CN109942366A - A kind of devices and methods therefor reacting production chloromethanes with methanol using hydrogen chloride and ammonium chloride - Google Patents
A kind of devices and methods therefor reacting production chloromethanes with methanol using hydrogen chloride and ammonium chloride Download PDFInfo
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Abstract
The present invention provides a kind of to react the devices and methods therefor for producing chloromethanes using hydrogen chloride and ammonium chloride with methanol, apparatus of the present invention include fluidized-bed reactor, spray column, bag filter, cooler, dehydrating tower, compressor, deammoniation tower, chloromethanes treating column, scrubbing tower, chloromethanes compressor, chloromethanes storage tank etc., reacting for hydrogen chloride and methanol is introduced on the basis of ammonium chloride reacts with methanol synthesis chloromethanes using apparatus of the present invention, to supplement heat required for ammonium chloride decomposes, reduce its demand for externally adding to heat.The present invention has recycled chlorine element and ammonia in ammonium chloride, while having handled the hydrogen chloride of chlorination work byproduct in process, not only improves the comprehensive utilization of ammonium chloride, hydrogen chloride, and advantageously reduces energy consumption, has broad application prospects.
Description
Technical field
The invention belongs to chemical technology fields, are related to a kind of react using hydrogen chloride and ammonium chloride with methanol and produce chloromethane
The devices and methods therefor of alkane, the method for specially preparing chloromethanes and ammonia using hydrogen chloride, ammonium chloride and methanol gas solid method.
Background technique
Join alkali industry and other chemical production process side product sodium chlorides, due to containing chlorine element in ammonium chloride, is used for chemical fertilizer
When will cause agricultural product quality decline, soil hardening etc., limited using by more, and ammonium chloride industry, medicine etc. row
The dosage of industry is extremely limited, and superfluous ammonium chloride processing limits the development of soda industry, the comprehensive utilization new way of ammonium chloride
Exploitation it is particularly significant.By reacting for methanol and ammonium chloride, chloromethanes not only can be obtained, but also ammonia therein can be recycled.Chloromethanes
The important source material of synthesizing methyl-chloro-silane, methylcellulose, quaternary ammonium salt etc., pesticide, synthetic resin, in terms of answer
With extensive.Ammonia is important industrial chemicals, can both recycle in connection alkali industry, and can be used for other industry.Therefore, chlorine
Change ammonium and methanol-fueled CLC chloromethanes technique, not only can solve a large amount of residue problems of ammonium chloride, but also synthesis has high added value
Chloromethanes, realize the recycling of chlorine and the recycling of ammonia.
Twentieth century beginning of the fifties, Olin Mathieson chemical company, the U.S. propose with ammonium chloride and methanol reaction
The method (US2755311, US2755316, US3315441) of chloromethanes and ammonia is prepared, and proposes two class reaction process: one,
Gaseous state ammonium chloride and methanol steam are passed through in the fixed bed equipped with catalyst and reacted, catalyst is alumina particle, removes chloromethane
There are also a small amount of methylamine and dimethyl ether by-products outside alkane, and by-product circulation can be reacted again and be converted into chloromethanes；Two, will consolidate
Body ammonium chloride is mixed with molten state catalyst, then, is then reacted with methanol, is separated catalyst after the reaction was completed and is being recycled, urges
Agent is stannous chloride.But the gasification of solid ammonium chloride needs more energy, by one mole of ammonium chloride gas at 350 DEG C
Change needs 166kJ heat, and ammonium chloride itself thermal conductivity is bad, and rear surface of being heated is shunk, and is easy agglomeration, direct gasification
It acquires a certain degree of difficulty.
Chinese patent CN201010153240.7 discloses a kind of method for preparing chloromethanes with ammonium chloride.First by chlorination
Enter multi-tubular fixed-bed reactor with methanol steam after ammonium gasification decomposition, after the reaction was completed through adding water to remove mixing except acid tower
Impurity in gas, tower top obtain methyl chloride gas, but still there are also part ammonia, methanol and dimethyl ether in methyl chloride gas.China
Patent CN201110388852.9 disclose it is a kind of by the decomposition of ammonium chloride and methanol and ammonium chloride react be coupled in one it is anti-
Answer the method in device.Fluidized-bed reactor will be entered from bottom after methyl alcohol vaporizing, ammonium chloride powder enters fluidisation through mechanical transmission
Bed lower part, the gas after reaction pass through separating-purifying, obtain chloromethanes and ammonia.Heat needed for being decomposed due to ammonium chloride is chlorine
Exothermic four times of methane synthetic reaction, in 350 DEG C or more more difficult, the in addition separation processes to reactor offer heat
It not can be removed dimethyl ether, lead to the decline of product purity.Chinese patent CN201410008694.3 discloses one kind with chlorination
The method that ammonium prepares chloromethanes.Will ammonium chloride and concentrated phosphoric acid mix after be pumped into tubular reactor, reaction obtain diammonium hydrogen phosphate and
Hydrogen chloride gas, obtained in hydrogen chloride gas for synthesizing chloromethanes, obtained after diammonium hydrogen phosphate heat resolve ammonia and
The mixture of phosphoric acid and metaphosphoric acid；Phosphoric acid and metaphosphoric acid are recycled, and obtain liquefied ammonia after ammonia pressure Suo Lengning.It is closed from chloromethanes
The gas come out at reactor obtains pure chloromethanes after pickling, alkali cleaning, drying.But it is acid or alkaline in continuous contact
Under conditions of solution, chloromethanes meeting partial hydrolysis reduces yield.
Summary of the invention
The present invention is to solve the problems of the prior art, provides and a kind of reacts life with methanol using hydrogen chloride and ammonium chloride
The devices and methods therefor of chloromethanes is produced, to solve in reactor to heat problem and product purity temperature problem.
The technical solution adopted by the invention is as follows:
The device of the invention is a kind of device for reacting production chloromethanes with methanol using hydrogen chloride and ammonium chloride, including
Sequentially connected fluidized-bed reactor, spray column, bag filter, cooler, dehydrating tower, compressor, deammoniation tower, chloromethanes
Treating column, throttle valve, scrubbing tower, chloromethanes compressor, chloromethanes storage tank；The top of the fluidized-bed reactor connects chlorination
The methanol preheater and hydrogen chloride preheater that ammonium pipeline, the lower part of fluidized-bed reactor or side lower part are connected with and connect through pipeline,
The other end of the methanol preheater and hydrogen chloride preheater is connected separately with methanol pipeline and hydrogen chloride pipeline；The fluidisation
The middle and lower part of the upper lateral part connection spray column of bed reactor, the lower part of spray column is equipped with spray column discharge valve and pipeline, spray column
Upper lateral part be equipped with spray water inlet, the side middle and upper part of the top of spray column by pipeline connection bag filter, the pocket type
The gas vent of filter top side connects cooler, the middle side part of the other end connection rectifying and dewatering tower of cooler, rectifying
Middle side part of the top of dehydrating tower through compressor connection deammoniation tower, the top of deammoniation tower are equipped with ammonia outlet conduit, the bottom of deammoniation tower
Portion connects the middle side part of chloromethanes treating column, and the top of chloromethanes treating column is connected through pipeline with throttle valve under the side of scrubbing tower
Portion, the top that the upper lateral part of scrubbing tower is equipped with scrubbing tower charging methanol inlet scrubbing tower connect chloromethanes pressure through chloromethanes pipeline
The other end of contracting machine, chloromethanes compressor connects chloromethanes storage tank；
The lower part of the bag filter is equipped with powder recovery bin；
The lower section of the rectifying and dewatering tower is equipped with dehydrating tower kettle liquid dump valve and pipeline；
The lower section of the chloromethanes treating column connects rework solution pipeline with pressure reducing valve through pipeline；
The lower section of the scrubbing tower connects rework solution pipeline with liquid phase dump valve through pipeline；
The lower section of the scrubbing tower connects circulating cleaning solution pipeline, circulation washing with circulating cleaning solution control valve through pipeline
Liquid pipe road is connected to scrubbing tower methanol feed entrance together with fresh methanol rinses liquid pipe road.
