CN110075835A - A kind of catalyst and its preparation method and application of step oxidative esterification legal system methyl methacrylate - Google Patents
A kind of catalyst and its preparation method and application of step oxidative esterification legal system methyl methacrylate Download PDFInfo
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- CN110075835A CN110075835A CN201910438644.1A CN201910438644A CN110075835A CN 110075835 A CN110075835 A CN 110075835A CN 201910438644 A CN201910438644 A CN 201910438644A CN 110075835 A CN110075835 A CN 110075835A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
Abstract
The invention discloses a kind of catalyst and its preparation method and application of a step oxidative esterification legal system methyl methacrylate, the catalyst is using the material of the oxide containing electron rich as complex carrier, using Metal Palladium as active component, it is to help active component with rare earth metal, using surfactant as auxiliary agent, chemical general formula be can be expressed as: XaPdbYc/Md- N, wherein Pd is palladium, and X is surfactant, and Y is one of rare earth Sc, yttrium, lanthanum or cerium, and M is electron rich oxide, and N is carrier.The catalyst can be applied to metering system it is oxidation of aldehydes and in one step of methanol esterification production the reacting of methyl methacrylate (MMA).The catalyst is by forming special supply electronic structure between active component, carrier and surfactant three, overcome some disadvantages of existing oxidative esterification catalyst, reaction applied to step oxidative esterification method production MMA also has the characteristics that preparation process is simple and reaction condition is mild other than having the advantages that high conversion rate and selectivity are good.
Description
Technical field
The invention belongs to catalysis technical fields, and in particular to an a kind of step oxidative esterification legal system methyl methacrylate is urged
Agent and its preparation method and application.
Background technique
MMA is a kind of industrially widely used Organic Chemicals, is mainly with acetone cyanogen before synthetic method
Based on alcohol method (ACH method), industrial application technology maturation is reliable, but its there are raw material hydrogen cyanide have severe toxicity, byproduct of reaction difficulty
The disadvantages of reason, Atom economy difference and environmental protection are restricted, gradually replaced environmentally friendly technique, wherein with the conjunction of carbon four
Based on technique.Four synthesis technology of carbon is broadly divided into following 4 process routes: isobutene (IB)/three step of the tert-butyl alcohol (TBA) oxidation
Method, isobutene/tert-butyl alcohol two-step penetration method, isobutene/tert-butyl alcohol direct esterification and oxidation of isobutane method；Wherein, Japan's touching
Isobutene (IB)/three step oxidizing process of the tert-butyl alcohol (TBA) is respectively adopted in nineteen eighty-two reality in matchmaker chemical company and mitsubishi rayon
The industrialization of isobutylene oxidation method is showed, the complex process and long flow path, required production equipment is more, and comprehensive yield is low；Asahi Chemical Industry
Company begins one's study isobutene/tert-butyl alcohol two-step penetration method synthesis MMA from nineteen ninety-five, isobutene/tert-butyl alcohol direct esterification
It is Asahi Kasei Corporation in exploitation in 1984 and the technique of industrial applications, though the technique does not use severe poisonous chemicals hydrogen cyanide,
Production generates a large amount of by-product ammonium hydrogen sulfates, needs to solve a series of problems, such as waste acid treatment, environmental pollution and equipment are corroded, and
MMA yield is without direct oxidation method height, therefore Asahi Kasei Corporation in 1999 is transformed into isobutene/tert-butyl alcohol direct oxidation two
Footwork device.Rhom and Hass, the U.S. using heteropolyacid catalyst come catalyzing iso-butane alkane direct oxidation dehydrogenation be made MAA, then by
MAA is esterified MMA, that is, oxidation of isobutane method processed, and the technology investment is big, and the high production cost of product isobutene, reproduction MMA does not have
Standby competitiveness.
Isobutene/tert-butyl alcohol direct oxidation two-step method is that rear two step of three-step approach is integrated into a step, i.e. IB/TBA is first straight
It connects and is oxidized to MAL, then MAL, MeOH and O2A step oxidative esterification obtains product methyl methacrylate under the action of catalyst.
