CN106140156A - A kind of activated carbon supported rhodium base catalyst and its preparation method and application - Google Patents
A kind of activated carbon supported rhodium base catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to technical field of chemical engineering catalysts, it is specifically related to a kind of activated carbon supported rhodium base catalyst and preparation method thereof and in methanol application in carbonylation methyl acetate reacts, described rhodium base catalyst is made up of main active component and carrier two parts, main active component is Rh and transition metal promoter, and described transition metal is one or more in Ir, La, Pt, Pd, Ce, Ru, Fe, Co, Ni, Mn, Zr.Carrier is coconut husk charcoal or Fructus Pruni shell charcoal, the activated carbon supported Rh base catalyst provided by the present invention, in fixed bed reactors, under certain temperature and pressure and this catalyst action, and CH3OH/CO high activity, highly selective can be converted into methyl acetate, compared with prior art, the heterogeneous catalyst of the present invention is relatively easy in terms of product separation, simultaneously, byproduct of reaction only has fresh water (FW), the corrosivity of product is relatively low, simultaneously methanol conversion ratio and methyl acetate selectivity is the highest and reaction pressure is low, plant running low cost.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts, be specifically related to a kind of activated carbon supported rhodium base catalyst
And preparation method thereof and methanol through carbonylation methyl acetate react in application.
Background technology
Methyl acetate the most gradually replaces acetone, butanone, ethyl acetate, Pentamethylene. etc., because it is not
Belong to and limit the organic pollution discharge 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 methanol directly to carry out esterification generation crude methyl acetate with sulphuric acid for catalyst
Goods, then be dehydrated with calcium chloride, sodium carbonate neutralizes, and fractional distillation obtains methyl acetate finished product.(2) dimethyl ether exists
Synthesize through carbonylation on H-MOR molecular sieve catalyst, but molecular sieve carbon distribution inactivation is serious, and space-time yield is the lowest.
(3) when methanol carbonyl prepares acetic acid, methyl acetate exists as by-product, but selectivity is relatively low, separates
Cost is high.So the methyl acetate synthetic route overwhelming majority that at present industry is feasible will be through peracetic acid in the middle of this
Step.
At present, in the industrialized production of acetic acid, methanol carbonylation process is occupied an leading position, and uses this technique at present
The production capacity of acetic acid production device accounted for the 94% of acetic acid total productive capacity.In past 50 years, methanol
Carbonylation produces the course of industrialization of acetic acid and substantially experienced by three developmental stage:
First stage: BASF AG utilizes Co catalysts nineteen sixty under higher reaction temperature and pressure
(250 DEG C, 60MPa) first achieve the industrialized production producing acetic acid by methanol carbonylation.The method is raw
The acetic acid purity produced is the highest, and Main By product is higher alcohol, senior aldehyde and high carboxylic acid, product separation costs
Higher.Second stage: Monsanto company develops the higher rhodium of activity and selectivity-iodide (RhI3) urge
Change system.The temperature and pressure also ratio relatively low (about 175 DEG C, 3.0MPa) of reaction, acetic acid is on the basis of methanol
Selection rate more than 99%, the selection rate on the basis of CO has also reached more than 90%.Device is corrosion-resistant to be wanted
Ask the highest, need full zircaloy reactor.Phase III: methanol carbonylation produces the Ir catalyst of acetic acid
Industrialization.This technique substantially increases the stability of catalyst, and reaction is entered under conditions of water content is relatively low
OK, and decrease the generation of liquid by-product, improve the conversion ratio of CO.Celanese chemical company passes through
Add the inorganic iodide (mainly lithium iodide) of high concentration, improve the stability of Rh catalyst, add iodine
After changing lithium and iodomethane auxiliary agent, water content in reactor can be made to significantly reduce (about 4%～5%), can tie up again simultaneously
Hold higher carbonylation rate, make the separation costs of new technology significantly reduce.
