CN105753646A - Energy-saving inter-section high low temperature gradient alcohol-division two-stage alcohol generation method and energy-saving inter-section high low temperature gradient alcohol-division two-stage alcohol generation device - Google Patents
Energy-saving inter-section high low temperature gradient alcohol-division two-stage alcohol generation method and energy-saving inter-section high low temperature gradient alcohol-division two-stage alcohol generation device Download PDFInfo
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- CN105753646A CN105753646A CN201610087449.5A CN201610087449A CN105753646A CN 105753646 A CN105753646 A CN 105753646A CN 201610087449 A CN201610087449 A CN 201610087449A CN 105753646 A CN105753646 A CN 105753646A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses an inter-section high low temperature gradient alcohol-division two-stage alcohol generation method which comprises the following steps: respectively reheating fresh synthesis gas and recycle gas, mixing the fresh synthesis gas with the recycle gas, introducing the mixed gas into a first reactor, and enabling part of carbon oxides to react to obtain methyl alcohol; cooling a mixture containing synthesis gas and methyl alcohol steam output from the first reactor, guiding the mixture to flow to a first methyl alcohol separator, separating out methyl alcohol, pressurizing the separated gas, preheating, then introducing into a second reactor, and enabling part of carbon oxides to react to obtain methyl alcohol; cooling a mixture containing synthesis gas and methyl alcohol steam output from the second reactor, guiding the mixture to flow to a second methyl alcohol separator, separating out methyl alcohol, preheating the separated gas which separately serves as the recycle gas and fresh synthesis gas, mixing the recycle gas and the fresh synthesis gas, and feeding the mixture into the first reactor so as to perform next round of circulating preparation of methyl alcohol. The invention further discloses an inter-section high low temperature gradient alcohol-division two-stage alcohol generation device. The method is relatively high in single-pass alcohol net value and relatively small in circulation ratio, achieves a ton-alcohol steam yield as high as 1.2-1.3 ton, and is high in energy heat recovery amount.
Description
Technical field
The preparation method that the present invention relates to a kind of methanol that maximizes, is specifically related to a kind of energy-saving intersegmental high/low temperature gradient and divides alcohol two sections to produce alcohol method and device.
Background technology
Maximize methanol synthesizer at present, synthesis gas prepare the process of methanol mostly be string tower or and tower process, main typical technical matters has " gas cooled reactor+water cooled reactor " two sections of isothermal methanol synthesis technology of German Lurgi company, the IMC methanol synthesis technology (setting two-stage reaction in reactor) of Switzerland Casale, Davy (ICI) radial flow steam ascending manner methanol synthesis technology (string loop string tower process), DenmarkCompany adopts some shell-and-tube synthesis reactor connection in series-parallel forms etc..
After the maximization of the size of capacity, enterprise more focuses on the operation consumption of ton alcohol, and the good and bad main determining factor of methanol synthesizing process is exactly the operation consumption of device.But that a type of synthesis technique all has its advantage, also there is its limitation and weakness simultaneously.
Two sections of isothermal methanol synthesis technology of Lurgi company of Germany, as it is shown in figure 1, the synthesizing section of this technology comprises three reactors, including a gas cooled reactor 1a, two water-cooled reactor 2a in parallel, 3a, Intermediate Heat Exchanger 4a, methanol drum 5a.Fresh synthesis gas mixes with circulating air after compression, enter the tube layer of air cooling reactor 1a, the methanol-fueled CLC occurred by shell reacts institute's liberated heat and preheats, subsequently into two water-cooled reactor 2a in parallel, 3a reacts, filling catalyst in reactor tube, it it is boiled water between pipe, reaction liberated heat passes to the boiled water between pipe through tube wall, produce middle pressure steam, gas product is from two water-cooled reactor 2a, 3a out after first mix, shell subsequently into air cooling reactor 1a, unreacted synthesis gas completely reacts further in air cooling reactor 1a and generates methanol, final products pneumatic transmission cools down, crude carbinol is separated by centrifugal station.Main feature: the reaction scheme (high equilibrium driving force, high conversion) that heat coupling thinking optimizes, it is not necessary to reactor feedstock pre-heater.Main not enough: running (running on the lower load and reaction later stage) heat recovery efficiency under off-design operating mode low, system consumption is high.
