CN108579795A - A kind of using transition metal salt is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell and application - Google Patents

A kind of using transition metal salt is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell and application Download PDF

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CN108579795A
CN108579795A CN201810290081.1A CN201810290081A CN108579795A CN 108579795 A CN108579795 A CN 108579795A CN 201810290081 A CN201810290081 A CN 201810290081A CN 108579795 A CN108579795 A CN 108579795A
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transition metal
silicallite
solid
molecular sieve
shell
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赵文波
徐志勇
汪洋
赵倩
陈媛
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

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Abstract

It is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell and application that the present invention relates to a kind of using transition metal salt, belongs to catalyst technical field.The present invention first prepares transition metal oxide or transition metal hydroxide, and polyelectrolyte carries out surface modification to oxide, the hydroxide of transition metal keeps its surface positively charged or negative electricity；By electrostatic, self-assembly method coats one layer of 1 type nano molecular sieve crystal seed of silicallite in its appearance layer by layer, 1 type molecular screen membranes of diauxic growth silicallite are obtained using transition metal oxide or transition metal hydroxide as core on 1 type nano molecular sieve crystal seeds of silicallite again, 1 type molecular sieves of silicallite are the solid B of shell, and solid B obtains M with ammonium salt solid powder solid phase reactionɑ(NH3)nXβ@silicallite 1, Mɑ(NH3)nXβ@silicallite 1 are through low-temperature bake up to nucleocapsid catalyst MɑXβ@silicallite‑1.The nucleocapsid catalyst M of the present inventionɑXβ@silicallite 1 can catalyze and synthesize organic carbonate.

Description

A kind of using transition metal salt is core nano molecular sieve as the preparation of the nucleocapsid catalyst of shell Method and application
Technical field
The present invention relates to it is a kind of using transition metal salt be core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell with Using belonging to catalyst technical field.
Background technology
Dimethyl carbonate (Dimethyl Carbonate, DMC), methyl ethyl carbonate, diethyl carbonate, diphenyl carbonate (Diphenyl Carbonate, abbreviation DPC), ethylene carbonate, propene carbonate etc. are the Typical Representatives of organic carbonate, Most commonly used middle purposes is dimethyl carbonate and diphenyl carbonate.Wherein, dimethyl carbonate is among a kind of important chemical industry Body and solvent have a variety of reactivity worth, are widely used in containing reactive groups such as methyl, methoxyl group, carbonyls in molecular structure Tens kinds of fine chemicals such as medicine, pesticide, engineering plastics makrolon and fragrance intermediates are synthesized, there is extraordinary market Foreground and economic benefit.Diphenyl carbonate is mainly used for synthesizing the production of the chemical industry such as poly- aryl carbonates and P-hydroxybenzoic acid polyester Product also serve as the plasticizer of polyamide, polyester, and in pesticide, medicine, the numerous areas such as glazing, sheet material and auto industry have It is widely applied.The preparation method of organic carbonate has phosgenation and non-phosgene, phosgenation to make due to the use of the phosgene of severe toxicity Seriously pollute environment for raw material and safety be poor, at the same side product chlorinated Hydrogen Energy corrosion pipeline equipment and be gradually eliminated.It is comprehensive These unfavorable factors, people are just constantly seeking " green " synthetic method in past decades.Since eighties of last century the seventies, The technique for successively having developed a variety of non-phosgene synthesis organic carbonates both at home and abroad, non-phosgene include mainly oxidative carbonylation Method, ester-interchange method, alcoholysis of urea and carbon dioxide and alcohol the methods of directly synthesize.Oxidation carbonylation method is still not bery perfect, Have the shortcomings that various such as selectively low, catalyst is expensive, operation and control is difficult；The apparent disadvantage of ester-interchange method It is to be difficult to break the limitation of thermodynamical equilibrium and reaction balance is made to move right, that there are the production capacity of unit volume is low, sets The problems such as standby costly, high energy consumption and catalyst are difficult to recycle；Alcoholysis of urea needs a large amount of excessive, poor selectivities of alcohol； Carbon dioxide and alcohol directly synthesize very low at present also in phase of basic research due to being limited yield by thermodynamics.It integrates, Alcoholysis of urea prepare dimethyl carbonate have it is cheap and easy to get, ammonia is recyclable, corrosion-free, pollution-free, high income, at The advantages that this is relatively low.It is reaction method of the raw material under catalyst that ester-interchange method, which is based primarily upon dimethyl carbonate with phenol, at present, This synthetic method " green ", investment are small, but it is apparent the disadvantage is that being difficult to break the limitation of thermodynamical equilibrium and keep reaction flat Weighing apparatus moves right, by-product carbinol and dimethyl carbonate form azeotropic mixture, it is difficult to be detached.
