CN106540753A - A kind of modified solid catalyst containing phosphotungstic acid for Ketohexamethylene condensation reaction - Google Patents

A kind of modified solid catalyst containing phosphotungstic acid for Ketohexamethylene condensation reaction Download PDF

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CN106540753A
CN106540753A CN201610938977.7A CN201610938977A CN106540753A CN 106540753 A CN106540753 A CN 106540753A CN 201610938977 A CN201610938977 A CN 201610938977A CN 106540753 A CN106540753 A CN 106540753A
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ketohexamethylene
solid catalyst
modified solid
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孙国新
程沙沙
彭修静
崔玉
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University of Jinan
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/22—Magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

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  • Organic Chemistry (AREA)
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  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to catalysis technical field, and in particular to a kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：30 40 parts of zirconium dioxide, 10 20 parts of phosphotungstic acid, 20 30 parts of titanium dioxide, 15 parts of shitosan, 1 10 parts of ferric nitrate, 15 parts of ferrous nitrate, 1 10 parts of magnesium nitrate, 10 20 parts of silica gel, 20 30 parts of bentonite.Modified solid catalyst of the present invention, it is not only cheap and easy to get, free from environmental pollution, and easily reclaim and reusable, it is a kind of environmentally friendly solid catalyst, is adapted to industrialized production.

Description

A kind of modified solid catalyst containing phosphotungstic acid for Ketohexamethylene condensation reaction
Technical field
The invention belongs to catalysis technical field, and in particular to a kind of modified solid for Ketohexamethylene condensation reaction is catalyzed Agent.
Background technology
2-（1- cyclohexenyl groups）Ketohexamethylene and its isomerss hexamethylene alkylene pentylcyclohexanone are all important fine chemistries Product, in terms of chloroprophams, wood preservation, agrochemical being used for as special solvent.Its large-scale application is As synthesizing o-phenylphenol（OPP）Raw material.O-phenyl phenol is the organic product of important chemical industry, of many uses, be can be applicable to Antisepsis and sterilization, printing and dyeing assistant and surfactant, stabilizer and fire retardant of synthesizing new plastics, resin and macromolecular material etc. Field.O-phenyl phenol can also synthesize for synthesizing pressure-sensitive and temperature-sensitive paper developing agent, o-phenyl phenol and BCl3Reaction can Obtain the antioxidant and antifatigue for lubricating oil.By o-phenyl phenol and compound obtained in glycerine reaction, can be used for fibre Modified, the stabilizer of chlorine-containing organic compounds of dimension, synthetic resin reactive diluent and modifying agent, while and in the middle of reaction Body.
Yue Lili（Synthesis chemistry, 2003,11（2）, 147-149）Etc. have studied with Ketohexamethylene as raw material, acid or alkali are urged Agent condensation generates cyclohexanone dimer, and reaction temperature is high, and conversion ratio is low, and yield is not also high.
In the Chinese patent found, CN101205170A describes a kind of alumina base solid catalyst, and its shortcoming is Product postprocessing is bothered.
Used in CN101538196A, the solid acid of aromatic sulfonic acid class organic acid or load aromatic sulfonic acid class organic acid is catalyst, Although, up to 98%, Ketohexamethylene conversion ratio is low for the selectivity of dimer, only 60%.
CN101003471A and CN102500398A describe solid super-strong acid, and in two patents, Ketohexamethylene conversion ratio is not Height, only 45-65%, and the former production operation is complicated, including processes such as mixing, preheating, reaction of high order, washing, alkali cleanings.
CN102557908A describes a kind of solid acid catalyst, can be seen that from the case study on implementation of the patent When dimer selectivity is higher, Ketohexamethylene conversion ratio is relatively low, and when Ketohexamethylene conversion ratio is higher, the selectivity of dimer is relatively low, I.e. Ketohexamethylene conversion ratio is difficult while reaching higher level with dimer selectivity.
CN101613262A and CN102311326A describe a kind of method for preparing cyclohexenyl hexamethylene ketone, use solid Material makees catalyst, although the conversion ratio of Ketohexamethylene increases, but needs specific device to realize.
