CN102408301B - Method for preparing methyl chloride and ammonia by using ammonium chloride and methanol - Google Patents
Method for preparing methyl chloride and ammonia by using ammonium chloride and methanol Download PDFInfo
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- CN102408301B CN102408301B CN201110388852.9A CN201110388852A CN102408301B CN 102408301 B CN102408301 B CN 102408301B CN 201110388852 A CN201110388852 A CN 201110388852A CN 102408301 B CN102408301 B CN 102408301B
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Abstract
The invention belongs to the technical field of chemical engineering and relates to a method for preparing methyl chloride and ammonia by using ammonium chloride and methanol. In the method, ammonium chloride and methanol are utilized as raw materials and the method comprises the following steps: gasifying methanol, and sending the gasified methanol into a fluidized bed reactor from the bottom; using a mechanical transmission device to send ammonium chloride into a reaction device from the lower part of the fluidized bed reactor; and sending the reaction products of ammonium chloride and methanol to a cyclone separator, a bag filter, a dehydrating tower, a deaminizing tower, a rectifying tower and the like in turn to obtain the products, namely methyl chloride and ammonia. The method has the advantages of high conversion rate, good selectivity, low energy consumption, high yield, stability in operations and the like.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of method of preparing methyl chloride and ammonia with ammonium chloride and methyl alcohol gas solid method.
Background technology
China's connection alkali industrial development is at present swift and violent, has produced a large amount of byproduct ammonium chloride.Ammonium chloride, mainly for the production of composite fertilizer, is used rear because crop is to NH
4 +after ionic absorption, Chloride residue soil, if use excessively, will affect to crop and soil, and these drawbacks have all seriously limited the use of ammonium chloride as chemical fertilizer, thereby has restricted the development of connection alkali industry and soda industry.Therefore, should explore the new application of ammonium chloride actively.
React generation methyl chloride, simultaneously recyclable ammonia with ammonium chloride by introducing methyl alcohol.Methyl chloride is the important source material of synthesizing methyl-chloro-silane, cellulose ester, quaternary ammonium compound, weedicide etc., is widely used in the aspects such as agricultural chemicals, synthetic rubber, resin, industrial auxiliary agent.Ammonia is that connection alkali is produced one of essential raw material, reuse capable of circulation.Thereby ammonium chloride reacts with methyl alcohol prepares methyl chloride technique, can be by industrial reluctant side product sodium chloride the methyl chloride for the production of high added value, realize the recycle of chlorine element and ammonia, to promoting China's connection alkali industrial expansion to play an important role simultaneously.
Twentieth century beginning of the fifties, Olin Mathieson chemical company has proposed to prepare with ammonium chloride and methyl alcohol reaction the method (US2755311 of methyl chloride and ammonia, US2755316, US3315441), and provide two class reaction process: the one, gaseous state ammonium chloride is passed in the fixed bed that catalyzer is housed and reacted together with gaseous state alcohol, catalyzer is particulate alumina, product also has a small amount of methylamine and ether except methyl chloride, finds by product to be added back in raw material and to react and can be converted into methyl chloride again; Another is by the catalyst mix of solid ammonium chloride and molten state, then reacts with alcohol, separates catalyst recycle after reaction, and catalyzer is cuprous chloride.Solid ammonium chloride gasification is needed to more energy, need use 165.8kJ heat at every mole of ammonium chloride of 350 DEG C of decomposition gasifications, because the thermal conduction of ammonium chloride own is poor, its surface compressed in the time of heat, inner caking stops further and decomposes, and direct gasification acquires a certain degree of difficulty.When using high temperature organic solvent instead and making medium, ammonium chloride gasification result is better, but gaseous state ammonium chloride has very strong corrodibility, requires very high to equipment material.In the eighties subsequently, selectivity and the product separation method of the further Study of Catalyst of Mitsubishi gas chemical company.
