CN108906082A - A kind of method that precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid - Google Patents
A kind of method that precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid Download PDFInfo
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- CN108906082A CN108906082A CN201810854370.XA CN201810854370A CN108906082A CN 108906082 A CN108906082 A CN 108906082A CN 201810854370 A CN201810854370 A CN 201810854370A CN 108906082 A CN108906082 A CN 108906082A
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- solid super
- strong acid
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- iron oxide
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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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
Abstract
The present invention discloses a kind of method that precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid, and steps are as follows：(1) to FeCl3Ethylene glycol as dispersing agent is added in aqueous solution, mixes, then plus ammonium hydroxide, until pH=8~9, stand for 24 hours, filter, precipitating is washed with water to no chloride ion, and drying is ground into a powder；(2) powder that step (1) obtains is impregnated with sulfuric acid solution, is filtered, drying；(3) powder handled through step (2) is activated in 450~600 DEG C and loads sulfate ion type solid super-strong acid to get to iron oxide, is i.e. iron oxide loads sulfate ion type solid super-strong acid.Compared with prior art, method of the invention is easy to operate, easy to control, can get the nanoscale Fe of high dispersive2O3/SO4 2‑Solid super-strong acid has good catalytic performance.
Description
Technical field
The present invention relates to the sides that a kind of precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid
Method.
Background technique
Solid super-strong acid has high acid strength -16.02<H0<- 14.520, it is equivalent to 100% fluid sulphuric acid
10000 times, be the highest acid type catalyst of acid strength in solid acid, but to equipment without any corrosion.Catalytic activity is high, compared with molecule
Sieve catalyst has lower catalytic temperature.
It has extremely strong water-fast and alkali resistance as catalyst, is catalyzed for a long time under the conditions of high temperature, alkaline vapor
It is unobvious using being influenced on catalyst activity, and easily separated with reaction system, contaminated wastewater is not generated in reaction process, it is more other
The post-processing of liquid acid product is simpler, is a kind of environmentally protective catalyst advocated 21 century.
Fe2O3/SO4 2-Solid super-strong acid is SO4 2-/ MxOy type solid super-strong acid, the formation in acid site stem primarily from
SO4 2-Corresponding metal ion is promoted to increase to obtain electronics due to the inductive effect of S=O in metal oxide surface Coordination Adsorption
Ability makes electron cloud sharp deflections on M-O key, the acid site Lewis of generation.It is right after the acid site the Lewis adsorbed water molecule
There are strong suction-operateds for electronics in hydrone, so that bringing it about dissociation generates proton acid site.
“SO4 2-/Fe2O3The preparation of type solid super-strong acid and the active research of catalyzing esterification ", Huang is defended, petrochemical industry height etc.
School's journal, is disclosed by FeSO the 1st phase of volume 15 in 20024·7H2O roasting direct prepares SO4 2-/Fe2O3Type solid super strong
Acid, although the step of this method is simple, SO4 2-And Fe2O3Molar ratio be not easily controlled, and nanoscale solid can not be obtained
Super acids.The prior art, which also has, prepares Performance of Nanometer Solid Superacid using sol-gel method, but this kind of long preparation period being somebody's turn to do,
A few days or a few weeks are generally required, are made troubles to industrialization.
Summary of the invention
It is an object of the invention to the statuses according to above-mentioned background technique, provide a kind of precipitating-sulfuric acid acidization preparation
Iron oxide loads sulfate ion type solid super-strong acid (Fe2O3/SO4 2-Solid super-strong acid) method.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions：
A kind of method that precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid, step is such as
Under：
(1) to FeCl3Be added ethylene glycol as dispersing agent in aqueous solution, mixing, then plus ammonium hydroxide, until pH=8~9, quiet
It sets for 24 hours, filters, precipitating is washed with water to no chloride ion, dries, is ground into a powder；
(2) powder that step (1) obtains is impregnated with sulfuric acid solution, is filtered, drying；
(3) powder handled through step (2) is activated in 450~600 DEG C and loads sulfuric acid to get to iron oxide
Radical ion type solid super-strong acid.
Preferably, step (1) FeCl3The concentration of aqueous solution is 100~150g/L, and the dosage of ethylene glycol is FeCl3Weight
The 1~10% of amount.Preferably, ammonium hydroxide is added at 70 DEG C.
Preferably, the powder of step (1) crosses 200 meshes.
Preferably, the concentration of step (2) described sulfuric acid solution is 0.1~2.5mol/L.