CN1535945A describes spent ion exchange resin and does the condensation of catalyst Ketohexamethylene, although processing step letter It is single, convenient product separation, but the yield of dimer is only 75-85%.
CN1371897A and CN1490293A strong inorganic acids or highly basic do the condensation of catalyst Ketohexamethylene, strong acid and strong base It is big to equipment corrosion, and reacted water is mutually acid or alkalescence, there is larger environmental issue in post processing trouble.
CN201010616008 load phosphotungstic acids, cationic resin load FeCl3Or SiO2Load FeCl3, activated carbon bear Any one or more of load silico-tungstic acid is catalyst synthesis 2-（1- cyclohexenyl groups）Ketohexamethylene, only describes synthesis two in the patent The process conditions of aggressiveness, but do not introduce the selectivity of the conversion ratio and dimer of Ketohexamethylene, and do not illustrate load phosphorus The carrier of wolframic acid.Phosphotungstic acid is extremely active, and the patent controlling reaction temperature is 134-136 DEG C, at such high temperatures, although Increased the conversion ratio of Ketohexamethylene, but also increase the generation of side reaction, reduce the selectivity of dimer.Ketohexamethylene condensation is anti- The by-product answered is mainly polymer, and polymer is little in commercial Application, and difficult degradation, and this undoubtedly increased and is disposing waste liquid The consumption of aspect.
The content of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of modified solid for Ketohexamethylene condensation reaction is catalyzed Agent, the present invention are realized by following proposal：
A kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：Zirconium dioxide 30- 40 parts, phosphotungstic acid 10-20 parts, titanium dioxide 20-30 parts, shitosan 1-5 parts, ferric nitrate 1-10 parts, ferrous nitrate 1-5 parts, nitre Sour magnesium 1-10 parts, silica gel 10-20 parts, bentonite 20-30 parts.
A kind of preparation method of the modified solid catalyst for Ketohexamethylene condensation reaction, comprises the steps：（1）By phosphorus Wolframic acid is dissolved in the water, and adds afterwards and 1-2h is impregnated under zirconium dioxide, room temperature, adds cross-linking agents 1-2h, the material after crosslinking It is prepared into high-pressure molding instrument and can crosses 100 mesh sieves and obtain microsphere, amount of water is 1ml/g zirconium dioxides, the microsphere is designated as A；（2）Will Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, and are 5-6.8 with oxalic acid regulation mixed liquor pH value, add titanium dioxide afterwards The shitosan of titanium, silica gel and deacetylation more than 85% simultaneously vibrates 10-20min at 40 DEG C, stands de-bubble, adds cross-linking agent to hand over Connection 0.5-1h, the material high-pressure molding instrument after crosslinking is prepared into can be crossed 70 mesh sieves and obtain microsphere, and the microsphere is designated as B, B is existed 1-2h is soaked in the NaOH solution of 0.5mol/L and obtains porous microsphere C, C Surface is washed till into neutrality with water, amount of water is 1ml/g bis- Titanium oxide；（3）Xiang Shuizhong adds A, B and bentonite, is stirring evenly and then adding into cross-linking agents 1-2h, and the material after crosslinking is high Molded instrument is prepared into the microsphere that can cross 50 mesh sieves, is designated as C, and amount of water is 1ml/g bentonite, by C microwave radiations 5-10min both Obtain modified solid catalyst.
Preferably, above-mentioned steps（1）Middle cross-linking agent is 0.01-0.1 with the mass ratio of zirconium dioxide.
Preferably, above-mentioned steps（2）Middle cross-linking agent is 0.05-0.2 with the mass ratio of titanium dioxide.
Preferably, above-mentioned steps（3）Middle cross-linking agent is 0.05-0.15 with bentonitic mass ratio.
It is more highly preferred to, mixture of the above-mentioned cross-linking agent for isothiocyanate, epoxy resin and glyceraldehyde, above-mentioned different sulfur cyanogen The mass ratio of acid esters, epoxy resin and glyceraldehyde is 1:2:5.
Particularly, above-mentioned cross-linking agent is glyceraldehyde.
More particularly, above-mentioned steps（1）-（3）The parameter of described high-pressure molding instrument is：45～50kv of voltage, propulsion Speed is 80～85mm/h, and pulsewidth is 5ms, and frequency is 90Hz.
