CN107519946A - A kind of method for improving aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst activity - Google Patents
A kind of method for improving aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst activity Download PDFInfo
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- CN107519946A CN107519946A CN201710630042.7A CN201710630042A CN107519946A CN 107519946 A CN107519946 A CN 107519946A CN 201710630042 A CN201710630042 A CN 201710630042A CN 107519946 A CN107519946 A CN 107519946A
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- diatomite
- sulphur
- aluminium dihydrogen
- dihydrogen tripolyphosphate
- composite catalyst
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
A kind of method for improving aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst activity provided by the invention, comprises the following steps：The first step, with gamma-ray irradiation diatomite；Second step, prepared with the diatomite by irradiation and carry sulphur diatomite；3rd step, aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst is combined into the load sulphur diatomite and aluminium dihydrogen tripolyphosphate of preparation.The first step is to use60Co gamma-ray irradiation specific surface area is more than 1m2/ g diatomite, absorbed dose of radiation is between 1 ~ 100kGy.The second step is 600 ~ 800 DEG C, is incubated 4 ~ 8 hours, sulphur is loaded on the diatomite by irradiation.3rd step is to add to carry sulphur diatomite in the preparation process of aluminium dihydrogen tripolyphosphate, and powdery aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst is obtained after drying, grinding.
Description
Technical field
The present invention relates to a kind of method using diatomite as the catalyst activity of carrier, and in particular to one kind improves trimerization
The method of aluminium dihydrogen phosphate/load sulphur tripolite composite catalyst activity.
Technical background
Carboxylate is a kind of important fine chemical product, is widely used in spices, daily use chemicals, food, medicine, rubber, painting
The fields such as material.It with the concentrated sulfuric acid is catalyst that the conventional method of synthesizing carboxylate, which is, is raw material to synthesize by corresponding carboxylic acid and alcohol
's.There is the advantages of cheap, catalytic activity is high by catalyst of the concentrated sulfuric acid, but also there are many shortcomings.For example, concentrated sulfuric acid sheet
Body has oxidisability and dehydration property, causes in product containing the accessory substance such as sulfuric ester, ether, unsaturated compound, to refined and return
Receive raw material and bring difficulty, while also reduce yield；The concentrated sulfuric acid has strong corrosivity to equipment；The row of a large amount of spent acid
Put, can pollute.To solve these problems, patent of invention CN102584591 provide it is a kind of economic and environment-friendly, with diatomite
The method that immobilized Catalyzed by Titanic Sulfate prepares ATBC.Esterification efficiency is improved, also improves yield.But with sulfuric acid
Titanium is limited for reducing catalyst cost as raw material.Aluminium dihydrogen tripolyphosphate price is than relatively low, and nontoxic nothing
Evil, it is a kind of solid Lewis acid, with acid high the characteristics of low intensity, sulfuric acid can also be replaced to be used for catalytic esterification anti-
Catalytic efficiency is low when answering, but directly applying.Huang profit is impartial, and (Huang Runjun, Xie Wei, king's Jing, Chen Donglian, Huang Zengwei, Wei Dongping, horse are few
Younger sister, Yuan love group aluminium dihydrogen tripolyphosphates/load sulphur diatomite Catalytic Synthesis of Tri-n-butyl Citrate plastics industries, 2015,43 (1),
Aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst 105-120) is prepared for, as catalyst synthesizing citric acid tributyl,
Esterification yield can meet or exceed the catalytic effect of the concentrated sulfuric acid.
