CN109482183A - A kind of effective furfural is converted into the preparation method of 2- methylfuran catalyst - Google Patents
A kind of effective furfural is converted into the preparation method of 2- methylfuran catalyst Download PDFInfo
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- CN109482183A CN109482183A CN201811317827.XA CN201811317827A CN109482183A CN 109482183 A CN109482183 A CN 109482183A CN 201811317827 A CN201811317827 A CN 201811317827A CN 109482183 A CN109482183 A CN 109482183A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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Abstract
A kind of effective furfural is converted into the preparation method of 2- methylfuran catalyst, it is related to a kind of preparation method of catalyst, catalyst combines distillation treatment preparation method thereof using solvent heat (water, alcohol etc.) homogeneous precipitation, realizes active component Cu high degree of dispersion and effective collaborative combination with auxiliary agent.Catalyst main component CuO mass percentage is 10-50%, and the mass percentage of silica or aluminium oxide is 50-90% and other auxiliary agent mass percentages are 0-15%.For the catalyst for preparation by furfural gas phase hydrogenation for 2- methylfuran, furfural conversion ratio is that 100%, 2- methylfuran is selective up to 94% or more.The present invention realizes that Cu in the high degree of dispersion of carrier surface and the Effective Regulation of Cu structure, makes catalyst have high activity and stability in furfural hydrogenation synthesis 2- methylfuran reaction by effectively being combined with Cu and auxiliary agent.
Description
Technical field
The present invention relates to a kind of preparation methods of catalyst, are converted into 2- methylfuran more particularly to a kind of effective furfural
The preparation method of catalyst.
Background technique
2- methylfuran is a kind of important Organic Chemicals, is widely used in the side such as medicine, pesticide and fine chemistry industry
Face.A series of organic chemicals can be synthesized using it as raw material, such as pentadiene, pentanediol, acetylpropyl alcohol and ketone;In medical row
In industry, 2- methylfuran is for producing vitamin B1With antidysenteric chloroquine diphosphate, primaquine phosphate etc..Industrially produce 2- first
Base furans is all to be produced using furfural catalytic hydrogenation, and the key of the process is exploitation high performance catalyst.Industrially make at present
Catalyst is mainly Cu-Cr series catalysts, and the price is very expensive.
Using CuO-Cr2O3/ graphite or aluminium oxide are catalyst, when reaction temperature is 200-300 DEG C, reaction pressure
0.005-0.3MPa, liquid air speed 0.25-0.5hr-1When, the yield of 2- methyl can reach 90%.Being prepared for group using mixing method becomes
CuO 5%~15%, Cr2O30.5%~5%, Al2O380%~90%, 0.01%~2% at least one alkali and alkaline earth metal ions
Oxide (K2O、Na2O, CaO, BaO, MgO, convenient content 0.5%~1%), 0.01%~2% at least one be selected from P, Bi,
The oxide of Ce, Mo, Zn, B, Co (preferred range is 0.04%~1%).In atmospheric conditions, reaction temperature be 230~240 DEG C,
0.25~0.40 h of liquid air speed–1Under the conditions of, after laboratory continuously runs 1200 h, furfural conversion ratio is up to 99%~100%, 2- first
Base furans selectivity is up to 95% or more, and yield is up to 92.5~94%.Cu/SiO2 catalyst is synthesized using ammonia still process method, is shown excellent
Different catalysis furfural synthesizes 2- methylfuran performance, and furfural conversion ratio reaches 92% or more 100%, 2- methylfuran selectivity.
These catalyst members contain extremely toxic carcinogen Cr, not only bring injury to operator in production,
And it is caused serious environmental pollution again in catalyst waste treatment.And some catalyst stabilities need further to mention
It is high.For this purpose, researchers make great efforts exploitation efficiently without Cr catalyst positive.
Chinese patent reports " a kind of the catalyst of preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde and preparation method thereof " component
For CuO 18-22%, ZnO 3-7% and carrier Al2O373-77% without Cr catalyst.It is 230 degree in reaction temperature, often
Pressure, liquid air speed 0.4hr-1Under the conditions of, furfural conversion ratio is 100%.2- methylfuran is selectively 91%-94%.Although the catalyst
Higher 2- methylfuran selectivity is given, but the stability of catalyst is poor.
