CN204097372U - A kind of CO vapor phase carbonylation produces the catalyst-assembly of methylcarbonate - Google Patents
A kind of CO vapor phase carbonylation produces the catalyst-assembly of methylcarbonate Download PDFInfo
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- CN204097372U CN204097372U CN201420170787.1U CN201420170787U CN204097372U CN 204097372 U CN204097372 U CN 204097372U CN 201420170787 U CN201420170787 U CN 201420170787U CN 204097372 U CN204097372 U CN 204097372U
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- gas
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- way valve
- pipeline
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- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 230000006315 carbonylation Effects 0.000 title claims abstract description 13
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 13
- 239000012808 vapor phase Substances 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 68
- 238000004817 gas chromatography Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 7
- 238000003860 storage Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 10
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 9
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The utility model discloses the catalyst-assembly that a kind of CO vapor phase carbonylation produces methylcarbonate, this device comprises gas and controls tubing system (1), fixed bed reaction system (2), product separation purification system (3), this device is for connecting gas chromatography system (4), wherein gas control tubing system (1) comprises three road gases control pipelines, and wherein each road includes the gas pipe line, pressure maintaining valve (5), tensimeter (6), flow stabilizing valve (7), mass flow controller (8) and the switch-valve (9) that connect successively; Three road gas pipelines are merged into a road gas pipeline by straight cross joint, and the pipeline after merging is provided with gas mixing box (10).This device just can realize higher efficiency by means of only a gas-chromatography, and fund input is less, is also convenient to produce expeditiously and separation and purification methylcarbonate.
Description
Technical field
The utility model belongs to Catalyat Engideering development technique field and methylcarbonate production technical field, is specifically related to the catalyst-assembly that a kind of CO vapor phase carbonylation produces methylcarbonate.
Background technology
Methylcarbonate is the green chemical that the whole world is generally acknowledged, be widely used in medicine, agricultural chemicals, lubrication wet goods field, particularly alternative methyl tertiary butyl ether is as gasoline dope.The current methylcarbonate output in the whole world about 400,000 tons, China's methylcarbonate annual production is about 120,000 tons.Methylcarbonate adopted phosgenation to produce in the past, and usually adopt now the ester-interchange method of epoxy third (second) alkane to produce, production cost is high, is subject to the restriction of petroleum products equally.Current whole world petrol consumption is more than 200,000,000 tons/year, if the gasoline of 20% adopts methylcarbonate to substitute methyl tertiary butyl ether, then the annual requirement of methylcarbonate will increase by 1,200,000 tons.Polycarbonate, as the derived product of methylcarbonate, expects 2015, and world's polycarbonate demand will reach 5,150,000 tons, and domestic needs amount will reach 1,600,000 tons.Along with the application of methylcarbonate in non-phosgene synthesis polycarbonate and isocyanic ester and the popularization in fields such as medicine, solvent, gasoline dopes, its annual requirement is by with the speed increment of annual twice.Therefore, methylcarbonate has huge market development potential.It is a kind of competitive synthetic method that CO vapor phase carbonylation produces methylcarbonate, and CO transformation efficiency is very high, and methylcarbonate space-time yield is also very high.
The reaction principle that CO vapor phase carbonylation produces methylcarbonate is as follows:
CO+2CH
3ONO＝(CH
3O)
2CO+2NO
Raw material is CO and the methyl nitrite of gaseous state, and principal product is organism methylcarbonate, and by product is dimethyl oxalate, methyl-formiate and methyl alcohol.
The boiling point of methylcarbonate is 90 DEG C, and fusing point is 2-4 DEG C, is liquid under room temperature.
The boiling point of dimethyl oxalate is 174 DEG C, and fusing point is 54 DEG C, is solid under room temperature.
Prior art is got off by product collection by condensation, and uncondensed gas directly enters gas chromatography system.
Mainly there is following problem in prior art: 1, needs special messenger to wait at device limit timing sampling; 2, need outfit two gas-chromatographies, a configuration flame ionization ditector and capillary column, for for organic product, another configuration thermal conductivity detector and packed column, for for uncondensed gas, fund input is larger.