Preferably, the other end of the rework solution pipeline is connected in methanol pipeline.
The method that a kind of hydrogen chloride of the present invention and ammonium chloride react production chloromethanes with methanol, above-mentioned apparatus, feature exist
In, comprising the following steps:
A. methanol feedstock enters methanol preheater through methanol pipeline and is heated and vaporized, and hydrogen chloride gas is through hydrogen chloride
Pipeline enters the preheating of hydrogen chloride preheater, and the methanol gas after preheating is mixed with hydrogen chloride gas flows automatically as mixed raw material gas
Fluidized bed reactor bottom or side lower part enter through gas distributor to be preheated in the fluidized-bed reactor of operation temperature, convection current
Catalyst powder in fluidized bed reactor in fluidized bed is fluidized；Ammonium chloride powder is through ammonium chloride pipeline from fluidized-bed reaction
The top of device is added, into fluidized bed after decompose reaction；
The molar feed ratio of the ammonium chloride, hydrogen chloride and methanol is 3.5~0.5:1.5~4.5:5.02~5.1；
The catalyst is the alumina powder of carried metal active component or the work of carried metal active component
Property charcoal powder；
The catalytic bed temperature of the fluidized-bed reactor be 280 DEG C~400 DEG C, operating pressure be 0.03MPa~
0.5MPa, reaction gas empty tower gas velocity are 0.2m/s~0.8m/s；
B. in a fluidized bed reactor, the hydrogen chloride in the mixed raw material gas, methanol and come from rework solution pipeline
Methylamine substance, dimethyl ether and methanol and ammonium chloride in fluidized state catalyst action under react, generation contains
There is the gaseous reaction product of chloromethanes, ammonia and by-product；The by-product is methylamine substance and dimethyl ether；
C. the gaseous reaction product that gravity flow fluidized bed reactor upper lateral part comes out then enters spray from the middle and lower part of spray column
Tower, washing water enters through the upper lateral part of spray water inlet self-spray leaching tower, with spraying form and fluidized-bed reaction from bottom to top
The gaseous reaction product that device comes is contacted；Gaseous reaction product is after spray column spraying cooling, unreacted ammonium chloride
Gas is condensed into solid particle, is deposited on spray tower bottom with the catalyst granules taken out of with gaseous reaction product, passes through
Spray column discharge valve periodic cleaning；
D. from spray top of tower come out gas subsequently enter bag filter, be further separated out catalyst powder and
Ammonium chloride particle, catalyst powder and ammonium chloride particle enter the powder recycling can of lower section；
E. cool down from the gas that bag filter lateral roof comes out through cooler, subsequently into rectifying and dewatering tower；Essence
It evaporates the reaction of dehydration tower bottom out and generates water through the discharge of dehydrating tower kettle liquid dump valve, a part is made to be the spray of spray column
With water, remaining enters sewage treatment process for production waste water；The gaseous reaction product that rectifying and dewatering column overhead comes out enters compression
Machine is pressurized to 0.8~2.5MPa；
F. enter deammoniation tower after being cooled to 30 DEG C~50 DEG C from the gas-pressurized that compressor comes out, by rectifying, ammonia is by tower
It is ejected, enters liquid ammonia storage tank through ammonia outlet conduit after cooling；Product liquid after deamination is flowed out by deammoniation tower tower bottom；
G. enter chloromethanes treating column from product liquid after the deamination that deamination tower bottom comes out, by rectifying, tower bottom is obtained
Liquid be the mixture containing methylamine, dimethyl ether and methanol, can be used as a part of rework solution after pressure reducing valve, by returning
Back liquid pipeline, methanol pipeline and methanol preheater return to fluidized-bed reactor；Chloromethanes refined tower top is obtained containing dimethyl ether
Methyl chloride gas；
H. the methyl chloride gas containing dimethyl ether that chloromethanes refined tower top comes out enters scrubbing tower after throttle valve depressurizes
Bottom, methanol by scrubbing tower charging methanol inlet enter scrubbing tower, in a manner of spray with the methyl chloride gas containing dimethyl ether
Gas-liquid contact；Pure methyl chloride gas is obtained after washing removal dimethyl ether, and is come out from the top of scrubbing tower, into compressor
Enter chloromethanes storage tank after pressurized liquefied；The methanol solution containing dimethyl ether after washing, according to discharge liquor and circulating cleaning solution matter
Amount is than being that 1:10~100 are allocated, and wherein discharge liquor passes through return as a part of rework solution after liquid phase dump valve
Liquid pipe road, methanol pipeline and methanol preheater return to fluidized-bed reactor；The fresh methanol rinses of circulating cleaning solution and supplement
Enter scrubbing tower as cleaning solution by scrubbing tower charging methanol inlet after liquid mixing to be recycled, the fresh first of the supplement
The amount of alcohol cleaning solution is equal with the amount of scrubbing tower discharge liquor.
Preferably, in step a, the mixed raw material temperature degree after methanol preheater and the heating of hydrogen chloride preheater is
180℃-250℃。
Preferably, the granularity of the alumina catalyst powder is 80 μm~200 μm, catalyst activity charcoal powder grain
Degree is 200 μm~400 μm.
Preferably, the gas temperature that the spray column comes out is 120 DEG C~200 DEG C, through cooler gas after cooling
Temperature is 40 DEG C~65 DEG C.
Preferably, the rectifying and dewatering tower be atmospheric distillation tower, 60 DEG C~120 DEG C of operation temperature.
Preferably, the deammoniation tower is compression rectification tower, and operation temperature is -10 DEG C~60 DEG C, and operating pressure is
0.8MPa~2.5MPa.
Preferably, the chloromethanes treating column is compression rectification tower, and operation temperature is 40 DEG C~120 DEG C, operating pressure
For 0.8-2.5MPa.
Preferably, the scrubbing tower be absorption tower, 10~40 DEG C of operation temperature, liquid-gas ratio 10L/m3~20L/m3。
Compared with prior art, the present invention having the effect of following prominent and advantage:
(1) by the introducing of hydrogen chloride, required heat is decomposed to supply ammonium chloride with the reaction heat of hydrogen chloride and methanol
Reduce additional heat exchange, energy consumption reduces；
(2) heat exchange amount needed for reduces, equipment manufacture simplification；
(3) hydrogen chloride is re-used, is turned waste into wealth；
(4) using the dimethyl ether in methanol washing removal chloromethanes, product purity is improved；
The present invention has the characteristics that low energy consumption, equipment simple processing, can make low value-added ammonium chloride and hydrogen chloride gas
It is converted into the chloromethanes product of high added value and realizes the recycling of ammonia, have broad application prospects.
Detailed description of the invention
Fig. 1 is schematic structural diagram of the device of the invention.
Specific embodiment
Below by the drawings and specific embodiments, the present invention is described in further detail.
Referring to Fig. 1.
Each label in figure are as follows:
1, ammonium chloride pipeline；2, methanol pipeline；3, hydrogen chloride pipeline；4, methanol preheater；5, hydrogen chloride preheater；6,
Fluidized-bed reactor；7, spray column discharge valve；8, scrubbing tower feeds methanol inlet；9, spray column；10, water inlet is sprayed；11,
Bag filter；12, cooler；13, rectifying and dewatering tower；14, dehydrating tower kettle liquid dump valve；15, compressor；16, ammonia outlet
Road；17, deammoniation tower；18, chloromethanes pipeline；19, chloromethanes treating column；20, pressure reducing valve；21, scrubbing tower；22, throttle valve；23,
Liquid phase dump valve；24, chloromethanes compressor；25, chloromethanes storage tank；26, powder recovery bin；27, rework solution pipeline；28, it recycles
Wash hydraulic control valve；29, fresh methanol rinses liquid pipe road；30, circulating cleaning solution pipeline.
