CN1187303C - Solid alkali catalyst for synthesizing propanediol ether - Google Patents
Solid alkali catalyst for synthesizing propanediol ether Download PDFInfo
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- CN1187303C CN1187303C CNB021110204A CN02111020A CN1187303C CN 1187303 C CN1187303 C CN 1187303C CN B021110204 A CNB021110204 A CN B021110204A CN 02111020 A CN02111020 A CN 02111020A CN 1187303 C CN1187303 C CN 1187303C
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Abstract
The present invention relates to a solid alkali catalyst for synthesizing propanediol ether, which mainly overcomes the defects that the stability of a catalyst for synthesizing propanediol ether is poor, and reaction activity, stability and product isomer proportion can not simultaneously be in an ideal state in the prior art. The catalyst of the present invention comprises magnalium hydrotalcite, titanium oxide, alkali metal oxide and alkali earth metal oxide, wherein the weight of the titanium oxide is from 0.1 to 5%, the weight of at least one alkali metal oxide is from 0.1 to 4%, and the weight of at least one alkali earth metal oxide is from 10 to 30% measured by the weight of the magnalium hydrotalcite. The catalyst of the present invention not only has high reaction activity, high product yield, and high isomer proportion of primary propanediol ether to secondary propanediol ether, but also has long service life. The present invention can be used for industrial production.
Description
Technical field
The present invention relates to a kind of solid base catalyst of synthesis of propylene glycol.
Background technology
The propylene glycol product is a kind of good industrial solvent, be widely used in coating, printing, dyestuff, clean-out system, printing ink, photograph, rust-preventive agent, hydraulic efficiency oil, brake solution, frostproofer and the lubricant, in industries such as makeup, spices, also make solvent and use, therefore make the propylene glycol product in the short more than ten years, obtain fast development.
Propylene glycol mainly is to be raw material with propylene oxide and lower aliphatic alcohols, reacts to make in the presence of catalyzer.Because the asymmetry of propylene oxide molecule no matter adopt which kind of catalyzer all to have two kinds of isomer in reaction product, can be divided into propylene glycol uncle's ether and the secondary ether of propylene glycol according to the residing position of its hydroxyl.The glycol ethers product toxicological study of delivering according to European chemical industry toxicity center shows: propylene glycol uncle ether is littler several times than the toxicity of the secondary ether of propylene glycol, so catalyzer of synthesis of propylene glycol, not only to have the good activity of common catalyzer, stability, and require to contain in the product the little propylene glycol uncle ether of more toxicity.Many patents have been delivered in existing this technical field about solid basic catalyst, as alkaline water talcum, Ca/Mg exchange ion exchange resin, anionite-exchange resin etc., its activity is very low, or owing to its reason in essence can't be in industrial use.Therefore develop a kind of catalyzer of ideal synthesis of propylene glycol, make this catalyzer not only have high reaction activity and high, selectivity, higher isomer propylene glycol uncle ether/secondary ether ratio (hereinafter to be referred as isomer proportion), having long work-ing life simultaneously is the long-term targets of pursuing of people.
The method of classical industrial production propylene glycol, sodium alkoxide (potassium) commonly used, boron trifluoride are made catalyzer, two kinds of isomer proportions are about 90: 10 in the product that obtains, but problems such as this technological process exists that flow process complexity, yield are not high, catalyzer needs neutralizing treatment, quantity of three wastes is more, equipment corrosion is serious.
Chinese patent 92113418.5 discloses a kind ofly makes catalyzer with modified aluminas, produces propylene glycol by liquid-solid phase pressurization successive reaction, and the propylene oxide transformation efficiency is greater than 98.5%, and the monoether yield is greater than 92%.But the mol ratio of uncle's ether of the propylene glycol in the production propylene glycol and the secondary ether of propylene glycol is 3: 1, and the growing amount of the secondary ether of propylene glycol that toxicity is bigger is bigger, influences the quality and the class of product.
