CN109612203A - A kind of processing method of discharge gas in ammonia synthesis - Google Patents

A kind of processing method of discharge gas in ammonia synthesis Download PDF

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Publication number
CN109612203A
CN109612203A CN201811395958.XA CN201811395958A CN109612203A CN 109612203 A CN109612203 A CN 109612203A CN 201811395958 A CN201811395958 A CN 201811395958A CN 109612203 A CN109612203 A CN 109612203A
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China
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gas
ammonia
gaseous mixture
ammonia synthesis
delivered
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Inventor
林迥
何树文
李思华
刘丽华
李传栋
李强
李同强
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SHANDONG RUNYIN BIOCHEMICAL CO Ltd
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SHANDONG RUNYIN BIOCHEMICAL CO Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/024—Purification
    • 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
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    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
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    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0257—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of nitrogen
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J5/00—Arrangements of cold exchangers or cold accumulators in separation or liquefaction plants
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    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
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    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/80—Processes or apparatus using other separation and/or other processing means using membrane, i.e. including a permeation step
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/20—H2/N2 mixture, i.e. synthesis gas for or purge gas from ammonia synthesis
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/20—Boiler-condenser with multiple exchanger cores in parallel or with multiple re-boiling or condensing streams
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    • F25J2270/00—Refrigeration techniques used
    • F25J2270/14—External refrigeration with work-producing gas expansion loop
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    • F25J2270/00—Refrigeration techniques used
    • F25J2270/66—Closed external refrigeration cycle with multi component refrigerant [MCR], e.g. mixture of hydrocarbons

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Abstract

A kind of processing method of discharge gas in ammonia synthesis cryogenic liquefying of the present invention, comprising the following steps: discharge gas in ammonia synthesis pretreatment, cryogenic liquefying methane, purification methane.Discharge gas in ammonia synthesis pretreatment uses multi-level throttle decompression from Refrigeration Technique, obtains ammonia for producing urea；Hydrogen is obtained using bundled tube microfiltration membranes, can be used for ammonia synthesis；Refrigerant is pressurized acquisition mechanical energy by supercharger and is freezed by expanding machine constant entropy under adiabatci condition so that mix refrigerant reaches ultra low temperature state；In deep cooling box, ultrafiltration gaseous mixture and super low temperature refrigeration agent carry out it is cold for the first time exchange, again with from rectifying column fixed gas carry out second it is cold exchange, methane realizes whole liquid；Most Vehicular liquefied methane is obtained through built-in evaporator formula rectifying column rectifying afterwards.

Description

A kind of processing method of discharge gas in ammonia synthesis
Technical field
The present invention relates to the comprehensive utilization techniques of discharge gas in ammonia synthesis, and in particular to arrives a kind of discharge gas in ammonia synthesis deep cooling The method that liquefaction prepares methane.
Background technique
There are more than 500 families, nitrogen fertilizer plant in China, synthesizes 70,000,000 tons of hydrazine yield, occupies highly importantly in national economy Position.Production technology generallys use the fixed bed gasification technique using coal as raw material, which determines first in synthesis gas cyclic process Alkane gradually accumulates, and reduces the combined coefficient of ammonia and increases energy consumption, must be discharged when reaching 20% or so.It produces per ton Synthesize ammonia about discharge cycle gas 300Nm3, discharge and contain NH3:12%, H2:41%, CH4:24%, N2:19% etc. in gas.
The cycle bleeder gas of early stage nitrogen fertilizer plant is directly discharged into atmosphere, and wherein the efficient resources such as NH3, H2, CH4 can not be efficiently sharp With, while also polluted atmospheric environment.From the beginning of the nineties in last century, synthesizes ammonia industry and carried out energy-saving and emission-reduction comprehensive utilization in succession The research and development of technology.Using isobaric recovering ammonia technique, the ammonia of recycling is used for urea production.Have studied that " pressure-variable adsorption mentions hydrogen Technology and device " extracts hydrogen, returns to ammonia synthesis system through compression.Deamination mentions after hydrogen mainly containing the synthesis emission intensity of CH4 and N2 Gas is as three wastes boiler oil.Above-mentioned technology cannot all reach the efficient high-value-use of whole of discharge gas in ammonia synthesis efficient resource, Power consumption simultaneously is big, and economic benefit is unobvious.
