CN108067226A - A kind of activated carbon supported iridium based catalyst and its preparation and application - Google Patents
A kind of activated carbon supported iridium based catalyst and its preparation and application Download PDFInfo
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- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- 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
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- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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Abstract
A kind of iridium based catalyst and its preparation and application for methanol vapor-phase carbonylation methyl acetate.The catalyst is made of major catalyst, the first auxiliary agent, the second auxiliary agent and four part of carrier, and major catalyst active component is iridium；First auxiliary agent is manganese；Second auxiliary agent be containing cobalt, zirconium, copper, zinc, ruthenium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, holmium, ytterbium compound in one or two or more kinds, carrier be one or both of cocoanut active charcoal or apricot shell activated carbon.The present invention provides a kind of by containing manganese compound for the first auxiliary agent, one or two or more kinds in the compound of other cobalts, zirconium, copper, zinc, ruthenium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, holmium, ytterbium etc. are the second auxiliary agent, one or both of cocoanut active charcoal or apricot shell activated carbon are carrier composition, for the iridium based catalyst of methanol vapor-phase carbonylation methyl acetate.Under certain temperature and pressure and this catalyst action, CH3OH and CO can high activity, be converted into methyl acetate with high selectivity.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to and one kind contains manganese compound for the first auxiliary agent, other cobalts,
One or two or more kinds in the compound of zirconium, copper, zinc, ruthenium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, holmium, ytterbium etc. are the second auxiliary agent, coconut palm
One or both of shell activated carbon or apricot shell activated carbon are carrier composition, for methanol vapor-phase carbonylation methyl acetate
Iridium based catalyst.The catalyst is used in fixed bed reactors, under certain temperature and pressure and this catalyst action,
CH3OH and CO can high activity, be converted into methyl acetate with high selectivity.
Background technology
Methyl acetate gradually replaces acetone, butanone, ethyl acetate, pentamethylene etc. in the world.Because it is not belonging to limit
The organic pollution discharge used, can reach the new environmental protection standard of coating, ink, resin, adhesive producing works.Methyl acetate is hydrogenated with
Synthesizing alcohol is also one of main path of current coal ethyl alcohol.Its preparation method mainly have (1) acetic acid and methanol using sulfuric acid as
Catalyst directly carries out esterification generation methyl acetate semifinished product, then is dehydrated with calcium chloride, and sodium carbonate neutralizes, and fractionation obtains vinegar
Sour methyl esters finished product.(2) dimethyl ether on H-MOR molecular sieve catalysts through carbonyl compound into, but molecular sieve easy carbon distribution inactivation, and
Space-time yield is very low.(3) when methanol carbonyl prepares acetic acid, methyl acetate exists as by-product, but selectivity is relatively low, separation
It is of high cost.So the feasible methyl acetate synthetic route one's duty big absolutely of industry will be through this intermediate steps of peracetic acid at present.
At present, methanol carbonylation process is occupied an leading position in the industrialized production of acetic acid, at present using the acetic acid of the technique
The production capacity of process units has accounted for the 94% of acetic acid total productive capacity.In past 50 years, methanol carbonyl metaplasia production acetic acid
Course of industrialization substantially experienced three developing stage：
First stage：BASF AG's nineteen sixty using Co catalysts under higher reaction temperature and pressure (250 DEG C,
The industrialized production with methanol carbonylation production acetic acid 60MPa) is realized first.The acetic acid purity of this method production is not high,
Main By product is higher alcohol, advanced aldehyde and high carboxylic acid, and product separation costs are higher.Second stage：Monsanto companies open
The higher rhodium of activity and selectivity-iodide (RhI is sent out3) catalyst system and catalyzing.The temperature and pressure of reaction is also than relatively low (175 DEG C
Left and right, 3.0MPa), more than 99%, the selection rate on the basis of CO also reaches selection rate of the acetic acid on the basis of methanol
More than 90%.The corrosion-resistant requirement of device is very high, it is necessary to full zircaloy reaction kettle.Phase III：The industrialization of Ir catalyst is first
Alcohol carbonylation method produces acetic acid.The technique substantially increases the stability of catalyst, react under conditions of water content is relatively low into
Row, and reduce the generation of liquid by-product, improve the conversion ratio of CO.Celanese chemical companies are by adding high concentration
Inorganic iodide (mainly lithium iodide) improves the stability of Rh catalyst, adds in lithium iodide with that after iodomethane auxiliary agent, can make
Water content significantly reduces (about 4%~5%) in reactor, while can maintain higher carbonylation rate again, makes point of new process
It is significantly reduced from cost.