Currently without the limitation that can break when catalyzing and synthesizing organic carbonate thermodynamically, and balance is moved right It moves to improve the catalyst of the yield of dimethyl carbonate and diphenyl carbonate.
Invention content
The problem of existing for the above-mentioned prior art and deficiency, the present invention provide a kind of using transition metal salt as core nanometer point Son sieve is preparation method and the application of the nucleocapsid catalyst of shell；The nucleocapsid catalyst of the present invention is when catalyzing and synthesizing organic carbonate Limitation thermodynamically can be broken, and balance is moved right to improve the yield of dimethyl carbonate and diphenyl carbonate.
The present invention first prepares transition metal oxide or transition metal hydroxide, electrolyte to transition metal oxide or Transition metal hydroxide, which carries out surface modification, keeps its surface positively charged or negative electricity；By electrostatic, self-assembly method is golden in transition layer by layer Category oxide or transition metal hydroxide appearance one layer of silicallite-1 type nano molecular sieve crystal seed of cladding, then Diauxic growth silicallite-1 type molecular screen membranes are obtained with transition metal on silicallite-1 type nano molecular sieve crystal seeds Oxide or transition metal hydroxide are core, and silicallite-1 type molecular sieves are the core-shell material of shell；By core-shell material with Solid ammonium salt (NH4)ɑ(X represents NO to X3-、SO42-、PO3 2-、Cl-、Br-Or I-, ɑ represents its chemical valence) and effect makes consideration convey become phase The ammonia salt of the ammonia salt for the transition metal answered, transition metal is abbreviated as Mɑ(NH3)nXβ（Wherein M is transition metal element, and β is the mistake The chemical valence of metal is crossed, n represents ammonia ligancy）；Low-temperature bake makes Mɑ(NH3)nXβIn ammonia removing be changed into MɑXβ, obtain core Shell catalyst MɑXβ@silicallite-1；
A kind of using transition metal salt is core silicallite-1 types molecular sieve as the preparation method of the nucleocapsid catalyst of shell, specifically Steps are as follows：
（1）Prepare the transition metal oxide or transition metal hydroxide of monodispersity；
（2）By step（1）Transition metal oxide or transition metal hydroxide be dipped in negative polyelectrolyte solution reaction 10 ~ 30min, centrifugal filtration obtain filtrate I and filter residue I；
（3）By step（2）Filter residue I be dipped in positive polyelectrolyte solution 10 ~ 30min of reaction, centrifugal filtration obtains II He of filtrate Filter residue II；
（4）By II return to step of filter residue（2）Substitution transition metal oxide or transition metal hydroxide are dipped in positive polyelectrolyte It is reacted in solution；Circulate operation 1 ~ 3 time, centrifugal filtration obtains solid product；
（5）By step（4）Solid product is placed in 10 ~ 30 min of processing in silicallite-1 molecular sieve suspension, filters, washes It washs, be dried to obtain solid A；Under the conditions of temperature is 100 ~ 170 DEG C, solid A is placed in Crystallizing treatment 12 ~ 72 in mixed solution A H is filtered, washed, is dried in vacuo and obtains solid B, and wherein mixed solution A is ethyl orthosilicate, tetrapropylammonium hydroxide, deionization The mixed solution of water and absolute ethyl alcohol；Solid B is uniformly mixed with ammonium salt solid powder and under the conditions of temperature is 100 ~ 200 DEG C It carries out 1 ~ 10h of solid phase reaction and obtains Mɑ(NH3)nXβ@silicallite-1 wash M using methanol or ethyl alcoholɑ(NH3)nXβ@ Then silicallite-1 is dried in vacuo successively, low-temperature bake is up to core-shell material catalyst MɑXβ@silicallite- 1；
The step（1）In middle transition metal oxide the valence state of transition metal be divalent, transition metal oxide be zinc oxide, Magnesia, nickel oxide, cobalt oxide, copper oxide, cadmium oxide or manganese oxide；
The step（1）The valence state of transition metal is divalent in middle transition metal hydroxide, and transition metal hydroxide is hydrogen Zinc oxide, magnesium hydroxide, nickel hydroxide, cobalt hydroxide, Kocide SD, manganous hydroxide or cadmium hydroxide；
