CN109503310A - A kind of technique of natural gas preparation high concentration acetylene and hydrogen - Google Patents
A kind of technique of natural gas preparation high concentration acetylene and hydrogen Download PDFInfo
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- CN109503310A CN109503310A CN201811456721.8A CN201811456721A CN109503310A CN 109503310 A CN109503310 A CN 109503310A CN 201811456721 A CN201811456721 A CN 201811456721A CN 109503310 A CN109503310 A CN 109503310A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/80—Processes with the aid of electrical means
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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
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
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Abstract
The present invention provides the technique of a kind of natural gas preparation high concentration acetylene and hydrogen, belongs to acetylene preparation technical field.Include: that hydrogen 1) is passed through plasma cracking reactor, forms hot environment, then pass to methane gas, acetylene and by-product are obtained after Pintsch process and rapid cooling；2) product gas is passed sequentially through into cyclone separator, bag filter, scrubbing tower and electric precipitator slough carbon black；3) gas for sloughing carbon black enters weight-removing column, and the gas after weight-removing column absorbs enters absorption tower, and solvent enters desorber；4) fixed gas after absorption tower absorbs obtains the hydrogen of high-purity through membrane separation, and the solvent for absorbing acetylene gas enters the desorption of product tower, and acetylene gas product is taken out in the tower middle and upper part of product tower, and overhead gas is recycled back to absorption tower.Present invention process process is succinct, process is short, safe and reliable, non-environmental-pollution, low energy consumption, may be directly applied to industrialized production.
Description
Technical field
The invention belongs to acetylene preparation technical field, specially a kind of work of natural gas preparation high concentration acetylene and hydrogen
Skill.
Background technique
Acetylene is the important source material of Organic Chemical Industry, be widely used in produce 1,4-butanediol, vinyl chloride, acetylene black,
The chemicals such as neoprene, butanediol, butynediols, tetrahydrofuran and cyclo-octatetraene.
The production technology of acetylene has carbide, gas by partial oxidation of natural method, arc process and plasma pyrolysis method.Calcium carbide
Method is the earliest method of synthesis acetylene, while being also the highest method of technical maturity.This method needs to build huge calcium carbide
Furnace, energy consumption is high, and water consumption is big, and pollution is big, every production 1t acetylene, needs to consume 30~60t water, generates 2.6t calcium carbide waste slag, electricity
Stone waste residue is difficult to handle, and causes huge environmental protection pressure to the environment in enterprise location.Currently, in developed country's acetylene from calcium carbide
Technology is already replaced gas by partial oxidation of natural acetylene technology.But the acetylene production capacity of 95% or more the country also comes from
Carbide, only on a small quantity using natural gas oxidizing process.
Gas by partial oxidation of natural method is better than carbide in environmental protection, but the shortcomings that also have itself.Gas by partial oxidation of natural
Method has oxygen to participate in reaction, has a large amount of CO and H in the cracking gas of generation2, auxiliary construction methanol synthesizer is needed, is increased
Process flow.Due to the presence of oxygen, it is necessary to increase antiknock device, improve the expense of separating-purifying, increase cost.
Preparation of acetylene by cracking natural gas with plasma method has investment small, and production cost is low, and raw material availability is high, cracked gas
It can be easily separated, the features such as process flow is simple, and production safety is reliable, non-environmental-pollution, it is better than existing in technology, economic aspects
Some carbides, natural gas electrocracking method and partial oxidation process.The every production 1t acetylene of gas by partial oxidation of natural method needs to consume
6000m3Natural gas, and plasma pyrolysis method only needs about 2000m3Natural gas, raw material availability are higher.At abroad, the U.S. and
Germany all has ever done the research of plasma pyrolysis acetylene, and German ISP company has built up the natural gas etc. of a set of 3000t/a
The industrialized unit of ion system acetylene.The organic institute in domestic Chinese Academy of Sciences Chengdu, Sichuan University, Tsinghua University, metal institute, the Chinese Academy of Sciences
Also the research work of plasma pyrolysis acetylene unit and technique was once done, but domestic full-range energy a set of not yet is real
Existing industrialized device.
