CN106807367A - A kind of iridium based catalyst of carbon-based material load and its preparation method and application - Google Patents

A kind of iridium based catalyst of carbon-based material load and its preparation method and application Download PDF

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CN106807367A
CN106807367A CN201510868870.5A CN201510868870A CN106807367A CN 106807367 A CN106807367 A CN 106807367A CN 201510868870 A CN201510868870 A CN 201510868870A CN 106807367 A CN106807367 A CN 106807367A
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宋宪根
丁云杰
冯四全
陈维苗
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Dalian Institute of Chemical Physics of CAS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates

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Abstract

It is a kind of for elemental iodine and methyl alcohol through the catalyst and preparation method thereof of methyl acetate processed and iodomethane is carbonylated.It is made up of main active component and carrier two parts, main active component is Ir and metal promoter, its content is the 0.01~5.0% and 0.1~30% of catalyst weight；Including CNT, mesoporous carbon, carbon black and Graphene etc., specific surface area of carbon nanotube is 10~400m to carrier2/ g, average pore size is 1~10nm；The specific surface area of mesoporous carbon is 600~1200m2/ g, average pore size is 5~100nm；The specific surface area of carbon black is 300~1200m2/ g, average pore size is 1~200nm；The specific surface area of Graphene is 10~200m2/ g, average pore size is 1~500nm.The Ir base catalyst that a kind of carbon-based material is loaded is provided by the present invention.In fixed bed reactors, under certain temperature and pressure and this catalyst action, CH3OH/CO/H2/I2Can high activity, be converted into methyl acetate and iodomethane with high selectivity.