In above-mentioned published patent, adopt fixed bed or fluidized-bed reactor, and must first ammonium chloride be decomposed and be entered in reactor again, simultaneously because decomposition and the synthesizing in two conversion zones of methyl chloride of ammonium chloride carry out, if ammonium chloride decompose the hydrogenchloride that produces can not with rapidly reaction and consuming of methyl alcohol, easily in course of conveying due to the fluctuation blocking pipe with the synthesizing chlorinated ammonium of ammonification again of temperature.And produce the technology of soda ash and shift to developing country along with chemical method, external relevant ammonium chloride is developed in the eighties in 20th century and is just stopped with methanol fluidized bed reactor technology, and industrialization is not yet carried out.
Summary of the invention
The present invention is for overcoming problems of the prior art, and a kind of ammonium chloride and Methanol method for methyl chloride and ammonia of utilizing is provided, and it has, and transformation efficiency is high, selectivity good, energy consumption is low, smooth operation and the manageable feature of appearance.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
Use ammonium chloride and the Methanol method for methyl chloride and ammonia, it comprises the steps:
A. first gasify through methyl alcohol vaporizing device from the methanol liquid of methyl alcohol storage tank, then enter fluidized-bed reactor from fluidized-bed reactor bottom; Ammonium chloride from ammonium chloride storage tank enters fluidized-bed reactor by mechanical transmission device from fluidized-bed reactor bottom; Wherein the mol ratio of ammonium chloride and methyl alcohol is 0.6～2: 1.
B. methyl alcohol and ammonium chloride enter after fluidized-bed reactor, under catalyst action, react, and generate methyl chloride gas and other a small amount of by products; A small amount of by product comprises methylamine material and dme.
C. from the exit gas product of fluidized-bed reactor, contain a small amount of solid particulate, as catalyzer etc., first isolate solid particulate through cyclonic separator, and solid particulate is turned back in fluidized-bed reactor.
D. the gaseous product after described step c separates enters cloth bag separator subsequently, and described cloth bag separator is isolated because temperature reduces the ammonium chloride particle generating, and ammonium chloride particle returns to fluidized-bed reactor.
E. the gaseous product after described steps d separates is after cooling, and temperature is down to 20～100 DEG C, then enters dehydration tower, and through rectifying, moisture wherein discharges through water port as factory effluent at the bottom of by tower after energy recovery; In gaseous product, other compositions are discharged by tower top, and enter deammoniation tower after compressor is compressed to 0.5-2.0Mpa.
F. the gas of described step e enters after deammoniation tower, and through rectifying, ammonia is expelled to ammonia tank by ammonia relief outlet by tower top and stores, and the liquid of sloughing after ammonia is gone out by tower bottom flow.
G. the liquid at the bottom of described deammoniation tower tower enters rectifying tower subsequently, and through rectifying, tower top is isolated product methyl chloride, and discharges from methyl chloride outlet.
H. composition is methyl alcohol and methylamine material at the bottom of the tower, returns to methyl alcohol storage tank and recycles by returning to valve; At the bottom of tower, composition is methylamine material, discharges storage by control valve.
Preferably, described a kind of use ammonium chloride and Methanol are for the method for methyl chloride and ammonia, and described material benzenemethanol is to enter fluidized-bed reactor reaction with gaseous state; Described raw material ammonium chloride is to react with the solid-state fluidized-bed reactor that enters.
Preferably, described a kind of with ammonium chloride and Methanol the method for methyl chloride and ammonia, described normal temperature liquid methanol is through methyl alcohol vaporizing device, becomes the methanol gas of 80～250 DEG C of temperature under normal pressure.
Preferably, described a kind of use ammonium chloride and Methanol are for the method for methyl chloride and ammonia, and the molar feed ratio of described ammonium chloride and methyl alcohol is 1.2: 1.
Preferably, described a kind of use ammonium chloride and Methanol are for the method for methyl chloride and ammonia, and in described fluidized-bed reactor, temperature is 250～400 DEG C, and gas speed is 0.2-0.6m/s, and working pressure is 0.05-1.0MPa.