The step（2）The solid-to-liquid ratio g of transition metal oxide or transition metal hydroxide and negative polyelectrolyte solution:ML is (0.1~1):(50~60)；A concentration of 0.1 ~ 5.0 % of mass percent that polyelectrolyte is born in negative polyelectrolyte solution bears poly- electricity The poly- p styrene sulfonic acids of Xie Zhiwei；
The step（3）The solid-to-liquid ratio g of filter residue I and positive polyelectrolyte solution:ML is (0.1 ~ 1):(40~50)；Positive polyelectrolyte The mass percent a concentration of 0.1 ~ 5.0% of positive polyelectrolyte in solution, positive polyelectrolyte are O-phthalic acid diethylene glycol dipropyl Olefin(e) acid ester；
The step（5）The solid-to-liquid ratio g of solid product and silicallite-1 molecular sieve suspension:ML is (0.1 ~ 1):(10~ 30)；The mass percent a concentration of 2 ~ 10% of silicallite-1 molecular sieve suspension；
The step（5）The solid-to-liquid ratio g of solid A and mixed solution A:ML is (0.1 ~ 1):(35 ~ 45), positive silicon in mixed solution A Acetoacetic ester, tetrapropylammonium hydroxide, the molar ratio of deionized water and absolute ethyl alcohol are (5 ~ 15):(0.5~3.5):1000:20；
The step（5）The temperature of low-temperature bake is 250 ~ 300 DEG C, and the low-temperature bake time is 0.5 ~ 5 h；
The step（5）The molar ratio of transition metal and ammonium salt solid powder in solid B is 1:(1~8)；Ammonium salt solid powder For ammonium chloride, ammonium bromide, ammonium iodide, ammonium nitrate, ammonium sulfate or ammonium phosphate；
The method of the transition metal oxide for preparing monodispersity or transition metal hydroxide is according to document “Fabrication of β-Ni(OH)2 and NiO hollow spheres by a facile templatefree Process " or " self-assembled 3D photonic crystals from ZnO colloidal spheres " into It is prepared by row；
The silicallite-1 molecular sieves are according to document " Preparation of nanosized Silicalite-1 and its application in vapor-phase Beckmann Rearrangement of cyclohexannone Oxime " is prepared；
It is a further object of the present invention to provide be that core silicallite-1 types molecular sieve is catalyzed as the nucleocapsid of shell using transition metal salt Agent MɑXβApplications of the@silicallite-1 in catalyzing and synthesizing organic carbonate；
Catalyst prepared by the present invention is in Synthesis of Dimethyl Carbonate from Urea or urea (or carbamate) and phenol During synthesis of diphenyl carbonate by ester exchange reaction, nuclear material transition metal chloride by the coupling of reaction constantly Absorption ammonia decreases until being saturated then catalytic efficiency, selects the catalyst of suitable additive amount that can realize that reaction system is given birth to At ammonia be all coordinated to push the forward direction of reaction mobile in transition metal chloride, and then dimethyl carbonate and carbon The production capacity of diphenyl phthalate is improved.
The beneficial effects of the invention are as follows：
（1）The present invention is core silicallite-1 types molecular sieve as the nucleocapsid catalyst M of shell using transition metal saltɑXβ@ The preparation process of silicallite-1 is simple, raw material is easy to get, nucleocapsid catalyst MɑXβMorphology controllable, the grain of@silicallite-1 Diameter is controllable, and can make nucleocapsid catalyst M by simply heatingɑXβ@silicallite-1 regeneration；
（2）The present invention is core silicallite-1 types molecular sieve as the nucleocapsid catalyst M of shell using transition metal saltɑXβ@ Silicallite-1 improves the yield of producing dimethyl carbonate by alcoholysis of urea and carbonate production by transesterification diphenyl ester, production Rate is up to 90% or more；
（3）The present invention is core silicallite-1 types molecular sieve as the nucleocapsid catalyst M of shell using transition metal saltɑXβ@ The shell material of silicallite-1 be silicallite-1 molecular sieve film have make alcoholysis of urea and ester exchange reaction The ammonia that system generates is coordinated by duct with nuclear material, prevents such as phenol oxygen root coordination of other macromoleculars to improve The conversion ratio of reaction.
Specific implementation mode
With reference to embodiment, the invention will be further described.