Summary of the invention
The present invention cannot efficient high-value-use for efficient resource existing for existing discharge gas in ammonia synthesis comprehensive utilization technique And the problem that consumption power is big, a kind of liquefied methane that the discharge gas in ammonia synthesis cryogenic liquefying after deamination mentions hydrogen obtains is provided It is enough in production chemical fertilizer for vehicle fuel, obtained ammonia and Hydrogen Energy, realization has in discharge gas in ammonia synthesis under the conditions of low energy consumption Imitate the purpose of the whole efficiently high-value-uses of resource.The technical solution adopted by the invention is as follows:
A kind of processing method of discharge gas in ammonia synthesis cryogenic liquefying, comprising the following steps:
S1, discharge gas in ammonia synthesis pretreatment: being successively delivered to ammonia cooler after preliminary cooling, through two concatenated multi-step pressure reduction valves after It is continuous to be delivered to ammonia separator；
Liquefied ammonia is isolated in ammonia separator and ammonia divides fixed gas, liquefied ammonia is delivered to ammonia library, to divide ammonia fixed gas to be delivered to super Micro-filtration membrane separator；
In supermicro filtration membrane separator, hydrogen is filtered out and is delivered to ammonia synthesis post, remaining ultrafiltration gaseous mixture is delivered to depth Ice chest；
S2, cryogenic liquefying methane: ultrafiltration gaseous mixture cools down through deep cooling box deep cooling liquefies methane gas total condensation therein, after It is continuous that the ultrafiltration gaseous mixture is delivered to gas-liquid separator；
S3, purification methane: ultrafiltration gaseous mixture separates output gas-liquid two-phase in gas-liquid separator, separates gaseous mixture gas phase and liquid phase It is delivered in rectifying column respectively, output is prestored liquefied in tower reactor to subcooler after the tower reactor self-energy exchange of rectifying column Methane；
The tower top fixed gas of rectifying column is delivered to subcooler；
In subcooler, separate gaseous mixture gas phase and liquid phase and exported respectively into the tower body of rectifying column, tower top fixed gas export to Tail gas is discharged after deep cooling box, tail gas is delivered to three wastes boiler.
In above-mentioned steps S3, the separation gaseous mixture gas phase in the subcooler is delivered to tower body through a multi-step pressure reduction valve Above lower layer's filler, the separation gaseous mixture liquid phase in the subcooler is delivered to the upper layer filler of tower body through a multi-step pressure reduction valve Top.
In above-mentioned steps S3, temperature is -159 ~ -166 DEG C when separation gaseous mixture gas phase leaves tower reactor, on lower layer's filler The separation gaseous mixture gas phase temperature of side is -194 ~ -198 DEG C；
Separate gaseous mixture gas phase, by methane in tower reactor and the gaseous mixture of low boiling impurity gasification uplink, separation gaseous mixture liquid phase Three's cold exchange in tower body obtains supercooling fixed gas, and temperature is -175 when which goes upward to supercooling fixed gas outlet ~-186℃；
In subcooler, supercooling fixed gas with separate the cold exchange of gaseous mixture gas phase after, separate gaseous mixture gas phase be cooled to -174 ~ - 180℃。
Two groups of heat exchange mechanisms of A, B are equipped in the deep cooling box, the heat exchange mechanisms include left and right perpendicular support, upper and lower two pressures Tight screw rod and the several heat exchanger fins being fixed on clamping screw wherein form several intervals between the heat exchanger fin of A group heat exchange mechanisms The mix refrigerant channel of distribution and ultrafiltration mixed gas passage form several intervals point between the heat exchanger fin of B group heat exchange mechanisms The supercooling fixed gas channel of cloth and ultrafiltration mixed gas passage, the ultrafiltration mixed gas passage connection of two groups of heat exchange mechanisms of A, B.
