CN103007942A - Catalyst for preparing 2-methyl furan by furfural hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing 2-methyl furan by furfural hydrogenation and preparation method thereof Download PDFInfo
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- CN103007942A CN103007942A CN2012105806852A CN201210580685A CN103007942A CN 103007942 A CN103007942 A CN 103007942A CN 2012105806852 A CN2012105806852 A CN 2012105806852A CN 201210580685 A CN201210580685 A CN 201210580685A CN 103007942 A CN103007942 A CN 103007942A
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Abstract
The invention relates to a catalyst for preparing 2-methyl furan by furfural hydrogenation and a preparation method thereof, belonging to the field of catalysts and preparation methods thereof. In the catalyst, copper is used as an active component, and silicon and aluminum composite oxides are used as a supporter, wherein the copper accounts for 15-30 wt%, and the supporter accounts for 75-85 wt%. The catalyst uses copper as the active component, and silicon and composite oxides as the supporter. The catalyst has the dual functions of hydrogenation and acidity, and can control the direction of the reaction, so that the reaction can move towards 2-methyl furan. The catalyst has high low-temperature activity and 2-methyl furan selectivity, and can reach high activity at 180 DEG C; and at this time, the conversion rate of furfural is 100%, and the 2-methyl furan selectivity is higher than 98%. The catalyst adopts the chrome-free system to avoid environmental pollution, and thus, is an environment-friendly catalyst.
Description
Technical field
The present invention relates to a kind of furfural hydrogenation 2-methylfuran processed Catalysts and its preparation method, belong to the Catalysts and its preparation method field.
Background technology
China is a large agricultural country, and the deep processing industries of agricultural byproducts had had significant progress in recent years, and the production of furfural and deep processing are exactly an example wherein.Three provinces in the northeast of China are the main agrarian areas of China, furfural production and deep processing already develop rapidly, developed in recent years China furfural major production areas, and the deep processing industries of furfural also has been subject to attention, it is exactly illustration that the enterprise that adopts furfural to prepare the 2-methylfuran constantly increases.
2-methylfuran (being called for short 2-MF) is a kind of important organic chemical industry's intermediate, is widely used in the aspects such as medicine, agricultural chemicals, and especially in medical industry, the 2-methylfuran can be used for producing Cobastab, the multi-medicaments such as chloroquine diphosphate and phosphoric acid one hundred ammonia quinoline.Before the eighties in 20th century, the 2-methylfuran mainly obtains by the 1,3-pentadiene catalytic oxidation; After the eighties, mainly adopt furfural hydrogenation 2-methylfuran processed.
At present the furfural of China mainly is that raw material as cheapness exports, and needed 2-methylfuran mainly is import, and the main cause that causes this phenomenon is that the 2-methylfuran catalyst activity and selectivity of China is low.
Russian Patent SU941366 report CuO-Cr
2O
3/ graphite or aluminium oxide are made catalyst, carry out the reaction of preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde, and at 200 ~ 300 ° of C of temperature, reaction pressure is at 0.005 ~ 0.3MPa, liquid air 0.25 ~ 0.5h
-1Condition under, the yield of 2-methylfuran is 90%, accessory substance is too much, has increased the difficulty of later separation.
Chinese patent 95111759.9 has been reported " furfural plays the synthetic 2-methylfuran catalyst of phase hydrogenation ", this catalyst is take aluminium oxide, cupric oxide and chromium oxide as main active component, adding alkali metal, alkaline-earth metal and other element forms, wherein cupric oxide 5 ~ 15%, chrome green 0.5 ~ 5%, aluminium oxide 80 ~ 90%, other material of 0.01 ~ 2% is at 230 ~ 240 ° of C of reaction temperature, normal pressure, liquid air speed are 0.25 ~ 0.4h
-1Situation under, the conversion ratio of this catalyst furfural is that the yield of 99 ~ 100%, 2-methylfuran is 92.5 ~ 94%, although this catalyst has high 2-methylfuran yield, exists the problem of the lower and pollution of chromium of liquid air speed.
Chinese patent 00120872.1 has been reported " being used for catalyst of preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde and uses thereof ", and this catalyst is with CuO, Cr
2O
3With NiO be key component, catalyst consists of CuO50-53%, Cr
2O
346-49%, NiO0.2-1.1%.Reaction temperature 230-250 ° of C, reaction pressure is less than 0.06MPa, and furfural liquid air speed is 0.4 ~ 0.5h
-1The time, the conversion ratio of furfural be 100%, 2-methylfuran selectively be 95 ~ 97%.Although catalyst has the selective of higher furfural conversion ratio and 2-methylfuran, contains chromium in the catalyst, serious environment pollution.