The silicallite-1 molecular sieves of the embodiment of the present invention are according to document " Preparation of nanosized Silicalite-1 and its application in vapor-phase Beckmann It is prepared by Rearrangement of cyclohexannone oxime ", the specific steps are：
（1）Ethyl orthosilicate, tetrapropylammonium hydroxide, L-lysine, ultra-pure water are uniformly mixed and obtain reaction solution A, wherein Ethyl orthosilicate, tetrapropylammonium hydroxide, the molar ratio of ultra-pure water are 1 in reaction solution A:(0.3~0.5):(16.5 ~ 65), instead The mass percent of L-lysine in solution A a concentration of 0.15 ~ 3% is answered, is 80 ~ 120 DEG C, is aged instead under stirring condition in temperature 24 ~ 48h is answered, then it is crystallization 12 ~ for 24 hours under the conditions of 100 ~ 170 DEG C to be placed in temperature, centrifuges, is dry, then being placed in temperature and be 6 ~ 10h is calcined under the conditions of 550 ~ 650 DEG C up to silicallite-1 molecular sieves；
Effective channel diameter of the silicallite-1 molecular sieves of the present invention is 0.45 ~ 0.55nm.
Embodiment 1：The present embodiment is core silicallite-1 types molecular sieve as the nucleocapsid catalyst of shell using transition metal salt For ZnCl2@silicallite-1 nucleocapsid catalysts；
A kind of using transition metal salt is core silicallite-1 types molecular sieve as the preparation method of the nucleocapsid catalyst of shell, specifically Steps are as follows：
（1）Prepare the spherical Zinc oxide powder of monodispersity；
（2）By step（1）Spherical Zinc oxide powder be dipped in negative polyelectrolyte solution and react 10min, centrifugal filtration is filtered Liquid I and filter residue I；The solid-to-liquid ratio g of wherein spherical Zinc oxide powder and negative polyelectrolyte solution:ML is 0.1:50；Negative polyelectrolyte The mass percent a concentration of 0.3% that polyelectrolyte is born in solution, it is poly- p styrene sulfonic acid PPS to bear polyelectrolyte；
（3）By step（2）Filter residue I be dipped in positive polyelectrolyte solution and react 10min, centrifugal filtration obtains filtrate II and filter residue Ⅱ；The wherein solid-to-liquid ratio g of filter residue I and positive polyelectrolyte solution:ML is 0.1:40；Positive polyelectrolyte in positive polyelectrolyte solution Mass percent a concentration of 0.3%, positive polyelectrolyte are phthalic acid diethylene glycol diacrylate PDDA；
（4）By II return to step of filter residue（2）Substitution transition metal oxide or transition metal hydroxide are dipped in positive polyelectrolyte It is reacted in solution；Circulate operation 1 time, centrifugal filtration obtains solid product；
（5）By step（4）Solid product is placed in silicallite-1 molecular sieve suspension and handles 10min, is filtered, washed, does It is dry to obtain solid A, wherein the solid-to-liquid ratio g of solid product and silicallite-1 molecular sieve suspension:ML is 0.1:10； The mass percent a concentration of 2% of silicallite-1 molecular sieve suspension；Under the conditions of temperature is 170 DEG C, solid A is placed in Crystallizing treatment 72h in mixed solution A is filtered, washed, is dried in vacuo and obtains solid B, wherein the solid-liquid of solid A and mixed solution A Compare g:ML is 0.1:35, mixed solution A is the mixing of ethyl orthosilicate, tetrapropylammonium hydroxide, deionized water and absolute ethyl alcohol Solution, ethyl orthosilicate in mixed solution A, tetrapropylammonium hydroxide, the molar ratio of deionized water and absolute ethyl alcohol are 5:0.5: 1000:20；By solid B and ammonium salt solid powder（Ammonium salt solid powder is ammonium chloride）It is uniformly mixed and is 200 DEG C of items in temperature Solid phase reaction 1h is carried out under part obtains Zn (NH3)nCl2Transition metal and ammonium salt in@silicallite-1, wherein solid B is solid Body powder（Ammonium chloride）Molar ratio be 1:1；Using methanol washing Zn (NH3)nCl2Then@silicallite-1 are carried out successively Vacuum drying, low-temperature bake are up to core-shell material catalyst Z nCl2The temperature of@silicallite-1, wherein low-temperature bake is 300 DEG C, the low-temperature bake time is 0.5 h；
By the core-shell material catalyst Z nCl of the present embodiment2@silicallite-1 are applied reacts carbonate synthesis in urea with methanol In dimethyl ester, reaction equation is：
Reaction temperature is 90 DEG C, reaction time 4h, conversion rate of urea 97.7%, and dimethyl carbonate yield is 97.4%, catalysis Dimethyl carbonate yield is 93.2% after agent uses 5 times（It is shown in Table 1）；
By the core-shell material catalyst Z nCl of the present embodiment2@silicallite-1 are applied in urea and phenol reactant carbonate synthesis In diphenyl ester, reaction equation is：
Reaction temperature is 210 DEG C, reaction time 2h, conversion rate of urea 99.7%, and diphenyl carbonate yield is 98.2%, catalyst The use of diphenyl carbonate yield after 5 times is 94.7%（It is shown in Table 2）.
