CN106672898A - Method for synthesizing ammonia by taking byproduct tail gas in process of producing acetylene by pyrolyzing natural gas as raw material - Google Patents
Method for synthesizing ammonia by taking byproduct tail gas in process of producing acetylene by pyrolyzing natural gas as raw material Download PDFInfo
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- CN106672898A CN106672898A CN201710031681.1A CN201710031681A CN106672898A CN 106672898 A CN106672898 A CN 106672898A CN 201710031681 A CN201710031681 A CN 201710031681A CN 106672898 A CN106672898 A CN 106672898A
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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
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
Abstract
The invention discloses a method for synthesizing ammonia by taking byproduct tail gas in a process of producing acetylene by pyrolyzing natural gas as a raw material. The method comprises the following steps: step S1, carrying out a tail gas purification procedure, wherein the content of hydrogen in purification raw material gas is 99.0 percent or more; step S2, carrying out a methanation procedure and forming ammonia synthetic gas by the purified raw material gas in the step S1 and nitrogen gas; enabling the sum of the content of carbon monoxide and carbon dioxide in qualified synthetic gas to be smaller than 10ppm; step S3, carrying out an ammonia synthesis procedure: conveying the qualified synthetic gas in the step S2 into the ammonia synthesis procedure, so as to prepare the ammonia. According to the method disclosed by the invention, a purification method is adopted and pure hydrogen gas is directly extracted from byproduct tail gas; the pure hydrogen gas is used as raw material gas of the ammonia synthesis procedure, so that the method can be adaptive to application of synthesizing the ammonia by the byproduct tail gas with low methane content. The byproduct tail gas in the process of producing the acetylene by pyrolyzing the natural gas is utilized and a pollution problem, caused by byproduct tail gas emission, to the environment is avoided; reutilization of energy sources are also realized; the method has very good demonstration and popularization effects.
Description
Technical field
The present invention relates to the technical field of ammonia synthesis technology, and in particular to a kind of by-product tail with natural gas pyrolysis acetylene
Gas is the method for Material synthesis ammonia.
Background technology
Industrial conventional acetylene preparation method has carbide and natural gas pyrolysis method, on the ground that natural gas resource enriches
Area, using natural gas pyrolysis acetylene ratio the more economical environmental protection of carbide legal system acetylene is adopted.Can be produced by natural gas pyrolysis acetylene
Substantial amounts of by-product tail gas, by-product exhaust gas component is complex, if by-product tail gas is directly discharged, on the one hand can cause the wave of the energy
Take, still further aspect can also destroy ecological environment.
Synthesis ammonia technique be generally adopted by with coal or natural gas as raw material, by coal gasification or natural gas conversion so as to
Prepared synthesis gas, synthesis gas is obtained liquefied ammonia after purification, synthesis.If but the by-product tail gas for producing acetylene with natural gas pyrolysis
To produce ammonia, because the content of methane in the by-product tail gas only has 2.7%, therefore the work that ammonia is produced with coal can neither be suitable for
Skill, can not be suitable for the technique of production of ammonia natural gas.Due in natural gas as the technique of Material synthesis ammonia, raw hydrogen
Generate via conversion reaction and vapor for methane, if the by-product tail gas is adopted with the technique of production of ammonia natural gas, device
Cost of investment is high, and the cost of overall production process is also very high.
Therefore, if ammonia can will be synthesized as raw material using the by-product tail gas of natural gas pyrolysis acetylene, tail gas can be solved
The problem of discharge, can also solve the problems, such as ammonia synthesis, with extraordinary economic benefit, factory's tool of PVC be produced to acetylene method
There are demonstration and popularizing action.
The content of the invention
It is an object of the invention to provide a kind of side of by-product tail gas with natural gas pyrolysis acetylene as Material synthesis ammonia
Method, for solving the problems, such as the insoluble problem of by-product exhaust emissions of existing natural gas pyrolysis acetylene.