The device of the invention is a kind of device for reacting production chloromethanes with methanol using hydrogen chloride and ammonium chloride, including
Sequentially connected fluidized-bed reactor 6, spray column 9, bag filter 11, cooler 12, dehydrating tower 13, compressor 15, deamination
Tower 17, chloromethanes treating column 19, throttle valve 22, scrubbing tower 21, chloromethanes compressor 24, chloromethanes storage tank 25；The fluidized bed
The top of reactor 6 connects ammonium chloride pipeline 1, the first that the lower part of fluidized-bed reactor 6 or side lower part are connected with and connect through pipeline
The other end of alcohol preheater 4 and hydrogen chloride preheater 5, the methanol preheater 4 and hydrogen chloride preheater 5 is connected separately with first
Alcohol pipeline 2 and hydrogen chloride pipeline 3；The middle and lower part of the upper lateral part connection spray column 9 of the fluidized-bed reactor 6, spray column 9
Lower part is equipped with spray column discharge valve 7 and pipeline, and the upper lateral part of spray column 9 is equipped with spray water inlet 10, and the top of spray column 9 is logical
Piping connects the side middle and upper part of bag filter 11, and the gas vent of the 11 top side of bag filter connects cooling
Device 12, the middle side part of the other end connection rectifying and dewatering tower 13 of cooler 12, the top of rectifying and dewatering tower 13 connects through compressor 15
The middle side part of deammoniation tower 17 is connect, the top of deammoniation tower 17 is equipped with ammonia outlet conduit 16, the bottom connection chloromethanes essence of deammoniation tower 17
The middle side part of tower 19 processed, the top of chloromethanes treating column 19 connect the side lower part of scrubbing tower 21 through pipeline and throttle valve 22, washing
The upper lateral part of tower 21 is equipped with scrubbing tower and feeds methanol inlet 8, and the top of scrubbing tower 21 connects chloromethanes through chloromethanes pipeline 18
The other end of compressor 24, chloromethanes compressor 24 connects chloromethanes storage tank 25；
The lower part of the bag filter 11 is equipped with powder recovery bin 26；
The lower section of the rectifying and dewatering tower 13 is equipped with dehydrating tower kettle liquid dump valve 14 and pipeline；
The lower section of the chloromethanes treating column 19 connects rework solution pipeline 27 through pipeline and pressure reducing valve 20；
The lower section of the scrubbing tower 21 connects rework solution pipeline 27 through pipeline and liquid phase dump valve 23；
The lower section of the scrubbing tower 21 connects circulating cleaning solution pipeline 30 through pipeline and circulating cleaning solution control valve 28, follows
Ring washing liquid lines 30 and fresh methanol rinses liquid pipe road 29 are connected to scrubbing tower methanol feed entrance 8 together.
Preferably, the other end of the rework solution pipeline 27 is connected in methanol pipeline 2.
The method that a kind of hydrogen chloride of the present invention and ammonium chloride react production chloromethanes with methanol, above-mentioned apparatus, feature exist
In, comprising the following steps:
A. methanol feedstock is heated and is vaporized into methanol preheater 4 through methanol pipeline 2, and hydrogen chloride gas is through chlorination
Hydrogen pipeline 3 enters hydrogen chloride preheater 5 and preheats, and the methanol gas after preheating is mixed with hydrogen chloride gas as mixed raw material gas
Gravity flow 6 bottom of fluidized bed reactor or side lower part enter the fluidized-bed reactor 6 for being preheated to operation temperature through gas distributor
In, the catalyst powder in fluid bedreactors 6 in fluidized bed is fluidized；Ammonium chloride powder is through ammonium chloride pipeline 1 from stream
The top of fluidized bed reactor 6 is added, into fluidized bed after decompose reaction；
The molar feed ratio of the ammonium chloride, hydrogen chloride and methanol is 3.5~0.5:1.5~4.5:5.02~5.1；
The catalyst is the alumina powder of carried metal active component or the work of carried metal active component
Property charcoal powder；
The catalytic bed temperature of the fluidized-bed reactor 6 be 280 DEG C~400 DEG C, operating pressure be 0.03MPa~
0.5MPa, reaction gas empty tower gas velocity are 0.2m/s~0.8m/s；
B. in fluidized-bed reactor 6, hydrogen chloride, methanol in the mixed raw material gas and from returning to liquid pipe
Methylamine substance, dimethyl ether and the methanol and ammonium chloride in road 27 react under the catalyst action in fluidized state, raw
At the gaseous reaction product containing chloromethanes, ammonia and by-product；The by-product is methylamine substance and dimethyl ether；
C. the gaseous reaction product that gravity flow 6 upper lateral part of fluidized bed reactor comes out then enters spray from the middle and lower part of spray column 9
Tower 9 is drenched, washing water enters through spray water inlet 10 from the upper lateral part of spray column 9, with spraying form and fluidisation from bottom to top
The gaseous reaction product of bed reactor 6 is contacted；Gaseous reaction product is after 9 spraying cooling of spray column, unreacted
Chlorination ammonium gas be condensed into solid particle, be deposited on spray column with the catalyst granules taken out of with gaseous reaction product
Bottom passes through 7 periodic cleaning of spray column discharge valve；
D. the gas come out from the top of spray column 9 subsequently enters bag filter 11, is further separated out catalyst powder
And ammonium chloride particle, catalyst powder and ammonium chloride particle enter the powder recycling can 26 of lower section；
E. cool down from the gas that 11 lateral roof of bag filter comes out through cooler 12, subsequently into rectifying and dewatering
Tower 13；The reaction that 13 bottom of rectifying and dewatering tower comes out generates water and is discharged through dehydrating tower kettle liquid dump valve 14, and a part is made to be spray
The spray-water of tower 9 is drenched, remaining enters sewage treatment process for production waste water；The gas that 13 tower top of rectifying and dewatering tower comes out is anti-
It answers product to enter compressor 15 and is pressurized to 0.8~2.5MPa；
F. enter deammoniation tower 17 after being cooled to 30 DEG C~50 DEG C from the gas-pressurized that compressor 15 comes out, by rectifying, ammonia
It is come out by tower top, enters liquid ammonia storage tank through ammonia outlet conduit 16 after cooling；Product liquid after deamination is by 17 tower bottom stream of deammoniation tower
Out；
G. enter chloromethanes treating column 19 from product liquid after the deamination that 17 bottom of deammoniation tower comes out, by rectifying, tower bottom
Obtained liquid is the mixture containing methylamine, dimethyl ether and methanol, can be used as a part of rework solution after pressure reducing valve 20,
Fluidized-bed reactor 6 is returned by rework solution pipeline 27, methanol pipeline 2 and methanol preheater 4；19 tower top of chloromethanes treating column
Obtain the methyl chloride gas containing dimethyl ether；
H. the methyl chloride gas containing dimethyl ether that 19 tower top of chloromethanes treating column comes out enters after the decompression of throttle valve 22 washes
The bottom of tower 21 is washed, methanol enters scrubbing tower 21 by scrubbing tower charging methanol inlet 8, in a manner of spray and containing dimethyl ether
Methyl chloride gas gas-liquid contact；Pure methyl chloride gas is obtained after washing removal dimethyl ether, and is gone out from the top of scrubbing tower 21
Come, it is pressurized liquefied rear into chloromethanes storage tank 25 into compressor 24；The methanol solution containing dimethyl ether after washing, according to row
Liquid is that 1:10~100 are allocated with circulating cleaning solution mass ratio out, and wherein discharge liquor is after liquid phase dump valve 23 as return
A part of liquid returns to fluidized-bed reactor 6 by rework solution pipeline 27, methanol pipeline 2 and methanol preheater 4；Circulation is washed
It washs and scrubbing tower 21 is entered as cleaning solution by scrubbing tower charging methanol inlet 8 after liquid is mixed with the fresh methanol rinses liquid of supplement
It is recycled, the amount of the fresh methanol rinses liquid of the supplement is equal with the amount of scrubbing tower discharge liquor.
