CN1762578A - Supported solid alkali catalyst for synthesis of propylene glycol - Google Patents
Supported solid alkali catalyst for synthesis of propylene glycol Download PDFInfo
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- CN1762578A CN1762578A CNA2005101001290A CN200510100129A CN1762578A CN 1762578 A CN1762578 A CN 1762578A CN A2005101001290 A CNA2005101001290 A CN A2005101001290A CN 200510100129 A CN200510100129 A CN 200510100129A CN 1762578 A CN1762578 A CN 1762578A
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- propylene glycol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The carrier-type solid base catalyst to synthesize propylene glycol comprises: carrier selected at least one from potassium fluoride, potassium nitrate and potassium carbonate; and metal oxide. This invention is simple, can filter the catalyst for recycle, and has high activity and selectivity and isomerization proportion.
Description
Technical field
The present invention relates to a kind of load type solid body base catalyst from expoxy propane and lower aliphatic alcohols synthesis of propylene glycol.
Background technology
Propylene glycol is a kind of industrial solvent of function admirable, is widely used in industries such as coating, printing ink, dyestuff, printing, cleaning agent, antirust agent, anticoagulant.Propylene glycol is similar to the glycol ether performance, but its toxicity is far below glycol ether, and therefore, in the nearly more than ten years, the propylene glycol production development is swift and violent.
Propylene glycol is synthetic can be realized under catalyst action by expoxy propane and lower aliphatic alcohols.Because there is open loop orientation problem in expoxy propane, so have two kinds of isomers 2-hydroxypropyl methyl ethers (uncle's ether) and 1-hydroxypropyl methyl ether (secondary ether) in the product, result of study shows that the toxicity of uncle's ether is lower.The catalyst of synthesis of propylene glycol generally is a bronsted lowry acids and bases bronsted lowry, and from reaction mechanism, base catalyst more helps uncle's ether and generates, and experimental result has also proved this deduction.Traditional acid base catalysator mainly contains BF
3, NaOH (KOH), sodium alkoxide (potassium alcoholate) and tertiary amine, they are homogeneous catalysts, are characterized in the catalytic efficiency height, but exist equipment corrosion serious, problems such as product postprocessing complex process and liquid waste processing.By comparison, solid catalyst enjoys favor owing to overcoming above-mentioned shortcoming, wherein solid acid catalyst has cation exchange clay, cationic exchanger resin, modified zeolite molecular sieve etc., their activity and good stability, but uncle's ether/secondary ether ratio is lower in the product.In recent years, more active with the research of catalyzed by solid base synthesizing propanediol.The patent No. is that 97106452.0 Chinese patent discloses a kind of " being used for the synthetic solid base catalyst of propylene glycol ", and the chemical composition of this catalyst is: Mg
aAl
b(OH)
2a+3b, the a/b span is 1.0～12 in the formula, and a is the magnesium atom number, and b is the aluminium atomicity, uses this catalyst synthesis of propylene glycol, and the conversion ratio of expoxy propane reaches 90%, and uncle's ether and secondary ether ratio reach 95: 5; The patent No. provides a kind of " solid base catalyst of preparation propylene glycol " for 02111019.0 Chinese patent, it comprises magnalium hydrotalcite, iron oxide, cupric oxide, alkaline earth oxide and be selected from Co, Ni, Zn, Al, at least a oxide among Cr or the Ti, wherein in respect to magnalium hydrotalcite weight, the iron oxide amount is 0.1～5%, the cupric oxide amount is 0.05～5%, the alkaline earth oxide amount is 10～40%, Co, Ni, Zn, Al, at least a oxide amount is 0.1～15% among Cr or the Ti, this catalyst not only has high reaction activity and high and product yield, higher isomers propane diols uncle ether/secondary ether ratio has long service life simultaneously; The patent No. provides a kind of " solid base catalyst of synthesis of propylene glycol " for 02111020.4 Chinese patent, comprise magnalium hydrotalcite, titanium oxide, alkali metal and alkaline earth oxide, with respect to magnalium hydrotalcite weight meter, the titanium oxide amount is 0.1～5%, at least a alkali metal oxide amount is 0.1～4%, at least a alkaline earth oxide amount is 10～30%, catalyst of the present invention not only has high reaction activity and high and product yield, higher isomers propane diols uncle ether/secondary ether ratio has long service life simultaneously.Application number is that 200310109694.4 Chinese patent discloses " a kind of solid catalyst of synthesis of propylene glycol and preparation method and application ", with zinc nitrate, aqueous zinc acetate solution Immesion active carbon, after the drying in nitrogen roasting become the ZnO/ activated-carbon catalyst, this method for preparing catalyst is simple, easy to operate, be difficult for being polluted by Carbon Dioxide in Air, water, have expoxy propane conversion ratio height simultaneously, uncle's ether: secondary ether isomery ratio height, characteristics such as propylene glycol selectivity height.