To achieve these goals, the present invention provides following technical scheme：A kind of by-product with natural gas pyrolysis acetylene
Tail gas is the method for Material synthesis ammonia, comprises the steps：
Step S1 tail gas clean-up operation：
By the by-product tail gas of natural gas pyrolysis acetylene sequentially pass through desulfurization-hydrogenation operation, shift conversion step, decarbonization process and
Pressure swing adsorption hydrogen production operation, formed purification unstripped gas, the hydrogen volume percentage composition in the purification unstripped gas be 99.0% with
On；
Step S2 methanation operation：
Purification unstripped gas in step S1 is obtained into qualified hydrogen via methanation reaction；Step S3 synthetic ammonia process：
Qualified hydrogen and nitrogen in step S2 is transported in ammonia synthesis operation, ammonia is produced.
Preferably, nitrogen obtained in the space division is entered by the entrance of step S2 methanation operation, is pressed with qualified hydrogen
It is 1 according to the ratio of the amount of material：2.75~3.20 are mixed to form ammonia synthesis gas, and are transported in synthetic ammonia process.
Preferably, the ammonia synthesis gas obtains qualified synthesis gas after the process of step S2 methanation operation, described qualified
In synthesis gas, the content sum of carbon monoxide and carbon dioxide is less than 10ppm.
Specifically, the step S1 tail gas clean-up operation comprises the steps：
(a) desulfurization-hydrogenation operation：
Make by-product tail gas that the H in by-product tail gas is removed in the presence of desulfurizing agent2S compositions, and in the work of hydrogenation catalyst
With the lower C caused in by-product tail gas2H2And C2H4Hydrogenation becomes saturated hydrocarbons, the by-product tail gas shape Jing after the process of desulfurization-hydrogenation operation
Into the first unstripped gas, C in first unstripped gas2H2Content be below 5ppm, C in first unstripped gas2H4Content be
Below 20ppm；
(b) shift conversion step：
Make the first unstripped gas via shift conversion step to remove the first unstripped gas in CO, form the second unstripped gas, described the
In two unstripped gas, the volumn concentration of CO be 0.34% (butt) below；
(c) decarbonization process：
Make the second unstripped gas via decarbonization process to remove the second unstripped gas in CO2, form the 3rd unstripped gas, described the
In three unstripped gas, H2Volumn concentration be more than 95.4%；
(d) pressure swing adsorption hydrogen production operation：
The 3rd unstripped gas is made via pressure swing adsorption hydrogen production operation, purification unstripped gas is formed.
Preferably, the desulfurizing agent in step S1 (a) is Zinc Oxide.
Preferably, the shift conversion step in step S1 (b) becomes the low change operation of string for middle, the shift conversion step include according to
Secondary connected heating furnace, Middling Temp Shift Converter and low temperature shift converter.
Preferably, the Middling Temp Shift Converter includes the first Middling Temp Shift Converter and the second Middling Temp Shift Converter, wherein, 40~50%
First unstripped gas via heating furnace be input into the first Middling Temp Shift Converter in, 50~60% first unstripped gas is used as cold
Sharp gas is directly inputted in the second Middling Temp Shift Converter.
Preferably, waste heat recoverer is provided between second Middling Temp Shift Converter and the low temperature shift converter, it is described useless
Heat regenerator is connected by pipeline with heating furnace.
Preferably, decarbonization process is MDEA decarbonization process in step S1 (c), after decarbonization process process
High pressure flash gas is combined into tail gas clean-up operation with by-product tail gas.
Preferably, the periodic off-gases for exporting in the step S3 synthetic ammonia process are defeated from the porch of pressure swing adsorption hydrogen production operation
Enter.
Compared to prior art, the by-product tail gas with natural gas pyrolysis acetylene of the present invention is as Material synthesis ammonia
Method has the advantage that：The present invention is carefully studied based on the component to the by-product tail gas with natural gas pyrolysis acetylene, and is united
Raise and consider nitrogen balance that air separation plant is produced and the synthesis ammonia method that designs, different from the side with natural gas as Material synthesis ammonia
Method, is not adopted conversion procedure and raw hydrogen is obtained by methane, but adopts purification method, is directly extracted from by-product tail gas
Go out pure hydrogen, as the raw material of synthetic ammonia process.The present invention adapts to the by-product End gas production ammonia of low content methane
Method, realize utilizing to the by-product tail gas of natural gas pyrolysis acetylene, it is to avoid pollution problem of the by-product exhaust emissions to environment,
The recycling of the energy is also achieved simultaneously, with extraordinary economic benefit.
