CN101041418A - Processes and apparatus for gas production by methanol - Google Patents
Processes and apparatus for gas production by methanol Download PDFInfo
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- CN101041418A CN101041418A CN 200710061762 CN200710061762A CN101041418A CN 101041418 A CN101041418 A CN 101041418A CN 200710061762 CN200710061762 CN 200710061762 CN 200710061762 A CN200710061762 A CN 200710061762A CN 101041418 A CN101041418 A CN 101041418A
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- formic acid
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Abstract
The invention discloses a preparing method of a gas and device, which comprises the following steps: making the activator with 40-60% copper, 25-45% zinc, 10-15% aluminium and 4-5% potassium under low temperature. accumulating aminic acid solution through condensing heat exchanger and water cooler into aminic acid accumulating pot; realizing automatic discharge of aminic acid solution through liquid level sensor of controlling by the control unit; lowering erosion of device; assembling liquid level sensor of controlled by the control unit on the mix-allocating pot; realizing automatic allocation; reducing intensity of labor distinctly.
Description
Technical field
The present invention relates to the preparation method and the equipment of a kind of gas of chemical field, be specially the gas production by methanol Processes and apparatus.
Background technology
Traditional process for making hydrogen is an electrolytic hydrogen production, produce hydrogen in this way and need consume very big electric energy, and the hydrogen pressure that electrolytic process obtains is lower, can not directly be connected with user's pipe network, also need be equipped with expensive hydrogen supercharging equipment.Along with the continuous development of art technology, people begin to make feedstock production hydrogen with methyl alcohol, and methyl alcohol is made feedstock production hydrogen and had that save energy, cost are lower, hydrogen purity is than advantages such as height.But in existing technological process, there is following shortcoming: 1, in blending process, methyl alcohol and deionized water directly pump into the jar that is mixed respectively, open contactor pump or gas stirring device then, constantly in the jar that is mixed, stir, like this, having methanol steam constantly overflows, and said process all is by artificial execute-in-place, can breathe methanol steam inevitably, also can touch methanol liquid inevitably, it is healthy to have a strong impact on the workman, and by artificial execute-in-place, labor strength is big; 2, can contain a certain amount of formic acid in the reacted generation gas of methyl alcohol and water, this formic acid may be to be brought into by methyl alcohol, also may be to produce by side reaction, when the semi-invariant of formic acid acquire a certain degree and condensation (below 100 ℃) after, its phlegma can cause heavy corrosion to equipment.At present, have two kinds of methods to remove formic acid, the one, the acid-base neutralisation method, promptly add excessive alkali lye with in and formic acid, this method has been avoided acid corrosion, has brought the thermokalite corrosion again; The 2nd, the de-acidying agent method, this de-acidying agent is a solid adsorbent, and adsorptive capacity is limited, be not suitable for atm number and use, and de-acidying agent need regularly replace, and not only cost is higher, and normally carrying out of producing of influence; 3, in hydrogen from methyl alcohol technology, the advanced person that the quality of catalyst performance determines whole technology whether, catalyzer in more existing technologies is to be main component with Cu, Zn, Cr, not only the reduction temperature of catalyzer is higher, generally at 180-250 ℃, and wherein Cr can cause environmental pollution in making and use, makes people's nasal septum perforate membrane.
Summary of the invention
The present invention for solve existing gas production by methanol technology exist raw material be mixed artificial on-the-spot behaviour, level of automation is lower, the formic acid treatment process is improper and problem such as catalyst reduction temperature height, and a kind of gas production by methanol Processes and apparatus is provided.
The present invention adopts following technical scheme to realize: a kind of gas production by methanol technology, may further comprise the steps, methyl alcohol and water are mixed in proportion the back jar that is mixed that imports, enter heat exchanger after metering, carry out heat exchange with reacted reformed gas, methanol steam after the vaporization enters in the reactor that catalyzer is housed then, in reactor, carry out cracking, transformationreation is to obtain hydrogen and carbonic acid gas, the reformed gas of being come out by reactor enters heat exchanger and raw material carries out heat exchange, heat exchange is laggard goes into water cooler and further lowers the temperature, carry out purifying with pressure swing adsorption process then after dewatering, described catalyzer is made by following raw materials by weight percent:
Copper 40-60% zinc 25-45% aluminium 10-15% potassium 4-5%.