Description

A kind of iridium based catalyst of carbon-based material load and its preparation method and application
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to a kind of iridium base catalysis of carbon-based material load Agent and preparation method thereof and the application in methyl alcohol is through being carbonylated methyl acetate processed and iodomethane reaction.
Background technology
Methyl acetate gradually replaces acetone, butanone, ethyl acetate, pentamethylene etc. in the world.Because it is not Belong to the organic pollution discharge that limitation is used, coating, ink, resin, adhesive producing works can be reached new Environmental protection standard.Methyl acetate hydrogenation synthesis ethanol is also one of main path of current coal ethanol.It is prepared Method mainly has (1) acetic acid and methyl alcohol directly to carry out esterification with sulfuric acid as catalyst to generate crude methyl acetate Product, then be dehydrated with calcium chloride, sodium carbonate is neutralized, and fractionation obtains methyl acetate finished product.(2) dimethyl ether exists Through carbonyl compound into but molecular sieve carbon distribution inactivation is serious, and space-time yield is very low on H-MOR molecular sieve catalysts. (3) when methanol carbonyl prepares acetic acid, methyl acetate exists as accessory substance, but selectivity is relatively low, separates High cost.So the feasible methyl acetate synthetic route overwhelming majority of industry will be through peracetic acid in the middle of this at present Step.
At present, methanol carbonylation process is occupied an leading position in the industrialized production of acetic acid, at present using the technique The production capacity of acetic acid production device accounted for the 94% of acetic acid total productive capacity.In past 50 years, methyl alcohol The course of industrialization of carbonylation production acetic acid substantially experienced three developing stage：
First stage：BASF AG's nineteen sixty is using Co catalysts under reaction temperature and pressure higher (250 DEG C, 60MPa) realize the industrialized production that acetic acid is produced with methanol carbonylation first.The method is given birth to The acetic acid purity of product is not high, and Main By product is higher alcohol, senior aldehyde and high carboxylic acid, product separation costs It is higher.Second stage：Monsanto companies develop activity and selectivity rhodium higher-iodide (RhI3) urge Change system., also than relatively low (175 DEG C or so, 3.0MPa), acetic acid is on the basis of methyl alcohol for the temperature and pressure of reaction Selection rate more than 99%, the selection rate on the basis of CO has also reached more than 90%.Device is corrosion-resistant will Ask very high, it is necessary to full zircaloy reactor.Phase III：The industrialization of Ir catalyst is methanol carbonylation Production acetic acid.The technique substantially increases the stability of catalyst, and reaction is entered under conditions of water content is relatively low OK, and the generation of liquid by-product is reduced, improves the conversion ratio of CO.Celanese chemical companies pass through The inorganic iodide (mainly lithium iodide) of high concentration is added, the stability of Rh catalyst is improve, iodine is added After changing lithium and iodomethane auxiliary agent, water content significantly reduces (about 4%~5%) in can making reactor, while can tie up again Carbonylation rate higher is held, making the separation costs of new technology significantly reduces.
Thousand generations field (Chiyoda) company of Japan and Uop Inc. have developed jointly Acetica techniques, the technique base In a kind of multiphase Rh catalyst, wherein activity Rh complex compounds are chemically fixed on polyvinylpyridine tree On fat.The sequestering macromolecule of strong and weak coordinate bond that Yuan state of Institute of Chemistry, Academia Sinica minister in ancient times research is combined into is urged Agent also form independent intellectual property right system, the features such as the catalyst system has high stability, high activity, The selectivity of CO can be improved.
Although homogeneous Rh bases and Ir base catalyst system and catalyzings achieve good commercial Application, achieve at a relatively high Catalysis activity and selectivity, the selectivity of acetic acid are more than 99%.But homogeneous catalyst system is from its birth, Taken on certain shortcoming, such as, noble metal catalyst is easy to run off, product separates difficulty with catalyst, Catalyst circulates and reclaims complexity etc..
Not enough for above-mentioned homogeneous reaction catalyst system and catalyzing, it is non-that sight has then been invested support type by a part of researcher Homogeneous catalysis system.Compared with homogeneous catalysis system, heterogeneous catalysis system has natural advantage, such as, Catalyst and convenient product separation, catalyst concn do not receive solubility limit, can be dense by increasing catalyst Spend to improve production capacity etc..Support type heterogeneous catalysis system can be roughly divided into polymer supported according to carrier difference The systems such as body, absorbent charcoal carrier, inorganic oxide carrier, but load type catalyst system has active ratio Low, the active component of homogeneous catalysis system easily remove, it is higher to carrier media the problems such as.
