CN108067222A - The iridium based catalyst of the sulphur promotion of absorbent charcoal carrier load and its preparation and application - Google Patents
The iridium based catalyst of the sulphur promotion of absorbent charcoal carrier load and its preparation and application Download PDFInfo
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- CN108067222A CN108067222A CN201611003633.3A CN201611003633A CN108067222A CN 108067222 A CN108067222 A CN 108067222A CN 201611003633 A CN201611003633 A CN 201611003633A CN 108067222 A CN108067222 A CN 108067222A
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- 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
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- 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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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
Abstract
A kind of iridium based catalyst promoted for methanol through the sulphur of hererogeneous carbonylation methyl acetate and acetic acid and preparation method thereof.It is made of main active component, sulphur auxiliary agent and carrier three parts, main active component is Ir and metal oxide, and content is the 0.01~5.0% and 0.1~30% of catalyst weight；Sulfur-bearing auxiliary agent content is the 0.1~30% of catalyst weight.Carrier is coconut husk charcoal, and the specific surface area of coconut husk charcoal is 500~1100m2/ g, average pore size are 1~200nm.One kind is provided by the present invention main active component and sulfur-bearing presoma are supported on carrier by infusion process, form the Ir base catalyst that sulphur promotes.In fixed bed reactors, under certain temperature and pressure and this catalyst and iodomethane effect, CH3OH/CO can high activity, be converted into methyl acetate and acetic acid with high selectivity.
Description
Technical field
The invention belongs to heterogeneous catalysis carbonylation technology fields, and in particular to the iridium base that a kind of activated carbon supported sulphur promotes is urged
Agent and preparation method thereof and and its in methanol through the application in hererogeneous carbonylation methyl acetate and acetic acidreaction.
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 carbon distribution inactivation is serious, and
Space-time yield is relatively 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.Second stage：Monsanto companies develop
The higher rhodium of activity and selectivity-iodide (RhI3) catalyst system and catalyzing.The temperature and pressure of reaction is also than relatively low (175 DEG C of left sides
The right side, 3.0MPa), for selection rate of the acetic acid on the basis of methanol more than 99%, the selection rate on the basis of CO has also reached 90%
More than.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 methanol carbonyl
Base method produces acetic acid.The technique substantially increases the stability of catalyst, reacts and is carried out under conditions of water content is relatively low, and
Reduce the generation of liquid by-product, improve the conversion ratio of CO.
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 of CO.
The shortcomings of inherently there are active components to be easy to run off but due to homogeneous catalyst, and separation is difficult, therefore some are studied
Sight has then been invested support type heterogeneous catalysis system by person.Heterogeneous catalysis system can reach catalyst and the product side of separation
Just, the features such as catalyst concn is from solubility limit can improve production capacity etc. by increasing catalyst concn.Support type is non-
Homogeneous catalysis system can be roughly divided into the bodies such as polymer support, absorbent charcoal carrier, inorganic oxide carrier according to carrier difference
System, but load type catalyst system there is activity is lower than homogeneous catalysis system, the easy removing of active ingredient, to carrier media compared with
The problems such as high.And the highly selective methyl acetate processed of methanol hererogeneous carbonylation directly skips acetic acid synthetic route, avoids use
A small amount of acetic acid is further converted to ester by reaction-distillation technique, saves mass production cost by expensive zirconium material.
Activated carbon supported iridium system is applied to carbonylation, there are problems that two.First, although the system is being carbonylated
The TOF of acetyl group can reach 1000h in reaction-1, but its TOF is compared to similar hydroformylation reaction TOF (5000-
10000h-1) also differ greatly, therefore need to be improved and studied in terms of catalyst activity, it is desirable to further improve
With the activity for improving catalyst.Just in general, the activity for improving catalyst can be by adding some metals or nonmetallic helping
The methods of agent or change acid treatment mode, is improved.And sulfonated is a current research hotspot, sulfonic acid can conduct
A kind of auxiliary agent improves the reactivity of some reactions, therefore can be considered and improve carbonylation by adding in sulfuric acid or organic sulfonic acid
React TOF.