Two-step method is the boundless environment-protective process route of a prospect, with three step oxidizing process phase of isobutene (IB)/tert-butyl alcohol (TBA)
Than, two-step method significantly simplifies process flow, and Atom economy is higher, and energy consumption is lower, and cost of investment is lower with operating cost,
And intermediate methyl acrylic acid is not generated, reduce corrosion of the acidic materials to equipment, while reducing methacrylic acid
Polymerization side reactions, material benzenemethanol can be recycled, and be production method most competitive at present.Pd is methacrolein, first
Main active component in the catalyst of direct oxidation esterification production MMA, but single metal catalytic occur for pure and mild molecular oxygen
The result is that conversion ratio is low, by-product is more and poor selectivity (US3772381).Subsequent patent improves this, such as Japan
The Pd-Pb System Catalyst that patent JP-B-57-35856, JP-A-57-50545 and JP-A-61-243044 are proposed, Japan Patent
The Pd-Bi system that JP-B-61-60820, JP-B-62-7902 and JP-A-5-148184 are proposed, Japan Patent JP-A-61-
The 243044 Pd-Te systems proposed, the Pd-Tl-Hg system that Japan Patent JP-B-57-35860 is proposed, Japan Patent JP-B-
Pd- alkaline earth-Zn-Cd the system etc. that 57-19090 is proposed, but improved method disclosed in these Japan Patents is only limited to add
Many other metal components improve this defect, and catalyst preparation process is cumbersome, and reproducibility is poor.It is subsequent for Dan Jin
The research of metal catalyst is fabricated to such as the Au base catalyst that Japan Patent JP-2000154164 and JP-2003192632 are proposed
This height and should not regenerate, active component is easy to run off, the Pt base catalyst that Japan Patent JP-57048937 is proposed, activity it is not high and
Ru base catalyst expensive, that Japan Patent JP-2003260357 is proposed, catalytic activity still has larger with noble metal catalyst
Gap.It hereafter, is that there is no excessive explorations for corresponding carboxylate for monometallic Pd catalysis alcohol aldehyde direct oxidation esterification.Cause
This, improving to Pd base single-metal reforming catalyst and being used to produce MMA has challenge but is also to have bright prospects.
Summary of the invention
A kind of catalyst of step oxidative esterification legal system methyl methacrylate, the catalyst is with oxide containing electron rich
Material be complex carrier, using Metal Palladium as active component, with rare earth metal be help active component, with surfactant be help
Agent, chemical general formula can be expressed as: XaPdbYc/Md- N, wherein Pd be palladium, X be surfactant be selected from polyvinyl alcohol (PVA) or
One of polyethylene glycol (PEG), Y are that rare earth element is selected from one of scandium, yttrium, lanthanum or cerium, and M is that electron rich oxide is selected from
One of MgO, ZnO, CaO, N are that carrier is selected from Al2O3、SiO2、TiO2、CeO2、ZrO2, kaolin, SBA-15, SBA-16,
One kind of MCM-41, ZSM-5, cimita, activated carbon, carbon black, carbon nanotube or graphene, a represent surfactant and metal
The mass ratio of palladium, a=0.001~10.0, preferably a=2.5~4.0；B represents the mass ratio of metal Pd and carrier, and b=0.1~
10.0, preferably b=4.0~7.0；C represents the mass ratio of rare earth element and palladium, c=0~1.0, preferably c=0.4~0.6；D generation
The mass ratio of table M and carrier, d=1.0~99.0, preferably d=2.0~20.0.
A kind of preparation method of the catalyst of step oxidative esterification legal system methyl methacrylate, the specific steps are as follows:
1) carrier will be added after electron rich oxide precursor salt and the dissolution of rare earth precursor salt, heating stirring to solvent is steamed
It is dry, grind into powder after obtained solid is dried, after gained powder is roasted 2h~5h in 350 DEG C~550 DEG C nitrogen atmospheres
It is down to room temperature and complex carrier is made；
2) complex carrier obtained in step 1) is added after Metal Palladium precursor salt and surfactant being dissolved in water, by institute
Addition reducing agent is restored after obtaining mixture stirring, respectively washs 3 obtained solids with deionized water and dehydrated alcohol after filtering,
By the solid after washing in 25 DEG C~80 DEG C dry 3h~can be prepared by the step oxidative esterification legal system methyl methacrylate for 24 hours
The catalyst of ester.
Preferably, thulium precursor salt described in step 1) is selected from lanthanum nitrate, scandium nitrate, yttrium nitrate or nitre
One of sour cerium.
Preferably, Metal Palladium precursor salt described in step 2) is selected from one of palladium chloride or palladium nitrate.
Preferably, reducing agent described in step 2) is selected from one of HCHO, hydrazine hydrate or sodium borohydride；It is preferred that 5wt%
HCHO-5wt%NaOH solution, additional amount is HCHO and the molar ratio of Pd is 1:10~30:1；The reduction reaction temperature is
20 DEG C~100 DEG C, preferably 60~80 DEG C；The reduction reaction time is 15min~4h, preferably 25~40min.
A kind of application of the catalyst of step oxidative esterification legal system methyl methacrylate, the specific steps are as follows: by a step
It is molten that the catalyst of oxidative esterification legal system methyl methacrylate is added to the mixing being made of methacrolein, methanol and polymerization inhibitor
In liquid, then passing to oxygen progress oxidative esterification reaction can be prepared by methyl methacrylate.
