CN106179506A - A kind of support type palladium-based catalyst and its preparation method and application - Google Patents
A kind of support type palladium-based catalyst and its preparation method and application Download PDFInfo
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- CN106179506A CN106179506A CN201610472401.6A CN201610472401A CN106179506A CN 106179506 A CN106179506 A CN 106179506A CN 201610472401 A CN201610472401 A CN 201610472401A CN 106179506 A CN106179506 A CN 106179506A
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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
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
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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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Abstract
This application provides a kind of support type palladium-based catalyst and its preparation method and application, described catalyst includes active component and carrier；Described active component is palladio coordination compound；At least one in described support selected from alumina, silicon oxide, magnesium oxide, zinc oxide, zirconium oxide, titanium dioxide, metal organic framework compound, activated carbon, molecular sieve, CNT, Graphene.This support type palladium-based catalyst prepares the reaction of dimethyl carbonate for methyl nitrite vapor phase carbonylation, has catalysis activity height, selectivity of product height, the advantage of catalyst life length.
Description
Technical field
The invention belongs to field of fine chemical, relate in particular to a kind of support type palladium-based catalyst and preparation method thereof and
Application.
Background technology
Dimethyl carbonate is the industrial chemicals of a kind of environmental protection, and purposes is extremely wide.Current industrial carbonate synthesis two
Methyl ester method mainly includes phosgenation and ester-interchange method.Phosgenation is a kind of traditional synthetic method, uses the phosgene of severe toxicity to make
For raw material, not only poor stability and also pollute environment, the by-product HCl of generation is big to equipment corrosion.Ester-interchange method is with carbon
Acid propylene ester and methanol are raw material, carry out ester exchange, produce dimethyl carbonate.Raw material relies on oil, and production cost is higher.
It is the method the most gradually received publicity that methyl nitrite vapor phase carbonylation prepares dimethyl carbonate, has following
Technical advantage: a) reaction condition is gentle；B) production technology is pollution-free；C) fixed bed reactors are used, it is not necessary to separating catalyst
And product；D) the anhydrous generation of primary response, catalyst life；E) main reactor separates with methyl nitrite regenerator, reaction
During no oxygen introduce, the generation of by-product carbon dioxide, the system of the most non-oxygen can be avoided can to reduce blast
Danger, operates more safe and stable.
High activity, high selectivity, long-life catalyst are to realize methyl nitrite vapor phase carbonylation to prepare carbonic acid diformazan
The key of ester.How to make catalyst have high activity, high selectivity and long-life concurrently, be still the key technology difficult problem in this field.Mesh
Before some catalyst of having reported deactivation phenomenom can occur after reaction a period of time, under catalysis activity and selectivity is serious
Fall.
Therefore, in order to overcome the drawbacks described above existing for prior art, prepare and have high activity, high selectivity and longevity concurrently
The catalyst of life, this invention of special proposition.
Summary of the invention
The purpose of the application is, it is provided that a kind of support type palladium-based catalyst.Compared with existing catalyst, this catalyst has
There are catalysis activity height, selectivity of product height, the advantage of catalyst life length.
The another object of the application is, it is provided that the preparation method of a kind of support type palladium-based catalyst, uses ammonia still process legal system
Standby, active component is highly dispersed at carrier surface.
The application's it is further an object to provide support type palladium-based catalyst prepares carbon at methyl nitrite vapor phase carbonylation
Application in dimethyl phthalate reaction.
To achieve these goals, the application adopts the following technical scheme that
Support type palladium-based catalyst described herein, it is characterised in that described support type palladium-based catalyst includes activity
Component and carrier；
Described active component is palladio coordination compound；
Described support selected from alumina, silicon oxide, magnesium oxide, zinc oxide, zirconium oxide, titanium dioxide, metal organic frame
At least one in compound, activated carbon, molecular sieve, CNT, Graphene.
Preferably, in described support type palladium-based catalyst, carrier is Y molecular sieve.It is highly preferred that described Y molecular sieve is selected from sodium
At least one in type Y molecular sieve, Hydrogen Y molecular sieve, ammonium type Y molecular sieve.It is further preferred that described Y molecular sieve is sodium form Y
Molecular sieve.
Preferably, in described support type palladium-based catalyst, the mass ratio of palladium element and carrier is:
Pd: carrier=0.01～10:100；
It is highly preferred that palladium element with the mass ratio of carrier is in described support type palladium-based catalyst:
Pd: carrier=0.1～5:100.
Preferably, described catalyst also includes auxiliary agent, auxiliary agent chosen from Fe basigamy compound, cobalt-based coordination compound, Ni-based coordination compound,
At least one in cuprio coordination compound.