The IMC methanol synthesis technology of Switzerland Casale: maximization methanol device has two kinds of flow processs, one is adopt two water-cooled reactor 1b, 2b string tower flow process (as shown in Figure 2), increases the alcohol yield of individual system.Main feature: flow process is simple.Another kind is the single column flow process (as shown in Figure 3) only designing a synthesis reactor, adopt in reactor and two sections reaction is set, synthesis reactor 1c epimere arranges water-cooling type workshop section 2c radially water-cooled, hypomere arranges the axial air cooling of 3c of air cooled type workshop section, the string tower process that generally similar Shandong is strange.Main not enough: reactor epimere catalyst bed reaction peak district running temperature is higher, is typically in more than 280 DEG C, and the catalyst utilization of hypomere air cooling section is poor.
Britain Davy (ICI) radial flow steam ascending manner methanol synthesis technology: as shown in Figure 4, adopts two system series/parallel flow processs, and recycle compressor arranges the compression loss making up front system between the two systems；The alcohol yield balance of former and later two systems, then regulate the inlet tower gas hydrogen-carbon ratio realization of former and later two systems by compressor outlet and circulator inlet connecting branch.Main feature: fresh edema caused by disorder of QI two strands sends into former and later two systems, and front and back system enters the unstripped gas hydrogen-carbon ratio flexible adjustment of reactor, the inlet tower gas hydrogen-carbon ratio of former and later two systems, alcohol yield approximately equal；Main not enough: virgin gas is directly added into circulator import, and crushing is big.Recirculated cooling water consumption is big, synthesis loop total alcohol net value is relatively low, and about 8～9%.
DenmarkCompany's methanol synthesizing process, the maximization of device mainly adopts some shell-and-tube synthesis reactor connection in series-parallel forms to realize, and technological process is relatively conventional, without special feature.
Summary of the invention
Present invention aims to deficiency of the prior art, the preparation method of maximization methanol of a kind of energy-conservation, consumption reduction is provided, the method will comprise the synthesis gas of hydrogen and hydrocarbon by least two connected equipped with in the isothermal synthesis reactor of the water-cooled that granulated copper is catalyst based, pressure 5.0-12.0Mpa, is converted into methanol at temperature 200-300 DEG C.
It is an object of the invention to be achieved through the following technical solutions:
A kind of energy-saving intersegmental high/low temperature gradient divides alcohol two sections to produce alcohol method, comprises the following steps:
Step a, fresh synthesis gas through the 3rd gas-to-gas heat exchanger (10) preheating after with in synthesis loop through the first gas-to-gas heat exchanger (2) preheat after circulating air mix, gaseous mixture passes into the air inlet at the first reactor (1) top, from top to bottom through copper-based catalysts bed, at pressure 5.0-12.0MPa, at temperature 200-300 DEG C, part hydrocarbon and hydrogen is catalyzed is obtained by reacting methanol；
Step b, the mixture comprising synthesis gas and methanol steam exported from the first reactor (1) gas outlet are cooled to 30-50 DEG C, mixture is guided to the first methanol separator (6) again, isolate methanol, and pass in the second reactor (9) after isolated air-flow supercharging, preheating, air-flow is from top to bottom through copper-based catalysts bed, at pressure 5.0-12.0MPa, at temperature 200-300 DEG C, it is obtained by reacting methanol by catalyzed to part hydrocarbon and hydrogen further；
Step c, the mixture comprising synthesis gas and methanol steam exported from the second reactor (9) gas outlet are cooled to 70-100 DEG C, mixture is guided to the second methanol separator (11) again, isolate methanol, being mixed as circulating air with fresh synthesis gas by isolated air-flow, preheated rear infeed the first reactor carries out circulation next time and prepares methanol.