Preferably, the mixed raw material temperature degree in step a, after methanol preheater 4 and hydrogen chloride preheater 5 heat
It is 180 DEG C -250 DEG C.
Preferably, the granularity of the alumina catalyst powder is 80 μm~200 μm, catalyst activity charcoal powder grain
Degree is 200 μm~400 μm.
Preferably, the gas temperature that the spray column 9 comes out is 120 DEG C~200 DEG C, after cooling through cooler 12
Gas temperature is 40 DEG C~65 DEG C.
Preferably, the rectifying and dewatering tower 13 be atmospheric distillation tower, 60 DEG C~120 DEG C of operation temperature.
Preferably, the deammoniation tower 17 is compression rectification tower, and operation temperature is -10 DEG C~60 DEG C, and operating pressure is
0.8MPa~2.5MPa.
Preferably, the chloromethanes treating column 19 is compression rectification tower, and operation temperature is 40 DEG C~120 DEG C, operation pressure
Power is 0.8-2.5MPa.
Preferably, the scrubbing tower 21 be absorption tower, 10~40 DEG C of operation temperature, liquid-gas ratio 10L/m3~20L/
m3。
Embodiment 1
Flow is the methanol feedstock of 30.6kmol/h, is heated and is vaporized into methanol preheater 4 through methanol pipeline 2
Methanol gas is obtained, the hydrogen chloride gas that flow is 9kmol/h enters hydrogen chloride preheater 5 through hydrogen chloride pipeline 3 and preheats.Institute
The methanol gas and hydrogen chloride gas stated carry out being mixed to get the mixed raw material gas that temperature is 200 DEG C, and flow automatically fluidized bed reactor 6
Bottom enters through gas distributor to be preheated in 280 DEG C of fluidized-bed reactor 6, to the particle size range being equipped in fluidized bed
It is fluidized for 100 μm~150 μm alumina powder body catalysts.Feeding amount is the ammonium chloride powder of 21kmol/h through ammonium chloride
Pipeline 1 is added from the top of fluidized-bed reactor 6.Ammonium chloride, hydrogen chloride and methanol rub under the conditions of the feed rate
Your charge ratio is 3.5:1.5:5.1, and the catalytic bed temperature of fluidized-bed reactor 6 is 350 DEG C or so, and operating pressure is
0.10MPa, reaction gas empty tower gas velocity are 0.5m/s.Under the above-described reaction conditions, ammonium chloride and hydrogen chloride and methanol are being located
It reacts under the catalyst action of fluidized state, it is anti-to generate the gas containing chloromethanes, ammonia, methylamine substance and dimethyl ether
Answer product.
The gaseous reaction product that gravity flow 6 upper lateral part of fluidized bed reactor comes out then enters spray from the middle and lower part of spray column 9
Tower 9, washing water enters through spray water inlet 10 from the upper lateral part of spray column 9, with spraying form and fluidized bed from bottom to top
The gaseous reaction product of reactor 6 is contacted；Gaseous reaction product is passing through 9 spraying cooling of spray column to 150 DEG C, not
The chlorination ammonium gas of reaction is condensed into solid particle, is deposited on spray with the catalyst granules taken out of with gaseous reaction product
Tower bottom is drenched, 7 periodic cleaning of spray column discharge valve is passed through.
The gaseous reaction product come out from the top of spray column 9 subsequently enters bag filter 11, is further separated out catalysis
Agent powder and ammonium chloride particle, catalyst powder and ammonium chloride particle enter the powder recycling can 26 of lower section.From bag filter
The gas that 11 lateral roofs come out cools to 50 DEG C through cooler 12, subsequently into rectifying and dewatering tower 13.The behaviour of rectifying and dewatering tower 13
Make temperature range control at 60 DEG C~100 DEG C, operating pressure is normal pressure.The reaction that 13 bottom of rectifying and dewatering tower comes out generates water
It is discharged through dehydrating tower kettle liquid dump valve 14, a part is made to be the spray-water of spray column 9, remaining enters dirt for production waste water
Water process process.
The gaseous reaction product that 13 tower top of rectifying and dewatering tower comes out, is pressurized to 1.2MPa through compressor 15 and is cooled to 35
Enter deammoniation tower 17 after DEG C.The operation temperature control of deammoniation tower 17 is at -10 DEG C~40 DEG C, operating pressure 1.2MPa.Deammoniation tower
The ammonia that 17 tower tops come out enters liquid ammonia storage tank through ammonia outlet conduit 16 after cooling.Product liquid after deamination is by 17 tower of deammoniation tower
Bottom outflow subsequently enters chloromethanes treating column 19.The operation temperature of chloromethanes treating column 19 controls the operation at 40 DEG C~100 DEG C
Pressure is about 1.1MPa.The liquid that tower bottom obtains is the mixture containing methylamine, dimethyl ether and methanol, is made after pressure reducing valve 20
For a part of rework solution, fluidized-bed reactor 6 is returned to by rework solution pipeline 27, methanol pipeline 2 and methanol preheater 4；Chlorine
19 tower top of methane treating column obtains the methyl chloride gas containing dimethyl ether.
The methyl chloride gas containing dimethyl ether enters the bottom of scrubbing tower 21 after the decompression of throttle valve 22, amounts to stream
The fresh methanol rinses liquid and circulating cleaning solution that amount is 206.617.1kmol/h feed methanol inlet 8 by scrubbing tower and enter washing
After tower 21, with the methyl chloride gas gas-liquid contact containing dimethyl ether in a manner of spray, washs removal dimethyl ether and obtain pure chlorine
Methane gas.The operation temperature of scrubbing tower 21 is 20 DEG C, and operating pressure is normal pressure, liquid-gas ratio 13L/m3.Methyl chloride gas is certainly
It is come out at the top of scrubbing tower 21, it is pressurized liquefied rear into chloromethanes storage tank 25 into compressor 24.The first containing dimethyl ether after washing
Alcoholic solution is allocated according to discharge liquor with circulating cleaning solution mass ratio for 1:50, and wherein discharge liquor passes through rework solution pipeline
27, methanol pipeline 2 and methanol preheater 4 return to fluidized-bed reactor 6；The fresh methanol rinses of circulating cleaning solution and supplement
Enter scrubbing tower 21 as cleaning solution by scrubbing tower charging methanol inlet 8 after liquid mixing to be recycled, fresh methanol rinses liquid
Mass ratio with circulating cleaning solution is 1:50.
Product chloromethanes output is 26.1kmol/h, and purity is 99.98% (mass percent), by methanol collecting rate
It is 85.3%；The flow of product ammonia is 18kmol/h, and purity is 99.99% (mass percent).
Embodiment 2
The methanol feedstock and flow that flow is 18kmol/h are 12.3kmol/h (methanol, methylamine and dimethyl ether total moles stream
Amount) rework solution mixing after, through methanol pipeline 2 into methanol preheater 4 carry out heating and vaporization obtain methanol gas, flow
Enter the preheating of hydrogen chloride preheater 5 through hydrogen chloride pipeline 3 for the hydrogen chloride gas of 12kmol/h.The methanol gas and chlorine
Change hydrogen to carry out being mixed to get the mixed raw material gas that temperature is 240 DEG C, 6 bottom of fluidized bed reactor of flowing automatically is through gas distributor
It is 80 μm~150 μm oxidations to the particle size range being equipped in fluidized bed into the fluidized-bed reactor 6 for being preheated to 300 DEG C
Aluminium powder body catalyst is fluidized.The ammonium chloride powder that feeding amount is 18kmol/h is through ammonium chloride pipeline 1 from fluidized-bed reactor
6 top is added.The molar feed ratio of ammonium chloride, hydrogen chloride and methanol is 3.0:2.0 under the conditions of the feed rate:
5.05, the catalytic bed temperature of fluidized-bed reactor 6 is 360 DEG C or so, operating pressure 0.13MPa, reaction gas void tower gas
Speed is 0.4m/s.Under the above-described reaction conditions, ammonium chloride and hydrogen chloride and methanol are under the catalyst action in fluidized state
React, generate containing chloromethanes, ammonia, methylamine substance and dimethyl ether gaseous reaction product.