The formic acid solution that condensation is got off in described heat exchanger and the water cooler is collected automatically by the formic acid holding tank, because the temperature of heat exchanger and water cooler outlet is usually all below the liquefaction temperature of formic acid, so adopt the nature condensation, the method that relies on gravity to collect then removes the formic acid in the reformed gas.
The ratio of methyl alcohol of the present invention and water, temperature of reaction and reaction pressure are that those of ordinary skill in the art is known for existing known technology.The present invention in the specific implementation, the ratio of selecting methyl alcohol and water for use is 1: 0.7-1, temperature of reaction is 180 ℃-320 ℃, pressure is 0.8-2.0Mpa.In the methanol recapitalization reaction process, utilize the resulting reformed gas of above-mentioned catalyzer and reaction conditions after pressure swing adsorption process removes impurity, can obtain hydrogen and purity that purity is 99.5%-99.9995% is the carbon dioxide of 99-99.99%, and needed heat is provided by thermal oil in the reaction process.
Finish the equipment of above-mentioned gas production by methanol technology, comprise the automatic recipe maker that contains the jar that is mixed, the heat exchanger that links to each other with the jar that is mixed and the water cooler that links to each other with heat exchanger, also comprise the formic acid holding tank, formic acid holding tank top links to each other with water cooler, heat exchanger bottom by pipeline respectively, formic acid holding tank below is provided with the discharging of waste liquid pipe, on the discharging of waste liquid pipe pneumavalve is installed; The liquid level sensor of being handled by control unit also is set on the formic acid holding tank, and the input terminus of control unit is connected with liquid level sensor, and output terminal is connected with pneumavalve.Described control unit, liquid level sensor, the structure of pneumavalve and the principle of work between the three are that those of ordinary skill in the art knows.In technical solutions according to the invention, the formic acid solution that is got off by heat exchanger and water cooler condensation is flowed in the formic acid holding tank by pipeline, when liquid level reaches upper limit set value in the jar, liquid level sensor is with the liquid level signal Input Control Element, control unit is passed to pneumavalve on the discharging of waste liquid pipe with output signal then, pneumavalve is opened, and the formic acid solution in jar begins discharging; When the liquid level in the jar dropped to lower limit set value, pneumavalve cut out under the effect of control unit, had realized the collection of formic acid and discharging automatically.
Above-mentioned automatic recipe maker comprises the raw material storage tank of methyl alcohol and deionized water and methanol pump that links to each other with raw material storage tank respectively and deionization water pump, and two pumps are communicated with the jar that is mixed by methyl alcohol transfer lime and deionized water transfer lime respectively.The middle mixing tank of material is set on methyl alcohol transfer lime and the deionized water transfer lime, and the methyl alcohol transfer lime is connected with the top of mixing tank in the middle of the material, and the deionized water transfer lime is connected with the below of mixing tank in the middle of the material.In blending process, two kinds of materials are respectively under the effect of the surging force of pump, be introduced in the middle mixing tank of the less material of volume, and consider the difference of specific gravity of two kinds of materials, the top of methyl alcohol by mixing tank in the middle of the material imported, and deionized water is imported by its below, so that both thorough mixing.
The described jar that is mixed is gone up the liquid level sensor of being handled by control unit is set, the input terminus of control unit is connected with liquid level sensor, output terminal is connected with the deionization water pump with methanol pump respectively, when the liquid level of the jar that is mixed is lower than lower limit set value, liquid level sensor transmits signal to control unit, control unit is passed to methanol pump and deionization water pump with output signal then, and both are opened, and makes methyl alcohol and deionized water mix with certain proportion; When the liquid level in the jar that is mixed reaches upper limit set value, under the effect of control unit, close methanol pump and deionization water pump automatically.The structure of described control unit, liquid level sensor and the unlatching of how controlling two pumps according to the height of liquid level are that those of ordinary skill in the art is easy to realize.
