CN105478169A - Sepiolite loaded metal phthalocyanine catalyst, and applications thereof in catalytic preparation of humic acid - Google Patents
Sepiolite loaded metal phthalocyanine catalyst, and applications thereof in catalytic preparation of humic acid Download PDFInfo
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- CN105478169A CN105478169A CN201510902879.3A CN201510902879A CN105478169A CN 105478169 A CN105478169 A CN 105478169A CN 201510902879 A CN201510902879 A CN 201510902879A CN 105478169 A CN105478169 A CN 105478169A
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- sepiolite
- phthalocyanine
- metal phthalocyanine
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels
Abstract
The invention discloses a sepiolite loaded metal phthalocyanine catalyst. A preparation method comprises following steps: (1) pretreatment of sepiolite; and (2) preparation of sepiolite loaded metal phthalocyanine, wherein sepiolite obtained via pretreatment, metal phthalocyanine, and water or DMF or chloroform or dichloromethane are mixed, and an obtained mixture is subjected to stirring reaction, suction filtration, washing, and drying so as to obtain sepiolite loaded metal phthalocyanine, the metal phthalocyanine is selected from sulfonated phthalocyanin iron, sulfonated cobalt phthalocyanine, sulfonated phthalocyanine manganese, nitrated phthalocyanine iron, nitrated cobalt phthalocyanine, nitrated phthalocyanine manganese, alkoxy substituted phthalocyanine iron, alkoxy substituted cobalt phthalocyanine, or alkoxy substituted phthalocyanine manganese. The sepiolite loaded metal phthalocyanine catalyst can be used for preparing humic acid via catalytic oxidation of weathered coal. Catalyst using amount is less; reaction time is short; humic acid content of an obtained product is high; and application value of the sepiolite loaded metal phthalocyanine catalyst in industrial production is high.
Description
Technical field
The present invention relates to a kind of sepiolite supported metal phthalocyanine catalyst, and with it for catalyst oxidation weathered coal prepares application in humic acid.
Background technology
In recent years, metal phthalocyanine (MPc) is widely used in the fields such as chemical catalysis, optics, electricity and medical science due to its large conjugated system, stable chemical constitution and its excellent properties in optical, electrical, magnetic etc.But as homogeneous catalyst, metal phthalocyanine have easily formed dimer, oxidation resistance poor, not easily reclaim and easily cause the shortcomings such as secondary pollution, therefore, load-type metal phthalocyanine becomes study hotspot in recent years.The load of metal phthalocyanine has infusion process, blending method, bonding method, in-situ synthesis, axial coordination method etc.Yao etc. utilize infusion process binuclear metallo phthalocyanine to be loaded to obtained novel load catalyst on silk fiber, and the oxidation reaction of this catalyst to the 2 mercapto ethanol in the aqueous solution shows very high catalytic activity.Chen Wenxing etc. introduce active function groups by tetramino Phthalocyanine Zinc, are then loaded on cellulose by covalent bond.In whole catalytic oxidation process, the existence due to carrier reduces Phthalocyanine Zinc gathering in aqueous in loaded catalyst, thus avoids the reduction of catalyst activity, makes the photochemical catalytic oxidation conversion ratio of phenol reach 95% in 6h.
Sepiolite belongs to natural mineral resources, rich reserves.Sepiolite has in double-deck silicon-oxy tetrahedron and presss from both sides the octahedral natural bed of magnesia-chain transiens structure, and theoretical specific surface area is 900m
2/ g, belong to fibrous rich magnesium silicate clay mineral, there is good zeolite water passage and the architectural feature of high-specific surface area, exist with high degree of dispersion suspended state in water body, there is very strong absorption property and ion-exchange capacity, there is the characteristics such as good corrosion resistance, heat endurance, salt-resistance, be all widely used in heavy metal containing wastewater treatment, treatment of dyeing wastewater, heavy metal pollution of soil reparation, catalyst carrier etc.But by sepiolite supported metal phthalocyanine Kaolinite Preparation of Catalyst, be in the news not yet so far.
At present, oxidative degradation utilizes one of weathered coal common method preparing humic acid both at home and abroad.But there is the problems such as oxidant large usage quantity, the reaction time is longer, Humic Acid Production Rate is not high in this technique, the catalyst that choice and application is suitable is the effective measures solving above-mentioned technological problems always.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of novel heterogeneous catalysis---sepiolite supported metal phthalocyanine, and it prepares the purposes of humic acid as catalyst oxidation weathered coal.The present invention obtains the novel heterogeneous catalysis of sepiolite supported metal phthalocyanine by infusion process, it prepare simple, with low cost, be easy to realize, be applied to catalytic oxidation weathered coal and prepare humic acid, greatly can improve the productive rate of humic acid, industrial production has major application be worth.