The gaseous reaction product that gravity flow 6 upper lateral part of fluidized bed reactor comes out then enters spray from the middle and lower part of spray column 9
Tower 9, washing water enters through spray water inlet 10 from the upper lateral part of spray column 9, with spraying form and fluidized bed from bottom to top
The gaseous reaction product of reactor 6 is contacted；Gaseous reaction product is passing through 9 spraying cooling of spray column to 170 DEG C, not
The chlorination ammonium gas of reaction is condensed into solid particle, is deposited on spray with the catalyst granules taken out of with gaseous reaction product
Tower bottom is drenched, 7 periodic cleaning of spray column discharge valve is passed through.
The gaseous reaction product come out from the top of spray column 9 subsequently enters bag filter 11, is further separated out catalysis
Agent powder and ammonium chloride particle, catalyst powder and ammonium chloride particle enter the powder recycling can 26 of lower section.From bag filter
The gas that 11 lateral roofs come out cools to 45 DEG C through cooler 12, subsequently into rectifying and dewatering tower 13.The behaviour of rectifying and dewatering tower 13
Make temperature range control at 65 DEG C~110 DEG C, operating pressure is normal pressure.The reaction that 13 bottom of rectifying and dewatering tower comes out generates water
It is discharged through dehydrating tower kettle liquid dump valve 14, a part is made to be the spray-water of spray column 9, remaining enters dirt for production waste water
Water process process.
The gaseous reaction product that 13 tower top of rectifying and dewatering tower comes out, is pressurized to 1.5MPa through compressor 15 and is cooled to 40
Enter deammoniation tower 17 after DEG C.The operation temperature control of deammoniation tower 17 is at -5 DEG C~50 DEG C, operating pressure 1.5MPa.Deammoniation tower
The ammonia that 17 tower tops come out enters liquid ammonia storage tank through ammonia outlet conduit 16 after cooling.Product liquid after deamination is by 17 tower of deammoniation tower
Bottom outflow subsequently enters chloromethanes treating column 19.The operation temperature of chloromethanes treating column 19 controls the operation at 45 DEG C~105 DEG C
Pressure is about 1.4MPa.The liquid that tower bottom obtains is the mixture containing methylamine, dimethyl ether and methanol, is made after pressure reducing valve 20
For a part of rework solution, fluidized-bed reactor 6 is returned to by rework solution pipeline 27, methanol pipeline 2 and methanol preheater 4；Chlorine
19 tower top of methane treating column obtains the methyl chloride gas containing dimethyl ether.
The methyl chloride gas containing dimethyl ether enters the bottom of scrubbing tower 21 after the decompression of throttle valve 22, amounts to stream
The fresh methanol rinses liquid and circulating cleaning solution that amount is 184.812kmol/h feed methanol inlet 8 by scrubbing tower and enter scrubbing tower
After 21, with the methyl chloride gas gas-liquid contact containing dimethyl ether in a manner of spray, washs removal dimethyl ether and obtain pure chloromethane
Alkane gas.The operation temperature of scrubbing tower 21 is 15 DEG C, and operating pressure is normal pressure, liquid-gas ratio 12L/m3.Methyl chloride gas is washed certainly
It washs and is come out at the top of tower 21, it is pressurized liquefied rear into chloromethanes storage tank 25 into compressor 24.The methanol containing dimethyl ether after washing
Solution is allocated according to discharge liquor with circulating cleaning solution mass ratio for 1:80, wherein discharge liquor by rework solution pipeline 27,
Methanol pipeline 2 and methanol preheater 4 return to fluidized-bed reactor 6；Circulating cleaning solution and the fresh methanol rinses liquid of supplement are mixed
Enter scrubbing tower 21 as cleaning solution by scrubbing tower charging methanol inlet 8 after conjunction to be recycled, fresh methanol rinses liquid and circulation
The mass ratio of cleaning solution is 1:80.
Product chloromethanes output is 28.2kmol/h, and purity is 99.98% (mass percent), by methanol collecting rate
It is 93%；The flow of product ammonia is 17.3kmol/h, and purity is 99.98% (mass percent).
Embodiment 3
The methanol feedstock and flow that flow is 16kmol/h are 14.5kmol/h (methanol, methylamine and dimethyl ether total moles stream
Amount) rework solution mixing after, through methanol pipeline 2 into methanol preheater 4 carry out heating and vaporization obtain methanol gas, flow
Enter the preheating of hydrogen chloride preheater 5 through hydrogen chloride pipeline 3 for the hydrogen chloride gas of 15kmol/h.The methanol gas and chlorine
Change hydrogen to carry out being mixed to get the mixed raw material gas that temperature is 240 DEG C, 6 bottom of fluidized bed reactor of flowing automatically is through gas distributor
It is 80 μm~150 μm oxidations to the particle size range being equipped in fluidized bed into the fluidized-bed reactor 6 for being preheated to 300 DEG C
Aluminium powder body catalyst is fluidized.The ammonium chloride powder that feeding amount is 15kmol/h is through ammonium chloride pipeline 1 from fluidized-bed reactor
6 top is added.The molar feed ratio of ammonium chloride, hydrogen chloride and methanol is 2.5:2.5 under the conditions of the feed rate:
5.08, the catalytic bed temperature of fluidized-bed reactor 6 is 350 DEG C or so, operating pressure 0.15MPa, reaction gas void tower gas
Speed is 0.6m/s.Under the above-described reaction conditions, ammonium chloride and hydrogen chloride and methanol are under the catalyst action in fluidized state
React, generate containing chloromethanes, ammonia, methylamine substance and dimethyl ether gaseous reaction product.
The gaseous reaction product that gravity flow 6 upper lateral part of fluidized bed reactor comes out then enters spray from the middle and lower part of spray column 9
Tower 9, washing water enters through spray water inlet 10 from the upper lateral part of spray column 9, with spraying form and fluidized bed from bottom to top
The gaseous reaction product of reactor 6 is contacted；Gaseous reaction product is passing through 9 spraying cooling of spray column to 180 DEG C, not
The chlorination ammonium gas of reaction is condensed into solid particle, is deposited on spray with the catalyst granules taken out of with gaseous reaction product
Tower bottom is drenched, 7 periodic cleaning of spray column discharge valve is passed through.
The gaseous reaction product come out from the top of spray column 9 subsequently enters bag filter 11, is further separated out catalysis
Agent powder and ammonium chloride particle, catalyst powder and ammonium chloride particle enter the powder recycling can 26 of lower section.From bag filter
The gas that 11 lateral roofs come out cools to 55 DEG C through cooler 12, subsequently into rectifying and dewatering tower 13.The behaviour of rectifying and dewatering tower 13
Make temperature range control at 70 DEG C~115 DEG C, operating pressure is normal pressure.The reaction that 13 bottom of rectifying and dewatering tower comes out generates water
It is discharged through dehydrating tower kettle liquid dump valve 14, a part is made to be the spray-water of spray column 9, remaining enters dirt for production waste water
Water process process.
