CN106111191A - A kind of carbon nanotube loaded rhodium catalytic system and application thereof - Google Patents
A kind of carbon nanotube loaded rhodium catalytic system and application thereof Download PDFInfo
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- CN106111191A CN106111191A CN201610491192.XA CN201610491192A CN106111191A CN 106111191 A CN106111191 A CN 106111191A CN 201610491192 A CN201610491192 A CN 201610491192A CN 106111191 A CN106111191 A CN 106111191A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
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Abstract
The invention discloses a kind of carbon nanotube loaded rhodium catalytic system and application thereof, it is characterised in that with carbon nanotube loaded rhodium compound as active specy, add halogen catalyst；Through carbon nanotube loaded rhodium metal catalyst in carbonylation, reaction system can have high concentration Noble Metal Rhodium catalyst, can reach slurry liquid phase reactor, improve oxo process speed and low noble metal loss.The catalyst using the present invention can promote carbongl group synthesis reaction speed, can promote industrialized unit production capacity.
Description
Technical field
The present invention relates to a kind of for carbonyl synthesis of acetic and the catalyst system and catalyzing of acetic anhydride and application, concrete is a kind of for first
Carbon nanotube loaded rhodium catalytic system and application thereof.
Technical background
Acetic acid is a kind of important Organic Chemicals, mainly for the production of VAM, acetic anhydride, terephthaldehyde
Acid, polyvinyl alcohol, acetates, cellulose acetate etc..Have been widely used at industry tools such as chemical industry, light textile, medicine, dyestuffs.
In recent years, due to PTA and the development of acetic acid downstream product, acetic acid has been promoted to become one of petroleum chemicals of increasing rapidly.Acetic anhydride
Have another name called acetic anhydride, be a kind of compound used in a large number as producing the raw material of cellulose acetate, but also be synthetic drug,
The important source material of the chemical products such as spice and dyestuff.
The carbonylic preparation method that the 40-50 age in 20th century grows up, be carbon monoxide under catalyst action, with methanol
The method of acetic acid is prepared in reaction.The beginning of the seventies, Monsanto Company opened up about oxo-synthesis homogeneous rhodium catalyst (US3769329)
New process route.Through updating and perfect, have become as acetic acid industry with the oxo process technology of rhodium catalyst
Important and that yield is maximum production process route.Its course of reaction is the effect that methanol passes through rhodium catalyst, anti-with carbon monoxide
Should prepare acetic acid, catalyst uses diiodo-dicarbonyl rhodium anionic small molecule partner.This kind of rhodium active specy is in the reaction
Unstable, it is easy in course of reaction, to be converted into many iodine rhodium and lose activity.The most in the industrial production, holding is typically used
The HI of carbon monoxide pressure of tension and addition excess is to protect the existence of rhodium complex, but so significantly increases the corrosion of equipment.
The acetic anhydride production technology of the 79's of 20th century novel metal catalysis has obtained in-depth study, and creates with synthesis
Gas is the production technology of raw material.BASF(US2729651, US2730546) methyl acetate carbonyl with Co, Ni or Fe as catalyst
On the basis of base, and the methanol carbonylization research of the rhodium catalyst of Meng Shan all getting up early, Halcom(BE819,455),
Eastman, Ajinamoto(Japan Kokai 50/30.820), Showa Denko(Japan Kokai 50/47.922),
BP (B.von Schlotheim, Chem.Industrie 1994,9/89,80) and Hoechst(DE 2450965) etc. right
The research work that the acetic anhydride of Group VIII metal catalytic produces achieves the progress of essence, and determines the weight that Rh is research
Point.
The researchers at initial stage think that methyl acetate carbonylation is a simple extension of methanol carbonyl.But, will
With the presence of water methanol carbohylation process for methyl acetate carbonylation time, immediately encountered a difficult problem.Methyl acetate carbonyl
The thermodynamic driving force changing reaction is far smaller than methanol carbonylation, and this shows that this reaction does not exists a poised state, and not
It is to react complete smoothly as methanol carbonylation.The existence of this chemical reaction equilibrium limits in carbonylation
The conversion ratio that methyl acetate is likely to be breached, the participation of back reaction simultaneously makes reaction formation efficiency reduce.