Synthesis gas comprises hydrogen and hydrocarbon.In step a, in described fresh synthesis gas, hydrogen-carbon ratio is 1.9～2.05, and described hydrogen-carbon ratio is (H2-CO2)/(CO+CO2) mole fraction ratio.
In the mixture of described fresh synthesis gas and synthesis loop circulating air, the mole fraction of hydrogen is 60-70%, and the mole fraction of carbon monoxide is 10-20%, and the mole fraction of carbon dioxide is 2-8%, and the molar percentage of methanol steam is 1-3%.
In step a, fresh synthesis gas is through the 3rd gas-to-gas heat exchanger (10) and the mixture heat exchange comprising synthesis gas and methanol steam exported from the second reactor (9), synthesis loop circulating air is through the first gas-to-gas heat exchanger (2) and the mixture heat exchange comprising synthesis gas and methanol steam exported from the first reactor (1), fresh synthesis gas and circulating air after preheating (fresh synthesis gas and circulating air are preferably preheated to 200-220 DEG C respectively) mix, gaseous mixture passes into the air inlet at the first reactor (1) top, in first reactor (1), synthesis gas is from top to bottom with air speed 10000-20000Nm3/m3Copper-based catalysts bed in the first reactor；Preferably, the pressure in the first reactor (1) is that 6.0-9.0Mpa, temperature are 200-280 DEG C；The oxycarbide of 40-60% is catalytically converted into methanol.
In step b, the first gas-to-gas heat exchanger (2) is passed sequentially through from the mixture comprising synthesis gas and methanol steam of the first reactor (1) gas outlet output, boiler water preheater (3), air cooler (4) and water cooler (5), it is cooled to 30-50 DEG C, it is guided to the first methanol separator (6) point alcohol, first methanol separator (6) isolated temperature is that the air-flow of 30-50 DEG C is through circulator (7) supercharging, pass in the second reactor (9) after second gas-to-gas heat exchanger (8) preheating (being preferably preheated to 200-220 DEG C), synthesis gas is from top to bottom with air speed 6000-8000Nm3/m3Copper-based catalysts bed in the second reactor (9)；Preferably, the pressure in the second reactor (9) is that 6.0-9.0Mpa, temperature are 200-280 DEG C；The oxycarbide of 50-60% is catalytically converted into methanol.
In step c, it is divided into two strands from the mixture comprising synthesis gas and methanol steam of the second reactor (9) gas outlet output, through the second gas-to-gas heat exchanger (8) in parallel, 3rd gas-to-gas heat exchanger (10) respectively with the first methanol separator (6) isolated air-flow, fresh synthesis gas heat exchange remixes after being cooled to 70-100 DEG C, it is guided to the second methanol separator (11), isolate methanol, after dividing alcohol, temperature is that air-flow entrance synthesis loop (12) of 70-100 DEG C is as circulating air, mix with fresh synthesis gas after the 3rd gas-to-gas heat exchanger (10) preheating after the first gas-to-gas heat exchanger (2) preheats, feed the first reactor (1) to carry out circulation next time and prepare methanol.
It is a further object to provide a kind of energy-saving intersegmental high/low temperature gradient divides alcohol two sections to produce alcohol device, fresh synthesis gas conduit (13), the first reactor (1) connected and the second reactor (9), the first methanol separator (6), the second methanol separator (11), described fresh synthesis gas conduit (13) is connected with the air inlet of the first reactor (1), is provided with the 3rd gas-to-gas heat exchanger (10) on described fresh synthesis gas conduit (13)；nullThe gas outlet the first gas-to-gas heat exchanger (2) of described the first reactor (1)、Boiler water preheater (3)、Air cooler (4)、Water cooler (5) is connected with the air inlet of described the first methanol separator (6)，The gas outlet of the first methanol separator (6) is through circulator (7)、Second gas-to-gas heat exchanger (8) is connected with the air inlet of described the second reactor (9)，The gas outlet of the second reactor (9) the second gas-to-gas heat exchanger (8) through being arranged in parallel、3rd gas-to-gas heat exchanger (10) is connected with the air inlet of described the second methanol separator (11)，The gas outlet of the second methanol separator (11) is provided with synthesis loop (12)，Described synthesis loop (12) is connected with fresh synthesis gas conduit (13) through the first gas-to-gas heat exchanger (2)，Make fresh synthesis gas and circulating air respectively through the 3rd gas-to-gas heat exchanger (10)、It is mixed into the first reactor (1) after first gas-to-gas heat exchanger (2) preheating in parallel.