Preferably, the part in described active component palladium basigamy compound comprises at least one in oxygen, nitrogen, halogen；
Part in described auxiliary agent iron-based coordination compound, cobalt-based coordination compound, Ni-based coordination compound, cuprio coordination compound comprise oxygen, nitrogen,
At least one in halogen.
Preferably, described active component palladium basigamy compound is selected from palladium acetylacetonate Pd (acac)2, palladium Pd (OAc)2, nitre
Acid palladium Pd (NO3)2, Palladous chloride. PdCl2, dichloro diamino palladium Pd (NH3)2Cl2, four potassium chloropalladite K2PdCl4, dichloro four ammonia palladium Pd
(NH3)4Cl2In at least one.
Preferably, described auxiliary agent selected from iron acetate, ferric nitrate, iron chloride, cobaltous acetate, cobalt nitrate, cobaltous chloride, nickel acetate,
At least one in nickel nitrate, Nickel dichloride., Schweinfurt green, copper nitrate, copper chloride.
Preferably, stating the mass ratio of auxiliary agent and carrier in support type palladium-based catalyst is:
Auxiliary agent: carrier=0.01～10:100；
Wherein, the quality of described auxiliary agent is in terms of the quality of metallic element contained in auxiliary agent.
Another aspect according to the application, it is provided that the method preparing any one support type palladium-based catalyst above-mentioned.
As a kind of embodiment, the described method preparing support type palladium-based catalyst, it is characterised in that include walking as follows
Rapid:
(1), after will palladio coordination compound addition to solvent carrying out dissolving and/or disperseing, add ammonia, obtain system I；Body
It is the pH of I > 7；
(2) carrier is added in system I, stir, obtain system II；
(3) heating steps (2) gained system II to pH=6～7, separated, dry, roasting, obtain described load type palladium
Base catalyst.
As there being a kind of embodiment, the described method preparing support type palladium-based catalyst, it is characterised in that include as follows
Step:
(1) after palladio coordination compound and auxiliary agent are added carrying out dissolving and/or disperse to solvent, addition ammonia, obtain body
It is I；The pH of system I > 7；
(2) carrier is added in system I, stir, obtain system II；
(3) heating steps (2) gained system II to pH=6～7, separated, dry, roasting, obtain described load type palladium
Base catalyst.
Preferably, solvent described in step (1) selected from water, ethanol, methanol, acetone, benzene, toluene, dichloromethane, chloroform,
At least one in oxolane, dimethyl sulfoxide, dimethylformamide.
Preferably, the pH=9～14 of described system I.
Those skilled in the art according to actual needs, can select the consumption of suitable solvent and solvent.Preferably, institute
Stating palladio coordination compound quality/solvent volume in system I is 0.1～2g/L.It is highly preferred that palladio coordinates material in described system I
Amount/solvent volume is for for 0.45～1.1g/L.
Preferably, in described system I, auxiliary agent quality/solvent volume is 0.5～1.5g/L.It is highly preferred that in described system I
Auxiliary agent quality/solvent volume is 0.8～1.2g/L.
Preferably, in system II, the mass ratio of palladio coordination compound and carrier is:
Palladio coordination compound: carrier=1～20:1000.
It is highly preferred that palladio coordination compound with the mass ratio of carrier is in system II:
Palladio coordination compound: carrier=4.5～10.1:1000.
Preferably, in system II, the mass ratio of auxiliary agent and carrier is:
Auxiliary agent: carrier=5～15:1000.
It is highly preferred that auxiliary agent with the mass ratio of carrier is in system II:
Auxiliary agent: carrier=8～12:1000.
Preferably, in step (3), the temperature of described heating is 50～150 DEG C；Described dry temperature is 60～150 DEG C,
The time being dried is 1～12 hour；The temperature of described roasting is 150～300 DEG C, and the time of roasting is 1～12 hour.
Preferably, step (2) is to add in system I by carrier, stirs and impregnates no less than 3 hours, obtaining system
II.It is highly preferred that the time impregnated in step (2) is 3～8 hours.
Preferably, being separated into centrifugation described in step (3), time centrifugal, rotating speed is 3000～6000rpm.
Another aspect according to the application, it is provided that a kind of methyl nitrite vapor phase carbonylation prepares the side of dimethyl carbonate
Method, it is characterised in that comprise the following steps: by the unstripped gas containing CO and methyl nitrite, be 500～5000h in air speed-1、
Under conditions of temperature is 80～160 DEG C, pressure is 0.01～2MPa, it is passed through the reactor equipped with support type palladium-based catalyst, system
Standby dimethyl carbonate；
Described support type palladium-based catalyst is selected from any of the above-described support type palladium-based catalyst, prepares according to any of the above-described method
At least one in the support type palladium-based catalyst obtained.
