CN109133104A - A kind of technique, system and the application of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia - Google Patents
A kind of technique, system and the application of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia Download PDFInfo
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- CN109133104A CN109133104A CN201811087328.6A CN201811087328A CN109133104A CN 109133104 A CN109133104 A CN 109133104A CN 201811087328 A CN201811087328 A CN 201811087328A CN 109133104 A CN109133104 A CN 109133104A
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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
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/04—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from carbon dioxide and ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a kind of tail of semi coke and the technique of calcium carbide tail gas coproducing synthetic ammonia, system and application.The present invention is for the first time using tail of semi coke and calcium carbide tail gas mixing as the unstripped gas of synthesis ammonia, it is buffered after calcium carbide tail gas is mixed with tail of semi coke, mixed gas after buffering directlys adopt coke after level-one is pressurizeed and is filtered, the pretreatment purification of unstripped gas can be completed after temp.-changing adsorption process further removes in filtered mixed gas.The present invention pre-processes the step of purification reduces vent gas treatment, and simple flow reduces energy consumption.
Description
Technical field
The present invention relates to a kind of tail of semi coke and the technique of calcium carbide tail gas coproducing synthetic ammonia, system and application.
Background technique
Synthesize ammonia alias ammonia, molecular formula NH3.Refer to and is directly synthesized in the presence of the catalyst at elevated temperature and pressure by nitrogen and hydrogen
Ammonia.Ammonia in the world is except the ammonia on a small quantity from oven gas in addition to recycling by-product, mostly synthesized.Synthesize being mainly used as of ammonia
Fertilizer, refrigerant and industrial chemicals.
The raw material of existing main production synthesis ammonia has natural gas, naphtha, mink cell focus and coal (or coke) etc..For existing
Ammonia synthesis process raw material and environmental clean big situation requirement, using coal be raw material production synthesis ammonia by yield and ring
The limitation in border needs to develop a kind of raw material of new production synthesis ammonia.
Summary of the invention
Ingredient from the tail of semi coke that semi-coke device primary purifying comes are as follows: hydrogen 35~37%, carbon monoxide 13~
15%, carbon dioxide 15~18%.Since the hydrogen content in this tail of semi coke is higher, thus it can be used as the original of synthesis ammonia
Material.But it is easy to make subsequent ammonia synthesis process containing organic matters, these organic matters such as a large amount of tar, benzene, naphthalenes in tail of semi coke
In catalyst generate harm, so it is generally necessary to being purified to tail of semi coke.Tail of semi coke purification general process be dedusting,
Tar removing, temp.-changing adsorption removing benzene, naphthalene etc. are removed in cooling washing, and the purification process is complex.
In order to solve the deficiencies in the prior art, an object of the present invention is to provide a kind of tail of semi coke and calcium carbide tail gas connection
The raw material gas purifying method of synthesis ammonia is produced, first passage calcium carbide tail gas and tail of semi coke are combined combination, simplify semi-coke tail
The purifying step of organic matter in gas, makes full use of advantageous resource.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of feed gas preprocessing cleaning procedure of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia, by calcium carbide tail gas and orchid
It is buffered after the mixing of charcoal tail gas, the mixed gas after buffering directlys adopt coke after level-one is pressurizeed and is filtered, filtered
The pretreatment purification of unstripped gas can be completed after temp.-changing adsorption process further removes in mixed gas.
From calcium carbide device primary purifying come calcium carbide tail gas in gas component be hydrogen 11~13%, carbon monoxide 74~
76%, carbon dioxide 4~6%.The main production of calcium carbide is that calcium oxide reacts generation calcium carbide, carbon monoxide etc. with carbon.By
Contain a large amount of dust, in order to remove the dust in calcium carbide tail gas, one in the operational characteristic that calcium carbide generates, thus in calcium carbide tail gas
As need deduster dedusting, repeatedly washing.
After calcium carbide tail gas and tail of semi coke are mixed buffering by the present invention, find in the dust and tail of semi coke in calcium carbide tail gas
Tar can adhere to each other, the particle for causing dust to be formed with tar becomes larger, so that dust and semi-coke tail in calcium carbide tail gas
Tar in gas easily removes, i.e., settles the biggish impurity of particle voluntarily by buffering, by coke filtration that particle is smaller
Impurity further remove, then by temp.-changing adsorption by benzene, naphthalene Adsorption, realize the purification of unstripped gas.It should in the process both
The process that tar removing is removed in sub-cooled washing in tail of semi coke is omitted, avoids the sewage that cooling washing process generates, and
The step of reducing calcium carbide tail gas dust purification, simplifies process, reduces energy consumption.
