CN105879911B - A kind of high temperature resistant solid acid catalyst and its preparation method and application based on organic point of DCL/Direct coal liquefaction heavy - Google Patents
A kind of high temperature resistant solid acid catalyst and its preparation method and application based on organic point of DCL/Direct coal liquefaction heavy Download PDFInfo
- Publication number
- CN105879911B CN105879911B CN201610218203.7A CN201610218203A CN105879911B CN 105879911 B CN105879911 B CN 105879911B CN 201610218203 A CN201610218203 A CN 201610218203A CN 105879911 B CN105879911 B CN 105879911B
- Authority
- CN
- China
- Prior art keywords
- dcl
- coal liquefaction
- direct coal
- high temperature
- acid catalyst
- 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.)
- Active
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
-
- 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 invention discloses a kind of high temperature resistant solid acid catalyst and its preparation method and application based on organic point of DCL/Direct coal liquefaction heavy, method include the following steps: that (1) reacts organic point of DCL/Direct coal liquefaction heavy with curing agent, obtain product A；Organic be placed under air or inert atmosphere of product A or DCL/Direct coal liquefaction heavy is heat-treated, thermostabilization product B is obtained；(2) sulfonation: product B is mixed with sulfonating agent and is placed in closed reactor, is reacted under an inert atmosphere；The reaction mixture of generation is filtered, washed, is dried to get high temperature resistant solid acid catalyst.The present invention has expanded organic point of DCL/Direct coal liquefaction heavy of Land use systems, improves organic point of DCL/Direct coal liquefaction heavy of added value.High temperature resistant solid acid catalyst of the present invention have the characteristics that acid amount is high, thermal stability is good, it is low in cost, be used multiple times, can be used for the synthetic reaction of ester under hot conditions, such as: the synthesis of polyol ester, polybasic ester etc..
Description
Technical field
The present invention relates to a kind of high temperature resistant solid acid catalyst based on organic point of DCL/Direct coal liquefaction heavy and its preparation sides
Method and application, belong to technical field of fine.
Background technique
Compared with liquid acid catalyst used at present (such as: sulfuric acid, phosphoric acid or hydrofluoric acid), solid acid catalyst has
Easily separated, cyclic utilization rate is high and advantages of environment protection.In numerous solid acid catalysts, ion exchange resin is simultaneous
While having other solid acid catalyst advantages, also have that catalytic activity is adjustable, reaction condition is mild, selectivity is good and low corruption
The features such as corrosion, be widely used in esterification, condensation reaction and dehydration etc. fields.
In recent years, the attention that solid acid catalyst causes academia is prepared with the charing sulfonation of biomass low temperature part.
[the Chem Mater, 2006,18:3039-3045 such as M.Hara；Catal Today, 2006,116,157-161] with glucose and
Sucrose etc. is raw material, is carbonized to obtain amorphous carbon in advance, later will be obtained amorphous as sulfonating agent using sulfuric acid or oleum
Carbon sulfonation has obtained sulfonic group charcoal solid acid catalyst, and obtained solid acid catalyst thermal stability is good, and in acid catalysis field
Show good catalytic activity and stability.M.Hara etc. [Angew Chem Int Ed, 2004,43:2955-2958] is also
Using polycyclic aromatic hydrocarbons such as naphtha, carbolineums as raw material, first with sulfuric acid or oleum by its sulfonation, later by the polycyclic aromatic hydrocarbon of sulfonation
It is heat-treated at 400 DEG C or so, resulting materials not only acid amount with higher, and with good stability and catalytic activity.CN
102218342A discloses a kind of preparation method of high efficient sulfonated carbon solid acid catalyst.The catalyst acid amount is controllable, reaction is lived
Property it is high, stability is good, recyclable.Xu Zhong elm etc. [novel charcoal material, 2011,26 (2): 103-108] in bamboo processing to produce
Sawdust be raw material be made sulfonation bamboo charcoal, embodied in the condensation reaction of aldehyde, ketone and ethylene glycol good catalytic activity and
Repeat performance.Although above-mentioned novel solid acid shows certain thermal stability compared with ion exchange resin, its
It is lower (usually less than 120 DEG C) using temperature, cause its application field to be restricted；The disadvantages of it is expensive simultaneously also limits
Its application range, such as: the synthesis of polyol ester, high alcohol ester.