Diatomite is a kind of biogenic siliceous sedimentary rock, is made up of ancient times diatom remains, and its chemical composition is mainly
SiO2, contain a small amount of Al2O3、Fe2O3、CaO、MgO、K2O、Na2O、P2O5And organic matter.Diatomite has Porous construction, hole
Gap rate reaches 80-90%, is suitable as filter aid, adsorbent, sulfuric acid catalyst carrier.In actual applications, it is diatomaceous to carry sulphur
Catalyst activity depends on diatomaceous quality height.Patent of invention CN102923724 provides a kind of diatomite that improves and compares table
The method of area and nano-pore ratio.By simple acidleach, diatomaceous pore volume and specific surface area are improved.It is but special at this
Application of the profit without reference to modification infusorial earth in terms of sulfuric acid catalyst carrier.Min Wang etc. (M.Wang, Y.Xiang,
G.Zhang,J.Song,D.Cai,Z.Wu.A facile approach to improve the quality of
diatomite as sulfuric acid catalyst support.Applied Catalysis A:Genera,2013,
466,185-189) high-energy electron beam irradiation method modification infusorial earth is utilized, and is used as sulfuric acid catalyst carrier.By modified
Most of impurity in diatomite hole is all removed, pore-size distribution and specific surface area all be improved significantly, improve sulfuric acid
The performance of catalyst.It is expected to lift catalytic conversion efficiency in the production in future, receives more preferable effects of energy saving and emission reduction.The document
Gamma-ray irradiation is not involved with to diatomaceous modified effect.The industrial radiation source important as two kinds, electron accelerator and60Co gamma ray projectors have marked difference in close rate, energy and penetrability etc..Beam energy is high, but penetrability, surface
Energy deposition efficiency is high；Energy of γ ray is low, but penetrability is good, and there is similar radiation effect radiation exposed material surface and inside
Should, the homogeneous product of readily available performance.
The content of the invention
The purpose of the present invention is that radiation modification is carried out to diatomite by gamma-rays, and then prepares the tripolyphosphate of high activity
Aluminum dihydrogen/load sulphur tripolite composite catalyst, synthesized for catalytic citric acid tributyl, not only esterification yield is high, and reacts speed
Rate is fast, can reach higher conversion within a short period of time.
In order to realize the purpose of the present invention, a kind of raising aluminium dihydrogen tripolyphosphate/load sulphur tripolite compound provided by the invention
The method for closing catalyst activity, comprises the following steps：
The first step, with gamma-ray irradiation diatomite；
Second step, prepared with the diatomite by irradiation and carry sulphur diatomite；
3rd step, aluminium dihydrogen tripolyphosphate/load sulphur silicon is combined into the load sulphur diatomite and aluminium dihydrogen tripolyphosphate of preparation
Diatomaceous earth composite catalyst.
It is to be placed in diatomite with gamma-ray irradiation diatomite in the first step60Carried out in Co gamma Rays field
Irradiation, the diatomaceous specific surface area are more than 1m2/ g, absorbed dose of radiation is between 1~100kGy.
In the second step, it is first to add sublimed sulfur in Muffle furnace to be prepared with the diatomite by irradiation and carry sulphur diatomite
To 450~650 DEG C, insulation cools down heat after 0.5~2 hour, is equal to 1 according to diatomite and sublimed sulfur weight ratio:0.3~1:0.01
Ratio, will be put into by the diatomite of irradiation in Muffle furnace, and be heated to 600~800 DEG C, insulation cools down after 4~8 hours,
It is ground after taking-up, obtains powdery and carry sulphur diatomite.
In 3rd step, with the load sulphur diatomite of preparation and aluminium dihydrogen tripolyphosphate be combined into aluminium dihydrogen tripolyphosphate/
It is first to mix phosphoric acid with the distilled water of triplication to carry sulphur tripolite composite catalyst, according to Al after stirring2O3/P2O3=
1:3 ratio adds aluminum oxide, is warming up to 70~100 DEG C, to solution went clear, according to aluminium dihydrogen tripolyphosphate with carrying sulphur silicon
Diatomaceous earth 1:3~1:0.8 ratio adds powdery and carries sulphur diatomite, is well mixed, and is subsequently placed in the Muffle of 280~400 DEG C of constant temperature
In stove, insulation is taken out after 3~12 hours, with cold water water quenching, is ground after drying, is obtained powdery aluminium dihydrogen tripolyphosphate/load sulphur silicon
Diatomaceous earth composite catalyst.
Using a kind of side for improving aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst activity provided by the present invention
Method, can obtain that performance is homogeneous, modification infusorial earth of steady quality, with aluminium dihydrogen tripolyphosphate/load sulphur diatomite of its preparation
Composite catalyst is used for synthesizing citric acid tributyl, has the characteristics of esterification yield is high, reaction rate is fast.