Utility model content
For solving above-mentioned one or more technical problem, the utility model provides the catalyst-assembly that a kind of CO vapor phase carbonylation produces methylcarbonate, this device comprises gas and controls tubing system (1), fixed bed reaction system (2), product separation purification system (3), and this device is for connecting gas chromatography system (4);
Wherein:
Gas controls tubing system (1) and comprises three road gases control pipelines, and wherein each road includes the gas pipe line, pressure maintaining valve (5), tensimeter (6), flow stabilizing valve (7), mass flow controller (8) and the switch-valve (9) that connect successively; Three road gas pipelines are merged into a road gas pipeline by straight cross joint, and the pipeline after merging is provided with gas mixing box (10);
Fixed bed reaction system (2) comprises reactor (11), process furnace (12), catalyzer (13) and needle valve (14), reactor (11) is positioned at the middle part of process furnace (12), and catalyzer (13) is positioned at the middle part of reactor (11);
Product separation purification system (3) comprises gas-liquid separator (15), exhaust collection utilizes device (16), the first rectifying tower (17), dimethyl oxalate storage tank (18), Second distillation column (19), methylcarbonate storage tank (20) and by product storage tank (21);
Gas chromatography system (4) comprises pneumatic ten-way valve (22), pneumatic six-way valve (23), quantity tube (24), valve control (25), the first packed column (26), the second packed column (27), capillary column (28), thermal conductivity detector (29), flame ionization ditector (30);
Wherein:
Gas mixing box (10) is connected with the upper end of reactor (11), the lower end of reactor (11) is divided into two-way by isodiametric three-way connector, one tunnel is connected with gas-liquid separator (15), and needle type valve (14) of separately leading up to is connected with pneumatic ten-way valve (22);
Upper end outlet pipeline and the exhaust collection of gas-liquid separator (15) utilize device (16) to be connected, and lower end outlet conduit connects the first rectifying tower (17); The upper end outlet pipeline of the first rectifying tower (17) is connected with Second distillation column (19), and lower end outlet conduit is connected with dimethyl oxalate storage tank (18); The upper end outlet pipeline of Second distillation column (19) is connected with by product storage tank (21), and lower end outlet conduit is connected with methylcarbonate storage tank (20);
Pneumatic ten-way valve (22) is connected by pipeline with pneumatic six-way valve (23), pneumatic ten-way valve (22) and pneumatic six-way valve (23) are equipped with quantity tube (24), and pneumatic ten-way valve (22) is connected with valve control (25) with pneumatic six-way valve (23); Pneumatic ten-way valve (22) connects the first packed column (26) and the second packed column (27), and the first packed column (26) is connected with thermal conductivity detector (29); Pneumatic six-way valve (23) connects capillary column (28); Capillary column (28) is connected with flame ionization ditector (30); The outlet pipe of pneumatic six-way valve (23) is connected with the intake ducting of gas-liquid separator (15).
Preferably, three described road gases control pipeline and comprise CO gas pipeline, methyl nitrite gas pipeline and nitrogen argon gas gas mixture gas pipeline.
Preferably, the temperature range of described process furnace (12): room temperature-600 DEG C, temperature-controlled precision: ± 0.2 DEG C.
Preferably, described the first rectifying tower (17) and Second distillation column (19) are plate column or packing tower.
The beneficial effects of the utility model are:
The catalyst-assembly that CO vapor phase carbonylation disclosed in the utility model produces methylcarbonate only uses a gas-chromatography, and efficiency is high, and fund input is less, is also convenient to produce expeditiously and separation and purification methylcarbonate.