Summary of the invention
The purpose of the present invention is to provide the preparation method that a kind of effective furfural is converted into 2- methylfuran catalyst, the party
Method is cooperateed with distillation using hydro-thermal and synthesizes Cu catalyst, keeps active component scattered, and realizes the effective of active component and auxiliary agent
In conjunction with and catalyst structure Effective Regulation, performance stablize, have the characteristics that environmentally protective;Catalyst tool industry of the present invention is answered
Use characteristic.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of effective furfural is converted into the preparation method of 2- methylfuran catalyst, and the method includes following preparation process:
Copper salt and alkali or alkaline earth metal salt are dissolved in aqueous solution, and ethyl alcohol or other small molecular alcohols are added, then
Silica solution is added or is directly added into silica support, deposition load agent is then added, realizes the effective immobilized of each component, most passes through afterwards
It is filtered, washed, dries, forms and roasts, the oxidation state precursor of final obtained catalyst;
Wherein, after alcohol is added in metal salt solution, deposition load agent is added, is handled using hydro-thermal and distillation, makes Ph value 7, then
By being filtered, washed, drying and roast, oxide precursor is obtained;
Wherein, copper is active component, and alkali or alkaline earth metal is auxiliary agent;Copper salt, alkali or alkaline earth metal salt are phase
The soluble nitrate answered,
Wherein, deposition load agent is (NH4)2CO3, urea, one or both of NaOH or ammonium hydroxide;
The temperature of above-mentioned drying is 100-120 DEG C, and the temperature of roasting is 400-500 DEG C.
A kind of effective furfural is converted into the preparation method of 2- methylfuran catalyst, the nitre of the mantoquita and auxiliary agent
Concentration of the hydrochlorate in silica solution is 0.1-2mol/l, and is added in small molecular alcohol or copper salt solution and is directly added into silica powder,
Then deposition load agent is added, deposition load agent solution concentration is 0.1-2mol/l.
A kind of effective furfural is converted into the preparation method of 2- methylfuran catalyst, and the catalyst first passes through water
After thermal response, using distillation reaction, active component and the high-dispersion load and active component of auxiliary agent and having for auxiliary agent are realized
Effect combines, and improves catalyst activity and stability.
A kind of effective furfural is converted into the preparation method of 2- methylfuran catalyst, the auxiliary agent alkali metal or alkali
Earth metal is one or both of Na, Sr, Ca, Ba, Zn.
A kind of effective furfural is converted into the preparation method of 2- methylfuran catalyst, the active component CuO matter
Amount percentage composition is 10-50%, and the mass percentage of silica is 50-90%, auxiliary agent NaO, Sr2O, the one of CaO, BaO and ZnO
Kind or two kinds of gross mass percentage composition are 0-15%.
The advantages and effects of the present invention are:
1. the present invention cooperates with synthesis Cu catalyst with distillation compared with traditional infusion process, using hydro-thermal, keep active component scattered,
And realize effective combination of active component and auxiliary agent and the Effective Regulation of catalyst structure, performance is stablized;
2. catalyst of the present invention has a high activity and highly selective, furfural conversion ratio be 100%, 2- methylfuran selectivity 94% with
On;
3. being free of Cr in catalytic component of the present invention, have the characteristics that environmentally protective;
4. catalyst furfural hydrogenation preparation 2- methylfuran performance of the present invention is stablized, the great industrial application characteristic of catalyst.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Copper salt, alkali metal, alkali salt are dissolved in silica solution or Aluminum sol or silica by the present invention, and are added
In a certain amount of aqueous solution, then with a certain amount of alcoholic solvent, while urea, ammonium carbonate is added etc., and carry out hydro-thermal in a kettle
Certain time is reacted, be added distillation to Ph value about 7 after taking-up, is then being filtered, washed, dries and roasts in air
It burns, the oxidation state precursor of final obtained catalyst.
Specific reaction step is: by the content of each component, by required metal nitrate one or more, to be dissolved in silicon molten
Glue or Aluminum sol or silica, then with then a certain amount of solvent, including water and alcohol is added, and be added Cu deposition load agent, control
Temperature processed is 70-100 DEG C, hydro-thermal reaction 4-20 hours, is then distilled under the conditions of 80-100 DEG C, and pH value is controlled 7 or so;
Wherein copper is active component, and content 15-50%, alkali or alkaline earth metal is auxiliary agent, content 0-15%, silica
Or alumina content is 40-80%.
