CN1100049C - Method for preparing tetrahydrofuran by dehydrating and cyclization of 1,4-butanediol - Google Patents
Method for preparing tetrahydrofuran by dehydrating and cyclization of 1,4-butanediol Download PDFInfo
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- CN1100049C CN1100049C CN00100478A CN00100478A CN1100049C CN 1100049 C CN1100049 C CN 1100049C CN 00100478 A CN00100478 A CN 00100478A CN 00100478 A CN00100478 A CN 00100478A CN 1100049 C CN1100049 C CN 1100049C
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- zeolite
- tetrahydrofuran
- butyleneglycol
- reaction
- sio
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Abstract
The present invention provides a method for preparing tetrahydrofuran by dehydration and cyclization of 1, 4-butanediol. At the temperature of 120 to 250 DEG C, 1, 4-butanediol contacts with a Y or beta zeolite catalyst for a reaction, and products are collected. The method of the present invention keeps the high conversion rate of raw material and the high selectivity of tetrahydrofuran, and the processing capacity of the 1, 4-butanediol is obviously improved. 100 to 1400 grams of 1, 4-butanediol can be processed by each gram of catalyst per hour. The selectivity for the tetrahydrofuran can reach more than 99.8%.
Description
The invention relates to 1, the method for 4-butyleneglycol preparing tetrahydrofuran by dehydrating and cyclization.
1,4-butyleneglycol cyclodehydration is the topmost method of preparation tetrahydrofuran (THF), and wherein catalyzer plays keying action.Prior art was a catalyzer with sulfuric acid once, but sulfuric acid corrosion resistance is strong, and the spent acid of generation also pollutes the environment.At present, it is higher and be easy to isolating solid catalyst to have reported multiple efficient in the domestic and foreign literature.
The spy opens clear 48-1075 and discloses-kind with unformed SiO
2-Al
2O
3As the method for Preparation of Catalyst tetrahydrofuran (THF),, under the 53atm pressure, adopt SiO at 250 ℃
2The SiO of content 90%
2-Al
2O
3Amorphous catalyst, 1, the processing power of 4-butyleneglycol is 1.98g/g catalyzer hr, the tetrahydrofuran (THF) selectivity is 99.2%.
The spy opens clear 51-76263 and discloses-kind with SiO
2-Al
2O
3As the method for Preparation of Catalyst tetrahydrofuran (THF), adopt fixed bed to carry out gas-solid phase reaction, at 250 ℃, SiO
2Content is 87% SiO
2-Al
2O
3Under the catalyst action, the tetrahydrofuran (THF) yield is 97%, 1, and the processing power of 4-butyleneglycol is 1g/g catalyzer hr.
It is the method for Preparation of Catalyst tetrahydrofuran (THF) with the X molecular sieve that SU discloses a kind of, at 230～240 ℃, and 1,4-butyleneglycol liquid hourly space velocity (LHSV) is 0.7hr
-1Under the condition, 1,4-butyleneglycol transformation efficiency is 98%.
SU1294805 discloses-preparation method of kind of tetrahydrofuran (THF), be be respectively 16.1nm, 35.4nm, 70nm with mean pore size pore, mesopore, macroporous silica gel as catalyzer, this catalyzer needs activate 30～45min before use under 400 ℃～420 ℃ inert atmospheres.Adopt above-mentioned catalyzer 420 ℃, volume space velocity is 38g/cm when normal pressure, liquid
3.hr carry out gas-solid phase reaction under the condition, 1, the transformation efficiency 100% of 4-butyleneglycol; And under identical temperature, when liquid hourly space velocity increases to 61.5g/cm
3.hr the time, 1, the transformation efficiency of 4-butyleneglycol drops to 89.3%.
In sum, existing 1, though that 4-butyleneglycol cyclodehydration is produced the method transformation efficiency and the selectivity of tetrahydrofuran (THF) is higher, there is the low defective of catalyst treatment ability, as increasing liquid hourly space velocity, raw material 1, the transformation efficiency of 4-butyleneglycol then obviously descend.
