CN106040291B - A kind of preparation method and applications of core-shell material catalyst - Google Patents
A kind of preparation method and applications of core-shell material catalyst Download PDFInfo
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- CN106040291B CN106040291B CN201610495069.5A CN201610495069A CN106040291B CN 106040291 B CN106040291 B CN 106040291B CN 201610495069 A CN201610495069 A CN 201610495069A CN 106040291 B CN106040291 B CN 106040291B
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- oxide
- molecular sieve
- core
- catalyst
- shell material
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 66
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 239000002351 wastewater Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7053—A-type
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7607—A-type
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of preparation method and applications of core-shell material catalyst, belongs to core-shell catalyst preparation technical field.The nuclear material transition metal oxide of catalyst of the present invention coats one layer of molecular screen membrane in its appearance by positive and negative polyelectrolyte-modified electrification, by electrostatic self-assembled method, i.e. oxide is core, and molecular sieve is shell, is abbreviated as MɑOβ@molecular sieve (M is one of transition metal element, and ɑ, β are chemical valence)；It is set to make core M with the effect of certain density ammonium chloride againɑOβIt is changed into corresponding chlorine ammonia salt M (NH3)nClβ(n is the number of ammonia molecule, and being worth is 1 ~ 8)；It is MCl that low-temperature bake, which has deviate from the final catalyst structure after ammonia,β@molecular sieve, the catalyst can be used in urea or carbamate and the ester exchange reaction of phenol generates in the system of diphenyl carbonate, the ammonia that can be generated with reaction system carries out new Coordination Adsorption to which driving a reaction moves right, product of diphenyl carbonate yield is still good using catalytic effect after 5 times up to 90% or more.
Description
Technical field
The present invention relates to a kind of preparation method and applications of core-shell material catalyst, belong to core-shell catalyst preparation skill
Art field.
Background technique
" green " intermediate diphenyl carbonate (Diphenyl Carbonate, the letter of organic compound and high molecular material
DPC) molecular formula is referred to as C6H5OCOOC6H5, be used primarily in plastics industry, a most significant purposes be exactly and bisphenol-A into
Row polycondensation reaction polycarbonate synthesis (PC), polycarbonate have good optical property, very high anti-Beating Strength, good
The outstanding performance such as thermal stability and be widely used, such as in Sheet material for eyeglass, aerospace, automobile manufacture, pesticide, medical treatment, building
Application in field.The total quantity consumed of PC is only second to polyamide (PA) in engineering plastics and occupies second at present.The whole world in 2005
Aggregate consumption is more than 4,500,000 tons.The consumption figure of PC will be more than PA from now on.However, being in not assist with the burning hot phenomenon in the consumption market PC
Readjust the distribution exhibition is that but process units is had in state at a low ebb, current only a small number of manufacturers always for domestic PC technological development,
About 5000 tons of gross annual output ability, and grade is low, it is difficult to meet the market demand, it is big from the import of the states such as Japan, South Korea, U.S. every year
Product is measured, totally 63.48 ten thousand tons of country's import PC and PC alloy in 2005, imbalance between supply and demand is very prominent.In addition to this, DPC may be used also
Used in some other chemical products are synthesized, such as p-hydroxybenzoate, poly- arylcarbonic acid rouge, monoisocyanates and diisocyanate
Deng also acting as the plasticizer etc. of polyamide, polyester, in recent years, closed with environmentally friendly by reaction material of DPC and bisphenol-A
At a large amount of exploitations of polycarbonate new process, DPC becomes the compound to attract attention.
