CN1443740A - Method for preparing tetraethylene-glycol - Google Patents
Method for preparing tetraethylene-glycol Download PDFInfo
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- CN1443740A CN1443740A CN 02111017 CN02111017A CN1443740A CN 1443740 A CN1443740 A CN 1443740A CN 02111017 CN02111017 CN 02111017 CN 02111017 A CN02111017 A CN 02111017A CN 1443740 A CN1443740 A CN 1443740A
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- tetraglycol
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Abstract
The present invention relates to a method for preparing tetraglycol. It utilizes the mixture formed from acidic clay and diatomite to pretreat the material obtained after synthetic reaction, the treatment temp. is 30-90 deg.C, treatment time is 0.1-4 hr., and the does of the acidic clay and diatomite is 0.5-5 of total weight of reaction material, in which the weight ratio of the acidic clay and diamite is 8-15:1 and the treated material is undergone the processes of separation and purification so as to obtain the invented product tetraglycol and its by-product triglycol.
Description
Technical field
The present invention relates to prepare the method for Tetraglycol 99.
Background technology
Tetraglycol 99 is a kind of of great value Chemicals, the main extraction solvent that extracts arene (benzene, toluene and dimethylbenzene) in oil and the cracking tar light oil that generates as the refinery catalytic reforming, the raw material that also can be used as synthetic Tetraglycol 99 alkyl ether and vibrin, do in the arene extracting process of extraction solvent in glycols, Tetraglycol 99 belongs to a kind of high-efficiency and energy-saving type aromatic hydrocarbons extractant.
The preparation method of Tetraglycol 99 generally is to be reaction raw materials with oxyethane and glycol ether, makes catalyzer with alkaline matters such as alkali metal hydroxides, and under certain reaction temperature and pressure condition, through addition reaction step by step, obtaining structural formula is HO (C
2H
5O)
n(n=2,3,4 ...), have the mixtures such as triglycol, Tetraglycol 99 and five glycol of various addition degree, this method optimizing and revising by processing condition such as proportioning raw materials, can obtain product based on triglycol and Tetraglycol 99, purify through separating then, obtain the costly Tetraglycol 99 product of industrial utilization.
In the prior art for preparation method, because the material after the building-up reactions has strong basicity, the normal use carried out neutralizing treatment such as acid solutions such as acetic acid, sulfuric acid or phosphoric acid, the salt compounds of handling the back generation remains in the reaction mass, a small amount of basic catalyst also remains in the reaction mass, and these materials enter separation system together with reaction mass.Because the glycols boiling point substance is higher, 287.4 ℃ of triglycol boiling points (101.34 kPas), 327.3 ℃ of Tetraglycol 99 boiling points (101.34 kPas), in follow-up multitower rectifying separation process, the service temperature of tower still need be at (vacuum tightness be about 10 mmhg) more than 200 ℃, these salt compounds in the rectifying separation system are under hot conditions, impel reaction product that catalytic decomposition takes place easily, multiple side reaction such as condensation or polymerization, cause that product yield descends, wherein decomposing the little impurity of molecular weight that generates enters in the overhead product fraction, reduce product purity, the coloring impurity that the condensation oxidizing reaction produces enters in the product, further deepen the outward appearance degree of staining of product, had a strong impact on quality product, directly had influence on the industrial application of Tetraglycol 99.
Document US 3847754 discloses a kind of method that reclaims glycol ether and triglycol in the glycol of mixing, regulate pH value to 6～8.5 of tower still material with phosphoric acid or sulfuric acid, the recyclable more triglycol of this method, the colourity of product also improves, but the salt compounds that produces after the neutralizing treatment is stayed in the reaction system, in the high temperature rectifying, is difficult to avoid taking place above-mentioned side reaction, reduce product yield, influence quality product.
In the Japanese kokai publication sho J50-82005 document, reported with the glycol ether to be raw material, with sodium hydroxide or potassium hydroxide is catalyzer, prepare the method for triglycol, coproduction Tetraglycol 99 with the reacting ethylene oxide of manipulated variable, but problem such as this patent exists that the yield of Tetraglycol 99 is lower, triglycol, Tetraglycol 99 reaction yield are low.