Wherein, above-mentioned zirconium dioxide, titanium dioxide, silica gel and bentonite were 200 mesh sieves and obtained powder.
Finally, above-mentioned modified solid catalyst is prepared in dimerization precursor reactant, in reaction temperature 100-110 in Ketohexamethylene condensation DEG C, between reaction pressure -0.07MPa to -0.05MPa, response time 1-2h, catalyst are ring under the 1-5% of Ketohexamethylene quality The conversion ratio of hexanone is more than 98%, and the selectivity of dimer is more than 99%.
Metal ion can be with-the NH in chitosan molecule2,-OH coordination, formed chitosan metal complexes, shitosan gold Metal complex adheres on the titanium dioxide as an entirety, reduces metal ion and is lost in during the course of the reaction, makes titanium dioxide Four crystalline phase of titanium is more stable；
B is soaked into 1-2h in the NaOH solution of 0.5mol/L, the dissolving of the silica gel in B is made and is obtained porous microsphere C, use swelling Micropore filling in C is made modified solid catalyst integration by soil and A, reduces the crushing of catalyst during the course of the reaction, is increased The service life of catalyst.
Modified solid catalyst of the present invention, it is not only cheap and easy to get, free from environmental pollution, and easily reclaim and repeat Use, be a kind of environmentally friendly solid catalyst, be adapted to industrialized production.
Specific embodiment
Embodiment 1
A kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：Zirconium dioxide 30 Part, 10 parts of phosphotungstic acid, titanium dioxide 20-3 parts, 1 part of shitosan, 1 part of ferric nitrate, 1 part of ferrous nitrate, 1 part of magnesium nitrate, silica gel 10 Part, 20 parts of bentonite；Its preparation process is such as：（1）Phosphotungstic acid is dissolved in the water, and to be added afterwards and 1h is impregnated under zirconium dioxide, room temperature, Cross-linking agents 1h is added, the material high-pressure molding instrument after crosslinking is prepared into can be crossed 100 mesh sieves and obtain microsphere, and amount of water is 1ml/ G zirconium dioxides, the microsphere are designated as A；（2）Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, and adjust mixed with oxalic acid It is 5 to close liquid pH value, adds the shitosan of titanium dioxide, silica gel and deacetylation more than 85% afterwards and vibrates 10min at 40 DEG C, De-bubble is stood, cross-linking agents 0.5h is added, the material high-pressure molding instrument after crosslinking is prepared into can be crossed 70 mesh sieves and obtain microsphere, institute State microsphere and be designated as B, B is soaked into 1h in the NaOH solution of 0.5mol/L and obtains porous microsphere C, C Surface is washed till into neutrality with water, Amount of water is 1ml/g titanium dioxide；（3）Xiang Shuizhong adds A, B and bentonite, is stirring evenly and then adding into cross-linking agents 1h, hands over Material high-pressure molding instrument after connection is prepared into the microsphere that can cross 50 mesh sieves, is designated as C, and amount of water is 1ml/g bentonite, and C is micro- Wave radiation 5min had both obtained modified solid catalyst；Step（1）Middle cross-linking agent is 0.01 with the mass ratio of zirconium dioxide；Step（2） Middle cross-linking agent is 0.05 with the mass ratio of titanium dioxide；Step（3）Middle cross-linking agent is 0.05 with bentonitic mass ratio；Cross-linking agent For the mass ratio of the mixture of isothiocyanate, epoxy resin and glyceraldehyde, above-mentioned isothiocyanate, epoxy resin and glyceraldehyde For 1:2:5；Step（1）-（3）The parameter of described high-pressure molding instrument is：Voltage 45kv, fltting speed is 80mm/h, and pulsewidth is 5ms, frequency are 90Hz；Zirconium dioxide, titanium dioxide, silica gel and bentonite were 200 mesh sieves and obtained powder.