In the method that the deep cooling box carries out cryogenic liquefying methane are as follows: ultrafiltration gaseous mixture and refrigerant are in A group heat exchange mechanisms Heat exchange cooling after, ultrafiltration gaseous mixture be delivered to B group heat exchange mechanisms continue with by subcooler conveying Lai supercooling fixed gas progress Secondary heat exchange cooling, discharge gas in ammonia synthesis is cooled to -166 DEG C at this time, is then sent to gas-liquid separator.
The deep cooling box is communicated with circular refrigerating mechanism, the refrigeration mechanism include the supercharger of connection, water cooler and Expanding machine, the outlet of the expanding machine and the entrance of the supercharger are respectively communicated with deep cooling box and form circulation canal；
The refrigerating method of refrigeration mechanism are as follows: be pressurized 1.10 ~ 1.18MPa after refrigerant is added in the supercharger, refrigerant enters Temperature is down to -178 ~ -188 DEG C when deep cooling box.
In above-mentioned steps S3, it is equipped with built-in evaporator in the tower reactor, several intervals point are equipped in the built-in evaporator The gas phase channel and liquid channel of cloth, the gas phase channel are used to separate the circulation of gaseous mixture gas phase, and the liquid channel is used for Separate the circulation of gaseous mixture liquid phase；The bottom end of the tower reactor is equipped with methane outlet.
In above-mentioned steps S1, discharge gas in ammonia synthesis is tentatively cooled to 60 ~ 65 DEG C, when discharge gas in ammonia synthesis is delivered to ammonia cooler Pressure be 28MPa, -20 ~ -27 DEG C are cooled in ammonia cooler, discharge gas in ammonia synthesis is finally depressured to 8.5 through multi-step pressure reduction valve ~ 9.2MPa, -72 ~ -75 DEG C are cooled to.
In above-mentioned steps S1, the ingredient of the discharge gas in ammonia synthesis and corresponding percentage by volume are as follows: 41%H2、12% NH3、24%CH4、19%N2And 4%Ar.
The invention has the benefit that
First, taking full advantage of the interior energy of discharge gas in ammonia synthesis, in the case where non-power consumption, discharge gas in ammonia synthesis is tentatively located Hydrogen is obtained after reason, ammonia can be used for chemical fertilizer production, constant entropy expansion Refrigeration Technique prepares methane by deep cooling box cryogenic liquefying, and Methane is further purified by rectifying column, realizes the efficient high-value-use of whole efficient resources in discharge gas in ammonia synthesis.
It is small in size, heat exchange area is big, high cold energy utilization rate second, deep cooling box is provided with two groups of heat exchange mechanisms.Cryogenic liquefying When make full use of the fixed gas of rectifying column output to carry out secondary heat exchange, greatly improve the liquefied fraction of methane, take full advantage of Resource reduces exhaust gas discharge.
Third, the built-in corrugated plate heat exchanger of tower reactor, can make full use of condensation by mixing gas it is interior can, without outer for energy Under the conditions of, rectifying imurity-removal gas reaches the purification of liquefied methane.
Detailed description of the invention
Fig. 1 is the process flow diagram of the embodiment of the present invention；
Fig. 2 is the refrigeration case structural schematic diagram of the embodiment of the present invention；
Fig. 3 is the rectifying tower structure schematic diagram of the embodiment of the present invention；
Fig. 4 is Fig. 3 partial enlargement diagram.