Accompanying drawing explanation
Accompanying drawing 1 CO vapor phase carbonylation disclosed in the utility model produces the schematic diagram of the catalyst-assembly of methylcarbonate, wherein: 1 for gas, to control tubing system, 2 be fixed bed reaction system, 3 is product separation purification system, 4 for gas chromatography system, 5 be pressure maintaining valve, 6 be tensimeter, 7 be flow stabilizing valve, 8 be mass flow controller, 9 be switch-valve; 10 is gas mixing box; 11 be reactor, 12 be process furnace, 13 be catalyzer, 14 for needle valve; 15 for gas-liquid separator, 16 for exhaust collection utilize device, 17 be the first rectifying tower, 18 for dimethyl oxalate storage tank, 19 for Second distillation column, 20 for methylcarbonate storage tank, 21 be by product storage tank; 22 be pneumatic ten-way valve, 23 be pneumatic six-way valve, 24 be quantity tube, 25 be capillary column, 29 be thermal conductivity detector, 30 be flame ionization ditector for valve control, 26 to be the first packed column, 27 be the second packed column, 28.
Embodiment
Below in conjunction with drawings and Examples, the utility model is described in further detail.
Embodiment 1:
The catalyst-assembly that CO vapor phase carbonylation disclosed in the utility model produces methylcarbonate comprises gas control tubing system (1), fixed bed reaction system (2), product separation purification system (3), and this device is for connecting gas chromatography system (4);
Wherein:
Gas controls tubing system (1) and comprises three road gases control pipelines, and wherein each road includes the gas pipe line, pressure maintaining valve (5), tensimeter (6), flow stabilizing valve (7), mass flow controller (8) and the switch-valve (9) that connect successively; Three road gas pipelines are merged into a road gas pipeline by straight cross joint, and the pipeline after merging is provided with gas mixing box (10);
Fixed bed reaction system (2) comprises reactor (11), process furnace (12), catalyzer (13) and needle valve (14), reactor (11) is positioned at the middle part of process furnace (12), and catalyzer (13) is positioned at the middle part of reactor (11);
Product separation purification system (3) comprises gas-liquid separator (15), exhaust collection utilizes device (16), the first rectifying tower (17), dimethyl oxalate storage tank (18), Second distillation column (19), methylcarbonate storage tank (20) and by product storage tank (21);
Gas chromatography system (4) comprises pneumatic ten-way valve (22), pneumatic six-way valve (23), quantity tube (24), valve control (25), the first packed column (26), the second packed column (27), capillary column (28), thermal conductivity detector (29), flame ionization ditector (30);
Wherein:
Gas mixing box (10) is connected with the upper end of reactor (11), the lower end of reactor (11) is divided into two-way by isodiametric three-way connector, one tunnel is connected with gas-liquid separator (15), and needle type valve (14) of separately leading up to is connected with pneumatic ten-way valve (22);
Upper end outlet pipeline and the exhaust collection of gas-liquid separator (15) utilize device (16) to be connected, and lower end outlet conduit connects the first rectifying tower (17); The upper end outlet pipeline of the first rectifying tower (17) is connected with Second distillation column (19), and lower end outlet conduit is connected with dimethyl oxalate storage tank (18); The upper end outlet pipeline of Second distillation column (19) is connected with by product storage tank (21), and lower end outlet conduit is connected with methylcarbonate storage tank (20);
Pneumatic ten-way valve (22) is connected by pipeline with pneumatic six-way valve (23), pneumatic ten-way valve (22) and pneumatic six-way valve (23) are equipped with quantity tube (24), and pneumatic ten-way valve (22) is connected with valve control (25) with pneumatic six-way valve (23); Pneumatic ten-way valve (22) connects the first packed column (26) and the second packed column (27), and the first packed column (26) is connected with thermal conductivity detector (29); Pneumatic six-way valve (23) connects capillary column (28); Capillary column (28) is connected with flame ionization ditector (30); The outlet pipe of pneumatic six-way valve (23) is connected with the intake ducting of gas-liquid separator (15).
Preferably, three described road gases control pipeline and comprise CO gas pipeline, methyl nitrite gas pipeline and nitrogen argon gas gas mixture gas pipeline.