In commercially producing, the catalyst of acetic acid synthesis from methanol carbonylation and technique thereof are applied to methyl acetate carbonylation
Synthesis acetic anhydride, in addition it is also necessary to have two critical improvement.One is the introducing of hydrogen, in the less reaction system of water content,
The hydrogen produced by transformationreation is very limited amount of.Another is the interpolation of promoter, promotes the work in catalysis system
Property coordination compound stable and active.
During due to temperature more than 180 DEG C, rhodium complex begins to decompose inactivation, but high temperature beneficially reaction is carried out, and this makes
Selectivity and the activity that how must improve catalytic reaction become commercial production and face critically important problem.
For existing catalyst problem in course of reaction, people are exploring the catalyst that performance is more excellent always,
Wish to that there is higher catalyst activity and more preferable stability simultaneously.
Summary of the invention
It is an object of the invention to provide one and produce acetic acid and methyl acetate carbonylation production vinegar for methanol carbonyl metaplasia
The liquid phase reactor catalyst system of acid anhydride；Another purpose is that providing above-mentioned caltalyst to tie up to methanol carbonyl metaplasia produces acetic acid and vinegar
Acid methyl ester carbonylation produces the application in acetic anhydride reaction.
Concrete technical scheme is as follows:
A kind of rhodium catalytic system for carbonylation, it is characterised in that with carbon nanotube loaded rhodium compound as active specy,
Adding the catalyst system of halogen catalyst composition, in catalyst system, CNT is 0.5-10 times of rhodium compound, halogen
Element promoter is 1-150 times of rhodium compound.
It is added with accelerator Li+、K+、Na+、Rb+、LiI、KI、NaI、RbI、LiBr、KBr、NaBr、RbBr、LiCl、KCl、
One or more in NaCl and RbCl.
Described rhodium compound is Rh, RhI3, [Rh(CO)2I2], [Rh(CO)2Cl2], [Rh(CO)2Br2] and Rh(OAc)2
In one or more；Described halogen catalyst is HI, CH3I、HCl、CH3Cl, HBr and CH3One or more in Br.
Described CNT is the one in SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes or many
Kind, a length of 50-3000nm of CNT, bore is 0.1nm-30nm.
CNT used uses dressing agent to modify, dressing agent be dodecylbenzene sodium sulfonate, sodium lauryl sulphate, ten
Six alkyl trimethyl ammonium bromides, polyoxyethylene nonylphenol ether, vinyl acetate, polyvinyl alcohol one or more.
Rhodium catalytic system described in a kind of claim 1 or 2 is applied to methanol, methyl acetate and alcohol-ester mixture
Reactant is prepared in the carbonylation liquid phase reactor of acetic acid, acetic anhydride, acetas, and in described liquid phase reactor, rhodium catalyst concentration is
6000-30000ppm。
In liquid phase reactor, the concentration of halogen catalyst is 3% ~ 20%, and the concentration of accelerator is 0ppm ~ 5000ppm, reaction
Condition is: temperature is at 150 DEG C-220 DEG C, and pressure is at 3.0Mpa-6.0Mpa.
Described rhodium compound is Rh, RhI3, [Rh(CO)2I2], [Rh(CO)2Cl2], [Rh(CO)2Br2] and Rh(OAc)2
In one or more；Described halogen catalyst is HI, CH3I、HCl、CH3Cl, HBr and CH3One or more in Br,
Described accelerator is Li+、K+、Na+、Rb+, LiI, KI, NaI, RbI, LiBr, KBr, NaBr, RbBr, LiCl, KCl, NaCl and
One or more in RbCl.
During Studies of Producing Acetic Acid by Carbonylation of Methanol, controlling at 180 DEG C-190 DEG C, pressure is at 3.0MPa-4.0Mpa；Acetate carbonyl
When changing acetic anhydride processed, controlling at 185 DEG C-195 DEG C, pressure is at 3.0MPa-5.0MPa.
Preferably, described rhodium compound is RhI3[Rh(CO)2I2One or both in]；Described halogen helps urges
Agent is CH3I；Described accelerator is LiI；Described CNT is 1.5-4 times of rhodium compound, and halogen catalyst is
30-50 times of rhodium compound；The a length of 100-200nm of described CNT, bore is 0.4-1nm；Liquid phase reactor
The concentration of middle halogen catalyst is 7.5%, and the concentration of accelerator is 4000ppm.