The traditional approach of DPC is synthesized with phosgene and phenol (PhOH) as raw material.However, phosgene has severe toxicity and to production equipment
Corrosivity is big, this causes many unfavorable factors to environmental protection and production safety, and phosgenation is made using a large amount of methylene chloride
For solvent can generate a large amount of villaumite and production equipment is caused to be corroded.These comprehensive unfavorable factors, people in past decades
Just constantly seek " green " synthetic method.Since eighties of last century the seventies, more than ten non-light have successively been had developed both at home and abroad
Gas method diphenyl carbonate synthesis (DPC) technique.Currently, the non-phosgene of synthesis DPC mainly has the oxidation carbonyl of ester-interchange method, phenol
Base method.Oxidation carbonylation method is using phenol, carbon monoxide and oxygen as raw material direct carbonate synthesis two under the action of catalyst
The reaction method of phenyl ester, however the synthetic method system is complicated and high as major catalyst price using precious metal such as platinum
Expensive, by-product shipwreck removing causes DPC hydrolysis, CO to be easily oxidized to CO2Etc. reasons can not temporarily put into production this feature significantly
Limit its process of industrialization；Ester-interchange method refers to dialkyl carbonate and phenol, dialkyl oxalate and phenol, carbonic acid two
Methyl esters (DMC) synthesizes the synthetic method of DPC with phenylacetate.It integrates, ester-interchange method is based primarily upon dimethyl carbonate at present
It is reaction method of the raw material under catalyst with phenol, this synthetic method " green ", investment are small, but it is apparent the disadvantage is that difficult
Reaction balance is set to move right to break the limitation of thermodynamical equilibrium, by-product carbinol and dimethyl carbonate formation azeotropic mixture,
It is difficult to be separated.Therefore, this project group selection carbamate, which react with phenol, prepares diphenyl carbonate, reaction product
Only ammonia, if the ammonia after reaction can be adsorbed by the limitation that can break thermodynamically in time, so that balance moves right.
So developing one or more of excellent catalytic effects, new catalyst cheap and easy to get and recyclable is to promote diphenyl carbonate
The key of process of industrialization.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome carbamate and phenol ester-interchange method carbonate synthesis hexichol
Ester thermodynamics is difficult to the shortcomings that breaking, prepare it is a kind of it is cheap be easy to get, high catalytic efficiency, reuse often for carbon
The core-shell material catalyst of diphenyl phthalate synthesis.
The purpose of the present invention is to provide a kind of preparation methods of core-shell material catalyst, specifically includes the following steps:
(1) by transition metal oxide be impregnated in mass percent concentration be 0.3~1.0 % positive/negative polyelectrolyte it is molten
0.5~2 h in liquid, centrifugal filtration, residue washing (Electrostatic Absorption the solute of polyelectrolyte)；Filter residue repeats above-mentioned mistake after washing
Journey 2~secondary, positive polyelectrolyte solution and negative polyelectrolyte solution are used alternatingly during entirely immersing, i.e., that immerses for the first time is poly-
If electrolyte is positive when polyelectrolyte solution, immersed for the second time with negative polyelectrolyte solution；
(2) filter residue that step (1) obtains is transferred to mass percent concentration in the ratio of 1 ~ 20 g/L is 2% ~ 10%
(deionized water is added makes molecular sieve solution mass fraction percent concentration 2~10% simultaneously to A-type nano zeolite molecular sieve suspension
It is allowed to disperse with ultrasonic wave decentralized processing) 0.5 ~ 12 h of middle processing, so that A-type nano zeolite molecular sieve is passed through electrostatic interaction equably
It is adsorbed on oxide particle surface, the solid after being filtered, washed, drying is placed in 90 ~ 120 DEG C of crystallization in molecular sieve initial reaction liquid
1 ~ 5 h(of processing makes it carry out secondary cladding and diauxic growth, and oxide surface is made to obtain one layer of fine and close molecular screen membrane), mistake
The ammonium chloride solution for being again 10% ~ 90% with mass percent concentration after filter, washing, vacuum drying is reacted at 60 ~ 140 DEG C
2 ~ 10h obtains M (NH3)nClβ@molecular sieve, wherein n=1 ~ 8, are coordinated number, low-temperature bake after being filtered, washed, being dried in vacuo for ammonia
Core-shell material catalyst MCl is made in (it is made to remove ammonia and polyelectrolyte in nuclear material)β@molecular sieve.
Preferably, transition metal oxide of the present invention be zinc oxide, copper oxide, cadmium oxide, nickel oxide, cobalt oxide,
Iron oxide, manganese oxide, chromium oxide, scandium oxide, titanium oxide, vanadium oxide, lanthana, cerium oxide, praseodymium oxide, one in neodymia
Kind.
Preferably, positive polyelectrolyte of the present invention is phthalic acid diethylene glycol diacrylate.
