CN106905112A - A kind of method and system of new synthesizing methanol - Google Patents
A kind of method and system of new synthesizing methanol Download PDFInfo
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- CN106905112A CN106905112A CN201710130473.7A CN201710130473A CN106905112A CN 106905112 A CN106905112 A CN 106905112A CN 201710130473 A CN201710130473 A CN 201710130473A CN 106905112 A CN106905112 A CN 106905112A
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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
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
Abstract
The present invention discloses a kind of method and system of new synthesizing methanol, can more convenient synthesizing methanol.The method includes：Methyl alcohol and vapor are blended in generation hydrogen as the molecular hydrogen of seed of being reformed under catalyst；By the molecular hydrogen, adsorption-decomposition function is hydrogen atom or hydrogen ion under hydrogenation catalyst effect；The vapor and the hydrogen atom or hydrogen ion are caused that hydrone is broken down into hydrogen molecule and oxygen molecule under hydrogenation catalyst effect, hydrogen molecule is combined generation hydrogen with hydrogen atom or hydrogen ion；The hydrogenation of carbon dioxide gas of input is downconverted into carbon monoxide in hydrogenation catalyst effect；Setting ratio synthesizing methanol under catalst for synthesis of methanol effect is pressed by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen.
Description
Technical field
The present invention relates to energy technology field, more particularly to a kind of method and system of new synthesizing methanol.
Background technology
The various energy can be carried out the secondary utilization of the energy at present.Liquid methanol is basic chemical industry raw material, is by CO, H2
It is the unstripped gas of main component, CO is a small amount of gas, and 1 is compared by CH:2, or CH compares 1:3 under catalyst synthetic fluid methyl alcohol.State
Inside and outside generation methyl alcohol enterprise, CO, CO are made using natural gas, coal or oil product2、H2Unstripped gas, first is synthesized under catalyst
Alcohol.At present, the production method of external generation methyl alcohol 80% uses natural gas unstripped gas synthesizing methanol, it is domestic also have be with coal
Raw material methyl alcohol.
The content of the invention
The present invention provides a kind of method and system of new synthesizing methanol, can more convenient synthesizing methanol.
A kind of first aspect according to embodiments of the present invention, there is provided method of new synthesizing methanol, including：
Methyl alcohol and vapor are blended in generation hydrogen as the molecular hydrogen of seed of being reformed under catalyst；
By the molecular hydrogen, adsorption-decomposition function is hydrogen atom or hydrogen ion under hydrogenation catalyst effect；
The vapor is caused that hydrone is broken down into the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Hydrogen molecule and oxygen molecule, hydrogen molecule are combined generation hydrogen with hydrogen atom or hydrogen ion；
The hydrogenation of carbon dioxide gas of input is downconverted into carbon monoxide in hydrogenation catalyst effect；
Setting ratio is pressed in catalst for synthesis of methanol by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
The lower synthesizing methanol of effect.
Optionally, it is described to synthesize by setting ratio by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
The lower synthesizing methanol of catalyst for methanol effect includes：
The carbon monoxide and hydrogen are pressed 1:2 ratios synthesizing methanol under catalst for synthesis of methanol effect；Or,
The carbon dioxide and hydrogen are pressed 1:3 ratios synthesizing methanol under catalst for synthesis of methanol effect.
Optionally, the vapor is caused into hydrone quilt with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Being decomposed into hydrogen molecule and oxygen molecule includes：
The vapor is caused that hydrone is broken down into 1 with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Individual hydrogen molecule and 1 oxygen molecule, wherein 1 hydrogen molecule is combined 2 hydrogen molecules of generation with 2 hydrogen atoms.
Second aspect according to embodiments of the present invention, there is provided a kind of system of new synthesizing methanol, including methanol steam
The sub- hydrogen reactor of the reformation production of hybrid seeds, hydrogenation reactor, methanol synthesis reactor；
The wherein described sub- hydrogen reactor of the Methanol cluster production of hybrid seeds, for methyl alcohol and vapor to be blended under catalyst
Reformation generates molecular hydrogen of the hydrogen as seed；
The hydrogenation reactor, for adsorption-decomposition function to be hydrogen atom or hydrogen under hydrogenation catalyst effect by the molecular hydrogen
Ion；The vapor is caused that hydrone is broken down into hydrogen point with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Son and oxygen molecule, hydrogen molecule are combined generation hydrogen with hydrogen atom or hydrogen ion；The hydrogenation of carbon dioxide gas of input is urged in hydrogenation
Agent effect is downconverted into carbon monoxide；
The methanol synthesis reactor, for by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen by setting
Certainty ratio synthesizing methanol under catalst for synthesis of methanol effect.