The second object of the present invention is to provide a kind of pretreatment purification system for realizing above-mentioned pretreatment cleaning procedure, according to
Gas flow is successively made of gas holder, stage compressor, coke filter, temperature-change adsorption tower, wherein the gas of coke filter
Import and gas vent are separately positioned on the lower end and upper end of coke filter, and the filter layer of coke filter is from the bottom to top successively
For coke layer, active carbon layer and coke layer.Coke filter setting filter layer can guarantee remaining dust in mixed gas,
Blended tars completely remove, and increase temperature swing adsorption process Hu always to the adsorption efficiency of benzene, naphthalene etc..
The third object of the present invention is to provide the technique of a kind of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia, above-mentioned pre- place
The unstripped gas that reason cleaning procedure generates successively can be obtained after primary purifying process, deep purifying process and ammonia synthesis process
Synthesize ammonia；
Primary purifying process is that the carbon monoxide in unstripped gas is obtained after reacting to carbon dioxide and hydrogen with water
Process；
Deep purifying process is by carbon dioxide, remaining carbon monoxide and the process of methane removal after primary purifying；
Ammonia synthesis process is that the process of nitrogen and hydrogen reaction generation ammonia can occur.
The present invention replaces coal as raw material using tail of semi coke and calcium carbide tail gas, eliminates de- in coal quality ammonia synthesis process
Sulphur process, further simplifies process, reduces consumption.
The fourth object of the present invention is to provide a kind of synthesis ammonia system for realizing above-mentioned technique, successively net by above-mentioned pretreatment
Change system, split-compressor, carbon monoxide conversion device, decarbonization device, three-stage blower and ammonia synthesizer composition；
Carbon monoxide conversion device is to be able to carry out carbon monoxide to react the device for generating hydrogen and carbon dioxide with water；
Decarbonization device is the device that can remove carbon monoxide, carbon dioxide and methane.
The fifth object of the present invention is to provide a kind of above-mentioned technique and is preparing the application in urea.
The sixth object of the present invention is to provide a kind of urea production process, with the synthesis ammonia that is prepared in above-mentioned technique with it is above-mentioned
The carbon dioxide that deep purifying process is discharged in technique is as the direct urea synthesis of raw material.
The invention has the benefit that
1. the present invention is mixed using tail of semi coke and calcium carbide tail gas as the unstripped gas of synthesis ammonia, and tail of semi coke for the first time
Make the purification process of unstripped gas that the step of cooling water washing removes tar removing be omitted with after calcium carbide tail gas mixing, not only simplifies work
Skill process, and the waste water for avoiding cooling water washing that tar removing is gone to generate, reduce energy consumption.Partial coagulation water in gas can lead to
Waster water incinerator is crossed to be burned.
2. the present invention ammonia and urea high using tail of semi coke and calcium carbide tail gas production added value are grown fat as treasured, reduction dirt
Dye, it is energy saving, achieve the purpose that circular economy.
3. the present invention replaces coal as the raw material of synthesis ammonia using tail of semi coke and calcium carbide tail gas, simplify with the synthesis of coal system
The process of ammonia process, reduces energy consumption.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is process flow chart of the invention.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
The application is based on the improvement carried out using coal as the technique that raw material produces synthesis ammonia, in the work that coal is Material synthesis ammonia
In skill, general process are as follows: anthracite or coke crushing and screening → coal gasification → coal gas pretreatment → residual sulphur of gas conversion → removing
Or removing CO ↓ → methanation → synthesis gas compression → ammonia synthesis.
As background technique is introduced, it is complicated as synthetic ammonia feedstock purification process that tail of semi coke exists in the prior art
Deficiency, in order to solve technical problem as above, present applicant proposes a kind of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonias
Technique, system and application.
A kind of exemplary embodiment of the application provides the raw material of a kind of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia
Gas pre-processes cleaning procedure, buffers after calcium carbide tail gas is mixed with tail of semi coke, and the mixed gas after buffering is pressurizeed by level-one
After directly adopt coke and be filtered, filtered mixed gas can be completed after temp.-changing adsorption process further removes
The pretreatment of unstripped gas purifies.