Summary of the invention
The purpose of this invention is to provide the high activity that is used for synthesis of propylene glycol, high uncle's ether/secondary ether ratio, easy, the inexpensive load type solid body base catalyst of preparation.
Purpose of the present invention can realize by following technical measures: a kind of load type solid body base catalyst of synthesis of propylene glycol, make by the raw material of following weight portion:
By 5～25 parts of loaded articles, 75～95 parts of metal oxides;
Wherein be selected from least a in potassium fluoride, potassium nitrate, the potash by loaded article.
Described metal oxide is selected from Al
2O
3, BaO, SrO, MgO, ZnO, ZrO
2, SnO
2, TiO
2In at least a.
Metal oxide also can be metal mixing oxide, is selected from MgO-ZnO, MgO-ZrO
2, MgO-TiO
2, CaO-ZnO, ZnO-ZrO
2, CaO-SrO, TiO
2-ZrO
2, SnO
2-ZrO
2, at least a among Mg-Al-O, Mg-Zn-Al-O, Mg-Ni-Al-O, the Mg-Co-Al-O.
Wherein, metal mixing oxide MgO-ZnO, MgO-ZrO
2, MgO-TiO
2, CaO-ZnO, ZnO-ZrO
2, CaO-SrO, TiO
2-ZrO
2, SnO
2-ZrO
2In the part by weight of every kind of metal oxide be 10: 4～23.
In addition, magnesium/al atomic ratio is 2～5 among metal mixing oxide Mg-Al-O, Mg-Zn-Al-O, Mg-Ni-Al-O, the Mg-Co-Al-O.
Method for preparing catalyst of the present invention is as follows:
(1) with metal oxide 300～1000 ℃ of following roasts 2～6 hours; MgO-ZnO, MgO-ZrO
2, MgO-TiO
2, CaO-ZnO, ZnO-ZrO
2, CaO-SrO, TiO
2-ZrO
2, SnO
2-ZrO
2Then precipitate with ammoniacal liquor with its corresponding nitrate mixture, be deposited in 300～1000 ℃ of following roastings 3～6 hours and corresponding mixed oxide; If Mg-Al-O, Mg-Zn-Al-O, Mg-Ni-Al-O, Mg-Co-Al-O then prepare its presoma hydrotalcite or houghite according to coprecipitation, obtained its corresponding mixed oxide in 3～6 hours 300～1000 ℃ of following roastings.
(2) preparation process of hydrotalcite or houghite is as follows: be the mixed solution of 2～5 preparation magnesium nitrates and aluminum nitrate (houghite then adds zinc nitrate or nickel nitrate or cobalt nitrate in proportion) by the Mg/Al atomic ratio, with NaOH and sodium carbonate mixed liquor as precipitating reagent, adopt and the drip add mode with nitrate mixed liquor and alkali lye stirring reaction 2～6 hours at room temperature, be warming up to 50～100 ℃ then and left standstill crystallization 6～36 hours, suction filtration, washing, pH to filtrate is 7～8, filter cake gets hydrotalcite or houghite 110～130 ℃ of dryings.
(3) in (1) gained metal oxide and potassium fluoride, potassium nitrate or the potash one or more are mixed in proportion, add the proper amount of deionized water ground and mixed again, 120 ℃ of dryings 12～36 hours, then 300～1000 ℃ of following roasts 3～8 hours, catalyst.
Catalyst of the present invention is mainly used in the catalysis expoxy propane and the lower aliphatic alcohols reaction generates propylene glycol, is 2～6: 1 with fatty alcohol and expoxy propane with mol ratio, together add in the reactor with 0.5～6% catalyst of expoxy propane quality, charging into nitrogen to initial pressure is 0.1～0.5Mpa, stir, reacted 1～5 hour down at 90～180 ℃, sedimentation is filtered, the product gas chromatographic analysis.
The present invention compared with prior art has following characteristics:
Raw material is easy to get, and the preparation method is simple and easy, and cost is low; Be used for synthesis of propylene glycol, expoxy propane conversion ratio height, the reaction condition gentleness generates propylene glycol selectivity height, simultaneously the isomery ratio height of uncle's ether/secondary ether in the product; Do not cause environmental pollution.
