CN106731477A - The technique that a kind of conversion gas pressure-variable adsorption combines decarburization with ammoniacal liquor after-purification - Google Patents

The technique that a kind of conversion gas pressure-variable adsorption combines decarburization with ammoniacal liquor after-purification Download PDF

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Publication number
CN106731477A
CN106731477A CN201611181335.3A CN201611181335A CN106731477A CN 106731477 A CN106731477 A CN 106731477A CN 201611181335 A CN201611181335 A CN 201611181335A CN 106731477 A CN106731477 A CN 106731477A
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gas
tower
ammoniacal liquor
sulphur
ammonia
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杨皓
曲思霖
宁平
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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
    • B01D53/047—Pressure swing adsorption
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

The present invention relates to the technique that a kind of conversion gas pressure-variable adsorption combines decarburization with ammoniacal liquor after-purification, a whole set of synthetic ammonia installation has Partial Transformation gas to enter carbonizing apparatus and produces carbon ammonium, and carbonization outlet gas concentration lwevel control is 0.1 ~ 0.2%；Partial Transformation gas enters pressure-swing absorption apparatus decarburization, outlet gas concentration lwevel control is 1.1 ~ 5.0%, referred to as one-level decarbonization gas, one-level decarbonization gas are sent to and specially set up 12 without sulphur weak aqua ammonia tower continuation purification carbon dioxide, last weak aqua ammonia tower exit gas gas concentration lwevel is controlled 0.1 ~ 0.2%, referred to as purified gas, last is controlled in 30 ~ 50 titres without sulphur weak aqua ammonia tower ammoniacal liquor inlet concentration, ammoniacal liquor changes 20 ~ 30% for every eight hours, ammonia temperature is controlled below 35 DEG C, fixation pair tower without sulphur ammoniacal liquor tower exit gas and carbonizing apparatus is worked off one's feeling vent one's spleen and is mixed into recovery and rinsing tower, conversion gas carbonisation is sent to use without sulphur carbonated aqueous ammonia.

