2H2HCl is enriched with gaseous mixture
Method it is as follows：Porosu solid loaded metal matrix ionic liquid of the present invention, Ran Hou are loaded in fixed bed reactors
HCl/C is passed through at a temperature of relatively low adsorption operations2H2Gaseous mixture carries out cryogenic absorption, in porosu solid loaded metal matrix ionic liquid
Can reaches very high HCl/C in body2H2Ratio；And utilize HCl and C2H2With active force power difference in ionic liquid
(active force of HCl and ionic liquid is far above C2H2With the active force of ionic liquid), then by microwave action in absorption mixed air
Porosu solid loaded metal matrix ionic liquid afterwards, optionally by micro C2H2Gas is desorbed from ionic liquid, and is protected
Most of HCl is stayed in ionic liquid；Temperature is raised again and reduces pressure, and HCl is desorbed, obtains high-purity HCl gases.
Specifically, porosu solid loaded metal matrix ionic liquid of the present invention is loaded in fixed bed reactors,
HCl/C is passed through during 0~80 DEG C of relatively low adsorption operations temperature2H2Gaseous mixture carries out cryogenic absorption, first selective through microwave action
By micro C2H2Gas is desorbed from ionic liquid；HCl can be desorbed through high-temperature low-pressure again, obtain high-purity HCl, realize enrichment
HCl；
Described HCl/C2H2Initial HCl/C in gaseous mixture2H2Ratio is 0.3~1.2:1；
Described mixed air volume space velocity is 10~500h-1；
Described cryogenic absorption operating pressure is 0.1~1.1MPa；
Described microwave action operation temperature is 0~80 DEG C；
The described microwave action operating time is 0.5~8h；
It is 0.01~0.05MPa that desorption manipulation pressure is carried out after described cryogenic absorption；
It is 40~140 DEG C that desorption manipulation temperature is carried out after described cryogenic absorption.
Further, porosu solid loaded metal matrix ionic liquid of the present invention can be applied to HCl/C2H2Mixed material
HCl is enriched with gas and the method for catalyzing acetylene hydrochlorination is as follows：
Described porosu solid loaded metal matrix ionic liquid is loaded in fixed bed reactors, then in higher absorption
HCl/C is passed through at 100~200 DEG C of operation temperature2H2Mixed material gas is adsorbed, and adsorbs the porosu solid carried metal after HCl
The catalyst that base ionic liquid reacts as acetylene hydrochlorination, realize enrichment HCl and carry out acetylene hydrochlorination reaction；
Described HCl/C2H2Initial HCl/C in mixed material gas2H2Ratio is 0.3~1.2:1；
Described mixed air volume space velocity is 10~500h-1；
It is 100~200 DEG C that hydrochlorination operation temperature is carried out after described high temperature adsorption；
The operating pressure that acetylene hydrochlorination reaction is carried out after the high temperature adsorption is 0.1~0.5MPa.
Porosu solid loaded metal matrix ionic liquid of the present invention can be applied to acetylene hydrochlorination synthesis vinyl chloride thereof work
The method that HCl is enriched with industry tail gas is as follows：Using porosu solid loaded metal matrix ionic liquid as adsorbent, fixed bed is loaded into
Absorption tower, then passes to acetylene hydrochlorination synthesis vinyl chloride thereof industrial tail gas, and porosu solid loaded metal matrix ionic liquid can have
HCl in effect absorption gaseous mixture；Through microwave action first selectivity by micro vinyl chloride and C2H2Etc. foreign gas from ionic liquid
It is desorbed in body；The HCl gases of high-purity are just can obtain after being desorbed HCl again, realize enrichment HCl；
HCl volume content is 0.01~50% in described industrial tail gas；
The volume space velocity of described industrial tail gas is 10~500h-1；
Described absorption HCl operation temperature is 0~120 DEG C；
Described absorption HCl operating pressure is 0.1~1.1MPa；
Described microwave action operation temperature is 0~80 DEG C；
The described microwave action operating time is 0.5~8h；
Described desorption HCl operation temperature is 80~220 DEG C；
Described desorption HCl operating pressure is 0.01~0.05MPa；
The porosu solid loaded metal matrix ionic liquid of the present invention is used as adsorbent, can be effectively by HCl/C2H2It is mixed
Close gas, the HCl adsorption and enrichments in acetylene hydrochlorination synthesis vinyl chloride thereof industrial tail gas, adsorption recovery rate reaches as high as 99.5%, and
And thus obtained HCl purity is high, reaches as high as 99.99%.And porosu solid supported ion liquid of the present invention can
As the catalyst of acetylene hydrochlorination reaction, not only there is enrichment HCl effect, but also efficient acetylene hydrogen chlorine can be realized
Change reaction, conversion of alkyne can be achieved>99.5%, selectivity>99.96%, stability was up at least 12 months.
