CN105947981A - High pressure water-cooling phase change heat transfer methanolization and methanation refining technology - Google Patents
High pressure water-cooling phase change heat transfer methanolization and methanation refining technology Download PDFInfo
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- CN105947981A CN105947981A CN201610299235.4A CN201610299235A CN105947981A CN 105947981 A CN105947981 A CN 105947981A CN 201610299235 A CN201610299235 A CN 201610299235A CN 105947981 A CN105947981 A CN 105947981A
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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Abstract
The invention relates to a high pressure water-cooling phase change heat transfer methanolization and methanation refining technology. The technology involves three high pressure water-cooling reactors. Under room temperature, feed gas containing CO and CO2 firstly passes through a first high pressure water-cooling reaction device, a lot of CO and CO2 transform into CH3OH under the action of a copper based methanol catalyst, the heat of the reacted gas is recovered by a heat exchanger, then after cooling and CH3OH separation, the reacted gas enter a second high pressure water-cooling reaction device, the remaining little CO and CO2 are transformed into CH3OH, the reacted gas is subjected to heat recovery by a heat exchanger, cooling and CH3OH separation, then the left gas enters a third high pressure water-cooling reaction device, very little CO and CO2 in the gas are transformed into CH4 under the action of a nickel based methanation catalyst, and finally in the refined gas, the sum of CO and CO 2 is less than or equal to 15ppm. The technology provided by the invention has the advantages of good heat transfer effect, stable operation, energy saving and environmental protection, and also can achieve deep removal of CO and CO2 from the feed gas.
Description
Technical field
The present invention relates to a kind of Chemical Engineering Technology, particularly to unstripped gas deep removal CO in a kind of Ammonia Production
And CO2High pressure water-cooled phase transformation move hot alcohol alkanisation process for refining.
Background technology
Unstripped gas deep removal CO, CO in currently known traditional coal Ammonia Production2Purification techniques mainly may be used
It is divided into following 2 kinds:
1) depth conversion string cuprammonia absorption process (being called for short: copper washing process).
2) connection alcohol string methanation (being called for short: alcohol alkylation process).
Above purification techniques is the most commutative is combined into other technique.Domestic most Middle Scale Ammonia factory or part are large-scale
Ammonia factory uses CO, CO in process above removing unstripped gas2, and this type of technology is primarily present problems with:
(1) environment operation energy consumption, is polluted high
Copper washing process mainly relies on cuprammonia to absorb CO and CO remained in unstripped gas2, in generation often
There are the lamination produce such as CuS raw occluding device, pipeline；Harmful gas such as ammonia and acetic acid is had during preparing copper liquid
Body discharges, and has bigger pollution to environment.Either copper is washed or double first technique, will drive copper pump in operation
Or circulator and electric furnace, relatively more electric energy will be consumed.
(2), labor intensity is big produces instability
Need in operating due to copper washing process to control the composition of cuprammonia, copper flow quantity, regeneration temperature, again
Many technological parameters such as raw pressure, therefore labor intensity and operation easier are bigger；Alcohol alkylation process is due to reactor
Design be cold shock or cold pipe gas-gas heat exchange, operation needs also exist for adjust circulating flow rate, cold pipe temperature,
The distribution of each section of bed temperature, that the parameter manipulation difficulty such as linear flow rate, furnace power paid by tower is the biggest.
In above-mentioned two kinds of process operations, easily changed by the operation of front workshop section and gas ingredients and affected, generation methanol,
Methanation catalyst " temperature runaway ", " collapse temperature ", copper liquid brings next workshop section into affects ammonia synthesis operation and synthesis catalytic
The accidents such as the service life of agent.The most either copper is washed or alcohol alkylation process, all there is operation easier
Greatly, CO, CO in the problem, and unstripped gas such as fluctuation of service2Can not deep removal.