Direct coal liquefaction technology is considered as one of important technology of clean coal utilization.But it is no matter straight using which kind of coal
Liquefaction process is connect, the liquefied residue for accounting for about raw coal total amount 20%~30% can be all generated.The conventional use of coal directly-liquefied residue
Mainly there is a gasification, burning and coking etc., these processing methods the problem of there is also technologies, environment at present.Therefore, no matter from coal
Economy or environmental protection angle consider that it is all a urgent problem to be solved that so a large amount of coal directly-liquefied residue, which utilizes,.
Coal directly-liquefied residue is mainly by inorganic mineral, extra catalyst, together with the partial liquefaction mink cell focus and asphaltene being entrained with and
The composition such as preasphaltene.The wherein such as asphaltene of the organic component in addition to ash content, preasphaltene etc. are referred to as DCL/Direct coal liquefaction weight
Organic point of matter, not only contain higher carbon content, and be easy to be crosslinked, is the excellent presoma for preparing carbon material.But by
It is divided into point and structure is complicated in these heavys are organic, causes it to process and using difficult.
Summary of the invention
Difficult problem, the present invention are utilized for conventional solid acid catalyst high temperature resistance difference and organic point of coal liquefaction heavy
It is designed to provide a kind of high temperature resistant solid acid catalyst based on organic point of DCL/Direct coal liquefaction heavy and preparation method thereof and answers
With.Obtained solid acid catalyst has the characteristics that high, the not soluble in water and organic solvent of acid amount, not dissolve in soda acid, thermal stability good.
The present invention is achieved through the following technical solutions:
A kind of preparation method of the high temperature resistant solid acid catalyst based on organic point of DCL/Direct coal liquefaction heavy, including walk as follows
It is rapid: (1) that organic point of DCL/Direct coal liquefaction heavy of thermostabilization: organic point of DCL/Direct coal liquefaction heavy being reacted with curing agent, is obtained
Product A；Organic be placed under air or inert atmosphere of product A or DCL/Direct coal liquefaction heavy is heat-treated, thermostabilization is obtained
Change product B；(2) sulfonation: product B being mixed in a certain ratio with sulfonating agent, is placed in closed reactor, under an inert atmosphere plus
Heat reacts certain time to certain temperature.The reaction mixture of generation is filtered, washed, is dried, obtaining product C is high temperature resistant
Solid acid catalyst.
In step (1), the curing agent is selected from one of terephthalyl alcohol, benzaldehyde, furfural, paraformaldehyde or more
Kind.
Further, in the above-mentioned technical solutions, the preparation method of the product A in step (1) is DCL/Direct coal liquefaction heavy
Organic point of powder and curing agent in certain mass ratio mechanical mixture it is uniform after, reacted under inert gas, catalysts conditions
To organic point of polymer of DCL/Direct coal liquefaction heavy；The mass ratio is 10:4~10:2；The reaction condition are as follows: reaction temperature
120 DEG C~180 DEG C；Catalyst is one of sulfuric acid or p-methyl benzenesulfonic acid, and dosage is the 1% of organic point of DCL/Direct coal liquefaction heavy
~10%；Reaction time is 1~4h.Organic point of thermal stability with higher of DCL/Direct coal liquefaction heavy after crosslinking and abundant
, reaction position (fragrant hydrogen) for sulfonation, may be used as sulfonation precursor preparation high temperature resistant solid acid catalyst.
