CN108940322A - Iron oxide loads application of the sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification - Google Patents
Iron oxide loads application of the sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification Download PDFInfo
- Publication number
- CN108940322A CN108940322A CN201810854368.2A CN201810854368A CN108940322A CN 108940322 A CN108940322 A CN 108940322A CN 201810854368 A CN201810854368 A CN 201810854368A CN 108940322 A CN108940322 A CN 108940322A
- Authority
- CN
- China
- Prior art keywords
- solid super
- strong acid
- acid
- powder
- application according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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 application of the iron oxide load sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification, and the iron oxide load sulfate ion type solid super-strong acid is Fe2O3/SO4 2‑Solid super-strong acid, i.e., in Fe2O3/SO4 2‑Under the catalysis of solid super-strong acid, citric acid mixes back flow reaction with excessive n-butanol, generates tributyl citrate.Compared with the synthesis of existing tributyl citrate, the present invention is short with the reaction time, catalyst amount is small, product is easily isolated, and yield is up to 95% or so, the reusable multiple feature of catalyst, and catalyst is easily prepared, performance is stable, safe, easy to use, has no toxic side effect, do not corrode equipment, no pollution to the environment.
Description
Technical field
It is anti-in catalytic citric acid and n-butanol esterification that the present invention relates to iron oxide load sulfate ion type solid super-strong acids
Application in answering.
Background technique
Solid super-strong acid has high acid strength -16.02 < H0< -14.520 are 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.
Tributyl citrate also known as sour three n-butyric acies of structure edge are a kind of colourless transparent oil liquids, tasteless, and boiling point is high by 170
DEG C (133.3Pa), 185 DEG C of flash-point height (opening cup) is nontoxic, and it is a kind of plasticising of function admirable that 25 DEG C of whens, which are dissolved in water < 0.002%,
Agent can synthesize another nontoxic, more excellent performance plasticizer with acetic anhydride effect --- tributyl 2-acetylcitrate.
The synthesis of tributyl citrate generally makees catalyst with the concentrated sulfuric acid, cheap although technical maturity, sulfuric acid pair
Equipment seriously corroded, and by-product is more in reaction, subsequent processing trouble, product colour is deeper, while Waste Sulfuric Acid discharge is also made
At environmental pollution, it is necessary to find new catalyst to replace the concentrated sulfuric acid.
Summary of the invention
It is an object of the invention to the statuses according to above-mentioned background technique, and it is solid to provide iron oxide load sulfate ion type
Application of the body super acids in catalytic citric acid and n-butanol esterification.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
Iron oxide loads application of the sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification,
The iron oxide load sulfate ion type solid super-strong acid is Fe2O3/SO4 2-Solid super-strong acid, it is characterized in that, in Fe2O3/
SO4 2-Under the catalysis of solid super-strong acid, citric acid mixes back flow reaction with excessive n-butanol, generates tributyl citrate.
Preferably, the Fe2O3/SO4 2-Solid super-strong acid is obtained as follows:
(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 to get Fe is arrived2O3/SO4 2-Solid
Super acids.
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, 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.
Preferably, the Fe2O3/SO4 2-Solid super-strong acid is obtained as follows:
(1) FeCl for being 120g/L to concentration3The ethylene glycol as dispersing agent is added in aqueous solution, mixes, then at 70 DEG C
Lower addition ammonium hydroxide, until pH=8~9, stand for 24 hours, filter, precipitating is washed with water to no chloride ion, dries, is ground into a powder, and crosses 200
Mesh；
(2) powder for obtaining step (1) is impregnated with the sulfuric acid solution that concentration is 0.5mol/L, is filtered after impregnating 12h, is dried
It is dry；
(3) powder that will be handled through step (2) is in 550 DEG C of activations processing 3h to get to Fe2O3/SO4 2-Solid super-strong acid.
Preferably, the molar ratio of the citric acid and n-butanol is 0.1:0.45, Fe2O3/SO4 2-The dosage of solid super-strong acid
It is the 0.78% of citric acid weight, back flow reaction temperature is 150 DEG C, reaction time 120min.