The present invention is achieved by the following technical solutions:
A kind of sepiolite supported metal phthalocyanine, is prepared by following preparation method:
(1) pretreatment of sepiolite: sepiolite is immersed in the hydrochloric acid or salpeter solution that concentration is 1 ~ 6mol/L, after dipping 24 ~ 72h, suction filtration, washes with water, dry, is ground to 60 ~ 100 object particles, is pretreated sepiolite, for subsequent use;
One of (2) sepiolite supported metal phthalocyanine is prepared: in the following ways:
Mode one: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 200mg, water 10 ~ 50mL, is placed in flask, stirs 12 ~ 24h, suction filtration, water washing, dries 1 ~ 6 hour, obtains sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from sulfonated phthalocyanine iron, sulfonated phthalocyanine cobalt or sulfonated phthalocyanine manganese;
Mode two: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 500mg, DMF (DMF) 10 ~ 50mL, be placed in flask, stir 12 ~ 24h, suction filtration, DMF washs, and dries 1 ~ 6 hour, obtains sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from nitro FePC, nitro Cobalt Phthalocyanine or nitro manganese phthalocyanine;
Mode three: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 200mg, chloroform or carrene 10 ~ 50mL, be placed in flask, stir 12 ~ 24h, suction filtration, chloroform or washed with dichloromethane, dry 1 ~ 6 hour, obtain sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from alkoxyl substituted phthalocyanine iron, alkoxyl substituted phthalocyanine cobalt or alkoxyl substituted phthalocyanine manganese.
Described sepiolite supported metal phthalocyanine, may be used for catalytic oxidation weathered coal and prepare humic acid, during embody rule, method is as follows: get weathered coal, broken, crosses 80 mesh sieves; Take the coal sample 10g (being accurate to 0.1g) through deliming process, catalyst (sepiolite supported metal phthalocyanine) 0.05 ~ 0.1g, mix in rearmounted there-necked flask, add the salpeter solution of 10 ~ 20mL mass fraction 30% or the sulfuric acid solution of mass fraction 45%, make coal sample fully wetting, degrade in boiling water bath after 1h and take out, adding ammoniacal liquor, to be neutralized to pH value be 7; React 2 hours in 60 DEG C of water-baths; Suction filtration, dry, obtain humic acid.
Sepiolite supported metal phthalocyanine of the present invention, prepares humic acid for catalytic oxidation weathered coal, and used catalyst consumption is few, and the reaction time is short, and in products therefrom, humic acid content is high, and industrial production has great using value.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Instrument, reagent, material etc. involved in following embodiment, unless otherwise noted, be existing conventional instrument, reagent, material etc. in prior art, obtain by regular commercial sources.Experimental technique involved in following embodiment, detection method etc., unless otherwise noted, are existing normal experiment method in prior art, detection method etc.
Embodiment 1 prepares sepiolite supported nitro FePC
Method is as follows:
(1) be immersed in the hydrochloric acid of 6mol/L by sepiolite, both volume ratios are 1:9, after dipping 72, and suction filtration, washing, dry, be ground to 80 object particles, for subsequent use.
(2) above-mentioned pretreated sepiolite 10.0g is got, nitro FePC 200mg, DMF (DMF) 10mL, is placed in flask, stir 20h, suction filtration, DMF washs, in an oven after 100 DEG C of oven dry, be warmed up to 200 DEG C to dry 4 hours, obtain sepiolite supported nitro FePC.
Above-mentioned sepiolite supported metal phthalocyanine heterogeneous catalysis catalytic oxidation weathered coal is utilized to prepare the method for humic acid, as follows:
Weathered coal passes through 80 mesh sieves through fragmentation, take in the coal sample 10g (being accurate to 0.1g) and 0.08 gram of even rearmounted there-necked flask of catalyst mix of deliming process, add the salpeter solution of 20mL mass fraction 30%, make coal sample fully wetting, degrade in boiling water bath after 1h and take out, adding ammoniacal liquor, to be neutralized to pH value be 7.React 2 hours under 60 DEG C of water-baths; Suction filtration, dry, in products therefrom, the content of free humic acid is 39.9% (mass percent), and the content of total humic acid is 61.8% (mass percent).
Meanwhile, not add catalyst in contrast.After identical reaction condition, in products therefrom, the content of free humic acid is 26.7%, and the content of total humic acid is 32.8%.By comparison, the productive rate of free humic acid improves 13.2% in the present invention, and the productive rate of total humic acid improves 29.0%, Be very effective.