Optionally, the carbon monoxide and hydrogen are pressed 1 by the methanol synthesis reactor:2 ratios are catalyzed in synthesizing methanol
The lower synthesizing methanol of agent effect；Or, the carbon dioxide and hydrogen are pressed into 1:3 ratios synthesize first under catalst for synthesis of methanol effect
Alcohol.
From above-mentioned technical proposal as can be seen that the method for the present invention, methyl alcohol and vapor is blended under catalyst and is reformed
Generate molecular hydrogen of the hydrogen as seed；By the molecular hydrogen under hydrogenation catalyst effect adsorption-decomposition function be hydrogen atom or hydrogen from
Son；The vapor is caused that hydrone is broken down into hydrogen molecule with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
And oxygen molecule, hydrogen molecule is combined with hydrogen atom or hydrogen ion generates hydrogen；The hydrogenation of carbon dioxide gas that will be input into is in hydrogenating catalytic
Agent effect is downconverted into carbon monoxide；Finally compare by setting by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
Example synthesizing methanol under catalst for synthesis of methanol effect, it is thus more convenient to realize a kind of new synthesizing methanol method,
Cost is lower, reusable edible, with more economic worth.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Below in conjunction with accompanying drawing, the present invention will be further described, in accompanying drawing：
Fig. 1 is the schematic flow sheet of the method for new synthesizing methanol of the invention；
Fig. 2 is the schematic diagram of technological process first of the method for new synthesizing methanol of the invention；
Fig. 3 is the schematic diagram of technological process second of the method for new synthesizing methanol of the invention；
Fig. 4 is the first schematic diagram of the structure of the system of new synthesizing methanol of the invention；
Fig. 5 is the second schematic diagram of the structure of the system of new synthesizing methanol of the invention.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is all other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
It will be appreciated that though various information, but this may be described using term first, second, third, etc. in the present invention
A little information should not necessarily be limited by these terms.These terms are only used for being distinguished from each other open same type of information.For example, not departing from
In the case of the scope of the invention, the first information can also be referred to as the second information, and similarly, the second information can also be referred to as
One information.Depending on linguistic context, word as used in this " if " can be construed to " ... when " or " when ...
When " or " in response to determining ".
The present invention provides a kind of method and system of new synthesizing methanol, can more convenient synthesizing methanol.
Fig. 1 is the schematic flow sheet of the method for new synthesizing methanol of the invention, including：
In a step 101, methyl alcohol and vapor are blended in generation hydrogen as the molecular hydrogen of seed of being reformed under catalyst；
In a step 102, by the molecular hydrogen, adsorption-decomposition function is hydrogen atom or hydrogen ion under hydrogenation catalyst effect；
In step 103, the vapor is caused into water with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Molecule is broken down into hydrogen molecule and oxygen molecule, and hydrogen molecule is combined generation hydrogen with hydrogen atom or hydrogen ion；
At step 104, the hydrogenation of carbon dioxide gas of input is downconverted into carbon monoxide in hydrogenation catalyst effect；
In step 105, closed by setting ratio by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
Into the lower synthesizing methanol of catalyst for methanol effect.