Preferably, the time of step (2) described dipping is 10~14h.
Preferably, the time of step (3) described activation processing is 2~5h, and high temperature is transformed into the S=O key of ionic altogether
Bond form S=O key, the covalent bond have inductive effect, and metal ion is made to have very strong electron-withdrawing ability, to present super
Highly acid.
Compared with prior art, method of the invention is easy to operate, easy to control, can get the nanoscale Fe of high dispersive2O3/
SO4 2-Solid super-strong acid.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings：
Fig. 1 is Fe prepared by embodiment 42O3/SO4 2-The scanning electron microscopic picture of solid super-strong acid；
Fig. 2 is Fe prepared by embodiment 42O3/SO4 2-The infared spectrum of solid super-strong acid；
Fig. 3 is Fe prepared by comparative example 12O3/SO4 2-The scanning electron microscopic picture of solid super-strong acid；
Fig. 4 is Fe prepared by comparative example 22O3/SO4 2-The scanning electron microscopic picture of solid super-strong acid.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
The characterization of catalyst：0.1mol citric acid and 0.45mol n-butanol are added in three-necked flask, heats under stiring
Make lemon acid dissolution, add the catalyst of 1.5g, load onto water segregator and reflux condensing tube, is heated to reflux a point water, reaction time
For 120min, reaction temperature is 150 DEG C, stops heating after reaction, after slightly cold, Filtration of catalyst.Filtrate first carries out
Air-distillation is recycled excessive n-butanol, then is evaporated under reduced pressure, and collects fraction, obtains three fourth of light yellow transparent liquid citric acid
Ester.The acid value of measurement reaction front and back, calculates esterification yield.Before esterification yield %=(acid value after acid value-reaction before reaction)/reaction
Acid value × 100%, acid value use determination of acid-basetitration.
Embodiment 1
Take 20g FeCl3·6H2O is placed in conical flask and is dissolved with the water of 100mL, and conical flask is placed in constant temperature magnetic force and is stirred
It mixes on device, and the ethylene glycol that a certain amount of (1ml) is added is stirred as dispersing agent, it is 28% that concentration is added under 70 DEG C of constant temperature
Ammonium hydroxide, it is strong to stir, make pH=8~9 of system, after precipitating completely, it is static for 24 hours, filter, and be washed with distilled water and be precipitated to
It without chloride ion, dries, grinding crosses 200 meshes, obtains FeO (OH)2Precursor；Precursor respectively with 50mL concentration be 0.1mo1/L,
The H of 0.3mo1/L, 0.5mo1/L, 0.7mo1/L, 0.9mo1/L2SO4Aqueous solution is impregnated, and suction filtration, drying after 12h are impregnated,
3h is roasted in 500 DEG C of muffle furnace to get to the solid super-strong acid Fe prepared under different sulfuric acid concentrations2O3/SO4 2-Catalyst.
Catalyst under the different sulfuric acid concentrations of table 1 synthesizes lemon acid tributyl esterification yield
Embodiment 2
Take 20g FeCl3·6H2O is placed in conical flask and is dissolved with the water of 100mL, and conical flask is placed in constant temperature magnetic force and is stirred
It mixes on device, and the ethylene glycol that a certain amount of (1ml) is added is stirred as dispersing agent, it is 28% that concentration is added under 70 DEG C of constant temperature
Ammonium hydroxide, it is strong to stir, make pH=8~9 of system, after precipitating completely, it is static for 24 hours, filter, and be washed with distilled water and be precipitated to
It without chloride ion, dries, grinding crosses 200 meshes, obtains FeO (OH)2Precursor；Precursor is respectively 0.5mo1/L with 50mL concentration
H2SO4Aqueous solution dipping 10h, 11h, 12h, 13h, 14h after filter, drying, 3h is roasted in 500 DEG C of muffle furnace to get arriving
The solid super-strong acid Fe prepared under different dip times2O3/SO4 2-Catalyst.