Compared with prior art, the invention has the advantages that：
1. the compound ionic liquid that uses of the present invention has excellent selective absorption performance to HCl, can effectively from
HCl/C2H2Separation and concentration HCl, HCl adsorption rate reach as high as in gaseous mixture, acetylene hydrochlorination synthesis vinyl chloride thereof industrial tail gas
99.5%.
2. material cellular solid loaded metal matrix ionic liquid of the present invention, allows it to be adsorbed in absorption tower
HCl, there is the advantages of easy to operate, good separating effect, parsing desorption is simple.
3. through adsorption and enrichment of the present invention, and parsing the HCl gas purities height obtained after desorption, 99.99% is reached as high as.
Acetylene hydrochlorination can also be used as to react 4. the cellular solid that the present invention uses loads compound ionic liquid
Catalyst, can be in HCl/C2H2Ratio is 1:When 1, realize enrichment HCl and carry out efficient acetylene hydrochlorination reaction.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1
100g N- hexyls pyridine chloride salt ions liquid and 5g copper chlorides are first heated into 20h at 80 DEG C respectively.By 100g's
N- hexyls pyridine chloride salt ions liquid and 5g copper chlorides are well mixed, and are put into beaker, are heated to 100 DEG C of stirring 2h, and melting is straight
To transparency liquid is obtained, stop heating；The Metal Substrate ionic liquid of preparation is transferred in closed container and is sealed.
It is carrier to select column-shaped active carbon, and its particle diameter is 20 mesh, content of ashes 6.0wt%, specific surface area 800m2/ g, hole
Hold 0.20mL/g, first by activated carbon in 100 DEG C of vacuum drying treatment 24h.By the above-mentioned Metal Substrate ion liquid dissolvings of 5g in 20g water
In, the solvent dissolved with Metal Substrate ionic liquid is then added drop-wise to 100g activated carbons dropwise under ul-trasonic irradiation at 20 DEG C
In carrier, 2h is impregnated under ul-trasonic irradiation after well mixed；Then in 100 DEG C of heating in vacuum 20h, both porous solid supported
Metal Substrate ionic liquid A.
2g load type metal base ionic liquid materials A is loaded into fixed bed absorption tower, is then passed through HCl/C at 20 DEG C2H2
Mixed air, wherein mixture pressure are 0.3MPa, and HCl volume content is 10%, and the volume space velocity of mixed air is 50h-1；Absorption
4h.Stopping is passed through mixed air, and microwave action 2h is used at 20 DEG C；Then HCl desorptions are carried out, temperature in tower is risen to 50 DEG C,
Pressure is down to 0.01MPa, just obtains the HCl gases that purity is 99.98%, and HCl adsorption recovery rate reaches 99.4%.
Embodiment 2
First respectively by 100g N- butyl-N- crassitude bromide ionic liquids and 10g palladium bichlorides in 120 DEG C of heating
16h.100g N- butyl-N- crassitude bromide ionic liquids and 10g palladium bichlorides are well mixed, is put into beaker, adds
Heat to 120 DEG C of stirring 3h, melting stops heating up to obtaining transparency liquid；The Metal Substrate ionic liquid of preparation is transferred to close
Close in container and be sealed.