Summary of the invention
The invention aims to overcome weak point of the prior art, it is provided that a kind of high pressure water-cooled phase transformation moves
Hot alcohol alkanisation process for refining, it not only moves, and thermal effect is good, stable operation, energy-conserving and environment-protective, and can the degree of depth take off
Except CO and CO in unstripped gas2。
The present invention is achieved in that a kind of high pressure water-cooled phase transformation moves hot alcohol alkanisation process for refining, and it includes three
Being sequentially connected the high pressure water-cooled reaction unit connect, every high pressure water-cooled reaction unit at least includes that high pressure water-cooled is anti-
Answer device and the heat exchanger being connected respectively and drum with water under high pressure cold reactor；It comprises the following steps that
(1), under front workshop section room temperature, CO, CO are contained2、H2Unstripped gas enter the first heat exchanger and be heated to
200-220℃；Unstripped gas after heated enters the first water under high pressure cold reactor, CO substantial amounts of in unstripped gas
And CO2It is converted into CH under copper system catalyst for methanol effect in the first water under high pressure cold reactor3OH, and produce
Heat；Desalination deoxygenated water in first drum enters shell side or the tube side of the first water under high pressure cold reactor, and first
The heat reacting generation in water under high pressure cold reactor is that steam is re-fed into by the water sorption enhanced of shell side or tube side
One drum；Go out the gas of the first water under high pressure cold reactor and reclaim heat through the first heat exchanger, and cooled,
Isolate CH3Second high pressure water-cooled reaction unit is entered after OH；
(2), step (1) isolates CH3Gas after OH initially enters the second heat exchanger and is heated to
190-220℃；Gas after heated enters the second water under high pressure cold reactor, a small amount of CO remaining in gas
And CO2It is converted into CH under copper system catalyst for methanol effect in the second water under high pressure cold reactor3OH, and produce
Heat；Desalination deoxygenated water in second drum enters shell side or the tube side of the second water under high pressure cold reactor, and second
The heat reacting generation in water under high pressure cold reactor is that steam is re-fed into by the water sorption enhanced of shell side or tube side
Two drums；Go out the gas of the second water under high pressure cold reactor and reclaim heat through the second heat exchanger, and cooled,
Isolate CH3The 3rd high pressure water-cooled reaction unit is entered after OH；
(3), step (2) isolates CH3Gas after OH initially enters the 3rd heat exchanger and is heated to
190-220℃；Gas after heated enters the 3rd water under high pressure cold reactor, very small amount CO remaining in gas
And CO2It is converted into CH under nickel system methanation catalyst effect in the 3rd water under high pressure cold reactor4, and produce
Heat；The shell side of desalination deoxygenated water entrance the 3rd water under high pressure cold reactor in the 3rd drum or tube side, the 3rd
The heat reacting generation in water under high pressure cold reactor is that steam is re-fed into by the water sorption enhanced of shell side or tube side
Three drums；Go out the 3rd water under high pressure cold reactor and remove CO and CO2Gas through the 3rd heat exchanger reclaim heat
Amount, and it is cooled and separated out H2Next workshop section is entered after O.
In order to reduce energy consumption and cost；Described first drum, the second drum and the 3rd drum are interconnected mutually by pipe network
Lead to and be connected to coupling cock, being controlled by coupling cock between the first drum, the second drum and the 3rd drum
Break-make processed.Steam in described first drum is transferred to the second drum and the 3rd drum by coupling cock, and second
Heat needed for water under high pressure cold reactor and the reaction of the 3rd water under high pressure cold reactor is respectively by being transferred to the second drum
Supply with the steam in the 3rd drum.
In order to reduce labor intensity and cost of labor；Described first drum, the second drum and the 3rd drum are respectively
Being connected by fluid level control valve and have liquid level controller, each coupling cock correspondence connects pressure intelligent controller；
Described first water under high pressure cold reactor, the second water under high pressure cold reactor and the reaction of the 3rd water under high pressure cold reactor
Temperature realizes by controlling corresponding the first drum, the second drum and the 3rd drum pressure, the first drum,
The pressure of the second drum and the 3rd drum is by corresponding coupling cock, liquid level controller and pressure intelligent controller
Control.
In order to energy-conservation and ensure to react institute calorific requirement；Described first water under high pressure cold reactor, the second high pressure water-cooled
Reactor and the 3rd water under high pressure cold reactor by the mutual UNICOM of pipe network and are connected to outer for steam addition
Valve, the first water under high pressure cold reactor, the second water under high pressure cold reactor and the 3rd water under high pressure cold reactor react institute
Need heat by respective outer for steam add valve control be individually added into steam heating.
Methanolizing reaction equation in described step (1) is 2H2+CO→CH3OH+△HCO、3H2+CO2→
CH3OH+H2O+△HCO2.Methanolizing reaction equation in described step (2) is 2H2+CO→CH3OH+
△HCO、3H2+CO2→CH3OH+H2O+△HCO2.Methanation reaction formula in described step (3) is
3H2+ CO=CH4+H2O+△HCO、4H2+CO2=CH4+2H2O+△HCO2。
High pressure water-cooled phase transformation of the present invention moves hot alcohol alkanisation process for refining and has the advantage that the present invention is at Chemical Engineering Technology
Field, in traditional coal Ammonia Production, especially not only move that thermal effect is good, stable operation, energy-conserving and environment-protective；
And can CO and CO2 in deep removal unstripped gas.