Compared with prior art, the present invention has the following advantages:
1, adopting Cu, Zn, Al, K is catalyzer, make and use in can not cause environmental pollution, and on technology reduction temperature lower (150-180 ℃), and this catalyst life is grown (3-5);
2, in burden process, the present invention adopts the liquid level sensor of being handled by control unit is installed on the jar that is mixed, it is on duty to need not the workman in the working process, realize automatic proportioning, alleviated labor strength greatly, guaranteed workman's physical and mental health, and methyl alcohol and deionized water are under the effect of the surging force of pump, in the middle of the less material of volume, mix in the mixing tank, can layering;
3, the formic acid solution that condensation in heat exchanger and the water cooler is got off is collected in the formic acid holding tank, and by realized the automatic discharging of formic acid solution by liquid level sensor, the pneumavalve of control unit control, greatly reduce the corrosion of formic acid, prolonged the work-ing life of equipment equipment
In a word, technology advanced person of the present invention has realized automatic production, and simple in structure, and equipment manufacturing cost is lower, can be widely used in the gas production by methanol industry.
Description of drawings
Fig. 1 is the process flow sheet of burden process of the present invention
Fig. 2 is the process flow sheet of reaction process of the present invention
Fig. 3 is the structural representation of formic acid holding tank among Fig. 2
Among the figure: the 1-mixing tank 16-gasification superheater 17-washing tower 18-volume pump 19-separator 20-cooling driers 21-surge tank 22-control unit 23-liquid level sensor in the middle of jar 2-heat exchanger 3-reactor 4-water cooler 5-formic acid holding tank 6-discharging of waste liquid pipe 7-pneumavalve 8-control unit 9-liquid level sensor 10-raw material storage tank 11-methanol pump 12-deionization water pump 13-methyl alcohol transfer lime 14-deionized water transfer lime 15-material that is mixed
Embodiment
Embodiment 1:
Gas production by methanol technology, may further comprise the steps, methyl alcohol and water are imported the jar 1 that is mixed in proportion, after volume pump 18 meterings, enter heat exchanger 2, carry out heat exchange with reacted reformed gas, methanol steam after the heat exchange enters gasification superheater 16 and further heats, make it reach temperature of reaction, this process methanol steam rises to more than 230 ℃ from 130 ℃, heat is provided by thermal oil, methanol steam after the vaporization enters in the reactor 3 that catalyzer is housed then, in reactor 3, carry out cracking, transformationreation is to obtain hydrogen and carbonic acid gas, the reformed gas of being come out by reactor 3 enters heat exchanger 2 and raw material carries out heat exchange, heat exchange is laggard goes into water cooler 4 and further lowers the temperature, make it reach normal temperature, gas after the cooling enters washing tower 17, the Trace Methanol (deionized water after the washing is used for batching) that does not have complete reaction with the deionized water flush away, again through gas-liquid separator 19, cooling driers 20 removes the moisture in the gas, obtain exsiccant hydrogen and carbonic acid gas, exsiccant reformed gas is through transformation fractionation by adsorption hydrogen and carbonic acid gas, described catalyzer is made by following raw materials by weight percent: copper 40%, zinc 45%, aluminium 10%, potassium 5%, described temperature of reaction is 230 ℃, pressure is 0.8Mpa, and the formic acid solution that condensation is got off in described heat exchanger and the water cooler is collected automatically by the formic acid holding tank.
Finish the used equipment of above-mentioned technology, comprise contain jar 1 the dosing unit of being mixed, with the water cooler 4 that is mixed jar 1 heat exchanger that links to each other 2 and links to each other with heat exchanger 2, also comprise formic acid holding tank 5, formic acid holding tank 5 tops link to each other with water cooler 4, heat exchanger 2 bottoms by pipeline respectively, formic acid holding tank 5 belows are provided with discharging of waste liquid pipe 6, and pneumavalve 7 is installed on the discharging of waste liquid pipe 6; The liquid level sensor of being handled by control unit 22 23 also is set on the formic acid holding tank 5, and the input terminus of control unit 22 is connected with liquid level sensor 23, and output terminal is connected with pneumavalve 7; Above-mentioned dosing unit comprises the raw material storage tank 10 of methyl alcohol and deionized water and methanol pump 11 that links to each other with raw material storage tank 10 respectively and deionization water pump 12, two pumps are communicated with the jar 1 that is mixed by methyl alcohol transfer lime 13 and deionized water transfer lime 14 respectively, the middle mixing tank 15 of material is set on methyl alcohol transfer lime 13 and the deionized water transfer lime 14, methyl alcohol transfer lime 13 is connected with the top of mixing tank 15 in the middle of the material, and deionized water transfer lime 14 is connected with the below of mixing tank 15 in the middle of the material; Being mixed is provided with the liquid level sensor of being handled by control unit 89 on jar 1, and the input terminus of control unit 8 is connected with liquid level sensor 9, and output terminal is connected with deionization water pump 12 with methanol pump 11 respectively.
Embodiment 2:
Gas production by methanol technology, may further comprise the steps, methyl alcohol and water are imported the jar 1 that is mixed in proportion, after volume pump 18 meterings, enter heat exchanger 2, carry out heat exchange with reacted reformed gas, methanol steam after the heat exchange enters gasification superheater 16 and further heats, make it reach temperature of reaction, this process methanol steam rises to more than 230 ℃ from 130 ℃, heat is provided by thermal oil, methanol steam after the vaporization enters in the reactor 3 that catalyzer is housed then, in reactor 3, carry out cracking, transformationreation is to obtain hydrogen and carbonic acid gas, the reformed gas of being come out by reactor 3 enters heat exchanger 2 and raw material carries out heat exchange, heat exchange is laggard goes into water cooler 4 and further lowers the temperature, make it reach normal temperature, gas after the cooling enters washing tower 17, the Trace Methanol (deionized water after the washing is used for batching) that does not have complete reaction with the deionized water flush away, again through gas-liquid separator 19, cooling driers 20 removes the moisture in the gas, obtain exsiccant hydrogen and carbonic acid gas, exsiccant reformed gas is through transformation fractionation by adsorption hydrogen and carbonic acid gas, described catalyzer is made by following raw materials by weight percent: copper 55%, zinc 25%, aluminium 15%, potassium 5%, described temperature of reaction is 320 ℃, pressure is 2.0Mpa, and the formic acid that condensation is got off in described heat exchanger and the water cooler is collected automatically by the formic acid holding tank.
The equipment of gas production by methanol as mentioned above.
Embodiment 3:
Gas production by methanol technology, may further comprise the steps, methyl alcohol and water are imported the jar 1 that is mixed in proportion, after volume pump 18 meterings, enter heat exchanger 2, carry out heat exchange with reacted reformed gas, methanol steam after the heat exchange enters gasification superheater 16 and further heats, make it reach temperature of reaction, this process methanol steam rises to more than 230 ℃ from 130 ℃, heat is provided by thermal oil, methanol steam after the vaporization enters in the reactor 3 that catalyzer is housed then, in reactor 3, carry out cracking, transformationreation is to obtain hydrogen and carbonic acid gas, the reformed gas of being come out by reactor 3 enters heat exchanger 2 and raw material carries out heat exchange, heat exchange is laggard goes into water cooler 4 and further lowers the temperature, make it reach normal temperature, gas after the cooling enters washing tower 17, the Trace Methanol (deionized water after the washing is used for batching) that does not have complete reaction with the deionized water flush away, again through gas-liquid separator 19, cooling driers 20 removes the moisture in the gas, obtain exsiccant hydrogen and carbonic acid gas, exsiccant reformed gas is through transformation fractionation by adsorption hydrogen and carbonic acid gas, described catalyzer is made by following raw materials by weight percent: copper 50%, zinc 35%, aluminium 11%, potassium 4%, described temperature of reaction is 280 ℃, pressure is 1.0Mpa, and the formic acid that condensation is got off in described heat exchanger and the water cooler is collected automatically by the formic acid holding tank.
The equipment of gas production by methanol as mentioned above.