The specific embodiment
Embodiment 1:
Magnesia, calcium oxide, zinc oxide, zirconia 400 ℃ of following roastings 3 hours, are pressed KNO then
3Be 15%, MgO, CaO, ZnO, ZrO
2Be that 85% composition (percentage by weight) is impregnated into KNO with magnesia, calcium oxide, zinc oxide, zirconia
3In the solution, vacuumize, left standstill 12 hours, through 120 ℃ of dryings, 600 ℃ of following calcination activations 5 hours, catalyst KNO
3/ MgO, KNO
3/ CaO, KNO
3/ ZnO, KNO
3/ ZrO
2, be designated as catalyst A, B, C, D respectively.
Embodiment 2:
Prepare catalyst according to the condition identical, just will be changed into potassium fluoride by loaded article with embodiment 1, catalyst KF/MgO, KF/CaO, KF/ZnO, KF/ZrO
2, be designated as catalyst E, F, G, H respectively.
Embodiment 3:
Magnesia, zinc oxide respectively account for 50% ratio magnesium nitrate, zinc nitrate are made into mixing salt solution when generating MgO-ZnO, ammoniacal liquor with 20% reacts as precipitating reagent, filters, washs, and filter cake is through 120 ℃ of dryings, in 400 ℃ of following roastings 3 hours, get MgO-ZnO again.
All the other prepare catalyst KNO according to embodiment 1 identical condition
3/ MgO-ZnO is designated as catalyst I.
Embodiment 4:
Prepare catalyst KNO according to embodiment 3 identical conditions
3/ MgO-ZrO
2, KNO
3/ ZnO-ZrO
2, KNO
3/ TiO
2-ZrO
2, and be designated as catalyst J, K, L respectively.
Embodiment 5:
Take by weighing 45 gram Al (NO
3)
39H
2O and 92 gram Mg (NO
3)
26H
2O is dissolved in 400 milliliters of redistilled waters, gets salting liquid; Take by weighing 25.4 gram Na
2CO
3Be dissolved in 400 milliliters of redistilled waters with 38.4 gram NaOH, get precipitating reagent.Under the room temperature strong agitation with the Al (NO for preparing
3)
3, Mg (NO
3)
2Mixed liquor and Na
2CO
3, the NaOH mixed liquor with and stream mode splash into, the rate of addition of two kinds of mixed liquors of control, keeping the pH of solution is 9～11, solution added in 2 hours, continue to stir under the room temperature 1 hour, again in 65 ℃ of following crystallization 24 hours, to precipitate the making beating washing then for several times, pH to filtrate is 7～8, with filter cake 70 ℃ down dry, obtain the Mg/Al atomic ratio and be 3 magnalium hydrotalcite.The above-mentioned hydrotalcite that obtains in 500 ℃ of following roastings 3 hours, is got the Mg-Al-O composite oxides.
By Mg-Al-O is 85%, KNO
3Be that 15% composition (percentage by weight) is impregnated into KNO with the above-mentioned Mg-Al-O composite oxides that make
3The aqueous solution in, all the other are with embodiment 1, catalyst KNO
3/ Mg-Al-O is designated as catalyst M.
With the same manner with K
2CO
3Be carried on the Mg-Al-O composite oxides, get catalyst K
2CO
3/ Mg-Al-O is designated as catalyst n.
Embodiment 6:
Prepare catalyst according to the condition identical with embodiment 5, just zinc is introduced in the oxide, the Mg/Zn/Al atomic ratio is 2: 1: 1 in the oxide, makes catalyst KNO
3/ Mg-Zn-Al-O and K
2CO
3/ Mg-Zn-Al-O is designated as catalyst O and P respectively.
Embodiment 7:
In 250 milliliters of autoclaves, the catalyst that adds methyl alcohol, expoxy propane and prepare by embodiment 1～6, the mol ratio of methyl alcohol and expoxy propane is 4: 1, catalyst amount is 3% of an expoxy propane quality.Sealed reactor, charging into nitrogen to system pressure is 0.2MPa, is warming up to 120 ℃ of reactions 2 hours under stirring, sedimentation is filtered, the product gas chromatographic analysis.The results are shown in Table 1.