The present invention is to realize under high temperature, high pressure, High Pressure Difference process environments: 1, use water-cooled phase transformation to move heat
Replacing gas-gas heat exchange, shifting thermal effect is good, stable operation；Can pay product a large amount of steam, be not required to open cycle machine,
Without electric furnace, energy-conserving and environment-protective；2, use methanation to replace copper to wash, there is no emission, clean environment firendly；3、
Stop " temperature runaway ", " collapse temperature " of catalyst；3, properly functioning need not open cycle machine, SR is little,
Need not use electric furnace and steam-heating apparatus, reduce energy consumption, investment and operating cost；4, by methanol,
Methanation reaction institute thermal discharge and absorption heat, contact into a mutual heat supply including outer supplying heat source by drum
And temperature-controlling system；By the setting to heat supply and temperature-controlling system, it is possible to achieve artificial intelligence's temperature control and unmanned behaviour
Run；5, the heat needed for the second water under high pressure cold reactor and the 3rd water under high pressure cold reactor react is by first
Water under high pressure cold reactor reacts the steam supply produced, or controls to be individually added into for steam addition valve by outer
Steam heating, it is not necessary to power supply, energy-conservation and environmental protection.
Accompanying drawing explanation
The present invention is further illustrated the most in conjunction with the embodiments.
Fig. 1 is the flow chart that high pressure water-cooled phase transformation of the present invention moves hot alcohol alkanisation process for refining.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be described in detail.
(1) detailed description of the invention is as follows: a kind of high pressure water-cooled phase transformation moves hot alcohol alkanisation process for refining, and it includes
Three are sequentially connected the high pressure water-cooled reaction unit connect, and First High Pressure water-cooled reaction unit includes the first high pressure
Water-cooled reactor and the first heat exchanger being connected with the first water under high pressure cold reactor respectively and the first vapour
Bag, second high pressure water-cooled reaction unit include the second water under high pressure cold reactor and respectively with the second water under high pressure
The second heat exchanger that cold reactor is connected and the second drum, the 3rd high pressure water-cooled reaction unit includes
Three water under high pressure cold reactors and the 3rd heat exchanger being connected with the 3rd water under high pressure cold reactor respectively and
Three drums.Described first drum, the second drum and the 3rd drum are by the mutual UNICOM of pipe network and are connected to
Coupling cock, controls break-make by coupling cock between the first drum, the second drum and the 3rd drum.Described
One drum, the second drum and the 3rd drum are all connected to water pipe, and desalination deoxygenated water supplies the first vapour by water pipe
Bag, the second drum and the 3rd drum.
Described first water under high pressure cold reactor, the second water under high pressure cold reactor and the 3rd water under high pressure cold reactor pass through
The mutual UNICOM of pipe network is also connected to outer for steam addition valve, the first water under high pressure cold reactor, the second high pressure
Heat needed for water-cooled reactor and the reaction of the 3rd water under high pressure cold reactor is by respective outer for steam addition valve
Control to be individually added into steam heating.