It is carrier to select column CNT, and its particle diameter is 80 mesh, content of ashes 3.0wt%, specific surface area 400m2/ g,
Pore volume 0.50mL/g, first by CNT in 110 DEG C of vacuum drying treatment 20h.By the above-mentioned Metal Substrate ion liquid dissolvings of 20g in
In 50g ethanol, then the solvent dissolved with Metal Substrate ionic liquid is added drop-wise to dropwise under ul-trasonic irradiation at 30 DEG C
In 100g carbon nanotube carriers, 2h is impregnated under ul-trasonic irradiation after well mixed；Then in 100 DEG C of heating in vacuum 20h, both obtained
Porosu solid loaded metal matrix ionic liquid B.
2g load type metal base ionic liquid materials B is loaded into fixed bed absorption tower, is then passed through HCl/C at 10 DEG C2H2
Mixed air, wherein mixture pressure are 0.2MPa, and HCl volume content is 30%, and the volume space velocity of mixed air is 20h-1；Absorption
3.5h.Stopping is passed through mixed air, and microwave action 8h is used at 10 DEG C；Then HCl desorptions are carried out, temperature in tower is risen to 80
DEG C, pressure is down to 0.02MPa, just obtains the HCl gases that purity is 99.99%, and HCl adsorption recovery rate reaches
99.5%.
Embodiment 3
100g 1- propyl group -3- methylimidazole villaumites ionic liquid and 7g ruthenic chlorides are first heated into 14h at 140 DEG C respectively.
100g 1- propyl group -3- methylimidazole villaumites ionic liquid and 7g ruthenic chlorides are well mixed, is put into beaker, is heated to 130
DEG C stirring 4h, melting stop heating until obtain transparency liquid；The Metal Substrate ionic liquid of preparation is transferred in closed container
It is sealed.
Select column γ-Al2O3For carrier, its particle diameter is 60 mesh, specific surface area 120m2/ g, pore volume 0.40mL/g, first will
γ-Al2O3In 150 DEG C of vacuum drying treatment 18h.By the above-mentioned Metal Substrate ion liquid dissolvings of 25g in 40g acetone, then 40
DEG C when the solvent dissolved with Metal Substrate ionic liquid is added drop-wise to 100g γ-Al dropwise under ul-trasonic irradiation2O3In carrier,
After well mixed 4h is impregnated under ul-trasonic irradiation；Then in 105 DEG C of heating in vacuum 15h, both porous solid supported Metal Substrate
Ionic liquid C.
2g load type metal base ionic liquid materials C is loaded into fixed bed absorption tower, is then passed through acetylene hydrogen at 30 DEG C
Chlorination synthesis vinyl chloride thereof industrial tail gas, wherein mixture pressure are 1.0MPa, and HCl volume content is 2.0%, the body of mixed air
Product air speed is 80h-1；Adsorb 4h.Stopping is passed through mixed air, and microwave action 4h is used at 30 DEG C；Then HCl desorptions are carried out, will
Temperature rises to 190 DEG C in tower, and pressure is down to 0.02MPa, just obtains the HCl gases that purity is 99.94%, and HCl absorption
The rate of recovery reaches 99.2%.
Embodiment 4
First respectively by the trifluoro sulfonamide ionic liquid of 100g tributyl-methyl phosphonium phosphine and 5g iron chloride at 170 DEG C
Heat 14h.The trifluoro sulfonamide ionic liquid of 100g tributyl-methyl phosphonium phosphine and 5g iron chloride are well mixed, are put into
In beaker, 170 DEG C of stirring 5h are heated to, until obtaining transparency liquid, stopping is heated for melting；By the Metal Substrate ionic liquid of preparation
It is transferred in closed container and is sealed.
Select column SiO2For carrier, its particle diameter is 65 mesh, specific surface area 100m2/ g, pore volume 0.90mL/g, first by SiO2
In 120 DEG C of vacuum drying treatment 5h.By the above-mentioned Metal Substrate ion liquid dissolvings of 40g in 90g DMF, then at 50 DEG C
Solvent dissolved with Metal Substrate ionic liquid is added drop-wise to 100g SiO dropwise under ul-trasonic irradiation2In carrier, after being well mixed
4.5h is impregnated under ul-trasonic irradiation；Then in 105 DEG C of heating in vacuum 8h, both porous solid supported Metal Substrate ionic liquid D.