And method of the present invention is high to the utilization rate of hydrogen, and the long-term continuous and stable production of achievable ammonia, operation
Process is simple and safe, and the integral device investment for being adopted is low, effectively reduces the production cost of synthesis ammonia.
Description of the drawings
By the detailed description for reading hereafter preferred implementation, various other advantages and benefit is common for this area
Technical staff will be clear from understanding.Accompanying drawing is only used for illustrating the purpose of preferred implementation, and is not considered as to the present invention
Restriction.In the accompanying drawings：
Fig. 1 shows that a kind of by-product tail gas with natural gas pyrolysis acetylene of preferred implementation of the invention is closed as raw material
The flow chart of the method for ammonification；
Fig. 2 shows the flow chart of shift conversion step in Fig. 1.
Specific embodiment
The invention provides many applicable creative concepts, the creative concept can be reflected in a large number of on specific
Hereinafter.Specific embodiment described in following embodiments of the present invention is only as specific embodiment of the invention
Exemplary illustration, and be not meant to limit the scope of the invention.
Below in conjunction with the accompanying drawings the invention will be further described with specific embodiment.
As shown in figure 1, the present embodiment provides a kind of by-product tail gas with natural gas pyrolysis acetylene as Material synthesis ammonia
Method, comprises the steps：
Step S1 tail gas clean-up operation：
By the by-product tail gas of natural gas pyrolysis acetylene sequentially pass through (a) desulfurization-hydrogenation operation, (b) shift conversion step, (c) take off
Carbon operation and (d) pressure swing adsorption hydrogen production operation, form purification unstripped gas, the volumn concentration of the hydrogen in the purification unstripped gas
For more than 99.0%.Wherein,
Desulfurization-hydrogenation operation in step S1 (a) includes desulfurization process and hydrogenation process.Contain H in by-product tail gas2S, H2S
Not only can etching process pipeline and equipment, and can cause transformation catalyst in step S1 (b) and with step S3 in ammino
Into catalyst poisoning, so what the desulfurization process in the present embodiment referred to is by the H in by-product tail gas2S is removed so that by-product tail
H in gas2The content of S is less than 0.1ppm.Specifically, the desulfurizing agent that the present embodiment is adopted for Zinc Oxide, Zinc oxide desulfurizer with
Activated zinc oxide is main component, is that a kind of internal surface area is big, the inoganic solids desulfurizing agent that Sulfur capacity is higher, and it can fast eliminating sulfur
Change hydrogen.Reaction principle is as follows：ZnO+H2S=ZnS+H2O。
Hydrogenation process is referred to the alkynes C in by-product tail gas in the presence of hydrogenation catalyst2H2With alkene C2H4Pass through
Hydrogenation, so as to form it into the saturated hydrocarbons of easy removing, alkynes C2H2Content be reduced to below 5ppm, alkene C2H4Content drop
It is low to below 20ppm.
The purpose of shift conversion step is to remove the CO in the first unstripped gas in step S1 (b), to meet later stage synthesis ammonia work
The requirement of skill, reaction principle is CO+H2O→CO2+H2, the H in equation2O is that reaction is participated in the way of vapor, generation
Hydrogen can increase the raw material Gas content of synthetic ammonia process in step S3.The second unstripped gas is formed after processing via shift conversion step,
In second unstripped gas, the volumn concentration of CO is less than 0.34%.
Wherein, the shift conversion step all can become operation (i.e. middle temperature transformation string using middle temperature transformation operation or middle change string are low
Connection low-temperature conversion operation), but, if all being processed the first unstripped gas using middle temperature transformation operation, based on to temperature
Require, cost of equipment and operating cost are very high, therefore, the shift conversion step in the present embodiment becomes the low change operation of string in being preferably.