Embodiment
Embodiment 1
Take 100 parts of diatomite (specific surface area 15m2/ g, water absorption rate 253%, oil factor 108%), load vinyon
In bag, after packing, it is put into60Irradiated in Co gamma Rays field, close rate 1kGy/h, absorbed dose of radiation 20kGy.Take
10 powder sublimed sulfurs, are put into crucible, are placed in Muffle furnace, then raise temperature to 520 DEG C, are incubated 2 hours, cooling.Irradiation will be passed through
Diatomite be put into crucible, be warming up to 650 DEG C, insulation cools down after 7 hours, is pulverized after taking-up, obtains the load sulphur of powdery
Diatomite, 12 μm of powder average grain diameter.
156 parts of distilled water are taken, 52 parts of phosphoric acid is added, is stirring evenly and then adding into 12.5 parts of aluminum oxide, is warming up to 80 DEG C, always
Stirring is transparent to solution.Then the load sulphur diatomite of powdery is added, constant temperature is put into 350 DEG C of Muffle furnace after well mixed,
Insulation is taken out after 5 hours, with cold water water quenching, efflorescence, is ground after drying, is obtained powdery aluminium dihydrogen tripolyphosphate/load sulphur diatomite
Composite catalyst.
192g citric acids, 370g n-butanols and 37g powderies aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst are put
In reaction vessel, heating, reflux dewatering.After esterification 4 hours, measure esterification yield is 98.5%.Esterification 5 hours
Afterwards, it is 99.3% to determine esterification yield.
Do contrast test.It will be modified with batch diatomite without gamma-ray irradiation, directly carry out carrying the preparation of sulphur diatomite,
And repeat above-mentioned other preparation processes.After esterification 4 hours, measure esterification yield is 88.7%.After esterification 5 hours, survey
Esterification yield is determined for 92.5%.
Embodiment 2
Take 100 parts of diatomite (specific surface area 40m2/ g, water absorption rate 370%, oil factor 156%), load vinyon
In bag, after packing, it is put into60Irradiated in Co gamma Rays field, close rate 2kGy/h, absorbed dose of radiation 60kGy.Take
10 powder sublimed sulfurs, are put into crucible, are placed in Muffle furnace, then raise temperature to 600 DEG C, are incubated 2 hours, cooling.Irradiation will be passed through
Diatomite be put into crucible, be warming up to 700 DEG C, insulation cools down after 6 hours, is pulverized after taking-up, obtains the load sulphur of powdery
Diatomite, powder average grain diameter 10m.
156 parts of distilled water are taken, 52 parts of phosphoric acid is added, is stirring evenly and then adding into 12.5 parts of aluminum oxide, is warming up to 80 DEG C, always
Stirring is transparent to solution.Then the load sulphur diatomite of powdery is added, constant temperature is put into 300 DEG C of Muffle furnace after well mixed,
Insulation is taken out after 5 hours, with cold water water quenching, efflorescence, is ground after drying, is obtained powdery aluminium dihydrogen tripolyphosphate/load sulphur diatomite
Composite catalyst.
192g citric acids, 370g n-butanols and 50g powderies aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst are put
In reaction vessel, heating, reflux dewatering.After esterification 4 hours, measure esterification yield is 99.1%.Esterification 5 hours
Afterwards, it is 99.3% to determine esterification yield.
Do contrast test.It will be modified with batch diatomite without gamma-ray irradiation, directly carry out carrying the preparation of sulphur diatomite,
And repeat above-mentioned other preparation processes.After esterification 4 hours, measure esterification yield is 87.3%.After esterification 5 hours, survey
Esterification yield is determined for 91.2%.
Claims (4)
- A kind of 1. method for improving aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst activity, it is characterised in that including with Lower step：The first step, with gamma-ray irradiation diatomite；Second step, prepared with the diatomite by irradiation and carry sulphur diatomite；3rd step, aluminium dihydrogen tripolyphosphate/load sulphur diatomite is combined into the load sulphur diatomite and aluminium dihydrogen tripolyphosphate of preparation Composite catalyst.
