CN110950737A - Method and device for producing methanol from carbon dioxide byproduct of nitric acid and application of method and device - Google Patents

Method and device for producing methanol from carbon dioxide byproduct of nitric acid and application of method and device Download PDF

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Publication number
CN110950737A
CN110950737A CN201911218661.0A CN201911218661A CN110950737A CN 110950737 A CN110950737 A CN 110950737A CN 201911218661 A CN201911218661 A CN 201911218661A CN 110950737 A CN110950737 A CN 110950737A
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carbon dioxide
gas
outlet
inlet
communicated
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唐印
秦艳妮
宋国天
龚元德
孔德利
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Beijing Edgein Technology Co Ltd
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Beijing Edgein Technology Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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

Abstract

The invention provides a method and a device for producing methanol from a nitric acid byproduct carbon dioxide and application thereof, relating to the technical field of chemical industry, and the method for producing methanol from the nitric acid byproduct carbon dioxide comprises the following steps: the melamine tail gas and nitric acid are subjected to neutralization reaction to obtain carbon dioxide and water vapor, and the carbon dioxide and hydrogen are subjected to synthesis reaction to obtain methanol. The method is simple and convenient to operate, easy to implement, low in cost, free of excessive energy consumption, capable of achieving zero emission of carbon dioxide and reducing the pressure of carbon dioxide emission.

Description

Method and device for producing methanol from carbon dioxide byproduct of nitric acid and application of method and device
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method and a device for producing methanol by using nitric acid byproduct carbon dioxide and application thereof.
Background
In the prior art, after the melamine tail gas is subjected to neutralization reaction with nitric acid, NH in the melamine tail gas3Formation of ammonium nitrate, and CO2After being treated, the waste is discharged into the atmosphere, which causes energy waste and harm to the environment. And the rapid development of modern industry leads the emission of carbon dioxide to be larger and larger, and the harm caused by the emission is also larger and larger. At present, the treatment effect of carbon dioxide generated after neutralization reaction of melamine tail gas and nitric acid is poor, the process is complicated, and excessive energy consumption is required.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for producing methanol by using nitric acid and byproduct carbon dioxide, which is simple and convenient to operate, easy to realize, low in cost and free from consuming excessive energy consumption, and can realize zero emission of carbon dioxide and reduce the pressure of carbon dioxide emission.
The method for producing methanol by using carbon dioxide as a byproduct of nitric acid provided by the invention comprises the following steps:
the melamine tail gas and nitric acid are subjected to neutralization reaction to obtain carbon dioxide and water vapor,
and carrying out synthetic reaction on the carbon dioxide and the hydrogen to obtain the methanol.
Further, the temperature of the carbon dioxide and the water vapor obtained after the neutralization reaction is respectively and independently 150-200 ℃;
preferably, the molar ratio of hydrogen to carbon dioxide is from 2 to 5: 1;
preferably, the temperature of the synthesis reaction is 190-270 ℃;
preferably, the pressure of the synthesis reaction is 3-10 MPa;
preferably, the volume space velocity of the synthesis reaction is 3000-10000h-1。
Further, carrying out first gas-liquid separation on carbon dioxide and water vapor, and carrying out the synthesis reaction by using carbon dioxide obtained after the first gas-liquid separation;
preferably, the carbon dioxide and the water vapor are subjected to first condensation and then to the first gas-liquid separation;
preferably, the temperature of the carbon dioxide and water obtained after the first condensation is each independently 80-130 ℃.
Further, a product obtained by the synthetic reaction of carbon dioxide and hydrogen sequentially undergoes second condensation and second gas-liquid separation to obtain the methanol;
preferably, the carbon dioxide and the water vapor obtained after the neutralization reaction are subjected to the first condensation by using a first mixed gas obtained after the second gas-liquid separation;
preferably, the temperature of the first mixed gas is 30-60 ℃;
preferably, the first mixed gas is used for carrying out the first condensation to obtain a second mixed gas, the second mixed gas is mixed with carbon dioxide obtained after the first gas-liquid separation, and then the second mixed gas and hydrogen are subjected to the synthesis reaction.