Preferably, described a kind of use ammonium chloride and Methanol are for the method for methyl chloride and ammonia, and described catalyzer is by γ-Al
2o
3carrier, modifier, active ingredient composition, wherein modifier is one or more in titanium dioxide, zirconia sol, silicon sol, white carbon black, aluminum solutions, the active ingredient of catalyzer is one or more in zinc, iron, cobalt, nickel, copper, magnesium, potassium, active ingredient exists with metal oxide form, and precursor is nitrate or chlorate.
Preferably, described a kind of use ammonium chloride and Methanol are for the method for methyl chloride and ammonia, and described cyclonic separator is multi-cyclone.
Preferably, described a kind of use ammonium chloride and Methanol are for the method for methyl chloride and ammonia, and the solids mouth of described cloth bag separator bottom is connected with raw material ammonium chloride hopper.
Preferably, described a kind of use ammonium chloride and Methanol are for the method for methyl chloride and ammonia, and described dehydration tower is rectifying tower, and operation pressure is 0.1-2.0MPa.
Preferably, described a kind of use ammonium chloride and Methanol are for the method for methyl chloride and ammonia, and described deammoniation tower and rectifying tower are compression rectification tower, and operation pressure is 0.1-2.0MPa.
The present invention compared with prior art, specifically has following advantage:
1. in a reactor, realize two different reaction process, equipment is simple, technical process is short, less investment simultaneously.
2. easily quiet run and control, process cost is low.
3. product separation is simple, and separation after product can be recycled.
4. operate airtight carrying out, without discharging of waste liquid, environmental pollution is little.
5. the transformation efficiency of ammonium chloride selectivity high, methyl chloride is good, and transformation efficiency approaches 100, and selectivity is greater than 80%.
In a word, the present invention has that device integration is high, technique is simple, transformation efficiency is high, selectivity is good and hold manageable feature.Utilize this technique can make low value-added ammonium chloride be converted into the methyl chloride of high added value and realize the recycling of ammonia.
Brief description of the drawings
Fig. 1 is ammonium chloride and the Methanol process flow diagram for methyl chloride.
Each part description in figure:
1, methyl alcohol storage tank 2, methyl alcohol vaporizing device; 3, ammonium chloride storage tank; 4, ammonium chloride mechanical transport device; 5, fluidized-bed reactor; 6, cyclonic separator; 7, cloth bag separator; 8, dehydration tower 9, water port 10, compressor; 11, deammoniation tower; 12, ammonia relief outlet; 13, rectifying tower 14, methyl chloride outlet; 15, return to valve 16, control valve.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated:
A. methanol liquid is out successively gasified through methyl alcohol vaporizing device 2 by methyl alcohol storage tank 1 with certain flow, finally reaches temperature under normal pressure and be the methanol gas of 200 DEG C, and then it enters fluidized-bed reactor 5 from fluidized-bed reactor bottom; In ammonium chloride storage tank 3, ammonium chloride enters fluidized-bed reactor 5 by mechanical transmission device 4 from fluidized-bed reactor bottom, and wherein the mol ratio of ammonium chloride and methyl alcohol is 1.5: 1.
B. methyl alcohol and ammonium chloride enter after fluidized-bed reactor 5, under catalyst action, react, and generate methyl chloride gas and other a small amount of by products, and as methylamine material, dme etc., in fluidized-bed reactor, pressure is 0.3MPa, and temperature is 370 DEG C.
C. ammonium chloride reacts after product and contains a small amount of solid particulate with methyl alcohol, and as catalyzer etc., product gas goes out the rear cyclonic separator 6 that first passes through of fluidized-bed reactor 5, isolates solid particulate, returns it in fluidized-bed reactor 5;
D. the gas that separates solid particulate enters into cloth bag separator 7, and after temperature reduces, hydrogenchloride and ammonia in gas regenerate ammonium chloride, solidifies and is attached to cloth bag surface together with original ammonium chloride in gas.Cloth bag separator 7 is interior regularly to cloth bag ejection pulse gas, and cloth bag surface chlorination ammonium is departed from.After the ammonium chloride sedimentation departing from, separate and return fluidized-bed reactor 5;
E. product gas is after cooling, and temperature is down to normal temperature, then enters dehydration tower 8, and through rectifying, moisture is wherein discharged at the bottom of by tower, after energy recovery, discharges through water port 9 as factory effluent; In gas, other compositions are discharged by tower top, and enter deammoniation tower 11 after compressor 10 is compressed to 1.5Mpa.
