CN108516520A - A kind of useless refining methanol reforming hydrogen manufacturing method and device - Google Patents
A kind of useless refining methanol reforming hydrogen manufacturing method and device Download PDFInfo
- Publication number
- CN108516520A CN108516520A CN201810542918.7A CN201810542918A CN108516520A CN 108516520 A CN108516520 A CN 108516520A CN 201810542918 A CN201810542918 A CN 201810542918A CN 108516520 A CN108516520 A CN 108516520A
- Authority
- CN
- China
- Prior art keywords
- methanol
- useless
- hydrogen manufacturing
- reforming hydrogen
- steam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present invention provides a kind of useless refining methanol reforming hydrogen manufacturing method, includes the following steps:Step 1, grease-contained useless methanol is inputted into oil eliminator, after detaching the grease and impurity in giving up methanol, is stood into methanol tank;Step 2, stripper is inputted after the methanol pressurization after standing, after stripper purifies, methanol steam and water vapour is obtained in tower top;Step 3, methanol steam and water vapour enter vaporization superheater, obtain temperature be 240 260 DEG C, mass ratio 1:1 methanol steam and the mixture of vapor;Step 4, mixture enters reactor, and conversion gas is obtained by the reaction;Step 5, conversion gas obtains product hydrogen after heat recovery, cooling, washing, pressure-variable adsorption processing.The present invention also provides a kind of useless refining methanol reforming hydrogen manufacturing devices.Useless Methanol Recovery process for refining and methanol reforming hydrogen manufacturing are combined by the present invention, efficiently use useless methanol, are improved the utilization rate for the methanol that gives up, are reduced the discharge of waste, increase economic efficiency.
Description
Technical field
The present invention relates to chemical waste liquid recycling field more particularly to a kind of useless refining methanol reforming hydrogen manufacturing method and
Device.
Background technology
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 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
It is refined methanol often to require material benzenemethanol, 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 will produce 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.
Invention content
The technical problem to be solved by the present invention is to:In view of the drawbacks of the prior art, a kind of useless refining methanol conversion is provided
Useless Methanol Recovery process for refining and methanol reforming hydrogen manufacturing are combined by hydrogen production process and device, efficiently use useless methanol, are improved useless
The utilization rate of methanol reduces the discharge of waste, increases economic efficiency.
The present invention uses following technical scheme to solve above-mentioned technical problem:
On the one hand, the present invention provides a kind of useless refining methanol reforming hydrogen manufacturing method, includes the following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator, after detaching the grease and impurity in giving up 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, first is obtained 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 temperature be 240-260 DEG C, mass ratio 1:1 methanol steam and the mixture of vapor;
Step 4, the mixture that step 3 obtains enters reactor, and conversion gas is obtained by the reaction 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 present invention takes 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, adjusting control stripper overhead obtains the mass ratio of methanol steam and vapor, make into
The mass percent for entering to vaporize methanol steam in the methanol steam of superheater, steam mixture is 45%-50%;Further
Ground, the mass percent for making to enter methanol steam in the methanol steam of vaporization superheater, steam mixture is 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 group after washing process is divided into:H2:70%-
78%, CO2:20%-28%, CO:0.4%-1.2%, surplus are a small amount of CH4And saturated water;Further, by quality percentage
Than meter, the conversion gas group after washing process is divided into:H2:74%, CO2:24%, CO:0.8%, surplus is 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, cooled medium of the conversion gas as condenser, stripping
Cooling medium of the charging methanol of tower as condenser.It converts gas and carries out heat exchange with stripper charging methanol, realize heat
It recycles.
On the other hand, the present invention also provides a kind of devices of useless refining methanol reforming hydrogen manufacturing, include the oil of sequence setting
Pass through from device, methanol tank, stripper, vaporization superheater, reactor, water scrubber and pressure swing adsorption system, the methanol tank
Methanol 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, institute
The lower part for stating 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 present invention takes further include:
Further, condenser is also associated between the reactor and the water scrubber, the condenser is for cooling down
Conversion gas obtained by the reaction.
