CN100500550C - Method of preparing hydrogen by reforming methanol-water steam - Google Patents
Method of preparing hydrogen by reforming methanol-water steam Download PDFInfo
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- CN100500550C CN100500550C CN 200710048432 CN200710048432A CN100500550C CN 100500550 C CN100500550 C CN 100500550C CN 200710048432 CN200710048432 CN 200710048432 CN 200710048432 A CN200710048432 A CN 200710048432A CN 100500550 C CN100500550 C CN 100500550C
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Abstract
This invention discloses a method for reforming methyl alcohol vapour to prepare hydrogen including: preheating, vapouring to 230-280deg.C raw materials of methyl alcohol and water in the mol ratio of 1 :1-1.6, then carrying out catalyzing and reforming reaction in a reactor to be mixed and puried characterizing that : a, when starting, the method utilizes methyl alcohol as the heat-supply material and utilizes the discharge gas in reforming and puring alcohol and its vapour after starting up, b, the alcohol and its discharge gas supply heat by independent burning sprayers of alcohol and discharge gas in a heating furnace, c, waste gas after combustion is discharged after adsorption and purification, which replaces traditional coal and oil as the heat supply fuel.
Description
Technical field
The invention belongs to chemical technology field, particularly a kind of method of utilizing preparing hydrogen by reforming methanol-water steam.
Background technology
The fast development of hydrogen powered vehicle and fuel cell makes hydrogen become important clean energy.A large amount of hydrogen derives from coal, Sweet natural gas and oil at present, is insoluble problem because the storage of hydrogen is transported, so the less relatively industry of hydrogen usage needs other process for making hydrogen to realize always.Hydrogen production from methanol-steam reforming has less investment, extremely user's the favor of characteristics that the plant area area is little, however the methanol steam reforming reaction is a strong endothermic reaction, the carrying out that the continuous heat supply of this arts demand external heat source just can be kept reaction.Traditional hydrogen production from methanol-steam reforming technology general using coal or oil combustion are sent to reactor by thermal barrier, and coal and oil combustion cause certain pollution to air, if therefore use coal or oil combustion heat supply must solve problem of environmental pollution.Because device itself is smaller, solve coal or oil combustion and cause certain pollution cost higher air, therefore need a kind of better technology that medium and small user is provided the needs with hydrogen.The method that Chinese patent CN1064022.C provides a kind of methanol steam to transform the pure hydrogen of preparation, discharging gas directly emptying behind catalyticcombustion of transformation absorption and alternating temperature absorption.Though this technology has solved the environmental pollution that causes because of off-gas, do not solve the pollution that reaction heat supply problem is brought.
The development need of hydrogen powered vehicle and fuel cell provides movably device for producing hydrogen simultaneously, but traditional hydrogen production from methanol-steam reforming technology is owing to adopt coal or oil combustion heat supply, cumbersome, these fuel bring very big pollution to air, and the equipment that the contaminated solution problem needs is many, make whole device volume bigger, needs that can not fine satisfied portable hydrogen manufacturing.
In addition, throughput is that the consumption of coal that traditional hydrogen production from methanol-steam reforming device of 1000Nm3/h is used for combustion heat supplying is 0.6t/h, and energy consumption is bigger.
Summary of the invention
The novel method that the purpose of this invention is to provide the preparing hydrogen by reforming methanol-water steam of a kind of not only energy-conservation but also environmental protection.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of method of preparing hydrogen by reforming methanol-water steam, key step comprises: with material benzenemethanol and hydromassage you than for 1:1～1.6 through preheating, vaporize, be heated to 230～280 ℃, in reactor, carry out catalytic reforming reaction then, with the reformation gas mixture purification processes etc. of reaction gained, wherein:
A. this method utilizes methyl alcohol as fuel of heat supply when starting, and after device starts, utilizes off-gas in methyl alcohol and the methanol steam reforming gas mixture purification process as fuel of heat supply;
B. methyl alcohol and the off-gas as fuel of heat supply passes through methyl alcohol burning shower nozzle separate in the process furnace and off-gas burning shower nozzle combustion heat supplying respectively;
C. with waste gas after burning discharging after adsorption cleaning is handled.
In the inventive method, the off-gas in the methanol steam reforming gas mixture purification process can be fed earlier in the off-gas surge tank, enter off-gas burning shower nozzle combustion heat supplying with the pipeline that the off-gas surge tank links to each other with process furnace respectively by two ends again.