In figure: 1 for hydrogen-cooled device, 2 be ammonia separator, 3 be supermicro filtration membrane separator, 4 be deep cooling box, 5 be gas-liquid separator, 6 be rectifying column, 7 be subcooler, 8 be supercharger, 9 be water cooler, 10 be expanding machine, 11 be multi-step pressure reduction valve,
41 it is box shell, 42 be heat insulation layer, 43 be perpendicular support, 44 be clamping screw, 45 be heat exchanger fin, 46 is that mix refrigerant is logical Road, 47 be ultrafiltration mixed gas passage, 48 be supercooling fixed gas channel, 411 be refrigerant inlet, 412 be refrigerant outlet, 413 For ultrafiltration gaseous mixture entrance, 414 be mixed gas outlet, 415 be supercooling fixed gas import, 416 be offgas outlet,
61 be tower body, 62 be tower reactor, 63 be upper layer filler, 64 be lower layer's filler, 65 be built-in evaporator, 611 be separation mixing The import of gas gas phase, 612 be separation gaseous mixture fluid inlet, 613 tower top fixed gases outlet, 621 be separation gaseous mixture gaseous phase outlet, 622 it is separation gaseous mixture liquid-phase outlet, 623 is methane outlet.
Specific embodiment
The present invention is further explained with reference to the accompanying drawing.
The present invention is according to the cold effect of Joule-Thomson, the first law of thermodynamics, constant entropy expansion refrigeration principle and microfiltration membranes point Basic principle from technology studies a kind of technology of discharge gas in ammonia synthesis deep cooling condensation liquefaction.
The embodiment passes through pretreatment discharge gas in ammonia synthesis, cryogenic liquefying methane, the main technique step of purification three, methane It is rapid to realize, the ingredient of the discharge gas in ammonia synthesis and corresponding percentage by volume are as follows: 41%H2,12%NH3,24%CH4,19% N2 and 4%Ar.
S1, discharge gas in ammonia synthesis pretreatment
S1.1 discharge gas in ammonia synthesis is cooled to 65 DEG C through cool-heat-exchanger, is delivered to and continues to be cooled to -27 DEG C in ammonia cooler 1, so After at most grade pressure reducing valve 11 be discharged be depressured to 9MPa, synthesize ammonia at this time known to Joule-Thomson expenditure and pressure from refrigeration effect Row's discharge temperature is down to -72 ~ -75 DEG C or so, this temperature enables to gas ammonia to be all condensed into liquefied ammonia.Continue on to ammonia point From device 2；The ammonia cooler 1 absorbs heat by liquefied ammonia-gas ammonia and reaches cooling purpose；
S1.2 discharge gas in ammonia synthesis is defeated by the liquefied ammonia isolated in ammonia separator 2, until ammonia library is for producing urea, remaining ammonia point Fixed gas is delivered to bundled tube supermicro filtration membrane separator 3；Ammonia divides the main component of fixed gas to be H at this time2、CH4、N2And Ar；
For S1.3 in supermicro filtration membrane separator 3, ammonia divides fixed gas to be driven by pressure itself, and wherein the small hydrogen of molecular volume penetrates Filter membrane is in the big ultrafiltration gaseous mixture of the cylinder enrichment of supermicro filtration membrane separator 3, remaining molecular volume in supermicro filtration membrane separator 3 Lower end closure enrichment after be delivered to deep cooling box 4.The main component of ultrafiltration gaseous mixture is CH at this time4、N2And Ar.
S2, cryogenic liquefying methane
S2.1 is according to the first law of thermodynamics and constant entropy expansion refrigeration principle, the mix refrigerant prepared by nitrogen, propane, ethane Pressurization 1.18MPa is compressed through supercharger 8, obtains the energy of 9395KJ/mol, water cooled device 9 enters under adiabatci condition after cooling down Expanding machine 10.Energy conversion constant entropy expansion refrigeration, refrigerant own temperature are down to -178 DEG C and are delivered to deep cooling under adiabatci condition In case 4.