In the present invention, a kind of new synthesizing methanol method is that life is decomposed under hydrogenation catalyst as seed hydrogen using hydrogen
Into atomic hydrogen or ionic hydrogen.Vapor and atomic hydrogen or ionic hydrogen the hydrone H under catalyst2O be broken down into 1 hydrogen molecule and
1 oxygen molecule.1 hydrogen molecule is combined 2 hydrogen molecules of generation with 2 hydrogen atoms.In the presence of 1 seed hydrogen catalyst, water
Molecule H2O is decomposed out hydrogen molecule and oxygen molecule, and water becomes hydrogen is increased the quantity of hydrogen.1 seed hydrogen can generate 2 molecules
Hydrogen, 2 seed hydrogen can generate 4 molecular hydrogens, and so on, the quantity for increasing seed hydrogen can just increase by 1 times of hydrogen of quantity.Such as
This analogizes, and the quantity of hydrogen is increased, hydrogen as synthesizing methanol one of raw material.The carbon dioxide of outside input becomes under catalyst
It is changed to CO.Carbon monoxide and partial CO 2 hydrogenation on catalst for synthesis of methanol can with synthetic fluid methyl alcohol and reaction water,
, used as product methyl alcohol, second half hydrogen from methyl alcohol is used as seed hydrogen and CO for half methyl alcohol2Hydrogenation presses chemical equation synthesizing methanol product
Product.
A kind of new synthesizing methanol method of the present invention, is mainly blended in generation hydrogen of being reformed under catalyst using methyl alcohol and water
Gas as seed molecular hydrogen.Reaction equation：
Molecular hydrogen adsorption-decomposition function on hydrogenation catalyst is hydrogen atom or hydrogen ion.Reaction equation：
Meanwhile, vapor and hydrogen atom or hydrogen ion the hydrone 3H on hydrogenation catalyst2O is broken down into hydrogen molecule 3H2With
3O oxygen molecules, hydrogen molecule is combined generation 6H with hydrogen atom or hydrogen ion2, the quantity of hydrogen molecule is increased by one times.Reaction equation：
The CO of outside input2Hydrogenation is in hydrogenation catalyst up conversion into CO, reaction equation：
CO and 2H2Or CO2+3H2Compare 1 by CH:2 or 1:3 on catalst for synthesis of methanol synthesizing methanol.Reaction equation：
Methanol product half, as seed hydrogen, can be recycled as reaction equation (1-1) raw material hydrogen, second half work
It is methanol product to being refined into chemical products.
During the course of the reaction, the carbon dioxide and water of consumption of raw materials, output product is chemical products.
Shown in process chart reference picture 2 and Fig. 3, wherein Fig. 2 is the technique of the method for new synthesizing methanol of the invention
The schematic diagram of flow first；Fig. 3 is the schematic diagram of technological process second of the method for new synthesizing methanol of the invention.
Seed hydrogen 3H24H is generated in hydrogenation reactor2, outside carbon dioxide generates 2CO in hydrogenation reactor.4H2+
2CO synthesizes 2CH into methanol synthesis reactor in reactor3OH, liquid methanol is gone out through cooling down into gas-liquid separator separates
Enter hydrogenation reactor through compressor pressurized circulation with unreacting gas.Liquid methanol half is produced in steam reforming reaction device
Seed hydrogen 3H2, second half is used as product methyl alcohol.In course of reaction, consumption of raw materials is carbon dioxide and desalted water.
Technology data of the invention：
1st, the sub- hydrogen of the methanol steam reforming production of hybrid seeds
Raw material：
(1) methyl alcohol 0.58t
2nd, hydrogenation
(3) carbon dioxide
3rd, synthesizing methanol reaction
A kind of above-mentioned method of new synthesizing methanol of the invention in detail, a kind of new synthesizing methanol introduced below is
System.
A kind of system of new synthesizing methanol of the present invention, including the sub- hydrogen reactor of the Methanol cluster production of hybrid seeds, hydrogenation are instead
Answer device, methanol synthesis reactor.
Fig. 4 is the first schematic diagram of the structure of the system of new synthesizing methanol of the invention, and Fig. 5 is new conjunction of the invention
Into the second schematic diagram of the structure of the system of methyl alcohol, the composition of the more detailed display systems of Fig. 5 is constructed.
Reference picture 4, a kind of system of new synthesizing methanol, including the sub- hydrogen reactor 401, hydrogen of the Methanol cluster production of hybrid seeds
Change reactor 402, methanol synthesis reactor 403.