Embodiment 2：The present embodiment is core silicallite-1 types molecular sieve as the nucleocapsid catalyst of shell using transition metal salt For CuBr2@silicallite-1 nucleocapsid catalysts；
A kind of using transition metal salt is core silicallite-1 types molecular sieve as the preparation method of the nucleocapsid catalyst of shell, specifically Steps are as follows：
（1）Prepare the spherical cupric oxide powder of monodispersity；
（2）By step（1）Spherical cupric oxide powder be dipped in negative polyelectrolyte solution and react 15min, centrifugal filtration is filtered Liquid I and filter residue I；The solid-to-liquid ratio g of wherein spherical cupric oxide powder and negative polyelectrolyte solution:ML is 1:60；Negative polyelectrolyte is molten The mass percent a concentration of 5.0% that polyelectrolyte is born in liquid, it is poly- p styrene sulfonic acid PPS to bear polyelectrolyte；
（3）By step（2）Filter residue I be dipped in positive polyelectrolyte solution and react 15min, centrifugal filtration obtains filtrate II and filter residue Ⅱ；The wherein solid-to-liquid ratio g of filter residue I and positive polyelectrolyte solution:ML is 1:50；The matter of positive polyelectrolyte in positive polyelectrolyte solution It is 5.0% to measure percent concentrations, and positive polyelectrolyte is phthalic acid diethylene glycol diacrylate PDDA；
（4）By II return to step of filter residue（2）Substitution transition metal oxide or transition metal hydroxide are dipped in positive polyelectrolyte It is reacted in solution；Circulate operation 2 times, centrifugal filtration obtains solid product；
（5）By step（4）Solid product is placed in silicallite-1 molecular sieve suspension and handles 15min, is filtered, washed, does It is dry to obtain solid A, wherein the solid-to-liquid ratio g of solid product and silicallite-1 molecular sieve suspension:ML is 1:20； The mass percent a concentration of 6% of silicallite-1 molecular sieve suspension；Under the conditions of temperature is 100 DEG C, solid A is placed in Crystallizing treatment 12h in mixed solution A is filtered, washed, is dried in vacuo and obtains solid B, wherein the solid-liquid of solid A and mixed solution A Compare g:ML is 1:45, mixed solution A be ethyl orthosilicate, tetrapropylammonium hydroxide, L-lysine, ultra-pure water mixed solution, Ethyl orthosilicate in mixed solution A, tetrapropylammonium hydroxide, the molar ratio of deionized water and absolute ethyl alcohol are 10:2:1000: 20；By solid B and ammonium salt solid powder（Ammonium salt solid powder is ammonium bromide）Be uniformly mixed and temperature be 100 DEG C under the conditions of into Row solid phase reaction 10h obtains Cu (NH3)nCBr2Transition metal in@silicallite-1, wherein solid B and ammonium salt solid powder End（Ammonium bromide）Molar ratio be 1:8；Using methanol washing Cu (NH3)nCBr2Then@silicallite-1 are carried out true successively Empty drying, low-temperature bake are up to core-shell material catalyst CuBr2@silicallite-1, the wherein temperature of low-temperature bake are 250 DEG C, the low-temperature bake time is 5 h；
By the core-shell material catalyst CuBr of the present embodiment2@silicallite-1 are applied reacts carbonate synthesis in urea with methanol In dimethyl ester, reaction equation is：
Reaction temperature is 95 DEG C, reaction time 8h, conversion rate of urea 96.5%, and dimethyl carbonate yield is 96.3%, catalyst The use of dimethyl carbonate yield after 5 times is 92.9%（It is shown in Table 1）；
By the core-shell material catalyst CuBr of the present embodiment2@silicallite-1 are applied in urea and phenol reactant carbonate synthesis In diphenyl ester, reaction equation is：
Reaction temperature is 200 DEG C, reaction time 12h, conversion rate of urea 97.6%, and diphenyl carbonate yield is 96.1%, catalysis Diphenyl carbonate yield is 93.7% after agent uses 5 times（It is shown in Table 2）.