After calcium carbide tail gas and tail of semi coke are mixed buffering by the application, find in the dust and tail of semi coke in calcium carbide tail gas
Tar can adhere to each other, the particle for causing dust to be formed with tar becomes larger, so that dust and semi-coke tail in calcium carbide tail gas
Tar in gas easily removes, i.e., settles the biggish impurity of particle voluntarily by buffering, by coke filtration that particle is smaller
Impurity further remove, then by temp.-changing adsorption by benzene, naphthalene Adsorption, realize the purification of unstripped gas.It should in the process both
The process that tar removing is removed in sub-cooled washing in tail of semi coke is omitted, avoids the sewage that cooling washing process generates, and
The step of reducing calcium carbide tail gas dust purification, simplifies process, reduces energy consumption.
In one or more embodiments of present embodiment, tail of semi coke and calcium carbide tail gas volume ratio are 6.5~7:1.
The another embodiment of the application provides a kind of pretreatment purification system for realizing above-mentioned cleaning procedure, presses
It is successively made of gas holder, stage compressor, coke filter, temperature-change adsorption tower according to gas flow, wherein the gas of coke filter
Body import and gas vent are separately positioned on the lower end and upper end of coke filter, the filter layer of coke filter from the bottom to top according to
Secondary is coke layer, active carbon layer and coke layer.The filter layer of coke filter setting can guarantee remaining powder in mixed gas
Dirt, blended tars completely remove, and increase temperature swing adsorption process Hu always to the adsorption efficiency of benzene, naphthalene etc..
Embodiment there is provided the technique of a kind of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia in the third of the application,
The unstripped gas that above-mentioned pretreatment cleaning procedure generates is successively after primary purifying process, deep purifying process and ammonia synthesis process
It can be obtained synthesis ammonia；
Primary purifying process is that the carbon monoxide in unstripped gas is obtained after reacting to carbon dioxide and hydrogen with water
Process；
Deep purifying process is by carbon dioxide, remaining carbon monoxide and the process of methane removal after primary purifying；
Ammonia synthesis process is that the process of nitrogen and hydrogen reaction generation ammonia can occur.
The application replaces coal as raw material using tail of semi coke and calcium carbide tail gas, eliminates de- in coal quality ammonia synthesis process
Sulphur process, further simplifies process, reduces consumption.
The purpose of primary purifying process and deep purifying process is by carbon monoxide, carbon dioxide and to lack in the embodiment
The methane of amount is removed, and since carbon monoxide can make synthetic ammonia catalyst poisoning and deactivation, thus in the technique of synthesis ammonia, is led to
Carbon monoxide often can not only be generated into the raw hydrogen of synthesis ammonia, and be easy to by carrying out conversion reaction with water
The carbon dioxide of removing, the method for deep purifying process mainly have that PSA absorption, copper is washed, low-temp methanol is washed and the methods of liquid nitrogen washing.
In order to make full use of the gases such as carbon dioxide, methane in tail of semi coke and calcium carbide tail gas, present embodiment
One or more embodiments in, deep purifying process successively includes CO shift reaction, low-temp methanol is washed and liquid nitrogen washing.
The process can not only separate carbonaceous gas, and can separate carbon dioxide and methane, wherein titanium dioxide
Carbon can be as the synthesis material of urea, and methane can be that integrated artistic supplements energy as fuel.
In one or more embodiments of present embodiment, in ammonia synthesis process, nitrogen and hydrogen are carried out being forced into 15
~16MPa.
In the 4th kind of embodiment of the application, a kind of synthesis ammonia system for realizing above-mentioned technique is provided, successively by upper
State pretreatment purification system, split-compressor, carbon monoxide conversion device, decarbonization device, three-stage blower and ammonia synthesizer
Composition；
Carbon monoxide conversion device is to be able to carry out carbon monoxide to react the device for generating hydrogen and carbon dioxide with water；
Decarbonization device is the device that can remove carbon monoxide, carbon dioxide and methane.
Toxic action of certain micro substances to carbon monoxide transformation catalyst in tail of semi coke in order to prevent, this implementation
In one or more embodiments of mode, carbon monoxide conversion device includes concatenated pre-transform furnace and change furnace.Pass through setting
Pre-transform furnace can remove certain micro substances in tail of semi coke.Change furnace is set as three sections according to gas flow, mainly
It is to consider that oxygen runs Gao Shike spray cooling immediately, prevents catalyst overtemperature.Change furnace first segment is equipped with counterpoison, the work of counterpoison
With being the part poisonous substance and oxygen removed in semiwater gas, change furnace second segment, third section inlet are equipped with water jet.It can lead to
Water spray is crossed to adjust the temperature of change furnace second segment, third section.