Chinese patent 200610015668.9 has been reported " a kind of Catalysts and its preparation method of preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde " this catalyst take copper as active component, and silica is carrier, and alkali metal or alkaline-earth metal are auxiliary agent.Wherein the percentage by weight of cupric oxide is 18 ~ 22%, and the percentage by weight of carrier silica is 73 ~ 77%, and the percentage composition of metal oxide auxiliary agent is 3 ~ 7%.This catalyst is at 230 ° of C, normal pressure, liquid air speed 0.4h
-1Condition under, the conversion ratio of furfural be 100%, 2-methylfuran selectively can reach 90%, exist the problem that reaction temperature is high and 2-methylfuran yield is low.
Chinese patent 200710150025.X has reported " a kind of Catalysts and its preparation method of preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde ", this catalyst forms with cupric oxide, aluminium oxide and zinc oxide, wherein the percentage by weight of cupric oxide is 18 ~ 22%, zinc oxide is 3 ~ 7%, aluminium oxide consist of 73 ~ 77%.This catalyst is at 230 ° of C, normal pressure, liquid air speed 0.4h
-1Condition under, the conversion ratio of furfural be 100%, 2-methylfuran selectively can reach 90%, exist the problem that reaction temperature is high and 2-methylfuran yield is low.
Summary of the invention
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is: a kind of furfural hydrogenation 2-methylfuran processed Catalysts and its preparation method is provided, containing metal chromium not, free from environmental pollution, and catalyst has very high low-temperature reactivity, has avoided present catalyst to reach and has just had highly active problem more than 230 ° of C.
The technical solution adopted for the present invention to solve the technical problems is: a kind of furfural hydrogenation 2-methylfuran processed catalyst is provided, copper is active component, the sial composite oxides are as carrier, and wherein to be calculated in mass percent be 15 ~ 30% to the content of copper, and the content of carrier is 75 ~ 85% in mass.
The mass ratio of general sial is 30%:70%, and proportioning can be done a little and adjust.
Described furfural hydrogenation 2-methylfuran processed catalyst is prepared from by the precipitation method or infusion process.
The preparation method of the catalyst of the catalyst of described furfural hydrogenation 2-methylfuran processed is characterized in that may further comprise the steps:
1) hydrothermal synthesis method prepares the sial complex carrier
Aluminium source and silicon source are mixed, then regulate pH, make its precipitation fully, change said mixture over to crystallizing kettle, under 100 ~ 150 ° of C, carried out crystallization 12 hours, then washing, 400 ~ 550 ° of C carry out roasting;
2) infusion process prepares Cu-series catalyst
A. the copper source is mixed with solution;
B. then the sial composite oxides are sprayed;
C. catalyst is carried out drying, roasting;
D. compressing.
Described aluminium source is boehmite, carbonization aluminium glue, medicinal aluminium, aluminum sulfate, aluminum nitrate or aluminium chloride.
Described silicon source is waterglass, silica gel, white carbon or powder silica.
Described copper source is copper nitrate, copper sulphate or basic copper carbonate.
The invention has the beneficial effects as follows: this catalyst is take copper as active component, and the sial composite oxides are carrier.This catalyst has hydrogenation and bifunctional acidic character, can control the direction that reaction is carried out, so that reaction is carried out to the direction of 2-methylfuran.Advantage is as follows:
1, this catalyst has very high low temperature active and the 2-methylfuran is selective, namely reaches high activity under 180 ° of C, this moment furfural conversion ratio be 100%, 2-methylfuran selectively greater than 98%.
2, catalyst adopts the Chrome-free system, has avoided the pollution of environment, is a kind of environmentally benign catalysts.
The specific embodiment
Below in conjunction with embodiment the present invention is described further:
Embodiment 1
Being 25% Ludox with 100 kilograms of content mixes with 42 kilograms boehmite, in the situation that do not stop to stir, adds rare nitre acid for adjusting pH to 6, then change mixture over to crystallizing kettle, 120 ° of C crystallization 10 hours, then filtration washing, 450 ° of C roastings 3 hours obtain powder mixture.
With 12.5 kilograms of water-soluble wiring solution-formings of copper nitrate, then above-mentioned powder mixture is sprayed, spray finish after, dry 4 hours of 110 ° of C, 350 ° of C roastings 3 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 1#.
Embodiment 2
Being 25% Ludox with 100 kilograms of content mixes with 35.7 kilograms dried glue aluminium hydroxide, in the situation that do not stop to stir, adds dilute sulfuric acid and regulates pH to 5, then change mixture over to crystallizing kettle, 110 ° of C crystallization 8 hours, then filtration washing, 420 ° of C roastings 5 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 21.4 kilograms copper nitrate, then above-mentioned powder mixture is sprayed, spray finish after, dry 4 hours of 120 ° of C, 300 ° of C roastings 5 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 2#.