For S2.2 in deep cooling box 4, temperature is that -178 DEG C of refrigerant is entered by refrigerant inlet 411, logical by refrigerant It exports in refrigerant outlet 412 to supercharger 8 and recycles behind road 46；Supercooling fixed gas temperature from subcooler 7 is -186 DEG C, entered by supercooling fixed gas import 415, is exported after fixed gas channel 48 is subcooled in offgas outlet 416.At the same time, Ultrafiltration gaseous mixture by temperature after carrying out cold exchange with refrigerant be down to -153 DEG C, again with the supercooling fixed gas from subcooler 7 into The secondary cold exchange temperature of row is down to -166 DEG C, and the gases methane in ultrafiltration gaseous mixture is all condensed liquefaction at this time.By the ultrafiltration Gaseous mixture is delivered to gas-liquid separator 5.
Deep cooling box 4 includes two groups of box shell 41, the heat insulation layer 42 in box shell 41 and A, B heat exchange combined with Figure 1 and Figure 2, Mechanism.In the present embodiment, 21 heat exchanger fins 45 are designed in every group of heat exchange mechanisms, so in A group heat exchange mechanisms just The ultrafiltration mixed gas passage 47 that the mix refrigerant channel 46 that five head and the tail are sequentially connected to sequentially is connected to five head and the tail is formd, And mix refrigerant channel 46 and ultrafiltration mixed gas passage 47 are spaced apart to realize energy exchange.In B group heat exchange mechanisms just The ultrafiltration mixed gas passage 47 that the supercooling fixed gas channel 48 that five head and the tail are sequentially connected to sequentially is connected to five head and the tail is formd, And fixed gas channel 48 and ultrafiltration mixed gas passage 47 is subcooled, it is spaced apart to realize energy exchange.
S3, purification methane
S3.1 ultrafiltration gaseous mixture separates in gas-liquid separator 5 and exports gas-liquid two-phase, wherein separation gaseous mixture gas phase is mainly N2、H2, Ar, separation gaseous mixture liquid phase be methane.
It is equipped with built-in evaporator 65 in S3.2 tower reactor 62 and prestores liquefied methane；In the present embodiment, built-in steaming Gas phase channel that five head and the tail are sequentially connected to is formed by 20 bellows heat exchanger pieces in hair device 65 and five head and the tail are sequentially connected to Liquid channel, the gas phase channel and liquid channel arranged for interval are to improve the area of energy exchange, reduce built-in evaporator 65 volume；
Separation gaseous mixture gas phase exchanges heat to tower reactor 62 by the input of separation gaseous mixture gas phase import 611, by gas phase channel In methane after temperature be down to -159 DEG C, subcooler 7 be delivered to by separation gaseous mixture gaseous phase outlet 621；Separate gaseous mixture liquid phase By the input of separation gaseous mixture fluid inlet 612, heat is exchanged after liquid channel and is dropped to temperature after the methane in tower reactor 62 Subcooler 7 is delivered to -159 DEG C, by separation gaseous mixture liquid-phase outlet 622；At the same time, the methane in tower reactor 62 obtains heat Amount, in low boiling impurity gas N2、H2, Ar and portion of methane evaporation gasification, along 61 inside uplink of tower body；
The tower top fixed gas of gaseous mixture gas phase and liquid phase respectively with -186 DEG C is separated in subcooler 7 is cooled to -174 DEG C；
Separation gaseous mixture gas phase in subcooler 7 described in S3.3 is delivered to lower layer's filler of tower body 1 through a multi-step pressure reduction valve 11 64 tops, according to Joule-Thomson effect principle, the cooling capacity of the lower throttling refrigeration acquisition of temperature before throttling for particular medium More, separating gaseous mixture gas phase temperature at this time is -194 DEG C.Separation gaseous mixture liquid phase in the subcooler 7 subtracts through a multistage Pressure valve 11 is delivered to 63 top of upper layer filler of tower body 1, and liquidus temperature is constant；
S3.4 is in tower body 61, along the low boiling point of 61 uplink of tower body in separation gaseous mixture gas phase, separation gaseous mixture liquid phase and S3.2 Foreign gas and portion of methane gas carry out cold exchange；According to Kang Nuowa love law, the relatively high substance N of critical-temperature2、 H2, the foreign gases such as Ar be not liquefied and continue uplink, the relatively low methane of critical-temperature flows downwardly into tower after being liquefied then In kettle 62, tower top is gone upward to after remaining gas mixing becomes -186 DEG C of tower top fixed gas, defeated by the outlet 613 of tower top fixed gas It send to subcooler 7.
