CN208440278U - A kind of useless refining methanol reforming hydrogen manufacturing device - Google Patents
A kind of useless refining methanol reforming hydrogen manufacturing device Download PDFInfo
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- CN208440278U CN208440278U CN201820824182.8U CN201820824182U CN208440278U CN 208440278 U CN208440278 U CN 208440278U CN 201820824182 U CN201820824182 U CN 201820824182U CN 208440278 U CN208440278 U CN 208440278U
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Abstract
The utility model provides a kind of useless refining methanol reforming hydrogen manufacturing device, oil eliminator, methanol tank, stripper, vaporization superheater, reactor, water scrubber and pressure swing adsorption system including sequence setting, the methanol tank is connect by methanol pump with the stripper, the tower top discharge port of the stripper is connect with the feed inlet of the vaporization superheater, the lower part of the stripper is connected with vapor pipe, and vapor enters the stripper by the vapor pipe.The useless refining methanol reforming hydrogen manufacturing device of the utility model, useless Methanol Recovery process for refining and methanol reforming hydrogen manufacturing are combined, and efficiently use useless methanol, are improved the utilization rate of useless methanol, are reduced the discharge of waste, increase economic efficiency.
Description
Technical field
The utility model relates to chemical waste liquid recycling and reusing field more particularly to a kind of useless refining methanol reforming hydrogen manufacturing dresses
It sets.
Background technique
On the one hand, in recent years, due to fine chemistry industry, anthraquinone producing hydrogen peroxide, powder metallurgy, oil hydrogenation, forestry product and
Agriculture product add hydrogen, bioengineering, petroleum refining to add the rapid development of hydrogen and hydrogen fuel cleaning vehicle etc., rapidly to pure hydrogen demand
Increase.Therefore, methanol decomposition hydrogen manufacturing technique and schizolysis hydrogen production plant with methanol are industrially widely used.
Methanol reforming hydrogen manufacturing at 220~280 DEG C, is catalyzed on special-purpose catalyst using methanol and desalted water as raw material
Conversion obtains composition as main hydrogeneous and carbon dioxide conversion gas, and the principle is as follows:
Main reaction: CH3OH=CO+2H2+90.7KJ/mol
CO+H2O=CO2+H2-41.2KJ/mol
Overall reaction: CH3OH+H2O=CO2+3H2+49.5KJ/mol
Since catalyst is using Cu-series catalyst, the more demanding of material benzenemethanol is led in conventional methanol reforming hydrogen manufacturing
Often requiring material benzenemethanol is refined methanol, needs to meet GB338-2011 Grade A requirements above.The price of material benzenemethanol increases
The cost of methanol reforming hydrogen manufacturing device.
On the other hand, a large amount of methanol of the needs such as some pharmaceutical factories, chemical plant, methanol are used as some intermediate fluxes
After can generate largely useless methanol, these useless main oil-containings of methanol or some impurity.These useless methanol prices are cheap, and a large amount of useless
The unreasonable discharge of methanol also brings financial burden and environmental protection pressure to enterprise.
Utility model content
The technical problem to be solved by the utility model is in view of the drawbacks of the prior art, providing a kind of useless refining methanol
Reforming hydrogen manufacturing device combines useless Methanol Recovery process for refining and methanol reforming hydrogen manufacturing, efficiently uses useless methanol, improves useless first
The utilization rate of alcohol reduces the discharge of waste, increases economic efficiency.
The utility model uses following technical scheme to solve above-mentioned technical problem:
On the one hand, the utility model provides a kind of useless refining methanol reforming hydrogen manufacturing device, the oil separation including sequence setting
Device, methanol tank, stripper, vaporization superheater, reactor, water scrubber and pressure swing adsorption system, the methanol tank pass through first
Alcohol pump is connect with the stripper, and the tower top discharge port of the stripper is connect with the feed inlet of the vaporization superheater, described
The lower part of stripper is connected with vapor pipe, and vapor enters the stripper by the vapor pipe.
In order to optimize above-mentioned device, the technical measures that the utility model is taken further include:
Further, condenser is also connected between the reactor and the water scrubber, the condenser is for cooling down
React obtained conversion gas.