Load type metal base ionic liquid material D is loaded into fixed bed absorption tower, acetylene hydrogen chlorine is then passed through at 70 DEG C
Vinyl chloride industrial tail gas is combined to, wherein mixture pressure is 0.5MPa, and HCl volume content is 2.5%, the volume of mixed air
Air speed is 70h-1；Adsorb 4h.Stopping is passed through mixed air, and microwave action 0.5h is used at 70 DEG C；Then HCl desorptions are carried out, will
Temperature rises to 180 DEG C in tower, and pressure is down to 0.01MPa, just obtains the HCl gases that purity is 99.92%, and HCl absorption
The rate of recovery reaches 99.5%.
Embodiment 5
100g N- octylpyridinium chloride salt ions liquid and 1g chloraurides are first heated into 18h at 95 DEG C respectively.By 100g's
N- octylpyridinium chloride salt ions liquid and 1g chloraurides are well mixed, and are put into beaker, are heated to 170 DEG C of stirring 3h, and melting is straight
To transparency liquid is obtained, stop heating；The Metal Substrate ionic liquid of preparation is transferred in closed container and is sealed.
Select column TiO2For carrier, its particle diameter is 50 mesh, specific surface area 150m2/ g, pore volume 0.25mL/g, first by TiO2
In 140 DEG C of vacuum drying treatment 13h.By the above-mentioned Metal Substrate ion liquid dissolvings of 50g in 25g acetonitriles, then at 30 DEG C
Solvent dissolved with Metal Substrate ionic liquid is added drop-wise to 100g TiO dropwise under ul-trasonic irradiation2In carrier, after being well mixed
2.5h is impregnated under ul-trasonic irradiation；Then in 100 DEG C of heating in vacuum 12h, both porous solid supported Metal Substrate ionic liquid
E。
2g load type metal base ionic liquid materials E is loaded into fixed bed reactors, then passes to HCl/C2H2Mixed air,
Wherein HCl/C2H2For 1/1, the volume space velocity of mixed air is 20h-1, reaction temperature is 180 DEG C, pressure 0.2Mpa.Reaction is just
Phase conversion of alkyne 99.99%, selectivity 100%, after running 9 months, conversion of alkyne 99.7%, selectivity 99.9%.
Embodiment 6
First respectively by the trifluoro sulfonamide ionic liquid of 100g 1- butyl -2,3- methylimidazoles, 5g chlorinations
Palladium and 5g inidum chlorides heat 8h at 170 DEG C.By the trifluoro sulfonamide ion of 100g 1- butyl -2,3- methylimidazoles
Liquid, 5g palladium bichlorides and 5g inidum chlorides are well mixed, and are put into beaker, are heated to 160 DEG C of stirring 3.5h, melting is until obtain
Prescribed liquid, stop heating；The Metal Substrate ionic liquid of preparation is transferred in closed container and is sealed.
It is carrier to select spherical activated charcoal, and its particle diameter is 70 mesh, ash content 1.8%, specific surface area 1350m2/ g, pore volume
0.25mL/g, first by activated carbon in 150 DEG C of vacuum drying treatment 4h.By the above-mentioned Metal Substrate ion liquid dissolvings of 5g in 25g rosickyite
In alcohol, then the solvent dissolved with Metal Substrate ionic liquid is added drop-wise to 100g work dropwise at 30 DEG C under ul-trasonic irradiation
Property high-area carbon in, impregnate 5h under ul-trasonic irradiation after well mixed；Then in 190 DEG C of heating in vacuum 13h, porosu solid is both obtained
Loaded metal matrix ionic liquid F.
2g load type metal base ionic liquid materials F is loaded into fixed bed reactors, then passes to HCl/C2H2Mixed air,
Wherein HCl/C2H2For 0.8/1, the volume space velocity of mixed air is 50h-1, reaction temperature is 180 DEG C, pressure 0.3Mpa.Reaction
Initial stage conversion of alkyne 80%, selectivity 100%, operation 9 months after, conversion of alkyne 79.9%, selectivity 99.9%.