High pressure water-cooled phase transformation of the present invention moves hot alcohol alkanisation process for refining and comprises the following steps that
(1), under front workshop section room temperature, CO, CO are contained2、H2Unstripped gas enter the first heat exchanger and be heated to
200-220℃；Unstripped gas after heated enters the first water under high pressure cold reactor, CO substantial amounts of in unstripped gas
And CO2It is converted into CH under copper system catalyst for methanol effect in the first water under high pressure cold reactor3OH, and produce
Heat, methanolizing reaction equation is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△
HCO2；Desalination deoxygenated water in first drum enters shell side or the tube side of the first water under high pressure cold reactor, and first
The heat reacting generation in water under high pressure cold reactor is that steam is re-fed into by the water sorption enhanced of shell side or tube side
One drum；Go out the gas of the first water under high pressure cold reactor and reclaim heat through the first heat exchanger, and cooled,
Isolate CH3Second high pressure water-cooled reaction unit is entered after OH；
(2), step (1) isolates CH3Gas after OH initially enters the second heat exchanger and is heated to
190-220℃；Gas after heated enters the second water under high pressure cold reactor, a small amount of CO remaining in gas
And CO2It is converted into CH under copper system catalyst for methanol effect in the second water under high pressure cold reactor3OH, and produce
Heat, methanolizing reaction equation is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△
HCO2；Desalination deoxygenated water in second drum enters shell side or the tube side of the second water under high pressure cold reactor, and second
The heat reacting generation in water under high pressure cold reactor is that steam is re-fed into by the water sorption enhanced of shell side or tube side
Two drums；Go out the gas of the second water under high pressure cold reactor and reclaim heat through the second heat exchanger, and cooled,
Isolate CH3The 3rd high pressure water-cooled reaction unit is entered after OH；
(3), step (2) isolates CH3Gas after OH initially enters the 3rd heat exchanger and is heated to
190-220℃；Gas after heated enters the 3rd water under high pressure cold reactor, very small amount CO remaining in gas
And CO2It is converted into CH under nickel system methanation catalyst effect in the 3rd water under high pressure cold reactor4, and produce
Heat, methanation reaction formula is 3H2+ CO=CH4+H2O+△HCO、4H2+CO2=CH4+2H2O+△HCO2；3rd
Desalination deoxygenated water in drum enters shell side or the tube side of the 3rd water under high pressure cold reactor, and the 3rd water under high pressure is cold instead
Answering the heat reacting generation in device is that steam is re-fed into the 3rd drum by the water sorption enhanced of shell side or tube side；Go out
3rd water under high pressure cold reactor has removed CO and CO2Gas reclaim heat through the 3rd heat exchanger, and through cold
But, H is isolated2Next workshop section is entered after O.
The steam that described step (1) produces can store for future use, and can pass through the first drum and coupling cock simultaneously
It is transferred to the second drum and the 3rd drum, the second water under high pressure cold reactor and the reaction of the 3rd water under high pressure cold reactor
Required heat is respectively by the steam supply being transferred in the second drum and the 3rd drum.Outside load gentlier needs
During heating load, the first water under high pressure cold reactor, the second water under high pressure cold reactor and the 3rd water under high pressure can be passed through
The respective outer confession steam of cold reactor adds valve and controls to be individually added into steam heating.As long as controlling respective drum
Coupling cock and outer confession steam add valve, and the principle moving heat according to phase transformation can control the temperature of each reactor or make
The reaction temperature of each reactor is identical.
First drum of the present invention, the second drum and the 3rd drum are connected by fluid level control valve respectively liquid level
Controller, each coupling cock correspondence connects pressure intelligent controller；Described first water under high pressure cold reactor,
The reaction temperature of the second water under high pressure cold reactor and the 3rd water under high pressure cold reactor is by controlling the first corresponding vapour
Bag, the second drum and the 3rd drum pressure realize, the first drum, the second drum and the pressure of the 3rd drum
Controlled by corresponding coupling cock, liquid level controller and pressure intelligent controller.
(2) embodiment is as follows:
Embodiment 1: a kind of high pressure water-cooled phase transformation moves hot alcohol alkanisation process for refining, comprises the following steps that
(1), from front workshop section room temperature, pressure be under 6.0MPa, containing 1.9%CO, 0.5%CO2, 73.59%H2
Unstripped gas enter the first heat exchanger and be heated to 206 DEG C；Unstripped gas after heated enters the first high pressure water-cooled
Reactor, CO and CO substantial amounts of in unstripped gas2Copper system methanol oxidation in the first water under high pressure cold reactor
It is converted into CH under agent effect3OH, and produce heat, methanolizing reaction equation is 2H2+CO→CH3OH+△HCO、
3H2+CO2→CH3OH+H2O+△HCO2；It is anti-that desalination deoxygenated water in first drum enters the first high pressure water-cooled
Answer shell side or the tube side of device, the first water under high pressure cold reactor reacts the heat of generation by shell side or the water of tube side
Sorption enhanced is that steam is re-fed into the first drum, and the steam wherein produced is 1479.7kg/hr；Go out the first high pressure
The gas (temperature is 228 DEG C) of water-cooled reactor reclaims heat through the first heat exchanger, reclaims the temperature after heat
Degree is 56 DEG C, and is cooled and separated out CH3Second high pressure water-cooled reaction unit is entered after OH；This step
Isolate CH3In gas after OH the content of CO be 0.202%, CO2Content be 0.266%.