Preferably, described the first rectifying tower (17) and Second distillation column (19) are packing tower, and filler is ceramic raschig rings.
Exemplary, use the method for the catalyst-assembly of CO vapor phase carbonylation production methylcarbonate disclosed in the utility model as follows:
1, loading catalyst: measure 100mL1%PdCl
2-1%CuCl
2/ activated-carbon catalyst (13), put into reactor (11) middle part, inert stone sand is all filled at upper and lower two ends;
2, unstripped gas is passed into: the switch-valve (9) opening CO, methyl nitrite and nitrogen argon gas gas mixture gas pipeline, regulate pressure maintaining valve (5), flow stabilizing valve (7) and mass flow controller (8), the pressure controlling unstripped gas is 0.1MPa, total flux is 5L/min, wherein by volume, CO: methyl nitrite=1: 2;
3, open gas-chromatography: open the first carrier gas, the second carrier gas and the 3rd carrier gas, open gas-chromatography, thermal conductivity detector adds electric current, and flame ionization ditector is lighted a fire, and makes gas-chromatography keep ready state;
4, collected specimens: regulate needle type valve (14), makes a small amount of unstripped gas enter quantity tube (24) in gas chromatography system (4);
5, controlled ramp: after determining the initial peak area of unstripped gas, controls process furnace (12) and is warming up to temperature of reaction 120 DEG C;
6, collected specimens: when reacting balance runs, regulates needle type valve (14), makes a small amount of product gas enter quantity tube (24) in gas chromatography system (4);
7, valve control (25) controls pneumatic ten-way valve (22) and pneumatic six-way valve (23) rotates simultaneously, bring the product in quantity tube (24) into chromatographic column, methyl nitrite goes out peak after being separated by capillary column (28) with the organism in product on flame ionization ditector (30), organic product is fallen by blowback by the second packed column (27), and residue inorganic gas goes out peak by the first packed column (26) on thermal conductivity detector (29).
Exemplary, the method that the catalyst-assembly using CO vapor phase carbonylation disclosed in the utility model to produce methylcarbonate produces methylcarbonate is as follows:
1, loading catalyst: measure 100mL1%PdCl
2-1%CuCl
2/ activated-carbon catalyst (13), put into reactor (11) middle part, inert stone sand is all filled at upper and lower two ends;
2, unstripped gas is passed into: the switch-valve (9) opening CO, methyl nitrite and nitrogen argon gas gas mixture gas pipeline, regulate pressure maintaining valve (5), flow stabilizing valve (7) and mass flow controller (8), the pressure controlling unstripped gas is 0.1MPa, total flux is 5L/min, wherein by volume, CO: methyl nitrite=1: 2;
3, controlled ramp: control process furnace (12) and be warming up to temperature of reaction 120 DEG C;
4, catalyzed reaction: unstripped gas generates product in catalyzer (13) surface reaction;
5, product separation purifying: product enters gas-liquid separator (15) and carries out gas-liquid separation, uncondensed gas enters exhaust collection and utilizes device (16) to recycle; Condensed fluid enters the first rectifying tower (17) and carries out first time separation, first rectifying tower (17) lower end effluent I enters dimethyl oxalate storage tank (18), first rectifying tower (17) upper end effluent II enters Second distillation column (19) and carries out second time separation, Second distillation column (19) upper end effluent III enters by product storage tank (21), and Second distillation column (19) lower end effluent IV enters methylcarbonate storage tank (20).
Above-described embodiment is only for illustration of the composition, mode of connection etc. of catalyst device disclosed in the utility model; do not limit the utility model; all do within spirit of the present utility model and principle any amendment, parts equivalent replacement and improvement etc., be all included within protection domain of the present utility model.