Further, the liquid obtained by the second gas-liquid separation is rectified to obtain the methanol.
A device for producing methanol from nitric acid byproduct carbon dioxide comprises:
the neutralization tower comprises a melamine tail gas inlet, a nitric acid inlet, an ammonium nitrate outlet and a carbon dioxide outlet;
a reactor, which comprises a raw material inlet and a product outlet, wherein the raw material inlet is communicated with the carbon dioxide outlet,
wherein hydrogen enters the reactor from the feed inlet and the methanol exits from the product outlet;
preferably, the reactor comprises a fixed bed reactor.
Further, still include: a first gas-liquid separator comprising a first mixture inlet, a first gas outlet, and a first liquid outlet,
wherein the first mixture inlet is communicated with the carbon dioxide outlet, and the first gas outlet is communicated with the raw material inlet;
preferably, the heat exchanger comprises a heat medium inlet, a heat medium outlet, a cold medium inlet and a cold medium outlet, wherein the heat medium inlet is communicated with the carbon dioxide outlet, and the heat medium outlet is communicated with the first mixture inlet.
Further, still include:
the condenser comprises a mixed gas inlet and a gas-liquid mixture outlet, and the mixed gas inlet is communicated with the product outlet;
a second gas-liquid separator comprising a second mixture inlet, a second gas outlet, and a second liquid outlet, the second mixture inlet being in communication with the gas-liquid mixture outlet,
preferably, the second gas outlet is communicated with the cold medium inlet;
preferably, the device further comprises a rectifying tower, wherein the rectifying tower comprises a feeding hole and a discharging hole, and the feeding hole is communicated with the second liquid outlet.
Further, still include:
the mixer comprises a first inlet, a second inlet, a hydrogen inlet and a mixed gas outlet, wherein the first inlet is communicated with the first gas outlet, the second inlet is communicated with the cold medium outlet, and the mixed gas outlet is communicated with the raw material inlet.
Use of a device as hereinbefore described for the preparation of methanol.
Compared with the prior art, the invention can at least obtain the following beneficial effects:
in the inventionThe melamine tail gas is subjected to neutralization reaction with nitric acid to obtain ammonium nitrate and water, ammonia gas is removed, and residual carbon dioxide (CO) in the melamine tail gas is removed2) The method has the advantages that the method creatively utilizes the melamine tail gas and the tail gas obtained after the neutralization of the nitric acid to produce the methanol, and is favorable for fully utilizing the melamine tail gas to ensure that CO is reacted with the hydrogen to generate the methanol2Obtain higher value-added utilization, and CO is used for preparing methanol by adopting the method of the invention2Convenient source and low cost, improves the sustainable utilization of carbon resources, can reduce the consumption of fossil resources, and is beneficial to environmental protection. Moreover, the method disclosed by the invention is simple and convenient to operate, easy to realize, low in cost and free from consuming excessive energy consumption, and can realize zero emission of carbon dioxide and reduce the pressure of carbon dioxide emission.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a diagram showing a device for producing methanol from carbon dioxide by-produced from nitric acid according to an embodiment of the present invention;
FIG. 2 is a diagram showing a device for producing methanol from carbon dioxide by-produced from nitric acid according to another embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
In one aspect of the present invention, the present invention provides a method for producing methanol from carbon dioxide byproduct of nitric acid, comprising:
the melamine tail gas and nitric acid are subjected to neutralization reaction to obtain carbon dioxide and water vapor,
and carrying out synthetic reaction on the carbon dioxide and the hydrogen to obtain the methanol.
In the invention, ammonium nitrate and water are obtained after the melamine tail gas is subjected to neutralization reaction with nitric acid, ammonia gas is removed, and residual carbon dioxide (CO) in the melamine tail gas is removed2) The method has the advantages that the method creatively utilizes the melamine tail gas and the tail gas obtained after the neutralization of the nitric acid to produce the methanol, and is favorable for fully utilizing the melamine tail gas to ensure that CO is reacted with the hydrogen to generate the methanol2Obtain higher value-added utilization, and CO is used for preparing methanol by adopting the method of the invention2Convenient source and low cost, improves the sustainable utilization of carbon resources, can reduce the consumption of fossil resources, and is beneficial to environmental protection. Moreover, the method disclosed by the invention is simple and convenient to operate, easy to realize, low in cost and free from consuming excessive energy consumption, and can realize zero emission of carbon dioxide and reduce the pressure of carbon dioxide emission.