Further, in the above-mentioned technical solutions, organic point of DCL/Direct coal liquefaction heavy of thermostabilization product in step (1)
The preparation condition of B are as follows: be placed in product A or DCL/Direct coal liquefaction heavy are organic in 180 DEG C~600 DEG C of air or inert atmosphere
Reaction 0.5~for 24 hours, the inert atmosphere be one of nitrogen, helium, argon gas or a variety of, the gas flow be 100~
500mL/min；
Further, in the above-mentioned technical solutions, the sulfonating agent in step (2) is chlorosulfonic acid, the concentrated sulfuric acid or oleum
One of；The concentrated sulfuric acid concentration is 90~98wt.%；The oleum sulfur trioxide content is 15~50wt.%.
Further, in the above-mentioned technical solutions, organic point of the DCL/Direct coal liquefaction heavy of the thermostabilization in step (2) with
The mass ratio of sulfonating agent is 1:2~1:20.
Further, in the above-mentioned technical solutions, the inert gas in step (2) is nitrogen, argon gas or helium, gas stream
Amount is 100~500mL/min.
Further, in the above-mentioned technical solutions, the reaction temperature in step (2) be 0~200 DEG C, the reaction time be 2~
48h。
The present invention separately provides the high temperature resistant solid acid catalyst that above-mentioned preparation method obtains.
The present invention is provided with application of the above-mentioned high temperature resistant solid acid catalyst in catalysis Lipase absobed or ion exchange.
Further, in the above-mentioned technical solutions, in catalytic reaction temperature up to 180 DEG C.
In the present invention, the organic organic component being divided into coal directly-liquefied residue in addition to ash content of DCL/Direct coal liquefaction heavy,
It mainly include asphaltene, preasphaltene etc..Preparation method are as follows: after crushing coal directly-liquefied residue, extracted with organic solvent
To organic solvent true qualities, vacuum distillation removes in extract organic solvent to get organic point of DCL/Direct coal liquefaction heavy.Wherein, have
Solvent be selected from n-hexane, tetrahydrofuran, toluene, furfural, N, dinethylformamide, N, N- dimethyl acetamide, ethylenediamine,
At least one of quinoline, liquefied light oil and mink cell focus.
Invention beneficial effect
1. the preparation of the invention proposes a kind of high temperature resistant solid acid catalyst based on organic point of DCL/Direct coal liquefaction heavy
Method.The Land use systems for having expanded organic point of DCL/Direct coal liquefaction heavy improve organic point of DCL/Direct coal liquefaction heavy of added value,
A new way is provided to solve the problems, such as that coal directly-liquefied residue and its organic point of utilization ways of heavy are single, added value is low
Diameter.
2. the present invention solves the problems, such as conventional ion exchanger resin solid acid catalyst poor heat resistance, provide a kind of resistance to
High-temp solid acid catalyst is for substituting conventional liq acid catalyst.There is resulting catalyst acid to measure, and high, thermal stability is good, machine
Tool intensity is high, low in cost, the features such as being used multiple times, and can be used for the synthetic reaction of ester under hot conditions, such as: polyalcohol
The synthesis of ester, polybasic ester etc..
Specific embodiment
Following nonlimiting examples can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
In the present invention, the organic organic component being divided into coal directly-liquefied residue in addition to ash content of DCL/Direct coal liquefaction heavy,
It mainly include asphaltene, preasphaltene etc..Preparation method are as follows: after crushing coal directly-liquefied residue, with organic solvent tetrahydro
Furans is extracted to organic solvent true qualities, and vacuum distillation removes organic solvent in extract, by obtained solid object be ground to 100um with
Lower organic point of DCL/Direct coal liquefaction heavy to obtain the final product.