Preferably, negative polyelectrolyte of the present invention is poly- p styrene sulfonic acid.
Preferably, low-temperature bake of the present invention is 0.5 ~ 2 h of processing under the conditions of 250 ~ 300 DEG C.
Another object of the present invention is to the core-shell material catalyst that the present invention is prepared to be used for urea or amino first
In acid esters and phenol reactant diphenyl carbonate synthesis, reaction carries out 2 ~ 48 h at 190 DEG C ~ 210 DEG C.
A-type nano zeolite molecular sieve described in step (2) of the present invention is prepared for existing method；Step (2) of the present invention
Described in molecular sieve initial reaction liquid be reaction solution during system with molecular sieve for preparing is standby before crystallization.
Transition metal oxide of the present invention be conventional method be prepared have specific morphology (such as spherical, just
Rectangular, rectangle, spheroid shape, cylindricality etc.) diameter be 1 ~ 5 micron of transition metal oxide or rare-earth oxide.
Catalyst prepared by the present invention generates carbonic acid two in the ester exchange reaction of urea (or carbamate) and phenol
During phenyl ester, nuclear material transition metal chloride constantly adsorbs ammonia until being saturated then by the coupling of reaction
Catalytic efficiency decreases, and the ammonia for selecting the catalyst of suitable additive amount that can realize that reaction system generates all was coordinated to
It crosses to push the forward direction of reaction mobile in metal chloride, and then the production capacity of diphenyl carbonate is improved.
Beneficial effects of the present invention:
(1) yield of carbonate production by transesterification diphenyl ester is improved, yield is up to 90% or more；(2) of the present invention to urge
Agent synthesis technology is simple, raw material is easy to get；Catalyst shell material obtained is fine and close NaA type molecular sieve film, and aperture exists
0.4nm or so, the ammonia that can effectively make ester exchange reaction system generate are coordinated by duct and nuclear material, prevent it
His macromolecular such as phenol oxygen root is coordinated to improve the conversion ratio of reaction；(4) catalyst morphology is controllable, size tunable, after 5 times
Catalytic effect is still good.(5) catalyst regeneration can be made by simply heat treatment.
Specific embodiment
The present invention is described in further details below with reference to example, but protection scope of the present invention is not limited in described
Hold.
Embodiment 1
The method for preparing the zinc chloride catalyst of molecular sieve cladding is as follows:
(1) " the Preparation of that Easir A. Khan, Enping Hu, Zhiping Lai etc. is delivered is referred to
Metal oxide/zeolite core-shell nanostructures " prepares the spherical oxidation that partial size is 1~5 micron
Zinc powder body determines that the zinc oxide surface of solids is positively charged using conventional Zeta potential analyzer；
(2) preparation of molecular sieve refers to " Mechanism of Zeolite A Nanocrystal Growth from
Colloids at Room Temperature”
1. pressing SiO2:Al2O3:NaOH: (TMA)2O:H2The molar ratio of O is the ratio of 11.25:1.8:1.2:13.4:700
Example weighs reaction raw materials silica solution (30% in water), aluminium isopropoxide, sodium hydroxide, tetramethyl corresponding to above-mentioned substance
Ammonium hydroxide, deionized water, it is spare；
2. weighing 8.0 g of deionized water in step (1), 9.0 g of silica solution is added under stirring at normal temperature, stirs,
It makes and carrys out solution A；
3. 28 g of deionized water is weighed, it is under room temperature magnetic agitation that 3.0 g aluminium isopropoxides, 9.2 g (1M) NaOH is molten
Liquid and 20 g tetramethylammonium hydroxide, are configured to solution B；
4. solution A is poured into B solution, uniformly ageing is stirred at room temperature and obtains molecular sieve initial reaction liquid after 3 days；
5. molecular sieve initial reaction liquid is put into the hydrothermal reaction kettle of 100ml, 80 DEG C crystallization 1 day, after crystallization product pass through
Ultrasonic (150W, 5min) is centrifugated (1000rpm, 30min), nanometer is obtained after 80 DEG C of dryings 12 h, 550 DEG C of 2 h of calcining
Type A zeolite molecular sieve selects Zeta potential analyzer to carry out surface potential analysis to gained molecular sieve to determine its surface band
Negative electricity.