(2), step (1) isolates CH3Gas after OH initially enters the second heat exchanger and is heated to 192 DEG C；
Gas after heated enters the second water under high pressure cold reactor, a small amount of CO and CO remaining in gas2Second
It is converted into CH under copper system catalyst for methanol effect in water under high pressure cold reactor3OH, and produce heat, methanolizing
Reaction equation is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2；Second drum
In desalination deoxygenated water enter shell side or the tube side of the second water under high pressure cold reactor, the second water under high pressure cold reactor
The heat that middle reaction produces is that steam is re-fed into the second drum by the water sorption enhanced of shell side or tube side, wherein produces
Raw steam is-792.32kg/hr；Go out the gas (temperature is 215 DEG C) of the second water under high pressure cold reactor through
Two heat exchangers reclaims heat, and reclaiming the temperature after heat is 57 DEG C, and is cooled and separated out CH3After OH
Enter the 3rd high pressure water-cooled reaction unit；This step isolates CH3In gas after OH, the content of CO is
0.0204097%, CO2Content be 0.1611296%.
(3), step (2) isolates CH3Gas after OH initially enters the 3rd heat exchanger and is heated to 204 DEG C；
Gas after heated enters the 3rd water under high pressure cold reactor, very small amount CO remaining in gas and CO2?
It is converted into CH under nickel system methanation catalyst effect in three water under high pressure cold reactors4, and produce heat, methane
Change reaction equation is 3H2+ CO=CH4+H2O+△HCO、4H2+CO2=CH4+2H2O+△HCO2；Taking off in the 3rd drum
Salt deoxygenated water enters shell side or the tube side of the 3rd water under high pressure cold reactor, reacts in the 3rd water under high pressure cold reactor
The heat produced is that steam is re-fed into the 3rd drum by the water sorption enhanced of shell side or tube side, the steaming wherein produced
Vapour is-599.51kg/hr；The gas (temperature is 224 DEG C) going out the 3rd water under high pressure cold reactor is handed over through the 3rd heat
Parallel operation reclaims heat, and reclaiming the temperature after heat is 57 DEG C, and is cooled and separated out H2Next is entered after O
Workshop section；This step isolates H2CO and CO in gas after O2Content be 1E-05.Polishing gas
Middle CO+CO2≤15ppm.In described second water under high pressure cold reactor and the 3rd water under high pressure cold reactor, reaction is required
Steam by first water under high pressure cold reactor reaction produce steam supply.
Embodiment 2: a kind of high pressure water-cooled phase transformation moves hot alcohol alkanisation process for refining, comprises the following steps that
(1), from front workshop section room temperature, pressure be 160/2Under, containing 1.8%CO, 0.5%CO2, 73.6%
H2Unstripped gas enter the first heat exchanger and be heated to 212 DEG C；Unstripped gas after heated enters the first high pressure
Water-cooled reactor, CO and CO substantial amounts of in unstripped gas2Copper system methanol in the first water under high pressure cold reactor
It is converted into CH under catalyst action3OH, and produce heat, methanolizing reaction equation is 2H2+CO→CH3OH+
△HCO、3H2+CO2→CH3OH+H2O+△HCO2；It is high that desalination deoxygenated water in first drum enters first
The shell side of setting-out cold reactor or tube side, the first water under high pressure cold reactor reacts the heat of generation by shell side or
The water sorption enhanced of tube side is that steam is re-fed into the first drum, and the steam wherein produced is 1698.9kg/hr；Go out
The gas (temperature is 228 DEG C) of the first water under high pressure cold reactor reclaims heat through the first heat exchanger, reclaims heat
Temperature after amount is 62 DEG C, and is cooled and separated out CH3Second high pressure water-cooled reaction unit is entered after OH；
This step isolates CH3In gas after OH the content of CO be 0.134%, CO2Content be 0.213%.
(2), step (1) isolates CH3Gas after OH initially enters the second heat exchanger and is heated to 192 DEG C；
Gas after heated enters the second water under high pressure cold reactor, a small amount of CO and CO remaining in gas2Second
It is converted into CH under copper system catalyst for methanol effect in water under high pressure cold reactor3OH, and produce heat, methanolizing
Reaction equation is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2；Second drum
In desalination deoxygenated water enter shell side or the tube side of the second water under high pressure cold reactor, the second water under high pressure cold reactor
The heat that middle reaction produces is that steam is re-fed into the second drum by the water sorption enhanced of shell side or tube side, wherein produces
Raw steam is-871.469kg/hr；Go out the gas (temperature is 215 DEG C) of the second water under high pressure cold reactor through
Two heat exchangers reclaims heat, and reclaiming the temperature after heat is 57 DEG C, and is cooled and separated out CH3After OH
Enter the 3rd high pressure water-cooled reaction unit；This step isolates CH3In gas after OH, the content of CO is
0.00948%, CO2Content be 0.086%.