Preferably, described the first reactor (1) and the second reactor (9) are the isothermal synthesis reactor of water-cooled, described the first reactor (1) is connected with the methanol drum of relative set respectively with the conduit of the second reactor (9), methanol reaction heat in first reactor (1) and the second reactor (9) is by the heat exchange element (cooled plate) in reactor and boiler water heat exchange, boiler water after heat exchange is under the siphon principle effect of water, by in the conduit that is connected with methanol drum from being transferred in drum in reactor by-product saturated vapor.In described the first reactor (1) and the second reactor (9), load copper-based catalysts respectively form the first beds and the second beds.
Described circulator (7) is compressor.
First reactor air inlet in methanol preparation method of the present invention, higher CO concentration, slightly higher methanol concentration, high-speed, thus ensureing in the conversion ratio of the first reactor and reactor reaction temperature conveniently；Second reactor air inlet, slightly higher CO concentration, low methanol concentration, low-speed, it is achieved in the second reactor, reaction temperature conveniently and CO concentration ensure the conversion ratio of reactor.The total alcohol net value of system is high, and synthesis loop recycle ratio is little, and compression power consumption is little.It is different from the water of Lurgi company to collaborate heat coupling process, overall flow is also different from Davy (ICI) series/parallel technique (connect two and synthesis loop flow process), by the first reactor and the second reactors in series are arranged formation closed circuit, first synthesis gas is first passed through the first reactor, a portion oxycarbide is catalytically converted into methanol, then by isolated air-flow by the second reactor, another part carbon oxide conversion is become methanol.Reacted by one way and as much as possible synthesis gas is converted into methanol, obtain alcohol net value high as far as possible.Profit can be down to the most rational scope system operation energy consumption and investment in this way.The present invention has a characteristic that
(1), by controlling the loaded catalyst that the first reactor is suitable for, guide the second methanol separator outlet circulating air gaseous mixture with fresh synthesis gas with 10000-20000Nm3/m3High-speed pass through beds；Synthesizing methanol reaction heat removes in part through hot water byproduct steam, and another portion incorporates circulating air.Reaction velocity higher in first reactor, bigger ventilation can effectively evade the localized heat cumulative appearance of beds, are beneficial to reduction catalytic reaction hot(test)-spot temperature, slow down excessive exothermic in catalyst for methanol regional area under Gao Qing, high-carbon dividing potential drop；Make the above conversion zone of beds 80-90% be in high temperature (250-270 DEG C), high conversion reaction warm area, improve overall service efficiency and the service life of catalyst.
(2), by the bigger loaded catalyst of control the second reactor, guide circulator outlet circulating air with 6000-8000Nm3/m3Air speed pass through beds；In second reactor, synthesis gas low-speed, low-carbon (LC) dividing potential drop make reaction bed more uniform temperature, make beds be in low temperature 230-250 DEG C, high conversion level reaction warm area, and to improving, synthesis loop conversion per pass is favourable.
(3) mixture of the synthesis gas by the second reactor outlet and methanol steam, is guided, through the second gas-to-gas heat exchanger (8) in parallel, secondary divides alcohol after the 3rd gas-to-gas heat exchanger (10) is cooled to 70-100 DEG C, divide alcohol ability up to about 70-95%, the synthesis loop circulating air acquired after dividing alcohol mixes with fresh synthesis gas, containing relatively high methanol content (1.0-3.0%) in gaseous mixture, can effectively press down reaction for preparing methanol peak district excessively to concentrate, it is to avoid catalyst local overheating.
(4) after, synthesis gas is directed through first, second reactor, in synthesis gas, inert material (nitrogen, argon, methane) content obtains bigger concentration, in synthesis loop circulating air after 70-100 DEG C of secondary divides alcohol, inert material is in synthesis loop lofty perch, mixes with from out-of-bounds fresh synthesis gas.
