CN106179506B - 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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- 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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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- 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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- 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
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- 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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Abstract
This application provides a kind of support type palladium-based catalysts and its preparation method and application, and the catalyst includes active component and carrier；The active component is palladium base complex；The carrier is selected from least one of aluminium oxide, silica, magnesia, zinc oxide, zirconium oxide, titanium dioxide, metal organic framework compound, active carbon, molecular sieve, carbon nanotube, graphene.The support type palladium-based catalyst prepares the reaction of dimethyl carbonate for methyl nitrite vapor phase carbonylation, has the advantages that catalytic activity is high, selectivity of product is high, catalyst life is long.
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
Using.
Background technique
Dimethyl carbonate is a kind of environmentally protective industrial chemicals, and purposes is extremely wide.Industrial carbonate synthesis two at present
Methyl esters method mainly includes phosgenation and ester-interchange method.Phosgenation is a kind of traditional synthetic method, is made using the phosgene of severe toxicity
For raw material, not only safety is poor but also pollution environment, the by-product HCl of generation are big to equipment corrosion.Ester-interchange method is with carbon
Acid propylene ester and methanol are raw material, carry out transesterification, produce dimethyl carbonate.Raw material relies on petroleum, and production cost is higher.
It is the method gradually to attract attention in recent years that methyl nitrite vapor phase carbonylation, which prepares dimethyl carbonate, is had following
Technical advantage: a) reaction condition is mild；B) production technology is pollution-free；C) fixed bed reactors are used, separating catalyst is not needed
And product；D) the anhydrous generation of main reaction, catalyst life；E) main reactor and methyl nitrite regenerator separate, reaction
No oxygen introduces in the process, can be to avoid the generation of by-product carbon dioxide, while the system of non-oxygen can reduce explosion
Risk operates more safe and stable.
High activity, highly selective, the long-life catalyst are to realize that methyl nitrite vapor phase carbonylation prepares carbonic acid diformazan
The key of ester.So that catalyst is had both high activity, highly selective and long-life, is still the key technology difficulty in the field.Mesh
Deactivation phenomenom can occur after reacting a period of time for preceding reported some catalyst, under catalytic activity and selectivity are serious
Drop.
Therefore, it in order to overcome drawbacks described above present in the prior art, prepares and has both high activity, highly selective and long-lived
The catalyst of life, spy propose the invention.
Summary of the invention
The purpose of the application is, provides a kind of support type palladium-based catalyst.Compared with existing catalyst, catalyst tool
Have the advantages that catalytic activity is high, selectivity of product is high, catalyst life is long.
The another object of the application is, a kind of preparation method of support type palladium-based catalyst is provided, using 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 in methyl nitrite vapor phase carbonylation
Application in dimethyl phthalate reaction.
To achieve the goals above, the application adopts the following technical scheme that
Support type palladium-based catalyst described herein, which is characterized in that the support type palladium-based catalyst includes activity
Component and carrier；
The active component is palladium base complex；
The carrier is selected from aluminium oxide, silica, magnesia, zinc oxide, zirconium oxide, titanium dioxide, metal organic frame
At least one of compound, active carbon, molecular sieve, carbon nanotube, graphene.
Preferably, carrier is Y molecular sieve in the support type palladium-based catalyst.It is highly preferred that the Y molecular sieve is selected from sodium
At least one of type Y molecular sieve, Hydrogen Y molecular sieve, ammonium type Y molecular sieve.It is further preferred that the Y molecular sieve is sodium form Y
Molecular sieve.
Preferably, in the support type palladium-based catalyst palladium element and carrier mass ratio are as follows:
Pd: carrier=0.01~10:100；
It is highly preferred that in the support type palladium-based catalyst palladium element and carrier mass ratio are as follows:
Pd: carrier=0.1~5:100.
Preferably, the catalyst further includes auxiliary agent, auxiliary agent be selected from iron-based complex, cobalt-based complex, Ni-based complex,
At least one of copper-based complex.