Embodiment 7
First respectively by chloride salt ions liquid, 1.5g ruthenic chlorides and the 4g aluminium chloride of 100g tributyl hexyl phosphine at 200 DEG C
Heat 3h.Chloride salt ions liquid, 1.5g ruthenic chlorides and the 4g aluminium chloride of 100g tributyl hexyl phosphine are well mixed, are put into burning
In cup, 200 DEG C of stirring 2h are heated to, melting stops heating up to obtaining transparency liquid；The Metal Substrate ionic liquid of preparation is turned
Move on in closed container and be sealed.
It is carrier to select granular pattern ZSM-5 molecular sieve, and its particle diameter is 10 mesh, specific surface area 400m2/ g, pore volume 0.5mL/g,
First by ZSM-5 molecular sieve in 90 DEG C of vacuum drying treatment 18h.By the above-mentioned Metal Substrate ion liquid dissolvings of 25g in 50g chloroazotic acid,
Then the solvent dissolved with Metal Substrate ionic liquid is added drop-wise to ZSM-5 points of 100g dropwise under ul-trasonic irradiation at 55 DEG C
In son sieve carrier, 5h is impregnated under ul-trasonic irradiation after well mixed；Then in 180 DEG C of heating in vacuum 18h, porosu solid is both obtained
Loaded metal matrix ionic liquid G.
2g load type metal base ionic liquid materials G is loaded into fixed bed reactors, then passes to HCl/C2H2Mixed air,
Wherein HCl/C2H2For 0.6/1, the volume space velocity of mixed air is 40h-1, reaction temperature is 160 DEG C, pressure 0.4Mpa.Reaction
Initial stage conversion of alkyne 60%, selectivity 100%, operation 9 months after, conversion of alkyne 59.8%, selectivity 99.9%.
Embodiment 8
First respectively by the chloride salt ions liquid, 0.5g chloraurides and 6g barium chlorides of 100g tetraphenyl phosphine in 190 DEG C of heating
12h.The chloride salt ions liquid, 0.5g chloraurides and 6g barium chlorides of 100g tetraphenyl phosphine are well mixed, is put into beaker, adds
Heat to 190 DEG C of stirring 0.5h, melting stops heating up to obtaining transparency liquid；The Metal Substrate ionic liquid of preparation is transferred to
It is sealed in closed container.
It is carrier to select column-shaped active carbon, and its particle diameter is 25 mesh, ash content 7.1%, specific surface area 1100m2/ g, pore volume
0.55mL/g, first by activated carbon in 120 DEG C of vacuum drying treatment 5h.By the above-mentioned Metal Substrate ion liquid dissolvings of 15g in 55g dioxygens
In water, then the solvent dissolved with Metal Substrate ionic liquid is added drop-wise to 100g work dropwise at 45 DEG C under ul-trasonic irradiation
Property high-area carbon in, impregnate 5h under ul-trasonic irradiation after well mixed；Then in 145 DEG C of heating in vacuum 15h, porosu solid is both obtained
Loaded metal matrix ionic liquid H.
2g load type metal base ionic liquid materials H is loaded into fixed bed reactors, then passes to HCl/C2H2Mixed air,
Wherein HCl/C2H2For 0.3/1, the volume space velocity of mixed air is 70h-1, reaction temperature is 190 DEG C, pressure 0.5Mpa.Reaction
Initial stage conversion of alkyne 30%, selectivity 100%, operation 9 months after, conversion of alkyne 29.9%, selectivity 99.9%.
Comparative example 1
0.5g chloraurides are first heated into 18h at 95 DEG C.Select column TiO2For carrier, its particle diameter is 50 mesh, specific surface area
150m2/ g, pore volume 0.85mL/g, first by TiO2In 100 DEG C of vacuum drying treatment 24h.The above-mentioned chloraurides of 0.5g are dissolved in 85g
In acetonitrile, then the solvent dissolved with chlorauride is added drop-wise to 100g TiO dropwise at 30 DEG C under ul-trasonic irradiation2Carrier
In, impregnate 2.5h under ul-trasonic irradiation after well mixed；Then in 160 DEG C of heating in vacuum 12h, comparative catalyst W is both obtained.