The gaseous reaction product that 13 tower top of rectifying and dewatering tower comes out, is pressurized to 1.8MPa through compressor 15 and is cooled to 45
Enter deammoniation tower 17 after DEG C.The operation temperature control of deammoniation tower 17 is at 0 DEG C~60 DEG C, operating pressure 1.8MPa.Deammoniation tower 17
The ammonia that tower top comes out enters liquid ammonia storage tank through ammonia outlet conduit 16 after cooling.Product liquid after deamination is by 17 tower bottom of deammoniation tower
Outflow subsequently enters chloromethanes treating column 19.The operation temperature of chloromethanes treating column 19 is controlled at 55 DEG C~120 DEG C, operation pressure
Power is about 1.7MPa.The liquid that tower bottom obtains is the mixture containing methylamine, dimethyl ether and methanol, the conduct after pressure reducing valve 20
A part of rework solution returns to fluidized-bed reactor 6 by rework solution pipeline 27, methanol pipeline 2 and methanol preheater 4；Chloromethane
19 tower top of alkane treating column obtains the methyl chloride gas containing dimethyl ether.
The methyl chloride gas containing dimethyl ether enters the bottom of scrubbing tower 21 after the decompression of throttle valve 22, amounts to stream
After the fresh methanol and circulating cleaning solution that amount is 235.114kmol/h enter scrubbing tower 21 by scrubbing tower charging methanol inlet 8,
With the methyl chloride gas gas-liquid contact containing dimethyl ether in a manner of spray, washs removal dimethyl ether and obtain pure chloromethanes gas
Body.The operation temperature of scrubbing tower 21 is 25 DEG C, and operating pressure is normal pressure, liquid-gas ratio 15L/m3.Methyl chloride gas is from scrubbing tower
21 tops come out, pressurized liquefied rear into chloromethanes storage tank 25 into compressor 24.The methanol containing dimethyl ether after washing is molten
Liquid is allocated according to discharge liquor with circulating cleaning solution mass ratio for 1:40, and wherein discharge liquor passes through rework solution pipeline 27, first
Alcohol pipeline 2 and methanol preheater 4 return to fluidized-bed reactor 6；Circulating cleaning solution is mixed with the fresh methanol rinses liquid of supplement
Enter scrubbing tower 21 as cleaning solution by scrubbing tower charging methanol inlet 8 afterwards to be recycled, fresh methanol rinses liquid and circulation
The mass ratio of cleaning solution is 1:40.
Product chloromethanes output is 28.7kmol/h, and purity is 99.97% (mass percent), by methanol collecting rate
It is 94%；The flow of product ammonia is 14.6kmol/h, and purity is 99.98% (mass percent).
Embodiment 4
The methanol feedstock and flow that flow is 16.2kmol/h are 14.0kmol/h (methanol, methylamine and dimethyl ether total moles
Flow) rework solution mixing after, through methanol pipeline 2 into methanol preheater 4 carry out heating and vaporization obtain methanol gas, flow
The hydrogen chloride gas that amount is 18kmol/h enters hydrogen chloride preheater 5 through hydrogen chloride pipeline 3 and preheats.The methanol gas with
Hydrogen chloride gas carries out being mixed to get the mixed raw material gas that temperature is 240 DEG C, and gravity flow 6 bottom of fluidized bed reactor is distributed through gas
Device, which enters, to be preheated in 300 DEG C of fluidized-bed reactor 6, is 200 μm~300 μm to the particle size range being equipped in fluidized bed
Absorbent charcoal powder body catalyst is fluidized.Feeding amount is that the ammonium chloride powder of 12kmol/h is anti-from fluidized bed through ammonium chloride pipeline 1
The top of device 6 is answered to be added.The molar feed ratio of ammonium chloride, hydrogen chloride and methanol is 2.0 under the conditions of the feed rate:
3.0:5.03, the catalytic bed temperature of fluidized-bed reactor 6 are 350 DEG C or so, operating pressure 0.20MPa, and reaction gas is empty
Tower gas velocity is 0.45m/s.Under the above-described reaction conditions, ammonium chloride and hydrogen chloride and methanol are in the catalyst for being in fluidized state
React under effect, generate containing chloromethanes, ammonia, methylamine substance and dimethyl ether gaseous reaction product.
The gaseous reaction product that gravity flow 6 upper lateral part of fluidized bed reactor comes out then enters spray from the middle and lower part of spray column 9
Tower 9, washing water enters through spray water inlet 10 from the upper lateral part of spray column 9, with spraying form and fluidized bed from bottom to top
The gaseous reaction product of reactor 6 is contacted；Gaseous reaction product is passing through 9 spraying cooling of spray column to 190 DEG C, not
The chlorination ammonium gas of reaction is condensed into solid particle, is deposited on spray with the catalyst granules taken out of with gaseous reaction product
Tower bottom is drenched, 7 periodic cleaning of spray column discharge valve is passed through.
The gaseous reaction product come out from the top of spray column 9 subsequently enters bag filter 11, is further separated out catalysis
Agent powder and ammonium chloride particle, catalyst powder and ammonium chloride particle enter the powder recycling can 26 of lower section.From bag filter
The gas that 11 lateral roofs come out cools to 60 DEG C through cooler 12, subsequently into rectifying and dewatering tower 13.The behaviour of rectifying and dewatering tower 13
Make temperature range control at 80 DEG C~120 DEG C, operating pressure is normal pressure.The reaction that 13 bottom of rectifying and dewatering tower comes out generates water
It is discharged through dehydrating tower kettle liquid dump valve 14, a part is made to be the spray-water of spray column 9, remaining enters dirt for production waste water
Water process process.
The gaseous reaction product that 13 tower top of rectifying and dewatering tower comes out, is pressurized to 1.3MPa through compressor 15 and is cooled to 38
Enter deammoniation tower 17 after DEG C.The operation temperature control of deammoniation tower 17 is at -7 DEG C~48 DEG C, operating pressure 1.3MPa.Deammoniation tower
The ammonia that 17 tower tops come out enters liquid ammonia storage tank through ammonia outlet conduit 16 after cooling.Product liquid after deamination is by 17 tower of deammoniation tower
Bottom outflow subsequently enters chloromethanes treating column 19.The operation temperature of chloromethanes treating column 19 controls the operation at 43 DEG C~103 DEG C
Pressure is about 1.2MPa.The liquid that tower bottom obtains is the mixture containing methylamine, dimethyl ether and methanol, is made after pressure reducing valve 20
For a part of rework solution, fluidized-bed reactor 6 is returned to by rework solution pipeline 27, methanol pipeline 2 and methanol preheater 4；Chlorine
19 tower top of methane treating column obtains the methyl chloride gas containing dimethyl ether.
The methyl chloride gas containing dimethyl ether enters the bottom of scrubbing tower 21 after the decompression of throttle valve 22, amounts to stream
After the fresh methanol and circulating cleaning solution that amount is 290.9kmol/h enter scrubbing tower 21 by scrubbing tower charging methanol inlet 8, with
The mode of spray and the methyl chloride gas gas-liquid contact containing dimethyl ether, washing removal dimethyl ether obtain pure methyl chloride gas.
The operation temperature of scrubbing tower 21 is 30 DEG C, and operating pressure is normal pressure, liquid-gas ratio 18L/m3.Methyl chloride gas is from scrubbing tower 21
Top comes out, pressurized liquefied rear into chloromethanes storage tank 25 into compressor 24.The methanol solution containing dimethyl ether after washing,
It is allocated according to discharge liquor with circulating cleaning solution mass ratio for 1:30, wherein discharge liquor passes through rework solution pipeline 27, methanol pipe
Road 2 and methanol preheater 4 return to fluidized-bed reactor 6；Circulating cleaning solution with supplement fresh methanol rinses liquid mix after by washing
It washs tower charging methanol inlet 8 and enters scrubbing tower 21 as cleaning solution recycling, fresh methanol rinses liquid and circulating cleaning solution
Mass ratio be 1:30.
Product chloromethanes output is 29.6kmol/h, and purity is 99.97% (mass percent), by methanol collecting rate
It is 98%；The flow of product ammonia is 11.4kmol/h, and purity is 99.97% (mass percent).
