CN105367449B - Absorb the method for acrylonitrile - Google Patents
Absorb the method for acrylonitrile Download PDFInfo
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- CN105367449B CN105367449B CN201410427732.9A CN201410427732A CN105367449B CN 105367449 B CN105367449 B CN 105367449B CN 201410427732 A CN201410427732 A CN 201410427732A CN 105367449 B CN105367449 B CN 105367449B
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- absorption tower
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- acrylonitrile
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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
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Abstract
The present invention relates to the absorption process of acrylonitrile, mainly solves prior art and the problem of absorption water content consumption is big, and acrylonitrile concentration is low in absorbing liquid be present.The bottom and middle part on the first absorption tower are respectively enterd by using the raw material gaseous stream containing acrylonitrile etc. and raw material liquid phase stream, gaseous stream III is isolated in tower top, the first absorption tower absorbing liquid is produced in the first absorption tower tower reactor；The part of first absorption tower absorbing liquid is returned in the middle part of the first absorption tower as the first absorption tower circulating absorption solution through circulating cooling；Gaseous stream III enters second absorption tower bottom, absorbed in second absorption tower through poor-water, it is outer after cold recovery to ranked second absorption tower light component, second absorption tower tower bottoms is back to the technical scheme of the first absorption tower tower top, preferably solves the problem, available in ammoxidation of propylene acrylonitrile production industrial production.
Description
Technical field
The present invention relates to the method for the absorption acrylonitrile in process for production of acrylonitrile.
Background technology
Acrylonitrile is a kind of important organic chemical industry's base stock, is mainly used to produce acrylic fibers, acrylonitrile-butadiene-benzene
The chemical products such as vinyl plastics (ABS), polyacrylonitrile, acrylamide, nitrile rubber, its by-product acetonitrile are fine solvents and organic
Synthetic intermediate, Cymag can be made nearby for by-product hydrogen cyanide, or acetone cyanohydrin is made, the original as synthesizing methyl acrylic acid
Material.Process for production of acrylonitrile undergoes cyanoethanol method and acetylene method.At present, the main propylene ammoxidation method of domestic and international production method.
In the technique, unstripped gas propylene, ammonia, air are passed through fluidized-bed reactor from bottom with certain proportion and reacted, and reaction heat is used
Soft water circulation and stress, high steam occurs, gas can obtain high-purity propylene nitrile through chilling, absorption, rectifying etc. after reaction.
Acrylonitrile absorptive unit is the main processes in acrylonitrile process.Because ammoxidation of propylene reaction is an individual
Product iodine, the progress that reaction pressure is advantageous to acrylonitrile main reaction is reduced, the cured once through yield of propylene can be improved, be this
It is required that acrylonitrile absorbing tower tower has the characteristics of pressure drop is low.Meanwhile to prevent the cohesion for absorbing polymer in water from blocking up tower.Patent
CN1055917C disclose it is a kind of have that pressure drop is low, production capacity is big, while can be anti-blocking acrylonitrile absorbing tower.Document
US363607 describes the technique for reducing methacrylonitrile content in acrylonitrile product.In the technique, from acrylonitrile heavy constituent gas
Stripper tower reactor draws a part of logistics and returns to absorption tower medium position, and the methacrylonitrile that stripping tower tower reactor is enriched with is in absorption tower
Part vaporizes, and is vented from absorption tower tower top, so as to reduce the content of methacrylonitrile in acrylonitrile product.Document US363608 is situated between
The technique of methacrylonitrile content in another reduction acrylonitrile product that continued.Document CN1153760C discloses a kind of acrylonitrile
Production technology, its improvements are that absorption tower provides the second absorption water using nozzle.
In existing literature or report, the absorption technique problem of shorter mention acrylonitrile, particularly in absorption tail gas is ensured
On the premise of content containing cyanogen compound is up to standard, how to improve absorbing liquid acrylonitrile concentration, reduce the problem of absorbing water.