Embodiment 1
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground is uniform with 3g terephthalyl alcohol mechanical mixture, lazy at 120 DEG C
Property atmosphere under, the mixture of viscous form melted through mechanical stirring, later be added 0.5g p-methyl benzenesulfonic acid, react 3h after,
Temperature is risen to 160 DEG C again, heat preservation 4h obtains product A.It weighs a certain amount of product A to be placed in Muffle furnace, in flowing helium gas
Product B is obtained in 500 DEG C of heat preservation 6h under atmosphere (100ml/min).Product B 1g is weighed in reactor, the hair of 20g 50% is added
Cigarette sulfuric acid.Under the argon flow of 100ml/min, 80 DEG C are warming up to, and be stirred continuously.After reacting 2h, stop reaction, by institute
Obtaining product and filtering, wash to filtrate is neutrality, is detected in filtrate until sulfate radical-free ion, then until with barium chloride solution
Filter cake is dried to get high temperature resistant solid acid catalyst.
Embodiment 2
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground is uniformly mixed with 4g benzaldehyde, in 140 DEG C of inert atmospheres
Under, the sulfuric acid solution of 0.1g 98% is added in the mixture of viscous form melted through mechanical stirring later, after reacting 3h, then will
Temperature rises to 160 DEG C, and heat preservation 4h obtains product A.It weighs a certain amount of product A to be placed in Muffle furnace, in flowing argon atmospher
600 DEG C are warming up under (100ml/min), heat preservation 3h obtains product B.Product B 1g is weighed in reactor, chlorosulfonic acid 20 is added
Gram.Under the nitrogen flow of 300ml/min, 60 DEG C are warming up to, and be stirred continuously.After reacting for 24 hours, stop reaction, by gained
It is neutrality that product, which is filtered, washed to filtrate, until with sulfate radical-free ion in barium chloride solution detection filtrate, then will
Filter cake is dried to get high temperature resistant solid acid catalyst.Embodiment 3
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground is uniform with 3g paraformaldehyde mechanical mixture, in 120 DEG C of inertia
Under atmosphere, the sulfuric acid solution of 0.5g 50% is added in the mixture of viscous form melted through mechanical stirring later, after reacting 4h,
Temperature is risen to 160 DEG C again, heat preservation 4h obtains product A.It weighs a certain amount of product A to be placed in Muffle furnace, in moving air gas
(500ml/min) obtains product B in 180 DEG C of heat preservation 12h under atmosphere.Product B1g is weighed in reactor, 30 grams of oleums are added
(15wt%SO3).Under the nitrogen flow of 250ml/min, ice bath is cooled to 0 DEG C, and is stirred continuously.After reacting 48h, stop
Reaction, it is neutrality that products therefrom, which is filtered, is washed to filtrate, until with sulfate radical-free ion in barium chloride solution detection filtrate
Until, then filter cake is dried to get high temperature resistant solid acid catalyst.
Embodiment 4
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground is uniformly mixed with 3g furfural, under 140 DEG C of inert atmospheres,
The sulfuric acid solution of 0.5g 50% is added in the mixture of viscous form melted through mechanical stirring later, after reacting 3h, then will be warm
Degree rises to 180 DEG C, and heat preservation 4h obtains product A.It weighs a certain amount of product A to be placed in Muffle furnace, in moving air atmosphere
350 DEG C are warming up under (200ml/min), heat preservation 0.5h obtains product B.Product B 1g is weighed in reactor, is added 40 grams
90% concentrated sulfuric acid.Under the helium gas flow of 100ml/min, 200 DEG C are warming up to, and be stirred continuously.After reacting 2h, stop anti-
It answers, it is neutrality that products therefrom, which is filtered, is washed to filtrate, until being with sulfate radical-free ion in barium chloride solution detection filtrate
Only, then filter cake is dried to get high temperature resistant solid acid catalyst.