The content of the invention
It is an object of the invention to provide a kind of iridium based catalyst of activated carbon supported sulphur promotion and its in methanol through carbonyl
Application in base methyl acetate and acetic acidreaction largely improves catalyst activity, reduces byproduct methane selection
Property.
The technical scheme is that：
Iridium based catalyst promoted for methanol through the sulphur of methyl acetate and acetic acid processed is carbonylated and preparation method thereof, mainly
It is that the catalyst is made of main active component, sulphur auxiliary agent and carrier three parts, main active component is Ir and metal oxide, and sulphur helps
Agent presoma is common sulfur-bearing inorganic acid and organic acid；Carrier is coconut husk charcoal, and specific surface area is 500~1100m2/ g is put down
Equal aperture is 1~200nm；
Wherein main active component Ir contents are the 0.1~5.0% of catalyst weight；Wherein metal oxide is La2O3、
Mo3O4、Fe2O3、Co3O4、NiO、CeO2、RuO2, content is the 0.1~30.0% of catalyst weight.
The wherein sulfuric acid of 1~18mol/L of acid, the benzene sulfonic acid of 0.1~5mol/L, the thioacetic acid of 1~12mol/L, 1~
The benzenethiol of 5mol/L, content are the 0.1~30.0% of catalyst weight.According to claim 1, a kind of methanol described in 7
The iridium based catalyst that sulphur through methyl acetate and acetic acid processed is carbonylated promotes, it is characterised in that in the inorganic acid or organic acid of sulfur-bearing
Under the conditions of existing, Ir metals and metal oxide precursor are dissolved in water or ethyl alcohol, obtained solution co-impregnation is in work
Property charcoal on, 60~80 DEG C of water bath method solvents, 100~120 DEG C of drying 5~15h, N in baking oven2Lower 200~800 DEG C of roastings of protection
2~6h.
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.
The temperature of carbonylation is at 180~280 DEG C, and 0.5~3.5MPa, liquid volume air speed is in 0.1~15h-1。
Co-catalyst reactant further includes iodomethane, is the 1~35.0% of methanol weight.
The volume ratio of hydrogen and CO are 0.1~2 in reaction gas.
The main reactor material used is Hastelloy.
The iridium based catalyst promoted for sulphur of the methanol through carbonylation is used to be converted into methyl acetate as raw material using methanol/CO
And in acetic acidreaction.
Beneficial effects of the present invention are：
Compared with existing activated carbon supported iridium catalyst methanol carbonyl technology, activated carbon supported sulphur of the invention promotees
Into iridium based catalyst methanol hererogeneous carbonylation reaction in have higher activity.
Specific embodiment
Following embodiments illustrate but do not limit present invention content to be protected.
The mass fraction of dense HCl described in embodiment is 37.5%, and the mass fraction of the concentrated sulfuric acid is 98%, and dilute sulfuric acid is dense
It spends for 2mol/L, dilute benzene sulfonic acid concentration is 1mol/L, and thioacetic acid concentration is 2mol/L, and benzenethiol concentration is 3mol/L, and benzene is sub-
Sulfonic acid concentrations are 3mol/L, and benzene sulfenic acids concentration is 3mol/L.
Embodiment 1
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 3mL dense HCl and 0.0423gLa2O3It stirs
It mixes to dissolving, then impregnates 5g coconut husk charcoals.Solvent, 120 DEG C of oven for drying 10h, 280 DEG C of nitrogen protective roasts are evaporated in 65 DEG C of water-baths
4h, obtained activated carbon supported iridium based catalyst.