Rhodium and rhodium compound active body are loaded to CNT by the present invention, i.e. prepare carbon nanotube loaded rhodium compound,
Catalyst concentration in the reaction is obviously improved, and there is more preferable stability, maintain original liquid phase anti-
Answer system.
The catalyst of the present invention has excellent performance, in the following aspects in catalysis methanol carbonylation produces acetic acid
An obvious advantage is had with traditional rhodium catalysis carbonylation liquid phase reactor:
(1) high concentration catalyst；
(2) reaction system low water content can ensure stability and the high activity of catalyst；
(3) reduction of halogen addition；Existing industrial production device fills, and in reaction system, halogen addition (in terms of CH3I) is about
For 10%wt ~ 25%wt, the present invention is when catalyst concn (in terms of Rh) is higher than 3000ppm, and halogen addition can be reduced to 8
%wt。
Catalyst of the present invention is in methyl acetate carbonylation produces acetic anhydride, and catalyst has higher concentration and stability,
Metal ion or metal halogen additive can be reduced, promote space-time yield, reduce simultaneously and separate with thick product in subsequent catalyst
During the loss amount of catalyst.
Detailed description of the invention
Embodiment emphasis simulates industrial reactive component, adds a certain amount of acetic acid and vinegar the most before the reaction
Acid anhydride.
In embodiment 1, embodiment 3, embodiment 5 and embodiment 7, rhodium compound is RhI3；Embodiment 2, embodiment 4, enforcement
In example 6 and embodiment 8 rhodium compound be [Rh(CO)2I2]。
In embodiment, a length of 100-200nm of CNT, bore is 0.4-1nm.
Embodiment uses U.S. parr-4848 type nickel-base alloy reactor, vapour phase chromatograph be Japanese Shimadzu gas chromatogram-
GC-MS (GC-MS) (GCMS-TQ8040), liquid chromatograph is Japan's Shimadzu HPLC-MS instrument
(HPLC-MS) (LCMS-2020), metal analysis is profit Man of U.S. Inductively coupled plasma optical emission spectrometer (ICP)
(Prodigy XP), pressed powder is carried out material phase analysis, qualitative analysis for Japan Shimadzu Corporation's X-ray diffractometer (XRD)
(XRD-6100), catalyst characterization is AMI company of U.S. chemistry Sorption Analyzer (AMI-90).
Embodiment 1
SWCN load rhodium compound: in catalyst system, CNT is 1.5 times of rhodium compound quality, and halogen helps
Catalyst is 20 times of rhodium compound quality.
SWCN load rhodium compound 1.0g(is added in terms of Rh in 1900ml nickel-base alloy autoclave pressure), methanol
5.9mol, acetic acid 9mol, iodomethane 1.52mol, use carbon monoxide replacement reaction kettle, and boost to 4.0MPa, arranges stirring and turns
Speed is 800 turns, and reaction is warming up to 180 DEG C-185 DEG C, controls constant temperature, and the response time is 20min.Methanol conversion is 91.2%, second
The space-time yield of acid is 36molAcOH/(L h).
Embodiment 2
SWCN load rhodium compound: in catalyst system, CNT is 4 times of rhodium compound quality, and halogen helps urges
Agent is 30 times of rhodium compound quality.
SWCN load rhodium compound 1.0g(is added in terms of Rh in 1900ml nickel-base alloy autoclave pressure), methanol
5.9mol, acetic acid 9mol, iodomethane 1.52mol, use carbon monoxide replacement reaction kettle, and boost to 4.0MPa, arranges stirring and turns
Speed is 800 turns, and reaction is warming up to 180 DEG C-185 DEG C, controls constant temperature, and the response time is 24min.Methanol conversion is 96.2%, second
The space-time yield of acid is 34molAcOH/(L h).
Embodiment 3
SWCN load rhodium compound: in catalyst system, CNT is 1.5 times of rhodium compound quality, and halogen helps
Catalyst is 30 times of rhodium compound quality.
SWCN load rhodium compound 1.5g(is added in terms of Rh in 1900ml nickel-base alloy autoclave pressure), catalysis
Agent concentration is 1585ppm, methanol 5.9mol, acetic acid 9mol, and iodomethane 1.52mol uses carbon monoxide replacement reaction kettle, and boosts
To 4.0MPa, arranging speed of agitator is 800 turns, and reaction is warming up to 180 DEG C-185 DEG C, controls constant temperature, and the response time is 20min.