The objective of the invention is to overcome the above-mentioned defective of prior art, provide two kind 1, the novel method of 4-butyleneglycol preparing tetrahydrofuran by dehydrating and cyclization, this two method has higher raw material processing power keeping high transformation efficiency and while optionally than prior art.
Provided by the invention-kind of a method is under 120～250 ℃, makes 1, the 4-butyleneglycol contacts with the Y zeolite catalyzer, reacts and collects product.
Second method provided by the invention is under 120～250 ℃, makes 1, and the 4-butyleneglycol contacts with beta-zeolite catalyst, reacts and collects product.
Specifically, preparation method provided by the invention is with 1, and the 4-butyleneglycol feeds and is equipped with in the reactor of whipping appts and Y or beta-zeolite catalyst, at 120～250 ℃, reacts under preferred 150～230 ℃ temperature, and reaction steams the product tetrahydrofuran (THF) simultaneously.Reactor can have or not have separator column.
For reaction system of the present invention, the raising temperature of reaction helps reaction carries out, but the too high meeting of temperature increases side reaction, and the selectivity of tetrahydrofuran (THF) is descended, and the too low then transformation efficiency of temperature of reaction descends, so the optimum temperature of the present invention is 150～230 ℃.
For reaction system of the present invention, reduce reaction pressure and help molecular balance and move to the direction that generates tetrahydrofuran (THF), common 1, being reflected under the normal pressure of tetrahydrofuran (THF) of 4-butyleneglycol dehydration preparation just can be carried out.
The used catalyzer of the present invention is Y zeolite or β zeolite, and wherein the sial molecular ratio of Y zeolite is 2～25, and is preferred 4～20, and the sial molecular ratio of β zeolite is 10～60, preferred 15～55.
The used Y zeolite of the present invention can also can be prepared as follows by any ordinary method preparation;
Commercially available Na-Y zeolite is handled with ammonium chloride, made its sodium content (with Na
2The O meter) is not more than 0.1 heavy %,, promptly gets the used H-Y zeolite catalyst of the present invention than low silica-alumina ratio again through 450～650 ℃ of roastings 3 hours.
If obtain Y zeolite than high silica alumina ratio, after commercially available Na-Y zeolite can being handled with ammonium sulfate and oxalic acid solution, handle with high-temperature vapor and alum liquor again, get final product required y-type zeolite than high silica alumina ratio.
The used β zeolite of the present invention can also can be prepared as follows by any ordinary method preparation:
(1) solid-state aluminium source, tetraethylammonium cation source and sodium hydroxide is soluble in water, form working solution, with granularity is that 20～200 purpose silica gel particles are the silicon source, silica gel is mixed with working solution, make silica gel surface wetting, need not under the condition of plus seed, 140～170 ℃ of crystallizations 10～60 hours by working solution, after filtration, washing, drying, promptly get Na-β zeolite.
The mol ratio that each raw material is formed in the reaction system is as follows: SiO
2/ Al
2O
3=10～100, best 10～80, Na
2O/SiO
2=0.01～0.1, TEAOH (tetraethyl ammonium hydroxide)/SiO
2=0.05～0.15, H
2O/SiO
2=1～3.Wherein the aluminium source is selected from pseudo-boehmite, solid-state sodium aluminate, SB aluminium hydroxide, aluminium hydroxide, and used tetraethylammonium cation can replace with tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide and composition thereof.Sodium ion in the sodium hydroxide can be replaced by other basic metal or alkaline-earth metal ions that does not influence reaction.Solid silicone can be any aperture, comprises the silica gel of gross porosity, mesopore, pore.
(2) above-mentioned Na-β zeolite is handled respectively with ammonium chloride and hydrochloric acid, made its sodium content (with Na
2O meter) reduce to below the 0.5 heavy %, silica alumina ratio reaches necessary requirement, more after filtration, washing, drying, and 450～650 ℃ of roastings 3 hours, promptly get the used H-beta-zeolite catalyst of the present invention.For simplifying modifying process, also can adopt the mixing solutions of ammonium chloride and hydrochloric acid to handle, before filtration, add the particle raising agent, as ammonium nitrate, filtration is carried out easily, the catalyzer yield obviously improves.
Before using, the used catalyzer of the present invention need not carry out any processing of giving.
The preparation method of tetrahydrofuran (THF) provided by the invention is a catalyzer owing to having adopted Y or β zeolite, make catalyzer to 1, the processing power of 4-butyleneglycol increases substantially, for example at 208 ± 2 ℃, every gram beta-zeolite catalyst per hour can handle 1,4-butyleneglycol 1349 gram can reach 99.9% to the selectivity of tetrahydrofuran (THF); At 218 ± 2 ℃, every gram Y zeolite catalyzer per hour can handle 1, and 4-butyleneglycol 570 gram can reach 99.8% to the selectivity of tetrahydrofuran (THF).Though the Y zeolite treatment capacity is a bit weaker, has cheap advantage.
In addition, the inventive method non-corrosiveness does not need special equipment in the reaction process, and temperature of reaction is low, and energy consumption can descend significantly.
The invention will be further described below by example, but not thereby limiting the invention.
Example 1
This example is the β prepare zeolite.
Play in the reactor with sodium aluminate (production of Shanghai reagent two factories), sodium hydroxide, TEAOH, water uniform mixing and with silica gel (production of Qingdao silica gel factory) one, it is SiO that raw material is formed (mol ratio)
2/ Al
2O
3=29.4, Na
2O/SiO
2=0.057, TEAOH/SiO
2=0.109, H
2O/SiO
2=1.94,150 ± 2 ℃ of following crystallization 40 hours, through cooling off, filter, wash, be drying to obtain Na-β zeolite (silica alumina ratio SiO
2/ Al
2O
3=25).The ammonium chloride solution that adds 3wt% in Na-β zeolite adds ammonium nitrate then and stirs, filters, washs through deionized water 90～95 ℃ of exchanges 3 hours, 120 ℃ of dryings, and twice, 550 ± 50 ℃ of roastings of repetitive operation promptly get Na
2O content＜0.1wt%H-β zeolite (SiO
2/ Al
2O
3Mol ratio is 25, and specific surface is 470m
2/ g), be catalyst A.
Example 2
This example is the β prepare zeolite.
Make Na-β (SiO by example 1 described method
2/ Al
2O
3Mol ratio is 25), the NH of adding 3wt% in Na-β
4The mixing solutions of Cl solution and 3wt%HCl after 3 hours, adds NH 90～95 ℃ of exchanges
4NO
3Through stir, filter, with the deionized water washing, 120 ℃ of dryings, twice, 550 ± 50 ℃ of roastings of repetitive operation promptly get Na
2O content＜0.1wt%H-β zeolite (SiO
2/ Al
2O
3Mol ratio is 50, and specific surface is 521m
2/ g), be catalyst B.
Example 3
This example is the β prepare zeolite.
With industrial pseudo-boehmite (Shandong Aluminum Plant's production), sodium hydroxide is dissolved in the tetraethyl ammonium hydroxide aqueous solution (Beijing Chemical Plant's production), silica gel (production of Qingdao silica gel factory) is added wherein again, and each material mol ratio is SiO
2/ Al
2O
3=20.5, Na
2O/SiO
2=0.055, TEAOH/SiO
2=0.109, H
2O/SiO
2=1.94,150 ± 2 ℃ of following crystallization 24 hours, through cooling off, filter, wash, be drying to obtain Na-β (SiO
2/ Al
2O
3=17 mol ratios).Promptly get Na after handling with the method identical with example 1
2O content＜0.1wt%H-β zeolite (SiO
2/ Al
2O
3Mol ratio 17, specific surface 450m
2/ g), be catalyzer C.