Embodiment 3
Being 20% waterglass with 125 kilograms of content mixes with 33.3 kilograms medicinal aluminium hydroxide, in the situation that do not stop to stir, adds watery hydrochloric acid and regulates pH to 6, then change mixture over to crystallizing kettle, 130 ° of C crystallization 12 hours, then filtration washing, 440 ° of C roastings 5 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 16.7 kilograms copper nitrate, then above-mentioned powder mixture is sprayed, spray finish after, dry 4 hours of 110 ° of C, 350 ° of C roastings 4 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 3#.
Embodiment 4
Being 30% waterglass with 83.3 kilograms of content mixes with 37 kilograms dried glue, in the situation that do not stop to stir, adds rare nitre acid for adjusting pH to 7, then change mixture over to crystallizing kettle, 120 ° of C crystallization 18 hours, then filtration washing, 420 ° of C roastings 4 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 11 kilograms copper nitrate, then above-mentioned powder mixture is sprayed, spray finish after, dry 4 hours of 120 ° of C, 330 ° of C roastings 4 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 4#.
Embodiment 5
183.88 kilograms industrial nitric acid aluminium is dissolved in water, then 25 kilograms white carbon is dispersed in the mentioned solution, then drip ammoniacal liquor, regulating pH is 8, then changes mixture over to crystallizing kettle, 130 ° of C crystallization 15 hours, then filtration washing, 450 ° of C roastings 3 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 66.87 kilograms copper sulphate, then above-mentioned powder mixture is sprayed, spray finish after, dry 4 hours of 130 ° of C, 340 ° of C roastings 4 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 5#.
Embodiment 6
65.36 kilograms industrial aluminium chloride is dissolved in water, then 27 kilograms powder silica is dispersed in the mentioned solution, then drip NaOH, regulating pH is 7, then change mixture over to crystallizing kettle, 120 ° of C crystallization 20 hours, then filtration washing, 430 ° of C roastings 5 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 63 kilograms copper sulphate, then above-mentioned powder mixture is sprayed, spray finish after, dry 4 hours of 120 ° of C, 350 ° of C roastings 3 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 6#.
Embodiment 7
167.86 kilograms industrial aluminum sulphate is dissolved in water, then 30 kilograms white carbon is dispersed in the mentioned solution, then drip potassium hydroxide, regulating pH is 7.5, then change mixture over to crystallizing kettle, 150 ° of C crystallization 12 hours, then filtration washing, 450 ° of C roastings 3 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 64.58 kilograms copper sulphate, then above-mentioned powder mixture is sprayed, spray finish after, dry 5 hours of 110 ° of C, 320 ° of C roastings 5 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 7#.
Embodiment 8
91.45 kilograms industrial nitric acid aluminium is dissolved in water, then 37.5 kilograms powder silica is dispersed in the mentioned solution, then drip NaOH, regulating pH is 7, then change mixture over to crystallizing kettle, 120 ° of C crystallization 18 hours, then filtration washing, 440 ° of C roastings 4 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 34.55 kilograms basic copper carbonate, then above-mentioned powder mixture is sprayed, spray finish after, dry 5 hours of 120 ° of C, 350 ° of C roastings 3 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 8#.
Embodiment 9
26 kilograms industrial aluminium chloride is dissolved in water, then 40 kilograms white carbon is dispersed in the mentioned solution, then drip ammoniacal liquor, regulating pH is 7, then changes mixture over to crystallizing kettle, 130 ° of C crystallization 18 hours, then filtration washing, 450 ° of C roastings 3 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 37.8 kilograms basic copper carbonate, then above-mentioned powder mixture is sprayed, spray finish after, dry 5 hours of 110 ° of C, 330 ° of C roastings 6 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 9#.
Embodiment 10
Being 30% waterglass with 34 kilograms of content mixes with 58 kilograms dried glue, in the situation that do not stop to stir, adds rare nitre acid for adjusting pH to 7, then change mixture over to crystallizing kettle, 110 ° of C crystallization 17 hours, then filtration washing, 450 ° of C roastings 3 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 42 kilograms basic copper carbonate, then above-mentioned powder mixture is sprayed, spray finish after, dry 5 hours of 120 ° of C, 350 ° of C roastings 5 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 10#.
Embodiment 11
Being 20% waterglass with 100 kilograms of content mixes with 50 kilograms boehmite, in the situation that do not stop to stir, adds dilute sulfuric acid and regulates pH to 7, then change mixture over to crystallizing kettle, 120 ° of C crystallization 15 hours, then filtration washing, 430 ° of C roastings 5 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 39.5 kilograms basic copper carbonate, then above-mentioned powder mixture is sprayed, spray finish after, dry 4 hours of 130 ° of C, 350 ° of C roastings 4 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 11#.