The sorbent material that adopts in the above-mentioned adsorption cleaning treating processes is preferably activated carbon.
In the inventive method, the ratio of material benzenemethanol and water, the condition of reforming reaction (as temperature, pressure, catalyst type) etc. all get final product with reference to the corresponding conditions in traditional hydrogen production from methanol-steam reforming technology.The reformation gas mixture isolating method of purifying can be adopted transformation adsorption method of separation or membrane separation process etc.
In the method for preparing hydrogen by reforming methanol-water steam of the present invention, vaporization, heating and three steps of reforming reaction all need outside heat supply.When device starts, hydrogen generating system needs a temperature-rise period, at this moment, adopt methyl alcohol as single supplying heat source, make the hydrogen generating system temperature rise to temperature of reaction, enter the reformed gas surge tank after the heat exchange of reformation gas mixture process, cooling, the washing, by regulating methyl alcohol flow control system temperature, after treating that system pressure reaches requirement, the reformation gas mixture is introduced the separation system lock out operation of purifying; Hydrogen after the purification is as the product extraction, and the off-gas of compositions such as remaining main hydrogen then enters in the process furnace as one of supplying heat source by pipeline, promptly utilizes two kinds of fuel combustion heat supplies of methyl alcohol and off-gas.
The heat supply approach of methanol steam reforming reaction has two in the inventive method, and one of them approach derives from the methyl alcohol burning; In addition, utilize the off-gas in the methanol steam reforming gas mixture purification process to burn as another important channel of methanol steam reforming reaction heat supply, as utilize pressure swing adsorption or membrane separation technique etc. that the off-gas that methanol steam reforming reaction gained reformation gas mixture carries out producing in the purification and separation process is all contained a large amount of hydrogen, can provide a big chunk heat of methanol steam reforming reaction needed, as the heat that adopts pressure swing adsorption can provide the reforming reaction more than 40% to need; The heat that utilizes membrane separation technique can provide the reforming reaction more than 35% to need.And, utilize methyl alcohol burner noz(zle) and off-gas burner noz(zle) independently to control in the inventive method, can make fuel combustion complete, obtain higher thermo-efficiency.Therefore, compare with traditional hydrogen production from methanol-steam reforming technology, the energy consumption in the inventive method entire reaction course obviously reduces.
Simultaneously, after the methyl alcohol of heat supply raw material and off-gas burning, dispose just discharging behind the formaldehyde that wherein may pollute environment through adsorption cleaning, discharge in the gas and only contain water vapour and carbonic acid gas, environmental pollution is little, can reach environmental requirement.
And the inventive method adopts single raw material, and environmental pollution is little, only needs a simple tail gas adsorber to get final product the contaminated solution problem, does not need too many equipment, makes whole device volume reduce much to realize mobile on-site hydrogen manufacturing easily.
Compared with prior art, the invention has the beneficial effects as follows:
1. adopt alternative traditional coal of methyl alcohol and off-gas and oil as fuel of heat supply, environmental pollution is little, has environment-friendly advantage;
2. make full use of off-gas in the purification process as the part of fuel of heat supply, and utilize methyl alcohol burner noz(zle) and off-gas burner noz(zle) independently to control, fuel combustion is complete, and the thermo-efficiency height has bigger power savings advantages;
3. adopt methyl alcohol and off-gas as fuel of heat supply, in save energy, its production cost also obviously reduces, and compares with traditional hydrogen production from methanol-steam reforming technology, can reduce 10-20%;
4. adopt the method for preparing hydrogen by reforming methanol-water steam of the present invention also can easier realize mobile on-site hydrogen manufacturing.