Embodiment 2 prepares sepiolite supported alkoxyl substituted phthalocyanine manganese
Method is as follows:
(1) be immersed in the hydrochloric acid of 6mol/L by sepiolite, both volume ratios are 1:9, after dipping 72, and suction filtration, washing, dry, be ground to 80 object particles, for subsequent use.
(2) get above-mentioned pretreated sepiolite 10.0g, alkoxyl substituted phthalocyanine manganese 200mg, chloroform 40mL, is placed in flask, stir 20h, suction filtration, chloroform, in an oven after 100 DEG C of oven dry, be warmed up to 200 DEG C and dry 4 hours, obtain sepiolite supported manganese phthalocyanine.
Above-mentioned sepiolite supported metal phthalocyanine heterogeneous catalysis catalytic oxidation weathered coal is utilized to prepare the method for humic acid, as follows:
Weathered coal passes through 80 mesh sieves through fragmentation, take in the coal sample 10g (being accurate to 0.1g) and 0.05 gram of even rearmounted there-necked flask of catalyst mix of deliming process, add the salpeter solution of 20mL mass fraction 30%, make coal sample fully wetting, degrade in boiling water bath after 1h and take out, adding ammoniacal liquor, to be neutralized to pH value be 7.React 2 hours under 60 DEG C of water-baths; Suction filtration, dry, in products therefrom, the content of free humic acid is 38.5%, and the content of total humic acid is 61.2%.
Meanwhile, not add catalyst in contrast.After identical reaction condition, in products therefrom, the content of free humic acid is 26.7%, and the content of total humic acid is 32.8%.By comparison, the productive rate of humic acid improves 11.8% in the present invention, and the productive rate of total humic acid improves 28.4%, Be very effective.
Embodiment 3 prepares sepiolite supported sulfonated phthalocyanine cobalt
Method is as follows:
(1) be immersed in the salpeter solution of 3mol/L by sepiolite, both volume ratios are 1:9, after dipping 60, and suction filtration, washing, dry, be ground to 80 object particles, for subsequent use.
(2) get above-mentioned pretreated sepiolite 10.0g, sulfonated phthalocyanine cobalt 100mg, water 30mL, is placed in flask, stirs 20h, suction filtration, water washing, in an oven after 100 DEG C of oven dry, is warmed up to 200 DEG C and dries 4 hours, obtain sepiolite supported sulfonated phthalocyanine cobalt.
Above-mentioned sepiolite supported metal phthalocyanine heterogeneous catalysis catalytic oxidation weathered coal is utilized to prepare the method for humic acid, as follows:
Weathered coal passes through 80 mesh sieves through fragmentation, take in the coal sample 10g (being accurate to 0.1g) and 0.10 gram of even rearmounted there-necked flask of catalyst mix of deliming process, add the sulfuric acid solution of 20mL mass fraction 45%, make coal sample fully wetting, degrade in boiling water bath after 1h and take out, adding ammoniacal liquor, to be neutralized to pH value be 7.React 2 hours under 60 DEG C of water-baths; Suction filtration, dry, in products therefrom, the content of free humic acid is 40.6%, and the content of total humic acid is 63.7%.
Meanwhile, not add catalyst in contrast.After identical reaction condition, in products therefrom, the content of free humic acid is 26.9%, and the content of total humic acid is 33.6%.By comparison, the productive rate of free humic acid improves 13.7% in the present invention, and the productive rate of total humic acid improves 30.1%, Be very effective.
Claims (8)
1. a sepiolite supported metal phthalocyanine, is characterized in that: prepared by following preparation method:
(1) pretreatment of sepiolite: sepiolite is immersed in the hydrochloric acid or salpeter solution that concentration is 1 ~ 6mol/L, after dipping 24 ~ 72h, suction filtration, washes with water, dry, is ground to 60 ~ 100 object particles, is pretreated sepiolite, for subsequent use;
(2) sepiolite supported metal phthalocyanine is prepared: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 200mg, water 10 ~ 50mL, mixing, stirs 12 ~ 24h, suction filtration, water washing, dries 1 ~ 6 hour, obtains sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from sulfonated phthalocyanine iron, sulfonated phthalocyanine cobalt or sulfonated phthalocyanine manganese.
2. the preparation method of sepiolite supported metal phthalocyanine according to claim 1, is characterized in that: comprise the following steps:
(1) pretreatment of sepiolite: sepiolite is immersed in the hydrochloric acid or salpeter solution that concentration is 1 ~ 6mol/L, after dipping 24 ~ 72h, suction filtration, washes with water, dry, is ground to 60 ~ 100 object particles, is pretreated sepiolite, for subsequent use;
(2) sepiolite supported metal phthalocyanine is prepared: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 200mg, water 10 ~ 50mL, mixing, stirs 12 ~ 24h, suction filtration, water washing, dries 1 ~ 6 hour, obtains sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from sulfonated phthalocyanine iron, sulfonated phthalocyanine cobalt or sulfonated phthalocyanine manganese.