Chinese patent CN1217315A relates to a kind of glycol decolouring process, and glycol is in distillation tower, with C
12～C
20Alkane make solvent, the adding mode of solvent is before glycol steam arrives the overhead condenser condensation, contacts with glycol steam in the mode of atomizing shape, this technology has decolorizing effect preferably to glycol, product colourity is 20～30 (Pt-Co methods).
Chinese patent CN1145357A discloses a kind of preparation method of Tetraglycol 99, be with alkaline earth metal oxide and a kind of or its mixture as catalyst that is selected from alkali-metal oxyhydroxide or the carbonate, by glycol and oxyethane 90～220 ℃ of temperature of reaction, reaction pressure 2～21 kg/cm, oxyethane: Tetraglycol 99 or mixed glycol are under 1: the 1～4wt/wt condition, reaction generates Tetraglycol 99, the highest yield of Tetraglycol 99 is 41.2%, triglycol and Tetraglycol 99 total recovery are 83%, and this method does not relate to the separating treatment problem of reaction solution and catalyzer.
Summary of the invention
Technical problem to be solved by this invention is to overcome that the basic catalyst consumption that exists in the conventional art is big, the Tetraglycol 99 product recovery rate is not high, quality product is undesirable, reach the defective that does not relate to catalyzer and reaction mass separating treatment, a kind of method for preparing Tetraglycol 99 is provided, this method has that the basic catalyst consumption is little, Tetraglycol 99 product recovery rate height, good product quality, characteristics simple to operate and that implement easily.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing Tetraglycol 99, with glycol and oxyethane is raw material, with a kind of or its mixture in alkali metal hydroxide and the alkaline earth metal oxide as catalyzer, catalyst levels accounts for raw material 0.02～1.5% of the weight that feeds intake, 90～220 ℃ of temperature of reaction, reaction pressure 0.2～0.5MPa, oxyethane and glycol weight ratio are to react under 1: 1～4 conditions, obtain containing the reaction mass of triglycol and Tetraglycol 99, make this material enter rectifying tower and separate purification, obtain the Tetraglycol 99 product, the coproduction triglycol, before wherein reaction mass enters rectifying tower separation purification, use the mixture of forming by acidic white earth and diatomite to carry out pre-treatment, treatment temp is 30～90 ℃, treatment time is 0.1～4 hour, and acidic white earth and diatomaceous consumption account for 0.5～5% of reaction mass gross weight, and wherein acidic white earth and diatomite weight ratio are 8～15: 1.
In the technique scheme, described raw material glycol can be glycol ether, triglycol or their mixture, the catalyst levels preferable range accounts for raw material 0.02～0.5% of the weight that feeds intake, the reaction mass treatment temp is preferably 40～60 ℃, treatment time is preferably 0.3～2 hour, acidic white earth and diatomite that acidic white earth that uses and diatomite are commercially available common model, its consumption preferable range accounts for 1～3% of reaction mass gross weight, and acidic white earth and diatomite weight ratio are preferably 9～12: 1.
In reaction process, the catalyst component that uses, its alkali metal hydroxide can be selected from one of lithium hydroxide, sodium hydroxide, potassium hydroxide or their mixture, alkaline earth metal oxide can be selected from one of calcium oxide, strontium oxide, barium oxide or their mixture, in the reaction preferably temperature of reaction be that 110～170C, reaction pressure are that 0.2～0.4MPa, oxyethane and glycol weight ratio are 1: 2～3, use the preparation method of above-mentioned catalyzer and processing condition, can obtain the Tetraglycol 99 product, the triglycol of coproduction simultaneously.
In the preparation method of Tetraglycol 99, the variation of system pH value has a significant impact product stability.Under acidic conditions, the glycols less stable, dehydration reaction easily takes place and resolves into materials such as dioxane, acetaldehyde in glycol ether, under alkalescence and hot conditions, side reactions such as glycols easily and alkali decomposes, condensation or polymerization, and in and the salt compounds that produces of strong alkali catalyst, for example calcium phosphate remains in the reaction system, can impel the polyvalent alcohol catalytic dehydration, produce the low by product of acetaldehyde equimolecular quantity, these side reactions are under the situation of multitower operate continuously, the heating of reaction mass continuous high temperature, and the degree of generation is more serious.