G. gas enters after deammoniation tower 11, and through rectifying, ammonia is expelled to gas holder through ammonia relief outlet 12 by tower top and stores, and in gas, other compositions are discharged at the bottom of by tower.
A. methanol liquid is out successively gasified through methyl alcohol vaporizing device 2 by methyl alcohol storage tank 1 with certain flow, finally reaches temperature under normal pressure and be the methanol gas of 200 DEG C, and then it enters fluidized-bed reactor 5 from fluidized-bed reactor bottom; In ammonium chloride storage tank 3, ammonium chloride enters fluidized-bed reactor 5 by mechanical transmission device 4 from fluidized-bed reactor bottom, and wherein the mol ratio of ammonium chloride and methyl alcohol is 0.8: 1.
B. methyl alcohol and ammonium chloride enter after fluidized-bed reactor 5, under catalyst action, react, and generate methyl chloride gas and other a small amount of by products, and as methylamine material, dme etc., in fluidized-bed reactor, pressure is 0.3MPa, and temperature is 370 DEG C.
C. ammonium chloride reacts after product and contains a small amount of solid particulate with methyl alcohol, and as catalyzer etc., product gas goes out the rear cyclonic separator 6 that first passes through of fluidized-bed reactor 5, isolates solid particulate, returns it in fluidized-bed reactor 5.
D. the gas that separates solid particulate enters into cloth bag separator 7, and after temperature reduces, hydrogenchloride and ammonia in gas regenerate ammonium chloride, solidifies and is attached to cloth bag surface together with original ammonium chloride in gas.Cloth bag separator 7 is interior regularly to cloth bag ejection pulse gas, and cloth bag surface chlorination ammonium is departed from.After the ammonium chloride sedimentation departing from, separate and return fluidized-bed reactor 5.
E product gas is after cooling, and temperature is down to normal temperature, then enters dehydration tower 8, and through rectifying, moisture is wherein discharged at the bottom of by tower, after energy recovery, discharges through water port 9 as factory effluent; In gas, other compositions are discharged by tower top, and enter deammoniation tower 11 after compressor 10 is compressed to 1.5Mpa.
G. gas enters after deammoniation tower 11, and through rectifying, ammonia is expelled to gas holder through ammonia relief outlet 12 by tower top and stores, and in gas, other compositions are discharged at the bottom of by tower.
A. methanol liquid is out successively gasified through methyl alcohol vaporizing device 2 by methyl alcohol storage tank 1 with certain flow, finally reaches temperature under normal pressure and be the methanol gas of 200 DEG C, and then it enters fluidized-bed reactor 5 from fluidized-bed reactor bottom; In ammonium chloride storage tank 3, ammonium chloride enters fluidized-bed reactor 5 by mechanical transmission device 4 from fluidized-bed reactor bottom, and wherein the mol ratio of ammonium chloride and methyl alcohol is 0.8: 1.
B. methyl alcohol and ammonium chloride enter after fluidized-bed reactor 5, under catalyst action, react, and generate methyl chloride gas and other a small amount of by products, and as methylamine material, dme etc., in fluidized-bed reactor, pressure is 0.8MPa, and temperature is 300 DEG C.
C. ammonium chloride reacts after product and contains a small amount of solid particulate with methyl alcohol, and as catalyzer etc., product gas goes out the rear cyclonic separator 6 that first passes through of fluidized-bed reactor 5, isolates solid particulate, returns it in fluidized-bed reactor 5.
D. the gas that separates solid particulate enters into cloth bag separator 7, and after temperature reduces, hydrogenchloride and ammonia in gas regenerate ammonium chloride, solidifies and is attached to cloth bag surface together with original ammonium chloride in gas.Cloth bag separator 7 is interior regularly to cloth bag ejection pulse gas, and cloth bag surface chlorination ammonium is departed from.After the ammonium chloride sedimentation departing from, separate and return fluidized-bed reactor 7.