Embodiment 2
A kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：Zirconium dioxide 40 Part, 20 parts of phosphotungstic acid, 30 parts of titanium dioxide, 5 parts of shitosan, 10 parts of ferric nitrate, 5 parts of ferrous nitrate, 10 parts of magnesium nitrate, silica gel 20 Part, 30 parts of bentonite；Its preparation process is such as：（1）Phosphotungstic acid is dissolved in the water, and to be added afterwards and 2h is impregnated under zirconium dioxide, room temperature, Cross-linking agents 2h is added, the material high-pressure molding instrument after crosslinking is prepared into can be crossed 100 mesh sieves and obtain microsphere, and amount of water is 1ml/ G zirconium dioxides, the microsphere are designated as A；（2）Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, and adjust mixed with oxalic acid It is 6.8 to close liquid pH value, adds the shitosan of titanium dioxide, silica gel and deacetylation more than 85% afterwards and vibrates at 40 DEG C 20min, stands de-bubble, adds cross-linking agents 1h, and the material high-pressure molding instrument after crosslinking is prepared into can be crossed 70 mesh sieves and obtain micro- Ball, the microsphere are designated as B, B is soaked 2h in the NaOH solution of 0.5mol/L and obtains porous microsphere C, be washed till C Surface with water Neutrality, amount of water are 1ml/g titanium dioxide；（3）Xiang Shuizhong adds A, B and bentonite, is stirring evenly and then adding into cross-linking agents 2h, the material high-pressure molding instrument after crosslinking are prepared into the microsphere that can cross 50 mesh sieves, are designated as C, and amount of water is 1ml/g bentonite, C microwave radiations 10min had both been obtained modified solid catalyst；Step（1）Middle cross-linking agent is 0.1 with the mass ratio of zirconium dioxide；Step Suddenly（2）Middle cross-linking agent is 0.2 with the mass ratio of titanium dioxide；Step（3）Middle cross-linking agent is 0.15 with bentonitic mass ratio；Hand over Connection agent is glyceraldehyde；Step（1）-（3）The parameter of described high-pressure molding instrument is：Voltage 50kv, fltting speed is 85mm/h, arteries and veins A width of 5ms, frequency are 90Hz；Zirconium dioxide, titanium dioxide, silica gel and bentonite were 200 mesh sieves and obtained powder.
Embodiment 3
A kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：Zirconium dioxide 33 Part, 13 parts of phosphotungstic acid, 24 parts of titanium dioxide, 2 parts of shitosan, 4 parts of ferric nitrate, 2 parts of ferrous nitrate, 4 parts of magnesium nitrate, silica gel 13 Part, 22 parts of bentonite；Its preparation process is such as：（1）Phosphotungstic acid is dissolved in the water, zirconium dioxide is added afterwards, is impregnated under room temperature 1.2h, adds cross-linking agents 1.2h, and the material high-pressure molding instrument after crosslinking is prepared into can be crossed 100 mesh sieves and obtain microsphere, add water Measure as 1ml/g zirconium dioxides, the microsphere is designated as A；（2）Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, and with grass It is 5.5 that acid adjusts mixed liquor pH value, adds the shitosan of titanium dioxide, silica gel and deacetylation more than 85% afterwards and at 40 DEG C Vibration 14min, stands de-bubble, adds cross-linking agents 0.6h, and the material high-pressure molding instrument after crosslinking is prepared into can cross 70 mesh Microsphere is sieved to obtain, the microsphere is designated as B, B is soaked into 1.4h in the NaOH solution of 0.5mol/L and obtains porous microsphere C, with water by C Surface is washed till neutrality, and amount of water is 1ml/g titanium dioxide；（3）Xiang Shuizhong adds A, B and bentonite, is stirring evenly and then adding into friendship Connection agent crosslinking 1.4h, the material high-pressure molding instrument after crosslinking are prepared into the microsphere that can cross 50 mesh sieves, are designated as C, and amount of water is 1ml/g bentonite, C microwave radiations 7min had both been obtained modified solid catalyst；Step（1）The quality of middle cross-linking agent and zirconium dioxide Than for 0.01-0.1；Step（2）Middle cross-linking agent is 0.1 with the mass ratio of titanium dioxide；Step（3）Middle cross-linking agent with it is bentonitic Mass ratio is 0.09；Cross-linking agent is the mixture of isothiocyanate, epoxy resin and glyceraldehyde, above-mentioned isothiocyanate, epoxy The mass ratio of resin and glyceraldehyde is 1:2:5；Step（1）-（3）The parameter of described high-pressure molding instrument is：Voltage 46kv, propulsion Speed is 81mm/h, and pulsewidth is 5ms, and frequency is 90Hz.