Preferably, the molar ratio of the methanol and methacrolein is 1~100, preferably 30~50.
Preferably, the polymerization inhibitor be selected from hydroquinone, methylnaphthohydroquinone, p-hydroxyanisole, tert-butyl catechol or
One of 2- tert-butyl hydroquinone.
Preferably, the flow of the oxygen is 10ml/min~30ml/min, preferably 18ml/min~22ml/min.
Preferably, the condition of the oxidative esterification reaction are as follows: 45 DEG C~85 DEG C of reaction temperature, preferably 55 DEG C~70 DEG C, instead
Answer 0.1~0.5MPa of pressure, preferably 0.1~0.2MPa, reaction time 2h~8h, preferably 3h~5h.
The principle of the present invention is: the catalyst of step oxidative esterification legal system methyl methacrylate provided by the present invention is
One kind is by main active Metal Palladium and rare earth, novel composite catalyst composed by surfactant and carrier；Wherein, it carries
Body is electron rich material, and surfactant is the protective agent containing the electron riches group such as hydroxyl, amino and alkoxy.It is anti-in catalysis
During answering, carrier and surfactant can provide electronics for active component Pd, so that Pd is in electron rich state, to mention
Ability (Diao YY, Yan RY, Zhang SJ, the etal.Effects of of high its activated methyl methacrylaldehyde, methanol and molecular oxygen
Pb and Mg doping in Al2O3-supported Pd catalyst on direct oxidative
esterification of aldehydes with alcohols to esters[J].Journal of Molecular
Catalysis A:Chemical,2009,303:35–42.)；In addition, Pd is wrapped up by surfactant moieties, this can cover Pd
Surface portion active site effectively inhibits reaction substrate excessive hydrogenation and depth to weaken its ability for adding hydrogen and oxidation
Side reaction (P.D.Scholes, A.G.A.Coombes, L.Illum, the etal.Detection and of oxidation
determination of surface levels of poloxamer and PVA surfactant on
biodegradable nanospheres using SSIMS and XPS[J].Journal of Controlled
Release,1999,59:261–278.)；In addition, the steric hindrance due to surfactant acts on, keep Metal Palladium mutual
Aggregation is restricted, to obtain high degree of dispersion and stable palladium nano-particles；And appropriate rare earth element, which is added, to be mentioned
The thermal stability of high catalyst, moreover it is possible to enhance its alkalinity, catalyst neutralisation surface portion acid site, to improve activity.
Relative to the existing catalyst and preparation method thereof for preparing MMA, advantages of the present invention is as follows:
(1) catalyst provided by the present invention is other than using active component palladium, also added surfactant and dilute
Earth metal.Special supply electronic structure is formed between active component, carrier and surfactant three overcomes existing oxidation
The disadvantages of conversion ratio and lower selectivity of esterification catalyst.
(2) method for preparing catalyst provided by the present invention has easy to operate, and active component particles size is easily controllable
And be evenly distributed, the advantages that precious metals pd utilization rate is high, and dosage is few and at low cost.
(3) catalyst prepared by the present invention is applied to the reaction of a step oxidative esterification legal system methyl methacrylate, removes
Have the advantages that high conversion rate and selectivity it is good outside, also have preparation process simple, reaction condition mild advantage.
Detailed description of the invention
Fig. 1 is catalyst PVA3-Pd5/MgO-Al2O3Infrared spectrogram；
Fig. 2 is catalyst PVA3-Pd5/MgO-Al2O3XPS spectrum figure.
Specific embodiment
Further below in conjunction with the embodiments with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, specific quality, reaction time in example
With the example that temperature, technological parameter etc. are also only in OK range, those skilled in the art is according to the present invention above-mentioned
Some nonessential modifications and adaptations that content is made all belong to the scope of protection of the present invention.Particular technique is not specified in embodiment
Or condition person, it is described technology or conditions or to be carried out according to the literature in the art according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be bought by market.
