CN1145356A - Prodn. tech for isopropyl ether - Google Patents
Prodn. tech for isopropyl ether Download PDFInfo
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- CN1145356A CN1145356A CN 96116960 CN96116960A CN1145356A CN 1145356 A CN1145356 A CN 1145356A CN 96116960 CN96116960 CN 96116960 CN 96116960 A CN96116960 A CN 96116960A CN 1145356 A CN1145356 A CN 1145356A
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- isopropyl ether
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- virahol
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- extraction
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Abstract
A process for producing isopropyl ether from isopropanol in fixed bed reactor by such steps as continuous dewatering reaction by acidically modified zeolite molecular sieve to generate isopropyl ether, removing the most residual isopropanol and resultant water from reaction liquid by triple azeotropic distillation in raw ditillation tower, continuously removing rest of isopropanol by use of water as extractant in extracting tower to obtain crude isopropyl ether, and rectifying in rectifying tower to obtain high-purity isopropyl ether. Its advantages include high transform rate and purity of product.
Description
The present invention relates to acyclic compound, be meant the producing and manufacturing technique of a kind of liquid Virahol continuously dehydrating reaction system isopropyl ether under the solid-phase catalyst effect especially.
Isopropyl ether is of many uses, can be used as the solvent of animal-plant oil, mineral oil, pharmacy, smokeless powder, coating, paint cleaning, also can be used as the gasoline antifreezing agent, is used as the extraction agent that reclaims Sodium Thiocyanate 99 (NaSCN) especially in the wet spinning acrylic fiber production technique.The isopropyl ether of existing domestic production mainly is the by product that propylene reclaims during with sulfuric acid hydration preparing isopropanol.Because the by product limited amount can not satisfy the needs in market, the isopropyl ether purity that simultaneously this method obtains is low, of poor quality, especially can't use in wet spinning acrylic fiber production at all, thereby can not satisfy the needs of use.
The objective of the invention is to overcome the defective of prior art, the production technique of employing liquid Virahol continuously dehydrating system isopropyl ether under the solid-phase catalyst effect that a kind of raw material is easy to get, technology is simple, product purity is higher is provided.
Isopropyl ether production technique of the present invention adopts fixed-bed reactor, with the Virahol is raw material, generate isopropyl ether through the reaction of acid modification zeolite molecular sieve solid-phase catalyst continuously dehydrating, reaction solution removes the water of most of unreacted Virahol and reaction generation with ternary azeotropic distillation method by topping still.Remove the Virahol that the ternary azeotropic distillation do not remove through the extraction tower water as extraction agent then and make rough isopropyl ether, make highly purified isopropyl ether finished product through rectifying tower by rectified purified again.The main chemical reactions of this technology is as follows:
1. main reaction
2. side reaction
Because this process using NKC-6D type modified zeolite molecular sieve catalyzer, its selectivity is more than 97%, has controlled the generation of side reaction, thereby the by product propylene that generates is few.And propylene can reclaim as byproduct by the compressor compresses condensation.
This technology main control parameters is as follows:
1. raw material isopropanol content (wt%) 〉=99.5%
2. reaction pressure (MPa) 0.2-1.2
Temperature of reaction (℃) 50-150
4. weight space velocity (h in the reactor
-1) 0.3-1.2
5. topping still pressure (MPa) cat head 0.08-0.15 tower still 0.09-0.2
6. topping still reflux ratio R=4-8
The topping still temperature (℃) cat head 30-80 tower still 60-95
8. extraction tower pressure normal pressure
9. extraction tower temperature normal temperature
10. rectifying tower pressure (MPa) cat head 0.08-0.15 tower still 0.09-0.2
11. rectifying tower reflux ratio R=15-25
12. the rectifying tower temperature (℃) cat head 30-75 tower still 60-100
13. pure recovery tower pressure (MPa) cat head 0.08-0.15 tower still 0.09-0.2
14. pure recovery tower reflux ratio R=40-80
15. pure recovery tower temperature (℃) cat head 60-100 tower still 80-120
Isopropyl ether production technique of the present invention adopts the commercially available NKC-6D type acid modified zeolite molecular sieve solid-phase catalyst that dewaters, and this catalyzer is a carrier with the small crystal grain molecular sieve, has catalytic activity and higher selectivity preferably, and selectivity is 97%-99%.Conversion unit is fixed-bed reactor, wherein loads most of solid-phase catalyst.It is cylindric that fixed-bed reactor are, and the bottom is provided with opening for feed, and top is a little vaporizing chamber, the vaporizing chamber top is a discharge port, reactor is established the stainless steel coil heat exchanger in the middle part, will react liberated heat and shift out, and the bottom is provided with screen upper berth silk screen puts thereon catalyzer.Reaction is liquid phase reaction in the reactor, and its range of reaction temperature is 50-150 ℃, and 125 ℃ of optimum tempss, reaction pressure scope are 0.2-1.2MPa, optimum pressure 0.80MPa.The reaction conversion ratio of Virahol system isopropyl ether can reach about 20%.Separate the Virahol that obtains through topping still and return conversion unit again.Extraction phase after extraction tower extraction enters pure recovery tower and reclaims Virahol and then enter topping still, circulates like this to return conversion unit and carry out dehydration reaction system isopropyl ether again, and the total recovery of isopropyl ether (by weight) can reach more than 96%.Topping still, extraction tower, rectifying tower and pure recovery tower are sieve-tray tower.
The quality index of the isopropyl ether that this technology is produced is:
The index name index
1. appearance colorless transparent liquid
2. proportion ρ 20 0.724-0.726
3. moisture≤0.1% (wt%)
4. acid number≤0.002% (wt%)
5. boiling range 67-70 ℃
6. content 〉=99.5% (wt%)
Advantage of the present invention just is owing to adopt Virahol to make raw material, and raw material is easy to get and has avoided must depending on bigger device and all inconvenience of causing as by product; Because technology starts simply easily, can determine the industrial scale size simultaneously with suiting measures to local conditions; And the acid solid-phase catalyst of the dehydration of adopting has selectivity preferably, reduced the generation of side reaction, this catalyzer also has catalytic activity preferably, can spread effectively, thereby improved isopropyl ether transformation efficiency and product purity, guaranteed the quality of product.
The present invention is further illustrated below in conjunction with accompanying drawing, and Fig. 1 is a process flow diagram of the present invention, and Fig. 2 is a fixed-bed reactor synoptic diagram of the present invention.
With reference to Fig. 1, technological process of the present invention comprises isopropyl alcohol storage tank [1], reactor [2], topping still [3], bypass channel [4], extraction tower [5], thick ether groove [6], rectifying column [7], pure recovery tower [8], reclaims the equipment such as thick pure groove [9] and tank [10], alphabetical A represents the finished product isopropyl ether among the figure, and B represents the charging aperture of topping still [3]. When producing, the raw material isopropyl alcohol is forced into 0.8MPa, is heated to and sends into continuously about 127 ℃ in the reactor [2] through delivery pump and heat exchanger by isopropyl alcohol storage tank [1], fill NKC-6D type acid modification zeolite molecular sieve solid-phase catalyst in the reactor [2], the optimal reaction temperature of reactor [2] is 125 ℃, reaction pressure is 0.80MPa, generates isopropyl ether and water and side reaction occurs through the catalytic reaction iso-propanol conversion to produce a small amount of propylene. A small amount of propylene enters gas holder and becomes propylene liguid by compressor compresses, condensation and send into storage tank and sell as byproduct, after reaction product and unreacted isopropyl alcohol go out reactor [2], enters topping still [3] behind expenditure and pressure. Topping still [3] cat head controlled pressure is 0.1MPa, and cat head control temperature is 66 ℃; The tower reactor controlled pressure is 0.14MPa, and tower reactor control temperature is 89 ℃; The isopropyl alcohol that tower reactor is discharged is sent isopropyl alcohol storage tank [1] back to again as reaction raw materials, and ternary azeotrope and isopropyl ether that the isopropyl ether that cat head is sent, isopropyl alcohol and water form are admitted to bypass channel [4] with the binary azeotrope that isopropyl alcohol forms. It is isopropyl ether 71%, isopropyl alcohol 6%, water 23% that topping still cat head ternary azeotrope forms (mo1%), and it is isopropyl ether 75.12%, isopropyl alcohol 24.88% that the binary azeotrope forms (mol%). Through bypass channel [4] sedimentation layering, upper, the ether layer overflows through a delivery pump part from overfall sends into extraction tower [5] to water layer at lower ether layer, and another part returns topping still [3] charging aperture. The ether layer enters from extraction tower [5] bottom, adds at cat head from the clear water of tank [10], and the ether layer is up leaked water toward dirty, and the most of isopropyl alcohol in Liquid-liquid Extraction Processes in the isopropyl ether is taken at the bottom of the tower by water. Nearly cat head place, extraction tower [5] top raffinate phase is that ether enters in the thick ether groove [6] mutually, and the water layer that discharge the extraction phase of discharging from the tower reactor bottom and bypass channel [4] bottom is sent into pure recovery tower [8] charging aperture through delivery pump. Extraction tower [5] operates under normal pressure, normal temperature. Rough isopropyl ether is sent in the rectifying column [7] through delivery pump by thick ether groove [6] bottom, the controlled pressure cat head is that 0.1MPa, tower reactor are 0.13MPa in rectifying column [7] tower, control temperature cat head is that 67 ℃, tower reactor are 80 ℃, the ternary azeotrope of the isopropyl ether that cat head is sent, isopropyl alcohol and water and isopropyl ether return to topping still [3] charging aperture with the binary azeotrope of isopropyl alcohol, tower reactor output finished product isopropyl ether. Isopropyl alcohol and a small amount of isopropyl ether in the extraction phase water that discharge the water layer that discharge alcohol recovery tower [8] recovery bypass channel [4] bottom and extraction tower [5] bottom, alcohol recovery tower [8] controlled pressure cat head is that 0.1MPa, tower reactor are 0.11MPa, control temperature cat head is 105.8 ℃ of 82.5 ℃, tower reactor, the water of discharging at the bottom of the tower after reclaiming enters tank [10] to be used as extraction water through cooling, the isopropyl alcohol of recovered overhead is sent into and is reclaimed thick pure groove [9], and the isopropyl alcohol that reclaims in the thick pure groove [9] is sent into topping still [3] charging aperture by delivery pump.
With reference to Fig. 2, it is cylindric that fixed bed reactors are, and top is a little vaporizer, establishes the stainless steel coil heat exchanger in the middle part, and the bottom is provided with screen upper berth silk screen. A is charging aperture, and c is discharging opening, and d is relief valve port, and f is gauge port, and g is for subsequent use mouthful, and k is thermocouple port, m1And m2For being arranged on screen two hand-holes up and down, b2And b1Import and outlet for the stainless steel coil heat exchanger. The cooling medium of coil heat exchanger can be the raw material isopropyl alcohol, to reach the purpose with raw material preheating. The screen center is provided with a pumping board, and when pumping board was taken out out, catalyst can fall automatically from the pumping board hole, makes that more catalyst changeout is comparatively convenient.
Below be embodiment of the present utility model, actual production of the present invention is not limited to embodiment.
Isopropyl ether is produced in the reaction of example 1 isopropanol dehydration
1500 tons/year of throughput;
Raw material isopropanol content 〉=99.5% (wt%);
Catalyzer specification NKC-6D type (Catalyst Factory, Nankai Univ production)
2. reactor Φ 1600 * 12mm h=4200mm;
3. topping still Φ 1400mm, stage number N=40,
Distance between plates h=450mm;
4. bypass channel Φ 3000 * 12mm
H=2500mm (not comprising tapered bottom);
5. extraction tower Φ 900mm, stage number N=30,
Distance between plates h=450mm;
6. thick ether groove Φ 2000 * 10mm h=2000mm;
7. rectifying tower Φ 1000mm, stage number N=60,
Distance between plates h=450mm;
8. pure recovery tower Φ 800mm, stage number N=42,
Distance between plates h=450mm;
9. reclaim thick pure groove Φ 2500 * 12mm, h=2500mm;
10. tank Φ 2500 * 12mm, h=2500mm.
Mixing Virahol raw material 32.44Kmol/hr fresh and that reclaim from topping still is forced into 0.8MPa, enters reactor when being heated to 127 ℃, generate 2.36Kmol/hr isopropyl ether, 0.20Kmol/hr propylene, 2.62Kmol/hr water through catalyzed reaction, a spot of propylene is sold as byproduct after reclaiming, other resultants and unreacted 26.56Kmol/hr Virahol enter topping still through expenditure and pressure again.Topping still bottom discharge 26.44Kmol/hr Virahol and 0.076Kmol/hr water return the Virahol storage tank to be mixed with fresh feed, and its top obtains 11.19 Kmol/hr isopropyl ethers, 3.54Kmol/hr water and 1.33Kmol/hr Virahol and enters bypass channel.Obtain 11.16Kmol/hr isopropyl ether, 1.18Kmol/hr water and 1.18Kmol/hr Virahol at the bypass channel top, this part material is divided into two strands, one is that 3.99Kmol/hr isopropyl ether, 0.42Kmol/hr water and 0.42Kmol/hr Virahol enter extraction tower through transferpump, and another strand returns the topping still opening for feed for 7.17Kmol/hr isopropyl ether, 0.76Kmol/hr water and 0.76Kmol/hr Virahol through transferpump; Obtain 0.03Kmol/hr isopropyl ether, 2.36Kmol/hr water and 0.15Kmol/hr Virahol in the bypass channel bottom and send into pure recovery tower opening for feed through transferpump.Obtain 3.92Kmol/hr isopropyl ether, 0.40Kmol/hr water and 0.11Kmol/hr Virahol at the nearly top of tower of extraction tower and send into rectifying tower through thick ether groove with transferpump, its bottom extraction phase is that 0.07Kmol/hr isopropyl ether, 16.69Kmol/hr water and 0.31Kmol/hr Virahol are sent into pure recovery tower opening for feed through transferpump.By rectifying tower rectifying, its top obtains 1.66Kmol/hr isopropyl ether, 0.40Kmol/hr water and 0.10Kmol/hr Virahol and delivers to the topping still opening for feed through transferpump, obtains the isopropyl ether finished product in its bottom.Obtain sending into the topping still import again after 0.1Kmol/hr isopropyl ether, 0.21Kmol/hr water and 0.35Kmol/hr Virahol enter the thick pure groove of recovery in pure recovery tower recovered overhead, the water of discharging at the bottom of the tower after reclaiming enters tank to make the extraction water through cooling.
Through trial production continuously in 3 months, technology of the present invention can adapt to production requirement, and the isopropyl ether constant product quality of production conforms to quality requirements as extraction agent in the acrylic fiber production process, and the user is satisfied.
Reactant under example 2 differing tempss, the pressure is formed.
Throughput, raw material Virahol specification, catalyzer specification and main equipment specification are equal to example 1.
Reactor is under different temperature and pressures, and the composition of reactant isopropyl ether, Virahol and three kinds of components of water is listed in the table below.
| Temperature (℃) | Pressure (MPa) | Component (wt%) | ||
| Isopropyl ether | Virahol | Water | ||
| ????110 | ???0.70 | ???5.35 | ?91.29 | ??3.36 |
| ????120 | ???0.75 | ??14.71 | ?81.55 | ??3.74 |
| ????125 | ???0.80 | ??23.30 | ?71.24 | ??5.46 |
| ????140 | ???0.85 | ??16.60 | ?76.79 | ??6.61 |
| ????150 | ???0.90 | ??14.72 | ?80.06 | ??5.22 |
The correlation data of forming according to reactant under above-mentioned differing temps and the pressure is as can be seen: the reactor reaction top condition should be 125 ℃ of controlled temperature, pressure 0.80MPa.
Claims (5)
1, a kind of isopropyl ether production technique, it is characterized in that its employing fixed-bed reactor, with the Virahol is raw material, generate isopropyl ether through the reaction of acid modification zeolite molecular sieve solid-phase catalyst continuously dehydrating, reaction solution removes the water of most of unreacted Virahol and reaction generation with ternary azeotropic distillation method by topping still.Remove the Virahol that the ternary azeotropic distillation do not remove through the extraction tower water as extraction agent then and make rough isopropyl ether, make highly purified isopropyl ether finished product through rectifying tower by rectified purified again.
2, the isopropyl ether production technique of employing fixed-bed reactor according to claim 1 is characterized in that acid modification zeolite molecular sieve solid-phase catalyst is a NKC-6D type modified zeolite molecular sieve catalyzer.
