CN111848352A - Reduction of CO by coke2Process for preparing methanol - Google Patents
Reduction of CO by coke2Process for preparing methanol Download PDFInfo
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- CN111848352A CN111848352A CN202010786883.9A CN202010786883A CN111848352A CN 111848352 A CN111848352 A CN 111848352A CN 202010786883 A CN202010786883 A CN 202010786883A CN 111848352 A CN111848352 A CN 111848352A
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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
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- 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
- C01B32/40—Carbon monoxide
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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
- C07C29/1512—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 reaction conditions
Abstract
To solve CO2The invention provides a problem of high hydrogen consumption in the process of preparing methanol by hydrogenation, and provides a method for reducing CO by coke2A process for the preparation of methanol. Reduction of CO with coke2Preparing CO reducing gas, and preparing the methanol by reacting the hydrogen with the reducing gas CO. With CO2The coke is converted into CO reducing gas by adopting a gasification technology as a raw material, so that the content of CO effective gas in the reducing gas can be increased while the using amount of water vapor is reduced; reduction of CO by coke2On one hand, the carbon source can be used as a supplementary carbon source of CO, and simultaneously, the system energy can be supplemented.
Description
Technical Field
The invention relates to CO2Process for the preparation of methanol, in particular the reduction of CO by coke2A process for the preparation of methanol.
Background
With the increasing emphasis on climate change, the greenhouse gas CO2The emission reduction becomes the focus of attention of people, China clearly proposes that the emission of greenhouse gases reaches the peak value in 2030 years, and the emission of carbon dioxide of the total production value in China is reduced by 60-65% compared with 2005.
CO2The resource utilization is to realize CO2The important way of emission reduction is to seek reasonable CO2Emission reduction and utilization aspect, in 1945, scientists report CO on Cu-Al catalyst for the first time2And H2Study on the Synthesis of methanol at 5.15MPa and 275 ℃ in Cu-Zn-Al2O3CO for catalyst2And H2Synthetic reaction, CO2The conversion rate reaches 16 percent, and the selectivity of the methanol reaches 28.2 percent.
CO2CO is simultaneously present in a reaction system for synthesizing methanol by hydrogenation2And H2Synthesizing methanol, reverse steam shift, and synthesizing methanol by CO hydrogenation for 3 reactions:
CO2+3H2→CH3OH+H2O+49.5kJ/mol
CO2+H2→CO+H2O-41.2kJ/mol
CO+2H2→CH3OH+H2O+90.7kJ/mol
the methanol synthesis reactions (1) and (3) are reversible exothermic reactions, and the reverse steam shift reaction (2) is a reversible endothermic reaction. CO22The methanol synthesis reaction mainly uses a Cu-based catalyst, the carrier also has influence on the activity of the copper-based catalyst, and the catalyst activity of different carriers: (TiO)2、Al2O3、MoO2、V2O3)＞(MgO、La2O3)。
From the thermodynamic point of view, low temperature is favorable for the methanol synthesis reactions (1) and (3), the rising of the reaction temperature is unfavorable for the forward reaction direction of the reactions (1) and (3), and the reverse steam shift reaction (2) hasAnd (6) benefiting. From the reaction kinetics point of view, CO2And H2The chemical equilibrium constants of (a) and (b) are all directly related to the reaction temperature, and increasing the reaction temperature can increase the reaction rate of 3 reactions. Therefore, there is a competition in reaction thermodynamics and kinetics for the methanol synthesis reactions (1) and (3), so that the methanol yield is maximized with temperature variation.
From CO2In the process of the reaction for preparing methanol by hydrogenation, the hydrogen consumption of the process is high, and the hydrogen is needed to convert CO2The oxygen in the process is reduced to generate water, so that the utilization rate of the hydrogen is low, and the economical efficiency of the process is limited.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The methanol preparation method provided by the invention can solve the problem of CO2The problem of high hydrogen consumption in the process of preparing methanol by hydrogenation is as follows: reduction of CO with coke2Preparing CO reducing gas, and preparing the methanol by reacting the hydrogen with the reducing gas CO. With CO2The coke is converted into CO reducing gas by adopting a gasification technology as a raw material, so that the content of CO effective gas in the reducing gas can be increased while the using amount of water vapor is reduced; reduction of CO by coke2On one hand, the carbon source can be used as a supplementary carbon source of CO, and simultaneously, the system energy can be supplemented.