Summary of the invention
It is an object of the invention to propose a kind of technique by natural gas preparing high-purity acetylene and hydrogen, present invention process ratio
Traditional calcium carbide legal system acetylene is more environmentally friendly, and is different from the technique of coal as raw material acetylene.Present invention process process is succinct, flows
Journey is short, can be realized using existing conventional equipment, industrialized production may be implemented.
The object of the invention is achieved through the following technical solutions:
A kind of technique of natural gas preparation high concentration acetylene and hydrogen, the technique are as follows:
1) hydrogen is passed through plasma cracking reactor, forms hot environment, methane gas is then passed to, by high anneal crack
Acetylene and by-product are obtained after solution and rapid cooling；
2) product gas is passed sequentially through into cyclone separator, bag filter, scrubbing tower and electric precipitator slough carbon black；
3) gas for sloughing carbon black enters weight-removing column, and the gas after weight-removing column absorbs enters absorption tower, and solvent enters solution
Inhale tower；
4) fixed gas after absorption tower absorbs obtains the hydrogen of high-purity through membrane separation, absorbs the molten of acetylene gas
Agent enters the desorption of product tower, and acetylene gas product is taken out in the tower middle and upper part of product tower, and overhead gas is recycled back to absorption tower.
Cyclone separator realizes gas solid separation using the gas principle different with carbon black density of solid, can remove about half
Carbon black removes thinner particle then using bag filter.Carbon black is less in gas at this time, and particle also very little passes through
The mode of electric precipitation and washing can almost remove whole carbon blacks.First removing the purpose of carbon black is that carbon black is mentioned in back segment in order to prevent
Enter in solvent in dense process, solvent slop, increases solvent consumption, so must remove in advance.
Remove carbon black gas in 80% or so hydrogen, 9% or so acetylene, 1.2% higher alkyne and methane
Equal gases.Gas initially enters weight-removing column, the removing of weight-removing column be 1.2% or so higher alkyne, utilize higher alkyne, second
The different principles of alkynes solubility in a solvent separate.Solvent used in weight-removing column is N-Methyl pyrrolidone, kerosene, water etc.
One or more of, for acetylene and higher alkyne selective dissolution ratio up to 10 times or more, reduce solvent recovery workshop section
The consumption of solvent, average 1 ton of acetylene of every production only consume solvent 3kg.
Removing higher alkyne is a step of the deimpurity second step of acetylene and most critical in cracking gas, because of advanced alkynes
Hydrocarbon is easy polymerization, if higher alkyne removing is not clean, will be absorbed together tower solvent absorption with acetylene in absorption tower, increase
Big product tower circulating flow rate and energy consumption, and product tower desorption temperature is high, is easier to polymerize under higher alkyne high temperature, causes to produce
Consumption is bigger when solvent recovery in product tower.And the lower higher alkyne of solubility, reduced second can be mixed in acetylene product
The purity of alkynes.
Gas into absorption tower is mainly fixed gas hydrogen, methane gas and acetylene gas.Since hydrogen and methane are molten
Solubility in agent is very low, so, what is dissolved in solvent is nearly all acetylene, and the solvent for having dissolved acetylene enters back into product tower
Heating desorption obtains the acetylene product of high-purity.
Further, it is desorbed at the heating temperature into the solvent of desorber, while with the fixed gas after UF membrane from tower bottom
It is purged, removes the higher alkyne in solvent.Desorber be fixed gas purge and heat by way of remove it is molten in solvent
The higher alkyne of solution, the higher alkyne desorbed is burned as tail gas or other modes processing, molten after removing higher alkyne
Agent can be recycled.It is purged using fixed gas, steam use can be reduced in higher alkyne desorber, is carried using gas
Mode, take partial higher alkynes out of.Membrane separation technique is, the mode of approximation filtering different according to different material molecular size
The hydrogen of high-purity is obtained, the mode of pressure-variable adsorption can also obtain eminence degree hydrogen, meeting during continuous pressurization decompression
Energy consumption can also be reduced using membrane separation technique by consuming energy.
Further, the hydrogen portion for obtaining high-purity through UF membrane is recycled back to plasma cracking reactor as unstripped gas
Body, it is partially recycled to be used as product.
Further, the by-product includes ethylene, allene, diacetylene, allylene and carbon black.