Claims (4)
1. the catalyst-assembly of a CO vapor phase carbonylation production methylcarbonate, this device comprises gas and controls tubing system (1), fixed bed reaction system (2), product separation purification system (3), and this device is for connecting gas chromatography system (4);
It is characterized in that:
Gas controls tubing system (1) and comprises three road gases control pipelines, and wherein each road includes the gas pipe line, pressure maintaining valve (5), tensimeter (6), flow stabilizing valve (7), mass flow controller (8) and the switch-valve (9) that connect successively; Three road gas pipelines are merged into a road gas pipeline by straight cross joint, and the pipeline after merging is provided with gas mixing box (10);
Fixed bed reaction system (2) comprises reactor (11), process furnace (12), catalyzer (13) and needle valve (14), reactor (11) is positioned at the middle part of process furnace (12), and catalyzer (13) is positioned at the middle part of reactor (11);
Product separation purification system (3) comprises gas-liquid separator (15), exhaust collection utilizes device (16), the first rectifying tower (17), dimethyl oxalate storage tank (18), Second distillation column (19), methylcarbonate storage tank (20) and by product storage tank (21);
Gas chromatography system (4) comprises pneumatic ten-way valve (22), pneumatic six-way valve (23), quantity tube (24), valve control (25), the first packed column (26), the second packed column (27), capillary column (28), thermal conductivity detector (29), flame ionization ditector (30);
Wherein:
Gas mixing box (10) is connected with the upper end of reactor (11), the lower end of reactor (11) is divided into two-way by isodiametric three-way connector, one tunnel is connected with gas-liquid separator (15), and needle type valve (14) of separately leading up to is connected with pneumatic ten-way valve (22);
Upper end outlet pipeline and the exhaust collection of gas-liquid separator (15) utilize device (16) to be connected, and lower end outlet conduit connects the first rectifying tower (17); The upper end outlet pipeline of the first rectifying tower (17) is connected with Second distillation column (19), and lower end outlet conduit is connected with dimethyl oxalate storage tank (18); The upper end outlet pipeline of Second distillation column (19) is connected with by product storage tank (21), and lower end outlet conduit is connected with methylcarbonate storage tank (20);
Pneumatic ten-way valve (22) is connected by pipeline with pneumatic six-way valve (23), pneumatic ten-way valve (22) and pneumatic six-way valve (23) are equipped with quantity tube (24), and pneumatic ten-way valve (22) is connected with valve control (25) with pneumatic six-way valve (23); Pneumatic ten-way valve (22) connects the first packed column (26) and the second packed column (27), and the first packed column (26) is connected with thermal conductivity detector (29); Pneumatic six-way valve (23) connects capillary column (28); Capillary column (28) is connected with flame ionization ditector (30); The outlet pipe of pneumatic six-way valve (23) is connected with the intake ducting of gas-liquid separator (15).
2. device according to claim 1, is characterized in that: three described road gases control pipeline and comprise CO gas pipeline, methyl nitrite gas pipeline and nitrogen argon gas gas mixture gas pipeline.
3. device according to claim 1, is characterized in that: the temperature range of described process furnace (12): room temperature-600 DEG C, temperature-controlled precision: ± 0.2 DEG C.
4. device according to claim 1, is characterized in that: described the first rectifying tower (17) and Second distillation column (19) are plate column or packing tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420170787.1U CN204097372U (en) | 2014-04-10 | 2014-04-10 | A kind of CO vapor phase carbonylation produces the catalyst-assembly of methylcarbonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420170787.1U CN204097372U (en) | 2014-04-10 | 2014-04-10 | A kind of CO vapor phase carbonylation produces the catalyst-assembly of methylcarbonate |
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| Publication Number | Publication Date |
|---|---|
| CN204097372U true CN204097372U (en) | 2015-01-14 |
Family
ID=52265817
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818568A (en) * | 2018-08-07 | 2020-02-21 | 上海华谊能源化工有限公司 | Device for continuously producing methyl nitrite gas and application thereof |
-
2014
- 2014-04-10 CN CN201420170787.1U patent/CN204097372U/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818568A (en) * | 2018-08-07 | 2020-02-21 | 上海华谊能源化工有限公司 | Device for continuously producing methyl nitrite gas and application thereof |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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Granted publication date: 20150114 |