Example 4
This example is the preparation of Y zeolite.
With commercially available Na-Y molecular sieve (SiO
2/ Al
2O
3Mol ratio 5) joins 90～100 ℃ that have stirring, in the 10wt% ammoniumsulphate soln, slowly add the 1M oxalic acid solution again, react after 1 hour, after filtration, the washing, the oven dry again with it through 100% water vapor, 600 ℃, 2hr and 0.5M alum liquor are handled two times, get final product SiO
2/ Al
2O
3Mol ratio is 19 y-type zeolite, as catalyzer D.
Example 5
This example is the preparation of Y zeolite.
With commercially available Na-Y molecular sieve (SiO
2/ Al
2O
3Mol ratio is 5), with 80～90 ℃ of 5% ammonium chloride solutions exchange 1 hour, repetitive operation twice, filter then, wash, 500 ± 50 ℃ of roastings, obtain Na
2H-Y zeolite (the SiO of O content＜0.1wt%
2/ Al
2O
3Mol ratio is 5), be catalyzer E.
Example 6
This example is the preparation of Y zeolite.
With commercially available Na-Y molecular sieve (SiO
2/ Al
2O
3Mol ratio 5) handle by the mode of example 4, different is shortens to 1hr with time of steam-treated, gets final product with commercially available Na-Y molecular sieve SiO
2/ Al
2O
3Mol ratio is 11 y-type zeolite, as catalyzer F
Example 7
This example is the preparation of tetrahydrofuran (THF).
Getting the 0.3g catalyst A packs into and has in the there-necked flask of stirring, add 1000g 1,4-butyleneglycol (technical grade, German BASF AG produces), normal pressure stirs down, temperature of reaction is risen to 208 ± 2 ℃, and reaction product can steam simultaneously, after reaction in 1 hour, steam product 404.7g altogether, with gc analysis (PEG20000 packed column, FID detects), the results are shown in Table 1.
Example 8
This example is the preparation of tetrahydrofuran (THF).
Get the 0.1g catalyst B and operate by the mode of example 7, temperature of reaction that different is is 216 ± 2 ℃, and it steams product 100.1g after reaction in 1 hour, and analytical results sees Table 1.
Example 9
This example is the preparation of tetrahydrofuran (THF).
Get 0.1g catalyzer E and operate by the mode of example 7, different is that temperature of reaction is 222 ± 2 ℃, steams product 23.1g after 1 hour altogether, and analytical results sees Table 1.
Example 10
This example is the preparation of tetrahydrofuran (THF).
Get 0.4g catalyzer D and operate by the mode of example 7, different is to add 240g 1, the 4-butyleneglycol, and temperature of reaction is 218 ± 2 ℃, steams product 228g after 1 hour altogether, analytical results sees Table 1.
Example 11
This example is the preparation of tetrahydrofuran (THF):
Get the 1g catalyst B and operate by the mode of example 7, different is to add 350g 1, the 4-butyleneglycol, and temperature of reaction is 179 ± 2 ℃, steams product 330g after 1 hour altogether, analytical results sees Table 1.
Example 12
This example is the preparation of tetrahydrofuran (THF).
Get 0.3g catalyzer C, operate by the mode of example 7, different is to add 419g 1, the 4-butyleneglycol, and temperature of reaction is 207 ± 2 ℃, after reaction in 1 hour, steams product 391.2g altogether, analytical results sees Table 1.
Example 13
This example is the preparation of tetrahydrofuran (THF).
Get 1g catalyzer F, operate by the mode of example 7, different is to add 307g 1,4 butyleneglycol, and temperature of reaction is 200 ± 2 ℃, after reaction in 1 hour, steams product 232g altogether, and analytical results sees Table 1.