It should be noted that the melamine off-gas refers to off-gas generated in the production of melamine, and the off-gas contains NH3、CO2、N2And other small amounts of impurity gases, will not be redundantly described here.
In some embodiments of the invention, the temperature of the carbon dioxide and water vapor obtained after the neutralization reaction is 150-. Therefore, the carbon dioxide has higher temperature, and can carry out subsequent synthesis reaction without preheating, thereby reducing the consumption of heat energy and reducing the cost.
In some embodiments of the invention, the molar ratio of hydrogen to carbon dioxide is from 2 to 5: 1 (e.g., 2: 1, 3: 1, 4: 1, or 5: 1, etc.). When the molar ratio of hydrogen to carbon dioxide is too small relative to the above range, the reaction is not completed, the utilization rate of carbon dioxide is low, and when the molar ratio of hydrogen to carbon dioxide is too large, other side reactions are generated.
In some embodiments of the present invention, the temperature of the synthesis reaction is 190-; the pressure of the synthesis reaction is 3-10MPa (for example, 3MPa, 5MPa, 7MPa, 9MPa or 10 MPa); the volume space velocity of the synthesis reaction is 3000-10000h-1(for example, 3000h can be used)-1、5000h-1、7000h-1、9000h-1Or 10000h-1Etc.). Therefore, the synthesis effect is good, and the full reaction of carbon dioxide and hydrogen is facilitated.
In some embodiments of the present invention, a first gas-liquid separation is performed on carbon dioxide and water vapor, and the synthesis reaction is performed using carbon dioxide obtained after the first gas-liquid separation. Therefore, after water is removed, the carbon dioxide and the hydrogen are in full contact, and the synthetic reaction is facilitated.
In some embodiments of the invention, the first gas-liquid separation is performed after the first condensation of carbon dioxide and water vapor. Therefore, the subsequent first gas-liquid separation is facilitated, and the energy is saved.
In some embodiments of the present invention, the temperatures of the carbon dioxide and water obtained after the first condensation are each independently 80 to 130 ℃ (for example, may be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, or 130 ℃, etc.). Compared with the temperature range, when the temperature of the carbon dioxide and the water obtained after the first condensation is too high, part of water vapor is carried into the carbon dioxide to influence the subsequent reaction, and when the temperature is too low, the temperature of the carbon dioxide does not reach the required temperature, and the carbon dioxide needs to be heated again before entering the reactor, so that the energy consumption is increased.
In some embodiments of the present invention, the methanol is obtained by subjecting a product obtained by a synthesis reaction of carbon dioxide and hydrogen to second condensation and second gas-liquid separation in sequence.
In some embodiments of the present invention, the carbon dioxide and water vapor obtained after the neutralization reaction are subjected to the first condensation using a first mixed gas obtained after the second gas-liquid separation. Thereby, the second gas-liquid is utilizedThe first mixed gas obtained by separation is CO2And H2And the O is cooled, so that the water vapor brought out by the neutralization reaction is condensed into water to be discharged, the synthetic reaction is prevented from being influenced, and meanwhile, the first mixed gas is used for cooling the heat exchanger, so that the energy consumption can be saved (in some specific embodiments of the invention, the 4000KW energy consumption can be saved), and the cost is reduced.
The first mixed gas contains carbon dioxide and hydrogen which are not completely reacted in the neutralization reaction, and may contain by-products of the reaction such as carbon monoxide.
In some embodiments of the present invention, the temperature of the first mixed gas is 30 to 60 ℃ (for example, 30 ℃, 40 ℃, 50 ℃ or 60 ℃) relative to the above temperature range, when the temperature of the first mixed gas is too high, the water vapor cannot be condensed into water when the carbon dioxide and the water vapor are condensed, and when the temperature of the first mixed gas is too low, the temperature of the condensed carbon dioxide is too low, and the carbon dioxide needs to be heated again, which increases energy consumption.