Embodiment there is provided a kind of above-mentioned techniques to prepare the application in urea for the 5th kind of the application.
Embodiment there is provided a kind of urea production process for the 6th kind of the application, with the synthesis prepared in above-mentioned technique
The carbon dioxide of deep purifying process discharge is as the direct urea synthesis of raw material in ammonia and above-mentioned technique.
In one or more embodiments of present embodiment, synthesis ammonia gas is pressed after entering ammonia liquor separator removal drop
Contracting is condensed into liquefied ammonia subsequently into evaporative type cooler after entering back into oil eliminator removal oil droplet, is carried out using liquefied ammonia as raw material
Urea synthesis.
In one or more embodiments of present embodiment, the method that urea synthesis uses is carbon dioxide stripping their.It closes
At condition are as follows: 186~190 DEG C, pressure is 19.5~20.5MPa.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment of body.
Embodiment
The technique of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia, as shown in Figure 1, steps are as follows:
1, the collection and pretreatment of tail gas
(hydrogen is 35~37%, carbon monoxide 13~15%, dioxy to the tail of semi coke come from semi-coke device primary purifying
Change carbon 15~18%, room temperature, 0.03MPa) and calcium carbide tail gas (the hydrogen 11-13%, one next from calcium carbide device primary purifying
Carbonoxide 74-76%, carbon dioxide 4-6%, room temperature, 0.03MPa) enter gas holder be collected (tail of semi coke and calcium carbide tail gas
Volume ratio is 6.5~7:1).By the gas that gas holder buffers, send through level-one pressurization (being forced into 0.8MPa) to coke filter and go
After the tar in gas, the tar in dust and tail of semi coke in calcium carbide tail gas is by after coke and activated carbon adsorption, then send
It send after to de- benzene, de- naphthalene tower removing organic matter to compression and carries out primary pressure.
The some processes use coke filtration tar removing, and for coke filter using three layers of filling, lowest level is coke, intermediate
Layer is active carbon, and topmost one layer is coke, you can guarantee all to get rid of the tar in gas in this way；Temp.-changing adsorption is de-
Remove the organic matters such as benzene and naphthalene.
Temp.-changing adsorption is that heating parsing --- the process of cooling is changed using three purifying columns and one for absorption at normal temperature-
Hot device composition, one tower absorption when production, a regeneration, one spare, and tower bottom enters adsorbed gas again, tower top discharge, regeneration gas
Then there is tower top entrance, tower bottom discharge is reversed to regenerate.Heating resolving is completed by the indirect heating of steam, due to naphthalene
Fusing point is 80.5 DEG C, and regenerated temperature is arranged at 100 DEG C for foundation according to this, facilitates regenerated effect.
2, primary gas purifies
Carbon monoxide in gas is not only useless but also harmful in Ammonia Production, and synthetic ammonia catalyst poisoning can be made to lose
Deactivation.But it under the effect of the catalyst, can occur to react as follows:
CO+H2O(g)——CO2+H2+Q
Reaction is conversion reaction.This reaction not only creates hydrogen, and CO is made to become readily removed CO2.The mistake
Journey is both the continuation of the purification process and raw material hydrogen production process of syngas for synthetic ammonia, so CO converts work in Ammonia Production
Sequence is essential.
Pure syngas for synthetic ammonia in order to obtain, the gas for removing the organic matters such as benzene and naphthalene (will add by two-stage pressurizing
Be depressed into 4.0MPa) after, gas after pressurization (hydrogen be 32~35%, carbon monoxide 22~25%, carbon dioxide 13~
16%) it is carbon dioxide that, the purpose of primary purifying, which is exactly by the carbon monodixe conversion in gas,.The portion gas is in conversion process
In, multi-stage transformation (pre-transform furnace, change furnace) can be used.
If becoming furnace in advance is the complicated components because of semi-coke gas, some of them is micro to the toxic effect of transformation catalyst, must
It must remove in advance.Change furnace is set as three sections, mainly considers oxygen content Gao Shike spray cooling immediately, prevents catalyst super
Temperature.One section of change furnace is equipped with counterpoison (sulfur resistant catalyst SB303Q counterpoison), and the effect of counterpoison is in removing semiwater gas
Part poisonous substance and oxygen, two sections, three sections inlet temperatures of change furnace adjust with amount of water sprayed.