Further, the pressure swing adsorption system includes at least two adsorption towers being connected in parallel.
Further, concentration detection apparatus is equipped at the reactor inlet, to control the methanol steam for entering reactor
Mass ratio with vapor is 1:1.
Further, flow control valve, the Concentration Testing dress are equipped on the vapor pipe that the lower part of stripper connects
It sets and is electrically connected with the flow control valve, to control the flow for the vapor for being passed through stripper.
Or it is also possible to be connected with vapor supplement pipe, the vapor supplement pipe in the exit of the stripper
It is equipped with flow control valve, the concentration detection apparatus is electrically connected with the flow control valve, to adjust stripper exit first
The mass ratio of alcohol steam and vapor.
Further, the concentration detection apparatus is methanol concentration detector.
Or being also possible to the concentration detection apparatus is water vapor concentration detection device.
Further, it is connected with methanol recovery device on the water scrubber, for recycling the methanol in unreacted conversion gas.
Further, the stripper feed inlet is equipped with feed preheater, for preheating the charging methanol of stripper, carries out
Subsequent stripping processing.
On the other hand, the utility model also provides a kind of useless refining methanol reforming hydrogen manufacturing method for above-mentioned apparatus, packet
Include following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator, after separating the grease and impurity in useless methanol, into first
Alcohol storage tank is stood；
Step 2, stripper is inputted after the methanol pressurization after step 1 being stood, after stripper purifies, obtains first in tower top
Alcohol steam and water vapour；
Step 3, the methanol steam and water vapour that step 2 obtains enter vaporization superheater, in the discharge port of vaporization superheater
Obtain the mixture of temperature is 240-260 DEG C, mass ratio is 1:1 methanol steam and vapor；
Step 4, the mixture that step 3 obtains enters reactor, and reaction obtains conversion gas under the effect of the catalyst；
Step 5, the conversion gas that step 4 obtains obtains product hydrogen after heat recovery, cooling, washing, pressure-variable adsorption processing
Gas.
In order to optimize above-mentioned method, the technical measures that the utility model is taken further include:
Further, in step 1, by weight percentage, 3%-4% containing grease, water 10%- in the useless methanol
12%, surplus is methanol.
Further, in step 2, adjust control stripper overhead obtain the mass ratio of methanol steam and vapor, make into
Enter to vaporize the methanol steam of superheater, the mass percent of methanol steam is 45%-50% in steam mixture；Further
Ground, make to enter the vaporization methanol steam of superheater, in steam mixture methanol steam mass percent 50%.
Further, in step 3, the heat source for vaporizing superheater is supplied by out-of-bounds conduction oil.
Further, in step 4, the pressure of the conversion gas is 1.0MPa, temperature is 250-270 DEG C, and group is divided into H2、
CO2、CO、CH4、H2O and CH3OH；Further, temperature is preferably 260 DEG C.
Further, in step 4, the catalyst is Cu-series catalyst.
Further, in step 5, by mass percentage, the conversion gas component after washing process are as follows: H2: 70%-
78%, CO2: 20%-28%, CO:0.4%-1.2%, surplus are a small amount of CH4And saturated water；Further, by quality percentage
Conversion gas component than meter, after washing process are as follows: H2: 74%, CO2: 24%, CO:0.8%, surplus are a small amount of CH4And saturation
Water.
Further, it in step 5, is washed after the conversion air cooling to less than 40 DEG C.
Further, in step 5, cooling carries out within the condenser, converts cooled medium of the gas as condenser, stripping
Cooling medium of the charging methanol of tower as condenser.Conversion gas carries out heat with stripper charging methanol and exchanges, and realizes heat
It recycles.
The utility model by adopting the above technical scheme, compared with prior art, has the following technical effect that
1) the utility model combines useless Methanol Recovery process for refining and methanol reforming hydrogen manufacturing, efficiently uses useless methanol,
The utilization rate for improving useless methanol reduces the discharge of waste, improves economic benefit.