If additionally, in the present embodiment by the way of a Middling Temp Shift Converter is connected with a low temperature shift converter, needing whole the
One unstripped gas is directly configured in input Middling Temp Shift Converter, hts catalyst is filled with Middling Temp Shift Converter, in generally adopting
Change catalyzer is with Fe2O3For active component, active temperature is more than 320 DEG C, and low change catalyzer is filled with low temperature shift converter,
The low change catalyzer for generally adopting is for cobalt-molybdenum series catalyst or copper-zinc system catalyst.In the first whole unstripped gas is input to
In warm change furnace, the active temperature due to causing to be reached in Middling Temp Shift Converter hts catalyst, therefore, need first using heating
Stove is heated to first unstripped gas, it will consume substantial amounts of furnace fuel.Meanwhile, and due to former according to above-mentioned reaction
Reason, transformationreation is reversible exothermic reaction, and from from the perspective of kinetics, temperature is raised, the speed constant of the reaction
Increase so as to favourable to the carrying out reacted, but the equilibrium constant of the reaction diminishes with the rising of temperature, then the balance of CO
Content can increase, and reaction motive force diminishes, to reaction carry out it is unfavorable, therefore, Middling Temp Shift Converter domestic demand keep one it is suitable
Reaction temperature, generally realized by controlling the temperature of Middling Temp Shift Converter porch, therefore, if by the first whole unstripped gas
In being transported to Middling Temp Shift Converter, it is difficult to meet in technical process to the requirement of reaction temperature.Additionally, after testing, the first unstripped gas
In CO contents reach more than 30%, from from the perspective of reaction raw materials vapor, increase vapor consumption, the flat of CO can be improved
Weighing apparatus interconversion rate, so as to advantageously reduce the residual content of CO, accelerates the carrying out of transformationreation.Due to the presence of excessive vapor,
Ensure active component Fe in catalyst2O3It is stable and be not reduced, and make analysis carbon and generate the side reactions such as methane to be not susceptible to,
But, vapor consumption is topmost consumption indicators in conversion process, and economy of its consumption to conversion process is reduced as far as possible
Have great importance, if steam rates are too high, catalyst bed layer resistance will be caused to increase, CO shorter residence times, waste heat
The problems such as reclaimer load increases, therefore in conversion process, should try one's best and reduce the input of vapor, and the technical requirements are not yet
Directly configure in input Middling Temp Shift Converter beneficial to the first whole unstripped gas.
Based on above-mentioned analysis, as shown in Fig. 2 the present embodiment is provided with two preferably between heating furnace and low temperature shift converter
The mode of Middling Temp Shift Converter, including the first Middling Temp Shift Converter and the second Middling Temp Shift Converter, heating furnace, the first Middling Temp Shift Converter,
It is sequentially connected between two Middling Temp Shift Converters and low temperature shift converter.And drawn by calculating and experiment, by the present embodiment step S1 (a)
In obtained first unstripped gas 40~50% be transported in the first Middling Temp Shift Converter, control the entrance temperature of the first Middling Temp Shift Converter
Spend for 360 DEG C；The second middle temperature transformation is transported to using 50~60% of obtained first unstripped gas in step S1 (a) as cold shock gas
In stove, the inlet temperature of the second Middling Temp Shift Converter is 366 DEG C.That is after 40~50% heated stove heats of the first unstripped gas with it is outer
The vapor in portion is transported in the first Middling Temp Shift Converter jointly, and transformationreation occurs in the first Middling Temp Shift Converter, then with it is surplus
The first unstripped gas mixing of remaining 50~60% is transported in the second middle temperature transformation jointly, due to defeated from the first Middling Temp Shift Converter
The gas temperature for going out is very high, and after the first unstripped gas with remaining 50~60% mixes, the temperature of mixed gas can also meet change
The requirement of reaction is changed, the demand for fuel of heating furnace and the expense of relevant device can be reduced, while saving substantial amounts of steam, be also easy to
Meet each temperature index in conversion process.
The content of CO is 3.8% (dry in the Middling Temp Shift Converters of Jing first and the reacted gas material of the second Middling Temp Shift Converter
Base) left and right, cooling is realized to the gas material, and be transported in low temperature shift converter so that it is anti-further to there is conversion in CO
Should, so that in the second unstripped gas exported from low temperature shift converter, the volumn concentration of CO is less than 0.34% (dry
Base).