Description of drawings
Fig. 1 is the method flow diagram of preparing hydrogen by reforming methanol-water steam of the present invention.
Among the figure, the 1st, methyl alcohol, the 2nd, water, the 3rd, vaporizer, the 4th, superheater, the 5th, reactor, the 6th, interchanger, the 7th, separation system, the 8th, off-gas surge tank, the 9th, process furnace, the 10th, product hydrogen, the 11st, off-gas burner noz(zle), the 12nd, methyl alcohol burner noz(zle), the 13rd, tail gas adsorber.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment
The method flow of present embodiment preparing hydrogen by reforming methanol-water steam as shown in Figure 1, its method is as follows:
Is the 1:1.6 access equipment with material benzenemethanol 1 and soft water 2 with the mol ratio, through interchanger 6 be preheated to 90 ℃, in vaporizer 3 vaporizations, overheated at superheater 4 again, reach 230 ℃ of temperature of reaction after, in reactor 5, carry out reforming reaction, adopt CuO/ZnO/Al
2O
3Catalyzer, reaction pressure 0.85Mpa, reacted gas obtains the gas mixture of reforming after interchanger 6 heat exchange; The reformation gas mixture enters pressure swing adsorption system 7 separation of purifying, product hydrogen 10 and off-gas two portions;
In present embodiment hydrogen production from methanol-steam reforming technology, vaporization, overheated, the outside heat supply of three steps needs of reforming reaction; As shown in Figure 1, heat-transfer medium (thermal oil) is introduced into reactor 5 shells after flowing out from process furnace, enters superheater 4 shells then, enters vaporizer 3 shells again, flow to heat-conducting oil furnace at last, forms a thermal oil recycle system;
The reformation gas mixture that reaction is obtained obtains the off-gas of product hydrogen 10 and hydrogen after heat exchange, cooling, washing, purification separate; Hydrogen 10 after purification separates is as the product extraction, off-gas then enters off-gas surge tank 8, flow to process furnace 9 by pipeline, in process furnace 9, methyl alcohol enters two different burner noz(zle)s (methyl alcohol burner noz(zle) 12 and off-gas burner noz(zle) 11) combustion heat supplying respectively with off-gas, discharging after the activated carbon adsorption of the tail gas after the burning in tail gas adsorber 13 handled.
When the hydrogen production from methanol-steam reforming device started, hydrogen generating system needed a temperature-rise period, at this moment, adopted methyl alcohol as supplying heat source, made the hydrogen generating system temperature rise to temperature of reaction; Material benzenemethanol 1 and soft water 2 is in proportion by the volume pump injected system, wait to enter vaporizer 3 vaporizations evenly after, overheated through superheater 4, enter reactor 5 and carry out reforming reaction; The reformation gas mixture enters the reformed gas surge tank through after the heat exchange, cooling, washing, regulates the methyl alcohol flow simultaneously with till satisfying the system temperature requirement, and after system pressure reached processing requirement, the reformation gas mixture was introduced pressure swing adsorption system 7 lock out operation of purifying; Hydrogen 10 after the purification is as the product extraction, off-gas enters off-gas surge tank 8, flow to process furnace 9 by special pipeline, regulates the flow of methyl alcohol simultaneously by variable valve, with till satisfying the system temperature requirement, reduce the methyl alcohol flow to satisfying till the system temperature requirement as far as possible.
Utilize the present embodiment method, throughput is 1000Nm
3The methyl alcohol that the hydrogen production from methanol-steam reforming device of/h is used for combustion heat supplying is 132kg/h, compares with traditional hydrogen production from methanol-steam reforming method, and fuel cost can descend about 15.4%.