Two-stage compression comes about 40 DEG C of temperature, and the water-gas of pressure 4.0MPa removes degassing through mechanical oil expeller, dry filter
Body entrained oil, water etc. exchange heat into main heat exchanger and the second change furnace second stage exit gas, reach water-gas temperature
To 140 DEG C or so.Enter intermediate heat exchanger and pre- change together by a certain percentage with external 2.0MPa, 225 DEG C of superheated steam
It changes furnace one section outlet conversion gas to exchange heat to after 220 DEG C, by entering the progress conversion reaction of one section of change furnace upper layer after electric heater.
Change furnace one section outlet gas (362 DEG C) through 1# humidifier top spraying cooling to after 199 DEG C or so, into pre-transform furnace lower layer two
Section participates in reaction, and (276 DEG C) of second stage exit gas enter 2# humidifier, after cooling to 200 DEG C, into the progress of one section of change furnace upper layer
Reaction, out one section of change furnace of conversion gas (219 DEG C) through 3# humidifier top spraying cooling to after 189 DEG C or so, into transformation
The two sections of participation reactions of furnace lower layer, gas a part after reaction go main heat exchanger and semiwater gas to exchange heat, and a part goes desalination
Water preheater and desalted water exchange heat, and the gas after heat exchange once passes through desalination water cooler, transformation Gas Cooler transformation after converging
Temperature degree reaches 40 DEG C, 3.8MPa, is sent into next system after transformed moisture trap separation moisture.
3, deep purifying
After primary purifying gas componant (hydrogen be 44~45%, carbon monoxide 0.8~1.0%, carbon dioxide 30~
32%, remaining is nitrogen, methane), production synthesis ammonia is needed gas removals such as carbon dioxide in gas.
The technique uses low-temp methanol washing process and liquid nitrogen washing cryogenic technology, by carbon dioxide, the carbon monoxide in gas
It is removed with methane, obtains pure hydrogen and nitrogen.
It containing saturation moisture content in shift conversion step conversion gas, first exchanges heat with purified gas, then cold through ammonia, is separated into conversion gas
Device isolates condensate liquid.The moisture content of gas institute band freezes, blocks the pipeline of coiled heat exchanger when low temperature in order to prevent, is converting
A small amount of methanol is injected before air cooling, gas is first sent into absorption tower after being cooled to about -7 DEG C, with from CO2The rich methanol on absorption tower
Liquid washing, removes most of H in conversion gas2S, COS and CO2。
Conversion gas after washing enters CO2Absorption tower lower part is washed for the poor methanol liquid of self-heating regenerator, is further removed
Remove H micro in gas2S and CO2Purification gas (CO2≤ 20ppm, H2S < 1ppm) it is discharged from tower top, through heat exchange temperature rise to normal
Subsequent handling is sent to after temperature.
Absorb major part H in conversion gas2S, COS and CO2Methanol-rich liquid into hot recycling tower, utilize low-pressure steam or heat
The heat that conversion gas provides is regenerated.Hot methanol-rich liquid is extracted out from hot recycling tower bottom, enters separator after cooling, contains H2S
The sour gas of about 25%vol is therefrom separated, and is sent to three wastes boiler.Another part methanol-rich liquid is extracted out from hot recycling tower bottom
With pumping to methanol/water knockout tower, methanol is separated from water by the heat provided using tower bottom reboiler.Waste water is discharged from tower bottom
Battery limit (BL), methanol steam are discharged from tower top into the middle part of regenerator, are absorbed by the recycle methanol liquid of hot recycling tower.What is obtained after regeneration is poor
Methanol is gone out with pumping, through a series of laggard CO of heat exchange2Absorption tower top is as washing absorption agent.CO2One of absorption tower lower part
Divide methanol-rich liquid into middle pressure flash column, useful hydrogen-containing gas is flashed off, through flashed vapour recycle compressor pressure recovery, is returned
It returns in conversion gas raw material.Methanol solution after middle pressure flash column flash distillation is into reabsorber, with the low-pressure nitrogen from air separation unit
Air lift is carried out, by the CO in solution2Gas proposes discharge.
Carbon dioxide gas send the unstripped gas to urea process as production urea.