1 PVA of embodiment3-Pd5/MgO10-Al2O3Catalyst
PVA3-Pd5/MgO10-Al2O3Catalyst the preparation method is as follows:
(1) by 6.4gMg (NO3)2·6H2O is dissolved in 200ml deionized water, and carrier 10g γ-Al is added2O3, heating stirs
It mixes to solvent and is evaporated, grind into powder after obtained solid is dried roasts gained powder in 350 DEG C~550 DEG C nitrogen atmospheres
It is down to room temperature after 2h~5h, complex carrier MgO is made10-Al2O3；
(2) 0.225g PVA and 0.125g PdCl are taken2It is dissolved in 9ml deionized water, adds 0.0825g NaCl, often
Warm magnetic agitation to being completely dissolved, then plus 1.5g step (1) in the MgO for preparing10-Al2O3Then carrier stirs gained mixture
The solution that 10ml5wt%NaOH-5wt%HCHO is added after mixing carries out reduction reaction, and reduction reaction temperature is 60 DEG C, the recovery time
For 15min；It filters, is respectively washed obtained solid 3 times with deionized water and ethyl alcohol, finally in 80 DEG C of vacuum after reduction reaction
Dry 3h can be prepared by the PVA in drying box3-Pd5/MgO10-Al2O3Catalyst.To prepared PVA3-Pd5/MgO10-
Al2O3Catalyst carries out IR Characterization and XPS characterization: the results of FT-IR such as Fig. 1, the results showed that in 3000cm-1There is methyl at place
Or the vibration peak that methylene species are faint, in 3600cm-1Place illustrates that catalyst surface remains there are the infrared absorption peak of hydroxyl
There is organic matter PVA and contains great amount of hydroxy group.XPS characterization result is as shown in Figure 2: after surface modification PVA is processed, urging
The combination of active metal Pd can be deviated in agent, Pd5/MgO10-Al2O33d5/2The Pd of track0Combination can be
336.22V (Fig. 2 a), and become 335.78eV (Fig. 2 b) after PVA processing, same Pd5/MgO10-Al2O33d3/2Track
Pd0、3d5/2The Pd of track2+、3d3/2The Pd of track2+Combination can be both less than surfactant processing catalyst, illustrate Pd with
Have occurred electronics transfer phenomenon between surface modification PVA, part electronics transfer combines each track of Pd to Pd by PVA can be to
The offset of low combination energy direction, so that Pd is in electron rich state, this will increase substantially it for one step oxide ester of alcohol aldehyde
Change prepares the catalytic activity of carboxylate.
Use PVA3-Pd5/MgO10-Al2O3Catalyst passes through the reaction of a step oxidative esterification legal system methyl methacrylate
Steps are as follows: catalysis reaction is carried out in pressure-resistant reaction flask, reaction temperature is 60 DEG C, reaction pressure 0.1Mpa, and catalyst is thrown
Material is 0.4g, and polymerization inhibitor HQ's feeds intake as 100ppm, and reaction substrate MeOH's feeds intake as 20ml, and MAL's feeds intake as 1ml, O2Stream
20ml/min is measured, the content of sample detection product, calculates the conversion ratio of reaction substrate and the selectivity of product after successive reaction 4h,
It the results are shown in Table 1.
2 PVA of embodiment0.001-Pd10/MgO1.0-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the Mg in embodiment 1
(NO3)2·6H2The quality of O is changed to 0.64g, and the quality of PVA is changed to 0.00015g, PdCl2Quality be changed to 0.25g, NaCl's
Quality is changed to 0.165g, and the dosage of reducing agent 5wt%NaOH-5wt%HCHO is changed to 20ml, remaining condition is identical.
3 PVA of embodiment2.5-Pd4/MgO2.0-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the Mg in embodiment 1
(NO3)2·6H2The quality of O is changed to 1.28g, and the quality of PVA is changed to 0.15g, PdCl2Quality be changed to 0.1g, the quality of NaCl
It is changed to 0.066g, the dosage of reducing agent 5wt%NaOH-5wt%HCHO is changed to 8ml, remaining condition is identical.
4 PEG of embodiment4.0-Pd7/MgO20-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the Mg in embodiment 1
(NO3)2·6H2The quality of O is changed to 12.8g, and PVA is changed to 0.42g PEG, PdCl2Quality be changed to 0.175g, the quality of NaCl
It is changed to 0.1155g, the dosage of reducing agent 5wt%NaOH-5wt%HCHO is changed to 14ml, remaining condition is identical.
5 PEG of embodiment10.0-Pd0.1/MgO99-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the Mg in embodiment 1
(NO3)2·6H2The quality of O is changed to 12.8g, γ-Al203Quality be changed to 2.02g, PVA is changed to 0.015g PEG, PdCl2Matter
Amount is changed to 0.0025g, and the quality of NaCl is changed to 0.0017g, and the dosage of reducing agent 5wt%NaOH-5wt%HCHO is changed to 0.2ml,
Remaining condition is identical.
6 PVA of embodiment3-Pd5La0.4/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(1) it needs that 0.1263g La (NO is added in3)3·6H2O and 6.4g magnesium nitrate hexahydrate, which is dissolved in 200ml deionized water, to be dissolved,
Then carrier 10g γ-Al is being added2O3, remaining condition is identical.