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 into reactor
Mass ratio with vapor is 1:1.
Further, flow control valve, the Concentration Testing dress are equipped on the vapor pipe of the lower part of stripper connection
It sets and is electrically connected with the flow control valve, the flow of the vapor of stripper is passed through with control.
Or can also be 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 can also be that 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, and the charging methanol for preheating stripper carries out
Subsequent stripping processing.
The present invention is had the following technical effect that compared with prior art using above-mentioned technical proposal:
1) useless Methanol Recovery process for refining and methanol reforming hydrogen manufacturing are combined by the present invention, efficiently use useless methanol, are improved
The utilization rate of useless methanol, reduces the discharge of waste, improves economic benefit.
2) present invention by useless methanol by modes such as oil removing, standing, pressurization, strippings, by useless methanol grease and
The impurity of other influences methanol translation hydrogen making catalyst is removed, and stripping temperature is remained;And adjusting control methanol and water quality
Than 1:Methanol rectification need not can be met methanol reforming hydrogen manufacturing requirement at technical grade refined methanol, is greatly saved by 1 ratio
Energy consumption and cost.
Description of the drawings
Fig. 1 is the process flow chart of a preferred embodiment of the present invention;
Reference numeral therein is:1- oil eliminators;2- methanol tanks;3- methanol pumps;4- strippers;5- vaporization overheats
Device;6- reactors;7- condensers;8- water scrubbers;9- pressure swing adsorption systems.
Specific implementation mode
Technical scheme of the present invention is described in further detail with embodiment below in conjunction with the accompanying drawings.Following embodiment is only
For clearly illustrating technical scheme of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
The methanol that gives up the present embodiment provides a kind of useless refining methanol reforming hydrogen manufacturing method, in the present embodiment is molten from chemical plant
Agent tank field, wherein grease-contained weight percent is 3%-4%, the weight percent of water is 10%-12%, and a small amount of impurity is remaining
Amount is methanol;As shown in Figure 1, including the following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator 1, the grease in useless methanol is detached, removed by oil eliminator 1
Useless methanol after oil enters methanol tank 2 by the road, stands the impurity removed in giving up 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, methanol steam and vapor (predominantly methanol steam and vapor) are obtained in the outlet of stripper 4;
Step 3, the mass ratio of 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 after the vaporization of vaporization superheater 5, overheat, obtain temperature be 250 DEG C, pressure 1.0MPa, mass ratio 1:1
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 for going out water scrubber 8 enters pressure swing adsorption system 9, 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 is by 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 2
The methanol that gives up the present embodiment provides a kind of useless refining methanol reforming hydrogen manufacturing method, in the present embodiment is molten from chemical plant
Agent tank field, wherein grease-contained weight percent is 3%-4%, the weight percent of water is 10%-12%, and a small amount of impurity is remaining
Amount is methanol;As shown in Figure 1, including the following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator 1, the grease in useless methanol is detached, removed by oil eliminator 1
Useless methanol after oil enters methanol tank 2 by the road, stands the impurity removed in giving up 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, methanol steam and vapor (predominantly methanol steam and vapor) are obtained in the outlet of stripper 4;
Step 3, the mass ratio of 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 after the vaporization of vaporization superheater 5, overheat, obtain temperature be 240 DEG C, pressure 1.0MPa, mass ratio 1:1
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 for going out water scrubber 8 enters pressure swing adsorption system 9, 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 is by 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 methanol that gives up the present embodiment provides a kind of useless refining methanol reforming hydrogen manufacturing method, in the present embodiment is molten from chemical plant
Agent tank field, wherein grease-contained weight percent is 3%-4%, the weight percent of water is 10%-12%, and a small amount of impurity is remaining
Amount is methanol;As shown in Figure 1, including the following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator 1, the grease in useless methanol is detached, removed by oil eliminator 1
Useless methanol after oil enters methanol tank 2 by the road, stands the impurity removed in giving up 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, methanol steam and vapor (predominantly methanol steam and vapor) are obtained in the outlet of stripper 4;
Step 3, the mass ratio of 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 after the vaporization of vaporization superheater 5, overheat, obtain temperature be 260 DEG C, pressure 1.0MPa, mass ratio 1:1
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 for going out water scrubber 8 enters pressure swing adsorption system 9, 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 is by 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 devices of the method for embodiment 1-3, such as Fig. 1 institutes
Show, including the oil eliminator of sequence setting, methanol tank, stripper, vaporization superheater, reactor, condenser, water scrubber and change
Press adsorption system, methanol tank connect by methanol pump with stripper, the tower top discharge port of stripper and vaporize superheater into
Material mouth connects, and the lower part of stripper is connected with vapor pipe, and vapor enters stripper by vapor pipe, is used for isolated first
Alcohol steam and vapor.