Thousand generations field (Chiyoda) company of Japan and Uop Inc. have developed jointly Acetica techniques, which is based on one kind
Multiphase Rh catalyst, wherein activity Rh complex compounds are chemically fixed on polyvinylpyridine resin.The Chinese Academy of Sciences
It learns the sequestering polymer catalyst of strong and weak coordinate bond that the minister in ancient times's research of Yuan state of research institute is combined into and also forms independent intellectual property right body
System, the catalyst system have the characteristics that high stability, high activity, can improve the selectivity that CO is utilized.
Although homogeneous Rh bases and Ir base catalyst system and catalyzings achieve good commercial Application, quite high catalytic activity is achieved
And selectivity, the selectivity of acetic acid are more than 99%.But homogeneous catalyst system has taken on certain lack from its birth
Point, for example, noble metal catalyst is easy to run off, product separates difficult, catalyst circulation with catalyst and recycles complexity etc..
For above-mentioned homogeneous reaction catalyst system and catalyzing deficiency, a part of researcher has then invested sight that support type is heterogeneous to urge
Change system.Compared with homogeneous catalysis system, heterogeneous catalysis system has natural advantage, for example, catalyst is separated with product
Convenient, catalyst concn can improve production capacity etc. from solubility limit by increasing catalyst concn.Support type is heterogeneous
Catalyst system and catalyzing can be roughly divided into the systems such as polymer support, absorbent charcoal carrier, inorganic oxide carrier according to carrier difference, but
There is activity is lower than homogeneous catalysis system, the easy removing of active ingredient, higher etc. to carrier media for load type catalyst system
Problem.
Therefore, to be combined to exploiting potentialities for acetic acid limited for methanol carbonyl at present.Methanol is through being carbonylated highly selective system
Methyl acetate directly skips acetic acid synthetic route, that is, avoids using expensive zirconium material, and reduces esterification technique, saves a large amount of
Production cost.
The content of the invention
It is an object of the invention to provide one kind by containing manganese compound for the first auxiliary agent, other cobalts, zirconium, copper, zinc, ruthenium, lanthanum,
One or both of compound of cerium, praseodymium, neodymium, samarium, gadolinium, holmium, ytterbium etc. is above to live for the second auxiliary agent, cocoanut active charcoal or apricot shell
Property one or both of charcoal be carrier composition, for methanol vapor-phase carbonylation methyl acetate iridium based catalyst and its
In methanol through the application in the methyl acetate reaction processed of Fixed Bed Gas Phase carbonylation, primary product is methyl acetate.
The technical scheme is that：
It is a kind of to be used for the catalyst of methanol through vapor phase carbonylation methyl acetate and preparation method thereof, it is characterised in that this is urged
Agent is made of major catalyst, the first auxiliary agent and the second auxiliary agent and four part of carrier.Major catalyst active component is the change of iridium
Close object, the first auxiliary agent for one or both of compound of manganese more than, the second auxiliary agent is, zirconium, copper, zinc, ruthenium, lanthanum, cerium, praseodymium,
One kind in the compound of neodymium, samarium, gadolinium, holmium, ytterbium etc. is two or more, and carrier is cocoanut active charcoal, and the specific surface area of coconut husk charcoal is
500~1000m2/ g, average pore size are 1~200nm, and the specific surface area of apricot shell charcoal is 600~1200m2/ g, average pore size for 1~
200nm。
The major catalyst is the compound of iridium, such as oxide, hydroxide, chloride, chloro-iridic acid, preferably chlorination
Object and chloro-iridic acid, wherein the content of main active component iridium is the 0.1~5.0% of catalyst weight.
First auxiliary agent is more than one or both of compound of manganese, and content is the 0.1~30% of catalyst weight.
Second auxiliary agent is, two kinds of one kind in the compound of zirconium, copper, zinc, ruthenium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, holmium, ytterbium etc.
More than, content is the 0.1~30.0% of catalyst weight.
The activated carbon is cocoanut active charcoal charcoal or apricot shell activated carbon, wherein the specific surface area of coconut husk charcoal for 550~
900m2/ g, average pore size most preferably 5~100nm；The specific surface area of apricot shell charcoal is 650~1000m2/ g, average pore size most preferably 5
~100nm.
Catalyst of the methanol through vapor phase carbonylation methyl acetate, by IrCl3Or H2IrCl6And first, second auxiliary agent oxygen
Compound or chloride are impregnated in the one or two kinds of solvents for being dissolved in hydrochloric water, ethyl alcohol or acetone on activated carbon, leaching
2~4h of stain, 60~80 DEG C of water bath method solvents, 100~120 DEG C of drying 8h in baking oven, lower 250~400 DEG C of roastings of nitrogen protection
4h。
The reactants such as CO and the methanol that is pumped into are entered in the fixed bed reactors of the pellet type catalyst equipped with the present invention,
Methanol carbonylation is carried out, primary product is methyl acetate, there is micro or a small amount of acetic acid by-product generation.
The temperature of its carbonylation is at 180~280 DEG C, and 0.5~3.5MPa, liquid volume air speed is in 0.1~15h-1。
The preparation method of methyl acetate, co-catalyst reactant further include iodomethane, be methanol weight 5~
35.0%.
The main reactor material used is Hastelloy.
It can be also used for being converted into acetic acid as raw material using methanol/CO through the catalyst of methyl acetate processed is carbonylated for methanol
The reaction of methyl esters needs to add in a certain amount of H in reaction gas2, H2Volume ratio with CO is 0.01~2.
Beneficial effects of the present invention are：
Compared with prior art, heterogeneous catalyst of the invention is relatively easy in terms of product separation, simultaneous reactions liquid
In phase product, byproduct of reaction only has process water and a small amount of or micro acetic acid, and water content is relatively low and also has a large amount of unreacted
Methanol and non-corrosive methyl acetate, therefore, the corrosivity of product is relatively low, and the material of the core of reaction unit only needs
Hastelloy has and invests low advantage.The conversion ratio of methanol and the higher and reaction pressure of methyl acetate selectivity are low simultaneously,
Device operating cost is low.
Specific embodiment
Following embodiments illustrate but are not limited only to present invention content to be protected.
Embodiment 1
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gLaCl3、0.10gMnCl3Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 2
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gCeCl3、0.10gMnCl3Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 3
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gCo2O3、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 4
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gZrCl4、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 5
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gCuCl2、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 6
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gZnCl2、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 7
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gSmCl3、0.10gZnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 8
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gNdCl3、0.10gRuCl3Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 9
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gRuCl3、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 10
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gLiCl、0.10g MnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 11
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gPrCl3、0.10g MnCl2
It is dissolved in above-mentioned 15mL hydrochloric acid solutions, then impregnates 10.0g coconut husk charcoals.80 DEG C of water-baths evaporation solvents, 120 DEG C of oven for drying 8h,
300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported iridium based catalyst.
Embodiment 12
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gPmCl3、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 13
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gGdCl3、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 14
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gHoCl3、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 15
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gYbCl3、0.10gMnCl2Upper
It states and is dissolved in 15mL hydrochloric acid solutions, then impregnate 10.0g coconut husk charcoals.Solvents are evaporated in 80 DEG C of water-baths, 120 DEG C of oven for drying 8h, and 300
DEG C nitrogen protective roast 4h, obtains activated carbon supported iridium based catalyst.
Embodiment 15
It measures the dense HCl of 5mL and adds in 10mL deionized waters, weigh 0.24g IrCl3、0.10gZnCl2、0.10gLiCl、
0.10gMnCl2It is dissolved in above-mentioned 15mL hydrochloric acid solutions, then impregnates 10.0g coconut husk charcoals.80 DEG C of water-baths evaporation solvents, 120 DEG C
Oven for drying 8h, 300 DEG C of nitrogen protective roast 4h obtain activated carbon supported iridium based catalyst.
Application case is application of the catalyst prepared in methyl acetate reaction is prepared using methanol, CO as raw material
The activation of catalyst：In catalyst before use, CO/H in the reactor2=4, GHSV=7500h-1It is middle to carry out original position
Reduction activation, condition are：Normal pressure, 5 DEG C/min is from room temperature to 230 DEG C, when holding 1 is small, the iridium base catalysis after being activated
Agent.
Carbonylation condition is：235 DEG C, 2.5Mpa, CH3OH/CO/H2=4/4/1 (molar ratio), methanol LHSV=
10h-1.For reaction end gas after cold-trap cools down, gas-phase product carries out on-line analysis, and chromatographic apparatus is filled out for Agilent 7890B GC, PQ
Fill column, TCD detectors.Liquid product off-line analysis, FFAP capillary chromatographic columns, fid detector.Internal standard method is analyzed, isobutanol
For internal standard compound.
The iridium based catalyst being prepared using embodiment 1-15 prepares methyl acetate according to aforesaid operations, and methanol turns
Rate and the selectivity of methyl acetate such as table 1.
Table 1：The conversion ratio of methanol and the selectivity of methyl acetate
| Embodiment | Methanol conversion (%) | Methyl acetate selectivity * (%) |
| 1 | 65 | 92 |
| 2 | 55 | 97 |
| 3 | 58 | 95 |
| 4 | 62 | 94 |
| 5 | 55 | 96 |
| 6 | 53 | 97 |
| 7 | 54 | 96 |
| 8 | 62 | 93 |
| 9 | 59 | 94 |
| 10 | 55 | 92 |
| 11 | 45 | 98 |
| 12 | 45 | 92 |
| 13 | 60 | 93 |
| 14 | 62 | 95 |
| 15 | 59 | 92 |
* in terms of the methanol of conversion, other products are mainly acetic acid.
Claims (10)
1. a kind of activated carbon supported iridium based catalyst, it is characterised in that：The catalyst includes major catalyst, the first auxiliary agent
It is formed with the second auxiliary agent and four part of carrier：
Major catalyst is the one or two or more kinds (preferably chloride, chloro-iridic acid) in iridic compound；
First auxiliary agent is one or two or more kinds (preferably manganese chloride, manganese nitrate, manganese sulfate, manganese acetate, the oxidation in manganese compound
More than one or both of manganese)；
Second auxiliary agent for cobalt, zirconium, copper, zinc, ruthenium, lithium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, holmium, ytterbium compound one or two with
On；
Carrier is coconut husk charcoal or one kind in apricot shell charcoal or two kinds；
Iridium accounts for 0.01~5.0wt% of catalyst gross mass, preferably 0.1~5.0wt% of accounting, and optimal accounting 0.5~
4.0wt%；First auxiliary agent be catalyst gross mass 0.1~30.0wt%, preferably 0.1~15wt% of accounting, optimal accounting 0.5
~5wt%；Second auxiliary agent be catalyst gross mass 0.1~30.0wt%, preferably 0.1~15wt% of accounting, optimal accounting 0.5
~5wt%.
2. iridium based catalyst according to claim 1, it is characterised in that：
The carrier is one or both of cocoanut active charcoal or apricot shell activated carbon, the specific surface area of coconut husk charcoal for 500~
1100m2/ g, the preferred specific surface area of coconut husk charcoal is 550~900m2/ g, the average pore size of coconut husk charcoal are 1~200nm, coconut husk charcoal
Preferred average pore size be 1~100nm；The specific surface area of apricot shell charcoal is 600~1200m2/ g, the preferred specific surface area of apricot shell charcoal
For 650~1000m2/ g, the average pore size of apricot shell charcoal is 1~200nm, and the preferred average pore size of apricot shell charcoal is 1~100nm.
3. a kind of preparation method of any iridium based catalysts of claim 1-2, it is characterised in that：
Under the action of an acid, by iridium presoma, the first auxiliary agent presoma, the second auxiliary agent presoma, in water, ethyl alcohol or acetone
It is dissolved in a kind of or two kinds of solvents, obtained solution is impregnated on carrier, impregnates 2~4h, then molten in 60~100 DEG C of water bath methods
Agent, 100~120 DEG C of drying in baking oven, 250~400 DEG C of 1~4h of roasting under the inert gas shieldings such as nitrogen or argon gas.
4. preparation method according to claim 3, it is characterised in that：
The acid is hydrochloric acid, nitric acid or sulfuric acid, and preferably molar concentration is concentrated hydrochloric acid, the dense nitre of 14.4mol/L of 12mol/L
Acid or 18mol/L the concentrated sulfuric acid in any one.