Table 1 embodiment 7 analysis results:
| Catalyst | Expoxy propane conversion ratio (%) | Uncle's ether selectivity (%) | Uncle's ether: secondary ether isomery ratio |
| A | 97.5 | 98.7 | 96.4∶3.6 |
| B | 95.4 | 98.8 | 96.3∶3.7 |
| C | 96.3 | 98.4 | 96.5∶3.5 |
| D | 97.4 | 98.3 | 95.8∶4.2 |
| E | 98.4 | 98.7 | 97.2∶2.7 |
| F | 94.5 | 98.5 | 96.7∶3.3 |
| G | 95.5 | 98.6 | 95.6∶4.4 |
| H | 98.7 | 98.5 | 95.5∶4.5 |
| I | 95.5 | 98.3 | 95.4∶4.6 |
| J | 97.3 | 98.4 | 96.5∶3.5 |
| K | 96.8 | 98.6 | 95.5∶4.5 |
| L | 96.2 | 98.1 | 95.0∶5.0 |
| M | 95.7 | 98.3 | 95.3∶4.7 |
| N | 93.6 | 98.2 | 94.5∶5.5 |
| O | 95.3 | 98.7 | 95.6∶4.4 |
| P | 94.7 | 98.1 | 94.1∶5.9 |
Claims (5)
1, a kind of load type solid body base catalyst of synthesis of propylene glycol is characterized in that being made by the raw material of following weight portion:
By 5～25 parts of loaded articles, 75～95 parts of metal oxides;
Wherein be selected from least a in potassium fluoride, potassium nitrate, the potash by loaded article.
2, load type solid body base catalyst according to claim 1 is characterized in that metal oxide is selected from Al
2O
3, BaO, SrO, MgO, ZnO, ZrO
2, SnO
2, TiO
2In at least a.
3, load type solid body base catalyst according to claim 1 is characterized in that metal oxide is a metal mixing oxide, is selected from MgO-ZnO, MgO-ZrO
2, MgO-TiO
2, CaO-ZnO, ZnO-ZrO
2, CaO-SrO, TiO
2-ZrO
2, SnO
2-ZrO
2, at least a among Mg-Al-O, Mg-Zn-Al-O, Mg-Ni-Al-O, the Mg-Co-Al-O.
4, load type solid body base catalyst according to claim 3 is characterized in that metal mixing oxide MgO-ZnO, MgO-ZrO
2, MgO-TiO
2, CaO-ZnO, ZnO-ZrO
2, CaO-SrO, TiO
2-ZrO
2, SnO
2-ZrO
2In the part by weight of two kinds of metal oxides be 10: 4～23.
5, load type solid body base catalyst according to claim 3 is characterized in that magnesium/al atomic ratio is 2～5 among metal mixing oxide Mg-Al-O, Mg-Zn-Al-O, Mg-Ni-Al-O, the Mg-Co-Al-O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005101001290A CN1762578A (en) | 2005-09-28 | 2005-09-28 | Supported solid alkali catalyst for synthesis of propylene glycol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005101001290A CN1762578A (en) | 2005-09-28 | 2005-09-28 | Supported solid alkali catalyst for synthesis of propylene glycol |
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| Publication Number | Publication Date |
|---|---|
| CN1762578A true CN1762578A (en) | 2006-04-26 |
Family
ID=36747027
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|---|---|---|---|
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|---|---|---|---|---|
| CN100386145C (en) * | 2006-06-07 | 2008-05-07 | 山东轻工业学院 | Solid catalyst for synthesizing propylene glycol ether and its preparing process |
| CN101921180A (en) * | 2010-08-12 | 2010-12-22 | 江苏怡达化工有限公司 | Method for synthesizing butyl cellosolve |
| CN102942479A (en) * | 2012-11-27 | 2013-02-27 | 福州大学 | Method for preparing propylene glycol methyl ether acetate through two-step coupling reaction |
| CN105503544A (en) * | 2015-12-27 | 2016-04-20 | 湘潭大学 | Method for catalytically synthesizing propylene glycol methyl ether by adopting solid base catalyst KF/ZrO2-SiO2 |
| CN106861726A (en) * | 2017-01-23 | 2017-06-20 | 山东玉皇化工有限公司 | A kind of preparation method and application of the solid base catalyst of synthesizing propylene glycol monomethyl ether |
| CN107032963A (en) * | 2017-05-18 | 2017-08-11 | 哈尔滨师范大学 | The regulation and control synthetic method of propylene glycol monomethyl ether |
| CN108620055A (en) * | 2018-06-29 | 2018-10-09 | 江苏华伦化工有限公司 | It is used to prepare solid super basic catalyst and its application of dihydroxypropane single-ether |
| CN109796335A (en) * | 2019-01-08 | 2019-05-24 | 江门谦信化工发展有限公司 | A kind of method of high efficiency joint production of propylene glycol methyl ether and propylene glycol methyl ether acetate |
