CN1137113C - Catalyst for liquid phase hydrogenation of furaldehyde to prepare furfuralcohol and its use - Google Patents
Catalyst for liquid phase hydrogenation of furaldehyde to prepare furfuralcohol and its use Download PDFInfo
- Publication number
- CN1137113C CN1137113C CNB021404895A CN02140489A CN1137113C CN 1137113 C CN1137113 C CN 1137113C CN B021404895 A CNB021404895 A CN B021404895A CN 02140489 A CN02140489 A CN 02140489A CN 1137113 C CN1137113 C CN 1137113C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- catalyzer
- furfuralcohol
- liquid phase
- furfural
- 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.)
- Expired - Fee Related
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 10
- 239000007791 liquid phase Substances 0.000 title claims abstract description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title abstract description 30
- 239000003054 catalyst Substances 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- GTUVXOOHBUUGBH-UHFFFAOYSA-N furan;methanol Chemical compound OC.C=1C=COC=1 GTUVXOOHBUUGBH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- -1 cobalt metals Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a catalyst for preparing furfuralcohol by the liquid phase hydrogenation of furfural for and an application thereof. The catalyst is prepared from the components of the percentage by weight: 50 to 53 wt% of CuO, 47 to 50 wt% of Cr2O3 and 0.08 to 0.15 wt% of Pt. The catalyst is put in a reaction vessel at the reaction temperature of 180 to 200 DEG C and under the reaction pressure of 3.5 to 5MPa. The catalyst of the present invention has high activity, the conversion rate of furfural is more than 99.5%, and the selectivity of furfuralcohol is more than 97%.
Description
Affiliated field:
The invention belongs to a kind of catalyzer for preparing furfuryl alcohol and uses thereof, relate in particular to a kind of catalyzer that is used for preparing furancarbinol from liquid-phase furol hydrogenation and uses thereof.
Background technology:
Furfuryl alcohol is a kind of important organic chemical industry's intermediate, is mainly used in the fine chemistry industry aspect, can make levulinic acid (having another name called oxysuccinic acid), the furane resin of various performances (as furfuryl resin, furans I, II type resin), furfuryl alcohol-Precondensed UreaFormaldehyde Resin and resol etc.; Be widely used in building, the foundary industry, particularly automotive industry.
The at present industrial furfuryl alcohol of producing all is to adopt furfural shortening method to produce.China is furfural big producing country, and in the furfural deep processed product, furfuryl alcohol is to be worth very high a kind of product.
German patent DE 3,425,758 have reported CuO-Cr
2O
3And CuO/SiO
2Two portions catalyst mix is formed, and carries out preparing furancarbinol from liquid-phase furol hydrogenation, 150-300 ℃ of reaction conditions temperature, reaction pressure 2-10Mpa.Because of catalyzer is divided into two portions, increased the difficulty of preparation process.
Chinese patent ZL 91103132.4, the composition of " producing furfuryl alcohol thunder Buddhist nun's cobalt hydrogenation catalyst and method for making thereof " disclosed catalyzer: cobalt 35.1-46.5%, aluminium 40.2-60.7%, chromium 4.2-13.3%.Its activation method is used the distilled water cleaning catalyst then for to take out reactive aluminum with 20% caustic soda soln, and the pH value about 7 that makes scavenging solution is for extremely.120 ℃ of temperature of reaction, carry out preparing furancarbinol from liquid-phase furol hydrogenation under the condition of 1Mpa, transformation efficiency is greater than 99%.In this catalyst preparation process, need a large amount of cobalt metals, increased the expense of catalyzer; Thunder Buddhist nun cobalt catalyst belongs to the spontaneous combustion type in addition, need be kept in the ethanol, has increased the use difficulty.
Summary of the invention:
The object of the present invention is to provide that a kind of cost is low, preparation catalyzer of preparing furancarbinol from liquid-phase furol hydrogenation and uses thereof that is used for simple, easy to use.
Catalyzer each component weight percent of the present invention is:
CuO 50-53％?Cr
2O
3?47-50％ Pt?0.08-0.15％
The weight percentage summation of each component is 100%.
Catalyzer of the present invention is to adopt precipitator method preparation, and concrete steps are as follows:
1. press the composition CuO 50-53% of catalyzer, Cr
2O
347-50%, Pt 0.08-0.15%, being mixed with concentration is the 1-2M metal salt solution;
2. with metal salt solution and alkaline precipitating agent, about 45 ℃ in temperature, mixing under stirring obtains precipitation, and churning time is 1 hour, aging 1-2 hour then;
3. throw out is through washing and filtering, 100-120 ℃ of drying 12 hours, and 300 ℃ of following roastings 5 hours, mills at last and promptly gets catalyzer.
As above-mentioned alkaline precipitating agent is ammoniacal liquor, yellow soda ash, volatile salt etc.