7 PVA of embodiment3-Pd5La0.6/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(1) it needs that 0.1894g La (NO is added in3)3·6H2O and 6.4g magnesium nitrate hexahydrate, which is dissolved in 200ml deionized water, to be dissolved,
Then carrier 10g γ-Al is being added2O3, remaining condition is identical.
8 PVA of embodiment3-Pd5La1.0/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(1) it needs that 0.3156g La (NO is added in3)3·6H2O and 6.4g magnesium nitrate hexahydrate, which is dissolved in 200ml deionized water, to be dissolved,
Then carrier 10g γ-Al is being added2O3, remaining condition is identical.
9 PVA of embodiment3-Pd5Sc0.4/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(1) it needs that 0.2259g Sc (NO is added in3)3·6H2O and 6.4g magnesium nitrate hexahydrate, which is dissolved in 200ml deionized water, to be dissolved,
Then carrier 10g γ-Al is being added2O3, remaining condition is identical.
10 PVA of embodiment3-Pd5Y0.4/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(1) it needs that 0.1291g Y (NO is added in3)3·6H2O and 6.4g magnesium nitrate hexahydrate, which is dissolved in 200ml deionized water, to be dissolved, so
Carrier 10g γ-Al is being added afterwards2O3, remaining condition is identical.
The catalytic performance of catalyst obtained by 1 Examples 1 to 10 of table
Data are as shown in table 1, and with the increase of Pd content, the conversion ratio of MAL is continuously increased, and the selectivity of MMA first increases
After reduce；The amount that surfactant is added is not The more the better, there is a desired value, when additional amount is 0.001wt%,
The electron rich group hydroxy lazy weight that PVA is provided to activate Pd completely；When additional amount is 10wt%, that wraps up around Pd has
Machine polymer is more and covers excessive effective active site.In addition, the addition of appropriate rare earth metal, can be improved target production
The selectivity of object, as shown in Example 7, the selectivity that the conversion ratio of MAL is 98.0%, MMA are 87.5%.
11 PVA of embodiment3-Pd5/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) dosage of the reducing agent 5wt%NaOH-5wt%HCHO solution in is 0.05ml, and reduction reaction temperature is 20 DEG C, when reduction
Between be 4h, remaining condition is identical.
PVA3-Pd5/MgO10-Al2O3The reaction condition of one step oxidative esterification legal system methyl methacrylate of catalyst
Become: reaction temperature is 45 DEG C, reaction pressure 0.2Mpa, and catalyst feeds intake as 0.4g, polymerization inhibitor methylnaphthohydroquinone feed intake for
100ppm's, reaction substrate MeOH feeds intake as 5ml, and MAL's feeds intake as 10ml, O2It is taken after flow 10ml/min, successive reaction 8h
Sample detects the content of product, calculates the conversion ratio of reaction substrate and the selectivity of product, the results are shown in Table 2.
12 PVA of embodiment3-Pd5/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) dosage of the reducing agent 5wt%NaOH-5wt%HCHO solution in is 13.5ml, and reduction reaction temperature is 80 DEG C, when reduction
Between be 25min, remaining condition is identical.
PVA3-Pd5/MgO10-Al2O3The reaction condition of one step oxidative esterification legal system methyl methacrylate of catalyst
Become: reaction temperature is 55 DEG C, reaction pressure 0.5Mpa, and catalyst feeds intake as 0.4g, the throwing of polymerization inhibitor p-hydroxyanisole
Material is 100ppm, and reaction substrate MeOH's feeds intake as 14.7ml, and MAL's feeds intake as 1ml, O2Flow 18ml/min, successive reaction
The content of sample detection product after 3h calculates the conversion ratio of reaction substrate and the selectivity of product, the results are shown in Table 2.
13 PVA of embodiment3-Pd5/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) reducing agent needed in replaces with 80wt% hydrazine hydrate, dosage 0.3ml, remaining condition is identical.
PVA3-Pd5/MgO10-Al2O3The reaction condition of one step oxidative esterification legal system methyl methacrylate of catalyst
Become: reaction temperature is 70 DEG C, reaction pressure 0.5Mpa, and catalyst feeds intake as 0.4g, polymerization inhibitor tert-butyl catechol
It feeds intake as 100ppm, reaction substrate MeOH's feeds intake as 24.5ml, and MAL's feeds intake as 1ml, O2Flow 22ml/min is continuous anti-
The content for answering sample detection product after 3h, calculates the conversion ratio of reaction substrate and the selectivity of product, the results are shown in Table 2.