- 2. a kind of method for improving aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst activity as claimed in claim 1, It is characterized in that it is to be placed in diatomite with gamma-ray irradiation diatomite60Irradiated in Co gamma Rays field, the silicon The specific surface area of diatomaceous earth is more than 1m2/ g, absorbed dose of radiation is between 1 ~ 100kGy.
- 3. a kind of method for improving aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst activity as claimed in claim 1, It is characterized in that it is that sublimed sulfur first is heated into 450 ~ 650 in Muffle furnace to prepare load sulphur diatomite with the diatomite by irradiation DEG C, insulation cools down after 0.5 ~ 2 hour, is equal to 1 according to diatomite and sublimed sulfur weight ratio:0.3~1:0.01 ratio, it will pass through The diatomite of irradiation is put into Muffle furnace, is heated to 600 ~ 800 DEG C, and insulation cools down after 4 ~ 8 hours, is ground after taking-up, Obtain powdery and carry sulphur diatomite.
- 4. a kind of method for improving aluminium dihydrogen tripolyphosphate/load sulphur tripolite composite catalyst activity as claimed in claim 1, It is characterized in that it is combined into aluminium dihydrogen tripolyphosphate/load sulphur tripolite compound with the load sulphur diatomite and aluminium dihydrogen tripolyphosphate prepared It is first to mix phosphoric acid with the distilled water of triplication to close catalyst, according to Al after stirring2O3/P2O3=1:3 ratio adds Aluminum oxide, be warming up to 70 ~ 100 DEG C, to solution went clear after add powdery and carry sulphur diatomite, be well mixed, be subsequently placed in 280 ~ In the Muffle furnace of 400 DEG C of constant temperature, insulation is taken out after 3 ~ 12 hours, with cold water water quenching, is ground after drying, is obtained powdery tripolyphosphate Aluminum dihydrogen/load sulphur tripolite composite catalyst.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS577427A (en) * | 1980-06-18 | 1982-01-14 | Teikoku Kako Kk | Preparation of hydrocarbon |
| CN1793228A (en) * | 2005-12-28 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing complete biological degradation high flexible polyalctic material |
| CN101733172A (en) * | 2008-11-26 | 2010-06-16 | 中国石油化工股份有限公司 | Supported metal catalyst, preparation method thereof and use thereof |
| CN102240547A (en) * | 2010-05-14 | 2011-11-16 | 中国石油化工股份有限公司 | C4 selective hydrogenation catalyst and preparation method thereof |
| CN103084152A (en) * | 2012-12-20 | 2013-05-08 | 中国科学院合肥物质科学研究院 | Treatment method for effectively improving microstructures and absorption properties of attapulgite and kieselguhr |
| CN103331177A (en) * | 2013-03-29 | 2013-10-02 | 广西民族大学 | A carried-type aluminium dihydrogen tripolyphosphate catalyst and a preparation method thereof |
-
2017
- 2017-07-28 CN CN201710630042.7A patent/CN107519946A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS577427A (en) * | 1980-06-18 | 1982-01-14 | Teikoku Kako Kk | Preparation of hydrocarbon |
| CN1793228A (en) * | 2005-12-28 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing complete biological degradation high flexible polyalctic material |
| CN101733172A (en) * | 2008-11-26 | 2010-06-16 | 中国石油化工股份有限公司 | Supported metal catalyst, preparation method thereof and use thereof |
| CN102240547A (en) * | 2010-05-14 | 2011-11-16 | 中国石油化工股份有限公司 | C4 selective hydrogenation catalyst and preparation method thereof |
| CN103084152A (en) * | 2012-12-20 | 2013-05-08 | 中国科学院合肥物质科学研究院 | Treatment method for effectively improving microstructures and absorption properties of attapulgite and kieselguhr |
| CN103331177A (en) * | 2013-03-29 | 2013-10-02 | 广西民族大学 | A carried-type aluminium dihydrogen tripolyphosphate catalyst and a preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MIN WANG: "A facile approach to improve the quality of diatomite as sulfuric acid catalyst support", 《APPLIED CATALYSIS A: GENERAL》 * |
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Application publication date: 20171229 |