2) the utility model is by passing through the modes such as oil removing, standing, pressurization, stripping to useless methanol, by the oil in useless methanol
The impurity of rouge and other influences methanol translation hydrogen making catalyst is removed, and stripping temperature is remained；And adjust control methanol and water
The ratio of mass ratio 1:1 is not needed methanol rectification being just able to satisfy methanol reforming hydrogen manufacturing requirement at technical grade refined methanol, be saved significantly
About energy consumption and cost.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of preferred embodiment of the utility model；
Appended drawing reference therein are as follows: 1- oil eliminator；2- methanol tank；3- methanol pump；4- stripper；5- vaporization overheat
Device；6- reactor；7- condenser；8- water scrubber；9- pressure swing adsorption system.
Specific embodiment
The technical solution of the utility model is described in further detail with embodiment with reference to the accompanying drawing.Implement below
Example is only used for clearly illustrating the technical solution of the utility model, and cannot be used as a limitation the protection model of limitation the utility model
It encloses.
Embodiment 1
The present embodiment provides a kind of useless refining methanol reforming hydrogen manufacturing devices, as shown in Figure 1, including the oil separation of sequence setting
Device, methanol tank, stripper, vaporization superheater, reactor, condenser, water scrubber and pressure swing adsorption system, methanol tank pass through
Methanol pump is connect with stripper, and the tower top discharge port of stripper is connect with the feed inlet of vaporization superheater, and the lower part of stripper connects
It is connected to vapor pipe, vapor enters stripper by vapor pipe, is used for isolated methanol steam and vapor.
In the above-described embodiments, pressure swing adsorption system 9 is by least 2 adsorption tower groups at being parallel with one another between adsorption tower
Connection, to improve the efficiency of pressure-variable adsorption.
In the above-described embodiments, it is equipped with concentration detection apparatus in 6 inlet of reactor, concentration detection apparatus real-time detection goes out
The methanol steam of superheater 5 and the mass ratio of vapor are vaporized, to adjust the methanol steam and vapor that control enters reactor 6
Mass ratio be 1:1.The principle that the mass ratio of methanol steam and vapor that control herein enters reactor 6 is 1:1 is methanol
In the overall reaction equation of reforming hydrogen manufacturing, the molar ratio of methanol and water is 1:1, i.e., the mass ratio of methanol and water is 16:9, is adjusted
The mass ratio 1:1 for controlling methanol steam and vapor, can be such that the methanol in reactor 6 sufficiently reacts, and be conducive to improve methanol
Utilization rate；Simultaneously it is not necessary to which methanol is become refined methanol, the cost of methanol reforming hydrogen manufacturing device is reduced.Wherein, control is adjusted
The mode of the mass ratio 1:1 of methanol steam and vapor processed is the vapor Guan Shangshe that can be in the connection of the lower part of stripper 4
Flow control valve is set, concentration detection apparatus is electrically connected with flow control valve, and the methanol steam and vapor obtained according to detection
Quality than feedback regulation flow control valve, the amount by adjusting the vapor that control is passed through stripper 4 is to obtain mass ratio
The methanol steam and vapor of 1:1；Or be also possible in addition connect vapor supplement pipe in the exit of stripper 4, water steams
Flow control valve, the electrical connection of concentration detection apparatus flow control valve are set on gas supplement pipe, and steamed according to the methanol that detection obtains
The quality of vapour and vapor is than feedback regulation flow control valve, by the intake for adjusting control 4 exit vapor of stripper
To obtain mass ratio as the methanol steam and vapor of 1:1.
In the above-described embodiments, concentration detection apparatus can be methanol concentration detector, and detection enters the mixing of reactor 6
Methanol concentration in steam, methanol concentration detector are electrically connected with flow control valve, when methanol concentration is lower, is adjusted flow and are adjusted
Valve reduces the intake of vapor, to obtain mass ratio as the methanol steam and vapor of 1:1.
In the above-described embodiments, concentration detection apparatus can be water vapor concentration detection device, and detection enters reactor 6
Water vapor concentration in mixed vapour, water vapor concentration detection device are preferably moisture probe, moisture probe and flow control valve electricity
Connection adjusts the intake that flow control valve increases vapor, when water vapor concentration is lower to obtain mass ratio as 1:1's
Methanol steam and vapor.
In the above-described embodiments, it is connected with methanol recovery device on water scrubber 8, for recycling the first in unreacted conversion gas
Alcohol.
In the above-described embodiments, 4 feed inlet of stripper is equipped with feed preheater.Feed preheater be used for enter vapour
The methanol steam of stripper 4 is preheated, to improve steam stripped efficiency and speed.
In the above-described embodiments, the embodiment for converting gas heat recovery is cooled Jie for converting gas as condenser 7
Matter, cooling medium of the charging methanol of stripper 4 as condenser 7, so that conversion gas and stripper 4, which feed methanol, carries out heat
Heat recovery and utilization is realized in exchange.
Embodiment 2
The present embodiment provides a kind of useless refining methanol reforming hydrogen manufacturing method of device for embodiment 1, in the present embodiment
Useless methanol derives from chemical plant vent tank farm, wherein grease-contained weight percent is 3%-4%, the weight percent of water is
10%-12%, a small amount of impurity, surplus are methanol；As shown in Figure 1, comprising the following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator 1, the grease in useless methanol is separated, removed by oil eliminator 1
Useless methanol after oil enters methanol tank 2 by the road, stands the impurity removed in useless methanol；
Step 2, oil removing, the methanol stood are pressurized to by 1.0MPa by methanol pump 3, into stripper 4, stripped simultaneously
It is passed through water vapour in tower 4, obtains methanol steam and vapor (predominantly methanol steam and vapor) in the outlet of stripper 4；
Step 3, the mass ratio for adjusting control methanol steam and vapor makes the methanol steam, the water that enter vaporization superheater 5
The mass percent of methanol steam is 50% in steam mixture；It vaporizes 5 heat source of superheater to be supplied by out-of-bounds conduction oil, methanol steams
Vapour and vapor obtain that temperature is 250 DEG C, pressure 1.0MPa, mass ratio are 1:1's after the vaporization of vaporization superheater 5, overheat
The mixture of methanol steam and vapor；
Step 4, the mixture that vaporization superheater 5 obtains enters reactor 6, in the work of methanol reforming hydrogen manufacturing special-purpose catalyst
Under (being preferably Cu-series catalyst in the present embodiment), the reaction of first alcohol and water generates conversion gas, and conversion gas group becomes H2、CO2、CO、
CH4、H2O and CH3OH, pressure 1.0MPa, temperature are about 260 DEG C；
Step 5, for conversion gas by recycling heat, condenser 7 enters water scrubber 8, remaining first after being cooled to less than 40 DEG C
The washed recycling of alcohol and water, it is about H that conversion gas, which goes out 8 component of water scrubber,2: 74%, CO2: 24%, CO:0.8%, remaining a small amount of CH4
And saturated water；The conversion gas of water scrubber 8 enters pressure swing adsorption system 9 out, pressure swing adsorption system 9 by least 2 adsorption tower groups at,
To be connected in parallel with each other between adsorption tower, after conversion gas passes through pressure swing adsorption system 9, by adjusting 9 parameter of pressure swing adsorption system,
Qualified product hydrogen is obtained in the tower top of adsorption tower.