Catalyst under the different dip times of table 2 synthesizes lemon acid tributyl esterification yield
Embodiment 3
Take 20g FeCl3·6H2O is placed in conical flask and is dissolved with the water of 100mL, and conical flask is placed in constant temperature magnetic force and is stirred
It mixes on device, and the ethylene glycol that a certain amount of (1ml) is added is stirred as dispersing agent, it is 28% that concentration is added under 70 DEG C of constant temperature
Ammonium hydroxide, it is strong to stir, make pH=8~9 of system, after precipitating completely, it is static for 24 hours, filter, and be washed with distilled water and be precipitated to
It without chloride ion, dries, grinding crosses 200 meshes, obtains FeO (OH)2Precursor；Precursor is 0.5mo1/LH with 50mL concentration2SO4
Aqueous solution dipping, impregnate 12h after filter, drying, be respectively placed at a temperature of 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, in horse
Fluorine kiln roasting 3h is to get to the solid super-strong acid Fe prepared under different maturing temperatures2O3/SO4 2-Catalyst.
Catalyst under the different maturing temperatures of table 3 synthesizes lemon acid tributyl esterification yield
Embodiment 4
Take 20g FeCl3·6H2O is placed in conical flask and is dissolved with the water of 100mL, and conical flask is placed in constant temperature magnetic force and is stirred
It mixes on device, and the ethylene glycol that a certain amount of (1ml) is added is stirred as dispersing agent, it is 28% that concentration is added under 70 DEG C of constant temperature
Ammonium hydroxide, it is strong to stir, make pH=8~9 of system, after precipitating completely, it is static for 24 hours, filter, and be washed with distilled water and be precipitated to
It without chloride ion, dries, grinding crosses 200 meshes, obtains the precursor of FeO (OH) alkali formula ferrous oxide；It is with 50mL concentration
0.5mo1/LH2SO4Aqueous solution dipping, impregnate 12h after filter, drying, respectively in 500 DEG C of muffle furnace roast 2h, 3h,
4h, 5h are to get to the solid super-strong acid Fe prepared under different calcining times2O3/SO4 2-Catalyst.
Catalyst under the different calcining times of table 4 synthesizes lemon acid tributyl esterification yield
The catalyst that embodiment 4 optimizes
Take 20g FeCl3·6H2O is placed in conical flask and is dissolved with the water of 100mL, and conical flask is placed in constant temperature magnetic force and is stirred
It mixes on device, and the ethylene glycol that a certain amount of (1ml) is added is stirred as dispersing agent, it is 28% that concentration is added under 70 DEG C of constant temperature
Ammonium hydroxide, it is strong to stir, make pH=8~9 of system, after precipitating completely, it is static for 24 hours, filter, and be washed with distilled water and be precipitated to
It without chloride ion, dries, grinding crosses 200 meshes, obtains FeO (OH)2Precursor；The H of precursor 50mL0.5mo1/L2SO4Water
Solution dipping impregnates suction filtration, drying after 12h, roasts 3h in 550 DEG C of muffle furnace to get solid super-strong acid Fe2O3/SO4 2-,
It is placed in spare in drier.
As shown in Figure 1, the Fe of above-mentioned preparation2O3/SO4 2-Solid super-strong acid is nano-scale particle, and particle is more uniform, substantially
There is no agglomeration.
As shown in Fig. 2, the sample of preparation is in (1375-1390) cm-1There is multi-absorption peak, and at (900-1200)
cm-1There is the absorption peak of wideization, it is consistent with document.The IR characteristic peak more than one that most of S=O keys generate, catalyst sample
Product are in (1000~1400) cm-1Two absorption peak 1382.74cm-1And 1072.74cm-1It is that S=O stretching vibration feature is inhaled
It receives.Lower wave number (800~1000) cm-1Absorption peak show that S=O key has partial double bond feature, similar inorganic double coordination chelatings
Object；High wave number (1100-1600) cm-1Absorption peak show S=O key be double covalent bonds feature, be similar to organo-sulfate in S
=O key, inductive effect make the electron cloud on Fe-O key deflect, and make catalyst that superpower acidity be presented.
Fig. 2 is also shown that in 1629.64cm-1There is Fe in place2O3The flexural vibrations peak of absorption-OH group, illustrates catalyst
The easy moisture absorption of sample easily adsorbs more polyhydroxy and further amounts of water, and solid super-strong acid is made to show that stronger B is acid；In 1382.74cm-1
There is SO in place4 2-With strong dehydration Fe2O3Surface action, absorption peak caused by increasing S=O stretching vibration, which belongs to S=O
Asymmetric stretching vibration peak, the S=O key have height double covalent bonds property, which is Fe2O3/SO4 2-Class solid super strong
The characteristic absorption peak that acid is formed；1072.74cm-1、544.24cm-1、471.54cm-1Three peaks are SO4 2-In Fe2O3Surface is double to match
Caused by the adsorption structure of position, show SO4 2-In Fe2O3Surface is with the double coordination modes of chelating and three kinds of double coordinations of bridge-type, single coordination shapes
Formula and Fe2O3In conjunction with 1382.74cm-1、1072.74cm-1、544.24cm-1、471.54cm-1Four peaks are also shown that super in solid
In strong acid catalyst, the number in acid site is more, and acid site has many different forms, this is also that solid super-strong acid is urged
One of the reason of agent good catalytic activity.