In some embodiments of the present invention, the first mixed gas is used to perform the first condensation to obtain a second mixed gas, the second mixed gas is mixed with the carbon dioxide obtained by the first gas-liquid separation, and then the second mixed gas and hydrogen are subjected to the synthesis reaction. Therefore, the method is beneficial to fully utilizing the raw materials, so that zero emission of carbon dioxide is realized, the sustainable utilization of carbon resources is improved, and the influence on the environment is reduced.
In some embodiments of the present invention, the liquid obtained by the second gas-liquid separation is rectified to obtain the methanol. Therefore, the method is favorable for obtaining the refined methanol with higher purity.
In another aspect of the present invention, the present invention provides an apparatus for producing methanol from carbon dioxide by-produced from nitric acid, which comprises, with reference to fig. 1:
a neutralization tower 100, wherein the neutralization tower 100 comprises a melamine tail gas inlet 110, a nitric acid inlet 120, an ammonium nitrate outlet 140 and a carbon dioxide outlet 130;
a reactor 200, said reactor 200 comprising a feedstock inlet 210 and a product outlet 220, said feedstock inlet 210 being in communication with said carbon dioxide outlet 130,
wherein hydrogen enters the reactor 200 from the feedstock inlet 210 and the methanol exits from the product outlet 220.
The water vapor obtained by the neutralization reaction is discharged from the carbon dioxide outlet; all parameters and conditions of the neutralization column correspond to the neutralization reaction described previously and all parameters and conditions in the reactor correspond to the synthesis reaction described previously.
It will be appreciated that the carbon dioxide outlet may be provided at the top of the neutralisation column from which carbon dioxide and water vapour are discharged.
In some preferred embodiments of the present invention, the reactor comprises a fixed bed reactor, which may contain a catalyst (e.g., copper-based catalyst, etc.) conventionally used in the production of methanol, and will not be described in detail herein.
In some embodiments of the invention, referring to fig. 2, the apparatus further comprises: a first gas-liquid separator 300, said first gas-liquid separator 300 comprising a first mixture inlet 310, a first gas outlet 320 and a first liquid outlet 330,
wherein the first mixture inlet 310 is in communication with the carbon dioxide outlet 130 and the first gas outlet 320 is in communication with the feedstock inlet 210. Thus, the gas-liquid separator can be used to separate water from carbon dioxide, avoiding water from affecting the synthesis reaction.
It should be noted that the parameters and conditions in the first gas-liquid separator described above correspond to those of the first gas-liquid separation described above.
In some embodiments of the present invention, referring to fig. 2, the apparatus further comprises a heat exchanger 400, wherein the heat exchanger 400 comprises a heat medium inlet 410, a heat medium outlet 420, a cold medium inlet 430 and a cold medium outlet 440, wherein the heat medium inlet 410 is communicated with the carbon dioxide outlet 130, and the heat medium outlet 420 is communicated with the first mixture inlet 310. Therefore, the heat exchanger is utilized to condense the carbon dioxide and the water vapor, and the subsequent gas-liquid separation is facilitated.
It should be noted that the parameters and conditions in the heat exchanger described above correspond to the first condensation described above.
The heat medium means a medium to be condensed, and in the present invention, the heat medium means a mixture of carbon dioxide and water vapor flowing out from the neutralization tower; the cooling medium refers to a medium for condensing a heat medium, and in the present invention, the cooling medium may be condensed water, or may be a first mixed gas obtained by performing a second gas-liquid separation, where the first mixed gas is consistent with the foregoing description, and will not be described herein again.
In some embodiments of the invention, referring to fig. 2, the apparatus further comprises:
a condenser 500, said condenser 500 comprising a mixture inlet 510 and a gas-liquid mixture outlet 520, said mixture inlet 510 being in communication with said product outlet 220;
a second gas-liquid separator 600, said second gas-liquid separator 600 comprising a second mixture inlet 610, a second gas outlet 620 and a second liquid outlet 630, said second mixture inlet 610 communicating with said gas-liquid mixture outlet 520. Therefore, products obtained by the synthesis reaction are condensed and subjected to gas-liquid separation, and the methanol product is favorably obtained.