Description

The technique that a kind of conversion gas pressure-variable adsorption combines decarburization with ammoniacal liquor after-purification
Technical field
It is a kind of effective reduction method of the energy consumption with cutting down the consumption of raw materials the present invention relates to chemical industry and field of Environment Protection.
Background technology
1st, for the Ammonia Production device for having carbonizing apparatus, at the beginning of construction, conversion gas are all removed by carbonizing apparatus Carbon dioxide, purifying carbon dioxide gas concentration Con trolling index is 0.1 ~ 0.2%.Due to simple production ammonium hydrogen carbonate influence enterprise pin Sell, it will usually Partial Transformation gas is used pressure swing absorption process carbon dioxide removal, a part of liquid ammonia is thus produced, generally Gas concentration lwevel Con trolling index is 0.1 ~ 0.2% in pressure-swing absorption apparatus exit gas.
2nd, pressure swing adsorption decarbonization exit concentration is controlled 0.1 ~ 0.2%, using a stage pressure swing adsorption apparatus, regeneration gas dioxy Change the construction cost of concentration of carbon device when can typically reach 85 ~ 89% than relatively low, pressure swing adsorption purge gas is straight with the purified gas that are carbonized Meet workshop section after mixing feeding.The loss of decarbonization device hydrogen and nitrogen gas is about into the 3.4 ~ 4.9% of pressure-swing absorption apparatus conversion gas.
3rd, pressure swing adsorption decarbonization exit concentration can be controlled 0.8 ~ 1.0%, using a stage pressure swing adsorption apparatus, regeneration gas The construction cost of device is than relatively low when gas concentration lwevel can typically reach 91 ~ 92%.Decarbonization device hydrogen and nitrogen gas lose Enter the 2.4 ~ 2.7% of pressure-swing absorption apparatus conversion gas.For the synthesis ammonia plant for having connection alcohol, pressure swing adsorption purge gas is purified with carbonization Gas directly mixes workshop section after feeding.For the synthesis ammonia plant without connection alcohol, pressure swing adsorption purge gas can not be purified directly with carbonization The direct Song Hou workshop sections of gas mixing, but pressure swing adsorption purge gas and a carbonization pair tower are worked off one's feeling vent one's spleen and is mixed into a fixed pair of tower.Due to Fixed to pay the control of tower ammoniacal liquor inlet concentration in 20 ~ 30 titres the need for carbonization pair tower tail gas clean-up, fixed pair of tower bottom ammoniacal liquor is dense Degree reaches 100 titres, therefore, there is no pressure swing adsorption purge gas to mix the ammonia ratio that gaseous mixture is taken out of from fixed pair of tower bubbling segment When how too many pay the ammonia that tower takes out of from fixed, cause recovery tower weak aqua ammonia superfluous serious, it is impossible to reach weak aqua ammonia 0 and discharge It is required that.When summer temperature is higher than 35 DEG C, weak aqua ammonia excess quantity is bigger.
4th, pressure swing adsorption decarbonization exit concentration can be controlled 4 ~ 5%, using a stage pressure swing adsorption apparatus, regeneration gas dioxy The construction cost of device is both economical when change concentration of carbon can typically reach 94 ~ 95%.The loss of decarbonization device hydrogen and nitrogen gas is about original The 1.3 ~ 1.6% of material gas.Pressure swing adsorption purge gas directly can not mix direct Song Hou workshop sections with carbonization purified gas, but transformation Adsorption cleaning gas is worked off one's feeling vent one's spleen with carbonization king-tower and is mixed into carbonization pair tower.The ammonia ratio that gaseous mixture is taken out of from Fu Ta do not had transformation How too many ammonia that adsorption cleaning gas is taken out of from Fu Ta when mixing is, and to pay the ammonia amount that tower takes out of also just big from fixed, causes Recovery tower weak aqua ammonia is superfluous serious, it is impossible to reach the emission request of weak aqua ammonia 0.When summer temperature is higher than 35 DEG C, weak aqua ammonia excess quantity It is bigger.
Conversion gas 15000NM3/ H, pressure-variable adsorption outlet carbon dioxide 0.1 ~ 0.2%, it is 100% to invest, and vavuum pump power consumption is 100%, average gas loss is calculated for 4%.Pressure-variable adsorption exports carbon dioxide 0.8 ~ 1.0%, and it is 80% to invest, and vavuum pump power consumption is 80%, average gas loss is 3.2%, pressure-variable adsorption outlet carbon dioxide 1.8 ~ 2.0%, and it is 70% to invest, and average gas loss is 2.4%, vavuum pump power consumption is 70%, pressure-variable adsorption outlet carbon dioxide 4 ~ 5%, and it is 60% to invest, and vavuum pump power consumption is 60%, averagely Gas loss is 1.5%.
The content of the invention
In order to reduce PSA Gas loss, pressure-variable adsorption power consumption is reduced, while reducing weak aqua ammonia growing amount, realized dilute Ammoniacal liquor 0 is discharged, and is worked off one's feeling vent one's spleen the different spy of characteristic from carbonization main and auxiliary tower by reasonably being worked off one's feeling vent one's spleen using pressure swing adsorption decarbonization equipment Point, the present inventor has invented the technique that a kind of conversion gas pressure-variable adsorption combines decarburization with ammoniacal liquor after-purification.
Characterized in that, there is the Ammonia Production device of conversion gas carbonizing apparatus, a whole set of synthetic ammonia installation has Partial Transformation Gas enters carbonizing apparatus and produces carbon ammonium, and carbonization is fixed to pay tower outlet gas concentration lwevel control 0.1 ~ 0.2%（Connection alcohol control exists 0.8~1.0%）Referred to as carbon gas；Partial Transformation gas enters pressure-swing absorption apparatus decarburization, outlet gas concentration lwevel control 1.1 ~ 5.0%, referred to as one-level decarbonization gas, one-level decarbonization gas be sent to it is special set up 1-2 and continue to purify carbon dioxide without sulphur weak aqua ammonia tower, Last weak aqua ammonia tower exit gas gas concentration lwevel is controlled 0.1 ~ 0.2%（Connection alcohol control is 0.8 ~ 1.0%）, referred to as only Change gas, last is controlled in 30 ~ 50 titres without sulphur weak aqua ammonia tower ammoniacal liquor inlet concentration, and ammoniacal liquor changes 20 ~ 30%, ammonia for every eight hours Coolant-temperature gage is controlled below 35 DEG C, and paying tower outlet carbon gas without sulphur ammoniacal liquor tower outlet purified gas and the fixation of carbonizing apparatus is mixed into Enter recovery and rinsing tower, send conversion gas carbonisation to use without sulphur carbonated aqueous ammonia.