Further, in order to reclaim conversion process in heat, between the second Middling Temp Shift Converter and low temperature shift converter arrange
There is waste heat recoverer, and the waste heat recoverer is connected by pipeline with heating furnace.The waste heat recoverer is to from Middling Temp Shift Converter
The heat of the gas material of output is reclaimed so that the temperature drop of gas material, reaches the technological requirement of low temperature shift converter.
The heat reclaimed by waste heat recoverer is present in the form of saturated steam, and the saturated vapor that the waste heat recoverer is reclaimed passes through pipeline
In returning heating furnace, play a part of that vapor is heated and provided for the first unstripped gas.
Waste heat recoverer in the present embodiment can reduce the temperature of gas material so as to the technique for meeting low temperature shift converter
Require, while also can reclaim to the gas heat exported in the second Middling Temp Shift Converter, and the partial heat is returned into heating
Recycle in stove, the fuel quantity for reducing heating furnace decreases the steam usage amount of transformationreation, with preferable economic effect
Benefit.
The purpose of decarbonization process is to go carbon dioxide in the second unstripped gas after via transformationreation in step S1 (c)
Remove, the decarbonization process in the present embodiment is preferably MEDA decarbonization process, MEDA refers to methyl diethanolamine, commonly referred to N- first
Base diethanolamine, MEDA decarbonization process refers to the MEDA aqueous solutions reagent using 45%~50% and adds in reagent a small amount of
Activator piperazine, the second unstripped gas can remove substantial amounts of carbon dioxide by the reagent, and the piperazine in reagent can also accelerate examination
Agent is to CO2Absorption rate, concrete technology method is well known to those skilled in the art, therefore will not be described here.Via MEDA
CO after decarbonization process process2Downstream drain or recycling are sent, the high pressure flash gas produced in MEDA decarbonization process is then returned
Previous step is returned, merging with by-product tail gas carries out the tail gas clean-up operation of a new round, so as to effectively increase the profit of by-product tail gas
With rate.It is the 3rd unstripped gas via the gas material after decarbonization process process.
Jing after (a) in step S1~(c) process, the volumn concentration of hydrogen typically can reach in the 3rd unstripped gas
More than 95.4%.
Pressure swing adsorption hydrogen production operation in step S1 (d) refers to carry out depth to the 3rd unstripped gas using adsorbent to carry
Pure, adsorbent is generally adopted by porous solid material, can be molecular sieve or activated carbon, and the adsorption is with adsorbent
Based on inner surface is to the physical absorption of gas molecule, reversible adsorption process of the gas molecule between two kinds of pressure states.Its
Principle is that impurities from mixed gas component has under high pressure larger absorbability, has less energy of adsorption again under low pressure
Power, i.e., stronger analytic ability, and preferably component H2Then high pressure or low pressure all have less absorbability, because
This, under high pressure, by increase impurities partial pressure it can be made as often as possible to adsorb on the sorbent, so as to improve mixed gas in H2
Purity.Be capable of achieving the parsing of adsorbent again under low pressure, so as to reduce adsorbent in each impurity residual volume, in the present embodiment
CH in 3rd unstripped gas4、C2H6, CO etc. be separated by the analytic function of adsorbent, step S1 can be transported to
In the heating furnace of (b), supplied as fuel gas, so as to reduce the comprehensive cost of whole technical process.
By the pressure swing adsorption hydrogen production operation in step S1 (d), hydrogen in purification unstripped gas, and the purification unstripped gas can be obtained
The volumn concentration of gas can reach more than 99.0%.
Step S2：Methanation operation
Methanation is referred in the presence of a catalyst, and with hydrogen reducing carbon monoxide and carbon dioxide methane and water are generated
Reaction, by rear portion cool down so that water vapor condensation separate, finally obtain the qualified hydrogen containing only trace methane impurity.