14 PVA of embodiment3-Pd5/MgO10-Al2O3Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) reducing agent in needing in replaces with sodium borohydride, dosage 0.16g: reduction reaction temperature is 100 DEG C, and the recovery time is
40min, remaining condition are identical.
PVA3-Pd5/MgO10-Al2O3The reaction condition of one step oxidative esterification legal system methyl methacrylate of catalyst
Become: reaction temperature is 85 DEG C, reaction pressure 0.5Mpa, and catalyst feeds intake as 0.4g, polymerization inhibitor 2- tert-butyl hydroquinone
Feed intake as 100ppm, reaction substrate MeOH's feeds intake as 24.5ml, and MAL's feeds intake as 0.5ml, O2Flow 30ml/min, even
The content of sample detection product, calculates the conversion ratio of reaction substrate and the selectivity of product, the results are shown in Table 2 after continuous reaction 2h.
The catalytic performance of 2 embodiment of table, 11~14 gained catalyst
Data are as shown in table 2, and reductant concentration is low in embodiment 11 and reducing condition is mild, the Pd particle restored
Diameter is bigger than normal, and active site is considerably less than the Pd particle restored in embodiment 1, when the reaction time extends to 8h, metering system
The conversion ratio of aldehyde reaches 100%.When the molar ratio of reducing agent HCHO and Pd in embodiment 12 are 30:1, alcohol aldehyde molar ratio is 30:1
When, the selectivity of methyl methacrylate significantly improves.Solution phase chemical reduction restores to obtain precious metals pd, reducing agent formaldehyde,
Hydrazine hydrate can achieve the effect that similar with sodium borohydride.For a step oxidative esterification reaction, extends the reaction time, help to increase
The conversion ratio of methacrolein；Alcohol aldehyde molar ratio is improved, the selectivity for increasing methyl methacrylate is conducive to.In embodiment 14
When alcohol aldehyde molar ratio is 100:1, the selectivity of methyl methacrylate reaches 91.7%, but for actual industrial production, mistake
High alcohol aldehyde ratio does not have practical application value.
15 PVA of embodiment3-Pd5/MgO10-TiO2Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) γ-Al in2O3Replace with TiO2, dosage 10g, remaining condition is identical.Catalysis reaction examination condition is examined with embodiment 1
It comments and the results are shown in Table 3.
16 PVA of embodiment3-Pd5/MgO10-CeO2Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with CeO2, dosage 10g, remaining condition is identical.Catalysis reaction examination condition is the same as embodiment 1, examination knot
Fruit is shown in Table 3.
17 PVA of embodiment3-Pd5/MgO10-ZrO2Catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with ZrO2, dosage 10g, remaining condition is identical.Catalysis reaction examination condition is the same as embodiment 1, examination knot
Fruit is shown in Table 3.
18 PVA of embodiment3-Pd5/MgO10- SBA-15 catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with molecular sieve SBA-15, dosage 10g, remaining condition is identical.The catalysis reaction same embodiment of examination condition
1, appraisal result is shown in Table 3.
19 PVA of embodiment3-Pd5/MgO10- MCM-41 catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with molecular sieve MCM-41, dosage 10g, remaining condition is identical.The catalysis reaction same embodiment of examination condition
1, appraisal result is shown in Table 3.
20 PVA of embodiment3-Pd5/MgO10- ZSM-5 catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with molecular sieve ZSM-5, dosage 10g, remaining condition is identical.The catalysis reaction same embodiment of examination condition
1, appraisal result is shown in Table 3.
21 PVA of embodiment3-Pd5/MgO10Kaolin catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with kaolin, dosage 10g, remaining condition is identical.Catalysis reaction examination condition is the same as embodiment 1, examination
It the results are shown in Table 3.
22 PVA of embodiment3-Pd5/MgO10Cimita catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with cimita, dosage 10g, remaining condition is identical.Catalysis reaction examination condition is the same as embodiment 1, examination
It the results are shown in Table 3.
23 PVA of embodiment3-Pd5/MgO10Activated carbon catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with activated carbon, dosage 10g, remaining condition is identical.Catalysis reaction examination condition is the same as embodiment 1, examination
It the results are shown in Table 3.
24 PVA of embodiment3-Pd5/MgO10Carbon nano-tube catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with carbon nanotube, dosage 10g, remaining condition is identical.Catalysis reaction examination condition is examined with embodiment 1
It comments and the results are shown in Table 3.
25 PVA of embodiment3-Pd5/MgO10Graphen catalyst
The step of preparation method of catalyst is used similarly to Example 1, the difference is that by the step in embodiment 1
(2) Al in2O3Replace with graphene, dosage 10g, remaining condition is identical.Catalysis reaction examination condition is the same as embodiment 1, examination
It the results are shown in Table 3.