Embodiment 4
A kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：Zirconium dioxide 38 Part, 19 parts of phosphotungstic acid, 26 parts of titanium dioxide, 4 parts of shitosan, 8 parts of ferric nitrate, 4 parts of ferrous nitrate, 9 parts of magnesium nitrate, silica gel 18 Part, 26 parts of bentonite；Its preparation process is such as：（1）Phosphotungstic acid is dissolved in the water, zirconium dioxide is added afterwards, is impregnated under room temperature 1.8h, adds cross-linking agents 1.9h, and the material high-pressure molding instrument after crosslinking is prepared into can be crossed 100 mesh sieves and obtain microsphere, add water Measure as 1ml/g zirconium dioxides, the microsphere is designated as A；（2）Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, and with grass It is 6.0 that acid adjusts mixed liquor pH value, adds the shitosan of titanium dioxide, silica gel and deacetylation more than 85% afterwards and at 40 DEG C Vibration 18min, stands de-bubble, adds cross-linking agents 0.8h, and the material high-pressure molding instrument after crosslinking is prepared into can cross 70 mesh Microsphere is sieved to obtain, the microsphere is designated as B, B is soaked into 1.8h in the NaOH solution of 0.5mol/L and obtains porous microsphere C, with water by C Surface is washed till neutrality, and amount of water is 1ml/g titanium dioxide；（3）Xiang Shuizhong adds A, B and bentonite, is stirring evenly and then adding into friendship Connection agent crosslinking 1-2h, the material high-pressure molding instrument after crosslinking are prepared into the microsphere that can cross 50 mesh sieves, are designated as C, and amount of water is 1ml/g bentonite, C microwave radiations 7min had both been obtained modified solid catalyst；Step（1）The quality of middle cross-linking agent and zirconium dioxide Than for 0.08；Step（2）Middle cross-linking agent is 0.15 with the mass ratio of titanium dioxide；Step（3）Middle cross-linking agent and bentonitic matter Amount is than being 0.13；Cross-linking agent is oily aldehyde；Step（1）-（3）The parameter of described high-pressure molding instrument is：Voltage 49kv, fltting speed For 84mm/h, pulsewidth is 5ms, and frequency is 90Hz.
Embodiment 5
A kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：Zirconium dioxide 35 Part, 15 parts of phosphotungstic acid, 25 parts of titanium dioxide, 3 parts of shitosan, ferric nitrate 1-105 parts, 3 parts of ferrous nitrate, 5 parts of magnesium nitrate, silica gel 150-20 parts, 25 parts of bentonite；Its preparation process is such as：（1）Phosphotungstic acid is dissolved in the water, zirconium dioxide is added afterwards, under room temperature Dipping 1.5h, adds cross-linking agents 1.5h, and the material high-pressure molding instrument after crosslinking is prepared into can be crossed 100 mesh sieves and obtain microsphere, Amount of water is 1ml/g zirconium dioxides, and the microsphere is designated as A；（2）Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, and It is 5.8 that mixed liquor pH value is adjusted with oxalic acid, adds the shitosan of titanium dioxide, silica gel and deacetylation more than 85% afterwards and in 40 10-20min is vibrated at DEG C, de-bubble is stood, cross-linking agents 0.8h is added, the material high-pressure molding instrument after crosslinking is prepared into can Cross 70 mesh sieves and obtain microsphere, the microsphere is designated as B, B is soaked into 1.5h in the NaOH solution of 0.5mol/L and obtains porous microsphere C, use C Surface is washed till neutrality by water, and amount of water is 1ml/g titanium dioxide；（3）Xiang Shuizhong adds A, B and bentonite, adds after stirring Enter cross-linking agents 1-2h, the material high-pressure molding instrument after crosslinking is prepared into the microsphere that can cross 50 mesh sieves, is designated as C, amount of water For 1ml/g bentonite, C microwave radiations 7min was both obtained modified solid catalyst；Step（1）The matter of middle cross-linking agent and zirconium dioxide Amount is than being 0.05；Step（2）Middle cross-linking agent is 0.12 with the mass ratio of titanium dioxide；Step（3）Middle cross-linking agent with it is bentonitic Mass ratio is 0.10；Cross-linking agent is the mixture of isothiocyanate, epoxy resin and glyceraldehyde, above-mentioned isothiocyanate, epoxy The mass ratio of resin and glyceraldehyde is 1:2:5；Step（1）-（3）The parameter of described high-pressure molding instrument is：Voltage 48kv, propulsion Speed is 83mm/h, and pulsewidth is 5ms, and frequency is 90Hz；Zirconium dioxide, titanium dioxide, silica gel and bentonite were 200 mesh sieves Obtain powder.