Embodiment 12
Being 25% waterglass with 120 kg content mixes with 25 kilograms medicinal aluminium, in the situation that do not stop to stir, adds rare nitre acid for adjusting pH to 6.5, then change mixture over to crystallizing kettle, 110 ° of C crystallization 20 hours, then filtration washing, 450 ° of C roastings 3 hours obtain powder mixture.
With the water-soluble wiring solution-forming of 42.5 kilograms basic copper carbonate, then above-mentioned powder mixture is sprayed, spray finish after, dry 5 hours of 120 ° of C, 340 ° of C roastings 6 hours.Then catalyst is played the sheet moulding.Obtain catalyst, be decided to be 12#.
Get respectively 1#, 2#, 3#, 4#, 5#, 6#, 7#, 8#, 9#, 10#, 11#, 12#, industrial sample 1#, industry sample 2# catalyst 2ml, the interior warp of packing into is the stainless steel reactor of 6mm, is preheating to 170 ° of C, then the ratio of regulating the amount of substance of hydrogen and furfural is 10:1, the temperature and pressure of conditioned reaction device, evaluation result such as table 1
The experimental result of the activity and selectivity of the catalyst that table 1 enforcement above-described embodiment is measured
Claims (6)
1. furfural hydrogenation 2-methylfuran processed catalyst, it is characterized in that: copper is active component, and the sial composite oxides are as carrier, and wherein to be calculated in mass percent be 15 ~ 30% to the content of copper, and the content of carrier is 75 ~ 85% in mass.
2. furfural hydrogenation 2-methylfuran processed catalyst as claimed in claim 1 is characterized in that described furfural hydrogenation 2-methylfuran processed catalyst is prepared from by the precipitation method or infusion process.
3. the preparation method of the catalyst of the catalyst of furfural hydrogenation 2-methylfuran processed as claimed in claim 1 or 2 is characterized in that may further comprise the steps:
1) hydrothermal synthesis method prepares the sial complex carrier
Aluminium source and silicon source are mixed, then regulate pH, make its precipitation fully, change said mixture over to crystallizing kettle, under 100 ~ 150 ° of C, carried out crystallization 12 hours, then washing, 400 ~ 550 ° of C carry out roasting;
2) infusion process prepares Cu-series catalyst
A. the copper source is mixed with solution;
B. then the sial composite oxides are sprayed;
C. catalyst is carried out drying, roasting;
D. compressing.
4. according to the preparation method of the catalyst of the described catalyst of stating furfural hydrogenation 2-methylfuran processed of right 3, it is characterized in that described aluminium source is boehmite, carbonization aluminium glue, medicinal aluminium, aluminum sulfate, aluminum nitrate or aluminium chloride.
5. according to the preparation method of the catalyst of the described catalyst of stating furfural hydrogenation 2-methylfuran processed of right 3, it is characterized in that described silicon source is waterglass, silica gel, white carbon or powder silica.
6. according to the preparation method of the catalyst of the described catalyst of stating furfural hydrogenation 2-methylfuran processed of right 3, it is characterized in that described copper source is copper nitrate, copper sulphate or basic copper carbonate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104162432A (en) * | 2014-06-24 | 2014-11-26 | 北京化工大学 | A homo-dispersed efficient biomass reforming catalyst and a preparing method thereof |
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| CN101143324A (en) * | 2006-09-15 | 2008-03-19 | 国家纳米技术与工程研究院 | Catalyst for preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde and its preparation method |
| CN101961652A (en) * | 2010-10-14 | 2011-02-02 | 来安县迅能催化剂有限公司 | Catalyst for preparing 2-methyl furan through gas phase hydrogenation of furfural and preparation method thereof |
| CN102614883A (en) * | 2012-02-22 | 2012-08-01 | 沈阳化工大学 | Environment-friendly 2-methyl furan catalyst and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143324A (en) * | 2006-09-15 | 2008-03-19 | 国家纳米技术与工程研究院 | Catalyst for preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde and its preparation method |
| CN101961652A (en) * | 2010-10-14 | 2011-02-02 | 来安县迅能催化剂有限公司 | Catalyst for preparing 2-methyl furan through gas phase hydrogenation of furfural and preparation method thereof |
| CN102614883A (en) * | 2012-02-22 | 2012-08-01 | 沈阳化工大学 | Environment-friendly 2-methyl furan catalyst and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104162432A (en) * | 2014-06-24 | 2014-11-26 | 北京化工大学 | A homo-dispersed efficient biomass reforming catalyst and a preparing method thereof |
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Application publication date: 20130403 |