WO92/11224 has described a kind of two hydroxyl clay catalysts of negatively charged ion with laminate structure, and general formula is [M
2+ aN
3+ b(OH)
(2a+2b)] [X]
b, wherein M is a divalent-metal ion, is generally magnesium, iron, cobalt, nickel, zinc, and N is a trivalent metal ion, is generally aluminium, chromium, iron, and X is a negatively charged ion of equal value, and M also can partly or entirely be replaced by lithium, and general formula becomes [Li like this
+ aN
3+ b(OH)
(a+b)] [X]
2b, when being used for the reaction of synthesis of propylene glycol with the catalyzer of document introduction, isomer proportion can reach 96: 4, but the propylene oxide transformation efficiency is only up to 82%.
EP0421677A1, EP0421678A1 have described the solid base catalyst of the hydrotalcite of alkaline water talcum and process roasting as synthetic alcohol ether, and the general formula of hydrotalcite is [M
2+ aN
3+ b(OH)
(2a+3b)] [X]
b, wherein M is a divalent-metal ion, and N is a trivalent metal ion, and X is a negatively charged ion of equal value, then becomes the Mg-Al-O mixture through roasting, and patent is characterised in that containing magnesium among the M/N does not then contain aluminium, contains aluminium and does not then contain magnesium.That over-all properties is best is Zr/Cr, in pure alkane mol ratio 10, and 140 ℃ of temperature of reaction, under the pressure 15bar condition, in 73 hours reaction times, the propylene oxide transformation efficiency drops to 72% from 77%, and the transformation efficiency of catalyzer is lower, and its stability is poor.
Patent EP0189246 has described a kind of catalyzer that contains amino ion exchange resin as synthetic alcohol ether, is 10 in pure alkane mol ratio, 98 ℃ of temperature of reaction, air speed 2h
-1Under the condition, the propylene oxide transformation efficiency is 85%, and selectivity is 85%, isomer proportion is 96: 4 (a synthesizing propanediol ether), its selectivity, transformation efficiency are all relatively low, owing to contain the amino resistant to elevated temperatures ability of ion exchange resin, infer that its stability can be not fine yet.
Chinese patent CN1201714A discloses a kind of propylene glycol synthetic solid base catalyst that is used for, and this catalyzer contains the following composition of chemical formula to be formed: Mg
aAl
b(OH)
2a+3bThe span of a/b is 1.0～12 in the formula, and a is the magnesium atom number, and b is the aluminium atomicity, and the X-diffracting spectrum shows that this catalyzer is not a hydrotalcite structure.Use this catalyzer synthesis of propylene glycol, the propylene oxide transformation efficiency reaches 90%, and the product isomer proportion reaches 95: 5, but this patent does not relate to the work-ing life of catalyzer, and according to inventor's checking, this catalyst stability is unsatisfactory.
Summary of the invention
Technical problem to be solved by this invention is to overcome the poor catalyst stability that is used for synthesis of propylene glycol in the prior art, reactive behavior, stability and product isomer proportion can not reach the defective of perfect condition simultaneously, a kind of solid base catalyst of synthesis of propylene glycol is provided, this catalyzer not only has high reaction activity and high and product yield, higher isomer proportion has long work-ing life simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of solid base catalyst of synthesis of propylene glycol, form by magnesium aluminum-hydrotalcite, titanium oxide, at least a alkalimetal oxide and at least a alkaline earth metal oxide, wherein in respect to magnesium aluminum-hydrotalcite weight, the titanium oxide amount is 0.1～5%, at least a alkalimetal oxide amount is 0.1～4%, and at least a alkaline earth metal oxide amount is 10～30%.
In the technique scheme, the Mg/Al atomic ratio of described magnesium aluminum-hydrotalcite is 2～4, basic metal preferred lithium or caesium, alkaline-earth metal preferably magnesium, calcium or barium; Each component concentration is with respect to magnesium aluminum-hydrotalcite weight meter in the catalyzer, and titanium oxide amount preferable range is 0.5～3%, and at least a alkalimetal oxide amount preferable range is 0.5～3%, and at least a alkaline earth metal oxide amount preferable range is 15～25%.