Therefore, to be combined to exploiting potentialities for acetic acid limited for current methanol carbonyl.Methyl alcohol is through being carbonylated high selection Property methyl acetate processed directly skip acetic acid synthetic route, that is, avoid using expensive zirconium material, reduce again Esterification technique, saves a large amount of production costs.
Iodomethane is a kind of important Coal Chemical Industry downstream product, mainly for the manufacture of medicine and the intermediate of agricultural chemicals, It is also the precursor of various methylation reactions, is alternatively arranged as fumigant to prevent and treat the insect of fruit tree and storage cereal, Bromomethane is commercially rapidly substituted, with wide market prospects.It is prepared by iodomethane both domestic and external Technique mainly has：Halogen atom exchange method, methyl alcohol-elemental iodine method, acetic acid-elemental iodine method, methanol-hydrogen acid iodide method With dimethyl sulfate ester process etc..Current domestic enterprise's production is used mostly methanol-hydrogen acid iodide method and dimethyl suflfate Method, methyl alcohol hydroiodic acid method yield is relatively low, and usually 40%, though dimethyl sulfate ester process yield is higher, but due to Dimethyl suflfate severe toxicity, does not meet the technology trends of current Chemical Manufacture, therefore the application of two kinds of techniques is received To greatly limiting.
Due to the great development of ammonia from coal technique, methyl alcohol based on industrial chemicals be applied to produce various height Added value chemical products.This technique with elemental iodine and methyl alcohol as raw material, the high selectivity in carbonylation process While synthesis of acetic acid methyl esters, iodine is changed into iodomethane completely.The production technology of the method has flow letter It is single, mild condition, it is easy to control, the advantages of product separates easy, with very big market popularization value.
The content of the invention
It is an object of the invention to provide a kind of iridium based catalyst of carbon-based material load and its in methyl alcohol through carbonyl Change the application in methyl acetate processed and iodomethane reaction, the primary product for obtaining is methyl acetate and iodomethane.
The technical scheme is that：
It is a kind of for methyl alcohol through the catalyst and preparation method thereof of methyl acetate processed and iodomethane is carbonylated, this is urged Agent is made up of main active component and carrier two parts, and main active component is Ir and metal promoter；Carrier includes CNT, mesoporous carbon, carbon black and Graphene etc..Specific surface area of carbon nanotube is 10~400m2/ g, averagely Aperture is 1~10nm；The specific surface area of mesoporous carbon is 600~1200m2/ g, average pore size is 5~100nm；Charcoal Black specific surface area is 300~1200m2/ g, average pore size is 1~200nm；The specific surface area of Graphene is 10~200m2/ g, average pore size is 1~500nm.
Ir accounts for 0.01~5.0wt% of catalyst gross mass.
Wherein described promoter metal is Li, Na, K, Mg, Al, Zn, Cu, La, Ce, Zr, and content is to urge The 0.1~30.0% of agent weight.
Catalyst according to claim 1, it is characterised in that the preferred specific surface area of CNT is 50~300m2/ g, the preferred average pore size of CNT is 5~100nm；The preferred specific surface area of mesoporous carbon is 800~1000m2/ g, the preferred average pore size of mesoporous carbon is 10~50nm；The preferred specific surface area of carbon black is 500~1000m2/ g, the preferred average pore size of carbon black is 10~100nm；The preferred specific surface area of Graphene is 50~150m2/ g, the preferred average pore size of Graphene is 10~100nm.
Under conditions of hydrochloric acid or nitric acid are present, by Ir metal precursors and promoter metal presoma in water or Dissolved in ethanol, the solution impregnation for obtaining on carrier, 60~80 DEG C of water bath method solvents, in baking oven 100~120 DEG C of drying 8~24h, N2Lower 250~400 DEG C of 4~12h of roasting of protection.
CO/H2With the methyl alcohol/I for pumping into2The fixation equipped with pellet type catalyst of the invention is entered into Deng reactant In bed reactor, methanol carbonylation is carried out, primary product is methyl acetate and iodomethane.
The temperature of carbonylation at 180~280 DEG C, 0.5~3.5MPa, liquid volume air speed is in 0.1~15h-1。
Reactant also includes elemental iodine, and it is the 2~35.0% of methanol weight.
The volume ratio of hydrogen and CO is 0.1~4 in reaction gas.
The material of the reaction system for using is Hastelloy.
The catalyst and activated carbon or the volume ratio of quartz sand being seated in fixed bed are 0.5~5.
It is described it is a kind of for methyl alcohol through the catalyst of methyl acetate processed and iodomethane is carbonylated for methyl alcohol /CO/H2/I2For raw material is converted into methyl acetate and iodomethane reaction.
Beneficial effects of the present invention are：
Compared with prior art, heterogeneous catalyst of the invention is relatively easy in terms of product separation, acetic acid Methyl esters and iodomethane are selectively high.Meanwhile, byproduct of reaction only has process water, and non-corrosive second The material of the core of sour methyl esters and iodomethane, only reaction unit just needs Hastelloy, with investment Poor benefit advantage high.Simultaneous reactions temperature and pressure is relatively low, and synthesis gas does not need purifies and separates, device fortune Row low cost.