Comparative example 1
A kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：Zirconium dioxide 25 Part, 25 parts of phosphotungstic acid, 10 parts of titanium dioxide, 7 parts of shitosan, 11 parts of ferric nitrate, 9 parts of ferrous nitrate, 5 parts of magnesium nitrate, silica gel 9 Part, 33 parts of bentonite；Its preparation process is such as：（1）Phosphotungstic acid is dissolved in the water, zirconium dioxide is added afterwards, is impregnated under room temperature 1.5h, adds cross-linking agents 1.5h, and the material high-pressure molding instrument after crosslinking is prepared into can be crossed 100 mesh sieves and obtain microsphere, add water Measure as 1ml/g zirconium dioxides, the microsphere is designated as A；（2）Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, and with grass It is 5.8 that acid adjusts mixed liquor pH value, adds the shitosan of titanium dioxide, silica gel and deacetylation more than 85% afterwards and at 40 DEG C Vibration 10-20min, stands de-bubble, adds cross-linking agents 0.8h, and the material high-pressure molding instrument after crosslinking is prepared into can cross 70 Mesh sieve obtains microsphere, and the microsphere is designated as B, B is soaked 1.5h in the NaOH solution of 0.5mol/L and obtains porous microsphere C, will with water C Surface is washed till neutrality, and amount of water is 1ml/g titanium dioxide；（3）Xiang Shuizhong adds A, B and bentonite, is stirring evenly and then adding into friendship Connection agent crosslinking 1-2h, the material high-pressure molding instrument after crosslinking are prepared into the microsphere that can cross 50 mesh sieves, are designated as C, and amount of water is 1ml/g bentonite, C microwave radiations 7min had both been obtained modified solid catalyst；Step（1）The quality of middle cross-linking agent and zirconium dioxide Than for 0.05；Step（2）Middle cross-linking agent is 0.12 with the mass ratio of titanium dioxide；Step（3）Middle cross-linking agent and bentonitic matter Amount is than being 0.10；Cross-linking agent is the mixture of isothiocyanate, epoxy resin and glyceraldehyde, above-mentioned isothiocyanate, asphalt mixtures modified by epoxy resin The mass ratio of fat and glyceraldehyde is 1:2:5；Step（1）-（3）The parameter of described high-pressure molding instrument is：Voltage 48kv, propulsion speed Spend for 83mm/h, pulsewidth is 5ms, and frequency is 90Hz；Zirconium dioxide, titanium dioxide, silica gel and bentonite were 200 mesh sieves and obtained Powder.