The catalytic performance of 3 embodiment of table, 15~25 gained catalyst
Data are as shown in table 3, and after electron rich oxide M gO modified support obtains complex carrier, catalytic activity is obviously improved,
The active promotion degree of different carriers is different.The catalyst of the modified obtained complex carrier synthesis of electron rich carbon material, it is special
It is not graphene, under 1 same reaction evaluation condition of embodiment, methyl methacrylate selectively reaches 88.7%.Consider
To the practical engineering application of catalyst, such as the shadow of carrier cost of manufacture, wearability, catalyst bulk density, service life factor
It rings, carrier S BA-15 is a better choice.The modified catalyst obtained of SBA-15 in embodiment 18, with embodiment 1
Under same reaction evaluation condition, the conversion ratio of methacrolein is 93.3%, and the selectivity of methyl methacrylate is 84.9%.
1 CTAB of comparative example3-Pd5/MgO-Al2O3Catalyst
Using similarly to Example 1 the step of prepare catalyst, the difference is that the PVA in embodiment 1 is changed to
The CTAB of quality, group, which is made, becomes CTAB3-Pd5/MgO-Al2O3Catalyst.
For catalysis reaction examination condition with embodiment 1, appraisal result is shown in Table 4.
2 SDBS of comparative example3-Pd5/MgO-Al2O3Catalyst
Using similarly to Example 1 the step of prepare catalyst, the difference is that the PVA in embodiment 1 is changed to
The SDBS of quality, group, which is made, becomes SDBS3-Pd5/MgO-Al2O3Catalyst.
For catalysis reaction examination condition with embodiment 1, appraisal result is shown in Table 4.
3 PVA of comparative example1-Pd5/MgO-Al2O3Catalyst
Using similarly to Example 8 the step of prepare catalyst, the difference is that by the quality of the PVA in embodiment 1
0.075g is changed to by 0.225g, group, which is made, becomes PVA1-Pd5/MgO-Al2O3Catalyst.
For catalysis reaction examination condition with embodiment 1, appraisal result is shown in Table 4.
4 PVA of comparative example5-Pd5/MgO-Al2O3Catalyst
Using similarly to Example 1 the step of prepare catalyst, the difference is that by the quality of the PVA in embodiment 1
0.375g is changed to by 0.25g, group, which is made, becomes PVA5-Pd5/MgO-Al2O3Catalyst.
For catalysis reaction examination condition with embodiment 1, appraisal result is shown in Table 4.
5 Pd of comparative example5/MgO-Al2O3Catalyst
Using similarly to Example 1 the step of prepare catalyst, the difference is that by the quality of the PVA in embodiment 1
0g is changed to by 0.25g, group, which is made, becomes Pd5/MgO-Al2O3Catalyst.
The catalytic performance of catalyst obtained by 4 the Comparative Examples 1 to 5 of table
Data are as shown in table 4, and when selection is rich in the surface modification PVA of hydroxyl, catalytic activity is compared to Pd5/MgO-
Al2O3It is improved largely；When selection contains Br-Surfactant CTAB and contain Na+Surfactant SDBS when, nothing
Method provides electronics for Pd to achieve the purpose that activate Pd, and as a result catalytic activity is very low.In addition, surface modification PVA is added
Amount is also not The more the better, but has a desired value, when additional amount is 1wt%, the electron rich group hydroxy number of PVA offer
Amount is not enough to activate Pd completely；When additional amount is 5wt%, the organic polymer PVA wrapped up around Pd is more and covers
More effective active sites；When additional amount is 3wt%, the quantity for the electron rich group hydroxy that PVA is provided is just suitable, is Pd
Suitable electronics is provided, the ability of Pd priming reaction substrate is improved；Secondly, Pd is wrapped up by surfactant moieties, Pd table is covered
Face part active site weakens its ability for adding hydrogen and oxidation, it is suppressed that the pair of reaction substrate excessive hydrogenation and deep oxidation
Reaction；In addition, the steric restriction due to surfactant acts on, the aggregation for keeping palladium particle mutual is restricted, to obtain
High degree of dispersion and stable palladium nano-particles.Therefore, the monometallic Pd catalyst obtained has good reactivity, strictly according to the facts
It applies shown in example 1, the selectivity that the conversion ratio of MAL is 97.9%, MMA is 85.8%.