Embodiment 5
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground is uniform with 1g terephthalyl alcohol mechanical mixture, lazy at 140 DEG C
Property atmosphere under, the mixture of viscous form melted through mechanical stirring, later be added 1g p-methyl benzenesulfonic acid, react 1h after, then
Temperature is risen to 160 DEG C, heat preservation 4h obtains product A.It weighs a certain amount of product A to be placed in Muffle furnace, in flowing nitrogen atmosphere
Under (500ml/min) in 200 DEG C of heat preservations obtain product B for 24 hours.Product B 1g is weighed in reactor, 40 gram 98% dense is added
Sulfuric acid.Under the nitrogen flow of 500ml/min, 150 DEG C are warming up to, and be stirred continuously.After reacting for 24 hours, stop reaction, by institute
Obtaining product and filtering, wash to filtrate is neutrality, is detected in filtrate until sulfate radical-free ion, then until with barium chloride solution
Filter cake is dried to get high temperature resistant solid acid catalyst.
Embodiment 6
Weigh 10g DCL/Direct coal liquefaction heavy it is organic be placed in Muffle furnace, at flowing nitrogen atmosphere (350ml/min)
In 200 DEG C of heat preservation 6h, it is warming up to 350 DEG C again later, heat preservation 3h obtains product B.Product B 1g is weighed in reactor, is added 2
Gram oleum (15wt%SO3).Under the nitrogen flow of 100ml/min, 150 DEG C are warming up to, and be stirred continuously.Wait react
After for 24 hours, stop reaction, it is neutrality that products therefrom, which is filtered, is washed to filtrate, until with nothing in barium chloride solution detection filtrate
Until sulfate ion, then filter cake is dried to get high temperature resistant solid acid catalyst.
Application examples 1
Neopentyl glycol and oleic acid are added with the ratio of 1:1.98 into reactor, reaction temperature is 150 DEG C, the reaction time
For 6h, the additional amount of high temperature resistant solid acid catalyst is neopentyl glycol mass percent 10%.High temperature resistant is consolidated after reaction
Body acid catalyst is filtered to remove, resistance to using gained in embodiment 3 later with remaining oleic acid in 0.1M KOH solution titration system
When high-temp solid acid catalyst, the conversion ratio of neopentyl glycol is 80%.
Application examples 2
The calcium chloride solution of 0.5mol/L is added in conical flask in high temperature resistant solid acid catalyst 2g in Example 3
100mL shakes up, and seals bottleneck, impregnates 2h at room temperature, urged with remaining high temperature resistant solid acid in 0.1M KOH solution titration system
Calcium ion exchange capacity of the acid amount of agent to calculate gained high temperature resistant solid acid catalyst, measuring calcium ion exchange capacity is
1.04mmol/g。
The performance of 1 solid acid catalyst of table
Claims (10)
1. a kind of preparation method of the high temperature resistant solid acid catalyst based on organic point of DCL/Direct coal liquefaction heavy, which is characterized in that
Described method includes following steps:
(1) organic point of DCL/Direct coal liquefaction heavy of thermostabilization: organic point of DCL/Direct coal liquefaction heavy is reacted with curing agent, is obtained
Product A；Product A is placed under air or inert atmosphere and is heat-treated, thermostabilization product B is obtained；
(2) sulfonation: product B is mixed with sulfonating agent and is placed in closed reactor, is reacted under an inert atmosphere；By the anti-of generation
Mixture is answered to be filtered, washed, dry, obtaining product C is high temperature resistant solid acid catalyst；
In step (1), the curing agent is selected from one of terephthalyl alcohol, benzaldehyde, furfural, paraformaldehyde or a variety of.
2. the preparation side of the high temperature resistant solid acid catalyst according to claim 1 based on organic point of DCL/Direct coal liquefaction heavy
Method, it is characterised in that: in step (1), product A's the preparation method comprises the following steps: organic point of powder of DCL/Direct coal liquefaction heavy is pressed with curing agent
After 10:4~10:1 mass ratio mechanical mixture is uniform, 120 DEG C~180 DEG C 1~4h of reaction under inert gas, catalysts conditions
Obtain organic point of polymer of DCL/Direct coal liquefaction heavy；
The catalyst is one of sulfuric acid or p-methyl benzenesulfonic acid；
Catalyst amount is the 1%~10% of organic point of weight of DCL/Direct coal liquefaction heavy.