Embodiment 3：The present embodiment is core silicallite-1 types molecular sieve as the nucleocapsid catalyst of shell using transition metal salt For Ni (NO3)2@silicallite-1 nucleocapsid catalysts；
A kind of using transition metal salt is core silicallite-1 types molecular sieve as the preparation method of the nucleocapsid catalyst of shell, specifically Steps are as follows：
（1）Prepare the ball-shape nickel hydroxide powder of monodispersity；
（2）By step（1）Ball-shape nickel hydroxide powder be dipped in positive polyelectrolyte solution and react 20min, centrifugal filtration obtains Filtrate I and filter residue I；The wherein solid-to-liquid ratio g of spherical nickel oxide powder body and negative polyelectrolyte solution:ML is 0.5:55；Negative poly- electrolysis The mass percent a concentration of 2.45% that polyelectrolyte is born in matter solution, it is poly- p styrene sulfonic acid PPS to bear polyelectrolyte；
（3）By step（2）Filter residue I be dipped in positive polyelectrolyte solution and react 20min, centrifugal filtration obtains filtrate II and filter residue Ⅱ；The wherein solid-to-liquid ratio g of filter residue I and positive polyelectrolyte solution:ML is 0.5:45；Positive polyelectrolyte in positive polyelectrolyte solution Mass percent a concentration of 2.45%, it is phthalic acid diethylene glycol diacrylate PDDA to bear polyelectrolyte；
（4）By II return to step of filter residue（2）Substitution transition metal oxide or transition metal hydroxide are dipped in positive polyelectrolyte It is reacted in solution；Circulate operation 3 times, centrifugal filtration obtains solid product；
（5）By step（4）Solid product is placed in silicallite-1 molecular sieve suspension and handles 20min, is filtered, washed, does It is dry to obtain solid A, wherein the solid-to-liquid ratio g of solid product and silicallite-1 molecular sieve suspension:ML is 0.5:15； The mass percent a concentration of 10% of silicallite-1 molecular sieve suspension；Under the conditions of temperature is 140 DEG C, solid A is set The Crystallizing treatment 45h in mixed solution A is filtered, washed, is dried in vacuo and obtains solid B, and wherein solid A and mixed solution A are consolidated Liquor ratio g:ML is 0.5:40, mixed solution A is that ethyl orthosilicate, tetrapropylammonium hydroxide, L-lysine, the mixing of ultra-pure water are molten Liquid, ethyl orthosilicate in mixed solution A, tetrapropylammonium hydroxide, the molar ratio of deionized water and absolute ethyl alcohol are 15: 3.5: 1000:20；By solid B and ammonium salt solid powder（Ammonium salt solid powder is ammonium nitrate）It is uniformly mixed and is 150 DEG C of items in temperature Solid phase reaction 6h is carried out under part obtains Ni (NH3)n(NO3)2Transition metal and ammonium salt in@silicallite-1, wherein solid B Solid powder（Ammonium nitrate）Molar ratio be 1:4；Using ethyl alcohol washing Ni (NH3)n(NO3)2@silicallite-1, then according to It is secondary be dried in vacuo, low-temperature bake is up to core-shell material catalyst n i (NO3)2@silicallite-1, wherein low-temperature bake Temperature is 280 DEG C, and the low-temperature bake time is 2.5h；
By the core-shell material catalyst n i (NO of the present embodiment3)2@silicallite-1 are applied reacts synthesis with methanol in urea In dimethyl carbonate, reaction equation is：
Reaction temperature is 110 DEG C, reaction time 16h, conversion rate of urea 98.2%, and dimethyl carbonate yield is 98.3%, catalysis Dimethyl carbonate yield is 94.9% after agent uses 5 times（It is shown in Table 1）；
By the core-shell material catalyst n i (NO of the present embodiment3)2@silicallite-1, which are applied, to be synthesized in urea with phenol reactant In diphenyl carbonate, reaction equation is：
Reaction temperature is 190 DEG C, reaction time 48h, conversion rate of urea 97.8%, and diphenyl carbonate yield is 96.3%, catalysis Diphenyl carbonate yield is 93.4% after agent uses 5 times（It is shown in Table 2）.