Methanol conversion is 97.0%, and the space-time yield of acetic acid is 39molAcOH/(L h).
Embodiment 4
SWCN load rhodium compound: in catalyst system, CNT is 4 times of rhodium compound quality, and halogen helps urges
Agent is 20 times of rhodium compound quality.
SWCN load rhodium compound 2.0g(is added in terms of Rh in 1900ml nickel-base alloy autoclave pressure), methanol
5.9mol, acetic acid 9mol, iodomethane 1.52mol, use carbon monoxide replacement reaction kettle, and boost to 4.0MPa, arranges stirring and turns
Speed is 800 turns, and reaction is warming up to 180 DEG C-185 DEG C, controls constant temperature, and the response time is 15min.Methanol conversion is 97.4%, second
The space-time yield of acid is 48molAcOH/(L h).
Embodiment 5
SWCN load rhodium compound: in catalyst system, CNT is 4 times of rhodium compound quality, and halogen helps urges
Agent is 30 times of rhodium compound quality.
SWCN load rhodium compound 3.0g(is added in terms of Rh in 1900ml nickel-base alloy autoclave pressure), catalysis
Agent concentration is 3165ppm, methanol 5.9mol, acetic acid 9mol, iodomethane 0.4mol, and iodomethane concentration is 7.2%wt, with an oxidation
Carbon replacement reaction kettle, and boost to 4.0MPa, arranging speed of agitator is 800 turns, and reaction is warming up to 180 DEG C-185 DEG C, controls perseverance
Temperature, the response time is 12min.Methanol conversion is 97.2%, and the space-time yield of acetic acid is 52.0molAcOH/(L h), now
Reaction presents slurry, and reaction reclaims slurry catalyst after terminating can continue on for catalytic reaction, repeats experiment and shows that its space-time is received
Rate is 51.7 AcOH/(L h), 52.2 AcOH/(L h).
Embodiment 6
Carbon multi-wall nano tube loaded rhodium compound: in catalyst system, CNT is 1.5 times of rhodium compound quality, and halogen helps
Catalyst is 20 times of rhodium compound quality.
Carbon multi-wall nano tube loaded rhodium compound 1.0g(is added in terms of Rh in 1900ml nickel-base alloy autoclave pressure), acetic acid
Methyl ester 5mol, acetic acid 3.3mol, iodomethane 1.8mol, lithium iodide 40g, use carbon monoxide replacement reaction kettle, and boost to
5.0MPa, arranging speed of agitator is 800 turns, and reaction is warming up to 185 DEG C-190 DEG C, controls constant temperature, and the response time is 20min.Second
Acid methyl ester conversion rate is 60.2%, and the space-time yield of acetic anhydride is 27.2molAcOH/(L h).
Embodiment 7
Carbon multi-wall nano tube loaded rhodium compound: in catalyst system, CNT is 4 times of rhodium compound quality, halogen helps urges
Agent is 30 times of rhodium compound quality.
Carbon multi-wall nano tube loaded rhodium compound 1.5g(is added in terms of Rh in 1900ml nickel-base alloy autoclave pressure), acetic acid
Methyl ester 5mol, acetic acid 3.3mol, iodomethane 1.8mol, lithium iodide 40g, use carbon monoxide replacement reaction kettle, and boost to
5.0MPa, arranging speed of agitator is 800 turns, and reaction is warming up to 185 DEG C-190 DEG C, controls constant temperature, and the response time is 15min.Second
Acid methyl ester conversion rate is 62.2%, and the space-time yield of acetic anhydride is 30.3molAcOH/(L h).
Embodiment 8
Carbon multi-wall nano tube loaded rhodium compound: in catalyst system, CNT is 4 times of rhodium compound quality, halogen helps urges
Agent is 30 times of rhodium compound quality.