(5), in the first reactor synthesis gas with 10000-20000Nm3/m3High-speed, suitable methanol concentration (1.0-3.0%), make CO in entrance the first Reactor inlet synthesis gas allow to produce in the concentration range that 15-20% is higher, catalyst occurs without local overheating, and relatively the traditional handicraft suitability is wider；String tower flow process allows the catalytic amount that in the second reactor, filling is relatively many, air speed 6000-8000Nm3/m3, molecular balance is more thorough；Double; two points of alcohol techniques of double-column in series can farthest obtain one way methanol conversion, synthesis loop alcohol net value up to～20%, circulate smaller, close to 1.1, ton alcohol steam production is up to 1.2～1.3 tons, compression power consumption is little, and energy recuperation of heat amount is higher, less expensive.
(6), twice point of alcohol, first time with air cooler connect water cooler cooling syngas, separate methanol；Second time is worked off one's feeling vent one's spleen and fresh synthesis gas respectively through the second gas-to-gas heat exchanger, the 3rd gas-to-gas heat exchanger warm-up cycle machine, it is directly separating methanol after reclaiming heat, the preheating yield of increase system, decreases the consumption of system ton alcohol recirculated water, and system recirculated water consumption is low compared with traditional handicraft many.
(7), in parallel the second reactor outlet steam (namely comprising the mixture of synthesis gas and methanol steam) is cooled down by guiding fresh synthesis gas to work off one's feeling vent one's spleen with circulator, two strands of cold air are concentrated and are reduced the second reactor outlet hot air temperature, make the second reactor outlet hot air temperature after cooling reach secondary and divide alcohol condition；Guide simultaneously the second methanol separator work off one's feeling vent one's spleen (70-100 DEG C) cool down the first reactor outlet steam.Preheat flow scheme design before this tower and not only acted as the air inlet purpose of preheating the first reactor and the second reactor, and be more conducive to the centralized recovery of system low-grade remaining heat.
It is 1.0-2.0 that intersegmental high/low temperature gradient of the present invention divides alcohol two sections to produce recycle ratio in alcohol method, and recycle ratio refers to the ratio between circulating air and the fresh synthesis gas entered in synthesis loop.
Accompanying drawing explanation
Fig. 1 is the route map of two sections of isothermal methanol synthesis technology of Lurgi company of Germany.
In Fig. 1,1a-air cooling reactor, 2a-water-cooled reactor, 3a-water-cooled reactor, 4a-Intermediate Heat Exchanger, 5a-methanol drum.
Fig. 2 is the route map of the string tower flow process of the IMC methanol synthesis technology of Switzerland Casale.
In Fig. 2,1b-water-cooled reactor, 2b-water-cooled reactor.
Fig. 3 is the route map of the single column flow process of the IMC methanol synthesis technology of Switzerland Casale.
In Fig. 3,1c-synthesis reactor, 2c-water-cooling type workshop section, 3-air cooled type workshop section.
Fig. 4 is the flow chart of Britain Davy (ICI) radial flow steam ascending manner methanol synthesis technology.
In Fig. 4,1d-fresh synthesis gas conduit, 2d-fresh synthesis gas conduit, 3d-water-cooled reactor, 4d-water-cooled reactor.
Fig. 5 is that a kind of energy-saving intersegmental high/low temperature gradient of the present invention divides alcohol two sections to produce the structural representation of alcohol device.
In Fig. 5,1-the first reactor, 2-the first gas-to-gas heat exchanger, 3-boiler water preheater, 4-air cooler, 5-water cooler, 6-the first methanol separator, 7-circulator, 8-the second gas-to-gas heat exchanger, 9-the second reactor, 10-the 3rd gas-to-gas heat exchanger, 11-the second methanol separator, 12-synthesis loop, 13-fresh synthesis gas conduit.
Detailed description of the invention
By detailed description of the invention, technical scheme is further described.
As shown in Figure 5, a kind of energy-saving intersegmental high/low temperature gradient divides alcohol two sections to produce alcohol device, including fresh synthesis gas conduit (13), the first reactor (1) connected and the second reactor (9), the first methanol separator (6), the second methanol separator (11)；Described fresh synthesis gas conduit (13) is connected with the air inlet of the first reactor (1), is provided with the 3rd gas-to-gas heat exchanger (10) on described fresh synthesis gas conduit (13)；nullThe gas outlet the first gas-to-gas heat exchanger (2) of described the first reactor (1)、Boiler water preheater (3)、Air cooler (4)、Water cooler (5) is connected with the air inlet of described the first methanol separator (6)，The gas outlet of the first methanol separator (6) is through circulator (7)、Second gas-to-gas heat exchanger (8) is connected with the air inlet of described the second reactor (9)，The gas outlet of the second reactor (9) the second gas-to-gas heat exchanger (8) through being arranged in parallel、3rd gas-to-gas heat exchanger (10) is connected with the air inlet of described the second methanol separator (11)，The gas outlet of the second methanol separator (11) is provided with synthesis loop (12)，Described synthesis loop (12) is connected with fresh synthesis gas conduit (13) through the first gas-to-gas heat exchanger (2)，Make fresh synthesis gas and circulating air respectively through the 3rd gas-to-gas heat exchanger (10)、It is mixed into the first reactor (1) after first gas-to-gas heat exchanger (2) preheating in parallel.
Described the first reactor (1) and the second reactor (9) are the isothermal synthesis reactor of water-cooled, described the first reactor (1) is connected with the methanol drum of relative set respectively with the conduit of the second reactor (9), methanol reaction heat in first reactor (1) and the second reactor (9) is by the heat exchange element (cooled plate) in reactor and boiler water heat exchange, boiler water after heat exchange under the siphon principle effect of water, by the conduit that is connected with methanol drum from being transferred in drum in reactor by-product saturated vapor.Loading copper-based catalysts respectively in described the first reactor (1) and the second reactor (9) and form the first beds and the second beds, the first beds is about 80m3, the second beds is about 100m3。
Described circulator (7) is compressor.
Embodiment 1
Adopt above-mentioned energy-saving intersegmental high/low temperature gradient to divide alcohol two sections to produce alcohol device and carry out the production of maximization methanol.
A kind of energy-saving intersegmental high/low temperature gradient divides alcohol two sections to produce alcohol method, comprises the following steps:
(1), fresh synthesis gas is through the 3rd gas-to-gas heat exchanger (10) and the mixture heat exchange comprising synthesis gas and methanol steam exported from the second reactor (9), synthesis loop circulating air is through the first gas-to-gas heat exchanger (2) and the mixture heat exchange comprising synthesis gas and methanol steam exported from the first reactor (1), it is preheated to fresh synthesis gas and the circulating air mixing of 200-220 DEG C respectively, pass into the air inlet of the first reactor head, the first beds that synthesis gas is loaded through copper-based catalysts from top to bottom, control air speed at 10000-20000Nm3/m3Between, control the pressure 7.5-8.0Mpa in the first reactor, temperature 200-280 DEG C, make 15～25% CO+CO of (mole fractions, lower with)2High H2Synthesis gas reacts generation methanol under the catalytic action of copper-based catalysts；
(2), the first gas-to-gas heat exchanger (2), boiler water preheater (3) and circulating air, boiler water heat exchange cooling are passed sequentially through from the mixture comprising synthesis gas and methanol steam (9～13%) of the first reactor (1) gas outlet output；Again through air cooler (4) and water cooler (5), it is cooled to 30-50 DEG C, mixture is guided to the first methanol separator (6) again, isolate methanol (point alcohol ability is up to 95.5%), and by isolated air-flow through circulator (7) supercharging, again in the second gas-to-gas heat exchanger (8) with the mixture heat exchange comprising synthesis gas and methanol steam exported from the second reactor (9), pass in the second reactor (9) after being preheated to 200-220 DEG C, the second beds that air-flow is loaded through copper-based catalysts from top to bottom, control air speed at 6000-8000Nm3/m3Between, at pressure 8.0Mpa, at temperature 200-280 DEG C, will wherein remaining a part of hydrocarbon be catalyzed is obtained by reacting methanol；
(3), it is divided into two strands from the mixture comprising synthesis gas and methanol steam (9～13%) of the second reactor (9) gas outlet output, through the second gas-to-gas heat exchanger (8) in parallel, 3rd gas-to-gas heat exchanger (10) respectively with the first methanol separator (6) isolated air-flow, fresh synthesis gas heat exchange remixes after being cooled to 70-100 DEG C, it is guided to the second methanol separator (11), isolate methanol (point alcohol ability is up to 79.9%), after dividing alcohol, temperature is that air-flow entrance synthesis loop (12) of 70-100 DEG C is as circulating air, mix with the fresh synthesis gas after the 3rd gas-to-gas heat exchanger (10) preheating after the first gas-to-gas heat exchanger (2) preheats, feed the first reactor (1) to carry out circulation next time and prepare methanol.
Table 1 is prepared in 5000 ton day methanol process for the present embodiment, the parameter of each device material.
The each device parameter of materials of table 15000 ton day methanol
In table 1, the mixture of the circulating air that the first reactor (1) air inlet is in fresh synthesis gas and synthesis loop (12), circulator air inlet is the first methanol separator (6) and gives vent to anger, circulator air inlet is pressurizeed through circulator (7), the second gas-to-gas heat exchanger (8) obtains the second reactor (9) air inlet after preheating, and the second methanol separator (11) is given vent to anger and is the circulating air entering synthesis loop.
Claims (7)
1. an energy-saving intersegmental high/low temperature gradient divides alcohol two sections to produce alcohol method, it is characterised in that it comprises the following steps:
Step a, fresh synthesis gas through the 3rd gas-to-gas heat exchanger (10) preheating after with in synthesis loop through the first gas-to-gas heat exchanger (2) preheat after circulating air mix, gaseous mixture passes into the air inlet at the first reactor (1) top, from top to bottom through copper-based catalysts bed, at pressure 5.0-12.0MPa, at temperature 200-300 DEG C, part hydrocarbon and hydrogen is catalyzed is obtained by reacting methanol；
Step b, the mixture comprising synthesis gas and methanol steam exported from the first reactor (1) gas outlet are cooled to 30-50 DEG C, mixture is guided to the first methanol separator (6) again, isolate methanol, and pass in the second reactor (9) after isolated air-flow supercharging, preheating, air-flow is from top to bottom through copper-based catalysts bed, at pressure 5.0-12.0MPa, at temperature 200-300 DEG C, it is obtained by reacting methanol by catalyzed to part hydrocarbon and hydrogen further；
Step c, the mixture comprising synthesis gas and methanol steam exported from the second reactor (9) gas outlet are cooled to 70-100 DEG C, mixture is guided to the second methanol separator (11) again, isolate methanol, being mixed as circulating air with fresh synthesis gas by isolated air-flow, preheated rear infeed the first reactor carries out circulation next time and prepares methanol.
2. the preparation method of maximization methanol according to claim 1, it is characterised in that in step a, in described fresh synthesis gas, hydrogen-carbon ratio is 1.9～2.05.
In the mixture of described fresh synthesis gas and synthesis loop circulating air, the mole fraction of hydrogen is 60-70%, and the mole fraction of carbon monoxide is 10-20%, and the mole fraction of carbon dioxide is 2-8%, and the molar percentage of methanol steam is 1-3%.
3. energy-saving intersegmental high/low temperature gradient according to claim 1 divides alcohol two sections to produce alcohol method, it is characterized in that in step a, fresh synthesis gas is through the 3rd gas-to-gas heat exchanger (10) and the mixture heat exchange comprising synthesis gas and methanol steam exported from the second reactor (9), synthesis loop circulating air is through the first gas-to-gas heat exchanger (2) and the mixture heat exchange comprising synthesis gas and methanol steam exported from the first reactor (1), fresh synthesis gas and circulating air after preheating mix, gaseous mixture passes into the air inlet at the first reactor (1) top, in first reactor (1), synthesis gas is from top to bottom with air speed 10000-20000Nm3/m3Copper-based catalysts bed in the first reactor (1)；The oxycarbide of 40-60% is catalytically converted into methanol.
4. energy-saving intersegmental high/low temperature gradient according to claim 1 divides alcohol two sections to produce alcohol method, it is characterized in that in step b, the first gas-to-gas heat exchanger (2) is passed sequentially through from the mixture comprising synthesis gas and methanol steam of the first reactor (1) gas outlet output, boiler water preheater (3), air cooler (4) and water cooler (5), it is cooled to 30-50 DEG C, it is guided to the first methanol separator (6) point alcohol, first methanol separator (6) isolated temperature is that the air-flow of 30-50 DEG C is through circulator (7) supercharging, pass in the second reactor (9) after second gas-to-gas heat exchanger (8) preheating, synthesis gas is from top to bottom with air speed 6000-8000Nm3/m3Copper-based catalysts bed in the second reactor (9)；The oxycarbide of 50-60% is catalytically converted into methanol.
5. energy-saving intersegmental high/low temperature gradient according to claim 1 divides alcohol two sections to produce alcohol method, it is characterized in that in step c, it is divided into two strands from the mixture comprising synthesis gas and methanol steam of the second reactor (9) gas outlet output, through the second gas-to-gas heat exchanger (8) in parallel, 3rd gas-to-gas heat exchanger (10) respectively with the first methanol separator (6) isolated air-flow, fresh synthesis gas heat exchange remixes after being cooled to 70-100 DEG C, it is guided to the second methanol separator (11), isolate methanol, after point alcohol, temperature is that the air-flow of 70-100 DEG C enters synthesis loop and mixes with fresh synthesis gas after the 3rd gas-to-gas heat exchanger (10) preheating after the first gas-to-gas heat exchanger (2) preheats as circulating air, feed the first reactor (1) to carry out circulation next time and prepare methanol.
6. one kind is divided alcohol two sections to produce alcohol device for the energy-saving intersegmental high/low temperature gradient described in claim 1, it is characterised in that it includes fresh synthesis gas conduit (13), the first reactor (1) connected and the second reactor (9), the first methanol separator (6), the second methanol separator (11)；Described fresh synthesis gas conduit (13) is connected with the air inlet of the first reactor (1), is provided with the 3rd gas-to-gas heat exchanger (10) on described fresh synthesis gas conduit (13)；nullThe gas outlet the first gas-to-gas heat exchanger (2) of described the first reactor (1)、Boiler water preheater (3)、Air cooler (4)、Water cooler (5) is connected with the air inlet of described the first methanol separator (6)，The gas outlet of the first methanol separator (6) is through circulator (7)、Second gas-to-gas heat exchanger (8) is connected with the air inlet of described the second reactor (9)，The gas outlet of the second reactor (9) the second gas-to-gas heat exchanger (8) through being arranged in parallel、3rd gas-to-gas heat exchanger (10) is connected with the air inlet of described the second methanol separator (11)，The gas outlet of the second methanol separator (11) is provided with synthesis loop (12)，Described synthesis loop (12) is connected with fresh synthesis gas conduit (13) through the first gas-to-gas heat exchanger (2)，Make fresh synthesis gas and circulating air respectively through the 3rd gas-to-gas heat exchanger (10)、It is mixed into the first reactor (1) after first gas-to-gas heat exchanger (2) preheating in parallel.
7. described energy-saving intersegmental high/low temperature gradient according to claim 6 divides alcohol two sections to produce alcohol device, it is characterised in that described the first reactor (1) and the second reactor (9) are the isothermal synthesis reactor of water-cooled；In described the first reactor (1) and the second reactor (9), load copper-based catalysts respectively form the first beds and the second beds.
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| CN112142558A (en) * | 2020-08-31 | 2020-12-29 | 南京聚拓化工科技有限公司 | Single-power double-circulation methanol production method |
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