It wherein deposits and is responsible for agent as urea, (NH4)2CO3, one or both of NaOH or ammonium hydroxide;
Resulting dry 12-24 h under the conditions of being deposited in 100-120 DEG C of temperature, then further roasts under the conditions of 400-500 DEG C
It burns 3-6 h and obtains catalyst.
25.6 grams of nitrate trihydrate copper are dissolved in 100ml deionized water by embodiment 1, are then added to 250ml silica solution
In.It takes 32 grams of ammonium carbonates to be dissolved in 200ml deionized water, then sal volatile is added in metal salt solution, and shifts
It into hydrothermal reaction kettle, is reacted under the conditions of 100 DEG C 4 hours, then carrying out distillation reaction to pH is 7, is then filtered and is washed
After washing, dry 12 hours under the conditions of 110 DEG C, then 400 DEG C of roastings, 4 hours obtained catalyst in Muffle furnace.
32 grams of nitrate trihydrate copper, 8.36 grams of barium nitrates are dissolved in 100ml deionized water, are then added to by embodiment 2
In 250ml silica solution.It takes 36 grams of urea to be dissolved in 100ml deionized water, under agitation mixes two kinds of solution, and shift
It into hydrothermal reaction kettle, is reacted under the conditions of 100 DEG C 4 hours, then carrying out distillation reaction to pH is 7, is then filtered and is washed
After washing, dry 12 hours under the conditions of 110 DEG C, then 450 DEG C of roastings, 4 hours obtained catalyst in Muffle furnace.
32 grams of nitrate trihydrate copper are dissolved in 150ml water and ethanol solution by embodiment 3, H2O:C2H5OH=2 are then added to
In 250ml silica solution.It takes 36 grams of urea to be dissolved in 100ml deionized water, under agitation mixes two kinds of solution, and shift
It into hydrothermal reaction kettle, is reacted under the conditions of 100 DEG C 4 hours, then carrying out distillation reaction to pH is 7, is then filtered and is washed
After washing, dry 12 hours under the conditions of 110 DEG C, then 450 DEG C of roastings, 4 hours obtained catalyst in Muffle furnace.
32 grams of nitrate trihydrate copper are then added in 250ml water and ethanol solution, H by embodiment 42O:C2H5OH=2.It takes
36 grams of urea are dissolved in 100ml deionized water, are under agitation mixed two kinds of solution, and be transferred in hydrothermal reaction kettle,
It is reacted under the conditions of 110 DEG C 4 hours, then progress distillation reaction to pH is 7, then after filtering and washing, in 110 DEG C of items
Dry 12 hours under part, then 450 DEG C of roastings, 4 hours obtained catalyst in Muffle furnace.
Embodiment 5 is by 140 grams of nitrate trihydrate copper, and 40.2 grams of zinc nitrates are dissolved in 300ml deionized water and ethyl alcohol, H2O:
C2H5OH=2 are then added in 1500ml silica solution.0.5mol/L ammonia spirit 700ml is taken, under agitation by two kinds
Solution mixing, and is transferred in hydrothermal reaction kettle, react 4 hours under the conditions of 110 DEG C, and then progress distillation reaction to pH is
7, then after filtering and washing, dry 12 hours under the conditions of 110 DEG C, then in Muffle furnace 500 DEG C be made within roasting 4 hours
Catalyst.
Catalytic performance test:
After the catalyst of preparation is mediated extrusion on smallest catalyst molding machine, the cylindrical particle of 3mm × 4mm is prepared.It takes
30g cylindrical particle catalyst is fitted into the stainless steel reaction pipe that internal diameter is 22mm, is passed through H2/N2For the nitrogen and hydrogen mixture of 1:10,
Nitrogen is closed after restoring 4 hours under the conditions of 250 degree, pure hydrogen is passed through and furfural is reacted, hydrogen is measured by mass flowmenter
Into vaporizer, furfural is transported to vaporizer by metering pump and is carried by hydrogen as reactor is reacted, and product passes through gas
Phase chromatography is analyzed.