3. based on the preparation side of organic point of DCL/Direct coal liquefaction heavy of high temperature resistant solid acid catalyst described according to claim 1
Method, it is characterised in that: in the step (1), the preparation condition of product B are as follows: by product A be placed in 180 DEG C~600 DEG C air or
In inert atmosphere reaction 0.5~for 24 hours, the inert atmosphere be one of nitrogen, helium, argon gas or a variety of, the gas stream
Amount is 100~500ml/min.
4. based on the preparation side of organic point of DCL/Direct coal liquefaction heavy of high temperature resistant solid acid catalyst described according to claim 1
Method, it is characterised in that: in the step (2), sulfonating agent is selected from one of chlorosulfonic acid, the concentrated sulfuric acid or oleum；It is described dense
Sulfuric acid concentration is 90~98wt.%；The oleum sulfur trioxide content is 15~50wt.%.
5. based on the preparation side of organic point of DCL/Direct coal liquefaction heavy of high temperature resistant solid acid catalyst described according to claim 1
Method, it is characterised in that: in the step (2), the mass ratio of product B and sulfonating agent is 1:2~1:40.
6. a kind of high temperature resistant solid acid catalyst based on organic point of DCL/Direct coal liquefaction heavy according to claim 1
Preparation method, it is characterised in that: inert atmosphere in the step (2) is nitrogen, argon gas or helium, gas flow is 100~
500mL/min。
7. based on the preparation side of organic point of DCL/Direct coal liquefaction heavy of high temperature resistant solid acid catalyst described according to claim 1
Method, it is characterised in that: the reaction temperature in the step (2) is 0~200 DEG C, and the reaction time is 2~48h.
8. the high temperature resistant solid acid catalyst that the preparation method as described in claim 1~7 any one obtains.
9. high temperature resistant solid acid catalyst as claimed in claim 8 is handed in catalytic polyol ester, the synthesis of polybasic ester or ion
Application in changing.
10. application according to claim 9, it is characterised in that: catalytic reaction temperature may be up to 180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610218203.7A CN105879911B (en) | 2016-04-07 | 2016-04-07 | A kind of high temperature resistant solid acid catalyst and its preparation method and application based on organic point of DCL/Direct coal liquefaction heavy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610218203.7A CN105879911B (en) | 2016-04-07 | 2016-04-07 | A kind of high temperature resistant solid acid catalyst and its preparation method and application based on organic point of DCL/Direct coal liquefaction heavy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105879911A CN105879911A (en) | 2016-08-24 |
| CN105879911B true CN105879911B (en) | 2019-02-12 |
Family
ID=57012414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610218203.7A Active CN105879911B (en) | 2016-04-07 | 2016-04-07 | A kind of high temperature resistant solid acid catalyst and its preparation method and application based on organic point of DCL/Direct coal liquefaction heavy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105879911B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101396669A (en) * | 2008-10-23 | 2009-04-01 | 福建师范大学 | Preparation method of asphalt base solid catalyst for producing biology diesel oil |
| CN102716767A (en) * | 2012-07-04 | 2012-10-10 | 太原理工大学 | Preparation method of high-acid-content carbon-based solid acid |
| CN103691483A (en) * | 2013-12-16 | 2014-04-02 | 太原理工大学 | Carbon-based solid acid catalyst and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4041409B2 (en) * | 2003-02-05 | 2008-01-30 | 独立行政法人科学技術振興機構 | Polycyclic aromatic carbon-based solid strong acid |
-
2016