The parameters and conditions in the condenser correspond to the second condensation described above, and the parameters and conditions in the second gas-liquid separator correspond to the second gas-liquid separation described above.
In some embodiments of the present invention, referring to fig. 2, the second gas outlet 620 communicates with the cooling medium inlet 430. Therefore, the energy is fully utilized, and the energy consumption is reduced.
In some embodiments of the present invention, referring to fig. 2, the apparatus further comprises a rectification column 700, wherein the rectification column 700 comprises a feed inlet 710 and a discharge outlet 720, and the feed inlet 710 is communicated with the second liquid outlet 630. Thereby, the refined methanol is favorably obtained.
The parameters and conditions in the rectifying column correspond to those of the rectification described above.
In some embodiments of the invention, with reference to fig. 2, the apparatus further comprises:
the mixer 800, the mixer 800 includes a first inlet 810, a second inlet 820, a hydrogen inlet 830, and a mixed gas outlet 840, wherein the first inlet 810 is communicated with the first gas outlet 320, the second inlet 820 is communicated with the cold medium outlet 440, and the mixed gas outlet 840 is communicated with the raw material inlet 210.
It should be noted that the ratio of carbon dioxide and hydrogen in the above mixer is consistent with the above description, and redundant description is omitted here.
It should be noted that the above-mentioned components may be communicated with each other through a pipe, for example, the second inlet 820 may be communicated with the cooling medium outlet 440 through a pipe disposed between the second inlet 820 and the cooling medium outlet 440, so as to communicate the second inlet 820 with the cooling medium outlet 440.
In some embodiments of the present invention, the specific process for producing methanol using the above-described apparatus may be as follows:
melamine tail gas enters the neutralizing tower 100 from the melamine tail gas inlet 110, nitric acid enters the neutralizing tower 100 from the nitric acid inlet 120, the nitric acid and ammonia gas in the melamine tail gas are subjected to neutralization reaction to generate ammonium nitrate, and the ammonium nitrate is discharged from the ammonium nitrate outlet 140; the gas and water vapor including carbon dioxide remaining in the melamine off-gas are discharged from the carbon dioxide outlet 130;
carbon dioxide and water vapor enter the heat exchanger 400 from the heat medium inlet 410, and the carbon dioxide and water obtained after condensation are discharged from the heat medium outlet 420, so that the subsequent first gas-liquid separation is performed;
the condensed carbon dioxide and water enter the first gas-liquid separator 300 from the first mixture inlet 310, and after gas-liquid separation, the carbon dioxide is discharged from the first gas outlet 320, and the water is discharged from the first liquid outlet 330;
carbon dioxide obtained after gas-liquid separation enters the mixer 800 from the first inlet 810, hydrogen enters the mixer 800 from the hydrogen inlet 830, and the hydrogen and the carbon dioxide are mixed in the mixer 800 so as to carry out subsequent synthesis reaction;
the mixed hydrogen and carbon dioxide enter the reactor 200 from the raw material inlet 210, the hydrogen and carbon dioxide undergo a synthesis reaction in the reactor to generate methanol gas, the generated methanol gas is discharged from the product outlet 220, water vapor and a byproduct carbon monoxide are generated while the methanol is generated, the water vapor and the carbon monoxide are discharged from the product outlet 220 along with the methanol gas, and part of the unreacted carbon dioxide and hydrogen are discharged from the product outlet 220 along with the methanol gas;
the mixed gas flowing out of the reactor enters the condenser 500 from the mixed gas inlet 510, and the condensed mixed gas is discharged from the gas-liquid mixture outlet 520;
the condensed mixed gas enters the second gas-liquid separator 600 from the second mixture inlet 610, the mixed gas is subjected to gas-liquid separation to obtain liquid containing methanol and discharged from the second liquid outlet 630, the mixed gas containing carbon dioxide, hydrogen and carbon monoxide is discharged from the second gas outlet 620, the mixed gas containing carbon dioxide, hydrogen and carbon monoxide enters the heat exchanger 400 through the cold medium inlet 430 to condense the mixture of carbon dioxide and water vapor discharged from the neutralization tower, and the condensed mixed gas is discharged from the cold medium outlet 440 and enters the mixer 800 through the second inlet 820 to be mixed with hydrogen and carbon dioxide again so as to participate in subsequent synthesis reaction, so that the energy consumption is saved and the cost is reduced;
the liquid containing methanol discharged from the second liquid outlet 630 enters the rectifying tower 700 through the feed inlet 710, and after rectification, the refined methanol with higher purity is discharged from the discharge outlet 720.