Embodiment 3
The present embodiment provides a kind of useless refining methanol reforming hydrogen manufacturing method of device for embodiment 1, in the present embodiment
Useless methanol derives from chemical plant vent tank farm, wherein grease-contained weight percent is 3%-4%, the weight percent of water is
10%-12%, a small amount of impurity, surplus are methanol；As shown in Figure 1, comprising the following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator 1, the grease in useless methanol is separated, removed by oil eliminator 1
Useless methanol after oil enters methanol tank 2 by the road, stands the impurity removed in useless methanol；
Step 2, oil removing, the methanol stood are pressurized to by 1.0MPa by methanol pump 3, into stripper 4, stripped simultaneously
It is passed through water vapour in tower 4, obtains methanol steam and vapor (predominantly methanol steam and vapor) in the outlet of stripper 4；
Step 3, the mass ratio for adjusting control methanol steam and vapor makes the methanol steam, the water that enter vaporization superheater 5
The mass percent of methanol steam is 45% in steam mixture；It vaporizes 5 heat source of superheater to be supplied by out-of-bounds conduction oil, methanol steams
Vapour and vapor obtain that temperature is 240 DEG C, pressure 1.0MPa, mass ratio are 1:1's after the vaporization of vaporization superheater 5, overheat
The mixture of methanol steam and vapor；
Step 4, the mixture that vaporization superheater 5 obtains enters reactor 6, in the work of methanol reforming hydrogen manufacturing special-purpose catalyst
Under (being preferably Cu-series catalyst in the present embodiment), the reaction of first alcohol and water generates conversion gas, and conversion gas group becomes H2、CO2、CO、
CH4、H2O and CH3OH, pressure 1.0MPa, temperature are about 250 DEG C；
Step 5, for conversion gas by recycling heat, condenser 7 enters water scrubber 8, remaining first after being cooled to less than 40 DEG C
The washed recycling of alcohol and water, it is about H that conversion gas, which goes out 8 component of water scrubber,2: 70%, CO2: 20%, CO:0.4%, remaining a small amount of CH4
And saturated water；The conversion gas of water scrubber 8 enters pressure swing adsorption system 9 out, pressure swing adsorption system 9 by least 2 adsorption tower groups at,
To be connected in parallel with each other between adsorption tower, after conversion gas passes through pressure swing adsorption system 9, by adjusting 9 parameter of pressure swing adsorption system,
Qualified product hydrogen is obtained in the tower top of adsorption tower.
Embodiment 4
The present embodiment provides a kind of useless refining methanol reforming hydrogen manufacturing method of device for embodiment 1, in the present embodiment
Useless methanol derives from chemical plant vent tank farm, wherein grease-contained weight percent is 3%-4%, the weight percent of water is
10%-12%, a small amount of impurity, surplus are methanol；As shown in Figure 1, comprising the following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator 1, the grease in useless methanol is separated, removed by oil eliminator 1
Useless methanol after oil enters methanol tank 2 by the road, stands the impurity removed in useless methanol；
Step 2, oil removing, the methanol stood are pressurized to by 1.0MPa by methanol pump 3, into stripper 4, stripped simultaneously
It is passed through water vapour in tower 4, obtains methanol steam and vapor (predominantly methanol steam and vapor) in the outlet of stripper 4；
Step 3, the mass ratio for adjusting control methanol steam and vapor makes the methanol steam, the water that enter vaporization superheater 5
The mass percent of methanol steam is 50% in steam mixture；It vaporizes 5 heat source of superheater to be supplied by out-of-bounds conduction oil, methanol steams
Vapour and vapor obtain that temperature is 260 DEG C, pressure 1.0MPa, mass ratio are 1:1's after the vaporization of vaporization superheater 5, overheat
The mixture of methanol steam and vapor；
Step 4, the mixture that vaporization superheater 5 obtains enters reactor 6, in the work of methanol reforming hydrogen manufacturing special-purpose catalyst
Under (being preferably Cu-series catalyst in the present embodiment), the reaction of first alcohol and water generates conversion gas, and conversion gas group becomes H2、CO2、CO、
CH4、H2O and CH3OH, pressure 1.0MPa, temperature are about 270 DEG C；
Step 5, for conversion gas by recycling heat, condenser 7 enters water scrubber 8, remaining first after being cooled to less than 40 DEG C
The washed recycling of alcohol and water, it is about H that conversion gas, which goes out 8 component of water scrubber,2: 78%, CO2: 28%, CO:1.2%, remaining a small amount of CH4
And saturated water；The conversion gas of water scrubber 8 enters pressure swing adsorption system 9 out, pressure swing adsorption system 9 by least 2 adsorption tower groups at,
To be connected in parallel with each other between adsorption tower, after conversion gas passes through pressure swing adsorption system 9, by adjusting 9 parameter of pressure swing adsorption system,
Qualified product hydrogen is obtained in the tower top of adsorption tower.