The principal character of the inventive method is synthetic reacted material, before rectifying separation, carry out pre-treatment, the mixture that employing is made up of acidic white earth and diatomite, as compound absorption-filter aid processing agent, under certain condition, reaction mass is handled, the residual catalyst in the reaction mass is removed in absorption, and by control treatment agent add-on simultaneously the pH value of reaction mass is adjusted to neutrality or slight alkalinity, like this, promptly eliminated basic catalyst disadvantageous effect to distillation system under the hot conditions, also eliminated the disadvantageous effect of some salt compounds of acid-base neutralisation reaction generation to distillation system, fundamentally avoided catalytic decomposition, condensation or polymerization etc. influence the generation of the various side reactions of quality product and yield, the rate of recovery and the purity of Tetraglycol 99 and triglycol product have been improved very significantly, make product have color and luster degree preferably simultaneously, and basically eliminate the corrosion of material to equipment.As adopt the embodiment of the invention 1 to prepare in the method for Tetraglycol 99, with the material after the building-up reactions, the mixture of forming with acidic white earth that accounts for reaction mass gross weight 1.8% and diatomite carries out pre-treatment, acidic white earth and diatomite weight ratio are 11: 1, material after the processing is purified through separating, obtain the Tetraglycol 99 product, the Tetraglycol 99 product recovery rate reaches 90.2%, colourity is 25 (Pt-Co methods), coproduction simultaneously obtains the triglycol product, the triglycol rate of recovery reaches 95.1%, and colourity is 10 (Pt-Co methods); Compare with the material treatment process after adopting the acetic acid neutralization reaction, the Tetraglycol 99 product recovery rate has improved 5%, and the color and luster degree has reduced by 3.6 times, has obviously improved product recovery rate, has increased substantially quality product, has obtained effect preferably.
Below by embodiment method of the present invention is further described.
Embodiment
[embodiment 1]
At volume is 1500 liters, in belt stirrer and the built-in spiral coil cooling tube autoclave pressure, add 700 kilograms of glycol ethers, catalyzer potassium hydroxide 250 grams, calcium oxide 500 grams, after the autoclave pressure sealing, drive air in the still with nitrogen replacement, keep the pressure of 0.2MPa, be warming up to 120 ℃, drip 340 kilograms of liquid epoxy ethanes, keep 130 ℃ of temperature of reaction, pressure 0.3MPa, intact until the oxyethane total overall reaction that reaction is required, reaction mass is cooled to 90 ℃, in the immigration and in the still, then in and add 16.5 kilograms of (acidic white earth model 1020# of acidic white earth in the still, specification 190 mmole H
+/ kilogram) and 1.5 kilograms in diatomite (No. 08, diatomite model), stirring reaction 0.5 hour is removed acidic white earth in the reaction mass and diatomite filtration with frame filter, obtains pH value and be 7.5,1035.5 kilograms of little yellow transparent reaction masses.Through gas chromatographic analysis, contain triglycol 48.3% in the reaction mass, Tetraglycol 99 29.5%.
After measured, contain K in the reaction mass
+5ppm, contain Ca
2+20ppm.
Reaction mass after handling is sent into separation system separate purification, separation system comprises recovery tower, triglycol tower and Tetraglycol 99 tower, reclaim unreacted glycol ether at recovery tower, obtain 475.6 kilograms of triglycol products at the triglycol tower successively, obtain 275.5 kilograms of Tetraglycol 99 products at the Tetraglycol 99 tower.Wherein the Tetraglycol 99 rate of recovery is 90.2%, and Tetraglycol 99 purity 98.8%, colourity are 25 (Pt-Co methods); The triglycol rate of recovery is 95.1%, and triglycol purity 99.2%, colourity are 10 (Pt-Co methods).
The reaction result of embodiment 1～5 is listed in table 1.
[embodiment 2]
Reaction conditions according to embodiment 1 prepares Tetraglycol 99, difference: the acidic white earth consumption is 11 kilograms, and the diatomite consumption is 1.2 kilograms, 1.5 hours treatment times.Obtain 1036.3 kilograms of reaction masses, through gas chromatographic analysis, wherein contain triglycol 48.2%, Tetraglycol 99 29.6%.
[embodiment 3]
Reaction conditions according to embodiment 1 prepares Tetraglycol 99, difference: the acidic white earth consumption is 22 kilograms of (acidic white earth model 1040#, specification 180 mmole H
+/ kilogram), 1.8 kilograms of diatomite consumptions.Obtain 1035.1 kilograms of reaction masses, through gas chromatographic analysis, wherein contain triglycol 48.5%, Tetraglycol 99 29.3%.
[embodiment 4]
Reaction conditions according to embodiment 1 prepares Tetraglycol 99, difference: 600 kilograms of raw material glycol ethers, catalyzer sodium hydroxide 200 grams, barium oxide 250 grams, 170 ℃ of temperature of reaction, reaction pressure 0.2MPa.Obtain 896.5 kilograms of reaction masses, through gas chromatographic analysis, wherein contain triglycol 47.9%, Tetraglycol 99 29.9%.
[embodiment 5]
Reaction conditions according to embodiment 1 prepares Tetraglycol 99, difference: 900 kilograms of raw material glycol ethers, catalyzer potassium hydroxide 600 grams, 110 ℃ of temperature of reaction, reaction pressure 0.4MPa.Obtain 1195.1 kilograms of reaction masses, through gas chromatographic analysis, wherein contain triglycol 36.7%, Tetraglycol 99 20.3%.
[comparative example 1]
At volume is in 1500 liters, belt stirrer and the built-in spiral coil cooling tube autoclave pressure, add 700 kilograms of glycol ethers, add catalyzer potassium hydroxide 250 grams, calcium oxide 500 grams, after the autoclave pressure sealing, drive air in the still with nitrogen replacement, keep the pressure of 0.2MPa, be warming up to 120 ℃, drip 340 kilograms of liquid epoxy ethanes, keep 130 ℃ of temperature of reaction, pressure 0.3MPa, intact until the oxyethane total overall reaction that reaction is required, with in the reaction mass immigration and in the still, in and add Glacial acetic acid in the still, regulate material pH value to 7.5.Obtain 1040.2 kilograms of reaction masses, through gas chromatographic analysis, contain triglycol 48.3%, Tetraglycol 99 29.5%.
After measured, contain K in the reaction mass
+170ppm, contain Ca
2+350ppm.
This reaction mass is without any pre-treatment, directly enter separation system and separate purification, separation system comprises recovery tower, triglycol tower and Tetraglycol 99 tower, reclaim unreacted glycol ether at recovery tower, obtain 451.2 kilograms of triglycol products at the triglycol tower, obtain 260.2 kilograms of Tetraglycol 99 products at the Tetraglycol 99 tower.Wherein the Tetraglycol 99 product recovery rate is 84.8%, and Tetraglycol 99 product purity 97.6%, colourity are 90 (Pt-Co methods); The rate of recovery is 89.8%, and triglycol product purity 98.4%, colourity are 60 (Pt-Co methods).