Generation field (Chiyoda) company of Japan thousand and Uop Inc. have developed jointly Acetica technique, this technique base
In a kind of heterogeneous Rh catalyst, wherein activity Rh complex is chemically fixed on polyvinylpyridine tree
On fat.The sequestering macromolecule of strong and weak coordinate bond of Yuan Guo minister in ancient times seminar of Institute of Chemistry, Academia Sinica synthesis is urged
Agent also form independent intellectual property right system, and this catalyst system has the feature such as high stability, high activity,
The selectivity of CO can be improved.
Although homogeneous Rh base and Ir base catalyst system and catalyzing achieve good commercial Application, achieve at a relatively high
Catalysis activity and selectivity, the selectivity of acetic acid is more than 99%.But homogeneous catalyst system is from it is born,
Take on certain shortcoming, such as, noble metal catalyst is easy to run off, product separates difficulty with catalyst,
Catalyst circulation and recovery complexity etc..
Not enough for above-mentioned homogeneous reaction catalyst system and catalyzing, it is non-that a part of researcher has then invested support type sight
Homogeneous catalysis system.Compared with homogeneous catalysis system, heterogeneous catalysis system has a natural advantage, such as,
Catalyst and convenient product separation, catalyst concn is not limited by dissolubility, can be dense by increasing catalyst
Degree improves 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 also exists specific activity
Low, the active component of homogeneous catalysis system easily remove, to problems such as carrier media are higher.
Therefore, to be combined to exploiting potentialities of acetic acid limited for current methanol carbonyl.Methanol selects through carbonylation height
Property methyl acetate processed directly skip acetic acid synthetic route, i.e. avoid and use expensive zirconium material, reduce again
Esterification technique, saves a large amount of production cost.
Summary of the invention
It is an object of the invention to provide a kind of activated carbon supported Rh base catalyst and at methanol through carbonylation
Application in methyl acetate processed reaction, the primary product obtained is methyl acetate.
The technical scheme is that
Disclose a kind of for methanol through the catalyst of carbonylation methyl acetate, this catalyst is by main active component
Forming with carrier two parts, main active component is Rh and transition metal or its oxides additive；Carrier coconut husk charcoal
Or Fructus Pruni shell charcoal, the specific surface area of coconut husk charcoal is 500～1000m2/ g, average pore size is 1～200nm, Fructus Pruni shell charcoal
Specific surface area is 600～1200m2/ g, average pore size is 1～200nm.
The most main active component Rh content is the 0.1～5.0% of catalyst weight.
During wherein transition metal promoter is Ir, La, Pt, Pd, Ce, Ru, Fe, Co, Ni, Mn, Zr
One or both, content is the 0.1～30.0% of catalyst weight.
Wherein the specific surface area of coconut husk charcoal is 550～900m2/ g, average pore size most preferably 5～100nm；Fructus Pruni shell charcoal
Specific surface area be 650～1000m2/ g, average pore size most preferably 5～100nm.
Under conditions of mineral acid exists, by Rh metal precursor and promoter metal presoma or metal-oxide
Presoma dissolves in water or ethanol, the solution impregnation obtained on activated carbon, 60～80 DEG C of water bath method solvents,
Baking oven is dried 6-10 hour for 100～120 DEG C, N2Protect lower 250～400 DEG C of roastings 3-6 hour.
CO and the methanol and the iodomethane mixed liquor reactant that pump into enter into the pellet type catalyst equipped with the present invention
Fixed bed reactors in, carry out methanol carbonylation, primary product is methyl acetate.
The temperature of carbonylation at 180～280 DEG C, 0.5～3.5MPa, liquid volume air speed is 0.1～15h-1。
Reactant also includes iodomethane, and it is the 5～35.0% of methanol weight.
In reaction gas, the volume ratio of hydrogen and CO is 0.1～2.
The response system ground material used is Hastelloy.
The volume ratio of the catalyst being seated in fixed bed and activated carbon or quartz sand is 0.5～5.
Described a kind of for methanol through carbonylation methyl acetate catalyst for methanol/CO as raw material
It is converted in methyl acetate reaction.