Comparative example 2
A kind of modified solid catalyst for Ketohexamethylene condensation reaction, including the raw material of following portions by weight：Zirconium dioxide 35 Part, 15 parts of phosphotungstic acid, 25 parts of titanium dioxide, 3 parts of shitosan, ferric nitrate 1-105 parts, 3 parts of ferrous nitrate, 5 parts of magnesium nitrate, silica gel 150-20 parts, 25 parts of bentonite；Its preparation process is such as：（1）Phosphotungstic acid is dissolved in the water, zirconium dioxide is added afterwards, under room temperature Dipping 3h, adds cross-linking agents 0.5h, and the material high-pressure molding instrument after crosslinking is prepared into can be crossed 100 mesh sieves and obtain microsphere, plus The water yield is 1ml/g zirconium dioxides, and the microsphere is designated as A；（2）Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, are used in combination It is 4 that oxalic acid adjusts mixed liquor pH value, adds the shitosan of titanium dioxide, silica gel and deacetylation more than 85% afterwards and at 40 DEG C Vibration 5min, stands de-bubble, adds cross-linking agents 1.1h, and the material high-pressure molding instrument after crosslinking is prepared into can cross 70 mesh sieves Microsphere, the microsphere is designated as B, B soaked 0.5h in the NaOH solution of 0.5mol/L and obtains porous microsphere C, with water by C tables Face is washed till neutrality, and amount of water is 2ml/g titanium dioxide；（3）Xiang Shuizhong adds A, B and bentonite, is stirring evenly and then adding into crosslinking Agent is crosslinked 1.5h, and the material high-pressure molding instrument after crosslinking is prepared into the microsphere that can cross 50 mesh sieves, is designated as C, and amount of water is 0.5ml/g bentonite, C microwave radiations 1min had both been obtained modified solid catalyst；Step（1）The matter of middle cross-linking agent and zirconium dioxide Amount is than being 0.11；Step（2）Middle cross-linking agent is 0.01 with the mass ratio of titanium dioxide；Step（3）Middle cross-linking agent with it is bentonitic Mass ratio is 0.04；Cross-linking agent is the mixture of isothiocyanate, epoxy resin and glyceraldehyde, above-mentioned isothiocyanate, epoxy The mass ratio of resin and glyceraldehyde is 1:5:5；Step（1）-（3）The parameter of described high-pressure molding instrument is：Voltage 55kv, propulsion Speed is 95mm/h, and pulsewidth is 5ms, and frequency is 90Hz；Zirconium dioxide, titanium dioxide, silica gel and bentonite were 200 mesh sieves Obtain powder；Modified solid catalyst is prepared in dimerization precursor reactant, in reaction temperature 100-110 DEG C, reaction pressure in Ketohexamethylene condensation Between power -0.07MPa to -0.05MPa, response time 1-2h, catalyst are the conversion of Ketohexamethylene under the 1-5% of Ketohexamethylene quality Rate is more than 98%, the selectivity of dimer be 99% with.
Modified solid catalyst obtained by embodiment 1-5 and comparative example 1-2 is prepared into dimerization precursor reactant in Ketohexamethylene condensation In, in 100 DEG C of reaction temperature, reaction pressure -0.07MPa, the response time 1, catalyst under the 2% of Ketohexamethylene quality, Ketohexamethylene Conversion ratio and dimer selectivity such as table 1 below：
Table 1
Modified solid catalyst obtained by embodiment 1-5 and comparative example 1-2 is prepared in dimerization precursor reactant in Ketohexamethylene condensation, 110 DEG C of reaction temperature, between reaction pressure -0.05MPa, response time 2h, catalyst are Ketohexamethylene under the 4% of Ketohexamethylene quality Conversion ratio and dimer selectivity such as table 2 below：
Table 2
Modified solid catalyst obtained by embodiment 1-5 and comparative example 1-2 is prepared in dimerization precursor reactant in Ketohexamethylene condensation, 105 DEG C of reaction temperature, between reaction pressure -0.06MPa, response time 1.5h, catalyst are hexamethylene under the 3% of Ketohexamethylene quality The selectivity such as table 3 below of the conversion ratio and dimer of ketone：
Table 3
Change the application each component content or technological parameter can be seen that by three above form, its effect is undesirable, hexamethylene Ketone conversion ratio and dimer selectivity are decreased obviously.

Claims (10)

1. a kind of modified solid catalyst for Ketohexamethylene condensation reaction, it is characterised in that including the original of following portions by weight Material：Zirconium dioxide 30-40 parts, phosphotungstic acid 10-20 parts, titanium dioxide 20-30 parts, shitosan 1-5 parts, ferric nitrate 1-10 parts, nitre Sour ferrous iron 1-5 parts, magnesium nitrate 1-10 parts, silica gel 10-20 parts, bentonite 20-30 parts.