Preferably, the ligand in the active component palladium base complex includes at least one of oxygen, nitrogen, halogen；
The iron-based complex of the auxiliary agent, cobalt-based complex, Ni-based complex, the ligand in copper-based complex include oxygen, nitrogen,
At least one of halogen.
Preferably, the active component palladium base complex is selected from palladium acetylacetonate Pd (acac)2, palladium acetate Pd (OAc)2, nitre
Sour palladium Pd (NO3)2, palladium chloride PdCl2, dichloro diamino palladium Pd (NH3)2Cl2, four potassium chloropalladite K2PdCl4, four ammonia palladium Pd of dichloro
(NH3)4Cl2At least one of.
Preferably, the auxiliary agent be selected from ferric acetate, ferric nitrate, iron chloride, cobalt acetate, cobalt nitrate, cobalt chloride, nickel acetate,
At least one of nickel nitrate, nickel chloride, copper acetate, copper nitrate, copper chloride.
Preferably, the mass ratio of auxiliary agent and carrier in support type palladium-based catalyst is stated are as follows:
Auxiliary agent: carrier=0.01~10:100；
Wherein, the quality of the auxiliary agent is in terms of the quality of metallic element contained in auxiliary agent.
According to the another aspect of the application, the method for preparation any one of the above support type palladium-based catalyst is provided.
As an implementation, the method for preparing support type palladium-based catalyst, which is characterized in that including walking as follows
It is rapid:
(1) palladium base complex is added after being dissolved and/or being dispersed into solvent, ammonium hydroxide is added, obtains system I；Body
It is pH > 7 of I；
(2) carrier is added in system I, stirs evenly, obtains system II；
(3) system II obtained by heating stepses (2) obtains the load type palladium through separation, drying, roasting to pH=6~7
Base catalyst.
As having a kind of embodiment, the method for preparing support type palladium-based catalyst, which is characterized in that including as follows
Step:
(1) palladium base complex and auxiliary agent are added after being dissolved and/or being dispersed into solvent, ammonium hydroxide is added, obtains body
It is I；PH > 7 of system I；
(2) carrier is added in system I, stirs evenly, obtains system II；
(3) system II obtained by heating stepses (2) obtains the load type palladium through separation, drying, roasting to pH=6~7
Base catalyst.
Preferably, solvent described in step (1) be selected from water, ethyl alcohol, methanol, acetone, benzene, toluene, methylene chloride, chloroform,
At least one of tetrahydrofuran, dimethyl sulfoxide, dimethylformamide.
Preferably, pH=9~14 of the system I.
Those skilled in the art can select the dosage of suitable solvent and solvent according to actual needs.Preferably, institute
Stating palladium base cooperation amount of substance/solvent volume in system I is 0.1~2g/L.It is highly preferred that palladium base cooperates substance in the system I
Amount/solvent volume is 0.45~1.1g/L.
Preferably, auxiliary agent quality/solvent volume is 0.5~1.5g/L in the system I.It is highly preferred that in the system I
Auxiliary agent quality/solvent volume is 0.8~1.2g/L.
Preferably, in system II palladium base complex and carrier mass ratio are as follows:
Palladium base complex: carrier=1~20:1000.
It is highly preferred that in system II palladium base complex and carrier mass ratio are as follows:
Palladium base complex: carrier=4.5~10.1:1000.
Preferably, in system II auxiliary agent and carrier mass ratio are as follows:
Auxiliary agent: carrier=5~15:1000.
It is highly preferred that in system II auxiliary agent and carrier mass ratio are as follows:
Auxiliary agent: carrier=8~12:1000.
Preferably, in step (3), the temperature of the heating is 50~150 DEG C；The temperature of the drying is 60~150 DEG C,
The dry time is 1~12 hour；The temperature of the roasting is 150~300 DEG C, and the time of roasting is 1~12 hour.
Preferably, step (2) is that carrier is added in system I, stirs evenly and impregnates no less than 3 hours, obtains system
II.It is highly preferred that the time impregnated in step (2) is 3~8 hours.
Preferably, it is separated into centrifuge separation described in step (3), revolving speed is 3000~6000rpm when centrifugation.
According to the another aspect of the application, the side that a kind of methyl nitrite vapor phase carbonylation prepares dimethyl carbonate is provided
Method, which comprises the following steps: be 500~5000h in air speed by the unstripped gas containing CO and methyl nitrite-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, is made
Standby dimethyl carbonate；
The support type palladium-based catalyst is selected from any of the above-described support type palladium-based catalyst, is prepared according to any of the above-described method
At least one of obtained support type palladium-based catalyst.
Preferably, in unstripped gas, the volume ratio of CO and methyl nitrite is 1:2~6.
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 is not limited to:
(1) active component of support type palladium-based catalyst provided herein is palladium base complex, and palladium is in electron deficient
State is conducive to highly selective generation dimethyl carbonate.
(2) preparation method of support type palladium-based catalyst provided herein is ammonia still process method, facilitates active component height
Degree is dispersed in the surface and duct of carrier.
(3) support type palladium-based catalyst provided herein, which is applied, prepares carbonic acid two in methyl nitrite vapor phase carbonylation
In the reaction of methyl esters, have the advantages that high activity, highly selective, long-life.
Detailed description of the invention
Fig. 1 is the conversion ratio and carbon that CAT-1 prepares CO in dimethyl carbonate for methyl nitrite vapor phase carbonylation
The selectivity of dimethyl phthalate with the reaction time variation diagram.
Specific embodiment
The technical solution of the application is further illustrated below by specific embodiment.
Those skilled in the art are not construed as the tool of the application it will be clearly understood that the embodiment only helps to understand the application
Body limitation.
Unless specifically stated otherwise, reagent used in the present embodiment and raw material 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]
It arrives.
It unless specifically stated otherwise, is experimentally conventional method.
1 catalyst CAT-1~CAT-16 of embodiment preparation
It takes a certain amount of complex containing palladium element to be dispersed in 10mL solvent, ammonia water conditioning system pH to A is added dropwise, obtains
To system I；1g carrier is added, after time of infusion is stirred at room temperature, obtains system II；The pH for being heated to system II is down to B and (steams
Ammonia), it is centrifuged, dry, roasting is to get support type palladium base catalyst sample.
The relationship of sample number into spectrum and specific preparation condition is as shown in table 1.
Table 1
Constituent content measurement in 2 catalyst CAT-1~CAT-16 of embodiment
The element composition of sample CAT-1~CAT-16 using Jobin Yvon company Ultima2 type inductive coupling etc. from
Daughter emission spectrum (ICP) measurement, the results are shown in Table 2.
Table 2
3 methyl nitrite vapor phase carbonylation of embodiment prepares the catalytic performance test of dimethyl carbonate
It takes 200mg catalyst CAT-1~CAT-16 to be put into fixed-bed tube reactor respectively, carries 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, 120 DEG C of reaction temperature, air speed=2500h-1Under conditions of contacted respectively with catalyst CAT-1~CAT-12, produced
Object dimethyl carbonate, see Table 3 for details for CO conversion ratio and the DMC selectivity of catalyst CAT-1~CAT-16.
Product using Shimadzu company GC-2014 type gas chromatograph detect, 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]outThe respectively concentration of reaction front and back Ar；[CO]in、[CO]outRespectively reaction front and back CO's
Concentration；SDMC、SDMOThe chromatographic peak area of respectively DMC and DMO；R-FDMC、R-FDMOThe relative correction of respectively DMC and DMO because
Son.
For the study on the stability of catalyst CAT-1 as shown in Figure 1, reacting 100 hours, CO conversion ratio maintains about 80%,
DMC is selectively remained greater 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 is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Embodiment please discloses as above, however not to limit the application, any person skilled in the art is not departing from this
In the range of applying for technical solution, a little variation or modification are made using the technology contents of the disclosure above and is equal to equivalent reality
Case is applied, is belonged in technical proposal scope.
Claims (7)
1. a kind of preparation method of support type palladium-based catalyst, which is characterized in that the method is made of following steps:
(1) palladium base complex and auxiliary agent are added after being dissolved and/or being dispersed into solvent, ammonium hydroxide is added, obtains system I；
PH > 7 of system I；
(2) carrier is added in system I, stirs evenly, obtains system II；
(3) system II obtained by heating stepses (2) obtains the support type palladium base and urges to pH=6~7 through separation, drying, roasting
Agent；
The support type palladium-based catalyst includes active component, auxiliary agent and carrier；
The active component is palladium base complex；
The palladium base complex is selected from palladium acetylacetonate Pd (acac)2, palladium acetate Pd (OAc)2, palladium nitrate Pd (NO3)2, palladium chloride
PdCl2, dichloro diamino palladium Pd (NH3)2Cl2, four potassium chloropalladite K2PdCl4, four ammonia palladium Pd (NH of dichloro3)4Cl2In at least one
Kind；
The carrier is selected from aluminium oxide, silica, magnesia, zinc oxide, zirconium oxide, titanium dioxide, metal organic frame chemical combination
At least one of object, active carbon, molecular sieve, carbon nanotube, graphene；
The auxiliary agent is selected from ferric acetate, ferric nitrate, iron chloride, cobalt acetate, cobalt nitrate, cobalt chloride, nickel acetate, nickel nitrate, chlorination
At least one of nickel, copper acetate, copper nitrate, copper chloride；
Palladium base cooperation amount of substance/solvent volume is 0.1~2g/L in the system I.
2. the preparation method of support type palladium-based catalyst according to claim 1, which is characterized in that the molecular sieve is Y
Molecular sieve.
3. the preparation method of support type palladium-based catalyst according to claim 1, which is characterized in that the support type palladium base
The mass ratio of palladium element and carrier in catalyst are as follows:
Pd: carrier=0.01~10:100.
4. the preparation method of support type palladium-based catalyst according to claim 3, which is characterized in that the support type palladium base
The mass ratio of palladium element and carrier in catalyst are as follows:
Pd: carrier=0.1~5:100.
5. the preparation method of support type palladium-based catalyst according to claim 1, which is characterized in that described in step (1)
Solvent is selected from water, ethyl alcohol, methanol, acetone, benzene, toluene, methylene chloride, chloroform, tetrahydrofuran, dimethyl sulfoxide, dimethyl methyl
At least one of amide.
6. the preparation method of support type palladium-based catalyst according to claim 1, which is characterized in that described in step (3)
The temperature of heating is 50~150 DEG C；The temperature of the drying is 60~150 DEG C, and the dry time is 1~12 hour；The roasting
The temperature of burning is 150~300 DEG C, and the time of roasting is 1~12 hour.
7. a kind of method that methyl nitrite vapor phase carbonylation prepares dimethyl carbonate, which comprises the following steps: will
Unstripped gas containing CO and methyl nitrite 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；
The support type palladium-based catalyst is selected from the load type palladium being prepared according to claim 1 to any one of 6 the methods
At least one of base catalyst.
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| CN116059998B (en) * | 2023-01-19 | 2024-08-16 | 利尔化学股份有限公司 | Bimetallic catalyst and preparation method and application thereof |
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| CN102553579A (en) * | 2011-05-27 | 2012-07-11 | 中国科学院福建物质结构研究所 | Preparation method of high-dispersity supported nano metal catalyst |
| CN105363485A (en) * | 2015-09-07 | 2016-03-02 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing dimethyl carbonate through indirect vapor phase method and preparation method of catalyst |
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