The reaction conditions of catalyzer of the present invention is temperature 180-200 ℃, pressure 3.5-5Mpa.
The present invention compared with prior art has following advantage:
Catalyst preparation process is simple, and higher activity and selectivity are arranged, and the furfural transformation efficiency is greater than 99.5%, and the selectivity of furfuryl alcohol is greater than 97%.
Embodiment:
Embodiment 1
(1) catalyst preparation process: take by weighing cupric nitrate 75.0g, ammonium chromate 50.0g, 1.0mg/ml platinum solution 4.5ml.Cupric nitrate, ammonium chromate are dissolved in respectively in about 500ml deionized water, are mixed with solution.Copper nitrate solution is slowly added ammonium chromate solution, under 45 ℃, constantly stir; And dropping ammonia solution, the pH value of solution is about about 6.5, mix to obtain precipitation, and then drip required platinum solution, aging 1.5hr, throw out be through washing and filtering, at 110 ℃ of dry 12hr, and at 300 ℃ of roasting 5hr.Mill to less than 120 purpose catalyst samples.
(2) reactivity worth:
Take by weighing 5g catalyzer (＜120 order) and 300ml furfural and pack in the high pressure stainless steel cauldron, steel cylinder hydrogen enters in the reactor by spinner-type flowmeter after the level pressure voltage stabilizing, 195 ℃ of temperature of reaction, under pressure 4Mpa (air speed) condition, furfural transformation efficiency 99.5%, the selecting property 97.8% of furfuryl alcohol.
Embodiment 2
(1) catalyst preparation process:
Take by weighing cupric nitrate 76.5g, ammonium chromate 49.0g, 1.0mg/ml platinum solution 5.5ml, other is together
Embodiment 1.
(2) reactivity worth:
At 185 ℃, under 4.5Mpa (air speed) condition, furfural transformation efficiency 99.4%, furfuryl alcohol selectivity 98.3%.
Embodiment 3
(1) catalyst preparation process:
Take by weighing cupric nitrate 78.0g, ammonium chromate 48.0g, 1.0mg/ml platinum solution 6.5ml, all the other are with implementing
Example 1.
(2) reactivity worth:
At 190 ℃, under the condition of 3.8Mpa (air speed), furfural transformation efficiency 99.7%, the selectivity 98.2% of furfuryl alcohol.
Claims (2)
1. catalyzer that is used for preparing furancarbinol from liquid-phase furol hydrogenation is characterized in that the each component weight percent of catalyzer is:
CuO?50-53％，Cr
2O
3?47-50％，Pt?0.08-0.15％
The weight percentage summation of each component is 100%.
2. catalyzer as claimed in claim 1 is characterized in that reaction conditions is temperature 180-200 ℃, pressure 3.5-5Mpa in the application of preparing furancarbinol from liquid-phase furol hydrogenation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021404895A CN1137113C (en) | 2002-07-19 | 2002-07-19 | Catalyst for liquid phase hydrogenation of furaldehyde to prepare furfuralcohol and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021404895A CN1137113C (en) | 2002-07-19 | 2002-07-19 | Catalyst for liquid phase hydrogenation of furaldehyde to prepare furfuralcohol and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1398670A CN1398670A (en) | 2003-02-26 |
| CN1137113C true CN1137113C (en) | 2004-02-04 |
Family
ID=4750320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021404895A Expired - Fee Related CN1137113C (en) | 2002-07-19 | 2002-07-19 | Catalyst for liquid phase hydrogenation of furaldehyde to prepare furfuralcohol and its use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1137113C (en) |
-
2002
- 2002-07-19 CN CNB021404895A patent/CN1137113C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1398670A (en) | 2003-02-26 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHONGKE OIL PROJECT CO., LTD. Free format text: FORMER OWNER: SHANXI INST. OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20081017 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20081017 Address after: 3, building 1, Tsinghua Science and Technology Park, No. 609, Zhongguancun East Road, Beijing, Haidian District Patentee after: Synefuels China Inc. Address before: 165 mailbox, Taiyuan City, Shanxi Province Patentee before: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences |
|
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: Synefuels China Inc. Address before: 100195, Haidian District Zhongguancun East Road, No. 1, building 3, Tsinghua Science and Technology Park, pioneering building, 609, Beijing Patentee before: Synefuels China Inc. |
|
| C56 | Change in the name or address of the patentee |
Owner name: SYNEFUELS CHINA CO., LTD. Free format text: FORMER NAME: SYNEFUELS CHINA INC. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: SYNFUELS CHINA Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee before: Synefuels China Inc. |
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| CP03 | Change of name, title or address |
Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone Park south two Street No. 1 Patentee after: SYNEFUELS CHINA Inc. Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee before: SYNFUELS CHINA |
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| CP03 | Change of name, title or address | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040204 Termination date: 20210719 |