2g comparative catalysts W is loaded into fixed bed reactors, then passes to HCl/C2H2Mixed air, wherein HCl/C2H2For
1/1, the volume space velocity of mixed air is 20h-1, reaction temperature is 180 DEG C, pressure 0.2Mpa.Initial reaction stage conversion of alkyne
95.7%, selectivity 99.9%, after running 9 months, conversion of alkyne 36.1%, selectivity 97.5%.
Claims (10)
1. a kind of application of porosu solid loaded metal matrix ionic liquid in HCl gases are enriched with, the porosu solid gold-supported
Category base ionic liquid is made up of porous solid carrier and the active component being supported on porous solid carrier, and the porosu solid carries
Body be selected from activated carbon, mesoporous carbon, CNT, silica, aluminum oxide, titanium oxide, molecular sieve, metal organic framework compound,
One kind in covalent organic framework compound；The active component is Metal Substrate ionic liquid, and the Metal Substrate ionic liquid is
The compound of ionic liquid and metal chloride, described ionic liquid be imidazoles, pyridines, quaternary phosphines class or pyrrolidines from
Sub- liquid, described metal chloride are chlorauride, palladium bichloride, ruthenic chloride, platinum chloride, copper chloride, aluminium chloride, inidum chloride, chlorine
Change the one or more in mercury, bismuth chloride, iron chloride, manganese chloride, barium chloride, calcium chloride.
2. application as claimed in claim 1, it is characterised in that：The cation of the ionic liquid is N- hexyls pyridine, N- fourths
Yl pyridines, N- octylpyridiniums, N- butyl-N- crassitudes, 1- butyl -3- methylimidazoles, 1- propyl group -3- methylimidazoles, 1-
Ethyl-3-methylimidazole, 1- hexyl -3- methylimidazoles, 1- octyl group -3- methylimidazoles, 1- pi-allyl -3- methylimidazoles, 1- fourths
Base -2,3- methylimidazole, 1- butyl -3- methylimidazoles, tributyl-methyl phosphonium phosphine, tributyl ethyl phosphine, tetrabutyl phosphine, tributyl
Hexyl phosphine, tributyl octyl group phosphine, tributyl decyl phosphine, tributyl dodecyl phosphine, tributyl myristyl phosphine, triphenyl ethyl
Phosphine, triphenyl butyl phosphine, trityl group phosphine, triphenyl propyl group phosphine, triphenyl amyl group phosphine, triphenyl acetonyl phosphine, triphenyl
Benzyl phosphine, triphenyl (3- bromopropyls) phosphine, triphenyl bromomethyl phosphine, triphenylmethoxy phosphine, triphenyl ethoxycarbonylmethyl group phosphine,
Triphenyl (3- bromopropyls) phosphine, triphenyl vinyl phosphine, tetraphenyl phosphine；The anion of the ionic liquid be chlorion, bromine from
Son, trifluoro methylsulfonimide or imines root.
3. application as claimed in claim 1, it is characterised in that the preparation side of the porosu solid loaded metal matrix ionic liquid
Method is：
(1) ionic liquid and metal chloride are heated into 3~20h at 80~200 DEG C respectively；By the ionic liquid and gold after heating
Belong to chloride to be well mixed, be heated to 60~200 DEG C of 0.5~6h of stirring, until obtaining transparent clear liquid, stopping adds for melting
Heat, Metal Substrate ionic liquid is prepared into, is transferred in closed container and is sealed；Total matter based on gained Metal Substrate ionic liquid
Amount, the quality dosage of metal chloride accounts for the 0.01~10% of gross mass, remaining as ionic liquid；
(2) first by porosu solid in 60~120 DEG C of 3~20h of vacuum drying treatment；Metal Substrate ionic liquid prepared by step (1)
Body is dissolved in solvent, then at 0~100 DEG C and under ul-trasonic irradiation by the solvent dissolved with Metal Substrate ionic liquid by
It is added drop-wise in porous solid carrier, impregnates 1~12h after being well mixed under ul-trasonic irradiation；Then it is true at 100~200 DEG C
Sky 12~24h of heating, produces the porosu solid loaded metal matrix ionic liquid.
4. application as claimed in claim 3, it is characterised in that：Described Metal Substrate ionic liquid and the mass ratio of porosu solid
For 0.05~0.5：1.