E product gas is after cooling, and temperature is down to normal temperature, then enters dehydration tower 8, and through rectifying, moisture is wherein discharged at the bottom of by tower, after energy recovery, discharges through water port 9 as factory effluent; In gas, other compositions are discharged by tower top, and enter deammoniation tower 11 after compressor 10 is compressed to 1.5Mpa.
G. gas enters after deammoniation tower 11, and through rectifying, ammonia is expelled to gas holder through ammonia relief outlet 12 by tower top and stores, and in gas, other compositions are discharged at the bottom of by tower.
A. methanol liquid is out successively gasified through methyl alcohol vaporizing device 2 by methyl alcohol storage tank 1 with certain flow, finally reaches temperature under normal pressure and be the methanol gas of 200 DEG C, and then it enters fluidized-bed reactor 5 from fluidized-bed reactor bottom; In ammonium chloride storage tank 3, ammonium chloride enters fluidized-bed reactor 5 by mechanical transmission device 4 from fluidized-bed reactor bottom, and wherein the mol ratio of ammonium chloride and methyl alcohol is 1.5: 1.
B. methyl alcohol and ammonium chloride enter after fluidized-bed reactor 5, under catalyst action, react, and generate methyl chloride gas and other a small amount of by products, and as methylamine material, dme etc., in fluidized-bed reactor, pressure is 0.3MPa, and temperature is 300 DEG C.
C. ammonium chloride reacts after product and contains a small amount of solid particulate with methyl alcohol, and as catalyzer etc., product gas goes out the rear cyclonic separator 6 that first passes through of fluidized-bed reactor 5, isolates solid particulate, returns it in fluidized-bed reactor 5.
D. the gas that separates solid particulate enters into cloth bag separator 7, and after temperature reduces, hydrogenchloride and ammonia in gas regenerate ammonium chloride, solidifies and is attached to cloth bag surface together with original ammonium chloride in gas.Cloth bag separator 7 is interior regularly to cloth bag ejection pulse gas, and cloth bag surface chlorination ammonium is departed from.After the ammonium chloride sedimentation departing from, separate and return fluidized-bed reactor 5.
E product gas is after cooling, and temperature is down to normal temperature, then enters dehydration tower 8, and through rectifying, moisture is wherein discharged at the bottom of by tower, after energy recovery, discharges through water port 9 as factory effluent; In gas, other compositions are discharged by tower top, and enter deammoniation tower 11 after compressor 10 is compressed to 1.5Mpa.
G. gas enters after deammoniation tower 11, and through rectifying, ammonia is expelled to gas holder through ammonia relief outlet 12 by tower top and stores, and in gas, other compositions are discharged at the bottom of by tower.
A. methanol liquid is out successively gasified through methyl alcohol vaporizing device 2 by methyl alcohol storage tank 1 with certain flow, finally reaches temperature under normal pressure and be the methanol gas of 200 DEG C, and then it enters fluidized-bed reactor 5 from fluidized-bed reactor bottom; In ammonium chloride storage tank 3, ammonium chloride enters fluidized-bed reactor 5 by mechanical transmission device 4 from fluidized-bed reactor bottom, and wherein the mol ratio of ammonium chloride and methyl alcohol is 0.7: 1.
B. methyl alcohol and ammonium chloride enter after fluidized-bed reactor 5, under catalyst action, react, and generate methyl chloride gas and other a small amount of by products, and as methylamine material, dme etc., in fluidized-bed reactor, pressure is 0.3MPa, and temperature is 270 DEG C.
C. ammonium chloride reacts after product and contains a small amount of solid particulate with methyl alcohol, and as catalyzer etc., product gas goes out the rear cyclonic separator 6 that first passes through of fluidized-bed reactor 5, isolates solid particulate, returns it in fluidized-bed reactor 5.
D. the gas that separates solid particulate enters into cloth bag separator 7, and after temperature reduces, hydrogenchloride and ammonia in gas regenerate ammonium chloride, solidifies and is attached to cloth bag surface together with original ammonium chloride in gas.Cloth bag separator 7 is interior regularly to cloth bag ejection pulse gas, and cloth bag surface chlorination ammonium is departed from.After the ammonium chloride sedimentation departing from, separate and return fluidized-bed reactor 5.