In normal pressure, reaction temperature is 220 DEG C, and under the conditions of liquid air speed is 0.35h-1, experimental result is as shown in table 1.
1 reaction result of table
It can be seen that the catalyst has industrial application performance.
Claims (5)
1. the preparation method that a kind of effective furfural is converted into 2- methylfuran catalyst, which is characterized in that the method includes with
Lower preparation process:
Copper salt and alkali or alkaline earth metal salt are dissolved in aqueous solution, and ethyl alcohol or other small molecular alcohols are added, then
Silica solution is added or is directly added into silica support, deposition load agent is then added, realizes the effective immobilized of each component, most passes through afterwards
It is filtered, washed, dries, forms and roasts, the oxidation state precursor of final obtained catalyst;
Wherein, after alcohol is added in metal salt solution, deposition load agent is added, is handled using hydro-thermal and distillation, makes Ph value 7, then
By being filtered, washed, drying and roast, oxide precursor is obtained;
Wherein, copper is active component, and alkali or alkaline earth metal is auxiliary agent;Copper salt, alkali or alkaline earth metal salt are phase
The soluble nitrate answered,
Wherein, deposition load agent is (NH4)2CO3, urea, one or both of NaOH or ammonium hydroxide;
The temperature of above-mentioned drying is 100-120 DEG C, and the temperature of roasting is 400-500 DEG C.
2. a kind of effective furfural according to claim 1 is converted into the preparation method of 2- methylfuran catalyst, feature
It is, concentration of the nitrate of the mantoquita and auxiliary agent in silica solution is 0.1-2mol/l, and small molecular alcohol or mantoquita is added
It is directly added into silica powder in solution, deposition load agent is then added, deposition load agent solution concentration is 0.1-2mol/l.
3. a kind of effective furfural according to claim 1 is converted into the preparation method of 2- methylfuran catalyst, feature
It is, after the catalyst first passes through hydro-thermal reaction, using distillation reaction, realizes that the high dispersive of active component and auxiliary agent is negative
Effective combination of load and active component and auxiliary agent improves catalyst activity and stability.
4. a kind of effective furfural according to claim 1 is converted into the preparation method of 2- methylfuran catalyst, feature
It is, the auxiliary agent alkali or alkaline earth metal is one or both of Na, Sr, Ca, Ba, Zn.
5. a kind of effective furfural according to claim 1 is converted into the preparation method of 2- methylfuran catalyst, feature
It is, the active component CuO mass percentage is 10-50%, and the mass percentage of silica is 50-90%, auxiliary agent
NaO、Sr2O, one or two kinds of gross mass percentage compositions of CaO, BaO and ZnO are 0-15%.
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Cited By (6)
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CN109796428A (en) * | 2019-03-28 | 2019-05-24 | 北京化工大学 | A kind of copper-based catalysts add the application in hydrogen in 5 hydroxymethyl furfural |
CN110180550A (en) * | 2019-04-04 | 2019-08-30 | 沈阳化工大学 | A kind of environmental protection furfural Efficient Conversion is the preparation method of 2- methylfuran catalyst |
CN110354854A (en) * | 2019-08-22 | 2019-10-22 | 华东师范大学 | A kind of liquid phase selective adds hydrogen furfural to prepare the catalyst of furfuryl alcohol |
CN111905759A (en) * | 2020-08-26 | 2020-11-10 | 江西理工大学 | Catalyst for preparing 2-methylfuran through selective hydrogenation of furfural, preparation method and application |
CN114618491A (en) * | 2022-04-06 | 2022-06-14 | 北京石油化工学院 | Preparation method of copper-based catalyst and method for preparing alkanol by catalytic hydrogenation of copper-based catalyst |
CN115364856A (en) * | 2022-09-20 | 2022-11-22 | 西北工业大学 | Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof |
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CN109796428A (en) * | 2019-03-28 | 2019-05-24 | 北京化工大学 | A kind of copper-based catalysts add the application in hydrogen in 5 hydroxymethyl furfural |
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CN115364856A (en) * | 2022-09-20 | 2022-11-22 | 西北工业大学 | Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof |
CN115364856B (en) * | 2022-09-20 | 2023-11-07 | 西北工业大学 | Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof |
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Application publication date: 20190319 |