Claims (10)
1. a kind of catalyst of a step oxidative esterification legal system methyl methacrylate, which is characterized in that the catalyst is containing richness
The material of electronics oxide is complex carrier, is to help active component with rare earth metal using Metal Palladium as active component, living with surface
Property agent be auxiliary agent, chemical general formula can be expressed as: XaPdbYc/Md- N, wherein Pd is palladium, and X is that surfactant is selected from polyethylene
One of alcohol (PVA) or polyethylene glycol (PEG), Y are that rare earth element is selected from one of scandium, yttrium, lanthanum or cerium, and M is electron rich
Oxide is selected from one of MgO, ZnO, CaO, and N is that carrier is selected from Al2O3、SiO2、TiO2、CeO2、ZrO2, kaolin, SBA-
15, one kind of SBA-16, MCM-41, ZSM-5, cimita, activated carbon, carbon black, carbon nanotube or graphene, it is living that a represents surface
The mass ratio of property agent and Metal Palladium, a=0.001~10.0, preferably a=2.5~4.0；B represents the quality of metal Pd and carrier
Than b=0.1~10.0, preferably b=4.0~7.0；C represents the mass ratio of rare earth element and palladium, c=0~1.0, preferably c=
0.4~0.6；D represents the mass ratio of M and carrier, d=1.0~99.0, preferably d=2.0~20.0.
2. a kind of preparation method of the catalyst of step oxidative esterification legal system methyl methacrylate as described in claim 1,
It is characterized in that, specific step is as follows:
1) carrier being added after electron rich oxide precursor salt and the dissolution of rare earth precursor salt, heating stirring to solvent is evaporated,
Grind into powder after obtained solid is dried is down to after gained powder is roasted 2h~5h in 350 DEG C~550 DEG C nitrogen atmospheres
Complex carrier is made in room temperature；
2) complex carrier obtained in step 1) is added after Metal Palladium precursor salt and surfactant being dissolved in water, gained is mixed
Addition reducing agent is restored after closing object stirring, is respectively washed 3 obtained solids with deionized water and dehydrated alcohol after filtering, will be washed
Solid after washing is in 25 DEG C~80 DEG C dry 3h~can be prepared by the step oxidative esterification legal system methyl methacrylate for 24 hours
Catalyst.
3. the preparation method of the catalyst of step oxidative esterification legal system methyl methacrylate as claimed in claim 2, special
Sign is that thulium precursor salt is in lanthanum nitrate, scandium nitrate, yttrium nitrate or cerous nitrate described in step 1)
It is a kind of.
4. the preparation method of the catalyst of step oxidative esterification legal system methyl methacrylate as claimed in claim 2, special
Sign is that Metal Palladium precursor salt described in step 2) is selected from one of palladium chloride or palladium nitrate.
5. the preparation method of the catalyst of step oxidative esterification legal system methyl methacrylate as claimed in claim 2, special
Sign is that reducing agent described in step 2) is selected from one of HCHO, hydrazine hydrate or sodium borohydride；It is preferred that 5wt%HCHO-
5wt%NaOH solution, additional amount is HCHO and the molar ratio of Pd is 1:10~30:1；The reduction reaction temperature be 20 DEG C~
100 DEG C, preferably 60~80 DEG C；The reduction reaction time is 15min~4h, preferably 25~40min.
6. a kind of application of the catalyst of step oxidative esterification legal system methyl methacrylate as described in claim 1, special
Sign is, the specific steps are as follows: the catalyst of a step oxidative esterification legal system methyl methacrylate is added to by metering system
In the mixed solution of aldehyde, methanol and polymerization inhibitor composition, then passing to oxygen progress oxidative esterification reaction can be prepared by metering system
Sour methyl esters.
7. the application of the catalyst of step oxidative esterification legal system methyl methacrylate as claimed in claim 6, feature exist
In the molar ratio of the methanol and methacrolein is 1~100, preferably 30~50.
8. the application of the catalyst of step oxidative esterification legal system methyl methacrylate as claimed in claim 6, feature exist
In the polymerization inhibitor is selected from hydroquinone, methylnaphthohydroquinone, p-hydroxyanisole, tert-butyl catechol or 2- tert-butyl to benzene
One of diphenol.
9. the application of the catalyst of step oxidative esterification legal system methyl methacrylate as claimed in claim 6, feature exist
In the flow of the oxygen is 10ml/min~30ml/min, preferably 18ml/min~22ml/min.
10. the application of the catalyst of step oxidative esterification legal system methyl methacrylate as claimed in claim 6, feature exist
In the condition of the oxidative esterification reaction are as follows: 45 DEG C~85 DEG C of reaction temperature, preferably 55 DEG C~70 DEG C, reaction pressure 0.1~
0.5MPa, preferably 0.1~0.2MPa, reaction time 2h~8h, preferably 3h~5h.
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