- 2016-04-07 CN CN201610218203.7A patent/CN105879911B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101396669A (en) * | 2008-10-23 | 2009-04-01 | 福建师范大学 | Preparation method of asphalt base solid catalyst for producing biology diesel oil |
| CN102716767A (en) * | 2012-07-04 | 2012-10-10 | 太原理工大学 | Preparation method of high-acid-content carbon-based solid acid |
| CN103691483A (en) * | 2013-12-16 | 2014-04-02 | 太原理工大学 | Carbon-based solid acid catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Industrial application of solid acid-base catalysts;Kozo Tanabe et al.;《Applied Catalysis A: General》;19991231;第181卷;第399-434页 |
| 磺化改性石油沥青催化苯酚与叔丁醇的反应;张康龙 等;《当代化工》;20110731;第40卷(第7期);第673-675页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105879911A (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Catalytic depolymerization of the hydrolyzed lignin over mesoporous catalysts | |
| Tang et al. | Preparation of carbon-based solid acid with large surface area to catalyze esterification for biodiesel production | |
| Zhang et al. | Catalytic production of Jatropha biodiesel and hydrogen with magnetic carbonaceous acid and base synthesized from Jatropha hulls | |
| Zhou et al. | Activity of the carbon-based heterogeneous acid catalyst derived from bamboo in esterification of oleic acid with ethanol | |
| CN103265008A (en) | Nitrogen-doped porous carbon and preparation method thereof | |
| Huang et al. | Lignin-derived layered 3D biochar with controllable acidity for enhanced catalytic upgrading of Jatropha oil to biodiesel | |
| CN102653397A (en) | Preparation method of coal tar-based mesocarbon microbead | |
| Niu et al. | Efficient biodiesel production from waste cooking oil using p-toluenesulfonic acid doped polyaniline as a catalyst | |
| CN107601450B (en) | Production process of coal tar pitch mesocarbon microbeads | |
| CN102559941A (en) | Method for hydrolyzing and saccharifying corncobs | |
| CN204685069U (en) | A kind of multisection type reaction tower for polymethoxy dimethyl ether synthesis and polymethoxy dimethyl ether synthesis technique device | |
| CN110801840A (en) | Cu-Ni bimetallic catalyst with biochar as carrier and application thereof | |
| CN106115699A (en) | Zinc oxide method prepares activated carbon | |
| EP3421126B1 (en) | A method of preparing a gas-adsorbing micro- and meso-porous carbon material | |
| Li et al. | Isomerization Kinetics of Glucose to Fructose in Aqueous Solution with Magnesium‐Aluminum Hydrotalcites | |
| Shen et al. | Production of 5-hydroxymethylfurfural from fructose catalyzed by sulfonated bamboo-derived carbon prepared by simultaneous carbonization and sulfonation | |
| Martínez-Klimov et al. | Synergy between sodium carbonate and sodium titanate nanotubes in the transesterification of soybean oil with methanol | |
| CN103540379B (en) | Solid fuel prepared by hydrothermal carbonization of aqueous phase component of biological oil as well as method thereof | |
| CN105879911B (en) | A kind of high temperature resistant solid acid catalyst and its preparation method and application based on organic point of DCL/Direct coal liquefaction heavy | |
| Wang et al. | Adsorption of CO2 by a novel zeolite doped amine modified ternary aerogels | |
| Han et al. | Production of phenolic compounds in catalytic pyrolysis of bagasse lignin in the presence of Ca0. 5Pr0. 5FeO3 | |
| CN104449916B (en) | In brown coal, high-concentration coal-water slurry method is prepared in warm upgrading | |
| CN108212197A (en) | A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether and its preparation and application | |
| CN110385114B (en) | Metal organic framework material/self-polymerization microporous polymer composite derivative multifunctional carbon molecular sieve and preparation method and application thereof | |
| Zhang et al. | Bimetallic MOF-derived synthesis of cobalt-cerium oxide supported phosphotungstic acid composites for the oleic acid esterification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |