CN102580628A - Device and method for simultaneously producing chloromethane and ammonia by taking ammonium chloride as raw material - Google Patents
Device and method for simultaneously producing chloromethane and ammonia by taking ammonium chloride as raw material Download PDFInfo
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- CN102580628A CN102580628A CN2012100530920A CN201210053092A CN102580628A CN 102580628 A CN102580628 A CN 102580628A CN 2012100530920 A CN2012100530920 A CN 2012100530920A CN 201210053092 A CN201210053092 A CN 201210053092A CN 102580628 A CN102580628 A CN 102580628A
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Abstract
A device and method for simultaneously producing chloromethane and ammonia by taking ammonium chloride as a raw material belong to the technical field of chemical equipment. The device is in a vertical cylinder type, an ammonium chloride inlet (1) and a reaction mixed gas outlet (7) are arranged at the top of the device, a methanol gas inlet (6) is arranged at the bottom of the device, and a cyclone separator (2), an inner barrel (3), a distribution plate (5) and a coil heat exchanger (9) are sequentially fixed from top to bottom in the device. The method is that: the whole process is continuously operated, the weight ratio of the ammonium chloride and methanol is 0.8:(1-1.1), the superficial gas velocity of the methanol steam in the inner barrel (3) is 0.01-0.05m/s, the superficial gas velocity in an annular space between a device shell (4) and the inner barrel (3) is 0.2-1m/s, the reaction temperature is 260-350 DEG C, and the weight hourly space velocities of the raw material of the ammonium chloride and the methanol are 10-50s<-1>. The device and method provided by the invention have the characteristics of high equipment integration level, simple technology, high conversion rate, synthesis of the ammonium chloride and methanol in a reactor at the same time, short technological process, small corrosion to equipment and no environment pollution.
Description
One, technical field
The invention belongs to technical field of chemical, particularly a kind of is the apparatus and method that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride.
Two, background technology
Chloromethanes is a raw material of producing methylchlorosilane, and it is the synthesizing organo-silicon polymer further.Because domestic organosilicon demand sharply increases, chloromethanes production and trade still are zooming trend.The production method of chloromethanes mainly contains methane chlorination method and methyl alcohol hydrogen chloride, and it generally all is the methyl alcohol hydrogen chloride that the method that adopts is gone up in industry at present.With soda ash byproduct ammonium chloride is raw material and methanol production high added value chloromethanes, the chlorine in the ammonium chloride molecule is introduced in the organic molecule generating chloromethanes, the ammonia that discharges the simultaneously soda ash production process that is used for capable of circulation.As far back as twentieth century beginning of the fifties, U.S. Olin Mathieson chemical company among the US2755316, has proposed the production method with ammonium chloride and methyl alcohol prepared in reaction chloromethanes and ammonia at publication US2755311.This technology is pointed out: gaseous state ammonium chloride and gaseous methanol are fed in the fixed bed that aluminium oxide catalyst is housed together react.Twentieth century eighties, Mitsubishi gas chemical company has further improved the reaction process of ammonium chloride and methyl alcohol prepared in reaction chloromethanes and ammonia.In its disclosed patent JP57130930, JP58146519 and JP58194823; Proposition directly joins the form of ammonium chloride with solid in the fixed bed or fluid bed that active carbon is a carrier impregnation Zinc compounds catalyst; Methyl alcohol is passed into bed the inside, both haptoreactions after gasification.The further research and the optimization of this technology have improved the yield and the selection of catalysts property of chloromethanes.In the above-mentioned disclosed patent, adopt fixed bed or fluidized-bed reactor, and must earlier the ammonium chloride decomposition be got in the reactor again.Although the chloromethanes yield among the part embodiment can reach than higher level; But owing to carrying out decomposition and synthesizing in two reactors of chloromethanes of ammonium chloride; If the hydrogen chloride that ammonium chloride decompose to produce can not with methyl alcohol reaction and consuming rapidly, might be in course of conveying since the fluctuation of temperature once more with the synthesizing chlorinated ammonium of ammonification and blocking pipe.In addition, the energy consumption of whole process is higher, and hydrogen chloride is also relatively more serious to the corrosion on Equipment problem.
Three, summary of the invention
The present invention is directed at present is that raw material is produced the problem that the apparatus and method of chloromethanes and ammonia exist simultaneously with ammonium chloride; Having proposed a kind of is the apparatus and method that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; The present invention intends and adopts following technical scheme to be achieved: a kind of is the device that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; It is characterized in that device is the vertical cylinder type, its top is provided with ammonium chloride import (1) and reaction mixture gas body outlet (7), and the bottom is provided with methanol gas import (6); The side is provided with heat conductive oil inlet (10) and conduction oil outlet (8); Its inside is being fixed cyclone separator (2) from top to bottom successively, inner core (3) and distribution grid (5), and distribution grid has the hole on (5); Distance between inner core (3) and the distribution grid (5) is 1/2～1 of inner core (a 3) diameter; The outer coil heat exchanger (9) that is equipped with of inner core (3), coil heat exchanger (9) is connected with heat conductive oil inlet (10) and conduction oil outlet (8) respectively, and the gas outlet of cyclone separator (2) is connected with reaction mixture gas body outlet (7).Wherein the height of device case (4) and diameter ratio are 1～4:1, and device case (4) diameter and inner core (3) diameter ratio are 2～4:1, and inner core (3) height is 1～4:1 with diameter ratio.Percent opening on the distribution grid (5) does not wait, middle part over against inner core (3), and percent opening is 1～2%, the remainder percent opening is 10～20%.Its method is: it is characterized in that whole process continued operation; Ammonium chloride is 0.8:1～1.1 with the ratio of the weight of methyl alcohol; The empty tower gas velocity of methanol steam in inner core (3) is 0.01～0.05 meter per second; Empty tower gas velocity in device case (4) and inner core (3) annular space is 0.2～1 meter per second, and reaction temperature is 260～350 ℃, and the weight space velocity of raw material ammonium chloride and methyl alcohol is 10～50 seconds
-1The present invention is like this work, and on distribution grid (5), catalyst is aluminium oxide or is the dipping Zinc compounds etc. of carrier with the active carbon with catalyst filling; Utilize temperature in coil heat exchanger (9) lifting device to reaction temperature, in the device in the ratio of ammonium chloride and the weight of methyl alcohol be the ratio of 0.8:1～1.1 from ammonium chloride import (1) and methanol gas import (6), feed chloride solid and methanol steam simultaneously; Because the percent opening on the distribution grid (5) does not wait, the empty tower gas velocity in device case (4) and inner core (3) annular space has surpassed the critical fludization velocity of solid, and material forms fluid bed; Empty tower gas velocity in the inner core (3) is less; Far below critical fludization velocity, form downward moving bed, like this; Circulation in catalyst and chloride solid material just form in device; Ammonium chloride and methyl alcohol is fully reaction under the effect of catalyst, can obtain the mist of chloromethanes and ammonia continuously, and this mist is through cyclone separator (2) and reaction mixture gas body outlet (7) discharger; Again this mist is separated, obtain chloromethanes and ammonia.The present invention has the device integration height, technology is simple, conversion ratio is high, the good and easy quiet run of selectivity and control, and operating cost is low, in a reactor, realizes the synthetic of chloromethanes and ammonia simultaneously; Equipment is simple, technological process is short, and energy consumption is low, and is little to corrosion on Equipment; Small investment; Operate airtight carrying out, no waste liquid, toxic emission, the characteristics of non-environmental-pollution.Utilize the present invention, can make low value-added ammonium chloride be converted into the chloromethanes of high added value and realize the recycling of ammonia, methanol conversion is greater than 97%, and the chloromethanes yield is greater than 94%, and the ammonia yield is greater than 91%.
Four,
Description of drawings
Fig. 1 is the structural representation of apparatus of the present invention.
Among the figure 1, ammonium chloride import 2, cyclone separator 3, inner core 4, device case 5, distribution grid 6, methanol gas import 7, reaction mixture gas body outlet 8, conduction oil outlet 9, coil heat exchanger 10, heat conductive oil inlet.
Five, the specific embodiment
Embodiment 1: a kind of is the device that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; It is the vertical cylinder type, and its top is provided with ammonium chloride import (1) and reaction mixture gas body outlet (7), and the bottom is provided with methanol gas import (6); The side is provided with heat conductive oil inlet (10) and conduction oil outlet (8); Its inside is being fixed cyclone separator (2) from top to bottom successively, inner core (3) and distribution grid (5), and the distance between inner core (3) and the distribution grid (5) is 1/2 of inner core (a 3) diameter; The outer coil heat exchanger (9) that is equipped with of inner core (3); Coil heat exchanger (9) is connected with heat conductive oil inlet (10) and conduction oil outlet (8) respectively, and the gas outlet of cyclone separator (2) is connected with reaction mixture gas body outlet (7), and wherein the height of device case (4) and diameter ratio are 1:1; Device case (4) diameter and inner core (3) diameter ratio are 4:1, and inner core (3) height is 2:1 with diameter ratio.The percent opening of distribution grid (5) does not wait, middle part over against inner core (3), and percent opening is 1%, the remainder percent opening is 10%.Its method is whole process continued operation; Ammonium chloride is 0.8:1 with the ratio of the weight of methyl alcohol; The empty tower gas velocity of methanol steam in inner core (3) is 0.01 meter per second; Empty tower gas velocity in device case (4) and inner core (3) annular space is 0.2 meter per second, and reaction temperature is 260 ℃, and the weight space velocity of raw material ammonium chloride and methyl alcohol is 10 seconds
-1The present embodiment methanol conversion is 98%, chloromethanes yield 95%, ammonia yield 92%.
Embodiment 2: a kind of is the device that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; It is the vertical cylinder type, and its top is provided with ammonium chloride import (1) and reaction mixture gas body outlet (7), and the bottom is provided with methanol gas import (6); The side is provided with heat conductive oil inlet (10) and conduction oil outlet (8); Its inside is being fixed cyclone separator (2) from top to bottom successively, inner core (3) and distribution grid (5), and the distance between inner core (3) and the distribution grid (5) is the diameter of inner core (3); The outer coil heat exchanger (9) that is equipped with of inner core (3); Coil heat exchanger (9) is connected with heat conductive oil inlet (10) and conduction oil outlet (8) respectively, and the gas outlet of cyclone separator (2) is connected with reaction mixture gas body outlet (7), and wherein the height of device case (4) and diameter ratio are 1:1; Device case (4) diameter and inner core (3) diameter ratio are 2:1, and inner core (3) height is 1:1 with diameter ratio.The percent opening of distribution grid (5) does not wait, middle part over against inner core (3), and percent opening is 2%, the remainder percent opening is 20%.Its method is whole process continued operation; Ammonium chloride is 0.8:1.1 with the ratio of the weight of methyl alcohol; The empty tower gas velocity of methanol steam in inner core (3) is 0.05 meter per second; Empty tower gas velocity in device case (4) and inner core (3) annular space is 1 meter per second, and reaction temperature is 350 ℃, and the weight space velocity of raw material ammonium chloride and methyl alcohol is 50 seconds
-1The present embodiment methanol conversion is 97%, chloromethanes yield 94%, ammonia yield 93%.
Embodiment 3: a kind of is the device that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; It is the vertical cylinder type, and its top is provided with ammonium chloride import (1) and reaction mixture gas body outlet (7), and the bottom is provided with methanol gas import (6); The side is provided with heat conductive oil inlet (10) and conduction oil outlet (8); Its inside is being fixed cyclone separator (2) from top to bottom successively, inner core (3) and distribution grid (5), and the distance between inner core (3) and the distribution grid (5) is 3/4 of inner core (a 3) diameter; The outer coil heat exchanger (9) that is equipped with of inner core (3); Coil heat exchanger (9) is connected with heat conductive oil inlet (10) and conduction oil outlet (8) respectively, and the gas outlet of cyclone separator (2) is connected with reaction mixture gas body outlet (7), and wherein the height of device case (4) and diameter ratio are 3:1; Device case (4) diameter and inner core (3) diameter ratio are 3:1, and inner core (3) height is 3:1 with diameter ratio.The percent opening of distribution grid (5) does not wait, middle part over against inner core (3), and percent opening is 1.5%, the remainder percent opening is 15%.Its method is whole process continued operation; Ammonium chloride is 0.8:1.05 with the ratio of the weight of methyl alcohol; The empty tower gas velocity of methanol steam in inner core (3) is 0.03 meter per second; Empty tower gas velocity in device case (4) and inner core (3) annular space is 0.8 meter per second, and reaction temperature is 300 ℃, and the weight space velocity of raw material ammonium chloride and methyl alcohol is 40 seconds
-1The present embodiment methanol conversion is 99%, chloromethanes yield 97%, ammonia yield 95%.
Claims (4)
1. one kind is the device that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; It is characterized in that device is the vertical cylinder type, its top is provided with ammonium chloride import (1) and reaction mixture gas body outlet (7), and the bottom is provided with methanol gas import (6); The side is provided with heat conductive oil inlet (10) and conduction oil outlet (8); Its inside is being fixed cyclone separator (2) from top to bottom successively, inner core (3) and distribution grid (5), and distribution grid has the hole on (5); Distance between inner core (3) and the distribution grid (5) is 1/2～1 of inner core (a 3) diameter; The outer coil heat exchanger (9) that is equipped with of inner core (3), coil heat exchanger (9) is connected with heat conductive oil inlet (10) and conduction oil outlet (8) respectively, and the gas outlet of cyclone separator (2) is connected with reaction mixture gas body outlet (7).
2. one kind is the method that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; It is characterized in that whole process continued operation; Ammonium chloride is 0.8:1～1.1 with the ratio of the weight of methyl alcohol, and the empty tower gas velocity of methanol steam in inner core (3) is 0.01～0.05 meter per second, and the empty tower gas velocity in device case (4) and inner core (3) annular space is 0.2～1 meter per second; Reaction temperature is 260～350 ℃, and the weight space velocity of raw material ammonium chloride and methyl alcohol is 10～50 seconds
-1
As claim a kind described a kind of be the device that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; It is characterized in that; The height of device case (4) and diameter ratio are 1～4:1; Device case (4) diameter and inner core (3) diameter ratio are 2～4:1, and inner core (3) height is 1～4:1 with diameter ratio.
As claim a kind described a kind of be device and the method for using thereof that raw material is produced chloromethanes and ammonia simultaneously with ammonium chloride; It is characterized in that the percent opening on the distribution grid (5) does not wait, middle part over against inner core (3); Percent opening is 1～2%, and the remainder percent opening is 10～20%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100530920A CN102580628A (en) | 2012-03-02 | 2012-03-02 | Device and method for simultaneously producing chloromethane and ammonia by taking ammonium chloride as raw material |
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| CN2012100530920A CN102580628A (en) | 2012-03-02 | 2012-03-02 | Device and method for simultaneously producing chloromethane and ammonia by taking ammonium chloride as raw material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738979A (en) * | 2014-01-08 | 2014-04-23 | 北京烨晶科技有限公司 | Method for joint production of liquid ammonia and methane chloride |
| CN110252213A (en) * | 2019-05-27 | 2019-09-20 | 河北科技大学 | A kind of fluidized bed reaction producing chloromethanes and ammonia |
Citations (6)
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| JPS5585531A (en) * | 1978-12-14 | 1980-06-27 | Metallgesellschaft Ag | Continuous manufacture of aliphatic alcohol |
| CN1605385A (en) * | 2004-09-17 | 2005-04-13 | 清华大学 | Annular space gas lifting type loop reactor |
| WO2005049194A1 (en) * | 2003-11-20 | 2005-06-02 | Lurgi Ag | Mehtod and reactor for continuously carrying out a chemical multiphase reaction |
| DE102004020640A1 (en) * | 2004-04-27 | 2005-11-24 | Kali-Umwelttechnik Gmbh | Loop reactor type controlled precipitation crystallization apparatus with integrated clarification zone, e.g. for forming metal hydroxides, having additional external clarifier to increase particle size |
| CN201632248U (en) * | 2010-03-08 | 2010-11-17 | 河北科技大学 | Device for preparing methyl chloride and ammonia |
| CN102019157A (en) * | 2010-10-26 | 2011-04-20 | 河北科技大学 | Method and device for preparing methyl chloride and ammonia by utilizing ammonium chloride and methyl alcohol |
-
2012
- 2012-03-02 CN CN2012100530920A patent/CN102580628A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5585531A (en) * | 1978-12-14 | 1980-06-27 | Metallgesellschaft Ag | Continuous manufacture of aliphatic alcohol |
| WO2005049194A1 (en) * | 2003-11-20 | 2005-06-02 | Lurgi Ag | Mehtod and reactor for continuously carrying out a chemical multiphase reaction |
| DE102004020640A1 (en) * | 2004-04-27 | 2005-11-24 | Kali-Umwelttechnik Gmbh | Loop reactor type controlled precipitation crystallization apparatus with integrated clarification zone, e.g. for forming metal hydroxides, having additional external clarifier to increase particle size |
| CN1605385A (en) * | 2004-09-17 | 2005-04-13 | 清华大学 | Annular space gas lifting type loop reactor |
| CN201632248U (en) * | 2010-03-08 | 2010-11-17 | 河北科技大学 | Device for preparing methyl chloride and ammonia |
| CN102019157A (en) * | 2010-10-26 | 2011-04-20 | 河北科技大学 | Method and device for preparing methyl chloride and ammonia by utilizing ammonium chloride and methyl alcohol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738979A (en) * | 2014-01-08 | 2014-04-23 | 北京烨晶科技有限公司 | Method for joint production of liquid ammonia and methane chloride |
| CN103738979B (en) * | 2014-01-08 | 2016-05-18 | 北京烨晶科技有限公司 | A kind of method of Joint Production liquefied ammonia and monochloro methane |
| CN110252213A (en) * | 2019-05-27 | 2019-09-20 | 河北科技大学 | A kind of fluidized bed reaction producing chloromethanes and ammonia |
| CN110252213B (en) * | 2019-05-27 | 2022-03-22 | 河北科技大学 | Fluidized bed reaction device for producing chloromethane and ammonia |
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Application publication date: 20120718 |