Embodiment 2
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 0.75ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 280
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 3
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 1.5ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 280
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 4
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 3.75ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 280
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 5
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 7.5ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 280
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 6
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 280
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 7
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 30ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 170 DEG C of oven for drying 10h, and 280
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 8
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 7.8ml 1mol/L benzene sulfonic acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 170 DEG C of oven for drying 10h, and 280
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 9
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 350
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 10
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 450
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 11
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 650
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 12
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 800
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 13
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L dilute sulfuric acids and
0.0256gRuO2Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 800
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 14
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L dilute sulfuric acids and
0.0288gCeO2Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 500
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 15
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L thioacetic acids and
0.0321gMo3O4Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 800
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 16
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 3mol/L benzenethiols and
0.0312gCo3O4Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 350
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 17
Weigh 0.0863gH2IrCl6It is dissolved at 65 DEG C in 17.17g water.Add 15ml 3mol/L benzenesulfinic acids and
0.0208gFe2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 350
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 18
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L benzene sulfenic acids and
0.0138gNiO is stirred to dissolving, then impregnates 5g coconut husk charcoals.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, 450 DEG C
Nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 19
Weigh 0.4001gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 15ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 800
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 20
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 60ml 2mol/L dilute sulfuric acids and
0.0423gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 800
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Embodiment 21
Weigh 0.0863gIrCl3It is dissolved at 65 DEG C in 17.17g water.Add 60ml 2mol/L dilute sulfuric acids and
0.4230gLa2O3Then stirring impregnates 5g coconut husk charcoals to dissolving.Solvents are evaporated in 65 DEG C of water-baths, 120 DEG C of oven for drying 10h, and 800
DEG C nitrogen protective roast 4h, the iridium based catalyst that obtained activated carbon supported sulphur promotes.
Application examples：Application of the catalyst of preparation 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=10 (GHSV=3840h-1) carry out in stream
In-situ reducing activates, and condition is：2.5MPa, 4 DEG C/min are from room temperature to 235 DEG C, when holding 1 is small, the sulphur after being activated
The iridium based catalyst of promotion.Reaction condition is：235 DEG C, 2.5MPa, CH3OH/CO/H2=20/30/3 (molar ratio), CH3OH/
CH3I (mass ratio)=8:1, methanol LHSV=4.8h-1, catalyst volume 0.5mL.Reaction end gas is after cold-trap cools down, gas phase
Product carry out on-line analysis, chromatographic apparatus be Agilent 7890A GC, PQ packed columns, TCD detectors.Liquid product divides offline
Analysis, FFAP capillary chromatographic columns, fid detector.Internal standard method is analyzed, and isobutanol is internal standard compound.
The iridium based catalyst that the sulphur being prepared using embodiment 1-18 is promoted, according to aforesaid operations prepare methyl acetate and
Acetic acid, conversion ratio, methane selectively, the selectivity of methyl acetate and the acetic acid selectivity such as table 1 of methanol.
1 embodiment methanol carbonylation result of table summarizes
The result shows that:Learn that its activity will be far better than saliferous containing sulfur catalyst by 1,6,7,18,19,20,21 comparison
Acid catalyst, and 0.5~2.0wt% of Ir mass fractions most preferably catalyst gross mass；Metal oxide mass fraction is optimal
For 0.2~8.0wt% of catalyst gross mass；Sulfur-containing compound mass fraction most preferably accounts for the 1- of catalyst gross mass
30.0wt%.
Claims (10)
1. a kind of iridium based catalyst that activated carbon supported sulphur promotes, it is characterised in that：The iridium based catalyst includes main work
Property component Ir, sulphur auxiliary agent and carrier, main active component is iridium and transition metal oxide, and carrier is activated carbon, and the sulphur helps
Agent is sulfur-containing compound；
Ir accounts for 0.01~5.0wt% of catalyst gross mass, preferably accounts for 0.1~4.0wt% of catalyst gross mass, most preferably accounts for and urge
0.5~2.0wt% of agent gross mass；Metal oxide is 0.1~30.0wt% of catalyst gross mass, is preferably catalyst
0.2~8.0wt% of the 0.1~10wt% of scope, most preferably catalyst gross mass of gross mass；It is total that sulfur-containing compound accounts for catalyst
0.01~60.0wt% of quality preferably accounts for 0.1~40.0wt% of catalyst gross mass, most preferably accounts for the 1- of catalyst gross mass
30.0wt%.