It is washed by low-temp methanol and sends pressure about 3.0MPa, -35 DEG C of temperature of purified gas because containing micro CO2And CH3OH,
To prevent CO2And CH3OH freezes to block heat exchanger channels at low temperature, and purified gas is introduced into absorber, after being adsorbed by molecular sieve,
Make CO2And CH3OH content is less than 0.1 × 10-6.It is stripped of CO2And CH3The purified gas of OH enters heat at 1.78MPa, -35 DEG C and hands over
It is cooled to -482 DEG C after parallel operation, makes most of CH4It condenses out collection and is stored in nitrogen wash column bottom.Rich CH4It is extracted out from nitrogen wash column bottom
Through the swell refrigeration that throttles, in heat exchanger and re-heat, this fraction of stream leaves this workshop section as fuel.In nitrogen wash column, clean coal
CO and small part CH of the gas by -182 DEG C of scrubbings with liquid nitrogen under tower top stream, in gas4, the components such as Ar be condensed into liquid, from nitrogen
The extraction of the lower part Xi Ta is sent to fuel gas holder to 34 DEG C by heat exchanger and re-heat through the swell refrigeration that throttles.
Through scrubbing with liquid nitrogen, nitrogen wash column ejects mouth CO and CH4Less than 1 × 10-6Hydrogen and nitrogen gas WOl match nitrogen, adjust H-N ratio
For 3:1, and after cooling capacity is recycled in heat exchange, gas leaves liquid nitrogen washing workshop section and goes compressor section.
Pressure 2.2MPa, 40 DEG C of temperature of nitrogen are sent after heat exchanger exchanges heat by nitrogen compressor, temperature is down to-
33.5 DEG C, after then low temperature nitrogen enters expansion turbine expansion, temperature is down to -105.6 DEG C, exchanges heat through heat exchanger and recycles cooling capacity
Emptying is sent out afterwards.Most of nitrogen is condensed into liquid nitrogen for washing through heat exchanger again.
H2:N2The fine tuning of ratio is realized by the way that directly elevated pressure nitrogen is passed through in synthesis gas outside ice chest.
4, gas matches nitrogen and compression
Supplement nitrogen is carried out so that hydrogen and nitrogen gas ratio reaches 3:1 according to gas componant.And compression pressure-raising is carried out extremely to hydrogen and nitrogen gas
15~16MPa.
5, ammonia synthesis
The synthetic reaction of production ammonia can be expressed as following formula:
The reaction need to can just be gone on smoothly under pressurised conditions with the presence of catalyst.
Ammonia synthesis is the exothermic reaction that a volume reduces, and under high pressure, the hydrogen and nitrogen that molar ratio is 3:1 are in catalyst
Participation under reaction generate ammonia.Synthetic tower uses three axis, one diameter type tower.
15.4MPa gas from compressor enters hot gas-to-gas heat exchanger.It is preheated in heat exchanger with from boiler feedwater
The reaction gas of device is heated to 173.5 DEG C by exchange.Then gas is sent to ammonia convertor under suitable ammonia synthesis catalyst
It reacts to increase the volumetric concentration of ammonia to 20.65%.Portion gas can be shunted by tap line to control the temperature into tower gas.
Waste heat can be recycled in reaction gas, can produce middle pressure saturated vapor.
Waste heat recovery plant is made of two heat exchangers:
Waste heat boiler generates the steam of 2.5MPa, and gas cooling is to 270 DEG C；
Feedwater preheater, preheating enter the water of waste heat boiler, and gas cooling is to 189 DEG C.
The tube side that reaction gas from waste heat boiler enters hot gas-to-gas heat exchanger is cooled to 74 DEG C, and heating synthesis is former
Expect gas.Reaction gas is sent to water cooler again, and gas is cooled and has part ammonia to be condensed herein.Outlet temperature is~39
℃.Synthesis gas and liquefied ammonia mixture enter cold gas-to-gas heat exchanger, are cooled down herein with from the cold circulating air of ammonia separator 1.
Gas is sent to warm condenser again, is cooled to 8 DEG C by the evaporation of the liquefied ammonia (at 4 DEG C) provided with ammonia freezing workshop section herein.
Low-temperature condenser is entered back into, -9 DEG C is cooled to liquefied ammonia (at -15 DEG C) evaporation, further ammonia condensing occurs.Into separator.