Embodiment 4：The present embodiment is core silicallite-1 types molecular sieve as the nucleocapsid catalyst of shell using transition metal salt For Cd2(SO4)2@silicallite-1 nucleocapsid catalysts；
A kind of using transition metal salt is core silicallite-1 types molecular sieve as the preparation method of the nucleocapsid catalyst of shell, specifically Steps are as follows：
（1）Prepare the spherical cadmium oxide powder of monodispersity；
（2）By step（1）Spherical cadmium oxide powder be dipped in negative polyelectrolyte solution and react 30min, centrifugal filtration is filtered Liquid I and filter residue I；The solid-to-liquid ratio g of wherein spherical cadmium oxide powder and negative polyelectrolyte solution:ML is 0.4:50；Negative polyelectrolyte The mass percent a concentration of 0.3% that polyelectrolyte is born in solution, it is poly- p styrene sulfonic acid PPS to bear polyelectrolyte；
（3）By step（2）Filter residue I be dipped in positive polyelectrolyte solution and react 30min, centrifugal filtration obtains filtrate II and filter residue Ⅱ；The wherein solid-to-liquid ratio g of filter residue I and positive polyelectrolyte solution:ML is 0.4:40；Positive polyelectrolyte in positive polyelectrolyte solution Mass percent a concentration of 0.3%, positive polyelectrolyte are phthalic acid diethylene glycol diacrylate PDDA；
（4）By II return to step of filter residue（2）Substitution transition metal oxide or transition metal hydroxide are dipped in positive polyelectrolyte It is reacted in solution；Circulate operation 3 times, centrifugal filtration obtains solid product；
（5）By step（4）Solid product is placed in silicallite-1 molecular sieve suspension and handles 30min, is filtered, washed, does It is dry to obtain solid A, wherein the solid-to-liquid ratio g of solid product and silicallite-1 molecular sieve suspension:ML is 0.4:15； The mass percent a concentration of 8% of silicallite-1 molecular sieve suspension；Under the conditions of temperature is 120 DEG C, solid A is placed in Crystallizing treatment 36h in mixed solution A is filtered, washed, is dried in vacuo and obtains solid B, wherein the solid-liquid of solid A and mixed solution A Compare g:ML is 0.4:40, mixed solution A is that ethyl orthosilicate, tetrapropylammonium hydroxide, l- lysines, the mixing of ultra-pure water are molten Liquid, ethyl orthosilicate in mixed solution A, tetrapropylammonium hydroxide, the molar ratio of deionized water and absolute ethyl alcohol are 5:1:1000: 20；By solid B and ammonium salt solid powder（Ammonium salt solid powder is ammonium sulfate）Be uniformly mixed and temperature be 200 DEG C under the conditions of into Row solid phase reaction 10h obtains Cd2(NH3)n(SO4)2Transition metal and ammonium salt solid in@silicallite-1, wherein solid B Powder（Ammonium sulfate）Molar ratio be 1:6；Cd is washed using ethyl alcohol2(NH3)n(SO4)2@silicallite-1, then successively into Row vacuum drying, low-temperature bake are up to core-shell material catalyst Cd2(SO4)2@silicallite-1, the wherein temperature of low-temperature bake Degree is 300 DEG C, and the low-temperature bake time is 1.5h；
By the core-shell material catalyst Fe (SO of the present embodiment4)2@silicallite-1 are applied reacts synthesis with methanol in urea In dimethyl carbonate, reaction equation is：
Reaction temperature is 130 DEG C, reaction time 32h, conversion rate of urea 96.1%, and dimethyl carbonate yield is 96.4%, catalysis Dimethyl carbonate yield is 93.5% after agent uses 5 times（It is shown in Table 1）；
1 Synthesis of dimethyl carbonate catalyst of table reuses number and catalytic efficiency
By the core-shell material catalyst Cd of the present embodiment2(SO4)2@silicallite-1, which are applied, to be synthesized in urea with phenol reactant In diphenyl carbonate, reaction equation is：
Reaction temperature is 190 DEG C, and reaction time 48h, reaction result is as shown in table 2,
2 diphenyl carbonate synthesis catalyst of table reuses number and catalytic efficiency
As known from Table 2, conversion rate of urea 97.8%, diphenyl carbonate yield are 96.3%, diphenyl carbonate after catalyst uses 5 times Yield is 93.4%.
The specific implementation mode of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art Go out various change.