Embodiment 4:
Gas production by methanol technology, may further comprise the steps, methyl alcohol and water are imported the jar 1 that is mixed in proportion, after volume pump 8 meterings, enter heat exchanger 2, carry out heat exchange with reacted reformed gas, methanol steam after the heat exchange enters gasification superheater 16 and further heats, make it reach temperature of reaction, this process methanol steam rises to more than 230 ℃ from 130 ℃, heat is provided by thermal oil, methanol steam after the vaporization enters in the reactor 3 that catalyzer is housed then, in reactor 3, carry out cracking, transformationreation is to obtain hydrogen and carbonic acid gas, the reformed gas of being come out by reactor 3 enters heat exchanger 2 and raw material carries out heat exchange, heat exchange is laggard goes into water cooler 4 and further lowers the temperature, make it reach normal temperature, gas after the cooling enters washing tower 17, the Trace Methanol (deionized water after the washing is used for batching) that does not have complete reaction with the deionized water flush away, again through gas-liquid separator 19, cooling driers 20 removes the moisture in the gas, obtain exsiccant hydrogen and carbonic acid gas, exsiccant reformed gas is through transformation fractionation by adsorption hydrogen and carbonic acid gas, described catalyzer is made by following raw materials by weight percent: copper 44%, zinc 40%, aluminium 12%, potassium 4%, described temperature of reaction is 300 ℃, pressure is 1.5Mpa, and the formic acid that condensation is got off in described heat exchanger and the water cooler is collected automatically by the formic acid holding tank.
The equipment of gas production by methanol as mentioned above.
Claims (5)
1, a kind of gas production by methanol technology, may further comprise the steps, methyl alcohol and water are imported be mixed jar (1) in proportion, enter heat exchanger (2) after metering, carry out heat exchange with reacted reformed gas, methanol steam after the vaporization enters in the reactor (3) that catalyzer is housed then, in reactor (3), carry out cracking, transformationreation is to obtain hydrogen and carbonic acid gas, the reformed gas of being come out by reactor (3) enters heat exchanger (2) and raw material carries out heat exchange, heat exchange is laggard goes into further cooling of water cooler (4), carry out purifying with pressure swing adsorption process then after dewatering, it is characterized in that: described catalyzer is made by following raw materials by weight percent:
Copper 40-60% zinc 25-45% aluminium 10-15% potassium 4-5%.
2, gas production by methanol technology according to claim 1 is characterized in that the formic acid solution that gets off of heat exchanger (2) and water cooler (4) outlet condensation collected automatically by formic acid holding tank (5).
3, finish the equipment of gas production by methanol technology as claimed in claim 1 or 2, comprise the dosing unit that contains be mixed jar (1), the heat exchanger (2) that links to each other be mixed jar (1) and the water cooler (4) that links to each other with heat exchanger (2), it is characterized in that also comprising formic acid holding tank (5), formic acid holding tank (5) top links to each other with water cooler (4), heat exchanger (2) outlet by pipeline respectively, formic acid holding tank (5) below is provided with discharging of waste liquid pipe (6), and pneumavalve (7) is installed on the discharging of waste liquid pipe (6); The liquid level sensor of being handled by control unit (22) (23) also is set on the formic acid holding tank (5), and the input terminus of control unit (22) is connected with liquid level sensor (23), and output terminal is connected with pneumavalve (7).
4, the equipment of finishing gas production by methanol technology according to claim 3, wherein dosing unit comprises the raw material storage tank (10) of methyl alcohol and deionized water and methanol pump (11) that links to each other with raw material storage tank (10) respectively and deionization water pump (12), two pumps are communicated be mixed jar (1) by methyl alcohol transfer lime (13) and deionized water transfer lime (14) respectively, it is characterized in that being provided with on methyl alcohol transfer lime (13) and the deionized water transfer lime (14) the middle mixing tank (15) of material, methyl alcohol transfer lime (13) is connected with the top of mixing tank (15) in the middle of the material, and deionized water transfer lime (14) is connected with the below of mixing tank (15) in the middle of the material.