Claims (3)
1. the method for a preparing hydrogen by reforming methanol-water steam, key step comprises: with material benzenemethanol and hydromassage you than being 1: 1～1.6 through preheating, vaporizing, be heated to 230～280 ℃, in reactor, carry out catalytic reforming reaction then, reformation gas mixture purification processes with the reaction gained is characterized in that:
A. this method utilizes methyl alcohol as fuel of heat supply when starting, and after device starts, utilizes off-gas in methyl alcohol and the methanol steam reforming gas mixture purification process as fuel of heat supply;
B. methyl alcohol and the off-gas as fuel of heat supply passes through methyl alcohol burning shower nozzle separate in the process furnace and off-gas burning shower nozzle combustion heat supplying respectively;
C. with waste gas after burning discharging after adsorption cleaning is handled.
2. the method for preparing hydrogen by reforming methanol-water steam according to claim 1, it is characterized in that: the off-gas in the methanol steam reforming gas mixture purification process is fed earlier in the off-gas surge tank, enter off-gas burning shower nozzle combustion heat supplying with the pipeline that the off-gas surge tank links to each other with process furnace respectively by two ends again.
3. the method for preparing hydrogen by reforming methanol-water steam according to claim 1, it is characterized in that: the sorbent material that adopts in the described adsorption cleaning treating processes is an activated carbon.
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| CN 200710048432 CN100500550C (en) | 2007-02-08 | 2007-02-08 | Method of preparing hydrogen by reforming methanol-water steam |
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| CN 200710048432 CN100500550C (en) | 2007-02-08 | 2007-02-08 | Method of preparing hydrogen by reforming methanol-water steam |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102616741B (en) * | 2012-03-29 | 2014-07-09 | 洁星环保科技投资（上海）有限公司 | Hydrogen preparation method and device |
| CN103569964B (en) * | 2013-10-29 | 2016-08-17 | 上海合既得动氢机器有限公司 | Methanol-water is utilized to prepare the equipment of hydrogen |
| CN103708418B (en) * | 2013-12-11 | 2015-08-26 | 浙江大学 | Residual heat of tail gas of automobile is utilized to carry out the device of preparing hydrogen by reforming methanol |
| CN105329853A (en) * | 2015-11-06 | 2016-02-17 | 江门市宏乔新材料科技有限公司江海区分公司 | Portable mobile hydrogen making machine based on principle of making hydrogen through methyl alcohol water |
| CN105347301B (en) * | 2015-12-10 | 2018-01-05 | 刘建安 | A kind of combustible gas generating device |
| CN105967144B (en) * | 2016-05-09 | 2017-12-29 | 中国船舶重工集团公司第七一二研究所 | A kind of heat supply method for preparing hydrogen by reforming methanol reaction |
| CN107640743B (en) * | 2016-07-20 | 2019-08-02 | 神华集团有限责任公司 | A kind of device and method of crude carbinol hydrogen manufacturing |
| CN111453699B (en) * | 2020-05-22 | 2021-08-31 | 力行氢能科技股份有限公司 | Hydrogen production and hydrogen purification device |
| CN112678770B (en) * | 2020-12-28 | 2022-11-29 | 四川天采科技有限责任公司 | Methanol and water hydrogen production device adopting PSA tail gas catalytic combustion for heat supply |
| 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 |
| CN113372957B (en) * | 2021-07-05 | 2022-06-24 | 南京林业大学 | Device and method for producing hydrogen energy by biomass gasification and heat supply |
| CN115367703B (en) * | 2022-10-24 | 2023-01-20 | 苏州高迈新能源有限公司 | Methanol reforming hydrogen production integrated equipment and hydrogen production method thereof |
| CN115784153A (en) * | 2022-12-02 | 2023-03-14 | 武汉氢能与燃料电池产业技术研究院有限公司 | Self-heating type alcohol reforming hydrogen production reactor |
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Address after: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee after: Southwest Chemical Research & Design Institute Co., Ltd. Address before: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee before: Xinan Chemical Research & Design Inst. |