In the above-described embodiments, pressure swing adsorption system 9 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 detects in real time
The mass ratio for vaporizing the methanol steam and vapor of superheater 5, the methanol steam and vapor of reactor 6 are entered with adjusting control
Mass ratio be 1:1.The mass ratio for the methanol steam and vapor that control herein enters reactor 6 is 1:1 principle 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, it adjusts
Control the mass ratio 1 of methanol steam and vapor:1, the methanol in reactor 6 can be made fully to react, 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 mass ratio 1 of methanol steam and vapor processed:1 mode be can be stripper 4 lower part connect vapor Guan Shangshe
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 that the vapor of stripper 4 is passed through by adjusting control is to obtain mass ratio
1:1 methanol steam and vapor;Or can also be in addition to 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 passes through the intake of 4 exit vapor of adjusting control stripper than feedback regulation flow control valve
To obtain mass ratio as 1:1 methanol steam and vapor.
In the above-described embodiments, concentration detection apparatus can be methanol concentration detector, mixing of the detection into reactor 6
Methanol concentration in steam, methanol concentration detector are electrically connected with flow control valve, when methanol concentration is relatively low, adjust flow-rate adjustment
Valve reduces the intake of vapor, to obtain mass ratio as 1:1 methanol steam and vapor.
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 relatively low, to obtain mass ratio as 1:1
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 the stripper is equipped with feed preheater.Feed preheater is used for entering vapour
The methanol steam of stripper 4 is preheated, to improve steam stripped efficiency and speed.
In the above-described embodiments, the embodiment of conversion gas heat recovery is cooled Jie for converting gas as condenser 7
Matter, the cooling medium of the charging methanol of stripper 4 as condenser 7 so that conversion gas feeds methanol with stripper 4 and carries out heat
It exchanges, realizes heat recovery and utilization.
By above-described embodiment it is found that the present invention a kind of useless refining methanol reforming hydrogen manufacturing method and device, using waste and old first
Alcohol reaches methanol reforming hydrogen manufacturing material condition, then uses methanol reforming hydrogen manufacturing technique productions hydrogen through refining.The present invention will give up
Methanol Recovery is refined to be combined with the production of methanol reforming hydrogen manufacturing and process characteristic, reduces the original energy of useless refining methanol
Consumption, need not become refined methanol by methanol, only need to meet first alcohol and water 1 in methanol reforming hydrogen manufacturing:1 mass ratio, at the same it is also big
The big cost for reducing methanol reforming hydrogen manufacturing device, has prodigious economy and the feature of environmental protection.
Specific embodiments of the present invention are described in detail above, but it is only used as example, the present invention is not intended to limit
In particular embodiments described above.To those skilled in the art, it is any to the practicality carry out equivalent modifications and replace
In generation, is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by impartial conversion and repair
Change, all should be contained within the scope of the invention.