In order to achieve the above purpose of the invention, the following technical scheme is adopted:
reduction of CO by coke2A process for the preparation of methanol comprising the steps of:
reduction of CO with coke2Preparation of CO, CO and H2The reaction produces methanol.
The CO is2CO removal from coal gasification shift2CO in the process of preparing ethylene oxide or ethylene glycol by ethylene oxidation2CO in the process of preparing acrylonitrile by propylene ammoxidation2By-product CO in the process of preparing hydrogen from naphtha2And flue gas trapped CO2Any one or more of.
The coke reduces CO2In the reaction for preparing CO, the reaction temperature is 700-1200 ℃, and the preferable reaction temperature isAt a temperature of 750-1000 ℃ and CO2The reaction space velocity of the catalyst is 18-200 m3/(hr·m3) The preferable reaction space velocity is 50-100 m3/(hr·m3)。
The particle size of the coke is 50-500 μm, preferably 100-300 μm, and the mass fraction of C element is more than 85%;
by K2CO3The solution impregnates the coke, K2CO3In solution, K2CO3The mass of (B) is 1 to 10% of the mass of the coke.
In the reduction reaction, oxygen is doped into the CO2In which is also doped with O2Said O is2The doping amount is the CO 220 to 80%, preferably 70 to 80% by volume of (a).
The CO and H2In the reaction for preparing the methanol, the reaction temperature is 220-270 ℃, the reaction pressure is 3.0-6.0 Mpa, and the hydrogen-carbon ratio of the reaction is 2.05-2.15.
The coke reduces CO2The CO is prepared and reacted in a fixed bed reactor or a fluidized bed reactor, preferably a fluidized bed reactor.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses CO2The coke is converted into CO reducing gas by adopting a gasification technology as a raw material, so that the content of CO effective gas in the reducing gas can be increased while the using amount of water vapor is reduced; on one hand, the coke reduced CO2 can be used as a supplementary carbon source of CO, and meanwhile, the system energy can be supplemented, and the cost is saved.
Drawings
To more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the embodiments and the drawings in the description of the prior art are briefly introduced. For a person skilled in the art, other figures can also be derived from these figures without inventive effort.
FIG. 1 is a process for reducing CO from coke2A thermodynamic equilibrium diagram of the system;
FIG. 2 is a schematic material flow diagram provided by an embodiment of the present invention;
FIG. 3 is 10 ten thousand tons of CO2Utilizing a device material flow diagram.
Detailed Description
The following described embodiments are some of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
A process method for preparing methanol by reducing CO2 with coke comprises the following steps:
reduction of CO with coke2Preparation of CO, CO and H2The reaction produces methanol.
Reduction of CO with coke2Can prepare CO and obviously reduce CO2Hydrogen consumption in the methanol production process.
Reduction of CO by coke2The reaction formula (c) is as follows:
CO2+C→2CO-164.96kJ/mol；
this reaction is endothermic and results in a decrease in the temperature of the coke bed. In the actual gasification coke reduction process, O is generally required to be added into a gasification agent2Or air partially combusting the coke to generate heat to maintain the coke with steam and CO2The reaction continues.
Reduction of CO by coke2The equilibrium concentration of produced CO varies greatly with temperature, as shown in figure 1.
When the reaction reaches the equilibrium at a lower temperature, the content of CO is low, and CO2The content is high; if the temperature is increased, the content of CO is high, and CO2The content is reduced. In order to achieve higher reaction conversion, the temperature for reducing CO2 by coke is not preferably lower than 750 ℃.
In addition, to solve CO2The invention discloses a method for reducing CO by using coke, and solves the problem of high hydrogen consumption in the process of preparing methanol by hydrogenation2Preparation of CO reducing gas, passing hydrogen gas through the reducing gasThe reaction produces methanol. With CO2The coke is converted into CO reducing gas by adopting a gasification technology as a raw material, so that the content of CO effective gas in the reducing gas can be increased while the using amount of water vapor is reduced; reduction of CO by coke2On one hand, the carbon source can be used as a supplementary carbon source of CO, and simultaneously, the system energy can be supplemented. The process is suitable for the process of preparing hydrogen by external sources such as water electrolysis hydrogen production and the like, and CO is required for coal gasification hydrogen production2Separate separations were performed.
In a preferred embodiment of the invention, the reduction of CO to achieve coke is carried out2In the reaction process, coke needs to be prepared into particles with a certain particle size range, the particle size of the coke is 50-500 μm, preferably 100-300 μm, and the proportion of carbon element in the coke element composition is more than 85%. Table 1 is a table of industrial analysis and elemental analysis of coke samples.
TABLE 1 Coke sample Industrial analysis and elemental analysis Table
At the same time, in order to maintain the temperature of the reaction bed layer, the O is required to be doped2The reaction is exothermic, namely the following reaction occurs:
2C+O2→2CO+221kJ/mol；
thus, from CO2The thermal effect of the reduction reaction and the reaction of C to CO can be calculated2And O2The theoretical ratio of (A) is 1: 0.74.
In a preferred embodiment of the invention, the coke is metered continuously into the gasifier and CO is added2Gasifying agent and O2After being mixed according to a certain proportion, the raw materials are added from the bottom and the side of the reaction furnace body. Coke and CO in the furnace body2And O2The reaction is carried out at a certain temperature. CO22Temperature, CO of coke reduction process2Parameters such as the airspeed of the raw material gas and the granularity of coke have influence on the reaction conversion rate, the product gas with higher CO content is obtained through the coke reaction, and pure CO gas can be obtained through washing, absorption and purification.
In the preferred embodiment of the present invention, the CO gas is mixed with the outside gasIntroducing hydrogen into a methanol synthesis reactor, wherein the reaction adopts a Cu-based catalyst, the reaction temperature is 220-270 ℃, and the reaction pressure is 3.0-6.0 Mpa; the hydrogen-carbon ratio has an important influence on the methanol synthesis reaction, and the control of the hydrogen-carbon ratio is too low, so that the synthesis side reaction is increased easily, and the inactivation of the catalyst activity is accelerated; the hydrogen-carbon ratio is too high, which causes the accumulation of hydrogen and the increase of the content of inert gas, increases the purge gas amount of a system, and causes the increase of consumption, and CO and H are controlled2With flow ratio for methanol synthesis reaction (H)2-CO2)/(CO+CO2)＝2.05～2.15。
Reduction of CO by the above coke2The process and the methanol synthesis process can result in a metered reaction of the overall process, namely:
CO2+C+4H2→2CH3OH；
unit methanol product H of the above reaction2Consumption of 2molH2Per mol of methanol and CO2The metering formula of the direct hydrogenation reaction is as follows:
CO2+3H2→CH3OH+H2O；
CO2unit methanol product H of direct hydrogenation reaction2Consumption of 3molH2Per mol methanol, reduction of CO by coke2The process hydrogen consumption can be significantly reduced.
In a preferred embodiment of the present invention, a fluidized bed reactor may be used for large-scale operation for carrying out the above-described coke reduction reaction, and a fixed bed or fluidized bed reactor may be used for small-scale operation.
The embodiments of the present invention will be described in detail with reference to examples, which are provided only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
Example 1
This example uses coke to reduce CO2Preparation of CO, CO and H2The reaction produces methanol.
Wherein coke reduces CO2The reaction temperature for preparing CO is 1000 ℃, and CO2Space velocity of reactionBetween 100m3/(hr·m3) The particle size of the coke is 200 mu m, and the mass fraction of C element in the coke is more than 85%; and the coke adopts K2CO3The solution is subjected to an impregnation treatment, K2CO3Is 5% of the coke mass.
Wherein, CO2Is also doped with oxygen in an amount of 60% of the volume.
The CO and H2In the reaction for preparing the methanol, a Cu-based catalyst is adopted, the reaction temperature is 250 ℃, the reaction pressure is 5.0Mpa, and the hydrogen-carbon ratio of the reaction is 2.10.
Example 2
Reduction of CO with some 10 million tons/year coke2The process design of the methanol preparation plant is taken as an example, and 10 ten thousand tons of CO are used for realizing the process2Pure oxygen of 5.38 million tons and coke of 6.74 million tons are required to be prepared.
6.74 ten thousand tons of coke is used as a raw material, 5.38 ten thousand tons of oxygen and 10 ten thousand tons of carbon dioxide are used as gasifying agents, and the raw CO gas with the CO content of 70 percent is prepared by high-temperature continuous gasification in a fixed bed gasification furnace. The crude CO gas is sent into a gas holder for storage after the waste heat of the process is recovered, and the crude reducing gas from the gas holder is subjected to removal of inorganic sulfur, organic sulfur and CO by a pre-desulfurization device2. Finally, high-purity CO gas (the CO content is 98%) is obtained through refining, and 22.12 ten thousand tons of CO is obtained.