Catalyzer of the present invention can prepare with blending method, is to be 2～4 magnesium aluminum-hydrotalcite with the Mg/Al atomic ratio, and even with the various metal oxide mechanically mixing of the required reacting weight that adds, extruded moulding obtains required catalyzer through super-dry, roasting.Concrete preparation process is as follows: at first prepare magnesium aluminum-hydrotalcite with coprecipitation method, prepare magniferous salt and aluminiferous mixed salt solution, making the Mg/Al atomic ratio is 2～4, with NaOH and Na
2CO
3Mixed solution or (NH
4)
2CO
3And NH
4The OH mixed solution is as precipitation agent, the precipitation agent that will react aequum under agitation condition joins in the mixed salt solution, ℃ carry out coprecipitation reaction in room temperature～35,3～6 hours reaction times, be warming up to 60～200 ℃, continued stirring reaction 10～18 hours, be cooled to room temperature, filtering reacting liquid, with distilled water repeatedly washing leaching cake sodium content to the filtrate obtain the Mg/Al atomic ratio and be 2～4 magnesium aluminum-hydrotalcite less than 0.01% (weight), add in the kneader, the mixture that adds metal oxide simultaneously, wherein with respect to magnesium aluminum-hydrotalcite weight meter, the titanium oxide amount is 0.1～5%, and at least a alkalimetal oxide amount is 0.1～4%, at least a alkaline earth metal oxide amount is 10～30%, be kneaded into the plasticity-material, extruded moulding is in 100～250 ℃ of dryings after 6～12 hours, in 400～600 ℃ of roastings 3～18 hours, obtain required catalyzer.
Catalyzer of the present invention is mainly used in synthetic good industrial solvent-propylene glycol product, as propylene glycol monomethyl ether, propylene-glycol ethyl ether and propylene glycol butyl ether etc.The catalyst activity evaluation is carried out in laboratory scale fixed-bed reactor, and reactor is 8 millimeters of internal diameters, long 900 millimeters stainless steel tubes, and the catalyzer loading capacity is 17 milliliters.Catalyst stability is reflected in the medium-sized fixed-bed reactor and carries out, also can in above-mentioned laboratory scale fixed-bed reactor, carry out, wherein medium-sized fixed-bed reactor are the vertical stainless steel reaction pipe of jacketed type, spent glycol-water is made thermal medium in the chuck, 25 millimeters of tube inner diameters, 2 meters of length, the catalyzer loading capacity is 1 liter, the catalyzer Stainless Steel Helices of packing into up and down.The catalyst reaction process is as follows: catalyzer is loaded in the reactor, with propylene oxide and lower aliphatic alcohols is reaction raw materials, make raw material enter reactor by volume pump, contact with catalyzer and carry out the synthesis of propylene glycol reaction, wherein lower aliphatic alcohols can be methyl alcohol, ethanol or butanols; Reaction process condition: 120～150 ℃ of temperature of reaction, reaction pressure: 1.0～2.0MPa, the pure and mild propylene oxide mol ratio of lower aliphatic is 4～8: 1, reaction bed liquid air speed 1.0～3.0 hours
-1, reaction solution is purified through separating, and obtains the propylene glycol product.With propylene oxide, the pure and mild propylene glycol content of lower aliphatic in gc analysis raw material, the reaction solution, calculate transformation efficiency, selectivity and isomer proportion.