The wherein described sub- hydrogen reactor 401 of the Methanol cluster production of hybrid seeds, for methyl alcohol and vapor to be blended in into catalysis
Reformation generates molecular hydrogen of the hydrogen as seed under agent；
The hydrogenation reactor 402, for adsorption-decomposition function to be hydrogen atom under hydrogenation catalyst effect by the molecular hydrogen
Or hydrogen ion；The vapor is caused that hydrone is broken down into the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Hydrogen molecule and oxygen molecule, hydrogen molecule are combined generation hydrogen with hydrogen atom or hydrogen ion；The hydrogenation of carbon dioxide gas that will be input into is in hydrogen
Change catalyst action and be downconverted into carbon monoxide；
The methanol synthesis reactor 403, for by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
By setting ratio catalst for synthesis of methanol effect under synthesizing methanol.
Reference picture 5, during reaction, heat is produced by an outside heat-conducting oil furnace, and methyl alcohol is transferred heat to by conduction oil
The sub- hydrogen reactor 1 of the steam reformation production of hybrid seeds, hydrogenation reactor 2, methanol synthesis reactor 3, heater 4, evaporator 5, superheater
6th, heater 7, conduction oil circulation makes reaction temperature between 225 DEG C -250 DEG C of ＞.
(1) methyl alcohol and aqueous mixtures enter first by measuring pump 8, heat exchanger 9 by heater 4, evaporator 5, superheater 6
The sub- hydrogen reactor 1 of the alcohol steam reformation production of hybrid seeds, methanol steam is changed into 3H inside reactor 1 under catalyst action2Point
Sub- hydrogen, molecular hydrogen kind is that initial seed hydrogen and vapor etc. enter hydrogenation reactor and inside reactor from reactor outlet
React the molecular hydrogen for generating a times on catalyst.
(2) by the carbon dioxide raw material of outside input by heater 7 urging into hydrogenation reactor 2 and inside reactor
React generation carbon monoxide in agent.
Carbon monoxide and molecule hydrogen mixed gas are exported by reactor 2 and enter gas-liquid through heat exchanger 9, cooler 10,11
Separator 12, gas tank 13, gas enter air accumulator 15 through the pressurization of compressor 14, and gas passes through electric superheater 16, into synthesis first
Alcohol reactor 3, under conditions of >=5MPa, 250 DEG C, carbon monoxide and hydrogen are synthesized methyl alcohol to pressure, and methanol steam is from reactor 3
Outlet is decompressed to 0.5Mpa into heat exchanger 9, cooler 10,11, gas-liquid separator 12 through pressure reducer 17, isolates liquid first
Alcohol and unreacting gas, unreacting gas are compressed to be back to reactor 3, so circulation.
Methyl alcohol half is isolated for doing the sub- hydrogen feedstock of the methanol steam production of hybrid seeds from the bottom of gas-liquid separator 12, and second half does
It is methanol product.The carbon dioxide and water being input into course of reaction, output is methanol product.
From above-mentioned technical proposal as can be seen that the method for the present invention, methyl alcohol and vapor is blended under catalyst and is reformed
Generate molecular hydrogen of the hydrogen as seed；By the molecular hydrogen under hydrogenation catalyst effect adsorption-decomposition function be hydrogen atom or hydrogen from
Son；The vapor is caused that hydrone is broken down into hydrogen molecule with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
And oxygen molecule, hydrogen molecule is combined with hydrogen atom or hydrogen ion generates hydrogen；The hydrogenation of carbon dioxide gas that will be input into is in hydrogenating catalytic
Agent effect is downconverted into carbon monoxide；Finally compare by setting by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
Example synthesizing methanol, the thus more convenient method for realizing new synthesizing methanol, cost under catalst for synthesis of methanol effect
It is lower, reusable edible, with more economic worth.
In sum, a kind of method and system of new synthesizing methanol of the present invention, its technical characterstic is that methanol steam is urged
Change reformation hydrogen production is seed hydrogen, and seed hydrogen and water vapour hydrogenation reactor generate one times of hydrogen, is carbon dioxide generation methyl alcohol
There is provided enough hydrogen, seed hydrogen participates in reaction generation methanol fractions as recycling, without outside input hydrogen feedstock or
Methanol feedstock.
The function of unit and the implementation process of effect correspond to step in specifically referring to the above method in said apparatus
Implementation process, will not be repeated here.