It is noted that in the step of the present embodiment S2, another unstripped gas nitrogen of synthetic ammonia process passes through methanation
The entrance of operation is entered, and is mixed to form ammonia synthesis gas with the purification unstripped gas obtained by step S1 first, wherein, nitrogen according to
The ratio of the amount of the material of purification unstripped gas is 1：The ratio of the amount of the material of 2.75~3.20 inputs, nitrogen and purification unstripped gas is preferred
For 1：3.
Although the purification unstripped gas in the present embodiment after tail gas clean-up operation via eliminating substantial amounts of CO and CO2But,
The purification unstripped gas is also difficult to meet the technological requirement of ammonia synthesis gas, in order to prevent the murder by poisoning to catalyst in synthetic ammonia process,
Final purification must be realized to purifying unstripped gas.Therefore, the step of the present embodiment S2 carries out methane chemical industry to above-mentioned ammonia synthesis gas
The process of sequence, i.e., by methanation operation, to obtain the qualified synthesis gas containing only trace methane impurity, in the qualified synthesis gas,
The content sum of carbon monoxide and carbon dioxide is less than 10ppm.
Wherein, above-mentioned nitrogen is provided by air separation plant, and content is more than 99.5%.Air separation plant refers to former with air
Material, causes air to be changed into liquid by compressing the method for depth of round freezing, then progressively divides from liquid air through rectification
From the noble gases equipment for producing oxygen, nitrogen and argon etc..
Nitrogen is filled into via the import of methanation working procedure systemses, can save the conversion work in raw natural gas synthetic ammonia process
The main equipments such as sequence, air compressor, can also reduce the investment of cleaning system pipeline, equipment so as to reduce synthesizing the production of ammonia
Cost, operating process is also simple and safe.
Step S3：Synthetic ammonia process
Synthetic ammonia process refers to be directly synthesized the work of ammonia in the presence of High Temperature High Pressure and catalyst by nitrogen and hydrogen
Skill, is transported to the qualified synthesis gas in step S2 in ammonia synthesis operation in the present embodiment, to produce via synthesic gas compressor
Ammonia.Specific embodiment is well known to those skilled in the art, therefore repeats no more again.
It should be noted that the recovered entrance by pressure swing adsorption hydrogen production operation of periodic off-gases produced in synthetic ammonia process is defeated
Enter, further to improve in the present embodiment to the utilization rate of raw material.Periodic off-gases are referred in Ammonia Production, in order to prevent closing
Into system. Inert gas (CH4+ Ar) accumulation and affect Synthesis conversion, need to release a part of synthesis gas to maintain to synthesize work
The inert gas content of sequence, the forming gas of the extraction is the periodic off-gases in the present embodiment.
The present embodiment is carefully studied based on the component to the by-product tail gas with natural gas pyrolysis acetylene, and considers sky as a whole
Nitrogen balance that subset is produced and the method for synthesis ammonia that designs, the method is high to the utilization rate of tail gas, and is capable of achieving ammonia
Long-term continuous and stable production, simple and safe operation process can effectively reduce synthesizing the production cost of ammonia.
It should be noted that above-described embodiment the present invention will be described rather than limits the invention, and this
Art personnel can design without departing from the scope of the appended claims alternative embodiment.In claim
In, any reference markss between bracket should not be configured to limitations on claims.Word "comprising" is not excluded for depositing
In element or step not listed in the claims.
Claims (10)
1. method of a kind of by-product tail gas with natural gas pyrolysis acetylene as Material synthesis ammonia, it is characterised in that including as follows
Step：
Step S1 tail gas clean-up operation：
The by-product tail gas of natural gas pyrolysis acetylene is sequentially passed through into desulfurization-hydrogenation operation, shift conversion step, decarbonization process and transformation
Adsorption Hydrogen operation, forms purification unstripped gas, and the hydrogen volume percentage composition in the purification unstripped gas is more than 99.0%；
Step S2 methanation operation：
Purification unstripped gas in step S1 is obtained into qualified hydrogen via methanation reaction；
Step S3 synthetic ammonia process：
Qualified hydrogen and nitrogen in step S2 is transported in ammonia synthesis operation, ammonia is produced.