(3) step (1) zinc oxide solid 2g is immersed in the poly- p styrene sulfonic acid that 1 L mass percent concentration is 0.3%
(PSS) 0.5 h is handled in solution, 6000rpm centrifugation is filtered, and filter residue is washed with deionized water 3 times；Filter residue is immersed in again after washing
0.5 h is handled in phthalic acid diethylene glycol diacrylate (PDDA) solution of mass percent concentration 0.3%, filters, wash
Solid is washed, is finally handled again with the PSS of mass percent concentration 0.3%；
(4) solid particle made from step (3) is transferred to quality percentage after ultrasonic wave decentralized processing in the ratio of 1g/L
2 h are handled in the A-type nano zeolite molecular sieve suspension that specific concentration is 2 %, electrostatic adsorption is made it through and completes primary packet
Cover to form core-shell material, filter, solid be placed in again after drying molecular sieve initial reaction liquid (step 4. obtained at the beginning of molecular sieve
Beginning reaction solution) in be filtered, washed after 90 DEG C of 1 h of crystallization, dry the zinc oxide core-shell material of obtained molecular sieve cladding.
(5) core-shell material of molecular sieve coating zinc oxide obtained by step (4) is placed in mass percent concentration is 10 %'s
Reaction kettle is gone in ammonium chloride solution makes nuclear material zinc oxide react with it generation chlorine ammonia zinc, and reaction condition is 140 DEG C, 2 h.
(6) by step (5) resulting materials Zn (NH3)2Cl2@molecular screen material is placed in 300 DEG C of 0.5 h of roasting in Muffle furnace and obtains
Catalyst Z nCl2@molecular sieve.
Above-mentioned catalyst is applied into the reaction in urea and phenol reactant diphenyl carbonate synthesis (reaction equation is as follows)
2 h, conversion rate of urea 98.8% are carried out at 210 DEG C, diphenyl carbonate yield is 97.3%, carbonic acid two after catalyst uses 5 times
Phenyl ester yield is 1) 93.8%(is shown in Table；
。
Embodiment 2
The method for preparing the caddy catalyst of molecular sieve cladding is as follows:
(1) M Risti, " the Formation and properties that S Popovi, S Musi etc. is delivered are referred to
of Cd (OH) 2And CdO particles " prepares the spherical cadmium oxide powder that partial size is 1~5 micron, using routine
Zeta potential analyzer determines that the cadmium oxide surface of solids is negatively charged；
(2) preparation of molecular sieve refers to " Investigations on hydrothermal synthesis
parameters in preparation of nanoparticles of LTA zeolite with the aid of
TMAOH”
1. pressing SiO2:Al2O3:Na2O: (TMA)2O:H2The molar ratio of O is the ratio of 6:1:0.32:7.27:350, is weighed
Sodium hydroxide, tetramethylammonium hydroxide, silica solution, aluminium isopropoxide and deionized water are spare；
2. 0.26g NaOH and 53.01g (TMA)2O is dissolved in 19.68g deionized water；
3. the solution in 2. is divided into two parts of A, B；
4. 4.21g aluminium isopropoxide is added in A and stirs evenly, 7.21g silica solution is added in B and stirs evenly,
Finally B solution is poured into A and is uniformly mixed to obtain molecular sieve initial reaction liquid.
5. molecular sieve initial reaction liquid is put into the hydrothermal reaction kettle of 50 ml, 100 DEG C of 12 h of crystallization, product after crystallization
It through ultrasonic (150W, 5min), is centrifugated (15000rpm, 25min), washing to pH < 9,80 DEG C of 12 h of drying, 550 DEG C of calcinings 2
A-type nano zeolite molecular sieve is obtained after h, and Zeta potential analyzer is selected to carry out surface potential analysis to gained molecular sieve with true
It is negatively charged to make its surface.