Preferably, in unstripped gas, CO is 1:2～6 with the volume ratio of methyl nitrite.
Preferably, air speed is 1000～3000h-1, temperature is 100～140 DEG C, and pressure is 0.05～0.15MPa.
The beneficial effect of the application includes but not limited to:
(1) active component of support type palladium-based catalyst provided herein is palladio coordination compound, and palladium is in electron deficiency
State, beneficially height selectively produce dimethyl carbonate.
(2) preparation method of support type palladium-based catalyst provided herein is ammonia still process method, contributes to active component high
Degree is dispersed in surface and the duct of carrier.
(3) support type palladium-based catalyst provided herein is applied and is prepared carbonic acid two at methyl nitrite vapor phase carbonylation
In the reaction of methyl ester, there is high activity, high selectivity, long-life advantage.
Accompanying drawing explanation
Fig. 1 is that CAT-1 prepares conversion ratio and the carbon of CO in dimethyl carbonate for methyl nitrite vapor phase carbonylation
The selectivity of dimethyl phthalate is along with the variation diagram in response time.
Detailed description of the invention
The technical scheme of the application is further illustrated below by detailed description of the invention.
Those skilled in the art, it will be clearly understood that described embodiment only helps to understand the application, are not construed as the tool of the application
Body limits.
Unless specifically stated otherwise, reagent used in the present embodiment and raw material all can be bought by commercial sources.
ZIF-8 is prepared into according to the method in document [Proc.Natl.Acad.Sci., 2006,103,10186-10191]
Arrive.
Unless specifically stated otherwise, it is experimentally conventional method.
Prepared by embodiment 1 catalyst CAT-1～CAT-16
Take a certain amount of coordination compound containing palladium element to be dispersed in 10mL solvent, drip ammonia regulation system pH to A,
To system I；Add 1g carrier, after time of infusion is stirred at room temperature, obtain system II；The pH being heated to system II is down to B (steaming
Ammonia), it is performing centrifugal separation on, dry, roasting, obtains support type palladio catalyst sample.
Sample number into spectrum is as shown in table 1 with the relation of concrete preparation condition.
Table 1
Constituent content in embodiment 2 catalyst CAT-1～CAT-16 measures
Ultima2 type inductive of elementary composition employing Jobin Yvon company of sample CAT-1～CAT-16 etc. from
Daughter emission spectrum (ICP) measures, and result is as shown in table 2.
Table 2
Embodiment 3 methyl nitrite vapor phase carbonylation prepares the catalytic performance test of dimethyl carbonate
Take 200mg catalyst CAT-1～CAT-16 respectively and put in fixed-bed tube reactor, carry out nitrous acid first respectively
Ester (being abbreviated as MN) vapor phase carbonylation prepares the reaction evaluating of dimethyl carbonate (being abbreviated as DMC).By carbon monoxide, nitrous acid first
Ester, carrier gas N2With internal standard gas Ar (volume ratio CO:MN:Ar:N2=0.17:0.51:0.03:0.29), in reaction pressure
0.1MPa, reaction temperature 120 DEG C, air speed=2500h-1Under conditions of contact respectively with catalyst CAT-1～CAT-12, it is thus achieved that produce
Thing dimethyl carbonate, CO conversion ratio and the DMC selectivity of catalyst CAT-1～CAT-16 refer to table 3.
Product use Shimadzu company GC-2014 type gas chromatograph detection, 5A and SE-30 chromatographic column, TCD and
FID dual detector.
The conversion ratio of CO is calculated according to following methods:
Conversion ratio (%)=[CO] of COin/[Ar]in-[CO]out/[Ar]out)/([CO]in/[Ar]in) × 100%
The selectivity of DMC is calculated according to following methods:
Selectivity (%)=(S of DMCDMC×R-FDMC)/(SDMC×R-FDMC+SDMO×R-FDMO) × 100%
Note: [Ar]in、[Ar]outIt is respectively the concentration of Ar before and after reacting；[CO]in、[CO]outIt is respectively CO before and after reacting
Concentration；SDMC、SDMOIt is respectively the chromatographic peak area of DMC and DMO；R-FDMC、R-FDMOBe respectively DMC and DMO relative correction because of
Son.
The study on the stability of catalyst CAT-1 is as it is shown in figure 1, react 100 hours, and CO conversion ratio maintains about 80%,
DMC selectivity remains more than 99%, shows that catalyst has good stability.
Table 3
| Sample number into spectrum | CO conversion ratio (%) | DMC selectivity (%) |
| CAT-1 | 80.3 | 99.5 |
| CAT-2 | 63.1 | 81.3 |
| CAT-3 | 22.3 | 46.2 |
| CAT-4 | 9.8 | 52.6 |
| CAT-5 | 60.1 | 52.1 |
| CAT-6 | 32.6 | 30.6 |
| CAT-7 | 42.3 | 20.1 |
| CAT-8 | 17.5 | 16.9 |
| CAT-9 | 26.8 | 21.4 |
| CAT-10 | 30.4 | 42.7 |
| CAT-11 | 71.4 | 98.6 |
| CAT-12 | 68.5 | 96.4 |
| CAT-13 | 70.9 | 98.3 |
| CAT-14 | 68.2 | 97.6 |
| CAT-15 | 74.2 | 98.1 |
| CAT-16 | 76.5 | 97.5 |
The above, be only several embodiments of the application, the application not does any type of restriction, although this Shen
Embodiment please discloses as above, but and be not used to limit the application, any those skilled in the art, without departing from this
In the range of application technical scheme, utilize the technology contents of the disclosure above to make a little variation or modification is all equal to equivalence in fact
Execute case, in the range of belonging to technical scheme.
Claims (10)
1. a support type palladium-based catalyst, it is characterised in that described support type palladium-based catalyst includes active component and carrier；
Described active component is palladio coordination compound；
Described support selected from alumina, silicon oxide, magnesium oxide, zinc oxide, zirconium oxide, titanium dioxide, metal organic frame chemical combination
At least one in thing, activated carbon, molecular sieve, CNT, Graphene.
Support type palladium-based catalyst the most according to claim 1, it is characterised in that described molecular sieve is Y molecular sieve.
Support type palladium-based catalyst the most according to claim 1, it is characterised in that palladium in described support type palladium-based catalyst
Element with the mass ratio of carrier is:
Pd: carrier=0.01～10:100；
Preferably, in described support type palladium-based catalyst, the mass ratio of palladium element and carrier is:
Pd: carrier=0.1～5:100.
Support type palladium-based catalyst the most according to claim 1, it is characterised in that described catalyst also includes auxiliary agent, helps
At least one in agent chosen from Fe basigamy compound, cobalt-based coordination compound, Ni-based coordination compound, cuprio coordination compound.
5. according to the support type palladium-based catalyst described in claim 1 or 4, it is characterised in that described active component palladium basigamy closes
Part in thing comprises at least one in oxygen, nitrogen, halogen；
Part in described auxiliary agent iron-based coordination compound, cobalt-based coordination compound, Ni-based coordination compound, cuprio coordination compound comprises oxygen, nitrogen, halogen
In at least one.
6. prepare the method for support type palladium-based catalyst described in any one of claims 1 to 3 for one kind, it is characterised in that include as
Lower step:
(1), after will palladio coordination compound addition to solvent carrying out dissolving and/or disperseing, add ammonia, obtain system I；System I
pH>7；
(2) carrier is added in system I, stir, obtain system II；
(3) heating steps (2) gained system II to pH=6～7, separated, dry, roasting, obtains described support type palladio and urges
Agent.
7. the method for the support type palladium-based catalyst that a kind is prepared described in claim 4 or 5, it is characterised in that include walking as follows
Rapid:
(1) after palladio coordination compound and auxiliary agent are added carrying out dissolving and/or disperse to solvent, addition ammonia, obtain system I；
The pH of system I > 7；
(2) carrier is added in system I, stir, obtain system II；
(3) heating steps (2) gained system II to pH=6～7, separated, dry, roasting, obtains described support type palladio and urges
Agent.
8. according to the preparation method of the support type palladium-based catalyst described in claim 6 or 7, it is characterised in that institute in step (1)
State solvent selected from water, ethanol, methanol, acetone, benzene, toluene, dichloromethane, chloroform, oxolane, dimethyl sulfoxide, dimethyl
At least one in Methanamide.
9. according to the preparation method of the support type palladium-based catalyst described in claim 6 or 7, it is characterised in that in step (3),
The temperature of described heating is 50～150 DEG C；Described dry temperature is 60～150 DEG C, and the time being dried is 1～12 hour；Institute
The temperature stating roasting is 150～300 DEG C, and the time of roasting is 1～12 hour.
10. the method that a methyl nitrite vapor phase carbonylation prepares dimethyl carbonate, it is characterised in that comprise the following steps:
By the unstripped gas containing CO and methyl nitrite, it is 500～5000h in air speed-1, temperature be 80～160 DEG C, pressure be 0.01～
Under conditions of 2MPa, it is passed through the reactor equipped with support type palladium-based catalyst, prepares dimethyl carbonate；
Described support type palladium-based catalyst is selected from the support type palladium-based catalyst described in any one of claim 1 to 5, according to right
At least one in the support type palladium-based catalyst that method described in requirement 6 to 9 any one prepares.
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