Embodiment 5
The methanol feedstock and flow that flow is 21kmol/h are 9.6kmol/h (methanol, methylamine and dimethyl ether total moles stream
Amount) rework solution mixing after, through methanol pipeline 2 into methanol preheater 4 carry out heating and vaporization obtain methanol gas, flow
Enter the preheating of hydrogen chloride preheater 5 through hydrogen chloride pipeline 3 for the hydrogen chloride gas of 21kmol/h.The methanol gas and chlorine
Change hydrogen to carry out being mixed to get the mixed raw material gas that temperature is 220 DEG C, 6 bottom of fluidized bed reactor of flowing automatically is through gas distributor
It is 250 μm~350 μm work to the particle size range being equipped in fluidized bed into the fluidized-bed reactor 6 for being preheated to 305 DEG C
Property powdered carbon body catalyst is fluidized.The ammonium chloride powder that feeding amount is 9kmol/h is through ammonium chloride pipeline 1 from fluidized-bed reaction
The top of device 6 is added.The molar feed ratio of ammonium chloride, hydrogen chloride and methanol is 1.5 under the conditions of the feed rate:
3.5:5.1, the catalytic bed temperature of fluidized-bed reactor 6 are 370 DEG C or so, operating pressure 0.11MPa, reaction gas void tower
Gas velocity is 0.55m/s.Under the above-described reaction conditions, ammonium chloride and hydrogen chloride and methanol are made in the catalyst in fluidized state
React under, generate containing chloromethanes, ammonia, methylamine substance and dimethyl ether gaseous reaction product.
The gaseous reaction product that gravity flow 6 upper lateral part of fluidized bed reactor comes out then enters spray from the middle and lower part of spray column 9
Tower 9, washing water enters through spray water inlet 10 from the upper lateral part of spray column 9, with spraying form and fluidized bed from bottom to top
The gaseous reaction product of reactor 6 is contacted；Gaseous reaction product is passing through 9 spraying cooling of spray column to 140 DEG C, not
The chlorination ammonium gas of reaction is condensed into solid particle, is deposited on spray with the catalyst granules taken out of with gaseous reaction product
Tower bottom is drenched, 7 periodic cleaning of spray column discharge valve is passed through.
The gaseous reaction product come out from the top of spray column 9 subsequently enters bag filter 11, is further separated out catalysis
Agent powder and ammonium chloride particle, catalyst powder and ammonium chloride particle enter the powder recycling can 26 of lower section.From bag filter
The gas that 11 lateral roofs come out cools to 40 DEG C through cooler 12, subsequently into rectifying and dewatering tower 13.The behaviour of rectifying and dewatering tower 13
Make temperature range control at 60 DEG C~110 DEG C, operating pressure is normal pressure.The reaction that 13 bottom of rectifying and dewatering tower comes out generates water
It is discharged through dehydrating tower kettle liquid dump valve 14, a part is made to be the spray-water of spray column 9, remaining enters dirt for production waste water
Water process process.
The gaseous reaction product that 13 tower top of rectifying and dewatering tower comes out, is pressurized to 1.2MPa through compressor 15 and is cooled to 34
Enter deammoniation tower 17 after DEG C.The operation temperature control of deammoniation tower 17 is at -10 DEG C~43 DEG C, operating pressure 1.2MPa.Deammoniation tower
The ammonia that 17 tower tops come out enters liquid ammonia storage tank through ammonia outlet conduit 16 after cooling.Product liquid after deamination is by 17 tower of deammoniation tower
Bottom outflow subsequently enters chloromethanes treating column 19.The operation temperature of chloromethanes treating column 19 controls the operation at 40 DEG C~100 DEG C
Pressure is about 1.1MPa.The liquid that tower bottom obtains is the mixture containing methylamine, dimethyl ether and methanol, is made after pressure reducing valve 20
For a part of rework solution, fluidized-bed reactor 6 is returned to by rework solution pipeline 27, methanol pipeline 2 and methanol preheater 4；Chlorine
19 tower top of methane treating column obtains the methyl chloride gas containing dimethyl ether.
The methyl chloride gas containing dimethyl ether enters the bottom of scrubbing tower 21 after the decompression of throttle valve 22, amounts to stream
After the fresh methanol and circulating cleaning solution that amount is 254.2kmol/h enter scrubbing tower 21 by scrubbing tower charging methanol inlet 8, with
The mode of spray and the methyl chloride gas gas-liquid contact containing dimethyl ether, washing removal dimethyl ether obtain pure methyl chloride gas.
The operation temperature of scrubbing tower 21 is 35 DEG C, and operating pressure is normal pressure, liquid-gas ratio 16L/m3.Methyl chloride gas is from scrubbing tower 21
Top comes out, pressurized liquefied rear into chloromethanes storage tank 25 into compressor 24.The methanol solution containing dimethyl ether after washing,
It is allocated according to discharge liquor with circulating cleaning solution mass ratio for 1:60, wherein discharge liquor passes through rework solution pipeline 27, methanol pipe
Road 2 and methanol preheater 4 return to fluidized-bed reactor 6；Circulating cleaning solution mixed with the fresh methanol rinses liquid of supplement after by
Scrubbing tower feeds methanol inlet 8 and enters scrubbing tower 21 as cleaning solution recycling, and fresh methanol rinses liquid is washed with circulation
The mass ratio of liquid is 1:60.
Product chloromethanes output is 29.1kmol/h, and purity is 99.97% (mass percent), by methanol collecting rate
It is 95%；The flow of product ammonia is 8.8kmol/h, and purity is 99.97% (mass percent).
Claims (10)
1. a kind of device for reacting production chloromethanes with methanol using hydrogen chloride and ammonium chloride, which is characterized in that including successively connecting
Fluidized-bed reactor (6), spray column (9), bag filter (11), cooler (12), the dehydrating tower (13), compressor connect
(15), deammoniation tower (17), chloromethanes treating column (19), throttle valve (22), scrubbing tower (21), chloromethanes compressor (24), chloromethane
Alkane storage tank (25)；The top of the fluidized-bed reactor (6) connects ammonium chloride pipeline (1), the lower part of fluidized-bed reactor (6) or
The methanol preheater (4) and hydrogen chloride preheater (5) that side lower part is connected with and connects through pipeline, the methanol preheater (4) and chlorine
The other end for changing hydrogen preheater (5) is connected separately with methanol pipeline (2) and hydrogen chloride pipeline (3)；The fluidized-bed reactor (6)
Upper lateral part connection spray column (9) middle and lower part, the lower part of spray column (9) is equipped with spray column discharge valve (7) and pipeline, spray column
(9) upper lateral part is equipped with spray water inlet (10), and the top of spray column (9) is connected by pipeline in the side of bag filter (11)
The gas vent on top, bag filter (11) top side connects cooler (12), and the other end of cooler (12) connects
Connect the middle side part of rectifying and dewatering tower (13), the top of rectifying and dewatering tower (13) connects deammoniation tower 17 through compressor (15)) side in
The top in portion, deammoniation tower (17) is equipped with ammonia outlet conduit (16), bottom connection chloromethanes treating column (19) of deammoniation tower (17)
Middle side part, side lower part of the top of chloromethanes treating column (19) through pipeline and throttle valve (22) connection scrubbing tower (21), scrubbing tower
(21) upper lateral part is equipped with scrubbing tower charging methanol inlet (8), and the top of scrubbing tower (21) connects chlorine through chloromethanes pipeline (18)
The other end of methane compressor (24), chloromethanes compressor (24) connects chloromethanes storage tank (25)；
The lower part of the bag filter (11) is equipped with powder recovery bin (26)；
The lower section of the rectifying and dewatering tower (13) is equipped with dehydrating tower kettle liquid dump valve (14) and pipeline；
The lower section of the chloromethanes treating column (19) is through pipeline and pressure reducing valve (20) connection rework solution pipeline (27)；
The lower section of the scrubbing tower (21) is through pipeline and liquid phase dump valve (23) connection rework solution pipeline (27)；
The lower section of the scrubbing tower (21) is followed through pipeline and circulating cleaning solution control valve (28) connection circulating cleaning solution pipeline (30)
Ring washing liquid lines (30) and fresh methanol rinses liquid pipe road (29) are connected to scrubbing tower methanol feed entrance (8) together.