The invention have the benefit that
Compared with prior art, the heterogeneous catalyst of the present invention is relatively easy in terms of product separation, meanwhile,
Byproduct of reaction only has fresh water (FW), and water content is relatively low and the most a large amount of unreacted methanol and non-corrosive second
Acid methyl ester, therefore, the corrosivity of product is relatively low, and the material of the core of reaction unit can use price
Cheap Hastelloy, has the advantage that investment is low.Conversion ratio and the methyl acetate selectivity of methanol are equal simultaneously
Higher and reaction pressure is low, plant running low cost.
Detailed description of the invention
Following embodiment illustrates but is not intended to present invention content to be protected.
The concentration of the dense HCl described in embodiment is 37%.
Embodiment 1
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.24 gram of LaCl3
Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.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 activated carbon supported rhodium base catalyst.
Embodiment 2
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.24 gram of LaCl3
With 0.26 gram of H2PtCl4Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 3
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.24 gram of LaCl3
With 0.17 gram of PdCl2Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 4
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.24 gram of LaCl3
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 5
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.24 gram of CeCl3
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 6
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.16 gram of FeCl3
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 7
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.24 gram of LaCl3
With 0.20 gram of RuCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 8
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.12 gram of MnCl2
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 9
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.13 gram of CoCl2
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 10
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.13 gram of NiCl2
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 11
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.17 gram of PdCl2
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 12
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.26 gram of PtCl2
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 13
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.20 gram of RuCl3
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 14
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.23 gram of ZrCl4
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of coconut husk charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 15
Weigh the dense HCl of 4mL and add 6mL deionized water, 0.25 gram of RhCl3·3H2O, 0.24 gram of LaCl3
With 0.29 gram of IrCl3Above-mentioned 10mL hydrochloric acid solution dissolves, then 10.0 grams of Fructus Pruni shell charcoals of dipping.80℃
Water-bath evaporation solvent, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h, obtain activated carbon supported
Rhodium base catalyst.
Embodiment 16
Weigh the dense HNO of 4mL65%3Add 6mL deionized water, 0.28 gram of Rh (NO3)3, 0.42 gram
La(NO3)3.6H2O and 0.22 gram of IrO2Above-mentioned 10mL salpeter solution dissolves, then impregnates 10.0
Gram coconut husk charcoal.80 DEG C of water-bath evaporation solvents, 120 DEG C of oven for drying 8h, 300 DEG C of nitrogen protective roast 4h,
To activated carbon supported rhodium base catalyst.
Application examples
Preparation catalyst with methanol/CO be raw material prepare methyl acetate reaction in application.
The activation of catalyst: before catalyst uses, CO/H in the reactor2=4 (GHSV=5000h-1) in stream
Carrying out in-situ reducing activation, condition is: normal pressure, and 5 DEG C/min, from room temperature to 240 DEG C, keeps 1 hour,
Rhodium base catalyst after being activated.Then pressure is risen to 2.4MPa, after pump pressure is more than 2.4MPa, will
Methanol and the reacted gas of iodomethane mixed reaction solution are brought into the fixed bed of the pellet type catalyst equipped with the present invention
In reactor.
Carbonylation condition is: 240 DEG C, 2.4MPa, CH3OH/CO/H2=4/4/1 (mol ratio),
CH3OH/CH3I=8 (mass ratio), methanol LHSV=10h-1.Reaction end gas is after cold-trap cools down, and gas-phase product enters
Row on-line analysis, chromatographic apparatus is Agilent 7890A GC, PQ packed column, TCD detector.Liquid product
Off-line analysis, FFAP capillary chromatographic column, fid detector.Internal standard method is analyzed, and isobutanol is internal standard substance.
The rhodium base catalyst using embodiment 1-16 to prepare, prepares methyl acetate, first according to aforesaid operations
The conversion ratio of alcohol and the selectivity of methyl acetate such as table 1.
Table 1
| Embodiment | Methanol conversion * (%) | Methyl acetate selectivity * * (%) |
| 1 | 35 | 96 |
| 2 | 45 | 97 |
| 3 | 40 | 97 |
| 4 | 85 | 99 |
| 5 | 40 | 96 |
| 6 | 35 | 97 |
| 7 | 50 | 95 |
| 8 | 50 | 95 |
| 9 | 70 | 96 |
| 10 | 60 | 97 |
| 11 | 55 | 96 |
| 12 | 45 | 96 |
| 13 | 50 | 96 |
| 14 | 60 | 96 |
| 15 | 85 | 98 |
| 16 | 90 | 96 |
* in terms of the methanol converted, including the methanol generated in methyl acetate.