And (3) introducing the CO gas and 3.16 ten thousand tons of externally supplied hydrogen into a methanol synthesis reaction unit to synthesize 25.3 ten thousand tons of methanol.
In CO2In different processes for preparing methanol, the cost of hydrogen accounts for over 70 percent of the material consumption cost, and the reduction of CO by coke is compared2Process for preparing methanol and CO2The feed consumption of the direct hydrogenation methanol preparation process is shown in table 2.
TABLE 210 million tons CO2Material balance comparison of different process routes
As can be seen from Table 2, coke reduced CO2Unit methanol product of the process H2The consumption was 0.124tH2T methanol, CO2H of direct hydrogenation process2Specific consumption of 0.188tH2The material consumption of the methanol is low-price raw materials such as coke and pure oxygen, so that the economical efficiency of the route is obviously enhanced.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same.
Claims (8)
1. Reduction of CO by coke2The process method for preparing the methanol is characterized by comprising the following steps:
reduction of CO with coke2Preparation of CO, CO and H2The reaction produces methanol.
2. Coke-reduced CO according to claim 12Process for the preparation of methanol, characterized in that the CO is2CO removal from coal gasification shift2CO in the process of preparing ethylene oxide or ethylene glycol by ethylene oxidation2CO in the process of preparing acrylonitrile by propylene ammoxidation2By-product CO in the process of preparing hydrogen from naphtha2And flue gas trapped CO2Any one or more of.
3. Coke-reduced CO according to claim 12Process for the preparation of methanol, characterized in that said coke reduces CO2In the reaction for preparing CO, the reaction temperature is 700-1200 ℃, the preferable reaction temperature is 750-1000 ℃, and CO is2The reaction space velocity of the catalyst is 18-200 m3/(hr·m3) The preferable reaction space velocity is 50-100 m3/(hr·m3)。
4. Coke-reduced CO according to claim 12The process method for preparing the methanol is characterized in that the particle size of the coke is 50-500 mu m, and preferably 100-300 mu m;
preferably, in the coke, the mass fraction of the C element is more than 85%;
preferably, K is used2CO3The solution impregnates the coke, K2CO3In solution, K2CO3The mass of (B) is 1 to 10% of the mass of the coke.
5. Coke-reduced CO according to claim 12Process for the preparation of methanol, characterized in that the CO is2In which is also doped with O2Preferably, said O is2The doping amount is the CO220 to 80%, preferably 70 to 80% by volume of (a).
6. Coke-reduced CO according to claim 12A process for the preparation of methanol, characterized in that said CO and H are2In the reaction for preparing the methanol, a Cu-based catalyst is adopted.
7. Coke-reduced CO according to claim 12A process for the preparation of methanol, characterized in that said CO and H are2In the reaction for preparing the methanol, the reaction temperature is 220-270 ℃, the reaction pressure is 3.0-6.0 Mpa, and the hydrogen-carbon ratio of the reaction is 2.05-2.15.
8. Coke-reduced CO according to claim 12Process for the preparation of methanol, characterized in that said coke reduces CO2The CO is prepared and reacted in a fixed bed reactor or a fluidized bed reactor, preferably a fluidized bed reactor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620240A (en) * | 2021-06-29 | 2021-11-09 | 东北大学 | Method for determining technological parameters for preparing hydrogen-based reducing gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105408308A (en) * | 2013-06-27 | 2016-03-16 | 国际壳牌研究有限公司 | Systems and methods for producing dimethyl sulfide from gasified coke |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105408308A (en) * | 2013-06-27 | 2016-03-16 | 国际壳牌研究有限公司 | Systems and methods for producing dimethyl sulfide from gasified coke |
Non-Patent Citations (2)
| Title |
|---|
| 李冉: "焦炭、焦炉煤气制甲醇新工艺", 《广州化工》 * |
| 程可扬等: "碱金属碳酸盐对焦炭气化反应的催化动力学研究", 《第十二届中国钢铁年会论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620240A (en) * | 2021-06-29 | 2021-11-09 | 东北大学 | Method for determining technological parameters for preparing hydrogen-based reducing gas |
| CN113620240B (en) * | 2021-06-29 | 2022-08-19 | 东北大学 | Method for determining technological parameters for preparing hydrogen-based reducing gas |
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