Comparative Examples
Described according to embodiment among the JP48-1075 1, the unformed SiO of 5g packs in reactor
2-Al
2O
3Catalyzer G, 50g 1, the 4-butyleneglycol, when temperature of reaction is 250 ℃, highest response pressure is 53atm, and during reaction 5hr, transformation efficiency is 98.9%, can calculate 1, and 4-butyleneglycol treatment capacity is 1.98g/g catalyzer hr, and reaction result sees Table 1.
As can be seen from Table 1, the preparation method of tetrahydrofuran (THF) provided by the invention has significantly improved 1 under the high optionally condition of maintenance, and the processing power of 4-butyleneglycol has favorable industrial application prospect.
Table 1
| Example | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Comparative Examples |
| The catalyzer numbering | A | B | E | D | B | C | F | G |
| Temperature of reaction, ℃ | 208±2 | 216±2 | 222±2 | 218±2 | 179±2 | 207±2 | 200±2 | 250 |
| Reaction pressure, atm | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 53 |
| The catalyst treatment amount, g/g catalyzer hr | 1349 | 1001 | 231 | 570 | 330 | 1304 | 232 | 1.98 |
| The tetrahydrofuran (THF) selectivity, mol% | 99.9 | 99.8 | 99.8 | 99.8 | 99.8 | 99.8 | 99.8 | 99.2 |
Annotate:
Claims (10)
1. one kind 1, the method for 4-butyleneglycol preparing tetrahydrofuran by dehydrating and cyclization is characterized in that, under 120～250 ℃, makes 1, and the 4-butyleneglycol contacts with the Y zeolite catalyzer, reacts and collects product.
2. according to the said method of claim 1, it is characterized in that temperature of reaction is 150～230 ℃.
3. according to the said method of claim 1, it is characterized in that the sial molecular ratio of Y zeolite is 2～25.
4. according to claim 1 or 3 said methods, it is characterized in that the sial molecular ratio of Y zeolite is 4～20.
5. according to the said method of claim 1, it is characterized in that, in tank reactor, react.
6. one kind 1, the method for 4-butyleneglycol preparing tetrahydrofuran by dehydrating and cyclization is characterized in that, under 120～250 ℃, makes 1, and the 4-butyleneglycol contacts with beta-zeolite catalyst, reacts and collects product.
7. according to the said method of claim 6, it is characterized in that temperature of reaction is 150～230 ℃.
8. according to the said method of claim 6, it is characterized in that the sial molecular ratio of β zeolite is 10～60.
9. according to claim 6 or 8 said methods, it is characterized in that the sial molecular ratio of β zeolite is 15～55.
10. according to the said method of claim 6, it is characterized in that, in tank reactor, react.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100478A CN1100049C (en) | 2000-02-01 | 2000-02-01 | Method for preparing tetrahydrofuran by dehydrating and cyclization of 1,4-butanediol |
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|---|---|---|---|
| CN00100478A CN1100049C (en) | 2000-02-01 | 2000-02-01 | Method for preparing tetrahydrofuran by dehydrating and cyclization of 1,4-butanediol |
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|---|---|
| CN1306961A CN1306961A (en) | 2001-08-08 |
| CN1100049C true CN1100049C (en) | 2003-01-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10738021B2 (en) * | 2016-08-19 | 2020-08-11 | Nitto Belgium B.V. | Preparation of TMTHF |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003350A (en) * | 2022-12-16 | 2023-04-25 | 华峰集团上海工程有限公司 | Preparation method of tetrahydrofuran |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208410A (en) * | 1996-01-16 | 1999-02-17 | 林德股份公司 | Process and device for the preparation of tetrahydrofuran |
-
2000
- 2000-02-01 CN CN00100478A patent/CN1100049C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208410A (en) * | 1996-01-16 | 1999-02-17 | 林德股份公司 | Process and device for the preparation of tetrahydrofuran |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10738021B2 (en) * | 2016-08-19 | 2020-08-11 | Nitto Belgium B.V. | Preparation of TMTHF |
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| Publication number | Publication date |
|---|---|
| CN1306961A (en) | 2001-08-08 |
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