Table 1
| Embodiment | Comparative example | |||||
| ????1 | ????2 | ????3 | ????4 | ??5 | ????1 | |
| Glycol ether (kilogram) | ????700 | ????700 | ????700 | ????600 | ??900 | ????700 |
| Oxyethane (kilogram) | ????340 | ????340 | ????340 | ????300 | ??300 | ????340 |
| Catalyzer (gram) | ????KOH：250 ????CaO：500 | ????KOH：250 ????CaO：500 | ????KOH：250 ????CaO：500 | ???NaOH：200 ???BaO：250 | ??KOH：600 | ????KOH：250 ????CaO：500 |
| Temperature of reaction ℃ | ????130 | ????130 | ????130 | ????170 | ??110 | ????130 |
| Reaction pressure (MPa) | ????0.3 | ????0.3 | ????0.3 | ????0.2 | ??0.4 | ????0.3 |
| Acidic white earth (kilogram) | ????16.5 | ????11 | ????22 | ????16.5 | ??16.5 | ????/ |
| Diatomite (kilogram) | ????1.5 | ????1.2 | ????1.8 | ????1.5 | ??1.5 | ????/ |
| Acidic white earth: diatomite | ????11∶1 | ????9∶1 | ????12∶1 | ????11∶1 | ??11∶1 | ????/ |
| Account for material total amount % (weight) | ????1.8 | ????1.2 | ????2.4 | ????2.0 | ???1.5 | ????/ |
| Handle metal ion content (ppm) in the material of back | ????K +：5 ????Ca 2+：20 | ????K +：6 ????Ca 2+：22 | ????K +：4 ????Ca 2+：16 | ????Na +：3 ????Ba 2+：19 | ???K +：6 | ???K +：170 ???Ca 2+：350 |
| Tetraglycol 99 rate of recovery % | ????90.2 | ????90.3 | ????90.1 | ????90.2 | ????90.1 | ????84.8 |
| Tetraglycol 99 colourity | ????25 | ????30 | ????20 | ????25 | ????30 | ????90 |
| Triglycol rate of recovery % | ????95.1 | ????95.4 | ????95.0 | ????95.2 | ????95.3 | ????89.8 |
| Triglycol colourity | ????10 | ????15 | ????10 | ????10 | ????15 | ????60 |
Claims (7)
1, a kind of method for preparing Tetraglycol 99, with glycol and oxyethane is raw material, with a kind of or its mixture in alkali metal hydroxide and the alkaline earth metal oxide as catalyzer, catalyst levels accounts for raw material 0.02～1.5% of the weight that feeds intake, 90～220 ℃ of temperature of reaction, reaction pressure 0.2～0.5MPa, oxyethane and glycol weight ratio are to react under 1: 1～4 conditions, obtain containing the reaction mass of triglycol and Tetraglycol 99, make this material enter rectifying tower and separate purification, obtain the Tetraglycol 99 product, the coproduction triglycol, before it is characterized in that reaction mass enters rectifying tower separation purification, use the mixture of forming by acidic white earth and diatomite to carry out pre-treatment, treatment temp is 30～90 ℃, treatment time is 0.1～4 hour, acidic white earth and diatomaceous consumption account for 0.5～5% of reaction mass gross weight, and wherein acidic white earth and diatomite weight ratio are 8～15: 1.
2,, it is characterized in that described glycol is glycol ether, triglycol or its mixture according to the described method for preparing Tetraglycol 99 of claim 1.
3,, it is characterized in that described catalyst levels accounts for raw material 0.02～0.5% of the weight that feeds intake according to the described method for preparing Tetraglycol 99 of claim 1.
4,, it is characterized in that described treatment temp is 40～60 ℃ according to the described method for preparing Tetraglycol 99 of claim 1.
5,, it is characterized in that the described treatment time is 0.3～2 hour according to the described method for preparing Tetraglycol 99 of claim 1.
6,, it is characterized in that described acidic white earth and diatomaceous consumption account for 1～3% of reaction mass gross weight according to the described method for preparing Tetraglycol 99 of claim 1.
7,, it is characterized in that described acidic white earth and diatomite weight ratio are 9～12: 1 according to the described method for preparing Tetraglycol 99 of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111017 CN1443740A (en) | 2002-03-13 | 2002-03-13 | Method for preparing tetraethylene-glycol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111017 CN1443740A (en) | 2002-03-13 | 2002-03-13 | Method for preparing tetraethylene-glycol |
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|---|---|
| CN1443740A true CN1443740A (en) | 2003-09-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237367A (en) * | 2015-09-02 | 2016-01-13 | 山东新时代药业有限公司 | Method of recycling triethylene glycol from synthetic mother liquid of sevoflurane |
-
2002
- 2002-03-13 CN CN 02111017 patent/CN1443740A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237367A (en) * | 2015-09-02 | 2016-01-13 | 山东新时代药业有限公司 | Method of recycling triethylene glycol from synthetic mother liquid of sevoflurane |
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