By pressure-variable adsorption work off one's feeling vent one's spleen feeding it is special set up without the purification of sulphur ammoniacal liquor tower, the conversion gas with equivalent are inhaled by transformation Directly send carbonization to pay tower or fix a pair tower after adsorption device to compare, send carbonizing apparatus ammoniacal liquor to reduce required for recovery and rinsing tower a lot, It is possible thereby to realize that weak aqua ammonia is reduced send outside or outer discharge capacity, realize that weak aqua ammonia 0 is discharged substantially.
Specific embodiment
Embodiment 1：Certain 60,000 tons/year of synthetic ammonia installation, 0.8MPa pressure adds up to 3.6 ten thousand mark sides/hour conversion gas, 2.1 Ten thousand mark sides/hour conversion pneumatic transmission carbonization king-tower, the carbonization king-tower outlet feeding of gas concentration lwevel 5 ~ 8% pays tower, pays tower outlet dioxy Change fixed pair of tower of the feeding of concentration of carbon 0.8 ~ 1.0%, fixed tower outlet gas concentration lwevel 0.1% of paying send recovery and rinsing tower.1.5 ten thousand marks Side/hour converts pneumatic transmission pressure-variable adsorption, and purified gas gas concentration lwevel is 1.1%, and it is net without sulphur ammoniacal liquor that purified gas feeding is newly set up Change tower, exit gas gas concentration lwevel reaches 0.1%, be 30 ~ 50 titres without sulphur ammoniacal liquor, 20 ~ 30% are changed for every eight hours, change Without sulphur carbonated aqueous ammonia send carbonization weak aqua ammonia groove.Tower is paid without sulphur ammoniacal liquor purifying column exit gas with the fixation of carbonizing apparatus to work off one's feeling vent one's spleen Mixing, send the recovery and rinsing tower of carbonizing apparatus.Directly controlled compared with 0.1% with pressure-variable adsorption outlet gas concentration lwevel, vacuum Pump power consumption reduction 132kw, hydrogen and nitrogen gas gas loss reduces 375NM3/H.Without sulphur ammoniacal liquor tower aqua ammonia pump power consumption average out to 0.4kw.With Pressure-variable adsorption is worked off one's feeling vent one's spleen and 1.1% is directly entered a fixed tower of paying and compares, and recovery and rinsing tower weak aqua ammonia reduces 40%, and weak aqua ammonia is realized substantially 0 discharge.
Embodiment 2：Certain 60,000 tons/year of synthetic ammonia installation, 1.3MPa pressure adds up to 3.6 ten thousand mark sides/hour conversion gas, 2.1 Ten thousand mark sides/hour conversion pneumatic transmission carbonization king-tower, the carbonization king-tower outlet feeding of gas concentration lwevel 5 ~ 8% pays tower, pays tower outlet dioxy Change fixed pair of tower of the feeding of concentration of carbon 0.8 ~ 1.0%, fixed tower outlet gas concentration lwevel 0.1% of paying send recovery and rinsing tower.1.5 ten thousand marks Side/hour converts pneumatic transmission pressure-variable adsorption, and purified gas gas concentration lwevel is 3.0%, and new 2 for setting up of purified gas feeding are without sulphur ammonia Water warfare tower, exit gas gas concentration lwevel reaches 0.1%, and the 1st tower is 80 ~ 100 titres without sulphur ammoniacal liquor, is changed for every eight hours 20 ~ 30%, replacing without sulphur carbonated aqueous ammonia send carbonization weak aqua ammonia groove.2nd tower is 30 ~ 50 titres without sulphur ammoniacal liquor, for every eight hours more Change 20 ~ 30%, what two towers were changed send carbonization weak aqua ammonia groove without sulphur carbonated aqueous ammonia.2nd without sulphur ammoniacal liquor purifying column exit gas with The fixation of carbonizing apparatus is paid tower and is worked off one's feeling vent one's spleen mixing, send the recovery and rinsing tower of carbonizing apparatus.Dense carbon dioxide is exported with pressure-variable adsorption Degree directly 0.1% compare by control, and vavuum pump power consumption reduction 264kw, hydrogen and nitrogen gas gas loss reduces 495NM3/H.Two without sulphur Ammoniacal liquor tower aqua ammonia pump power consumption average out to 1.8kw.With pressure-variable adsorption work off one's feeling vent one's spleen 3% be directly entered pay tower compared with, the dilute ammonia of recovery and rinsing tower Water reduces 40%, and weak aqua ammonia realizes 0 discharge substantially.
Embodiment 3：Certain 80,000 tons/year of synthetic ammonia installation, 0.8MPa pressure adds up to 4.8 ten thousand mark sides/hour conversion gas, 3.3 Ten thousand mark sides/hour conversion pneumatic transmission carbonization king-tower, the carbonization king-tower outlet feeding of gas concentration lwevel 5 ~ 8% pays tower, pays tower outlet dioxy Change fixed pair of tower of the feeding of concentration of carbon 0.8 ~ 1.0%, fixed tower outlet gas concentration lwevel 0.1% of paying send recovery and rinsing tower.1.5 ten thousand marks Side/hour converts pneumatic transmission pressure-variable adsorption, and purified gas gas concentration lwevel is 4.5%, and new 2 for setting up of purified gas feeding are without sulphur ammonia Water warfare tower, exit gas gas concentration lwevel reaches 0.1%, and the 1st tower is 80 ~ 100 titres without sulphur ammoniacal liquor, is changed for every eight hours 20 ~ 30%, replacing without sulphur carbonated aqueous ammonia send carbonization weak aqua ammonia groove.2nd tower is 30 ~ 50 titres without sulphur ammoniacal liquor, for every eight hours more Change 20 ~ 30%, what two towers were changed send carbonization weak aqua ammonia groove without sulphur carbonated aqueous ammonia.2nd without sulphur ammoniacal liquor purifying column exit gas with The fixation of carbonizing apparatus is paid tower and is worked off one's feeling vent one's spleen mixing, send the recovery and rinsing tower of carbonizing apparatus.Dense carbon dioxide is exported with pressure-variable adsorption Degree directly 0.1% compare by control, and vavuum pump power consumption reduction 264kw, hydrogen and nitrogen gas gas loss reduces 495NM3/H.Two without sulphur Ammoniacal liquor tower aqua ammonia pump power consumption average out to 2.8kw.With pressure-variable adsorption work off one's feeling vent one's spleen 4.5% be directly entered pay tower compared with, recovery and rinsing tower is dilute Ammoniacal liquor reduces 40%, and weak aqua ammonia realizes 0 discharge substantially.
Using the present invention will reduce pressure swing adsorption method invest, while reduce synthesis ammonia consumption, reduce weak aqua ammonia send outside or Outer discharge capacity.