2. a kind of preparation method of the modified solid catalyst for Ketohexamethylene condensation reaction, it is characterised in that including following steps Suddenly：（1）Phosphotungstic acid is dissolved in the water, is added afterwards and under zirconium dioxide, room temperature, is impregnated 1-2h, add cross-linking agents 1-2h, handed over Material high-pressure molding instrument after connection is prepared into can be crossed 100 mesh sieves and obtain microsphere, and amount of water is 1ml/g zirconium dioxides, the microsphere It is designated as A；（2）Ferric nitrate, ferrous nitrate, magnesium nitrate are dissolved in the water, and are 5-6.8 with oxalic acid regulation mixed liquor pH value, after Add the shitosan of titanium dioxide, silica gel and deacetylation more than 85% and 10-20min is vibrated at 40 DEG C, stand de-bubble, plus Enter cross-linking agents 0.5-1h, the material high-pressure molding instrument after crosslinking is prepared into can be crossed 70 mesh sieves and obtain microsphere, the microsphere note For B, B is soaked into 1-2h in the NaOH solution of 0.5mol/L and obtains porous microsphere C, C Surface is washed till into neutrality, amount of water with water For 1ml/g titanium dioxide；（3）Xiang Shuizhong adds A, B and bentonite, is stirring evenly and then adding into cross-linking agents 1-2h, after crosslinking Material high-pressure molding instrument be prepared into the microsphere that can cross 50 mesh sieves, be designated as C, amount of water is 1ml/g bentonite, by C microwave spokes Penetrate 5-10min and both obtain modified solid catalyst.
3. a kind of preparation method of the modified solid catalyst for Ketohexamethylene condensation reaction as claimed in claim 2, which is special Levy and be, the step（1）Middle cross-linking agent is 0.01-0.1 with the mass ratio of zirconium dioxide.
4. a kind of preparation method of the modified solid catalyst for Ketohexamethylene condensation reaction as claimed in claim 2, which is special Levy and be, the step（2）Middle cross-linking agent is 0.05-0.2 with the mass ratio of titanium dioxide.
5. a kind of preparation method of the modified solid catalyst for Ketohexamethylene condensation reaction as claimed in claim 2, which is special Levy and be, the step（3）Middle cross-linking agent is 0.05-0.15 with bentonitic mass ratio.
6. a kind of preparation method of the modified solid catalyst for Ketohexamethylene condensation reaction as claimed in claim 2, which is special Levy and be, mixture of the cross-linking agent for isothiocyanate, epoxy resin and glyceraldehyde, the isothiocyanate, asphalt mixtures modified by epoxy resin The mass ratio of fat and glyceraldehyde is 1:2:5.
7. a kind of preparation method of the modified solid catalyst for Ketohexamethylene condensation reaction as claimed in claim 2, which is special Levy and be, the cross-linking agent is glyceraldehyde.
8. a kind of preparation method of the modified solid catalyst for Ketohexamethylene condensation reaction as claimed in claim 2, which is special Levy and be, the step（1）-（3）The parameter of described high-pressure molding instrument is：45～50kv of voltage, fltting speed be 80～ 85mm/h, pulsewidth are 5ms, and frequency is 90Hz.
9. a kind of modified solid catalyst for Ketohexamethylene condensation reaction as claimed in claim 1, it is characterised in that described Zirconium dioxide, titanium dioxide, silica gel and bentonite were 200 mesh sieves and obtained powder.
10. a kind of modified solid catalyst for Ketohexamethylene condensation reaction as claimed in claim 1, the modified solid are urged Agent is prepared in dimerization precursor reactant, in reaction temperature 100-110 DEG C in Ketohexamethylene condensation, reaction pressure -0.07MPa to - Between 0.05MPa, response time 1-2h, catalyst are that, under the 1-5% of Ketohexamethylene quality, the conversion ratio of Ketohexamethylene is more than 98%, The selectivity of dimer is more than 99%.
CN201610938977.7A 2016-10-25 2016-10-25 A kind of modified solid catalyst containing phosphotungstic acid for Ketohexamethylene condensation reaction Pending CN106540753A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110787811A (en) * 2019-11-11 2020-02-14 怀化学院 Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110787811A (en) * 2019-11-11 2020-02-14 怀化学院 Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof
CN110787811B (en) * 2019-11-11 2022-07-12 怀化学院 Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof

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