The present invention is with Fe2O3/SO4 2-Solid super-strong acid is as esterification catalyst synthesizing citric acid tributyl, when having reaction
Between it is short, catalyst amount is small, product is easily isolated, and yield is up to 95% or so, the reusable multiple feature of catalyst.And
Catalyst is easily prepared, and performance is stable, safe, easy to use, has no toxic side effect, does not corrode equipment, no pollution to the environment.
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.
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 synthesis of tributyl citrate: 0.1mol citric acid and 0.45mol n-butanol are added in three-necked flask, is stirring
Lower heating makes lemon acid dissolution, adds the catalyst of 1.5g, loads onto water segregator and reflux condensing tube, is heated to reflux a point water, instead
It is 120min between seasonable, reaction temperature is 150 DEG C, stops heating after reaction, after slightly cold, Filtration of catalyst.Filtrate
Air-distillation is first carried out, recycles excessive n-butanol, then be evaporated under reduced pressure, fraction is collected, obtains light yellow transparent liquid lemon
Sour tributyl.The acid value of measurement reaction front and back, calculates esterification yield.Esterification yield %=(acid value after acid value-reaction before reaction)/
Acid value × 100% before reaction, 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 5 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%.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it 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 (9)
1. iron oxide loads application of the sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification, institute
Stating iron oxide load sulfate ion type solid super-strong acid is Fe2O3/SO4 2-Solid super-strong acid, which is characterized in that in Fe2O3/
SO4 2-Under the catalysis of solid super-strong acid, citric acid mixes back flow reaction with excessive n-butanol, generates tributyl citrate.
2. application according to claim 1, which is characterized in that the Fe2O3/SO4 2-Solid super-strong acid is by walking as follows
It is rapid to be made:
(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 Fe is arrived2O3/SO4 2-Solid super strong
Acid.
3. application according to claim 2, it is characterised 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.
4. application according to claim 2, it is characterised in that: the powder of step (1) crosses 200 meshes.
5. application according to claim 2, it is characterised in that: the concentration of step (2) described sulfuric acid solution be 0.1~
2.5mol/L。
6. application according to claim 2 or 5, it is characterised in that: the time of step (2) described dipping is 10~14h.
7. application according to claim 2, it is characterised in that: the time of step (3) described activation processing is 2~5h.
8. application according to claim 2, which is characterized in that the Fe2O3/SO4 2-Solid super-strong acid is by walking as follows
It is rapid to be made:
(1) FeCl for being 120g/L to concentration3The ethylene glycol as dispersing agent is added in aqueous solution, mixes, is added at 70 DEG C
Ammonium hydroxide, until pH=8~9, stand for 24 hours, filter, precipitating is washed with water to no chloride ion, dries, is ground into a powder, and crosses 200 meshes；
(2) powder for obtaining step (1) is impregnated with the sulfuric acid solution that concentration is 0.5mol/L, is filtered after impregnating 12h, is dried；
(3) powder that will be handled through step (2) is in 550 DEG C of activations processing 3h to get to Fe2O3/SO4 2-Solid super-strong acid.