5. application as claimed in claim 3, it is characterised in that：Described solvent be water, fatty alcohol, acetonitrile, hydrochloric acid, toluene,
Benzene, acetone, hexamethylene, DMF, NMP, chloroazotic acid, organic chloroazotic acid, nitrobenzene, tetrahydrofuran, propanethiol, thiocarbamide, chloromethane, two
Nitric sulfid or hydrogen peroxide.
6. application as claimed in claim 3, it is characterised in that：The mass ratio of the solvent and Metal Substrate ionic liquid is 0.5
~5：1.
7. application as claimed in claim 1, it is characterised in that the application is：In HCl/C2H2Gaseous mixture or acetylene hydrochlorination
HCl gases are enriched with synthesis vinyl chloride thereof industrial tail gas；Or in HCl/C2H2HCl gases are enriched with mixed material gas and are catalyzed second
Alkynes hydrochlorination.
8. application as claimed in claim 7, it is characterised in that be set forth in HCl/C2H2HCl is enriched with gaseous mixture is：In fixed bed
Described porosu solid loaded metal matrix ionic liquid is loaded in reactor, then at relatively low 0~80 DEG C of adsorption operations temperature
It is passed through HCl/C2H2Gaseous mixture carries out cryogenic absorption, through microwave action first selectivity by micro C2H2Gas is from ionic liquid
Middle desorption；HCl can be desorbed through high-temperature low-pressure again, obtain high-purity HCl, realize enrichment HCl；
Described HCl/C2H2Initial HCl/C in gaseous mixture2H2Ratio is 0.3~1.2:1；Described mixed air volume space velocity is 10
~500h-1；
Described cryogenic absorption operating pressure is 0.1~1.1MPa；
Described microwave action operation temperature is 0~80 DEG C；The described microwave action operating time is 0.5~8h；
It is 0.01~0.05MPa that desorption manipulation pressure is carried out after described cryogenic absorption；It is desorbed after described cryogenic absorption
Operation temperature is 40~140 DEG C.
9. application as claimed in claim 7, it is characterised in that be set forth in HCl/C2H2HCl is enriched with mixed material gas and is catalyzed
Acetylene hydrochlorination reacts：
Described porosu solid loaded metal matrix ionic liquid is loaded in fixed bed reactors, then in higher adsorption operations
HCl/C is passed through at 100~200 DEG C of temperature2H2Mixed material gas is adsorbed, adsorb HCl after porosu solid loaded metal matrix from
The catalyst that sub- liquid can react as acetylene hydrochlorination, realize enrichment HCl and carry out acetylene hydrochlorination reaction；Described
HCl/C2H2Initial HCl/C in mixed material gas2H2Ratio is 0.3~1.2:1；Described mixed air volume space velocity be 10~
500h-1；It is 100~200 DEG C that hydrochlorination operation temperature is carried out after described high temperature adsorption；Second is carried out after the high temperature adsorption
The operating pressure of alkynes hydrochlorination is 0.1~0.5MPa.
10. application as claimed in claim 7, it is characterised in that be set forth in acetylene hydrochlorination synthesis vinyl chloride thereof industrial tail gas rich
Collecting HCl gases is：
Using porosu solid loaded metal matrix ionic liquid as adsorbent, fixed bed absorption tower is loaded into, then passes to acetylene hydrogen
Chlorination synthesis vinyl chloride thereof industrial tail gas, porosu solid loaded metal matrix ionic liquid adsorb the HCl in gaseous mixture；Through microwave action
First selectivity by micro vinyl chloride and C2H2Foreign gas is desorbed from ionic liquid；Again height is just can obtain after being desorbed HCl
The HCl gases of purity, realize enrichment HCl；
HCl volume content is 0.01~50% in described industrial tail gas；
The volume space velocity of described industrial tail gas is 10~500h-1；
Described absorption HCl operation temperature is 0~120 DEG C；
Described absorption HCl operating pressure is 0.1~1.1MPa；
Described microwave action operation temperature is 0~80 DEG C；
The described microwave action operating time is 0.5~8h；
Described desorption HCl operation temperature is 80~220 DEG C；
Described desorption HCl operating pressure is 0.01~0.05MPa.
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