(3), step (2) isolates CH3Gas after OH initially enters the 3rd heat exchanger and is heated to 204 DEG C；
Gas after heated enters the 3rd water under high pressure cold reactor, very small amount CO remaining in gas and CO2?
It is converted into CH under nickel system methanation catalyst effect in three water under high pressure cold reactors4, and produce heat, methane
Change reaction equation is 3H2+ CO=CH4+H2O+△HCO、4H2+CO2=CH4+2H2O+△HCO2；Taking off in the 3rd drum
Salt deoxygenated water enters shell side or the tube side of the 3rd water under high pressure cold reactor, reacts in the 3rd water under high pressure cold reactor
The heat produced is that steam is re-fed into the 3rd drum by the water sorption enhanced of shell side or tube side, the steaming wherein produced
Vapour is-808.42kg/hr；The gas (temperature is 224 DEG C) going out the 3rd water under high pressure cold reactor is handed over through the 3rd heat
Parallel operation reclaims heat, and reclaiming the temperature after heat is 56 DEG C, and is cooled and separated out H2Next is entered after O
Workshop section；This step isolates H2CO and CO in gas after O2Content be 1E-05.Polishing gas
Middle CO+CO2≤15ppm.In described second water under high pressure cold reactor and the 3rd water under high pressure cold reactor, reaction is required
Steam by first water under high pressure cold reactor reaction produce steam supply.
Embodiment 3: a kind of high pressure water-cooled phase transformation moves hot alcohol alkanisation process for refining, comprises the following steps that
(1), from front workshop section room temperature, pressure be 220/2 times, containing 1.8%CO, 0.5%CO2, 73.6%
H2Unstripped gas enter the first heat exchanger and be heated to 214 DEG C；Unstripped gas after heated enters the first high pressure
Water-cooled reactor, CO and CO during unstripped gas is substantial amounts of2Copper system methanol in the first water under high pressure cold reactor
It is converted into CH under catalyst action3OH, and produce heat, methanolizing reaction equation is 2H2+CO→CH3OH+
△HCO、3H2+CO2→CH3OH+H2O+△HCO2；It is high that desalination deoxygenated water in first drum enters first
The shell side of setting-out cold reactor or tube side, the first water under high pressure cold reactor reacts the heat of generation by shell side or
The water sorption enhanced of tube side is that steam is re-fed into the first drum, and the steam wherein produced is 1892.9kg/hr；Go out
The gas (temperature is 228 DEG C) of the first water under high pressure cold reactor reclaims heat through the first heat exchanger, reclaims heat
Temperature after amount is 62 DEG C, and is cooled and separated out CH3Second high pressure water-cooled reaction unit is entered after OH；
This step isolates CH3In gas after OH the content of CO be 0.077%, CO2Content be 0.16%.
(2), step (1) isolates CH3Gas after OH initially enters the second heat exchanger and is heated to 192 DEG C；
Gas after heated enters the second water under high pressure cold reactor, a small amount of CO and CO remaining in gas2Second
It is converted into CH under copper system catalyst for methanol effect in water under high pressure cold reactor3OH, and produce heat, methanolizing
Reaction equation is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2；Second drum
In desalination deoxygenated water enter shell side or the tube side of the second water under high pressure cold reactor, the second water under high pressure cold reactor
The heat that middle reaction produces is that steam is re-fed into the second drum by the water sorption enhanced of shell side or tube side, wherein produces
Raw steam is-959.61kg/hr；Go out the gas (temperature is 215 DEG C) of the second water under high pressure cold reactor through
Two heat exchangers reclaims heat, and reclaiming the temperature after heat is 57 DEG C, and is cooled and separated out CH3After OH
Enter the 3rd high pressure water-cooled reaction unit；This step isolates CH3In gas after OH, the content of CO is
0.0031%, CO2Content be 0.0485%.
(3), step (2) isolates CH3Gas after OH initially enters the 3rd heat exchanger and is heated to 204 DEG C；
Gas after heated enters the 3rd water under high pressure cold reactor, very small amount CO remaining in gas and CO2?
It is converted into CH under nickel system methanation catalyst effect in three water under high pressure cold reactors4, and produce heat, methane
Change reaction equation is 3H2+ CO=CH4+H2O+△HCO、4H2+CO2=CH4+2H2O+△HCO2；Taking off in the 3rd drum
Salt deoxygenated water enters shell side or the tube side of the 3rd water under high pressure cold reactor, reacts in the 3rd water under high pressure cold reactor
The heat produced is that steam is re-fed into the 3rd drum by the water sorption enhanced of shell side or tube side, the steaming wherein produced
Vapour is-913.6kg/hr；Go out the gas (temperature is 224 DEG C) of the 3rd water under high pressure cold reactor through the 3rd heat exchange
Device reclaims heat, and reclaiming the temperature after heat is 54 DEG C, and is cooled and separated out H2Next work is entered after O
Section；This step isolates H2CO and CO in gas after O2Content be 1E-05.In polishing gas
CO+CO2≤15ppm.In described second water under high pressure cold reactor and the 3rd water under high pressure cold reactor needed for reaction
The steam supply that steam is produced by the first water under high pressure cold reactor reaction.
Second water under high pressure cold reactor described in above-described embodiment 1-3 and the 3rd water under high pressure cold reactor react institute
Need steam can also by respective outer for steam add valve control be individually added into steam heating.
Technical scheme is simply explained in detail by above-mentioned detailed description of the invention, and the present invention is the most only
It is limited only to above-described embodiment, every any improvement according to the principle of the invention or replacement, all should be in the present invention
Protection domain within.
Claims (8)
1. a high pressure water-cooled phase transformation moves hot alcohol alkanisation process for refining, it is characterised in that it includes three successively
The high pressure water-cooled reaction unit being connected, every high pressure water-cooled reaction unit at least includes water under high pressure cold reactor
And the heat exchanger that is connected with water under high pressure cold reactor respectively and drum；It comprises the following steps that
(1), under front workshop section room temperature, CO, CO are contained2、H2Unstripped gas enter the first heat exchanger and be heated to
200-220℃；Unstripped gas after heated enters the first water under high pressure cold reactor, substantial amounts of CO in unstripped gas
And CO2It is converted into CH under copper system catalyst for methanol effect in the first water under high pressure cold reactor3OH, and produce
Heat；Desalination deoxygenated water in first drum enters shell side or the tube side of the first water under high pressure cold reactor, and first
The heat reacting generation in water under high pressure cold reactor is that steam is re-fed into by the water sorption enhanced of shell side or tube side
One drum；Go out the gas of the first water under high pressure cold reactor and reclaim heat through the first heat exchanger, and cooled,
Isolate CH3Second high pressure water-cooled reaction unit is entered after OH；
(2), step (1) isolates CH3Gas after OH initially enters the second heat exchanger and is heated to
190-220℃；Gas after heated enters the second water under high pressure cold reactor, a small amount of CO remaining in gas
And CO2It is converted into CH under copper system catalyst for methanol effect in the second water under high pressure cold reactor3OH, and produce
Heat；Desalination deoxygenated water in second drum enters shell side or the tube side of the second water under high pressure cold reactor, and second
The heat reacting generation in water under high pressure cold reactor is that steam is re-fed into by the water sorption enhanced of shell side or tube side
Two drums；Go out the gas of the second water under high pressure cold reactor and reclaim heat through the second heat exchanger, and cooled,
Isolate CH3The 3rd high pressure water-cooled reaction unit is entered after OH；
(3), step (2) isolates CH3Gas after OH initially enters the 3rd heat exchanger and is heated to
190-220℃；Gas after heated enters the 3rd water under high pressure cold reactor, very small amount CO remaining in gas
And CO2It is converted into CH under nickel system methanation catalyst effect in the 3rd water under high pressure cold reactor4, and produce
Heat；The shell side of desalination deoxygenated water entrance the 3rd water under high pressure cold reactor in the 3rd drum or tube side, the 3rd
The heat reacting generation in water under high pressure cold reactor is that steam is re-fed into by the water sorption enhanced of shell side or tube side
Three drums；Go out the 3rd water under high pressure cold reactor and remove CO and CO2Gas through the 3rd heat exchanger reclaim heat
Amount, and it is cooled and separated out H2Next workshop section is entered after O.
High pressure water-cooled phase transformation the most according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that:
Described first drum, the second drum and the 3rd drum are by the mutual UNICOM of pipe network and are connected to coupling cock,
Break-make is controlled by coupling cock between first drum, the second drum and the 3rd drum.
High pressure water-cooled phase transformation the most according to claim 2 moves hot alcohol alkanisation process for refining, it is characterised in that:
Steam in described first drum is transferred to the second drum and the 3rd drum, the second high pressure water-cooled by coupling cock
Heat needed for reactor and the reaction of the 3rd water under high pressure cold reactor is respectively by being transferred to the second drum and the 3rd vapour
Steam supply in bag.
High pressure water-cooled phase transformation the most according to claim 3 moves hot alcohol alkanisation process for refining, it is characterised in that:
Described first drum, the second drum and the 3rd drum are connected by fluid level control valve respectively liquid level controller,
Each coupling cock correspondence connects pressure intelligent controller；Described first water under high pressure cold reactor, the second high pressure
Water-cooled reactor and the reaction temperature of the 3rd water under high pressure cold reactor by control corresponding the first drum, second
Drum and the 3rd drum pressure realize, and the pressure of the first drum, the second drum and the 3rd drum is by correspondence
Coupling cock, liquid level controller and pressure intelligent controller control.
High pressure water-cooled phase transformation the most according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that:
Described first water under high pressure cold reactor, the second water under high pressure cold reactor and the 3rd water under high pressure cold reactor are by pipe
Net mutual UNICOM and be connected to outer for steam addition valve, the first water under high pressure cold reactor, the second water under high pressure
Heat needed for cold reactor and the reaction of the 3rd water under high pressure cold reactor is by respective outer for steam addition valve control
System is individually added into steam heating.
High pressure water-cooled phase transformation the most according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that:
Methanolizing reaction equation in described step (1) is 2H2+CO→CH3OH+△HCO、3H2+CO2→
CH3OH+H2O+△HCO2。
High pressure water-cooled phase transformation the most according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that:
Methanolizing reaction equation in described step (2) is 2H2+CO→CH3OH+△HCO、3H2+CO2→
CH3OH+H2O+△HCO2。
High pressure water-cooled phase transformation the most according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that:
Methanation reaction formula in described step (3) is 3H2+ CO=CH4+H2O+△HCO、4H2+CO2=CH4+2H2O+
△HCO2。
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| US3967936A (en) * | 1975-01-02 | 1976-07-06 | The United States Of America As Represented By The United States Energy Research And Development Administration | Methanation process utilizing split cold gas recycle |
| CN101148250A (en) * | 2007-10-24 | 2008-03-26 | 西南化工研究设计院 | Joint production process of alcohol and ammonia |
| CN101659397A (en) * | 2009-08-06 | 2010-03-03 | 上海国际化建工程咨询公司 | Once-through isothermal methanol-methanation advanced purification process and device |
| CN103911196A (en) * | 2013-01-06 | 2014-07-09 | 杭州林达化工技术工程有限公司 | Method and apparatus for utilizing plant waste gas to prepare natural gas |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3967936A (en) * | 1975-01-02 | 1976-07-06 | The United States Of America As Represented By The United States Energy Research And Development Administration | Methanation process utilizing split cold gas recycle |
| CN101148250A (en) * | 2007-10-24 | 2008-03-26 | 西南化工研究设计院 | Joint production process of alcohol and ammonia |
| CN101659397A (en) * | 2009-08-06 | 2010-03-03 | 上海国际化建工程咨询公司 | Once-through isothermal methanol-methanation advanced purification process and device |
| CN103911196A (en) * | 2013-01-06 | 2014-07-09 | 杭州林达化工技术工程有限公司 | Method and apparatus for utilizing plant waste gas to prepare natural gas |
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Inventor after: Jin Linong Inventor after: Ni Ming Inventor after: Yuan Zhongqiu Inventor after: Dou Haifeng Inventor after: Xu Lei Inventor before: Jin Linong |
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Effective date of registration: 20190418 Address after: No. 88 Xingda Road, Nanjing Riverside Industrial Development Zone, Jiangsu Province, 210048 Co-patentee after: Nanjing Haoan Industry Equipment Co., Ltd. Patentee after: NanjingG Haoan Science And Technology Engineering Co., Ltd. Address before: No. 88 Xingda Road, Nanjing Riverside Industrial Development Zone, Jiangsu Province, 210048 Patentee before: NanjingG Haoan Science And Technology Engineering Co., Ltd. |