2. the iridium based catalyst that sulphur according to claim 1 promotes, it is characterised in that：The carrier be coconut husk charcoal, coconut palm
The specific surface area of shell charcoal is 500~1100m2/ g, the preferred specific surface area of coconut husk charcoal is 550~900m2/ g, coconut husk charcoal are averaged
Aperture is 1~200nm, and the preferred average pore size of coconut husk charcoal is 5~100nm.
3. the iridium based catalyst that sulphur according to claim 1 promotes, it is characterised in that：The sulfur-containing compound is sulfur acid
In 200~800 DEG C of product of roasting；The sulfur acid is benzene sulfonic acid, benzenesulfinic acid, benzene sulfenic acids, sulfuric acid, thioacetic acid, benzene
One or two or more kinds in thiophenol are preferably the one or two or more kinds in sulfuric acid, benzene sulfonic acid, thioacetic acid, benzenethiol.
4. the iridium based catalyst that sulphur according to claim 1 promotes, it is characterised in that：The transition metal oxide is
La2O3、Mo3O4、Fe2O3、Co3O4、NiO、CeO2、RuO2In one or two or more kinds.
5. the preparation method for the iridium based catalyst that a kind of any sulphur of claim 1-4 promotes, it is characterised in that：In sulfur-bearing
Under the conditions of existing for sour, Ir metal precursors and metal oxide are dissolved in water and/or ethyl alcohol, obtained solution is impregnated in
On activated carbon, 60~80 DEG C of water bath method solvents, 100~120 DEG C of drying 5~15h, N in baking oven2Lower 200~800 DEG C of roastings of protection
Burn 2~6h.
6. preparation method according to claim 5, it is characterised in that：The sulfur acid for 0.1~5mol/L benzene sulfonic acids,
1~5mol/L benzenesulfinic acids, 1~5mol/L benzene sulfenic acids, 1~18mol/L sulfuric acid, 1~12mol/L thioacetic acids, 1~
One or two or more kinds in 5mol/L benzenethiols；
The preferably sulfuric acid of 1~18mol/L of concentration, the benzene sulfonic acid of 0.1~5mol/L, the thioacetic acid of 1~12mol/L, 1~
The benzenethiol of 5mol/L；The Ir metal precursors are IrCl3·3H2O and/or H2IrCl6·6H2O；Metal oxide is
La2O3、Mo3O4、Fe2O3、Co3O4、NiO、CeO2、RuO2In one or two or more kinds.
7. the iridium based catalyst that a kind of any sulphur of claim 1-4 promotes prepares methyl acetate in multiphase methanol carbonyl
Application in reaction.
8. according to the application described in claim 7, it is characterised in that：The main reactor material used is Hastelloy；Reaction temperature
It spends for 180~280 DEG C, 0.5~3.5MPa of reaction pressure；Ir bases catalyst before use, is activated or without activating,
The condition of activation is：GHSV=4000h-1(CO/H2=10), 0.5~3.5MPa of pressure, 1~10 DEG C/min of heating rate are from room
Temperature is warming up to 170~290 DEG C, keeps 1~3h, the iridium based catalyst that the sulphur after being activated promotes.
9. application according to claim 8, it is characterised in that：Reaction liquid volume space velocity is 0.1~15h-1, CO and methanol
Molar ratio be 1~2, H2Volume ratio with CO is 0.1~2.
10. the application according to claim 7 or 8, it is characterised in that：Cocatalyst iodomethane in reaction raw materials, helps and urges
The addition of agent is 1~35.0wt% of methanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110013866A (en) * | 2019-04-19 | 2019-07-16 | 山东玉皇化工有限公司 | A kind of iridium based catalyst of high activity and high stability and its preparation method and application |
| CN114539056A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院大连化学物理研究所 | Method for preparing methyl acetate by methanol carbonylation |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101403A (en) * | 1984-02-16 | 1987-01-17 | Bp化学有限公司 | The carbonylation method improvement |
| CN1371349A (en) * | 1999-08-25 | 2002-09-25 | 伊斯曼化学公司 | Vapor phase carbonylation process using promoted iridium catalyst |
| CN1425499A (en) * | 2001-12-11 | 2003-06-25 | 中国科学院大连化学物理研究所 | Solid supported noble metal catalyst and its preparing method |
| DE60008118T2 (en) * | 1999-08-25 | 2004-07-08 | Eastman Chemical Co., Kingsport | STEAM PHASE CARBONYLATION METHOD USING ACTIVATED IRIDIUM CATALYSTS |
| CN1778469A (en) * | 2004-11-22 | 2006-05-31 | 中国科学院化学研究所 | Catalyst system for synthetizing acetic acid from methanol or synthetizing ethylanhydride from methyl acetate and use thereof |
| CN1823031A (en) * | 2003-07-17 | 2006-08-23 | 英国石油化学品有限公司 | Catalyst and process for the production of acetic acid |
| CN1978055A (en) * | 2005-12-08 | 2007-06-13 | 中国科学院化学研究所 | Hydroformylation catalytic system and use |
| CN103998125A (en) * | 2011-12-28 | 2014-08-20 | 伊士曼化工公司 | Iridium catalysts for carbonylation |
| CN104511275A (en) * | 2013-09-26 | 2015-04-15 | 中国科学院上海高等研究院 | Oxide catalyst for preparing methyl formate through oxidizing methanol, preparation method and applications thereof |
-
2016
- 2016-11-15 CN CN201611003633.3A patent/CN108067222B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101403A (en) * | 1984-02-16 | 1987-01-17 | Bp化学有限公司 | The carbonylation method improvement |
| CN1371349A (en) * | 1999-08-25 | 2002-09-25 | 伊斯曼化学公司 | Vapor phase carbonylation process using promoted iridium catalyst |
| DE60008118T2 (en) * | 1999-08-25 | 2004-07-08 | Eastman Chemical Co., Kingsport | STEAM PHASE CARBONYLATION METHOD USING ACTIVATED IRIDIUM CATALYSTS |
| CN1425499A (en) * | 2001-12-11 | 2003-06-25 | 中国科学院大连化学物理研究所 | Solid supported noble metal catalyst and its preparing method |
| CN1823031A (en) * | 2003-07-17 | 2006-08-23 | 英国石油化学品有限公司 | Catalyst and process for the production of acetic acid |
| CN1778469A (en) * | 2004-11-22 | 2006-05-31 | 中国科学院化学研究所 | Catalyst system for synthetizing acetic acid from methanol or synthetizing ethylanhydride from methyl acetate and use thereof |
| CN1978055A (en) * | 2005-12-08 | 2007-06-13 | 中国科学院化学研究所 | Hydroformylation catalytic system and use |
| CN103998125A (en) * | 2011-12-28 | 2014-08-20 | 伊士曼化工公司 | Iridium catalysts for carbonylation |
| CN104511275A (en) * | 2013-09-26 | 2015-04-15 | 中国科学院上海高等研究院 | Oxide catalyst for preparing methyl formate through oxidizing methanol, preparation method and applications thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110013866A (en) * | 2019-04-19 | 2019-07-16 | 山东玉皇化工有限公司 | A kind of iridium based catalyst of high activity and high stability and its preparation method and application |
| CN114539056A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院大连化学物理研究所 | Method for preparing methyl acetate by methanol carbonylation |
| CN114539056B (en) * | 2020-11-24 | 2023-03-14 | 中国科学院大连化学物理研究所 | Method for preparing methyl acetate by methanol carbonylation |
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