S3.5 tower top fixed gas forms supercooling fixed gas after the cold exchange of subcooler 7, is delivered in deep cooling box 4.
In the present invention, discharge gas in ammonia synthesis pretreatment uses multi-level throttle decompression from Refrigeration Technique, obtains ammonia for giving birth to Produce urea；Hydrogen is obtained using bundled tube microfiltration membranes, can be used for ammonia synthesis；Refrigerant is pressurized by supercharger and obtains mechanical energy, exhausted Under Warm status, freezed by expanding machine constant entropy so that mix refrigerant reaches ultra low temperature state；In deep cooling box, ultrafiltration gaseous mixture With super low temperature refrigeration agent carry out it is cold for the first time exchange, again with from rectifying column fixed gas carry out second it is cold exchange, methane realization Whole liquid；Most Vehicular liquefied methane is obtained through built-in evaporator formula rectifying column rectifying afterwards.

Claims (9)

1. a kind of processing method of discharge gas in ammonia synthesis cryogenic liquefying, which comprises the following steps:
S1, discharge gas in ammonia synthesis pretreatment: it is successively delivered to ammonia cooler (1) after preliminary cooling, through two concatenated multi-step pressure reductions Valve (11) continues on to ammonia separator (2)；
Liquefied ammonia is isolated in ammonia separator (2) and ammonia divides fixed gas, and liquefied ammonia is delivered to ammonia library, divides fixed gas to be delivered to ammonia Supermicro filtration membrane separator (3)；
In supermicro filtration membrane separator (3), hydrogen is filtered out and is delivered to ammonia synthesis post, is delivered to remaining ultrafiltration gaseous mixture Deep cooling box (4)；
S2, cryogenic liquefying methane: ultrafiltration gaseous mixture cools down through deep cooling box (4) deep cooling by methane gas total condensation liquid therein Change, continues for the ultrafiltration gaseous mixture to be delivered to gas-liquid separator (5)；
S3, purification methane: ultrafiltration gaseous mixture separation output gas-liquid two-phase in the gas-liquid separator (5), separation gaseous mixture gas phase and Liquid phase is delivered to respectively in rectifying column (6), is exported after tower reactor (62) the self-energy exchange of rectifying column (6) to subcooler (7), tower Kettle prestores liquefied methane in (62)；
The tower top fixed gas of rectifying column (6) is delivered to subcooler (7)；
In subcooler (7), separates gaseous mixture gas phase and liquid phase is exported respectively into the tower body of rectifying column (6) (61), tower top is not Solidifying gas exports to deep cooling box (4) and tail gas is discharged afterwards, and tail gas is delivered to three wastes boiler.
2. the processing method of discharge gas in ammonia synthesis cryogenic liquefying according to claim 1, it is characterised in that: above-mentioned steps S3 In, the separation gaseous mixture gas phase in the subcooler (7) is delivered to lower layer's filler of tower body (1) through a multi-step pressure reduction valve (11) (64) above, the separation gaseous mixture liquid phase in the subcooler (7) is delivered to the upper of tower body (1) through a multi-step pressure reduction valve (11) Above layer filler (63).