(3) step (1) cadmium oxide solid 4g is immersed in the phthalic acid diethyl that 1 L mass percent concentration is 0.5%
0.8 h is handled in omega-diol diacrylate (PDDA) solution, 6000rpm centrifugation is filtered, and filter residue is washed with deionized water 3 times；Washing
Filter residue is immersed in poly- p styrene sulfonic acid (PSS) solution of mass percent concentration 0.5% again and handles 0.8 h afterwards, filters, washes
Solid is washed, is finally handled again with the PDDA of mass percent concentration 0.5%；
(4) solid particle made from step (3) is transferred to quality percentage after ultrasonic wave decentralized processing in the ratio of 5 g/L
1.8 h are handled in the A-type nano zeolite molecular sieve suspension that specific concentration is 4%, electrostatic adsorption is made it through and completes primary packet
Cover to form core-shell material, filter, solid be placed in again after drying molecular sieve initial reaction liquid (step 4. obtained at the beginning of molecular sieve
Beginning reaction solution) in be filtered, washed after 100 DEG C of 2 h of crystallization, dry the cadmium oxide core-shell material of obtained molecular sieve cladding.
(5) core-shell material of the cladding cadmium oxide of molecular sieve obtained by step (4) is placed in mass percent concentration is 20 %'s
Reaction kettle is gone in ammonium chloride solution makes nuclear material cadmium oxide react with it generation chlorine ammonia cadmium, and reaction condition is 120 DEG C, 4 h.
(6) by step (5) resulting materials Cd (NH3)2Cl2@molecular screen material is placed in 280 DEG C of 1.5 h of roasting in Muffle furnace
Obtain catalyst CdCl2@molecular sieve.
Above-mentioned catalyst is applied into the reaction in urea and phenol reactant diphenyl carbonate synthesis (reaction equation is as follows)
12 h, conversion rate of urea 97.1% are carried out at 200 DEG C, diphenyl carbonate yield is 96.5%, carbonic acid two after catalyst uses 5 times
Phenyl ester yield is 1) 90.5%(is shown in Table；
。
Embodiment 3
The method for preparing the cobalt-chloride catalyst of molecular sieve cladding is as follows:
(1) Y the Li, " Morphology- that J Zhang, Z Liu, M Liu, H Lin, R Che etc. is delivered are referred to
dominant microwave absorption enhancement and electron tomography
It is 1~5 micron that characterization of CoO self-assembly 3D nano-flowers ", which prepares partial size,
Spherical cobalt oxide powder determines that the cobalt oxide surface of solids is negatively charged using conventional Zeta potential analyzer；
(2) preparation of molecular sieve refers to " Synthesis and Characterization of High-Quality
Zeolite LTA and FAU Single Nanocrystals”
1. pressing SiO2:Al2O3:NaCl: (TMA)2O:H2The molar ratio of O is the ratio of 3:1:0.007:1.5:276, is weighed
Aluminium powder, ethyl orthosilicate, tetramethylammonium hydroxide, sodium chloride and water are spare；
2. aluminium powder and sodium hydroxide are dissolved in the solution of tetramethylammonium hydroxide, it is 0.2 micro- that this solution passes through aperture again
The filter of rice is to remove impurity；
3. ethyl orthosilicate is slowly dropped in above-mentioned clarified solution system under stiring, two are aged after stirring to clarify
It obtains molecular sieve initial reaction liquid；
4. molecular sieve initial reaction liquid is put into the hydrothermal reaction kettle of 250ml, 100 DEG C crystallization 14 days, product after crystallization
It through ultrasonic (150W, 5min), is centrifugated (1000rpm, 30min), is received after 80 DEG C of dryings 12 h, 550 DEG C of 2 h of calcining
Rice type A zeolite molecular sieve selects Zeta potential analyzer to carry out surface potential analysis to gained molecular sieve to determine its surface
It is negatively charged.
(3) 6 g of step (1) cobalt oxide solid is immersed in the phthalic acid diethyl that 1L mass percent concentration is 0.6%
1 h is handled in omega-diol diacrylate (PDDA) solution, 6000rpm centrifugation is filtered, and filter residue is washed with deionized water 3 times；After washing
Filter residue is immersed in poly- p styrene sulfonic acid (PSS) solution of mass percent concentration 0.6% again and handles 1 h, is filtered, washed solid
Body is finally handled with the PDDA of mass percent concentration 0.6% again；
(4) solid particle made from step (3) is transferred to quality percentage after ultrasonic wave decentralized processing in the ratio of 10g/L
0.8 h is handled in the A-type nano zeolite molecular sieve suspension that specific concentration is 6%, electrostatic adsorption is made it through and completes primary packet
Cover to form core-shell material, filter, solid be placed in again after drying molecular sieve initial reaction liquid (step 3. obtained at the beginning of molecular sieve
Beginning reaction solution) in be filtered, washed after 120 crystallization, 1 h, dry the cobalt oxide core-shell material of obtained molecular sieve cladding.