Specific embodiment
Following embodiments are illustrated but do not limit content to be protected of the invention.
Embodiment 1
Weigh the dense HCl of 4mL 38wt% and add 6mL deionized waters, 0.25 gram of IrCl3, 0.24 gram of LaCl3 Dissolved in above-mentioned 10mL hydrochloric acid solutions, then impregnate 10.0 grams of CNTs.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain carbon nanotube loaded iridium based catalyst.
Embodiment 2
Weigh the dense HCl of 4mL 38wt% and add 6mL deionized waters, 0.25 gram of IrCl3, 0.05 gram of LiCl Dissolved in above-mentioned 10mL hydrochloric acid solutions, then impregnate 10.0 grams of mesoporous carbons.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain the iridium based catalyst of mesoporous carbon-loaded.
Embodiment 3
Weigh the dense HCl of 4mL 38wt% and add 6mL deionized waters, 0.25 gram of IrCl3, 0.08 gram of NaCl Dissolved in above-mentioned 10mL hydrochloric acid solutions, then impregnate 10.0 grams of CNTs.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain carbon nanotube loaded iridium based catalyst.
Embodiment 4
Weigh the dense HNO of 4mL 69wt%3Add 6mL deionized waters, 0.25 gram of IrCl3, 0.1 gram of KCl Dissolved in above-mentioned 10mL salpeter solutions, then impregnate 10.0 grams of carbon blacks.80 DEG C of water-bath evaporation solvents, 120 DEG C Oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain the iridium based catalyst of carbon black loadings.
Embodiment 5
Weigh the dense HNO of 4mL 69wt%3Add 6mL deionized waters, 0.25 gram of IrCl3, 0.12 gram of MgCl2 Dissolved in above-mentioned 10mL salpeter solutions, then impregnate 10.0 grams of mesoporous carbons.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain the iridium based catalyst of mesoporous carbon-loaded.
Embodiment 6
Weigh the dense HNO of 4mL 69wt%3Add 6mL deionized waters, 0.25 gram of IrCl3, 0.14 gram of AlCl3 Dissolved in above-mentioned 10mL salpeter solutions, then impregnate 10.0 grams of Graphenes.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain graphene-supported iridium based catalyst.
Embodiment 7
Weigh the dense HNO of 4mL 69wt%3Add 6mL deionized waters, 0.30 gram of H2IrCl6, 0.16 gram Zn(NO3)2.6H2O dissolves in above-mentioned 10mL salpeter solutions, then impregnates 10.0 grams of carbon blacks.80 DEG C of water-baths Evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, the iridium base for obtaining carbon black loadings is urged Agent.
Embodiment 8
Weigh the dense HNO of 4mL 69wt%3Add 6mL deionized waters, 0.30 gram of H2IrCl6, 0.18 gram Cu(NO3)2Dissolved in above-mentioned 10mL salpeter solutions, then impregnate 10.0 grams of CNTs.80 DEG C of water-baths Evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtains carbon nanotube loaded iridium Base catalyst.
Embodiment 9
Weigh the dense HNO of 4mL 69wt%3Add 6mL deionized waters, 0.30 gram of H2IrCl6, 0.28 gram Ce(NO3)3.6H2O dissolves in above-mentioned 10mL salpeter solutions, then impregnates 10.0 grams of CNTs.80℃ Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtains carbon nanotube loaded Iridium based catalyst.
Embodiment 10
Weigh the dense HCl of 4mL 38wt% and add 6mL deionized waters, 0.25 gram of IrCl3, 0.24 gram of ZrO2 Dissolved in above-mentioned 10mL hydrochloric acid solutions, then impregnate 10.0 grams of CNTs.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain carbon nanotube loaded iridium based catalyst.
Embodiment 11
Weigh the dense HCl of 4mL 38wt% and add 6mL deionized waters, 0.25 gram of IrCl3, 0.20 gram of La2O3 Dissolved in above-mentioned 10mL hydrochloric acid solutions, then impregnate 10.0 grams of CNTs.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain carbon nanotube loaded iridium based catalyst.
Embodiment 12
Weigh during the dense HCl of 4mL 38wt% add 6mL ethanol, 0.25 gram of IrCl3, 0.20 gram of La2O3 Dissolved in above-mentioned 10mL hydrochloric acid solutions, then impregnate 10.0 grams of Graphenes.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain graphene-supported iridium based catalyst.
Catalyst prepared by application examples is preparing the application in methyl acetate reaction by raw material of methyl alcohol/CO The activation of catalyst：In catalyst using preceding, CO/H in the reactor2=4 (GHSV=5000h-1) carry out in stream In-situ reducing is activated, and condition is：Normal pressure, 5 DEG C/min is kept for 1 hour from room temperature to 240 DEG C, is obtained Iridium based catalyst after to activation.
CO/H2With the methyl alcohol/I for pumping into2It is anti-the fixed bed equipped with pellet type catalyst of the invention to be entered into Deng reactant Answer in device, carry out methanol carbonylation.Condition is：230 DEG C, 2.4Mpa, CH3OH/CO/H2/I2=40/40/10/1 (mol ratio), methyl alcohol LHSV=10h-1.After reaction end gas are cooled down through cold-trap, Gas-phase product carries out on-line analysis, and chromatographic apparatus is Agilent 7890A GC, PQ packed columns, TCD detectors. Liquid product off-line analysis, FFAP capillary chromatographic columns, fid detector.Internal standard method is analyzed, and isobutanol is Internal standard compound.
The iridium based catalyst prepared using embodiment 1~12, methyl acetate, first are prepared according to aforesaid operations The conversion ratio of alcohol and the selectivity of methyl acetate such as table 1.
Table 1
* in terms of the methyl alcohol for converting, including the methyl alcohol in generation methyl acetate.
In terms of 100%, other products are mainly acetic acid to *.