2. a kind of device for reacting production chloromethanes with methanol using hydrogen chloride and ammonium chloride, which is characterized in that the rework solution
The other end of pipeline (27) is connected on methanol pipeline (2).
3. a kind of method that hydrogen chloride and ammonium chloride react production chloromethanes with methanol, special using claim 1 described device
Sign is, comprising the following steps:
A. methanol feedstock enters methanol preheater (4) through methanol pipeline (2) and is heated and vaporized, and hydrogen chloride gas is through hydrogen chloride
Pipeline (3) is preheated into hydrogen chloride preheater (5), and the methanol gas after preheating is mixed with hydrogen chloride gas as mixed raw material gas
Gravity flow fluidized bed reactor (6) bottom or side lower part enter the fluidized-bed reactor for being preheated to operation temperature through gas distributor
(6) in, the catalyst powder in fluid bedreactors (6) in fluidized bed is fluidized；Ammonium chloride powder is through ammonium chloride pipeline
(1) be added from the top of fluidized-bed reactor (6), into fluidized bed after decompose reaction；
The molar feed ratio of the ammonium chloride, hydrogen chloride and methanol is 3.5~0.5:1.5~4.5:5.02~5.1；
The catalyst is the alumina powder of carried metal active component or the active powdered carbon of carried metal active component
Body；
The catalytic bed temperature of the fluidized-bed reactor (6) is 280 DEG C~400 DEG C, and operating pressure is 0.03MPa~0.5MPa,
Reaction gas empty tower gas velocity is 0.2m/s~0.8m/s；
B. in fluidized-bed reactor (6), hydrogen chloride, methanol in the mixed raw material gas and rework solution pipeline is come from
(27) methylamine substance, dimethyl ether and methanol and ammonium chloride reacts under the catalyst action in fluidized state, raw
At the gaseous reaction product containing chloromethanes, ammonia and by-product；The by-product is methylamine substance and dimethyl ether；
C. the gaseous reaction product that gravity flow fluidized bed reactor (6) upper lateral part comes out then enters spray from the middle and lower part of spray column (9)
It drenches tower (9), washing water enters through spray water inlet (10) from the upper lateral part of spray column (9), in spraying form and from bottom to top
Fluidized-bed reactor (6) come gaseous reaction product contacted；Gaseous reaction product is passing through spray column (9) spraying cooling
Afterwards, unreacted chlorination ammonium gas is condensed into solid particle, deposits with the catalyst granules taken out of with gaseous reaction product
In spray tower bottom, pass through spray column discharge valve (7) periodic cleaning；
D. the gas come out from the top of spray column (9) subsequently enters bag filter (11), is further separated out catalyst powder
And ammonium chloride particle, catalyst powder and ammonium chloride particle enter the powder recycling can 26 of lower section；
E. cool down from the gas that bag filter (11) lateral roof comes out through cooler (12), subsequently into rectifying and dewatering tower
(13)；The reaction that rectifying and dewatering tower (13) bottom comes out generates water and is discharged through dehydrating tower kettle liquid dump valve (14), and a part is made can
For the spray-water of spray column (9), remaining enters sewage treatment process for production waste water；What rectifying and dewatering tower (13) tower top came out
Gaseous reaction product enters compressor (15) and is pressurized to 0.8~2.5MPa；
F. enter deammoniation tower (17) after being cooled to 30 DEG C~50 DEG C from the gas-pressurized that compressor (15) come out, by rectifying, ammonia
It is come out by tower top, enters liquid ammonia storage tank through ammonia outlet conduit (16) after cooling；Product liquid after deamination is by deammoniation tower (17) tower
Bottom outflow；
G. enter chloromethanes treating column (19) from product liquid after the deamination that deammoniation tower (17) bottom comes out, by rectifying, tower bottom
Obtained liquid is the mixture containing methylamine, dimethyl ether and methanol, can be used as a part of rework solution after pressure reducing valve (20),
Fluidized-bed reactor (6) are returned by rework solution pipeline (27), methanol pipeline (2) and methanol preheater (4)；Chloromethanes treating column
(19) tower top obtains the methyl chloride gas containing dimethyl ether；
H. chloromethanes treating column (19) tower top come out the methyl chloride gas containing dimethyl ether through throttle valve 22) decompression after enter washing
The bottom of tower (21), methanol enter scrubbing tower (21) by scrubbing tower charging methanol inlet (8), in a manner of spray and containing dimethyl ether
Methyl chloride gas gas-liquid contact；Pure methyl chloride gas is obtained after washing removal dimethyl ether, and from the top of scrubbing tower (21)
Out, pressurized liquefied rear into chloromethanes storage tank (25) into compressor (24)；The methanol solution containing dimethyl ether after washing, is pressed
It is allocated according to discharge liquor with circulating cleaning solution mass ratio for 1:10~100, wherein discharge liquor is made after liquid phase dump valve (23)
It is anti-back to fluidized bed by rework solution pipeline (27), methanol pipeline (2) and methanol preheater (4) for a part of rework solution
Answer device (6)；Circulating cleaning solution, which is entered after mixing with the fresh methanol rinses liquid of supplement by scrubbing tower charging methanol inlet (8), to be washed
Tower (21) is recycled as cleaning solution, the amount phase of the amount and scrubbing tower discharge liquor of the fresh methanol rinses liquid of the supplement
Deng.
4. reacting the method for production chloromethanes with methanol using hydrogen chloride and ammonium chloride as claimed in claim 3, feature exists
In, in step a, by methanol preheater (4) and hydrogen chloride preheater (5) heating after mixed raw material temperature degree be 180 DEG C-
250℃。
5. reacting the method for production chloromethanes with methanol using hydrogen chloride and ammonium chloride as claimed in claim 3, feature exists
In the granularity of the alumina catalyst powder is 80 μm~200 μm, and catalyst activity charcoal powder granularity is 200 μm~400
μm。
6. reacting the method for production chloromethanes with methanol using hydrogen chloride and ammonium chloride as described in claim 1, feature exists
In the gas temperature that the spray column (9) comes out is 120 DEG C~200 DEG C, is through cooler (12) gas temperature after cooling
40 DEG C~65 DEG C.
7. reacting the method for production chloromethanes with methanol using hydrogen chloride and ammonium chloride as described in claim 1, feature exists
In, the rectifying and dewatering tower (13) be atmospheric distillation tower, 60 DEG C~120 DEG C of operation temperature.
8. reacting the method for production chloromethanes with methanol using hydrogen chloride and ammonium chloride as described in claim 1, feature exists
Be compression rectification tower in, the deammoniation tower (17), operation temperature is -10 DEG C~60 DEG C, operating pressure be 0.8MPa~
2.5MPa。
9. reacting the method for production chloromethanes with methanol using hydrogen chloride and ammonium chloride as described in claim 1, feature exists
In the chloromethanes treating column (19) is compression rectification tower, and operation temperature is 40 DEG C~120 DEG C, operating pressure 0.8-
2.5MPa。
10. reacting the method for production chloromethanes with methanol using hydrogen chloride and ammonium chloride as described in claim 1, feature exists
In, the scrubbing tower (21) be absorption tower, 10~40 DEG C of operation temperature, liquid-gas ratio 10L/m3~20L/m3。
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| CN113582811A (en) * | 2020-04-30 | 2021-11-02 | 蓝星（北京）技术中心有限公司 | Deacidification method of methane chloride |
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Application publication date: 20190628 |