(5) core-shell material of the cladding cobalt oxide of molecular sieve obtained by step (4) is placed in mass percent concentration is 50 %'s
Reaction kettle is gone in ammonium chloride solution makes nuclear material cobalt oxide react with it generation chlorine ammonia cobalt, and reaction condition is 100 DEG C, 5 h.
(6) by step (5) resulting materials Co (NH3)6Cl2@molecular screen material is placed in 250 DEG C of 2 h of roasting in Muffle furnace and obtains
Catalyst CoCl2@molecular sieve.
Above-mentioned catalyst is applied into the reaction in urea and phenol reactant diphenyl carbonate synthesis (reaction equation is as follows)
48 h, conversion rate of urea 97.5% are carried out at 190 DEG C, diphenyl carbonate yield is 95.5%, carbonic acid two after catalyst uses 5 times
Phenyl ester yield is 1) 90.1%(is shown in Table；
。
Embodiment 4
The method for preparing the nickel chloride catalyst agent of molecular sieve cladding is as follows:
(1) Ting Zhu, " the Highly Efficient Removal of that Jun Song Chen etc. is delivered are referred to
Organic Dyes from Waste Water Using Hierarchical NiO Spheres with High
The standby spherical nickel oxide powder body that partial size is 1~5 micron out of Surface Area ", determines oxygen using conventional Zeta potential analyzer
It is positively charged to change the manganese surface of solids；
(2) preparation of molecular sieve refers to " Layer-by-Layer preparation of zeolite coatings of
nanosized crystals”
1. pressing SiO2:Al2O3:Na2O: (TMA)2O:H2The molar ratio of O is the ratio of 5:0.6::0.3:9:400, in weighing
State reaction raw materials silica solution corresponding to substance (30% in water), aluminium isopropoxide, sodium hydroxide, tetramethylammonium hydroxide,
Deionized water, it is spare；
2. by NaOH and (TMA)2O is dissolved in deionized water；
3. the solution in 2. is divided into two parts of A, B；
4. aluminium isopropoxide is added in A and stirs evenly, silica solution is added in B and stirs evenly, finally by B solution
It pours into A and is uniformly mixed to obtain molecular sieve initial reaction liquid.
5. molecular sieve initial reaction liquid is put into the hydrothermal reaction kettle of 100ml, 90 DEG C crystallization 2 days, after crystallization product pass through
Ultrasonic (150W, 5min) is centrifugated (1000rpm, 30min), nanometer is obtained after 60 DEG C of dryings 24 h, 550 DEG C of 5 h of calcining
Type A zeolite molecular sieve selects Zeta potential analyzer to carry out surface potential analysis to gained molecular sieve to determine its surface band
Negative electricity.
(3) 8 g of step (1) manganese oxide solid is immersed in the poly- p styrene sulfonic acid that 1L mass percent concentration is 0.9%
(PSS) 1.5 h are handled in solution, 6000rpm centrifugation is filtered, and filter residue is washed with deionized water 3 times；Filter residue is immersed in again after washing
1.5 h are handled in phthalic acid diethylene glycol diacrylate (PDDA) solution of mass percent concentration 0.9%, filters, wash
Solid is washed, is finally handled again with the PDDA of mass percent concentration 0.9%；
(4) solid particle made from step (3) is transferred to quality percentage after ultrasonic wave decentralized processing in the ratio of 15g/L
1.3 h are handled in the A-type nano zeolite molecular sieve suspension that specific concentration is 8%, electrostatic adsorption is made it through and completes primary packet
Cover to form core-shell material, filter, solid be placed in again after drying molecular sieve initial reaction liquid (step 4. obtained at the beginning of molecular sieve
Beginning reaction solution) in be filtered, washed after 110 DEG C of 4 h of crystallization, dry the nickel oxide core-shell material of obtained molecular sieve cladding.
(5) core-shell material of the cladding nickel oxide of molecular sieve obtained by step (4) is placed in mass percent concentration is 70 %'s
Reaction kettle is gone in ammonium chloride solution makes nuclear material nickel oxide react with it generation chlorine ammonia nickel, and reaction condition is 130 DEG C, 6 h.
(6) by step (5) resulting materials Ni (NH3)6Cl2@molecular screen material is placed in 250 DEG C of 2 h of roasting in Muffle furnace and must urge
Agent MnCl2@molecular sieve.
Above-mentioned catalyst is applied into the reaction in urea and phenol reactant diphenyl carbonate synthesis (reaction equation is as follows)
36 h, conversion rate of urea 96.6% are carried out at 190 DEG C, diphenyl carbonate yield is 93.7%, carbonic acid two after catalyst uses 5 times
Phenyl ester yield is 1) 90.5%(is shown in Table；
。
Embodiment 5
The method for preparing the lanthanum oxide catalyst of molecular sieve cladding is as follows:
(1) Z the Xu, " Preparation that S Bian, J Wang, T Liu, L Wang, Y Gao etc. is delivered are referred to
and luminescence of La2O3: Ln3+(Ln3+= Eu3+, Tb3+, Dy3+, Sm3+, Er3+, Ho3+, Tm3+, Yb3 +/Er3+, Yb3+/Ho3+) to prepare partial size be 1~5 micron of spherical lanthanum oxide powder to microspheres ", using routine
Zeta potential analyzer determines that the lanthana surface of solids is negatively charged；
(2) preparation of molecular sieve refers to " Assembly of Nanozeolite Monolayers on the Gold
Substrates of Piezoeletric Sensors”
1. pressing SiO2:Al2O3:Na2O: (TMA)2O:H2The molar ratio of O is the ratio of 11.9:1.9:0.4:14:700, is claimed
Measure reaction raw materials silica solution (30% in water), aluminium isopropoxide, sodium hydroxide, tetramethyl hydroxide corresponding to above-mentioned substance
Ammonium, deionized water, it is spare；
2. 28 g of deionized water is weighed, by 2.29 g aluminium isopropoxides, 0.1 gNaOH and 15.04 under room temperature magnetic agitation
G tetramethylammonium hydroxide is dissolved in 27.2g deionized water and stirs one day until clarification, is denoted as solution A；
3. 7.04g silica solution, which is slowly dropped under stiring in solution A, stirs evenly to obtain solution B, B passes through 72 hours rooms
Molecular sieve initial reaction liquid is obtained after temperature ageing；
4. molecular sieve initial reaction liquid is put into the hydrothermal reaction kettle of 100ml, 60 DEG C crystallization 1 day, after crystallization product pass through
Ultrasonic (150W, 5min) is centrifugated (1000rpm, 30min), nanometer is obtained after 60 DEG C of dryings 24 h, 500 DEG C of 4 h of calcining
Type A zeolite molecular sieve selects Zeta potential analyzer to carry out surface potential analysis to gained molecular sieve to determine its surface band
Negative electricity.
(3) 10 g of step (1) manganese oxide solid is immersed in the phthalic acid two that 1 L mass percent concentration is 1.0%
2h is handled in glycol diacrylate (PDDA) solution, 6000rpm centrifugation is filtered, and filter residue is washed with deionized water 3 times；Washing
Filter residue is immersed in poly- p styrene sulfonic acid (PSS) solution of mass percent concentration 1.0% again and handles 2 h afterwards, is filtered, washed
Solid is finally handled with the PDDA of mass percent concentration 1.0% again；
(4) solid particle made from step (3) is transferred to quality hundred after ultrasonic wave decentralized processing in the ratio of 20 g/L
Divide in the A-type nano zeolite molecular sieve suspension that specific concentration is 10 % and handle 9 h, makes it through electrostatic adsorption and complete once
Cladding form core-shell material, filter, solid be placed in again after drying molecular sieve initial reaction liquid (step 3. obtained in molecular sieve
Initial reaction liquid) in be filtered, washed after 115 DEG C of 4.5 h of crystallization, dry the lanthana core-shell material of obtained molecular sieve cladding.
(5) core-shell material of the cladding lanthana of molecular sieve obtained by step (4) is placed in mass percent concentration is 90 %'s
Reaction kettle is gone in ammonium chloride solution makes nuclear material lanthana react with it generation chlorine ammonia lanthanum, and reaction condition is 60 DEG C, 10 h.
(6) by step (5) resulting materials La (NH3)8Cl2@molecular screen material is placed in 250 DEG C of 2 h of roasting in Muffle furnace and must urge
Agent LaCl3@molecular sieve.
Above-mentioned catalyst is applied into the reaction in urea and phenol reactant diphenyl carbonate synthesis (reaction equation is as follows)
18 h, conversion rate of urea 98.6% are carried out at 195 DEG C, diphenyl carbonate yield is 98.3%, carbonic acid two after catalyst uses 5 times
Phenyl ester yield is 1) 93.2%(is shown in Table；
。
Seen from table 1, the catalyst effect prepared by the present invention is good, is still able to maintain after reusing 5 times higher
Catalytic activity, the metal oronain salt formed after catalysis can by simply heat make its deamination after and be used further to be catalyzed, from
And realize catalysis and the dual special efficacy that couples, it can be seen that, which can also be used in other similar reaction system, realize high
Effect catalysis.
Table 1: catalyst repeat performance
。
Claims (4)
1. a kind of preparation method of core-shell material catalyst, which is characterized in that specifically includes the following steps:
(1) it determines that the surface of transition metal oxide is positively charged or negative electricity, transition metal oxide is impregnated in quality percentage
Specific concentration is 0.5~2 h in the positive/negative polyelectrolyte solution of 0.3~1.0 %, centrifugal filtration, residue washing；Filter residue after washing
It repeats the above process 2~3 times, positive polyelectrolyte solution and negative polyelectrolyte solution are used alternatingly during entirely immersing；
(2) filter residue that step (1) obtains is transferred to the nanometer A that mass percent concentration is 2% ~ 10% in the ratio of 1 ~ 20 g/L
0.5 ~ 12 h is handled in type zeolite molecular sieve suspension, the solid after being filtered, washed, drying is placed in molecular sieve initial reaction liquid
90 ~ 120 DEG C of 1 ~ 5 h of Crystallizing treatment, the ammonium chloride for being again 10% ~ 90% with mass percent concentration after being filtered, washed, being dried in vacuo
Solution carries out 2 ~ 10h of reaction at 60 ~ 140 DEG C and obtains M (NH3)nClβ@molecular sieve, wherein n=1 ~ 8, are coordinated number, mistake for ammonia
Core-shell material catalyst MCl is made in low-temperature bake after filter, washing, vacuum dryingβ@molecular sieve；
Positive polyelectrolyte is phthalic acid diethylene glycol diacrylate；
Negative polyelectrolyte is poly- p styrene sulfonic acid.
2. the preparation method of core-shell material catalyst according to claim 1, it is characterised in that: transition metal oxide is oxygen
Change zinc, copper oxide, cadmium oxide, nickel oxide, cobalt oxide, iron oxide, manganese oxide, chromium oxide, scandium oxide, titanium oxide, in vanadium oxide
One kind, transition metal oxide is replaced with into one of lanthana, cerium oxide, praseodymium oxide, neodymia.
3. the preparation method of core-shell material catalyst according to claim 1, it is characterised in that: low-temperature bake be 250 ~
0.5 ~ 2 h is handled under the conditions of 300 DEG C.
4. core-shell material catalyst made from the preparation method of core-shell material catalyst described in any one of claim 1-3 is closing
At the application in diphenyl carbonate, it is characterised in that: the catalyst synthesizes carbon with phenol reactant for urea or carbamate
In diphenyl phthalate, reaction carries out 2 ~ 48 h at 190 DEG C ~ 210 DEG C.
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| CN105251526A (en) * | 2015-10-27 | 2016-01-20 | 昆明理工大学 | Preparing method and application of core-shell material catalyst |
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