For device embodiment, because it corresponds essentially to embodiment of the method, so related part is referring to method reality
Apply the part explanation of example.Device embodiment described above is only schematical, wherein described as separating component
The unit of explanation can be or may not be physically separate, and the part shown as unit can be or can also
It is not physical location, you can with positioned at a place, or can also be distributed on multiple NEs.Can be according to reality
Selection some or all of module therein is needed to realize the purpose of the present invention program.Those of ordinary skill in the art are not paying
In the case of going out creative work, you can to understand and implement.
The technical scheme for being provided the embodiment of the present invention above, is described in detail, used herein specifically individual
Example is set forth to principle of the invention and implementation method, and the explanation of above example is only intended to help and understands of the invention
Method and its core concept；Simultaneously for those of ordinary skill in the art, according to thought of the invention, in specific embodiment party
Be will change in formula and range of application, in sum, this specification content should not be construed as limiting the invention.
Claims (5)
1. a kind of method of new synthesizing methanol, it is characterised in that including：
Methyl alcohol and vapor are blended in generation hydrogen as the molecular hydrogen of seed of being reformed under catalyst；
By the molecular hydrogen, adsorption-decomposition function is hydrogen atom or hydrogen ion under hydrogenation catalyst effect；
The vapor is caused that hydrone is broken down into hydrogen point with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Son and oxygen molecule, hydrogen molecule are combined generation hydrogen with hydrogen atom or hydrogen ion；
The hydrogenation of carbon dioxide gas of input is downconverted into carbon monoxide in hydrogenation catalyst effect；
Acted in catalst for synthesis of methanol by setting ratio by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
Lower synthesizing methanol.
2. method according to claim 1, it is characterised in that：
It is described to press setting ratio in catalst for synthesis of methanol by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
The lower synthesizing methanol of effect includes：
The carbon monoxide and hydrogen are pressed 1:2 ratios synthesizing methanol under catalst for synthesis of methanol effect；Or,
The carbon dioxide and hydrogen are pressed 1:3 ratios synthesizing methanol under catalst for synthesis of methanol effect.
3. method according to claim 1, it is characterised in that：
The vapor is caused that hydrone is broken down into hydrogen point with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Son and oxygen molecule include：
The vapor is caused that hydrone is broken down into 1 hydrogen with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
Molecule and 1 oxygen molecule, wherein 1 hydrogen molecule is combined 2 hydrogen molecules of generation with 2 hydrogen atoms.
4. a kind of system of new synthesizing methanol, it is characterised in that：
Including the sub- hydrogen reactor of the Methanol cluster production of hybrid seeds, hydrogenation reactor, methanol synthesis reactor；
The wherein described sub- hydrogen reactor of the Methanol cluster production of hybrid seeds, reforms for methyl alcohol and vapor to be blended under catalyst
Generate molecular hydrogen of the hydrogen as seed；
The hydrogenation reactor, for by the molecular hydrogen under hydrogenation catalyst effect adsorption-decomposition function be hydrogen atom or hydrogen from
Son；The vapor is caused that hydrone is broken down into hydrogen molecule with the hydrogen atom or hydrogen ion under hydrogenation catalyst effect
And oxygen molecule, hydrogen molecule is combined with hydrogen atom or hydrogen ion generates hydrogen；The hydrogenation of carbon dioxide gas that will be input into is in hydrogenating catalytic
Agent effect is downconverted into carbon monoxide；
The methanol synthesis reactor, for comparing by setting by the carbon monoxide and hydrogen or by the carbon dioxide and hydrogen
Example synthesizing methanol under catalst for synthesis of methanol effect.
5. system according to claim 1, it is characterised in that：
The carbon monoxide and hydrogen are pressed 1 by the methanol synthesis reactor:2 ratios synthesize under catalst for synthesis of methanol effect
Methyl alcohol；Or,
The carbon dioxide and hydrogen are pressed 1:3 ratios synthesizing methanol under catalst for synthesis of methanol effect.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112645797A (en) * | 2019-10-12 | 2021-04-13 | 中石化南京化工研究院有限公司 | Process for synthesizing methanol from carbon dioxide-carbon-water |
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Application publication date: 20170630 |