Liquid ammonia is isolated from the synthesis gas in separator, circulating air is heated to 35 DEG C from 6 DEG C by cold gas-to-gas heat exchanger
Into the suction inlet of synthesic gas compressor circulation section, in order to keep inert gas concentration in ammonia synthesis circulating air anti-no more than ammonia synthesis
The allowance for answering process continuously discharges a certain amount of blow-out gas in the exit gas of ammonia separator, is sent to recovery ammonia workshop section.
6, it freezes
By synthesizing section process Lai -15 DEG C or so of gas ammonia, respectively after ammonia liquor separator separates drop, into ammonia
The 1.5MPa that compressor is compressed into, 40 DEG C of gases.Oil droplet is removed through oil eliminator again, it is cold that gas ammonia is sent into evaporative condenser
Congeal into liquefied ammonia.By storing up the buffering of ammonia device, returns to synthesizing section and use or be sent into liquid ammonia storage tank.
7, urea synthesizing
2NH3(liquid)+CO2(gas)=NH4COONH2(liquid)
NH4COONH2=CO (NH2)2(liquid)+H2O
The synthesis of urea uses carbon dioxide stripping their production technology, needs to carry out at high temperature under high pressure.
(1) compression, conveying of raw materials ammonia and carbon dioxide
Raw materials ammonia from battery limit (BL) is pressurized to about 16.0MPa through high-pressure ammonia pump, enters high pressure first by high-pressure injector
Ammonium condenser.
The carbon dioxide that battery limit (BL) comes enters stripping tower to about 15.3MPa through compressor boost, in order to which anti-corrosion need to be in compressor
Anti-corrosion air is added in entrance.
(2) high-pressure synthesis recycles
The reaction condition of urea synthesizer are as follows: 13.8~14.5MPa of synthesis pressure, 185~188 DEG C of synthesis temperature, NH3/
CO2 (molar ratio) 2.9~3.1, H2O/CO2 (molar ratio) 0.4~0.5.
The reaction mixture of synthetic tower is first sent to stripping tower, is heated herein using the steam of 2.16MPa, will be not converted into urine
The most first ammonium of element is separated with superfluous ammonolysis craft.Stripping tower goes out liquid and is sent after depressurizing to low pressure recycle system.Stripper overhead
Outlet is sent at the top of hp ammonium carbamate condenser, and liquefied ammonia and a solution A are also sent at the top of hp ammonium carbamate condenser, carries out first ammonium herein
Generate reaction, and by-product low-pressure steam.First ammonium liquid, ammonia and the carbon dioxide mixture that hp ammonium carbamate condenser lower curtate comes out enter
Urea synthesizer lower curtate carries out the generation reaction of urea.
Synthetic tower exit gas is sent into high pressure scrubber and carries out condensed absorbent, and the first ammonium liquid stream that high pressure scrubber comes out enters height
Injector is pressed, hp ammonium carbamate condenser is transported to by liquefied ammonia, the uncooled gas of high pressure scrubber is sent to low-pressure absorption tower.
(3) low pressure recycle
Enter rectifying column after leaving the urine decompression of air lift tower bottom, rectifying column lower section is bringing-up section, needed for first ammonium decomposes
Heat is provided by the low-pressure steam of hp ammonium carbamate condenser by-product, and the unreacted in urine is further decomposed by heating.It leaves
The urine of rectifying column is depressurized to about 0.045MPa (A) and is sent into flash tank, and flash drum outlet gas is condensed in vacuum system, flash tank
Urine out flows to urine storage tank.
The gas for leaving rectifying column lower curtate enters low pressure carbamate condenser, recycles ammonia and titanium dioxide by the condenser system
Carbon, low pressure stage first ammonium liquid after the recovery are sent to high pressure scrubber by high pressure carbamate pump.
(4) vacuum system
The urine that flash tank comes out respectively enters one, dual circulation system, so that urine is concentrated to 98% and removes granulation tower.
One, the gas that dual circulation separator comes out is sent to evaporative condenser system and carries out condensing recovery, and the evaporation of recycling is cold
Lime set is sent to desorption and hydrolysis system.