3. a sepiolite supported metal phthalocyanine, is characterized in that: prepared by following preparation method:
(1) pretreatment of sepiolite: sepiolite is immersed in the hydrochloric acid or salpeter solution that concentration is 1 ~ 6mol/L, after dipping 24 ~ 72h, suction filtration, washes with water, dry, is ground to 60 ~ 100 object particles, is pretreated sepiolite, for subsequent use;
(2) sepiolite supported metal phthalocyanine is prepared: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 500mg, N, dinethylformamide 10 ~ 50mL, mixing, stirs 12 ~ 24h, suction filtration, DMF washs, and dries 1 ~ 6 hour, obtains sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from nitro FePC, nitro Cobalt Phthalocyanine or nitro manganese phthalocyanine.
4. the preparation method of sepiolite supported metal phthalocyanine according to claim 3, is characterized in that: comprise the following steps:
(1) pretreatment of sepiolite: sepiolite is immersed in the hydrochloric acid or salpeter solution that concentration is 1 ~ 6mol/L, after dipping 24 ~ 72h, suction filtration, washes with water, dry, is ground to 60 ~ 100 object particles, is pretreated sepiolite, for subsequent use;
(2) sepiolite supported metal phthalocyanine is prepared: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 500mg, N, dinethylformamide 10 ~ 50mL, mixing, stirs 12 ~ 24h, suction filtration, DMF washs, and dries 1 ~ 6 hour, obtains sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from nitro FePC, nitro Cobalt Phthalocyanine or nitro manganese phthalocyanine.
5. a sepiolite supported metal phthalocyanine, is characterized in that: prepared by following preparation method:
(1) pretreatment of sepiolite: sepiolite is immersed in the hydrochloric acid or salpeter solution that concentration is 1 ~ 6mol/L, after dipping 24 ~ 72h, suction filtration, washes with water, dry, is ground to 60 ~ 100 object particles, is pretreated sepiolite, for subsequent use;
(2) sepiolite supported metal phthalocyanine is prepared: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 200mg, chloroform or carrene 10 ~ 50mL, mixing, stir 12 ~ 24h, suction filtration, chloroform or washed with dichloromethane, dry 1 ~ 6 hour, obtain sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from alkoxyl substituted phthalocyanine iron, alkoxyl substituted phthalocyanine cobalt or alkoxyl substituted phthalocyanine manganese.
6. the preparation method of sepiolite supported metal phthalocyanine according to claim 5, is characterized in that: comprise the following steps:
(1) pretreatment of sepiolite: sepiolite is immersed in the hydrochloric acid or salpeter solution that concentration is 1 ~ 6mol/L, after dipping 24 ~ 72h, suction filtration, washes with water, dry, is ground to 60 ~ 100 object particles, is pretreated sepiolite, for subsequent use;
(2) sepiolite supported metal phthalocyanine is prepared: get above-mentioned pretreated sepiolite 10.0g, metal phthalocyanine 50 ~ 200mg, chloroform or carrene 10 ~ 50mL, mixing, stir 12 ~ 24h, suction filtration, chloroform or washed with dichloromethane, dry 1 ~ 6 hour, obtain sepiolite supported metal phthalocyanine for 100 ~ 200 DEG C; Described metal phthalocyanine is selected from alkoxyl substituted phthalocyanine iron, alkoxyl substituted phthalocyanine cobalt or alkoxyl substituted phthalocyanine manganese.
7. sepiolite supported metal phthalocyanine described in claim 1 or 3 or 5 to prepare the application in humic acid at catalytic oxidation weathered coal as catalyst.
8. application according to claim 7, it is characterized in that: during embody rule, method is as follows: get weathered coal, broken, crosses 80 mesh sieves; Take the coal sample 10g through deliming process, sepiolite supported metal phthalocyanine 0.05 ~ 0.1g, mixes, and adds the salpeter solution of 10 ~ 20mL mass fraction 30% or the sulfuric acid solution of mass fraction 45%, degrade in boiling water bath after 1h and take out, adding ammoniacal liquor, to be neutralized to pH value be 7; React 2 hours in 60 DEG C of water-baths; Suction filtration, dry, obtain humic acid.
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Cited By (1)
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| CN109794294A (en) * | 2019-02-11 | 2019-05-24 | 盐城师范学院 | A kind of photochemical catalyst and its preparation method and application of sulfonated metal phthalocyanine@ZIF-8 |
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