3. the processing method of discharge gas in ammonia synthesis cryogenic liquefying according to claim 2, it is characterised in that: above-mentioned steps S3 In, temperature is -159 ~ -166 DEG C when separation gaseous mixture gas phase leaves tower reactor (62), and the separation above lower layer's filler (64) is mixed Closing gas gas phase temperature is -194 ~ -198 DEG C；
Separate gaseous mixture gas phase, by methane in tower reactor (62) and the gaseous mixture of low boiling impurity gasification uplink, separation gaseous mixture Liquid phase three cold exchange in tower body (1) obtains supercooling fixed gas, temperature when which goes upward to supercooling fixed gas outlet Degree is -175 ~ -186 DEG C；
In subcooler (7), supercooling fixed gas with separate the cold exchange of gaseous mixture gas phase after, separate gaseous mixture gas phase be cooled to -174 ~-180℃。
4. the processing method of discharge gas in ammonia synthesis cryogenic liquefying according to claim 1, it is characterised in that: the deep cooling box (4) two groups of heat exchange mechanisms of A, B are equipped in, the heat exchange mechanisms include left and right perpendicular support (43), upper and lower two clamping screws (44) And the several heat exchanger fins (45) being fixed on clamping screw (44) wherein formed between the heat exchanger fin (45) of A group heat exchange mechanisms it is several A mix refrigerant channel (46) being spaced apart and ultrafiltration mixed gas passage (47), the heat exchanger fins (45) of B group heat exchange mechanisms it Between form the supercooling fixed gas channel (48) and ultrafiltration mixed gas passage (47) that several are spaced apart, two groups of heat exchange mechanisms of A, B Ultrafiltration mixed gas passage (47) connection.
5. the processing method of discharge gas in ammonia synthesis cryogenic liquefying according to claim 4, which is characterized in that in the deep cooling box (4) method of cryogenic liquefying methane is carried out are as follows: ultrafiltration gaseous mixture and refrigerant are after A group heat exchange mechanisms heat exchange cooling, ultrafiltration The B group heat exchange mechanisms that gaseous mixture are delivered to continue with the secondary heat exchange cooling of supercooling fixed gas progress that is come by subcooler (7) conveying, Discharge gas in ammonia synthesis is cooled to -166 DEG C at this time, is then sent to gas-liquid separator (5).
6. the processing method of discharge gas in ammonia synthesis cryogenic liquefying according to claim 4, it is characterised in that: the deep cooling box (4) it is communicated with circular refrigerating mechanism, the refrigeration mechanism includes supercharger (8), water cooler (9) and the expanding machine of connection (10), the outlet of the expanding machine (10) and the entrance of the supercharger (8) are respectively communicated with deep cooling box (4) and form circulation canal；
The refrigerating method of refrigeration mechanism are as follows: be added in the supercharger (8) after refrigerant and be pressurized 1.10 ~ 1.18MPa, refrigerant into Enter deep cooling box (4) Shi Wendu and is down to -178 ~ -188 DEG C.
7. the processing method of discharge gas in ammonia synthesis cryogenic liquefying according to claim 1, it is characterised in that: above-mentioned steps S3 In, built-in evaporator (65) are equipped in the tower reactor (62), several gas being spaced apart are equipped in the built-in evaporator (65) Phase channel and liquid channel, the gas phase channel are used to separate the circulation of gaseous mixture gas phase, and the liquid channel is mixed for separating Close the circulation of liquid phase；The bottom end of the tower reactor (62) is equipped with methane outlet (623).
8. the processing method of discharge gas in ammonia synthesis cryogenic liquefying according to claim 1, it is characterised in that: in above-mentioned steps S1, close 60 ~ 65 DEG C are tentatively cooled at emission intensity gas, and pressure when discharge gas in ammonia synthesis is delivered to ammonia cooler (1) is 28MPa, cold in ammonia - 20 ~ -27 DEG C are cooled in device (1), discharge gas in ammonia synthesis is finally depressured to 8.5 ~ 9.2MPa, cooling through multi-step pressure reduction valve (11) To -72 ~ -75 DEG C.
9. the processing method of discharge gas in ammonia synthesis cryogenic liquefying according to claim 1, which is characterized in that in above-mentioned steps S1, institute State discharge gas in ammonia synthesis ingredient and corresponding percentage by volume are as follows: 41%H2,12%NH3,24%CH4,19%N2 and 4%Ar.
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