Claims (10)

1. the iridium based catalyst that a kind of carbon-based material is loaded, it is characterised in that：Described iridium based catalyst is by leading Active component and carrier two parts are constituted, main active component Ir and auxiliary agent, carrier be CNT, mesoporous carbon, One or two or more kinds in carbon black and Graphene；Described promoter metal be Li, Na, K, Mg, Al, Zn, One or two or more kinds in Cu, La, Ce, Zr.
2. iridium based catalyst according to claim 1, it is characterised in that：Described carrier is carbon nanometer One or two or more kinds in pipe, mesoporous carbon, carbon black and Graphene；
Specific surface area of carbon nanotube is 10~400m2/ g, the preferred specific surface area of CNT is 50~300m2/ g, CNT average pore size is 1~10nm, and the preferred average pore size of CNT is 5~100nm；
The specific surface area of mesoporous carbon is 600~1200m2/ g, the preferred specific surface area of mesoporous carbon is 800~1000m2/ g, the average pore size of mesoporous carbon is 5~100nm, and the preferred average pore size of mesoporous carbon is 10~50nm；
The specific surface area of carbon black is 300~1200m2/ g, the preferred specific surface area of carbon black is 500~1000m2/ g, charcoal Black average pore size is 1~200nm, and the preferred average pore size of carbon black is 10~100nm；
The specific surface area of Graphene is 10~200m2/ g, the preferred specific surface area of Graphene is 50~150m2/ g, The average pore size of Graphene is 1~500nm, and the preferred average pore size of Graphene is 10~100nm.
3. iridium based catalyst according to claim 1, it is characterised in that：Ir accounts for catalyst gross mass 0.01~5.0wt%, Ir preferably account for 0.1~5.0wt% of catalyst gross mass, and Ir most preferably accounts for the total matter of catalyst 0.5~4.0wt% of amount；
Auxiliary agent is 0.1~30.0wt% of catalyst gross mass, and auxiliary agent is preferably the scope of catalyst gross mass 0.5~25.0wt%, the 0.5~20.0wt% of scope of auxiliary agent most preferably catalyst gross mass.
4. the preparation method of any described iridium based catalysts of a kind of claim 1-3, it is characterised in that：
Under conditions of hydrochloric acid or nitric acid are present, by Ir metal precursors and promoter metal presoma in water and / or ethanol in dissolve, the solution impregnation for obtaining on carrier, 60~80 DEG C of water bath method solvents, in baking oven 100~120 DEG C of drying 8~24h, N2Lower 250~400 DEG C of 4~12h of roasting of protection.
5. preparation method according to claim 4, it is characterised in that：The acid is 37wt% for concentration Hydrochloric acid or 69wt% nitric acid；The Ir metal precursors are IrCl3·3H2O and H2IrCl6In one kind Or more than two kinds；Auxiliary agent presoma is the one kind or two in chloride, nitrate and the oxide of promoter metal More than kind.
6. a kind of any described iridium based catalyst of claims 1 to 3 methanol carbonyl prepare methyl acetate and Application in iodomethane reaction.
7. application according to claim 6, it is characterised in that：The methanol solution of iodine passes through constant flow pump pump Enter after air and liquid mixer and CO/H2Mixing, reaction temperature is 180~280 DEG C, 0.5~3.5MPa of reaction pressure；
Iridium based catalyst is activated or not activated using preceding, and the condition of activation is：Reactor Middle volume ratio CO/H2=0.5~4, normal pressure, 1~10 DEG C/min keeps 0.5~5h from room temperature to 180~280 DEG C, Iridium based catalyst after being activated.
8. application according to claim 7, it is characterised in that：Reaction liquid volume space velocity is 0.1~15h-1, The mol ratio of CO and methyl alcohol is 0.5~3, H2It is 0.1~4 with the volume ratio of CO, elemental iodine concentration is methyl alcohol 2~35.0wt%.
9. application according to claim 7, it is characterised in that：The reaction system material for using is Kazakhstan Alloy.
10. application according to claim 7, it is characterised in that：It is seated in the catalyst in fixed bed With the volume ratio of activated carbon or quartz sand 0.5~5.
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Cited By (3)

* Cited by examiner, † Cited by third party
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CN109759084A (en) * 2017-11-09 2019-05-17 中国科学院大连化学物理研究所 Catalyst and its preparation and application for methanol vapor-phase carbonylation methyl acetate
CN109759055A (en) * 2017-11-09 2019-05-17 中国科学院大连化学物理研究所 A kind of activated carbon supported sulfur-bearing iridium based catalyst and its preparation and application
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