As can be seen from the above embodiments, a kind of useless refining methanol reforming hydrogen manufacturing method and device of the utility model, using useless
Old methanol is refined, and methanol reforming hydrogen manufacturing material condition is reached, and then produces hydrogen using methanol reforming hydrogen manufacturing technique.This is practical
Novel refine useless Methanol Recovery combines with the production of methanol reforming hydrogen manufacturing and process characteristic, and it is former to reduce useless refining methanol
Some energy consumptions do not need methanol becoming refined methanol, need to only meet the mass ratio of first alcohol and water 1:1 in methanol reforming hydrogen manufacturing, together
When be greatly reduced the cost of methanol reforming hydrogen manufacturing device, there is very big economy and the feature of environmental protection.
Specific embodiment of the utility model is described in detail above, but it is only used as example, the utility model
It is not restricted to particular embodiments described above.To those skilled in the art, any that this practical is equal
Modifications and substitutions are also all among the scope of the utility model.Therefore, the institute under the spirit and scope for not departing from the utility model
The equal transformation and modification of work, should all cover in the scope of the utility model.
Claims (10)
1. a kind of useless refining methanol reforming hydrogen manufacturing device, which is characterized in that oil eliminator (1), methanol storage including sequence setting
Tank (2), stripper (4), vaporization superheater (5), reactor (6), water scrubber (8) and pressure swing adsorption system (9), the methanol storage
Tank (2) is connect by methanol pump (3) with the stripper (4), and the tower top discharge port of the stripper (4) and the vaporization overheat
The feed inlet of device (5) connects, and the lower part of the stripper (4) is connected with vapor pipe, and vapor is entered by the vapor pipe
The stripper (4).
2. useless refining methanol reforming hydrogen manufacturing device according to claim 1, which is characterized in that the reactor (6) and institute
It states and is also connected between water scrubber (8) condenser (7), the conversion gas that the condenser (7) obtains for cooling reaction.
3. useless refining methanol reforming hydrogen manufacturing device according to claim 1, which is characterized in that the pressure swing adsorption system
It (9) include at least two adsorption towers being connected in parallel.
4. useless refining methanol reforming hydrogen manufacturing device according to claim 1, which is characterized in that reactor (6) entrance
Place is equipped with concentration detection apparatus.
5. useless refining methanol reforming hydrogen manufacturing device according to claim 4, which is characterized in that in the lower part of stripper (4)
The vapor pipe of connection is equipped with flow control valve, and the concentration detection apparatus is electrically connected with the flow control valve.
6. useless refining methanol reforming hydrogen manufacturing device according to claim 4, which is characterized in that in the stripper (4)
Exit is connected with vapor supplement pipe, and vapor supplement pipe is equipped with flow control valve, the concentration detection apparatus with
The flow control valve electrical connection.
7. the useless refining methanol reforming hydrogen manufacturing device according to any one of claim 4-6, which is characterized in that the concentration
Detection device is methanol concentration detector.
8. the useless refining methanol reforming hydrogen manufacturing device according to any one of claim 4-6, which is characterized in that the concentration
Detection device is water vapor concentration detection device.
9. useless refining methanol reforming hydrogen manufacturing device according to claim 1, which is characterized in that connect on the water scrubber (8)
It is connected to methanol recovery device.
10. useless refining methanol reforming hydrogen manufacturing device according to claim 1, which is characterized in that stripper (4) charging
Mouth is equipped with feed preheater.
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| CN201820824182.8U CN208440278U (en) | 2018-05-30 | 2018-05-30 | A kind of useless refining methanol reforming hydrogen manufacturing device |
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| CN201820824182.8U CN208440278U (en) | 2018-05-30 | 2018-05-30 | A kind of useless refining methanol reforming hydrogen manufacturing device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516520A (en) * | 2018-05-30 | 2018-09-11 | 上海亿维工业科技股份有限公司 | A kind of useless refining methanol reforming hydrogen manufacturing method and device |
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2018
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516520A (en) * | 2018-05-30 | 2018-09-11 | 上海亿维工业科技股份有限公司 | A kind of useless refining methanol reforming hydrogen manufacturing method and device |
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