2. the by-product tail gas with natural gas pyrolysis acetylene according to claim 1 is the method for Material synthesis ammonia, and it is special
Levy and be, the nitrogen is entered by the entrance of step S2 methanation operation, according to the ratio of the amount of material be 1 with qualified hydrogen：
2.75~3.20 are mixed to form ammonia synthesis gas, and are transported in the step S3 synthetic ammonia process.
3. the by-product tail gas with natural gas pyrolysis acetylene according to claim 2 is the method for Material synthesis ammonia, and it is special
Levy and be, the ammonia synthesis gas obtains qualified synthesis gas, the qualified synthesis gas after the process of step S2 methanation operation
In, the content sum of carbon monoxide and carbon dioxide is less than 10ppm.
4. the by-product tail gas with natural gas pyrolysis acetylene according to claim 1 is the method for Material synthesis ammonia, and it is special
Levy and be, the step S1 tail gas clean-up operation comprises the steps：
(a) desulfurization-hydrogenation operation：
Make by-product tail gas that the H in by-product tail gas is removed in the presence of desulfurizing agent2S compositions, and make in the presence of hydrogenation catalyst
Obtain the C in by-product tail gas2H2And C2H4Hydrogenation becomes saturated hydrocarbons, and the by-product tail gas Jing after the process of desulfurization-hydrogenation operation forms first
Unstripped gas, C in first unstripped gas2H2Content be below 5ppm, C in first unstripped gas2H4Content be 20ppm
Below；
(b) shift conversion step：
Make the first unstripped gas via shift conversion step to remove the first unstripped gas in CO, formed the second unstripped gas, described second is former
In material gas, the volumn concentration of CO be 0.34% (butt) below；
(c) decarbonization process：
Make the second unstripped gas via decarbonization process to remove the second unstripped gas in CO2, the 3rd unstripped gas is formed, the described 3rd is former
In material gas, H2Volumn concentration be more than 95.4%；
(d) pressure swing adsorption hydrogen production operation：
The 3rd unstripped gas is made via pressure swing adsorption hydrogen production operation, purification unstripped gas is formed.
5. the by-product tail gas with natural gas pyrolysis acetylene according to claim 4 is the method for Material synthesis ammonia, and it is special
Levy and be, the desulfurizing agent in step S1 (a) is Zinc Oxide.
6. the by-product tail gas with natural gas pyrolysis acetylene according to claim 4 is the method for Material synthesis ammonia, and it is special
Levy and be, the shift conversion step in step S1 (b) becomes the low change operation of string for middle, and the shift conversion step includes what is be sequentially connected
Heating furnace, Middling Temp Shift Converter and low temperature shift converter.
7. the by-product tail gas with natural gas pyrolysis acetylene according to claim 6 is the method for Material synthesis ammonia, and it is special
Levy and be, the Middling Temp Shift Converter includes the first Middling Temp Shift Converter and the second Middling Temp Shift Converter, wherein, described the of 40~50%
One unstripped gas is input in the first Middling Temp Shift Converter via heating furnace, and 50~60% first unstripped gas is direct as cold shock gas
In being input into the second Middling Temp Shift Converter.
8. the by-product tail gas with natural gas pyrolysis acetylene according to claim 6 is the method for Material synthesis ammonia, and it is special
Levy and be, waste heat recoverer, the waste heat recoverer are provided between second Middling Temp Shift Converter and the low temperature shift converter
It is connected with heating furnace by pipeline.
9. the by-product tail gas with natural gas pyrolysis acetylene according to claim 4 is the method for Material synthesis ammonia, and it is special
Levy and be, the decarbonization process in step S1 (c) is MDEA decarbonization process, dodge via the high pressure after decarbonization process process
Steam is combined into tail gas clean-up operation with by-product tail gas.
10. the by-product tail gas with natural gas pyrolysis acetylene according to claim 1 is the method for Material synthesis ammonia, and it is special
Levy and be, the periodic off-gases exported in the step S3 synthetic ammonia process are input into from the porch of pressure swing adsorption hydrogen production operation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN115849400B (en) * | 2022-12-28 | 2024-04-26 | 青海盐湖元品化工有限责任公司 | Ammonia synthesis process taking mixed gas as raw material |
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