5, the equipment of finishing gas production by methanol technology according to claim 4, the jar (1) that it is characterized in that being mixed is gone up the liquid level sensor of being handled by control unit (8) (9) is set, the input terminus of control unit (8) is connected with liquid level sensor (9), and output terminal is connected with deionization water pump (12) with methanol pump (11) respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100617622A CN100534894C (en) | 2007-04-24 | 2007-04-24 | Processes and apparatus for gas production by methanol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100617622A CN100534894C (en) | 2007-04-24 | 2007-04-24 | Processes and apparatus for gas production by methanol |
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| Publication Number | Publication Date |
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| CN101041418A true CN101041418A (en) | 2007-09-26 |
| CN100534894C CN100534894C (en) | 2009-09-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2007100617622A Expired - Fee Related CN100534894C (en) | 2007-04-24 | 2007-04-24 | Processes and apparatus for gas production by methanol |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362973B (en) * | 2008-08-28 | 2011-09-21 | 西南化工研究设计院 | Technique for preparing mixed fuel of hydrogen and dimethyl ether from methanol |
| CN103086323A (en) * | 2011-10-31 | 2013-05-08 | 株式会社电装 | Reactor |
| CN103223343A (en) * | 2013-04-15 | 2013-07-31 | 天津大学 | Alkali metal modified copper-based catalyst for hydrogen production by dimethyl ether steam reforming and preparation method |
| CN103420337A (en) * | 2013-09-05 | 2013-12-04 | 山东乾鑫环保科技有限公司 | Method and device for preparing boiler hydrogen through methanol steam reforming |
| CN103980969A (en) * | 2014-05-06 | 2014-08-13 | 张松垒 | Method and apparatus for preparation of combustible gas from water |
| WO2016070590A1 (en) * | 2014-11-07 | 2016-05-12 | 广东合即得能源科技有限公司 | Hydrogen production machine utilizing methanol and water and hydrogen production method thereof |
| CN112573480A (en) * | 2020-12-28 | 2021-03-30 | 常州市蓝博净化科技有限公司 | Production line for efficient methanol hydrogen production |
| CN112707369A (en) * | 2021-02-19 | 2021-04-27 | 山东东昌精细化工科技有限公司 | Process and device for efficiently preparing carbon monoxide and hydrogen by utilizing methanol cracking |
| CN112707369B (en) * | 2021-02-19 | 2024-05-17 | 山东东昌精细化工科技有限公司 | Process and device for efficiently preparing carbon monoxide and hydrogen by utilizing methanol pyrolysis |
-
2007
- 2007-04-24 CN CNB2007100617622A patent/CN100534894C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362973B (en) * | 2008-08-28 | 2011-09-21 | 西南化工研究设计院 | Technique for preparing mixed fuel of hydrogen and dimethyl ether from methanol |
| CN103086323A (en) * | 2011-10-31 | 2013-05-08 | 株式会社电装 | Reactor |
| US9187321B2 (en) | 2011-10-31 | 2015-11-17 | Denso Corporation | Reactor |
| CN103223343A (en) * | 2013-04-15 | 2013-07-31 | 天津大学 | Alkali metal modified copper-based catalyst for hydrogen production by dimethyl ether steam reforming and preparation method |
| CN103420337A (en) * | 2013-09-05 | 2013-12-04 | 山东乾鑫环保科技有限公司 | Method and device for preparing boiler hydrogen through methanol steam reforming |
| CN103420337B (en) * | 2013-09-05 | 2015-09-09 | 山东乾鑫环保节能科技股份有限公司 | A kind of methanol steam reforming prepares the method for boiler hydrogen |
| CN103980969A (en) * | 2014-05-06 | 2014-08-13 | 张松垒 | Method and apparatus for preparation of combustible gas from water |
| WO2016070590A1 (en) * | 2014-11-07 | 2016-05-12 | 广东合即得能源科技有限公司 | Hydrogen production machine utilizing methanol and water and hydrogen production method thereof |
| CN112573480A (en) * | 2020-12-28 | 2021-03-30 | 常州市蓝博净化科技有限公司 | Production line for efficient methanol hydrogen production |
| CN112707369A (en) * | 2021-02-19 | 2021-04-27 | 山东东昌精细化工科技有限公司 | Process and device for efficiently preparing carbon monoxide and hydrogen by utilizing methanol cracking |
| CN112707369B (en) * | 2021-02-19 | 2024-05-17 | 山东东昌精细化工科技有限公司 | Process and device for efficiently preparing carbon monoxide and hydrogen by utilizing methanol pyrolysis |
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| CN100534894C (en) | 2009-09-02 |
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