E product gas is after cooling, and temperature is down to normal temperature, then enters dehydration tower 8, and through rectifying, moisture is wherein discharged at the bottom of by tower, after energy recovery, discharges through water port 9 as factory effluent; In gas, other compositions are discharged by tower top, and enter deammoniation tower 11 after compressor 10 is compressed to 1.5Mpa.
G. gas enters after deammoniation tower 11, and through rectifying, ammonia is expelled to gas holder through ammonia relief outlet 12 by tower top and stores, and in gas, other compositions are discharged at the bottom of by tower.
A. methanol liquid is out successively gasified through methyl alcohol vaporizing device 2 by methyl alcohol storage tank 1 with certain flow, finally reaches temperature under normal pressure and be the methanol gas of 200 DEG C, and then it enters fluidized-bed reactor 5 from fluidized-bed reactor bottom; In ammonium chloride storage tank 3, ammonium chloride enters fluidized-bed reactor 5 by mechanical transmission device 4 from fluidized-bed reactor bottom, and wherein the mol ratio of ammonium chloride and methyl alcohol is 1.2: 1;
B. methyl alcohol and ammonium chloride enter after fluidized-bed reactor 5, under catalyst action, react, and generate methyl chloride gas and other a small amount of by products, and as methylamine material, dme etc., in fluidized-bed reactor, pressure is 0.8MPa, and temperature is 330 DEG C.
C. ammonium chloride reacts after product and contains a small amount of solid particulate with methyl alcohol, and as catalyzer etc., product gas goes out the rear cyclonic separator 6 that first passes through of fluidized-bed reactor 5, isolates solid particulate, returns it in fluidized-bed reactor 5;
D. the gas that separates solid particulate enters into cloth bag separator 7, and after temperature reduces, hydrogenchloride and ammonia in gas regenerate ammonium chloride, solidifies and is attached to cloth bag surface together with original ammonium chloride in gas.Cloth bag separator 7 is interior regularly to cloth bag ejection pulse gas, and cloth bag surface chlorination ammonium is departed from.After the ammonium chloride sedimentation departing from, separate and return fluidized-bed reactor 5;
E. product gas is after cooling, and temperature is down to normal temperature, then enters dehydration tower 8, and through rectifying, moisture is wherein discharged at the bottom of by tower, after energy recovery, discharges through water port 9 as factory effluent; In gas, other compositions are discharged by tower top, and enter deammoniation tower 11 after compressor 10 is compressed to 1.5Mpa.
G. gas enters after deammoniation tower 11, and through rectifying, ammonia is expelled to gas holder through ammonia relief outlet 12 by tower top and stores, and in gas, other compositions are discharged at the bottom of by tower.