9. application according to claim 1 or 8, which is characterized in that the molar ratio of the citric acid and n-butanol is 0.1:
0.45, Fe2O3/SO4 2-The dosage of solid super-strong acid is the 0.78% of citric acid weight, and back flow reaction temperature is 150 DEG C, when reaction
Between 120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810854368.2A CN108940322A (en) | 2018-07-30 | 2018-07-30 | Iron oxide loads application of the sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810854368.2A CN108940322A (en) | 2018-07-30 | 2018-07-30 | Iron oxide loads application of the sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108940322A true CN108940322A (en) | 2018-12-07 |
Family
ID=64466266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810854368.2A Pending CN108940322A (en) | 2018-07-30 | 2018-07-30 | Iron oxide loads application of the sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108940322A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569912A (en) * | 2020-06-22 | 2020-08-25 | 南通百川新材料有限公司 | Improved method of catalyst for producing n-butyl acetate |
| CN114957002A (en) * | 2022-06-30 | 2022-08-30 | 蚌埠学院 | Green synthesis method of diisobutyl malonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246386A (en) * | 1998-08-27 | 2000-03-08 | 中国石油化工集团公司 | Process for preparing carried superstrong solid acid |
-
2018
- 2018-07-30 CN CN201810854368.2A patent/CN108940322A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246386A (en) * | 1998-08-27 | 2000-03-08 | 中国石油化工集团公司 | Process for preparing carried superstrong solid acid |
Non-Patent Citations (2)
| Title |
|---|
| 孟宪昌等: ""纳米固体超强酸SO42-/Fe2O3催化合成柠檬酸三丁酯"", 《河北师范大学学报(自然科学版)》 * |
| 李家贵等: ""纳米固体超强酸SO42-/Fe2O3催化合成尼泊金酸乙酯"", 《合成化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569912A (en) * | 2020-06-22 | 2020-08-25 | 南通百川新材料有限公司 | Improved method of catalyst for producing n-butyl acetate |
| CN114957002A (en) * | 2022-06-30 | 2022-08-30 | 蚌埠学院 | Green synthesis method of diisobutyl malonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100460056C (en) | Method for preparing sulfate akaganeite adsorbent for de-arsenation | |
| CN104831534A (en) | Super-hydrophobic and -oleophylic cloth producing method | |
| CN103523891B (en) | Containing the method for organism Catalytic Wet Air Oxidation for Wastewater | |
| CN108940322A (en) | Iron oxide loads application of the sulfate ion type solid super-strong acid in catalytic citric acid and n-butanol esterification | |
| CN105498707A (en) | Preparation method and application of modified graphene oxide/chitosan composite material | |
| CN105233799A (en) | Magnetic metal-organic framework material with core-shell structure and preparation method therefor | |
| CN102614918B (en) | Preparation method of dispersant modified iron nanoparticles | |
| CN105709690A (en) | Adsorbent capable of preferentially adsorbing gold and preparing method and application thereof | |
| CN103962108A (en) | Method for removing hexavalent chromium in water by utilizing polyethyleneimine modified graphite oxide | |
| CN104549146A (en) | Aluminum oxide modified multiwalled carbon nanotube nano composite material as well as preparation method and application thereof | |
| CN107138168A (en) | Ozone catalyst for high concentration organic nitrogen wastewater treatment | |
| CN105032375A (en) | Preparation method of magnetic graphite-based heavy metal adsorbing material | |
| CN107349905A (en) | The method that a kind of nitrogen co-doped magnetic carbon material of fluorine removes hexavalent chromium in industrial wastewater | |
| CN108906082A (en) | A kind of method that precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid | |
| CN107602089A (en) | A kind of preparation method of modified carbon nano-tube alumina composite material | |
| CN106278822B (en) | A kind of method that cellulose two-step method prepares ethylene glycol and 1,2- propylene glycol | |
| CN109179495A (en) | A kind of preparation method of high-dispersion nano titanium dioxide | |
| CN108525673A (en) | One type Fenton solid catalyst and its preparation method and application | |
| CN105749881B (en) | A kind of preparation method and application of CNT polyvinyl alcohol magnetic microsphere | |
| CN109420491A (en) | A kind of preparation method of carbon nanotube-manganese dioxide composite catalyst | |
| CN108940321A (en) | A kind of preparation method of high dispersive iron oxide load sulfate ion type solid super-strong acid | |
| CN106964333A (en) | The method that rare earth loaded catalyst for handling sewage and its preparation method and application and catalytic ozonation handle sewage | |
| CN109174199A (en) | A kind of microwave prepares the method and application of class fenton catalyst and synchronizing regeneration active carbon | |
| CN103801263B (en) | One utilizes iron and steel pickling waste liquid to prepare EDA-Fe 3o 4the method of nano particle and application | |
| CN106807360B (en) | A kind of preparation method of sulfur resistive denitrating catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181207 |