Further, the plasma pyrolysis temperature is 1200~2500 DEG C, plasma cracking reactor outlet cooling
Temperature is 60~150 DEG C.
Further, the molar ratio of the methane and hydrogen is 1:1~1:3.
Further, after electric precipitation is handled, the content of carbon black is lower than 0.5mg/Nm in gas3。
Further, the weight-removing column, solvent used in absorption tower are one in N-Methyl pyrrolidone, kerosene, water etc.
Kind is several.Section is removed in higher alkyne and acetylene concentration section selects above-mentioned solvent, can be reduced the consumption of solvent, be reduced product
The concentration of the middle-and-high-ranking alkynes of acetylene improves the quality of product acetylene, meets requirement of the different acetylene downstream product to purity acetylene.
Above-mentioned solvent is selected, solvent consumption can be reduced to 3kg or so from 7kg by 1 ton of acetylene of every production, advanced in acetylene product
Alkynes is reduced to 0.015% or so from 0.5% or so.
Further, the fixed gas that the absorption tower comes out obtains the hydrogen of purity > 99.9% by UF membrane.
Further, it is 10~25 DEG C that the weight-removing column, which absorbs temperature, and desorber desorption temperature is 50~80 DEG C, and absorption tower is inhaled
Shrinkage temperature is 15~30 DEG C, and product tower desorption temperature is 110~130 DEG C.
Compared with prior art, the invention has the following advantages:
This technique uses natural gas for raw material, and raw material methane content is high, and cleaning, no solid impurity brings reaction system into, can
The case where being the gummy solid coking agglomeration at high temperature that raw material is brought into avoid coal, blocking reactor.In addition high selection is used
Property solvent, high concentration acetylene is obtained by rationally succinct process flow, acetylene yield reaches 98% or more, and purity reaches
99.85% or more, while high concentration hydrogen is obtained by straightforward procedure, hydrogen purity can achieve 99.9%.Using fixed gas
Purging can reduce steam use in higher alkyne desorber, in the way of gas carrying, take partial higher alkynes out of.
Membrane separation technique is according to different material molecular size difference, and the mode of approximation filtering obtains the hydrogen of high-purity, reduces simultaneously
Energy consumption, the mode of pressure-variable adsorption can also obtain eminence degree hydrogen, but can consume energy during continuous pressurization decompression.This
Technical process is succinct, process is short, safe and reliable, non-environmental-pollution, low energy consumption, may be directly applied to industrialized production.
Detailed description of the invention
Fig. 1 is the process flow diagram that natural gas of the present invention prepares high concentration acetylene and hydrogen.
Appended drawing reference: 1- plasma cracking reactor, 2- cyclone separator, 3- bag filter, 4- scrubbing tower, 5- electricity
Deduster, 6- weight-removing column, 7- desorber, the absorption tower 8-, 9- product tower, 10- membrane separator.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
The process flow of this present embodiment as shown in Figure 1, natural gas or high methane gas and working gas hydrogen enter etc. from
Daughter cracking reactor 1, reaction temperature are 1500 DEG C, and exit is cooled to 80 DEG C with cooling water, and gas after cooling enters rotation
Wind separator 2, bag filter 3, scrubbing tower 4, electric precipitator 5 remove carbon black.Then gas enters weight-removing column 6, with 10 DEG C
Kerosene absorbs higher alkyne, and the gas after kerosene absorbs enters absorption tower 8, is inhaled with 15 DEG C of N-Methyl pyrrolidones and aqueous solvent
The gases such as the acetylene in getter body.Kerosene solvent after absorbing higher alkyne enters desorber 7, solves under 50 DEG C of heating temperature
It inhales, while being purged with the fixed gas after UF membrane from tower bottom, remove the higher alkyne in kerosene.After absorption tower absorbs
Fixed gas enters film separation system 10, separates the high-purity hydrogen of acquisition, is partially recycled back to reactor 1 as working gas, part
It can recycle and be sold as product.The N-Methyl pyrrolidone aqueous solvent of the gases such as acetylene is absorbed, into product tower 9,110
It is desorbed at DEG C, takes out acetylene gas product in tower middle and upper part, the gas that tower top contains a large amount of acetylene is recycled back to absorption tower 8.Methane
Conversion per pass 70%, selective acetylene 85%, acetylene concentration yield 99%, purity acetylene 99.88%, hydrogen purity are
99.9%.1 ton of acetylene of every production, solvent consumption 3kg.