| CN109867589A (en) * | 2017-12-01 | 2019-06-11 | 万华化学集团股份有限公司 | A kind of preparation method of propylene-glycol monoalky lether |
| WO2020051887A1 (en) * | 2018-09-14 | 2020-03-19 | 江苏华伦化工有限公司 | Method for preparing propylene glycol monoethyl ether by means of fixed bed reaction using solid superbase as catalyst |
| CN110947423A (en) * | 2019-12-13 | 2020-04-03 | 中国科学院过程工程研究所 | Catalyst for synthesizing propylene glycol ether and preparation method thereof |
| CN111250099A (en) * | 2020-03-31 | 2020-06-09 | 中国科学院过程工程研究所 | Preparation method and application of composite metal oxide catalyst |
| CN115999528A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof |
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2005
- 2005-09-28 CN CNA2005101001290A patent/CN1762578A/en active Pending
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| CN100386145C (en) * | 2006-06-07 | 2008-05-07 | 山东轻工业学院 | Solid catalyst for synthesizing propylene glycol ether and its preparing process |
| CN101921180A (en) * | 2010-08-12 | 2010-12-22 | 江苏怡达化工有限公司 | Method for synthesizing butyl cellosolve |
| CN101921180B (en) * | 2010-08-12 | 2013-08-28 | 江苏怡达化学股份有限公司 | Method for synthesizing butyl cellosolve |
| CN102942479A (en) * | 2012-11-27 | 2013-02-27 | 福州大学 | Method for preparing propylene glycol methyl ether acetate through two-step coupling reaction |
| CN105503544A (en) * | 2015-12-27 | 2016-04-20 | 湘潭大学 | Method for catalytically synthesizing propylene glycol methyl ether by adopting solid base catalyst KF/ZrO2-SiO2 |
| CN105503544B (en) * | 2015-12-27 | 2017-12-01 | 湘潭大学 | A kind of method that solid base catalyst KF/ZrO2 SiO2 catalyze and synthesize propylene glycol monomethyl ether |
| CN106861726B (en) * | 2017-01-23 | 2019-07-16 | 山东玉皇化工有限公司 | A kind of preparation method and application of the solid base catalyst of synthesizing propylene glycol monomethyl ether |
| CN106861726A (en) * | 2017-01-23 | 2017-06-20 | 山东玉皇化工有限公司 | A kind of preparation method and application of the solid base catalyst of synthesizing propylene glycol monomethyl ether |
| CN107032963A (en) * | 2017-05-18 | 2017-08-11 | 哈尔滨师范大学 | The regulation and control synthetic method of propylene glycol monomethyl ether |
| CN109867589B (en) * | 2017-12-01 | 2022-04-19 | 万华化学集团股份有限公司 | Preparation method of propylene glycol monoalkyl ether |
| CN109867589A (en) * | 2017-12-01 | 2019-06-11 | 万华化学集团股份有限公司 | A kind of preparation method of propylene-glycol monoalky lether |
| CN108620055A (en) * | 2018-06-29 | 2018-10-09 | 江苏华伦化工有限公司 | It is used to prepare solid super basic catalyst and its application of dihydroxypropane single-ether |
| WO2020051887A1 (en) * | 2018-09-14 | 2020-03-19 | 江苏华伦化工有限公司 | Method for preparing propylene glycol monoethyl ether by means of fixed bed reaction using solid superbase as catalyst |
| CN109796335A (en) * | 2019-01-08 | 2019-05-24 | 江门谦信化工发展有限公司 | A kind of method of high efficiency joint production of propylene glycol methyl ether and propylene glycol methyl ether acetate |
| CN110947423A (en) * | 2019-12-13 | 2020-04-03 | 中国科学院过程工程研究所 | Catalyst for synthesizing propylene glycol ether and preparation method thereof |
| CN110947423B (en) * | 2019-12-13 | 2021-05-07 | 中国科学院过程工程研究所 | Catalyst for synthesizing propylene glycol ether and preparation method thereof |
| CN111250099A (en) * | 2020-03-31 | 2020-06-09 | 中国科学院过程工程研究所 | Preparation method and application of composite metal oxide catalyst |
| CN111250099B (en) * | 2020-03-31 | 2021-05-07 | 中国科学院过程工程研究所 | Preparation method and application of composite metal oxide catalyst |
| CN115999528A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof |
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