Claims (10)
1. a kind of useless refining methanol reforming hydrogen manufacturing method, which is characterized in that include the following steps:
Step 1, grease-contained useless methanol is inputted into oil eliminator, after detaching the grease and impurity in giving up methanol, is stored up into methanol
Tank is stood;
Step 2, stripper is inputted after the methanol pressurization after step 1 being stood, after stripper purifies, methanol is obtained in tower top and steams
Vapour and water vapour;
Step 3, the methanol steam and water vapour that step 2 obtains enter vaporization superheater, are obtained in the discharge port of vaporization superheater
Temperature is 240-260 DEG C, mass ratio 1:1 methanol steam and the mixture of vapor;
Step 4, the mixture that step 3 obtains enters reactor, and conversion gas is obtained by the reaction 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.
2. useless refining methanol reforming hydrogen manufacturing method according to claim 1, which is characterized in that in step 1, percentage by weight
Than meter, 3%-4% containing grease, water 10%-12%, surplus are methanol in the useless methanol.
3. useless refining methanol reforming hydrogen manufacturing method according to claim 1, which is characterized in that in step 2, adjusting control vapour
Stripper overhead obtains the mass ratio of methanol steam and vapor, makes the methanol steam, the steam mixture that enter vaporization superheater
The mass percent of middle methanol steam is 45%-50%.
4. useless refining methanol reforming hydrogen manufacturing method according to claim 1, which is characterized in that in step 4, the conversion gas
Pressure be 1.0MPa, temperature is 250-270 DEG C, group is divided into H2、CO2、CO、CH4、H2O and CH3OH。
5. useless refining methanol reforming hydrogen manufacturing method according to claim 1, which is characterized in that in step 4, the catalyst
For Cu-series catalyst.
6. useless refining methanol reforming hydrogen manufacturing method according to claim 1, which is characterized in that in step 5, by quality percentage
Than meter, the conversion gas group after washing process is divided into:H2:70%-78%, CO2:20%-28%, CO:0.4%-1.2%, surplus
For a small amount of CH4And saturated water.
7. useless refining methanol reforming hydrogen manufacturing method according to claim 1, which is characterized in that in step 5, the conversion gas
It is washed after being cooled to less than 40 DEG C.
8. a kind of useless refining methanol reforming hydrogen manufacturing device for any one of claim 1-7 the methods, which is characterized in that packet
Include oil eliminator (1), methanol tank (2), stripper (4), vaporization superheater (5), reactor (6), the water scrubber of sequence setting
(8) it is connect with the stripper (4) by methanol pump (3) with pressure swing adsorption system (9), the methanol tank (2), the stripping
The tower top discharge port of tower (4) is connect with the feed inlet of the vaporization superheater (5), and the lower part of the stripper (4) is connected with water
Steam pipe, vapor enter the stripper (4) by the vapor pipe.
9. the device of useless refining methanol reforming hydrogen manufacturing according to claim 8, which is characterized in that the reactor (6) and
Condenser (7) is also associated between the water scrubber (8), the condenser (7) is for cooling down conversion gas obtained by the reaction.
10. the device of useless refining methanol reforming hydrogen manufacturing according to claim 8, which is characterized in that the pressure-variable adsorption system
System (9) includes at least two adsorption towers being connected in parallel.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810542918.7A CN108516520A (en) | 2018-05-30 | 2018-05-30 | A kind of useless refining methanol reforming hydrogen manufacturing method and device |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810542918.7A CN108516520A (en) | 2018-05-30 | 2018-05-30 | A kind of useless refining methanol reforming hydrogen manufacturing method and device |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108516520A true CN108516520A (en) | 2018-09-11 |
Family
ID=63426809
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810542918.7A Pending CN108516520A (en) | 2018-05-30 | 2018-05-30 | A kind of useless refining methanol reforming hydrogen manufacturing method and device |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108516520A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110342712A (en) * | 2019-06-28 | 2019-10-18 | 金澳科技(湖北)化工有限公司 | A kind of processing system and method applied to MTBE extraction water |