Catalytic effect：
0.1mol citric acid and 0.45mol n-butanol are added in three-necked flask, heating makes lemon acid dissolution under stiring,
The above-mentioned catalyst for adding 1.5g, loads onto water segregator and reflux condensing tube, is heated to reflux a point water, reaction time 120min,
Reaction temperature is 150 DEG C, stops heating after reaction, after slightly cold, Filtration of catalyst.Filtrate first carries out air-distillation,
Excessive n-butanol is recycled, then is evaporated under reduced pressure, fraction is collected, obtains light yellow transparent liquid tributyl citrate.Measurement is anti-
The acid value of front and back is answered, esterification yield is calculated.Carry out parallel laboratory test three times, esterification yield difference 95.21%, 94.76%, 94.69%.
Comparative example 1
Weigh 20g FeCl3·6H2O is added 100ml distilled water stirring and dissolving (120g/L) in 250ml beaker, stirring
Lower addition ammonium hydroxide, and make its pH=8~9, it is precipitated, is filtered, it is multiple with distilled water filter wash cake, until without Cl-, obtain solid.?
12h is dried in baking oven lower than 100 DEG C, taking-up is placed in Muffle furnace, and 3h is roasted at 250 DEG C, and taking-up is ground into a powder with mortar,
Cross 200 meshes.With 50ml 0.5mol/L H2SO4Powder solid 12h is impregnated, solid is dried in filtering, is packed into crucible, is placed in horse
Not in furnace, 3h is activated at 500 DEG C, taking-up is cooled to 100 DEG C and is placed in drier, obtains wine-colored Fe2O3/SO4 2-Solid
Super acids.
Comparative example 2
By 20g FeCl3·6H2O is dissolved in the water of 100mL, the ammonium hydroxide that concentration is 28% is added under stiring, until pH value of solution
=8~9, it generates Fe (OH)3Precipitating after filtering, gained precipitating is eluted with water to no chloride ion, people's oven drying 12h is put and obtains
Fe(OH)3, then ground, cross 200 meshes, then be dipped in the H that 50mL concentration is 0.5mo1/L2SO440min in solution,
Filtering, obtained precipitating is dry, and precipitating is finally put into Muffle furnace (temperature is 500 DEG C) calcination activation 3h to get russet
Fe2O3/SO4 2-Solid super-strong acid is placed in drier and saves.
The Fe that it can be seen from comparative example 1-2 prepared by the method for the invention2O3/SO4 2-Solid super-strong acid granular size is more
Uniformly, and substantially without particle agglomeration phenomenon.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (6)
1. the method that a kind of precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid, steps are as follows：
(1) to FeCl3Ethylene glycol as dispersing agent is added in aqueous solution, mixes, then plus ammonium hydroxide, until pH=8~9, standing for 24 hours,
It filters, precipitating is washed with water to no chloride ion, dries, is ground into a powder；
(2) powder that step (1) obtains is impregnated with sulfuric acid solution, is filtered, drying；
(3) powder handled through step (2) is activated in 450~600 DEG C to get to iron oxide load sulfate radical from
Subtype solid super-strong acid.
2. according to the method described in claim 1, it is characterized in that：Step (1) described FeCl3The concentration of aqueous solution be 100~
150g/L, the dosage of ethylene glycol are FeCl3The 1~10% of weight.
3. according to the method described in claim 1, it is characterized in that：The powder of step (1) crosses 200 meshes.
4. according to the method described in claim 1, it is characterized in that：The concentration of step (2) described sulfuric acid solution be 0.1~
2.5mol/L。
5. method according to claim 1 or 4, it is characterised in that：The time of step (2) described dipping is 10~14h.
6. according to the method described in claim 1, it is characterized in that：The time of step (3) described activation processing is 2~5h.
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Cited By (1)
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| CN114957002A (en) * | 2022-06-30 | 2022-08-30 | 蚌埠学院 | Green synthesis method of diisobutyl malonate |
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Application publication date: 20181130 |