Mg (Al) O composite oxides have caused people's attention as a kind of novel alkaline catalytic material, and people are constantly expanding its Application Areas.The present invention at first prepares magnesium aluminum-hydrotalcite with hydrotalcite structure precursor as catalyzer, and (XRD) characterizes this structure of matter with x-ray diffraction method, and the hydrotalcite of preparation synthetic magnesium aluminum-hydrotalcite and bibliographical information has similar characteristic spectrum, sees Fig. 1, Fig. 2.Magnesium aluminum-hydrotalcite forms Mg (Al) O composite oxides under the high-temperature roasting condition, characterize discovery Mg (Al) O by XRD and have the crystalline structure identical with MgO, Al is embedded in the MgO lattice, improved the catalytic performance of strong basicity MgO, be used for the synthesis of propylene glycol reaction, have catalytic activity preferably, the product isomer proportion is higher; The present invention simultaneously introduces the mixture of titanium oxide, at least a basic metal and alkaline earth metal oxide in magnesium aluminum-hydrotalcite, mechanically mixing, through high-temperature roasting, synergistic function takes place between each component in the catalyzer, improved the over-all properties of catalyzer, be in particular in: further improve the active and product isomer proportion of catalyst reaction, particularly increase substantially the stability and the work-ing life of catalyzer.Catalyst A of the present invention is used for the synthesizing propylene glycol monomethyl ether reaction, 130 ℃ of temperature of reaction, and reaction pressure 1.5MPa, pure alkane mol ratio 6: 1, reaction bed liquid air speed 2.0 hours
-1Processing condition under, successive reaction 1000 hours, the propylene oxide average conversion reaches 96.1%, the propylene glycol monomethyl ether selectivity reaches 94.9%, isomer proportion kept 95: 5, and catalyzer presents good reaction activity and higher isomer proportion, has obtained good result.
Fig. 1 is the X-diffracting spectrum of the magnesium aluminum-hydrotalcite for preparing of the present invention.
Fig. 2 is a magnesium aluminum-hydrotalcite X-diffracting spectrum.
The present invention is further illustrated below by embodiment.
Embodiment
[embodiment 1]
Take by weighing 256 gram Mg (NO
3)
26H
2O (chemical pure), 187.5 gram Al (NO
3)
39H
2O (chemical pure) is dissolved in 700 ml distilled waters, obtains salts solution, takes by weighing 140 gram NaOH, 100 gram Na
2CO
3Be dissolved in 1000 ml distilled waters, obtain precipitation agent, precipitation agent is added in the salts solution, carry out coprecipitation reaction at 30 ℃, 4 hours reaction times, be warming up to 100 ℃, continued stirring reaction 12 hours, be cooled to room temperature, filtering reacting liquid, with distilled water repeatedly washing leaching cake sodium content to the filtrate less than 0.01% (weight) filter cake is dropped in the kneader, simultaneously with 5 gram TiO
2, 85.5 the gram MgO and 4 the gram Li
2O joins in the kneading machine, is kneaded into the plasticity-material, and extruded moulding in 120 ℃ of dryings 8 hours, in 500 ℃ of roastings 10 hours, makes catalyst A.The catalyzer composition sees Table 1.
[embodiment 2]
Prepare catalyzer according to the condition identical with embodiment 1, just change catalyzer raw material Mg/Al mole and when introduce the kind and the weight percentage of titanium oxide, basic metal and alkaline earth metal oxide, make catalyst B, C, D, E respectively, the catalyzer composition sees Table 1.
Table-1 catalyzer is formed
| The catalyzer numbering | Catalyzer is formed | |
| Magnesium aluminum-hydrotalcite (Mg/Al mol ratio) | With respect to magnesium aluminum-hydrotalcite | |
| A | ||
| 2 | TiO 2：1.5％，MgO：25％，Li 2O：1.2％ | |
| | 2 | TiO 2：0.5％，CaO：25％，Li 2O：3％ |
| | 2 | TiO 2：2.5％，BaO：25％，Li 2O：2％ |
| D | 4 | TiO 2：3％，MgO：15％，Cs 2O：2％ |
| E | 3 | TiO 2：2％，MgO：20％，Cs 2O：2％，Li 2O：2％ |
[embodiment 3]
Catalyst A, B, C, D, E that embodiment 1～2 is made are loaded into respectively in the fixed-bed reactor, and reactor is 8 millimeters of internal diameters, long 900 millimeters stainless steel tubes, and the catalyzer loading capacity is 17 milliliters, and catalyzer is adorned Stainless Steel Helices up and down.Make raw material propylene oxide and methyl alcohol enter reactor by volume pump, contact with catalyzer and to be prepared the propylene glycol monomethyl ether reaction, the catalyst reaction processing condition are: 130 ℃ of temperature of reaction, reaction pressure 1.5MPa, methyl alcohol and propylene oxide mol ratio 6: 1, reaction bed liquid air speed 2.0 hours
-1Catalyst reaction the results are shown in Table 2.
Table-2 preparation propylene glycol monomethyl ether reaction results
| The catalyzer numbering | Propylene oxide transformation efficiency % | Propylene glycol monomethyl ether selectivity % | Isomer proportion |
| A | 97.4 | 95.5 | 95∶5 |
| B | 92.6 | 93.5 | 95∶5 |
| C | 93.5 | 92.8 | 93∶7 |
| D | 97.2 | 95.7 | 95∶5 |
| E | 97.6 | 95.4 | 96∶4 |
[embodiment 4]
The catalyst A that embodiment 1 is made is loaded in the reactor, according to the reaction process condition identical with embodiment 3, and difference: replace methyl alcohol with ethanol, the preparation propylene-glycol ethyl ether, reaction result is listed in table 3.
Table-3 preparation propylene-glycol ethyl ether catalyst reaction results
| The catalyzer numbering | Propylene oxide transformation efficiency % | Propylene-glycol ethyl ether selectivity % | Isomer proportion |
| A | 97.0 | 92.3 | 95∶5 |
[embodiment 5]
The catalyst A that embodiment 1 is made is loaded in the reactor, according to the reaction process condition identical with embodiment 3, and difference: replace methyl alcohol with butanols, preparation propylene glycol butyl ether, reaction result is listed in table 4.
Table-4 preparation propylene glycol butyl ether catalyst reaction results
| The catalyzer numbering | Propylene oxide transformation efficiency % | Propylene glycol butyl ether selectivity % | Isomer proportion |
| B | 95.8 | 80.8 | 94∶6 |
[embodiment 6]
The catalyst stability reaction.
The catalyst A that embodiment 1～2 is made, B, C, D, E is loaded into respectively in the medium-sized fixed-bed reactor, reactor is the vertical stainless steel reaction pipe of jacketed type, spent glycol-water is made thermal medium in the chuck, 25 millimeters of tube inner diameters, long 2 meters, the catalyzer loading capacity is 1 liter, the catalyzer Stainless Steel Helices of packing into up and down, make raw material propylene oxide and methyl alcohol enter reactor by volume pump, contact with catalyzer and to be prepared the propylene glycol monomethyl ether reaction, reaction process condition: 130 ℃ of temperature of reaction, reaction pressure 1.5MPa, methyl alcohol and propylene oxide mol ratio are 6: 1, reaction bed liquid air speed 2.0 hours
-1Reaction solution enters methanol distillation column, recovered overhead methyl alcohol, and the tower still obtains thick propylene glycol monomethyl ether, the methyl alcohol that reclaims mixes the back to be continued to use with fresh feed, the thick propylene glycol monomethyl ether of tower still enters the product rectifying tower, and the rectifying tower cat head obtains the propylene glycol monomethyl ether product, and tower bottoms uses after treatment.
Under above-mentioned reaction process condition, catalyst A successive reaction 1000 hours still has good reaction activity and ideal isomer proportion, the active no downtrending of catalyst reaction; Catalyst B, C, D, E successive reaction 800 hours still have good reaction activity and ideal isomer proportion, the active no downtrending of catalyst reaction, and the catalyst stability reaction result sees Table 5.
[comparative example 1]
Prepare the solid base catalyst of synthesis of propylene glycol according to CN1201714A embodiment 1 disclosed method, with aluminium glue (α-Al
2O
3H
2O) with magnesium oxide in proportion (25%: 75%) in kneader, mix, add suitable quantity of water, kneading is made can be for the plasticity-fluid of extrusion, extrusion, aged at room temperature, 120 ℃ of oven dry, 600 ℃ of roastings 3 hours, in 180 ℃ of hot water aging 3 hours, 280 ℃ of dryings, catalyst sample is made in pelletizing, and a/b is 2.
The catalyst sample that makes carries out the catalyst activity evaluation, evaluation result according to the reaction process condition of embodiment 3: propylene oxide transformation efficiency 97.5%, propylene glycol selectivity 95.0%, isomer proportion 95: 5; Under these processing condition, reaction was carried out 200 hours continuously, carried out 48 hours, 100 hours, 150 hours, 200 hours when reaction, and the propylene oxide transformation efficiency is respectively 95.5%, 97.5%, 92.6%, 90.2%, and catalyst activity is downtrending gradually.