3, the isopropyl ether production technique of employing fixed-bed reactor according to claim 1 and 2, it is characterized in that separating the Virahol that obtains through topping still returns conversion unit again, extraction phase after extraction tower extraction enters pure recovery tower and reclaims Virahol and then enter topping still, circulates like this to return the conversion unit system isopropyl ether that dewaters again.
4, the isopropyl ether production technique of employing fixed-bed reactor according to claim 1 and 2 is characterized in that the fixed-bed reactor optimal reaction temperature is that 125 ℃, reaction pressure are 0.80MPa.
5, the employed fixed-bed reactor of a kind of isopropyl ether production technique is characterized in that fixed bed is cylindric, and the bottom is provided with opening for feed, top is a little vaporizing chamber, the vaporizing chamber top is a discharge port, and reactor is established the stainless steel coil heat exchanger in the middle part, and the bottom is provided with screen upper berth silk screen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116960A CN1045001C (en) | 1996-06-07 | 1996-06-07 | Prodn. tech for isopropyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116960A CN1045001C (en) | 1996-06-07 | 1996-06-07 | Prodn. tech for isopropyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1145356A true CN1145356A (en) | 1997-03-19 |
| CN1045001C CN1045001C (en) | 1999-09-08 |
Family
ID=5123908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116960A Expired - Fee Related CN1045001C (en) | 1996-06-07 | 1996-06-07 | Prodn. tech for isopropyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1045001C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432438A (en) * | 2011-11-30 | 2012-05-02 | 济南大学 | Method for preparing and purifying isopropyl ether |
| CN102924241A (en) * | 2012-10-26 | 2013-02-13 | 浙江新化化工股份有限公司 | Diisopropyl ether production method |
| CN104177234A (en) * | 2014-08-06 | 2014-12-03 | 东营市海科新源化工有限责任公司 | Refining and purifying device and method used for diisopropyl ether byproduct during production of isopropanol |
| CN104211583A (en) * | 2014-08-28 | 2014-12-17 | 天津大学 | Reduced pressure rectification method for extracting bis-(2-chloroisopropyl)ether from chlorohydrin method epoxypropane liquid waste |
| CN117623879A (en) * | 2023-11-15 | 2024-03-01 | 山东达民化工股份有限公司 | Preparation method of diisopropyl ether |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666563A (en) * | 1985-11-20 | 1987-05-19 | Lloyd Berg | Separation of isopropyl ether from isopropanol and water by extractive distillation |
| JPH0341042A (en) * | 1989-07-10 | 1991-02-21 | Mitsui Toatsu Chem Inc | Preparation of isopropyl ether |
| JP3074343B2 (en) * | 1994-04-01 | 2000-08-07 | 日立造船株式会社 | Method for producing NOx adsorbent |
-
1996
- 1996-06-07 CN CN96116960A patent/CN1045001C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432438A (en) * | 2011-11-30 | 2012-05-02 | 济南大学 | Method for preparing and purifying isopropyl ether |
| CN102924241A (en) * | 2012-10-26 | 2013-02-13 | 浙江新化化工股份有限公司 | Diisopropyl ether production method |
| CN104177234A (en) * | 2014-08-06 | 2014-12-03 | 东营市海科新源化工有限责任公司 | Refining and purifying device and method used for diisopropyl ether byproduct during production of isopropanol |
| CN104177234B (en) * | 2014-08-06 | 2016-08-17 | 东营市海科新源化工有限责任公司 | The refined purifying plant of a kind of by-product diisopropyl ether in isopropanol produces and method |
| CN104211583A (en) * | 2014-08-28 | 2014-12-17 | 天津大学 | Reduced pressure rectification method for extracting bis-(2-chloroisopropyl)ether from chlorohydrin method epoxypropane liquid waste |
| CN104211583B (en) * | 2014-08-28 | 2016-08-17 | 天津大学 | A kind of rectification under vacuum method extracting double-(2-chloro isopropyl) ether from propylene oxide by chlorohydrination waste liquid |
| CN117623879A (en) * | 2023-11-15 | 2024-03-01 | 山东达民化工股份有限公司 | Preparation method of diisopropyl ether |
| CN117623879B (en) * | 2023-11-15 | 2024-05-03 | 山东达民化工股份有限公司 | Preparation method of diisopropyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1045001C (en) | 1999-09-08 |
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