Claims (3)
- With ammonium chloride and Methanol for a method for methyl chloride and ammonia, it is characterized in that, it comprises the steps:A. first passing through methyl alcohol vaporizing device (2) from the methanol liquid of methyl alcohol storage tank (1) gasifies, become the methanol gas of 200～250 DEG C of temperature under normal pressure, then enter fluidized-bed reactor (5) from fluidized-bed reactor bottom; Ammonium chloride from ammonium chloride storage tank (3) enters fluidized-bed reactor (5) from fluidized-bed reactor bottom by mechanical transmission device (4); Wherein the mol ratio of ammonium chloride and methyl alcohol is 1.2: 1;B. methyl alcohol and ammonium chloride enter after fluidized-bed reactor (5), under catalyst action, react, and generate methyl chloride gas and other a small amount of by products; A small amount of by product comprises methylamine material and dme;C. from the exit gas product of fluidized-bed reactor (5), contain a small amount of solid particulate, first pass through cyclonic separator (6) and isolate solid particulate, and solid particulate is turned back in fluidized-bed reactor (5);D. the gaseous product after described step c separates enters cloth bag separator (7) subsequently, described cloth bag separator (7) is isolated because temperature reduces the ammonium chloride particle generating, and ammonium chloride particle returns to fluidized-bed reactor (5);E. the gaseous product after described steps d separates is after cooling, and temperature is down to 20～100 DEG C, then enters dehydration tower (8), and through rectifying, moisture wherein discharges through water port (9) as factory effluent at the bottom of by tower after energy recovery; In gaseous product, other compositions are discharged by tower top, and enter deammoniation tower (11) after compressor (10) is compressed to 0.5-2.0Mpa; Described dehydration tower (8) is rectifying tower, and operation pressure is 0.1-2.0Mpa;F. the gas of described step e enters after deammoniation tower (11), and through rectifying, ammonia is expelled to ammonia tank by ammonia relief outlet (12) by tower top and stores, and the liquid of sloughing after ammonia is gone out by tower bottom flow;G. the liquid at the bottom of described deammoniation tower (11) tower enters rectifying tower (13) subsequently, and through rectifying, tower top is isolated product methyl chloride, and discharges from methyl chloride outlet (14);H. composition is methyl alcohol and methylamine material at the bottom of the tower, returns to methyl alcohol storage tank (1) and recycles by returning to valve (15); At the bottom of tower, composition is methylamine material, is discharged and is stored by control valve (16);Described deammoniation tower (11) and rectifying tower (13) are compression rectification tower, and operation pressure is 0.1-2.0MPa.
- 2. a kind of ammonium chloride and Methanol used as claimed in claim 1, for the method for methyl chloride and ammonia, is characterized in that,The described interior temperature of fluidized-bed reactor (5) is 250～400 DEG C, and gas speed is 0.2-0.6m/s, and working pressure is 0.05-1.0MPa.
- 3. a kind of ammonium chloride and Methanol used as claimed in claim 1, for the method for methyl chloride and ammonia, is characterized in that,Described catalyzer is by γ-Al 2o 3carrier, modifier, active ingredient composition, wherein modifier is one or more in titanium dioxide, zirconia sol, silicon sol, white carbon black, aluminum solutions, the active ingredient of catalyzer is one or more in zinc, iron, cobalt, nickel, copper, magnesium, potassium, described active ingredient exists with metal oxide form, and presoma is nitrate or chlorate.
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| CN201110388852.9A CN102408301B (en) | 2011-11-30 | 2011-11-30 | Method for preparing methyl chloride and ammonia by using ammonium chloride and methanol |
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| CN105859513A (en) * | 2016-05-23 | 2016-08-17 | 河南红东方化工股份有限公司 | Production method for chloromethane |
| CN109942366A (en) * | 2019-03-10 | 2019-06-28 | 河北科技大学 | A kind of devices and methods therefor reacting production chloromethanes with methanol using hydrogen chloride and ammonium chloride |
| CN109956481B (en) * | 2019-04-02 | 2020-03-10 | 原初科技（北京）有限公司 | Method for preparing ammonia gas by using ammonium salt and silicate |
| CN110252213B (en) * | 2019-05-27 | 2022-03-22 | 河北科技大学 | Fluidized bed reaction device for producing chloromethane and ammonia |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502733A (en) * | 1967-11-08 | 1970-03-24 | Allied Chem | Production of chloromethanes |
| CN101574657A (en) * | 2009-06-18 | 2009-11-11 | 河北科技大学 | Catalyst for preparing chloromethane and ammonia gas and preparation method thereof |
| CN201632248U (en) * | 2010-03-08 | 2010-11-17 | 河北科技大学 | Device for preparing methyl chloride and ammonia |
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- 2011-11-30 CN CN201110388852.9A patent/CN102408301B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502733A (en) * | 1967-11-08 | 1970-03-24 | Allied Chem | Production of chloromethanes |
| CN101574657A (en) * | 2009-06-18 | 2009-11-11 | 河北科技大学 | Catalyst for preparing chloromethane and ammonia gas and preparation method thereof |
| CN201632248U (en) * | 2010-03-08 | 2010-11-17 | 河北科技大学 | Device for preparing methyl chloride and ammonia |
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