The content of the invention
The technical problems to be solved by the invention be exist in previous literature acrylonitrile concentration in absorbing liquid it is low, absorb water
A kind of big topic, there is provided new absorption process containing acrylonitrile.Before content containing cyanogen compound in ensureing absorption tail gas is up to standard
Put, this method has the advantages of acrylonitrile concentration in absorbing liquid is high, to absorb water small.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：The method of acrylonitrile is absorbed, including it is as follows
Step：
Raw material gaseous stream and raw material liquid phase stream containing acrylonitrile, acetonitrile, hydrogen cyanide and water respectively enter the first absorption
The bottom and middle part of tower, the gaseous stream III containing acrylonitrile, acetonitrile, hydrogen cyanide and water is isolated in tower top, on the first absorption tower
Tower reactor produces the first absorption tower absorbing liquid containing acrylonitrile, acetonitrile, hydrogen cyanide and water；The part conduct of first absorption tower absorbing liquid
First absorption tower circulating absorption solution is returned in the middle part of the first absorption tower through circulating cooling；Gaseous stream III enters second absorption tower bottom
Portion, absorbed in second absorption tower through poor-water, outer after cold recovery to ranked second absorption tower light component, second absorption tower tower bottoms returns
It is back to the first absorption tower tower top.
In above-mentioned technical proposal, the operation temperature on the first absorption tower is preferably 3.0~40.0 DEG C.
In above-mentioned technical proposal, the operating pressure preferred scope on the first absorption tower is 0.02~0.05MPa.
In above-mentioned technical proposal, the theoretical cam curve on the first absorption tower is preferably 5~30.Raw material liquid phase at first absorption tower
Logistics feed entrance point is preferably at 2~28 theoretical trays.
In above-mentioned technical proposal, the operation temperature preferred scope of second absorption tower is 2.0~30.0 DEG C.
In above-mentioned technical proposal, the operating pressure preferred scope of second absorption tower is 0.01~0.04MPa.
In above-mentioned technical proposal, the theoretical cam curve preferred scope of second absorption tower is preferably 7~35.
In above-mentioned technical proposal, the first absorption tower preferably is selected from packed tower, plate column or void tower；More preferably use filler
Tower.
In above-mentioned technical proposal, second absorption tower preferably is selected from packed tower, plate column or void tower；More preferably use filler
Tower.
In above-mentioned technical proposal, the first absorption tower absorbing liquid circulation and extraction ratio preferably 0.1~1.0.
In above-mentioned technical proposal, the weight ratio of raw material gaseous stream of the poor-water with entering the first absorption tower is preferably
1.5~3.0.
In above-mentioned technical proposal, the circulating cooling temperature preferred scope of the first absorption tower circulating absorption solution is 3.0~20.0
℃.The feed entrance point preferred scope of first absorption tower circulating absorption solution is at 2~28 theoretical trays.
Pressure in the present patent application file refers both to gauge pressure.
Due to absorbing the propylene in composite absorption liquid circulation technology absorption acrylonitrile quenching gas using double tower in the present invention
Nitrile, acetonitrile, hydrogen cyanide, on the premise of content containing cyanogen compound in ensureing absorption tail gas is up to standard, poor-water (absorption water) is measured
Reduce, acrylonitrile concentration is improved in absorbing liquid, so that the energy consumption of the follow-up separation and purification of absorbing liquid decreases.Through examination
Verify it is bright use technical scheme, liquid vapour weight ratio is reduced to 1.83, and absorbing liquid acrylonitrile concentration is improved to 6.41%
Wt, achieve preferable technique effect.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the absorption process of the invention containing acrylonitrile.
Fig. 2 is industrial acrylonitrile absorbing tower schematic diagram.
In Fig. 1,1 is the raw material gaseous stream from aftercooler, and 2 be the raw material liquid phase stream from aftercooler, and 3 are
The gaseous stream III on the first absorption tower, 4 feed for the tower top on the first absorption tower, and 5 be the first absorption tower of the first absorption tower extraction
Absorbing liquid, 6 be the tower bottoms of second absorption tower, and 7 be second absorption tower poor-water, and 8 be the second absorption tower light component of outer row, and 9 are
Circulating absorption solution, 1a are the first absorption tower, and 2a is that second absorption tower tower reactor produces pump, and 3a is second absorption tower, and 4a is the first suction
Tower tower reactor extraction pump is received, 5a is circulating absorption solution cooler.
In Fig. 2,1 is the gaseous stream from aftercooler, and 2 be the liquid phase stream from aftercooler, and 7 be that absorption tower is inhaled
Water (poor-water) is received, 8 be outer exhaust phase light component, and 1a is absorption tower.
In ammoxidation of propylene acrylonitrile production production technology, except the gas after ammonia chilling is divided into gas phase after aftercooler cools down
With two strands of feed streams of liquid phase, in gas phase in addition to containing acrylonitrile, acetonitrile, hydrogen cyanide and a small amount of organic matter, also containing big
The light component such as the carbon dioxide of amount, nitrogen, water vapour, temperature are generally 20~45 DEG C, into the first absorption tower of the present invention
Bottom, the liquid phase aqueous solution, contain with gas phase it is mutually synthermal, be cooled to 10 DEG C or so enter the first absorption tower middle parts.From rear
(its temperature is generally 2~7 to the poor-water (most of is water, contains a small amount of organic impurities) of continuous refined unit after the temperature adjustment that exchanges heat
DEG C), enter second absorption tower tower top as water is absorbed, with the absorption tail gas counter current contacting of rising in second absorption tower, absorb
Row subsequent treatment is discharged into outside tail gas (main component is carbon dioxide, nitrogen, water vapour etc.) afterwards, second absorption tower absorbs
Acrylonitrile, acetonitrile, the organic aqueous solution such as hydrogen propylhomoserin be pumped up to the top on the first absorption tower, in the first absorption tower with it is upper
The gas phase counter current contacting risen, gaseous stream after absorption enter the bottom of second absorption tower, the first absorption tower absorb third
The absorbing liquid such as alkene nitrile, acetonitrile, hydrogen propylhomoserin (rich water), in addition to part circulating cooling is returned in the middle part of the first absorption tower, after remaining entrance
Continuous refined unit.
Below by embodiment, the present invention is further elaborated.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, the present invention is further with detail below
Embodiment illustrates, but the present invention is limited to absolutely not these examples.
【Embodiment 1】
By Fig. 1 schematic flow sheet, gas phase and liquid phase two streams from aftercooler, the first absorption tower is respectively enterd
Bottom and middle part, poor-water enter the top of second absorption tower.Gas phase each group shunt volume is：5986.5 kgs/hr of acrylonitrile, second
165.1 kgs/hr of nitrile, 594.7 kgs/hr of hydrogen cyanide, 1401.6 kgs/hr of water, 15.4 kgs/hr of methacrylaldehyde,
360.9 kgs/hr of carbon monoxide, 1214.5 kgs/hr of carbon dioxide, 705.1 kgs/hr of oxygen, nitrogen 32477.7
Kg/hr, 103.3 kgs/hr of propane, 248.9 kgs/hr of propylene.Liquid phase each group shunt volume is：Acrylonitrile 422.7
Kg/hr, 42.4 kgs/hr of acetonitrile, 46.4 kgs/hr of hydrogen cyanide, 12275.5 kgs/hr of water, methacrylaldehyde 1.6
Kg/hr.Poor-water is 79250.6 kgs/hr, and circulating absorption solution is 42882.0 kgs/hr.First absorption tower tower top
Gas phase flow rate be 35316.9 kgs/hr, wherein acrylonitrile, acetonitrile, hydrogen cyanide flow respectively for 8.4 kgs/hr, 0.0004
Kg/hr, 36.9 kgs/hr, into second absorption tower bottom.The tower top temperature on the first absorption tower is 5.0 DEG C, and pressure is
0.029MPa, bottom temperature are 25.7 DEG C, and feed entrance point is at middle part.
The tower top temperature of second absorption tower is 4.6 DEG C, pressure 0.014MPa, and bottom temperature is 4.7 DEG C.After absorption,
Tower top absorbs to be arranged outside tail gas, and flow is 35283.4 kgs/hr, wherein being containing acrylonitrile, acetonitrile, the total concentration of hydrogen cyanide
0.85ppm.Second absorption tower tower reactor flow quantity is at the top of 79284.1 kgs/hr of absorption towers of entrance first.
Poor-water is 1.83 with the raw material gaseous stream weight ratio for entering the first absorption tower, and absorbing liquid acrylonitrile concentration is
6.41%wt.
【Embodiment 2】
With embodiment 1, only change absorption pressure, second absorption tower pressure is 0.034MPa, the other the same as in Example 1.First
Absorbing tower top gas phase flow rate be 35264.0 kgs/hr, wherein acrylonitrile, acetonitrile, hydrogen cyanide flow respectively for 3.0 kilograms/it is small
When, 0.0001 kg/hr, 12.1 kgs/hr, into second absorption tower bottom.The tower top temperature on the first absorption tower is 4.9
DEG C, pressure 0.049MPa, bottom temperature is 25.8 DEG C, and feed entrance point is at middle part.
The tower top temperature of second absorption tower is 4.7 DEG C, pressure 0.034MPa, and bottom temperature is 4.6 DEG C.After absorption,
Tower top absorbs to be arranged outside tail gas, and flow is 35255.6 kgs/hr, wherein being containing acrylonitrile, acetonitrile, the total concentration of hydrogen cyanide
0.3ppm.Second absorption tower tower reactor flow quantity is at the top of 79259.0 kgs/hr of absorption towers of entrance first.
Poor-water is 1.83 with the raw material gaseous stream weight ratio for entering the first absorption tower, and absorbing liquid acrylonitrile concentration is
6.41%wt.
【Embodiment 3】
With embodiment 1, only change liquid-gas ratio, poor-water is 89250.6 kgs/hr.The other the same as in Example 1.First absorbs
Column overhead gas phase flow rate be 35288.8 kgs/hr, wherein acrylonitrile, acetonitrile, hydrogen cyanide flow respectively for 3.8 kgs/hr,
0.0002 kg/hr, 15.1 kgs/hr, into second absorption tower bottom.The tower top temperature on the first absorption tower is 4.8 DEG C,
Pressure is 0.029MPa, and bottom temperature is 23.9 DEG C, and feed entrance point is at middle part.
The tower top temperature of second absorption tower is 4.7 DEG C, pressure 0.014MPa, and bottom temperature is 4.6 DEG C.After absorption,
Tower top absorbs to be arranged outside tail gas, and flow is 35282.6 kgs/hr, wherein being containing acrylonitrile, acetonitrile, the total concentration of hydrogen cyanide
0.4ppm.Second absorption tower tower reactor flow quantity is at the top of 89256.7 kgs/hr of absorption towers of entrance first.
Poor-water is 2.06 with the raw material gaseous stream weight ratio for entering the first absorption tower, and absorbing liquid acrylonitrile concentration is
5.82%wt.
【Comparative example】
By Fig. 2 schematic flow sheet, gas phase and liquid phase two streams from aftercooler, the bottom on absorption tower is respectively enterd
And middle and lower part, poor-water enter the top on absorption tower.Gas phase each group shunt volume is：5986.5 kgs/hr of acrylonitrile, acetonitrile
165.1 kgs/hr, 594.7 kgs/hr of hydrogen cyanide, 1401.6 kgs/hr of water, 15.4 kgs/hr of methacrylaldehyde, one
360.9 kgs/hr of carbonoxide, 1214.5 kgs/hr of carbon dioxide, 705.1 kgs/hr of oxygen, nitrogen 32477.7 thousand
Grams Per Hour, 103.3 kgs/hr of propane, 248.9 kgs/hr of propylene.Liquid phase each group shunt volume is：Acrylonitrile 422.7 thousand
Grams Per Hour, 42.4 kgs/hr of acetonitrile, 46.4 kgs/hr of hydrogen cyanide, 12275.5 kgs/hr of water, methacrylaldehyde 1.6 thousand
Grams Per Hour.Poor-water is 79250.6 kgs/hr.
The tower top temperature on absorption tower is 4.6 DEG C, pressure 0.014MPa, and bottom temperature is 27.5 DEG C.After absorption, tower top
Absorb and arranged outside tail gas, flow is 35283.6 kgs/hr, wherein adding up to concentration to be 0.9ppm containing acrylonitrile, acetonitrile, hydrogen cyanide.
Poor-water is 2.29 with the raw material gaseous stream weight ratio for entering the first absorption tower, and absorbing liquid acrylonitrile concentration is
5.34%wt.
Claims (9)
1. absorbing the method for acrylonitrile, comprise the following steps：
Raw material gaseous stream (1) and raw material liquid phase stream (2) containing acrylonitrile, acetonitrile, hydrogen cyanide and water respectively enter the first suction
The bottom and middle part of tower (1a) are received, the gaseous stream III (3) containing acrylonitrile, acetonitrile, hydrogen cyanide and water is isolated in tower top,
First first absorption tower absorbing liquid (5) of the absorption tower tower reactor extraction containing acrylonitrile, acetonitrile, hydrogen cyanide and water；Inhale on the first absorption tower
The part for receiving liquid (5) is returned in the middle part of the first absorption tower as the first absorption tower circulating absorption solution (9) through circulating cooling；Gaseous stream
III (3) enters second absorption tower (3a) bottom, is absorbed in second absorption tower through poor-water (7), outer after cold recovery to ranked second suction
Tower light component (8) is received, second absorption tower (3a) tower bottoms (6) is back to the first absorption tower tower top, and the poor-water absorbs from second
The tower top input of tower；With extraction than being 0.1~1.0, the poor-water absorbs with entering first for the circulation of first absorption tower absorbing liquid
The weight ratio of the raw material gaseous stream of tower is 1.5~3.0.
2. according to the method for claim 1, it is characterised in that the operation temperature on the first absorption tower is 3.0~40.0 DEG C.
3. according to the method for claim 2, it is characterised in that the operating pressure on the first absorption tower is 0.02~0.05MPa.
4. according to the method for claim 2, it is characterised in that the theoretical cam curve on the first absorption tower is 5~30.
5. according to the method for claim 1, it is characterised in that the operation temperature of second absorption tower is 2.0~30.0 DEG C.
6. according to the method for claim 5, it is characterised in that the operating pressure of second absorption tower is 0.01~0.04MPa.
7. according to the method for claim 5, it is characterised in that the theoretical cam curve of second absorption tower is 7~35.
8. according to the method for claim 1, it is characterised in that the circulating cooling temperature of the first absorption tower circulating absorption solution is
3.0~20.0 DEG C.
9. according to the method for claim 1, it is characterised in that the feed entrance point of the first absorption tower circulating absorption solution is 2~28
At theoretical tray.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410427732.9A CN105367449B (en) | 2014-08-27 | 2014-08-27 | Absorb the method for acrylonitrile |
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| CN201410427732.9A CN105367449B (en) | 2014-08-27 | 2014-08-27 | Absorb the method for acrylonitrile |
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| CN105367449A CN105367449A (en) | 2016-03-02 |
| CN105367449B true CN105367449B (en) | 2018-01-09 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112441943A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Method for controlling PH in water circulation system in operation process of acrylonitrile device |
| CN112439296A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Low-temperature circulation process for bottom of absorption tower of acrylonitrile device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3885928A (en) * | 1973-06-18 | 1975-05-27 | Standard Oil Co Ohio | Acrylonitrile and methacrylonitrile recovery and purification system |
| CN1035661A (en) * | 1988-03-10 | 1989-09-20 | 中国石油化工总公司 | The novel method that vinyl cyanide and acetonitrile reclaim |
| CN1167757A (en) * | 1996-06-06 | 1997-12-17 | 标准石油公司 | Improved acrylonitrile recovery process |
| CN1201784A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Acrylonitrile absorbing tower |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172246A (en) * | 1999-12-14 | 2001-06-26 | Mitsubishi Chemicals Corp | Method for producing acrylonitrile |
| JP5246869B2 (en) * | 2009-03-24 | 2013-07-24 | 旭化成ケミカルズ株式会社 | Purification method of acrylonitrile |
-
2014
- 2014-08-27 CN CN201410427732.9A patent/CN105367449B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3885928A (en) * | 1973-06-18 | 1975-05-27 | Standard Oil Co Ohio | Acrylonitrile and methacrylonitrile recovery and purification system |
| CN1035661A (en) * | 1988-03-10 | 1989-09-20 | 中国石油化工总公司 | The novel method that vinyl cyanide and acetonitrile reclaim |
| CN1167757A (en) * | 1996-06-06 | 1997-12-17 | 标准石油公司 | Improved acrylonitrile recovery process |
| CN1201784A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Acrylonitrile absorbing tower |
Non-Patent Citations (2)
| Title |
|---|
| 丙烯腈装置吸收塔增产改造方案研究;肖珍平;《化工设计》;20030228;第13卷(第1期);第3-7页 * |
| 丙烯腈装置扩能改造研究;于飞 等;《当代化工》;20051030;第34卷(第5期);第345-349页 * |
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