In a further aspect of the invention, there is provided the use of an apparatus as hereinbefore described for the preparation of methanol.
Some embodiments of the present invention will be described in detail below with reference to specific examples. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
Examples
Example 1
The method for producing methanol by using the nitric acid byproduct carbon dioxide comprises the following steps:
1. introducing the melamine tail gas into a nitric acid pressurizing neutralization tower device (the pressure of the nitric acid pressurizing neutralization tower device is 0.35MPa), wherein NH contained in the tail gas3Reacting with nitric acid in a neutralization tower to generate ammonium nitrate; unreacted CO in tail gas2H produced by neutralization reaction with nitric acid2Filtering O in the neutralizing tower, discharging CO from the top of the neutralizing tower2And H2The O temperature is 180 ℃, and the pressure is 0.35 MPa;
2. CO discharged from the top of the neutralization tower2And H2Sending O to a heat exchanger to cool to 110 ℃, and then CO2And H2O enters a first gas-liquid separator to separate water and discharge, CO2And H2In a molar ratio of 1: 3, the mixture is mixed in a mixer at the airspeed of 4000h-1Introducing into a fixed bed reactor added with a copper-based catalyst, wherein the temperature of the reactor is 250 ℃, and the pressure of the reactor is 5MPa, and obtaining crude methanol gas after full reaction;
3. cooling the crude methanol gas in a condenser by cold water, performing gas-liquid separation by a second gas-liquid separator, and rectifying the obtained mixture of the crude methanol and water in a rectifying tower to obtain a refined methanol product, wherein the gas separated from the second gas-liquid separator contains CO at 40 DEG C2CO and H2Gas phase component of (2) to CO in the heat exchanger2And H2And cooling the O, and then feeding the O into a mixer for recycling.
Example 2
The method for producing methanol from carbon dioxide byproduct of nitric acid is the same as that in example 1, except that CO contained in the gas-liquid separator is separated2CO and H2The gas phase is directly vented, and cold water is used for CO in the heat exchanger2And H2And cooling the O.
Example 3
The method for producing methanol from carbon dioxide byproduct of nitric acid is the same as that in example 1, except that CO discharged from the top of the neutralization tower in step 22And H2The O is sent to a heat exchanger to be cooled to 80 ℃.
Example 4
The method for producing methanol from carbon dioxide byproduct of nitric acid is the same as that in example 1, except that CO discharged from the top of the neutralization tower in step 22And H2The O is sent to a heat exchanger to be cooled to 130 ℃.
Example 5
The method for producing methanol from carbon dioxide byproduct of nitric acid is the same as that in example 1, except that CO discharged from the top of the neutralization tower in step 22And H2The O is sent to a heat exchanger to be cooled to 60 ℃.
Example 6
The method for producing methanol from carbon dioxide byproduct of nitric acid is the same as that in example 1, except that CO discharged from the top of the neutralization tower in step 22And H2The O is sent to a heat exchanger to be cooled to 150 ℃.
The energy consumed and the cost to produce one kilogram of methanol in examples 1-6 are given in table 1 below:
TABLE 1
Energy consumed/W Cost ratio
Example 1 6939 1
Example 2 18993 2.74
Example 3 7266 1.05
Example 4 7045 1.01
Example 5 7364 1.06
Example 6 7146 1.03
Note that, the cost ratio in table 1 means: the ratio of the cost of each example to the cost of example 1, it is understood that the ratio of the cost of example 1 (the cost of producing one kilogram of methanol in example 1 is 1.3 yuan) is 1.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A method for producing methanol by nitric acid byproduct carbon dioxide is characterized by comprising the following steps:
the melamine tail gas and nitric acid are subjected to neutralization reaction to obtain carbon dioxide and water vapor,
and carrying out synthetic reaction on the carbon dioxide and the hydrogen to obtain the methanol.
2. The method as claimed in claim 1, wherein the temperature of the carbon dioxide and the water vapor obtained after the neutralization reaction is 150-200 ℃ independently of each other;
preferably, the molar ratio of hydrogen to carbon dioxide is from 2 to 5: 1;
preferably, the temperature of the synthesis reaction is 190-270 ℃;
preferably, the pressure of the synthesis reaction is 3-10 MPa;
preferably, the volume space velocity of the synthesis reaction is 3000-10000h-1。
3. The method according to claim 1 or 2, characterized in that carbon dioxide and water vapor are subjected to a first gas-liquid separation, and the synthesis reaction is carried out using carbon dioxide obtained after the first gas-liquid separation;
preferably, the carbon dioxide and the water vapor are subjected to first condensation and then to the first gas-liquid separation;
preferably, the temperature of the carbon dioxide and water obtained after the first condensation is each independently 80-130 ℃.
4. The method according to claim 3, wherein the methanol is obtained by subjecting a product obtained by the synthesis reaction of carbon dioxide and hydrogen to second condensation and second gas-liquid separation in sequence;
preferably, the carbon dioxide and the water vapor obtained after the neutralization reaction are subjected to the first condensation by using a first mixed gas obtained after the second gas-liquid separation;
preferably, the temperature of the first mixed gas is 30-60 ℃;
preferably, the first mixed gas is used for carrying out the first condensation to obtain a second mixed gas, the second mixed gas is mixed with carbon dioxide obtained after the first gas-liquid separation, and then the second mixed gas and hydrogen are subjected to the synthesis reaction.
5. The method according to claim 4, wherein the liquid obtained by the second gas-liquid separation is rectified to obtain the methanol.
6. The utility model provides a device of methyl alcohol is produced to nitric acid byproduct carbon dioxide which characterized in that includes:
the neutralization tower comprises a melamine tail gas inlet, a nitric acid inlet, an ammonium nitrate outlet and a carbon dioxide outlet;
a reactor, which comprises a raw material inlet and a product outlet, wherein the raw material inlet is communicated with the carbon dioxide outlet,
wherein hydrogen enters the reactor from the feed inlet and the methanol exits from the product outlet;
preferably, the reactor comprises a fixed bed reactor.
7. The apparatus of claim 6, further comprising: a first gas-liquid separator comprising a first mixture inlet, a first gas outlet, and a first liquid outlet,
wherein the first mixture inlet is communicated with the carbon dioxide outlet, and the first gas outlet is communicated with the raw material inlet;
preferably, the heat exchanger comprises a heat medium inlet, a heat medium outlet, a cold medium inlet and a cold medium outlet, wherein the heat medium inlet is communicated with the carbon dioxide outlet, and the heat medium outlet is communicated with the first mixture inlet.
8. The apparatus of claim 7, further comprising:
the condenser comprises a mixed gas inlet and a gas-liquid mixture outlet, and the mixed gas inlet is communicated with the product outlet;
a second gas-liquid separator comprising a second mixture inlet, a second gas outlet, and a second liquid outlet, the second mixture inlet being in communication with the gas-liquid mixture outlet,
preferably, the second gas outlet is communicated with the cold medium inlet;
preferably, the device further comprises a rectifying tower, wherein the rectifying tower comprises a feeding hole and a discharging hole, and the feeding hole is communicated with the second liquid outlet.
9. The apparatus of claim 8, further comprising:
the mixer comprises a first inlet, a second inlet, a hydrogen inlet and a mixed gas outlet, wherein the first inlet is communicated with the first gas outlet, the second inlet is communicated with the cold medium outlet, and the mixed gas outlet is communicated with the raw material inlet.
10. Use of a device according to any one of claims 6 to 9 for the preparation of methanol.
CN201911218661.0A 2019-12-02 2019-12-02 Method and device for producing methanol from carbon dioxide byproduct of nitric acid and application of method and device Pending CN110950737A (en)

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