Claims (10)

1. using transition metal salt it is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell a kind of, which is characterized in that tool Steps are as follows for body：
（1）Prepare the transition metal oxide or transition metal hydroxide of monodispersity；
（2）By step（1）Transition metal oxide or transition metal hydroxide be dipped in negative polyelectrolyte solution reaction 10 ~ 30min, centrifugal filtration obtain filtrate I and filter residue I；
（3）By step（2）Filter residue I be dipped in positive polyelectrolyte solution 10 ~ 30min of reaction, centrifugal filtration obtains II He of filtrate Filter residue II；
（4）By II return to step of filter residue（2）Substitution transition metal oxide or transition metal hydroxide are dipped in positive polyelectrolyte It is reacted in solution；Circulate operation 1 ~ 3 time, centrifugal filtration obtains solid product；
（5）By step（4）Solid product is placed in 10 ~ 30 min of processing in silicallite-1 molecular sieve suspension, filters, washes It washs, be dried to obtain solid A；Under the conditions of temperature is 100 ~ 170 DEG C, solid A is placed in Crystallizing treatment 12 ~ 72 in mixed solution A H is filtered, washed, is dried in vacuo and obtains solid B, and wherein mixed solution A is ethyl orthosilicate, tetrapropylammonium hydroxide, deionization The mixed solution of water and absolute ethyl alcohol；Solid B is uniformly mixed with ammonium salt solid powder and under the conditions of temperature is 100 ~ 200 DEG C It carries out 1 ~ 10h of solid phase reaction and obtains Mɑ(NH3)nXβ@silicallite-1 wash M using methanol or ethyl alcoholɑ(NH3)nXβ@ Then silicallite-1 is dried in vacuo successively, low-temperature bake is up to core-shell material catalyst MɑXβ@silicallite- 1。
2. it is according to claim 1 core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell using transition metal salt, It is characterized in that：Step（1）The valence state of transition metal is divalent in middle transition metal oxide, and transition metal oxide is oxidation Zinc, magnesia, nickel oxide, cobalt oxide, copper oxide, cadmium oxide or manganese oxide.
3. it is according to claim 1 core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell using transition metal salt, It is characterized in that：Step（1）The valence state of transition metal is divalent in middle transition metal hydroxide, and transition metal hydroxide is Zinc hydroxide, magnesium hydroxide, nickel hydroxide, cobalt hydroxide, Kocide SD, manganous hydroxide or cadmium hydroxide.
4. it is according to claim 1 core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell using transition metal salt, It is characterized in that：Step（2）The solid-to-liquid ratio g of transition metal oxide or transition metal hydroxide and negative polyelectrolyte solution: ML is (0.1 ~ 1):(50~60)；A concentration of 0.1 ~ 5.0 % of mass percent that polyelectrolyte is born in negative polyelectrolyte solution, bears Polyelectrolyte is poly- p styrene sulfonic acid.
5. it is according to claim 1 core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell using transition metal salt, It is characterized in that：Step（3）The solid-to-liquid ratio g of filter residue I and positive polyelectrolyte solution:ML is (0.1 ~ 1):(40~50)；Just poly- electricity The mass percent a concentration of 0.1 ~ 5.0% of positive polyelectrolyte in electrolyte solution, positive polyelectrolyte are O-phthalic acid diethylene glycol Diacrylate.
6. it is according to claim 1 core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell using transition metal salt, It is characterized in that：Step（5）The solid-to-liquid ratio g of solid product and silicallite-1 molecular sieve suspension:ML is (0.1 ~ 1): (10~30)；The mass percent a concentration of 2 ~ 10% of silicallite-1 molecular sieve suspension.
7. it is according to claim 1 core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell using transition metal salt, It is characterized in that：Step（5）The solid-to-liquid ratio g of solid A and mixed solution A:ML is (0.1 ~ 1):(35 ~ 45), in mixed solution A just Silester, tetrapropylammonium hydroxide, the molar ratio of deionized water and absolute ethyl alcohol are (5 ~ 15):(0.5~3.5):1000:20.
8. it is according to claim 1 core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell using transition metal salt, It is characterized in that：Step（5）The temperature of low-temperature bake is 250 ~ 300 DEG C, and the low-temperature bake time is 0.5 ~ 5 h.
9. it is according to claim 1 core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell using transition metal salt, It is characterized in that：Step（5）The molar ratio of transition metal and ammonium salt solid powder in solid B is 1:(1~8)；Ammonium salt solid powder End is ammonium chloride, ammonium bromide, ammonium iodide, ammonium nitrate, ammonium sulfate or ammonium phosphate.
10. claim 1 ~ 9 described using transition metal salt is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell institute The core-shell material catalyst M of preparationɑXβApplications of the@silicallite-1 in catalyzing and synthesizing organic carbonate.
CN201810290081.1A 2018-03-30 2018-03-30 A kind of using transition metal salt is core nano molecular sieve as the preparation method of the nucleocapsid catalyst of shell and application Pending CN108579795A (en)

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Application publication date: 20180928