CN113860996A (en) * | 2021-04-23 | 2021-12-31 | 东营市海科瑞林化工有限公司 | Raw material methanol oil removal treatment process in methanol hydrogen production process |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102627259A (en) * | 2012-03-27 | 2012-08-08 | 成都赛普瑞兴科技有限公司 | Method for preparing hydrogen by methanol-water reforming |
CN104086381A (en) * | 2014-07-22 | 2014-10-08 | 湖北潜江金华润化肥有限公司 | Method and device for preparing dimethyl ether from oil-containing waste methanol |
CN208440278U (en) * | 2018-05-30 | 2019-01-29 | 上海亿维工业科技股份有限公司 | A kind of useless refining methanol reforming hydrogen manufacturing device |
-
2018
- 2018-05-30 CN CN201810542918.7A patent/CN108516520A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102627259A (en) * | 2012-03-27 | 2012-08-08 | 成都赛普瑞兴科技有限公司 | Method for preparing hydrogen by methanol-water reforming |
CN104086381A (en) * | 2014-07-22 | 2014-10-08 | 湖北潜江金华润化肥有限公司 | Method and device for preparing dimethyl ether from oil-containing waste methanol |
CN208440278U (en) * | 2018-05-30 | 2019-01-29 | 上海亿维工业科技股份有限公司 | A kind of useless refining methanol reforming hydrogen manufacturing device |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110342712A (en) * | 2019-06-28 | 2019-10-18 | 金澳科技(湖北)化工有限公司 | A kind of processing system and method applied to MTBE extraction water |
CN113860996A (en) * | 2021-04-23 | 2021-12-31 | 东营市海科瑞林化工有限公司 | Raw material methanol oil removal treatment process in methanol hydrogen production process |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110040691B (en) | Device and method for preparing and producing high-purity sulfur dioxide by using acid gas | |
RU2762056C1 (en) | Apparatus and method for joint extraction of sulphur and hydrogen resources from a hydrogen sulphide-containing acid gas | |
CN101264862B (en) | Method for preparing heavy water and deuterium gas | |
CN113274755B (en) | Process and device for preparing oxygen by phase thermal decomposition of sulfuric acid in iodine-sulfur cycle | |
CN108516520A (en) | A kind of useless refining methanol reforming hydrogen manufacturing method and device | |
CN109384647A (en) | A kind of transformation methanolizing integrated production equipment and method | |
CN101007622A (en) | Device for tail chlorine degassing and absorption for preparing hydrochloride gas and its preparation method | |
CN104860264A (en) | Residual gas heat exchange combustion-supporting system and method based on methanol water reforming hydrogen production system | |
CN103588615B (en) | Device and technology for recovery of tetrachloroethylene | |
CN114634400A (en) | Method and production system for synthesizing methanol by using carbon dioxide | |
CN208440278U (en) | A kind of useless refining methanol reforming hydrogen manufacturing device | |
CN103254922B (en) | Two-stage coal direct liquefaction method and system | |
CN210710773U (en) | Industrial ammonia water and high-purity ammonia co-production system | |
CN210103457U (en) | Device for preparing and producing high-purity sulfur dioxide by utilizing acid gas | |
CN204643838U (en) | Based on the residual air heat exchange combustion-supporting system of methanol-water hydrogen production system employing reforming technology | |
CN110510636B (en) | Industrial ammonia water and high-purity ammonia co-production system and process | |
CN204848705U (en) | Purified terephthalic acid refines unit hydrogen edulcoration recovery unit | |
CN207828195U (en) | A kind of device producing high-quality lightweight white oil by base oil | |
CN111039752A (en) | Method for continuously producing methanol by hydrogenating methyl formate byproduct in process of preparing ethylene glycol from coal | |
CN106397121A (en) | A biogas-coke oven gas combined methanol production device | |
CN210796289U (en) | High-efficient low energy consumption sodium methoxide purification equipment | |
CN110388638B (en) | Steam heat energy recycling process in urea production by carbon dioxide gas stripping method | |
CN212246210U (en) | System for recovering heat energy of shift gas in hydrogen production device | |
CN220351721U (en) | Hydrogen production system is cooperated with methyl alcohol hydrogen steam to natural gas hydrogen production | |
CN216155481U (en) | Hydrogen impurity removal system for polycrystalline silicon production and polycrystalline silicon production system |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |