CN105947981B - The phase transformation of high pressure water cooling moves hot alcohol alkanisation process for refining - Google Patents
The phase transformation of high pressure water cooling moves hot alcohol alkanisation process for refining Download PDFInfo
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- CN105947981B CN105947981B CN201610299235.4A CN201610299235A CN105947981B CN 105947981 B CN105947981 B CN 105947981B CN 201610299235 A CN201610299235 A CN 201610299235A CN 105947981 B CN105947981 B CN 105947981B
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- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- 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
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Abstract
The present invention relates to a kind of high pressure water cooling phase transformations to move hot alcohol alkanisation process for refining, is made of three high pressure water-cooled reactor devices, and CO, CO are contained under room temperature2Unstripped gas first pass around First High Pressure water cooling reaction unit, a large amount of CO and CO2CH is converted under the action of copper system catalyst for methanol3OH, the gas through heat exchanger recycling heat after reaction, then it is cooled and separated CH3Enter second high pressure water cooling reaction unit, remaining a small amount of CO and CO after OH2It is converted into CH3OH, gas through heat exchanger recycling heat, cooling, separation CH after reaction3Enter third platform methanation high pressure water cooling reaction unit after OH, minute quantity CO and CO in gas2CH is converted under the action of nickel system methanation catalyst4, CO+CO in polishing gas2≤15ppm.The present invention not only moves that thermal effect is good, stable operation, energy conservation and environmental protection, and can be in deep removal unstripped gas CO and CO2。
Description
Technical field
The present invention relates to a kind of Chemical Engineering Technology, unstripped gas deep removal CO and CO in more particularly to a kind of Ammonia Production2
The phase transformation of high pressure water cooling move hot alcohol alkanisation process for refining.
Background technology
Unstripped gas deep removal CO, CO in currently known traditional coal Ammonia Production2Purification techniques can be divided mainly into
2 kinds below：
1) depth conversion string cuprammonia absorption process (abbreviation：Copper washing process).
2) connection alcohol string methanation (abbreviation：Alcohol alkylation process).
More than purification techniques is also commutative to be combined into other techniques.Domestic overwhelming majority Middle Scale Ammonia factory or part Large Scale Synthetic Ammonia Plants
CO, CO in unstripped gas are removed with process above2, and such technology is primarily present problems with：
(1), pollution environment operation energy consumption is high
Copper washing process mainly absorbs the CO and CO that are remained in unstripped gas by cuprammonia2, often there is CuS in generation
Etc. laminations object generate occluding device, pipeline；Prepare copper liquid during have the noxious gas emissions such as ammonia and acetic acid, have to environment compared with
Big pollution.Either copper washes still double first techniques, and copper pump or circulator and electric furnace will be opened in operation, to be consumed more
Electric energy.
(2), the big production of labor intensity is unstable
Composition, copper liquid flow, regeneration temperature, the regeneration pressure of control cuprammonia are needed in being operated due to copper washing process
Etc. many technological parameters, therefore labor intensity and operation difficulty are larger；Alcohol alkylation process due to the design of reactor be cold shock or
Cold pipe gas-gas heat exchange also needs adjustment circulating flow rate, cold tube temperature degree, each section of bed temperature distribution, tower pair line stream in operation
The parameter manipulations such as amount, furnace power difficulty is also very big.
In above-mentioned two kinds of process operations, easily influenced by the operation of preceding workshop section and gas ingredients variation, methanol, methane occurs
Change catalyst " temperature runaway ", " collapse temperature ", copper liquid, which brings next workshop section into, influences service life of ammonia synthesis operation and synthetic catalyst etc.
Accident.Therefore either copper is washed or alcohol alkylation process now, all there are the problems such as operation difficulty is big, fluctuation of service, and it is former
Expect CO, CO in gas2It is unable to deep removal.
Invention content
The purpose of the invention is to overcome shortcoming of the prior art, a kind of high pressure water cooling phase transformation is provided and moves hot alcohol
Alkanisation process for refining, it not only moves good thermal effect, stable operation, energy conservation and environmental protection, and can be in deep removal unstripped gas CO and
CO2。
The invention is realized in this way：A kind of high pressure water cooling phase transformation moves hot alcohol alkanisation process for refining, it includes three successively
The high pressure water cooling reaction unit being connected, every high pressure water cooling reaction unit include at least high pressure water-cooled reactor and respectively with
The heat exchanger and drum that high pressure water-cooled reactor is connected；It includes the steps：
(1), contain CO, CO under preceding workshop section's room temperature2、H2Unstripped gas enter first heat exchanger and be heated to 200-220
℃；Unstripped gas after heated enters the first high pressure water-cooled reactor, a large amount of CO and CO in unstripped gas2In the first high pressure water
CH is converted under copper system catalyst for methanol effect in cold reactor3OH, and generate heat；Desalination deoxygenated water in first drum
Into the shell side or tube side of the first high pressure water-cooled reactor, reacted in the first high pressure water-cooled reactor the heat of generation by shell side or
The water sorption enhanced of tube side is re-fed into the first drum for steam；Go out the gas of the first high pressure water-cooled reactor through first heat exchanger
Heat is recycled, and is cooled and separated out CH3Enter second high pressure water cooling reaction unit after OH；
(2), step (1) isolates CH3Gas after OH initially enters second heat exchanger and is heated to 190-220 DEG C；Through
Gas after heating enters the second high pressure water-cooled reactor, remaining a small amount of CO and CO in gas2It is reacted in the second high pressure water cooling
CH is converted under copper system catalyst for methanol effect in device3OH, and generate heat；Desalination deoxygenated water in second drum enters the
The shell side or tube side of two high pressure water-cooled reactors react the heat of generation in the second high pressure water-cooled reactor by shell side or tube side
Water sorption enhanced is re-fed into the second drum for steam；The gas for going out the second high pressure water-cooled reactor recycles heat through second heat exchanger
Amount, and it is cooled and separated out CH3Enter third platform high pressure water cooling reaction unit after OH；
(3), step (2) isolates CH3Gas after OH initially enters third heat exchanger and is heated to 190-220 DEG C；Through
Gas after heating enters third high pressure water-cooled reactor, remaining minute quantity CO and CO in gas2It is anti-in third high pressure water cooling
It answers and is converted into CH under the nickel system methanation catalyst effect in device4, and generate heat；Desalination deoxygenated water in third drum enters
The shell side or tube side of third high pressure water-cooled reactor react the heat of generation by shell side or tube side in third high pressure water-cooled reactor
Water sorption enhanced be re-fed into third drum for steam；Go out third high pressure water-cooled reactor and remove CO and CO2Gas through
Three heat exchangers recycle heat, and are cooled and separated out H2Enter next workshop section after O.
In order to reduce energy consumption and cost；First drum, the second drum and third drum by the mutual unicom of pipe network simultaneously
Coupling cock is connected separately with, break-make is controlled by coupling cock between the first drum, the second drum and third drum.Described first
Steam in drum is transferred to the second drum and third drum, the second high pressure water-cooled reactor and third high pressure water by coupling cock
Heat needed for cold reactor reaction is supplied respectively by the steam being transferred in the second drum and third drum.
In order to reduce labor intensity and cost of labor；First drum, the second drum and third drum pass through liquid respectively
Level control valve is connected with fluid level controller, and each coupling cock has been correspondingly connected with pressure intelligent controller；The first high pressure water cooling
The reaction temperature of reactor, the second high pressure water-cooled reactor and third high pressure water-cooled reactor is by controlling corresponding first vapour
Packet, the second drum and third drum pressure realize, the pressure of the first drum, the second drum and third drum passes through corresponding
Port valve, fluid level controller and pressure intelligent controller control.
In order to energy saving and ensure to react institute calorific requirement；The first high pressure water-cooled reactor, the second high pressure water-cooled reactor
By the mutual unicom of pipe network and outer confession steam addition valve is connected separately with third high pressure water-cooled reactor, the first high pressure water cooling is anti-
The heat needed for device, the second high pressure water-cooled reactor and the reaction of third high pressure water-cooled reactor is answered to add by respective outer confession steam
Enter valve control and be individually added into steam heating.
Methanolizing reaction equation in the step (1) is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△
HCO2.Methanolizing reaction equation in the step (2) is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2.Institute
It is 3H to state the methanation reaction formula in step (3)2+ CO=CH4+H2O+△HCO、4H2+CO2=CH4+2H2O+△HCO2。
High pressure water cooling phase transformation of the present invention moves hot alcohol alkanisation process for refining and has the following advantages that：The present invention is led in Chemical Engineering Technology
Good thermal effect, stable operation, energy conservation and environmental protection are especially not only moved in domain in traditional coal Ammonia Production；It and being capable of deep removal
CO and CO2 in unstripped gas.
The present invention is realized under high temperature, high pressure, High Pressure Difference process environments：1st, with water cooling phase transformation move heat replace gas-
Gas exchanges heat, and shifting thermal effect is good, stable operation；It can pay production a large amount of steam, open cycle machine is not required to, without electric furnace, energy conservation and environmental protection；2、
It is washed with methanation instead of copper, without emission, clean environment firendly；3rd, " temperature runaway ", " collapse temperature " of catalyst have been prevented；3rd, normal fortune
Row does not need to open cycle machine, and system resistance is small, does not need to, using electric furnace and steam-heating apparatus, reduce energy consumption, investment and fortune
Row cost；4th, by methanol, methanation reaction institute's thermal discharge with absorbing heat, outer supplying heat source is included into one by drum contact
Mutual heat supply and temperature-controlling system；By the setting to heat supply and temperature-controlling system, artificial intelligence temperature control and unattended fortune can be realized
Row；5th, the second high pressure water-cooled reactor and third high pressure water-cooled reactor reaction needed for heat by the first high pressure water-cooled reactor
The steam supply or be individually added into steam heating for steam addition valve control by outer that reaction generates, do not need to power, energy saving
And environmental protection.
Description of the drawings
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is the flow chart that high pressure water cooling phase transformation of the present invention moves hot alcohol alkanisation process for refining.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail.
(1) specific embodiment is as follows：A kind of high pressure water cooling phase transformation moves hot alcohol alkanisation process for refining, it include three according to
The secondary high pressure water cooling reaction unit being connected, First High Pressure water cooling reaction unit include the first high pressure water-cooled reactor and divide
The first heat exchanger not being connected with the first high pressure water-cooled reactor and the first drum, second high pressure water cooling reaction unit packet
Include the second high pressure water-cooled reactor and the second heat exchanger being connected respectively with the second high pressure water-cooled reactor and the second vapour
Packet, third platform high pressure water cooling reaction unit include third high pressure water-cooled reactor and respectively with third high pressure water-cooled reactor phase
The third heat exchanger of connection and third drum.First drum, the second drum and third drum pass through the mutual unicom of pipe network
And coupling cock is connected separately with, break-make is controlled by coupling cock between the first drum, the second drum and third drum.Described
One drum, the second drum and third drum are all connected to water pipe, and desalination deoxygenated water supplies the first drum, the second drum by water pipe
With third drum.
The first high pressure water-cooled reactor, the second high pressure water-cooled reactor and third high pressure water-cooled reactor pass through pipe network
Mutual unicom be simultaneously connected separately with it is outer add in valve for steam, the first high pressure water-cooled reactor, the second high pressure water-cooled reactor and the
Heat needed for the reaction of three high pressure water-cooled reactors is individually added into steam heating by respective outer controlled for steam addition valve.
High pressure water cooling phase transformation of the present invention moves hot alcohol alkanisation process for refining and includes the steps：
(1), contain CO, CO under preceding workshop section's room temperature2、H2Unstripped gas enter first heat exchanger and be heated to 200-220
℃；Unstripped gas after heated enters the first high pressure water-cooled reactor, a large amount of CO and CO in unstripped gas2In the first high pressure water
CH is converted under copper system catalyst for methanol effect in cold reactor3OH, and heat is generated, methanolizing reaction equation is 2H2+CO→
CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2；Desalination deoxygenated water in first drum is reacted into the first high pressure water cooling
The shell side or tube side of device react the heat of generation in the first high pressure water-cooled reactor by the water sorption enhanced of shell side or tube side to steam
Vapour is re-fed into the first drum；Go out the gas of the first high pressure water-cooled reactor and recycle heat through first heat exchanger, and through cooling down, point
Separate out CH3Enter second high pressure water cooling reaction unit after OH；
(2), step (1) isolates CH3Gas after OH initially enters second heat exchanger and is heated to 190-220 DEG C；Through
Gas after heating enters the second high pressure water-cooled reactor, remaining a small amount of CO and CO in gas2It is reacted in the second high pressure water cooling
CH is converted under copper system catalyst for methanol effect in device3OH, and heat is generated, methanolizing reaction equation is 2H2+CO→CH3OH+
△HCO、3H2+CO2→CH3OH+H2O+△HCO2；Desalination deoxygenated water in second drum enters the shell of the second high pressure water-cooled reactor
Journey or tube side, the heat that generation is reacted in the second high pressure water-cooled reactor are sent again by the water sorption enhanced of shell side or tube side for steam
Enter the second drum；The gas for going out the second high pressure water-cooled reactor recycles heat, and be cooled and separated out through second heat exchanger
CH3Enter third platform high pressure water cooling reaction unit after OH；
(3), step (2) isolates CH3Gas after OH initially enters third heat exchanger and is heated to 190-220 DEG C；Through
Gas after heating enters third high pressure water-cooled reactor, remaining minute quantity CO and CO in gas2It is anti-in third high pressure water cooling
It answers and is converted into CH under the nickel system methanation catalyst effect in device4, and heat is generated, methanation reaction formula is 3H2+ CO=CH4+
H2O+△HCO、4H2+CO2=CH4+2H2O+△HCO2；Desalination deoxygenated water in third drum enters third high pressure water-cooled reactor
Shell side or tube side, it is steam that the heat of generation is reacted in third high pressure water-cooled reactor by the water sorption enhanced of shell side or tube side
It is re-fed into third drum；Go out third high pressure water-cooled reactor and remove CO and CO2Gas through third heat exchanger recycle heat,
And it is cooled and separated out H2Enter next workshop section after O.
The steam that the step (1) generates can store for future use, while can be transferred to by the first drum and coupling cock
Second drum and third drum, the second high pressure water-cooled reactor and third high pressure water-cooled reactor reaction needed for heat respectively by
The steam supply being transferred in the second drum and third drum.When load gentlier needs outer heating load, the first high pressure can be passed through
Water-cooled reactor, the second high pressure water-cooled reactor and third high pressure water-cooled reactor are respective outer independent for steam addition valve control
Add in steam heating.As long as control the coupling cock of respective drum and the outer principle for adding in valve for steam, heat being moved according to phase transformation
It controls the temperature of each reactor or makes the reaction temperature of each reactor identical.
First drum of the present invention, the second drum and third drum are connected with Liquid level by fluid level control valve respectively
Device, each coupling cock have been correspondingly connected with pressure intelligent controller；The first high pressure water-cooled reactor, the reaction of the second high pressure water cooling
The reaction temperature of device and third high pressure water-cooled reactor is by controlling corresponding first drum, the second drum and third drum pressure
It realizes, the pressure of the first drum, the second drum and third drum passes through corresponding coupling cock, fluid level controller and pressure intelligent
Controller controls.
(2) embodiment is as follows：
Embodiment 1：A kind of high pressure water cooling phase transformation moves hot alcohol alkanisation process for refining, including the steps：
(1), it is under 6.0MPa, containing 1.9%CO, 0.5%CO from preceding workshop section's room temperature, pressure2, 73.59%H2Unstripped gas
206 DEG C are heated into first heat exchanger；Unstripped gas after heated enters the first high pressure water-cooled reactor, big in unstripped gas
The CO and CO of amount2CH is converted under copper system catalyst for methanol effect in the first high pressure water-cooled reactor3OH, and generate heat
Amount, methanolizing reaction equation are 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2；Desalination in first drum takes off
Oxygen water enters the shell side or tube side of the first high pressure water-cooled reactor, reacts the heat of generation by shell in the first high pressure water-cooled reactor
The water sorption enhanced of journey or tube side is re-fed into the first drum for steam, wherein the steam generated is 1479.7kg/hr；It is high to go out first
The gas (temperature is 228 DEG C) of water-cooled reactor is pressed to recycle heat through first heat exchanger, it is 56 DEG C to recycle the temperature after heat,
And it is cooled and separated out CH3Enter second high pressure water cooling reaction unit after OH；This step isolates CH3CO in gas after OH
Content for 0.202%, CO2Content be 0.266%.
(2), step (1) isolates CH3Gas after OH initially enters second heat exchanger and is heated to 192 DEG C；It is heated
Gas afterwards enters the second high pressure water-cooled reactor, remaining a small amount of CO and CO in gas2In the second high pressure water-cooled reactor
Copper system catalyst for methanol effect under be converted into CH3OH, and heat is generated, methanolizing reaction equation is 2H2+CO→CH3OH+△HCO、
3H2+CO2→CH3OH+H2O+△HCO2；Desalination deoxygenated water in second drum enter the second high pressure water-cooled reactor shell side or
Tube side reacts the heat of generation in the second high pressure water-cooled reactor and is re-fed into for steam by the water sorption enhanced of shell side or tube side
Two drums, wherein the steam generated is -792.32kg/hr；Go out gas (temperature is 215 DEG C) warp of the second high pressure water-cooled reactor
Second heat exchanger recycles heat, and it is 57 DEG C to recycle the temperature after heat, and is cooled and separated out CH3Enter third platform after OH
High pressure water cooling reaction unit；This step isolates CH3The content of CO is 0.0204097%, CO in gas after OH2Content be
0.1611296%.
(3), step (2) isolates CH3Gas after OH initially enters third heat exchanger and is heated to 204 DEG C；It is heated
Gas afterwards enters third high pressure water-cooled reactor, remaining minute quantity CO and CO in gas2In third high pressure water-cooled reactor
In the effect of nickel system methanation catalyst under be converted into CH4, and heat is generated, methanation reaction formula is 3H2+ CO=CH4+H2O+
△HCO、4H2+CO2=CH4+2H2O+△HCO2；Desalination deoxygenated water in third drum enters the shell of third high pressure water-cooled reactor
Journey or tube side, the heat that generation is reacted in third high pressure water-cooled reactor are sent again by the water sorption enhanced of shell side or tube side for steam
Enter third drum, wherein the steam generated is -599.51kg/hr；Go out the gas (temperature 224 of third high pressure water-cooled reactor
DEG C) through third heat exchanger recycling heat, it is 57 DEG C to recycle the temperature after heat, and is cooled and separated out H2Enter after O next
Workshop section；This step isolates H2CO and CO in gas after O2Content be 1E-05.CO+CO in polishing gas2≤
15ppm.Required steam is reacted in the second high pressure water-cooled reactor and third high pressure water-cooled reactor by the first high pressure water
The steam supply that cold reactor reaction generates.
Embodiment 2：A kind of high pressure water cooling phase transformation moves hot alcohol alkanisation process for refining, including the steps：
(1), it is 160 ㎏/㎝ from preceding workshop section's room temperature, pressure2Under, containing 1.8%CO, 0.5%CO2, 73.6%H2Raw material
Gas enters first heat exchanger and is heated to 212 DEG C；Unstripped gas after heated enters the first high pressure water-cooled reactor, in unstripped gas
A large amount of CO and CO2CH is converted under copper system catalyst for methanol effect in the first high pressure water-cooled reactor3OH, and generate
Heat, methanolizing reaction equation are 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2；Desalination in first drum
Deoxygenated water enters the shell side or tube side of the first high pressure water-cooled reactor, and the heat quilt of generation is reacted in the first high pressure water-cooled reactor
The water sorption enhanced of shell side or tube side is re-fed into the first drum for steam, wherein the steam generated is 1698.9kg/hr；Go out first
The gas (temperature is 228 DEG C) of high pressure water-cooled reactor recycles heat through first heat exchanger, and it is 62 to recycle the temperature after heat
DEG C, and it is cooled and separated out CH3Enter second high pressure water cooling reaction unit after OH；This step isolates CH3Gas after OH
The content of middle CO is 0.134%, CO2Content be 0.213%.
(2), step (1) isolates CH3Gas after OH initially enters second heat exchanger and is heated to 192 DEG C；It is heated
Gas afterwards enters the second high pressure water-cooled reactor, remaining a small amount of CO and CO in gas2In the second high pressure water-cooled reactor
Copper system catalyst for methanol effect under be converted into CH3OH, and heat is generated, methanolizing reaction equation is 2H2+CO→CH3OH+△HCO、
3H2+CO2→CH3OH+H2O+△HCO2；Desalination deoxygenated water in second drum enter the second high pressure water-cooled reactor shell side or
Tube side reacts the heat of generation in the second high pressure water-cooled reactor and is re-fed into for steam by the water sorption enhanced of shell side or tube side
Two drums, wherein the steam generated is -871.469kg/hr；Go out the gas of the second high pressure water-cooled reactor (temperature is 215 DEG C)
Heat is recycled through second heat exchanger, it is 57 DEG C to recycle the temperature after heat, and is cooled and separated out CH3Enter third after OH
Platform high pressure water cooling reaction unit；This step isolates CH3The content of CO is 0.00948%, CO in gas after OH2Content be
0.086%.
(3), step (2) isolates CH3Gas after OH initially enters third heat exchanger and is heated to 204 DEG C；It is heated
Gas afterwards enters third high pressure water-cooled reactor, remaining minute quantity CO and CO in gas2In third high pressure water-cooled reactor
In the effect of nickel system methanation catalyst under be converted into CH4, and heat is generated, methanation reaction formula is 3H2+ CO=CH4+H2O+
△HCO、4H2+CO2=CH4+2H2O+△HCO2；Desalination deoxygenated water in third drum enters the shell of third high pressure water-cooled reactor
Journey or tube side, the heat that generation is reacted in third high pressure water-cooled reactor are sent again by the water sorption enhanced of shell side or tube side for steam
Enter third drum, wherein the steam generated is -808.42kg/hr；Go out the gas (temperature 224 of third high pressure water-cooled reactor
DEG C) through third heat exchanger recycling heat, it is 56 DEG C to recycle the temperature after heat, and is cooled and separated out H2Enter after O next
Workshop section；This step isolates H2CO and CO in gas after O2Content be 1E-05.CO+CO in polishing gas2≤
15ppm.Required steam is reacted in the second high pressure water-cooled reactor and third high pressure water-cooled reactor by the first high pressure water
The steam supply that cold reactor reaction generates.
Embodiment 3：A kind of high pressure water cooling phase transformation moves hot alcohol alkanisation process for refining, including the steps：
(1), it is under 220 ㎏/㎝ 2, containing 1.8%CO, 0.5%CO from preceding workshop section's room temperature, pressure2, 73.6%H2Raw material
Gas enters first heat exchanger and is heated to 214 DEG C；Unstripped gas after heated enters the first high pressure water-cooled reactor, and unstripped gas is big
CO and CO in amount2CH is converted under copper system catalyst for methanol effect in the first high pressure water-cooled reactor3OH, and generate
Heat, methanolizing reaction equation are 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2；Desalination in first drum
Deoxygenated water enters the shell side or tube side of the first high pressure water-cooled reactor, and the heat quilt of generation is reacted in the first high pressure water-cooled reactor
The water sorption enhanced of shell side or tube side is re-fed into the first drum for steam, wherein the steam generated is 1892.9kg/hr；Go out first
The gas (temperature is 228 DEG C) of high pressure water-cooled reactor recycles heat through first heat exchanger, and it is 62 to recycle the temperature after heat
DEG C, and it is cooled and separated out CH3Enter second high pressure water cooling reaction unit after OH；This step isolates CH3Gas after OH
The content of middle CO is 0.077%, CO2Content be 0.16%.
(2), step (1) isolates CH3Gas after OH initially enters second heat exchanger and is heated to 192 DEG C；It is heated
Gas afterwards enters the second high pressure water-cooled reactor, remaining a small amount of CO and CO in gas2In the second high pressure water-cooled reactor
Copper system catalyst for methanol effect under be converted into CH3OH, and heat is generated, methanolizing reaction equation is 2H2+CO→CH3OH+△HCO、
3H2+CO2→CH3OH+H2O+△HCO2；Desalination deoxygenated water in second drum enter the second high pressure water-cooled reactor shell side or
Tube side reacts the heat of generation in the second high pressure water-cooled reactor and is re-fed into for steam by the water sorption enhanced of shell side or tube side
Two drums, wherein the steam generated is -959.61kg/hr；Go out gas (temperature is 215 DEG C) warp of the second high pressure water-cooled reactor
Second heat exchanger recycles heat, and it is 57 DEG C to recycle the temperature after heat, and is cooled and separated out CH3Enter third platform after OH
High pressure water cooling reaction unit；This step isolates CH3The content of CO is 0.0031%, CO in gas after OH2Content be
0.0485%.
(3), step (2) isolates CH3Gas after OH initially enters third heat exchanger and is heated to 204 DEG C；It is heated
Gas afterwards enters third high pressure water-cooled reactor, remaining minute quantity CO and CO in gas2In third high pressure water-cooled reactor
In the effect of nickel system methanation catalyst under be converted into CH4, and heat is generated, methanation reaction formula is 3H2+ CO=CH4+H2O+
△HCO、4H2+CO2=CH4+2H2O+△HCO2；Desalination deoxygenated water in third drum enters the shell of third high pressure water-cooled reactor
Journey or tube side, the heat that generation is reacted in third high pressure water-cooled reactor are sent again by the water sorption enhanced of shell side or tube side for steam
Enter third drum, wherein the steam generated is -913.6kg/hr；Go out the gas (temperature 224 of third high pressure water-cooled reactor
DEG C) through third heat exchanger recycling heat, it is 54 DEG C to recycle the temperature after heat, and is cooled and separated out H2Enter after O next
Workshop section；This step isolates H2CO and CO in gas after O2Content be 1E-05.CO+CO in polishing gas2≤
15ppm.Required steam is reacted in the second high pressure water-cooled reactor and third high pressure water-cooled reactor by the first high pressure water
The steam supply that cold reactor reaction generates.
Needed for being reacted in second high pressure water-cooled reactor described in above-described embodiment 1-3 and third high pressure water-cooled reactor
Steam can also be individually added into steam heating by respective outer controlled for steam addition valve.
Above-mentioned specific embodiment is only explained in detail technical scheme of the present invention, the present invention not only only office
It is limited to above-described embodiment, any improvement or replacement of every principle according to the present invention should all be within protection scope of the present invention.
Claims (6)
1. a kind of high pressure water cooling phase transformation moves hot alcohol alkanisation process for refining, which is characterized in that it goes here and there successively including at least 2 sets or more
And the high pressure water cooling reaction unit to connect, often cover high pressure water cooling reaction unit include at least high pressure water-cooled reactor and respectively with
The drum and heat exchanger that high pressure water-cooled reactor is connected；It includes the steps：
(1), under preceding workshop section's room temperature, pressure for 10.0~22.0MPa contain CO, CO2、H2Deng unstripped gas enter first heat hand over
Parallel operation is heated to 200-220 DEG C；Unstripped gas after heated enters the first high pressure water-cooled reactor, in unstripped gas a large amount of CO and
CO2CH is converted under copper system catalyst for methanol effect in the first high pressure water-cooled reactor3OH, and generate heat；First drum
In desalination deoxygenated water enter the shell side or tube side of the first high pressure water-cooled reactor, react in the first high pressure water-cooled reactor and generate
Heat the first drum is re-fed into for steam by the water sorption enhanced of shell side or tube side；Go out the gas of the first high pressure water-cooled reactor
Heat is recycled, and be cooled and separated out CH through first heat exchanger3Enter second high pressure water cooling reaction unit after OH；
(2), step (1) isolates CH3Gas after OH initially enters second heat exchanger and is heated to 190-220 DEG C；After heated
Gas enter the second high pressure water-cooled reactor, remaining a small amount of CO and CO in gas2In the second high pressure water-cooled reactor
CH is converted under the effect of copper system catalyst for methanol3OH, and generate heat；Desalination deoxygenated water in second drum enters the second high pressure
The shell side or tube side of water-cooled reactor, the heat that generation is reacted in the second high pressure water-cooled reactor are absorbed by the water of shell side or tube side
It is converted into steam and is re-fed into the second drum；The gas for going out the second high pressure water-cooled reactor recycles heat through second heat exchanger, and
It is cooled and separated out CH3Enter third platform high pressure water cooling reaction unit after OH；
(3), step (2) isolates CH3Gas after OH initially enters third heat exchanger and is heated to 190-220 DEG C；After heated
Gas enter third high pressure water-cooled reactor, remaining minute quantity CO and CO in gas2In third high pressure water-cooled reactor
The effect of nickel system methanation catalyst under be converted into CH4, and generate heat；Desalination deoxygenated water in third drum enters third height
The shell side or tube side of water-cooled reactor are pressed, the heat that generation is reacted in third high pressure water-cooled reactor is inhaled by the water of shell side or tube side
Receipts are converted into steam and are re-fed into third drum；Go out third high pressure water-cooled reactor and remove CO and CO2Gas through third heat hand over
Parallel operation recycles heat, and is cooled and separated out H2Enter next workshop section after O；
Wherein the first drum, the second drum and third drum are by the mutual unicom of pipe network and are connected separately with coupling cock, the first vapour
Break-make is controlled by coupling cock between packet, the second drum and third drum；Steam in first drum passes through coupling cock
It is transferred to the second drum and third drum, the heat needed for the second high pressure water-cooled reactor and the reaction of third high pressure water-cooled reactor
It is supplied respectively by the steam being transferred in the second drum and third drum.
2. high pressure water cooling phase transformation according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that：First vapour
Packet, the second drum and third drum are connected with fluid level controller by fluid level control valve respectively, and each coupling cock has been correspondingly connected with
Pressure intelligent controller；The first high pressure water-cooled reactor, the second high pressure water-cooled reactor and third high pressure water-cooled reactor
Reaction temperature realized by controlling corresponding first drum, the second drum and third drum pressure, the first drum, the second vapour
The pressure of packet and third drum is controlled by corresponding coupling cock, fluid level controller and pressure intelligent controller.
3. high pressure water cooling phase transformation according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that：Described first is high
Pressure water-cooled reactor, the second high pressure water-cooled reactor and third high pressure water-cooled reactor are connected by the mutual unicom of pipe network and respectively
There is outer confession steam to add in valve, the first high pressure water-cooled reactor, the second high pressure water-cooled reactor and third high pressure water-cooled reactor are anti-
Required heat is answered to be individually added into steam heating by respective outer controlled for steam addition valve.
4. high pressure water cooling phase transformation according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that：The step
(1) the methanolizing reaction equation in is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2。
5. high pressure water cooling phase transformation according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that：The step
(2) the methanolizing reaction equation in is 2H2+CO→CH3OH+△HCO、3H2+CO2→CH3OH+H2O+△HCO2。
6. high pressure water cooling phase transformation according to claim 1 moves hot alcohol alkanisation process for refining, it is characterised in that：The step
(3) the methanation reaction formula in is 3H2+ CO=CH4+H2O+△HCO、4H2+CO2=CH4+2H2O+△HCO2。
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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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2016
- 2016-05-06 CN CN201610299235.4A patent/CN105947981B/en active Active
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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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. |
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