Embodiment 2
Reaction temperature in embodiment 1 is become 1800 DEG C, outlet cooling temperature becomes 150 DEG C, and weight-removing column solvent is changed to
N-Methyl pyrrolidone, absorbing temperature is 25 DEG C.Desorber temperature is changed to 80 DEG C, and absorption tower temperature is changed to 30 DEG C, product tower solution
It inhales temperature and is changed to 130 DEG C, methane conversion per pass 70%, selective acetylene 80%, acetylene concentration yield 98%, purity acetylene is
99.2%, hydrogen purity 99.9%.1 ton of acetylene of every production, solvent consumption 7kg.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of technique of natural gas preparation high concentration acetylene and hydrogen, which is characterized in that the technique is as follows:
1) hydrogen is passed through plasma cracking reactor, forms hot environment, then pass to methane gas, by Pintsch process and
Acetylene and by-product are obtained after rapid cooling；
2) product gas is passed sequentially through into cyclone separator, bag filter, scrubbing tower and electric precipitator slough carbon black；
3) gas for sloughing carbon black enters weight-removing column, and the gas after weight-removing column absorbs enters absorption tower, and solvent enters desorber；
4) fixed gas after absorption tower absorbs obtains the hydrogen of high-purity through membrane separation, absorb the solvent of acetylene gas into
Enter the desorption of product tower, acetylene gas product is taken out in the tower middle and upper part of product tower, and overhead gas is recycled back to absorption tower.
2. a kind of technique of natural gas preparation high concentration acetylene and hydrogen as described in claim 1, which is characterized in that enter desorption
The solvent of tower desorbs at the heating temperature, while being purged with the fixed gas after UF membrane from tower bottom, and the height in solvent is removed
Grade alkynes.
3. a kind of technique of natural gas preparation high concentration acetylene and hydrogen as described in claim 1, which is characterized in that through UF membrane
The hydrogen portion for obtaining high-purity is recycled back to plasma cracking reactor as unstrpped gas, partially recycled as product.
4. a kind of technique of natural gas preparation high concentration acetylene and hydrogen as described in claim 1, which is characterized in that the by-product
Object includes ethylene, allene, diacetylene, allylene and carbon black.
5. the technique of a kind of preparation of natural gas high concentration acetylene and hydrogen as described in claim 1, which is characterized in that it is described it is equal from
Daughter cracking temperature is 1200~2500 DEG C, and it is 60~150 DEG C that plasma cracking reactor, which exports cooling temperature,.
6. a kind of technique of natural gas preparation high concentration acetylene and hydrogen as described in claim 1, which is characterized in that the methane
Molar ratio with hydrogen is 1:1~1:3.
7. a kind of technique of natural gas preparation high concentration acetylene and hydrogen as described in claim 1, which is characterized in that through electric precipitation
After processing, the content of carbon black is lower than 0.5mg/Nm in gas3。
8. a kind of technique of natural gas preparation high concentration acetylene and hydrogen as described in claim 1, which is characterized in that the de- weight
Solvent used in tower, absorption tower is one or more of N-Methyl pyrrolidone, kerosene, water etc..
9. a kind of technique of natural gas preparation high concentration acetylene and hydrogen as described in claim 1, which is characterized in that the absorption
The fixed gas that tower comes out obtains the hydrogen of purity > 99.9% by UF membrane.
10. a kind of technique of natural gas preparation high concentration acetylene and hydrogen as described in claim 1, which is characterized in that described de-
It is 10~25 DEG C that weight tower, which absorbs temperature, and desorber desorption temperature is 50~80 DEG C, and it is 15~30 DEG C that absorption tower, which absorbs temperature, product
Tower desorption temperature is 110~130 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118515238A (en) * | 2024-07-23 | 2024-08-20 | 北京琪玥环保科技股份有限公司 | Process and system for preparing conductive carbon nanomaterial and hydrogen by cracking methane by using plasma |
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Cited By (1)
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