Table-5 catalyst stability reaction results
| The catalyzer numbering | The accumulative total reaction times (hour) | Propylene oxide transformation efficiency % | Propylene glycol monomethyl ether selectivity % | Isomer proportion |
| A | 48 | 89.8 | 93.0 | 94∶6 |
| 100 | 95.6 | 94.5 | 95∶5 | |
| 200 | 97.5 | 95.4 | 95∶5 | |
| 400 | 97.2 | 95.8 | 95∶5 | |
| 600 | 96.8 | 95.2 | 95∶5 | |
| 700 | 97.4 | 95.6 | 95∶5 | |
| 800 | 97.2 | 94.8 | 95∶5 | |
| 1000 | 97.5 | 95.0 | 95∶5 | |
| B | 200 | 92.5 | 93.2 | 95∶5 |
| 800 | 91.2 | 92.0 | 95∶5 | |
| C | 200 | 92.3 | 91.8 | 95∶5 |
| 800 | 91.8 | 92.6 | 95∶5 | |
| D | 200 | 96.6 | 94.7 | 95∶5 |
| 800 | 97.8 | 95.4 | 95∶5 | |
| E | 200 | 95.6 | 94.7 | 93∶7 |
| 800 | 97.2 | 95.0 | 94∶6 |
Claims (7)
1, a kind of solid base catalyst of synthesis of propylene glycol, form by magnesium aluminum-hydrotalcite, titanium oxide, at least a alkalimetal oxide and at least a alkaline earth metal oxide, wherein in respect to magnesium aluminum-hydrotalcite weight, the titanium oxide amount is 0.1～5%, at least a alkalimetal oxide amount is 0.1～4%, and at least a alkaline earth metal oxide amount is 10～30%.
2, according to the solid base catalyst of the described synthesis of propylene glycol of claim 1, the Mg/Al atomic ratio that it is characterized in that magnesium aluminum-hydrotalcite is 2～4.
3,, it is characterized in that basic metal is selected from lithium or caesium according to the solid base catalyst of the described synthesis of propylene glycol of claim 1.
4,, it is characterized in that alkaline-earth metal is selected from magnesium, calcium or barium according to the solid base catalyst of the described synthesis of propylene glycol of claim 1.
5,, it is characterized in that with respect to magnesium aluminum-hydrotalcite weight meter, the titanium oxide amount is 0.5～3% according to the solid base catalyst of the described synthesis of propylene glycol of claim 1.
6,, it is characterized in that with respect to magnesium aluminum-hydrotalcite weight meter, at least a alkalimetal oxide amount is 0.5～3% according to the solid base catalyst of the described synthesis of propylene glycol of claim 1.
7,, it is characterized in that with respect to magnesium aluminum-hydrotalcite weight meter, at least a alkaline earth metal oxide amount is 15～25% according to the solid base catalyst of the described synthesis of propylene glycol of claim 1.
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|---|---|---|---|
| CNB021110204A CN1187303C (en) | 2002-03-13 | 2002-03-13 | Solid alkali catalyst for synthesizing propanediol ether |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021110204A CN1187303C (en) | 2002-03-13 | 2002-03-13 | Solid alkali catalyst for synthesizing propanediol ether |
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| Publication Number | Publication Date |
|---|---|
| CN1443745A CN1443745A (en) | 2003-09-24 |
| CN1187303C true CN1187303C (en) | 2005-02-02 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715575A (en) * | 2018-06-29 | 2018-10-30 | 江苏华伦化工有限公司 | Solid super base is the method that catalyst fixed bed reaction prepares dihydroxypropane single-ether |
| CN109603795B (en) * | 2018-12-13 | 2022-01-07 | 万华化学集团股份有限公司 | Solid base catalyst and production process for preparing 4- (2-furyl) -3-butylene-2-ketone |
| 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 |
-
2002
- 2002-03-13 CN CNB021110204A patent/CN1187303C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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