* is in terms of 100%, and other product is mainly acetic acid.
Claims (10)
1. an activated carbon supported rhodium base catalyst, it is characterised in that: described rhodium base catalyst is by main work
Property component and carrier two parts composition, main active component is Rh and auxiliary agent, and carrier is activated carbon；Described helps
Agent is transition metal.
Rhodium base catalyst the most according to claim 1, it is characterised in that: described carrier is coconut husk charcoal
Or Fructus Pruni shell charcoal, the specific surface area of coconut husk charcoal is 500～1100m2/ g, the preferred specific surface area of coconut husk charcoal is
550～900m2/ g, the average pore size of coconut husk charcoal is 1～200nm, and the preferred average pore size of coconut husk charcoal is 5～100nm；
The specific surface area of Fructus Pruni shell charcoal is 600～1200m2/ g, the preferred specific surface area of Fructus Pruni shell charcoal is 650～1000m2/ g,
The average pore size of Fructus Pruni shell charcoal is 1～200nm, and the preferred average pore size of Fructus Pruni shell charcoal is 5～100nm.
Rhodium base catalyst the most according to claim 1, it is characterised in that: described transition metal be Ir,
One or more in La, Pt, Pd, Ce, Ru, Fe, Co, Ni, Mn, Zr.
Rhodium base catalyst the most according to claim 1, it is characterised in that: Rh accounts for catalyst gross mass
0.01～5.0wt%, Rh preferably comprise the 0.1～5.0wt% of catalyst gross mass, and Rh most preferably accounts for the total matter of catalyst
The 0.5～4.0wt% of amount；Auxiliary agent is the 0.1～30.0wt% of catalyst gross mass, and auxiliary agent is preferably catalyst
The scope 0.2～20.0wt% of gross mass, the scope 0.3～10.0wt% of auxiliary agent most preferably catalyst gross mass.
5. the preparation method of the arbitrary described Rh base catalyst of claim 1-4, it is characterised in that:
Under conditions of acid exists, Rh metal precursor and promoter metal presoma are dissolved in water or ethanol,
The solution impregnation obtained is on activated carbon, and 60～80 DEG C of water bath method solvents, in baking oven, 100～120 DEG C are dried 6-10
Hour, N2Protect lower 250～400 DEG C of roastings 3-6 hour.
Preparation method the most according to claim 5, it is characterised in that: described acid be concentration be the salt of 37%
Acid, 50% perchloric acid, the concentrated nitric acid of 65%；Described Rh metal precursor is RhCl3·3H2O、Rh(NO3)3、
Rh(CO)2C5H7O2。
7. to prepare methyl acetate at methanol carbonyl anti-for the arbitrary described rhodium base catalyst of claim 1-4
Application in Ying, it is characterised in that: enter after CO and the methanol pumped into and the mixing of iodomethane mixed liquor reactant
In the fixed bed reactors equipped with described graininess rhodium base catalyst, the type of feed of optimization is to use inertia
Material carries out catalyst dilution, carries out methanol carbonylation, and reaction temperature is 180～280 DEG C, reaction pressure
0.5～3.5MPa；
Rh base catalyst activates before use, and the condition of activation is: CO/H in reactor2=4
(GHSV=5000h-1), normal pressure, 5 DEG C/min, from room temperature to 240 DEG C, keeps 1 hour, after being activated
Rh base catalyst.
Application the most 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 methanol is 1～2, H2It is 0.1～2 with the volume ratio of CO.
Application the most according to claim 7, it is characterised in that: the methanol reactant pumped into helps and urges
Agent iodomethane, the addition of iodomethane is the 5～35.0wt% of methanol.
Application the most according to claim 7, it is characterised in that: the response system material of employing is Kazakhstan
Alloy；Described inert substance is activated carbon or quartz sand, the catalyst being seated in fixed bed and inert material
The volume ratio of matter is 0.5～5.
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