5. preparation method according to claim 3, it is characterised in that：
The presoma of the iridium is Ir2O3、IrO2、Ir(OH)3、Ir(OH)4、IrCl3、IrCl4、H2IrCl6、[Ir(CO)2I2]-、
[Ir(CO)2I2]-In one or two or more kinds, (preferably IrCl3And H2IrCl6)；
The first auxiliary agent presoma is one or two or more kinds (preferably MnO, MnO in manganese compound2、Mn3O4、MnCl2、
C4H6MnO4、MnSO4；
The second auxiliary agent presoma is Co2O3, Co (NO3)2、ZrCl4、ZrOCl2、Zr(NO3)4、CuO、Cu(NO3)2、
CuCl2、ZnO、ZnSO4、ZnCl2、RuCl3、LiCl、LiNO3、La2O3、LaCl3、CeO2、CeCl3、Pr6O11、Nd2O3、Sm2O3、
Gd2O3、Ho2O3、Yb2O3In one or two or more kinds (preferably ZrCl4、ZnCl2、RuCl3、LaCl3、CeCl3、LiCl)。
6. a kind of any iridium based catalysts of claim 1-2 methanol vapor-phase carbonylation prepare acetic acid, methyl acetate or
Application in its mixture, wherein methyl acetate are required principal product.
7. according to the application described in claim 6, it is characterised in that：
Catalyst needs to be roasted in the inert atmospheres such as nitrogen or argon gas before use, and calcination temperature is 250~400 DEG C,
Roasting time is 1~4h；Catalyst is activated before use, and activation temperature is 200~280 DEG C in synthesis gas, when
Between for 1~3h, synthesis gas is CO and H2Molar ratio is 1~5, preferably 3~4.
8. application according to claim 6, it is characterised in that：
Reaction temperature is 180~280 DEG C, 0.5~6.5MPa of reaction pressure；Reaction liquid volume space velocity is 0.1~15h-1, CO and
The molar ratio of methanol is 0.25~2, H2Volume ratio with CO is 0.01~2.
9. application according to claim 6, it is characterised in that：
Needed in reactor add in co-catalyst iodomethane, addition be methanol 5~50.0wt%, preferably 5~25%.
10. application according to claim 6, it is characterised in that：
The main reactor material used is Hastelloy.
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| CN201611003623.XA CN108067226A (en) | 2016-11-15 | 2016-11-15 | A kind of activated carbon supported iridium based catalyst and its preparation and application |
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| CN111195516A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse rhodium-based catalyst, preparation method thereof and application of atomic-level monodisperse rhodium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN111195532A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst, preparation method thereof and application of atomic-level monodisperse iridium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN111195530A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst and preparation method and application thereof |
| CN114096347A (en) * | 2019-05-28 | 2022-02-25 | 埃讷肯公司 | Gas phase methanol carbonylation catalyst |
| CN114100609A (en) * | 2021-12-14 | 2022-03-01 | 中国天辰工程有限公司 | Catalyst for preparing large cyclic olefin through dehydrogenation reaction, and preparation method and application thereof |
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| CN111195516A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse rhodium-based catalyst, preparation method thereof and application of atomic-level monodisperse rhodium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN111195532A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst, preparation method thereof and application of atomic-level monodisperse iridium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
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| CN111195516B (en) * | 2018-11-20 | 2021-04-23 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse rhodium-based catalyst, preparation method thereof and application of atomic-level monodisperse rhodium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN111195530B (en) * | 2018-11-20 | 2021-04-23 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst and preparation method and application thereof |
| CN111195532B (en) * | 2018-11-20 | 2021-05-25 | 中国科学院大连化学物理研究所 | Atomic-level monodisperse iridium-based catalyst, preparation method thereof and application of atomic-level monodisperse iridium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation |
| CN114096347A (en) * | 2019-05-28 | 2022-02-25 | 埃讷肯公司 | Gas phase methanol carbonylation catalyst |
| CN114100609A (en) * | 2021-12-14 | 2022-03-01 | 中国天辰工程有限公司 | Catalyst for preparing large cyclic olefin through dehydrogenation reaction, and preparation method and application thereof |
| CN114100609B (en) * | 2021-12-14 | 2024-09-13 | 中国天辰工程有限公司 | Catalyst for preparing macrocyclic olefin by dehydrogenation reaction and preparation method and application thereof |
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