The carbon multi-wall nano tube loaded rhodium compound that addition hydrophilic group is modified in 1900ml nickel-base alloy autoclave pressure
1.5g(is in terms of Rh), methyl acetate 5mol, acetic acid 3.3mol, iodomethane 1.8mol, lithium iodide 40g, water 100g(are about 13%
Wt), using carbon monoxide replacement reaction kettle, and boost to 5.0MPa, arranging speed of agitator is 800 turns, reaction be warming up to 185 DEG C-
190 DEG C, controlling constant temperature, the response time is 15min.Methyl acetate conversion ratio is 62.2%, and the space-time yield of acetic anhydride is
29.6molAcOH/(L h), the carbon nanotube loaded rhodium catalyst that hydrophilic group is modified simultaneously there are no obvious sediment.
Claims (10)
1. the rhodium catalytic system for carbonylation, it is characterised in that with carbon nanotube loaded rhodium compound as active matter
Kind, adding the catalyst system of halogen catalyst composition, in catalyst system, CNT is 0.5-10 times of rhodium compound,
Halogen catalyst is 1-150 times of rhodium compound.
2. rhodium catalytic system as claimed in claim 1, it is characterised in that be added with accelerator Li+、K+、Na+、Rb+、LiI、
One or more in KI, NaI, RbI, LiBr, KBr, NaBr, RbBr, LiCl, KCl, NaCl and RbCl.
A kind of carbon nanotube loaded rhodium catalytic system the most as claimed in claim 1 or 2, it is characterised in that described rhodium
Compound is Rh, RhI3, [Rh(CO)2I2], [Rh(CO)2Cl2], [Rh(CO)2Br2] and Rh(OAc)2In one or more；Described
Halogen catalyst be HI, CH3I、HCl、CH3Cl, HBr and CH3One or more in Br.
4. rhodium catalytic system as claimed in claim 1, it is characterised in that described CNT be SWCN,
One or more in double-walled carbon nano-tube and multi-walled carbon nano-tubes, a length of 50-3000nm of CNT, bore is
0.1nm-30nm。
5. rhodium catalytic system as claimed in claim 1, it is characterised in that CNT used uses dressing agent to modify, and repaiies
Decorations agent is dodecylbenzene sodium sulfonate, sodium lauryl sulphate, cetyl trimethylammonium bromide, polyoxyethylene nonylphenol ether, vinyl acetate
Ester, polyvinyl alcohol one or more.
6. the rhodium catalytic system described in a claim 1 or 2 is applied to the anti-of methanol, methyl acetate and alcohol-ester mixture
Answering thing to prepare in the carbonylation liquid phase reactor of acetic acid, acetic anhydride, acetas, in described liquid phase reactor, rhodium catalyst concentration is
6000-30000ppm。
Apply the most as claimed in claim 6, it is characterised in that in liquid phase reactor, the concentration of halogen catalyst is 3% ~ 20%,
The concentration of accelerator is 0ppm ~ 5000ppm, and reaction condition is: temperature is at 150 DEG C-220 DEG C, and pressure is at 3.0Mpa-6.0Mpa.
Apply the most as claimed in claim 6, it is characterised in that described rhodium compound is Rh, RhI3, [Rh(CO)2I2]、[Rh
(CO)2Cl2], [Rh(CO)2Br2] and Rh(OAc)2In one or more；Described halogen catalyst is HI, CH3I、HCl、
CH3Cl, HBr and CH3One or more in Br, described accelerator is Li+、K+、Na+、Rb+、LiI、KI、NaI、RbI、
One or more in LiBr, KBr, NaBr, RbBr, LiCl, KCl, NaCl and RbCl.
Apply the most as claimed in claim 6, it is characterised in that during Studies of Producing Acetic Acid by Carbonylation of Methanol, control at 180 DEG C-190 DEG C,
Pressure is at 3.0MPa-4.0Mpa；During methyl acetate carbonylation acetic anhydride, controlling at 185 DEG C-195 DEG C, pressure is at 3.0MPa-
5.0MPa。
10. the rhodium catalytic system as described in claim 1,2,6, it is characterised in that described rhodium compound is RhI3[Rh
(CO)2I2One or both in]；Described halogen catalyst is CH3I；Described accelerator is LiI；Described carbon nanometer
Pipe is 1.5-4 times of rhodium compound, and halogen catalyst is 30-50 times of rhodium compound；Described CNT a length of
100-200nm, bore is 0.4-1nm；In liquid phase reactor, the concentration of halogen catalyst is 7.5%, and the concentration of accelerator is
4000ppm。
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Cited By (1)
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