(5) desorption and hydrolysis system
The evaporation condensate that evaporative condenser system is come, after desorber and hydrolyzer processing, ammonia and urea are dense in waste liquid
Degree is respectively smaller than 3~5ppm and sends out battery limit (BL), and the gas rich in ammonia and carbon dioxide after desorption is sent to low pressure absorption after condensing
Section.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. the feed gas preprocessing cleaning procedure of a kind of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia, characterized in that by calcium carbide
Tail gas buffers after mixing with tail of semi coke, and the mixed gas after buffering directlys adopt coke after level-one is pressurizeed and is filtered,
The pretreatment purification of unstripped gas can be completed after temp.-changing adsorption process further removes in filtered mixed gas.
2. a kind of pretreatment purification system for realizing cleaning procedure described in claim 1, characterized in that according to gas flow according to
It is secondary to be made of gas holder, stage compressor, coke filter, temperature-change adsorption tower, wherein the gas feed of coke filter and gas
Outlet is separately positioned on the lower end and upper end of coke filter, the filter layer of coke filter be followed successively by from the bottom to top coke layer,
Active carbon layer and coke layer.The filter layer of coke filter setting can guarantee remaining dust in mixed gas, tar mixing
Object completely removes, and increases temperature swing adsorption process Hu always to the adsorption efficiency of benzene, naphthalene etc..
3. the technique of a kind of tail of semi coke and calcium carbide tail gas coproducing synthetic ammonia, characterized in that pretreatment described in claim 1 is net
The unstripped gas that chemical industry sequence generates successively can be obtained synthesis after primary purifying process, deep purifying process and ammonia synthesis process
Ammonia；
Primary purifying process is that the carbon monoxide in unstripped gas is obtained after reacting to the process of carbon dioxide and hydrogen with water；
Deep purifying process is by carbon dioxide, remaining carbon monoxide and the process of methane removal after primary purifying；
Ammonia synthesis process is that the process of nitrogen and hydrogen reaction generation ammonia can occur.
4. technique as claimed in claim 3, characterized in that deep purifying process successively includes CO shift reaction, low
Warm methanol is washed and liquid nitrogen washing.The process can not only separate carbonaceous gas, and can by carbon dioxide and methane into
Row separation, wherein carbon dioxide can be as the synthesis material of urea, and methane can be that integrated artistic supplements energy as fuel
Amount.
5. technique as claimed in claim 3, characterized in that in ammonia synthesis process, be forced into 15 to nitrogen and hydrogen~
16MPa。
6. a kind of synthesis ammonia system for realizing technique as claimed in claim 3, characterized in that successively purify system by above-mentioned pretreatment
System, split-compressor, carbon monoxide conversion device, decarbonization device, three-stage blower and ammonia synthesizer composition；
Carbon monoxide conversion device is to be able to carry out carbon monoxide to react the device for generating hydrogen and carbon dioxide with water；
Decarbonization device is the device that can remove carbon monoxide, carbon dioxide and methane.
7. synthesis ammonia system as claimed in claim 6, characterized in that carbon monoxide conversion device includes concatenated pre-transform furnace
And change furnace.
8. a kind of any technique of claim 3~5 is preparing the application in urea.
9. a kind of urea production process, characterized in that with the synthesis ammonia that is prepared in any technique of claim 3~5 with
The carbon dioxide that deep purifying process is discharged in above-mentioned technique is as the direct urea synthesis of raw material.
10. urea production process as claimed in claim 9, characterized in that synthesis ammonia gas enters ammonia liquor separator removal liquid
It is compressed after drop, after entering back into oil eliminator removal oil droplet, liquefied ammonia is condensed into subsequently into evaporative type cooler, using liquefied ammonia as original
Material carries out urea synthesis；
Or, the method that urea synthesis uses is carbon dioxide stripping their, synthesis condition are as follows: 186~190 DEG C, pressure is 19.5~
20.5MPa。
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| CN110078076A (en) * | 2019-04-21 | 2019-08-02 | 刘伟 | A kind of process of tail of semi coke classification sub-prime comprehensive utilization Poly-generation chemicals |
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| CN107365602A (en) * | 2017-07-18 | 2017-11-21 | 宝鸡市泰和石化工程有限公司 | Tail of semi coke polychotomy integrates after-treatment system and new technology |
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| CN107365602A (en) * | 2017-07-18 | 2017-11-21 | 宝鸡市泰和石化工程有限公司 | Tail of semi coke polychotomy integrates after-treatment system and new technology |
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| CN110078076A (en) * | 2019-04-21 | 2019-08-02 | 刘伟 | A kind of process of tail of semi coke classification sub-prime comprehensive utilization Poly-generation chemicals |
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