Claims (1)

1. a kind of technique that conversion gas pressure-variable adsorption combines decarburization with ammoniacal liquor after-purification, it is characterised in that a whole set of synthetic ammonia installation, There is Partial Transformation gas to enter carbonizing apparatus and produce carbon ammonium, carbonization outlet gas concentration lwevel control is 0.1 ~ 0.2%；Partial Transformation Gas enters pressure-swing absorption apparatus decarburization, and outlet gas concentration lwevel control is in 1.1 ~ 5.0%, referred to as one-level decarbonization gas, one-level decarburization Pneumatic transmission sets up 1-2 without sulphur weak aqua ammonia tower continuation purification carbon dioxide, last weak aqua ammonia tower exit gas dioxy to special Change concentration of carbon control 0.1 ~ 0.2%, referred to as purified gas, last is controlled 30 ~ 50 without sulphur weak aqua ammonia tower ammoniacal liquor inlet concentration Titre, ammoniacal liquor changes 20 ~ 30% for every eight hours, and ammonia temperature is controlled below 35 DEG C, is set with carbonization without sulphur ammoniacal liquor tower exit gas Standby fixation pair tower is worked off one's feeling vent one's spleen and is mixed into recovery and rinsing tower, send conversion gas carbonisation to use without sulphur carbonated aqueous ammonia.
CN201611181335.3A 2016-12-20 2016-12-20 The technique that a kind of conversion gas pressure-variable adsorption combines decarburization with ammoniacal liquor after-purification Withdrawn CN106731477A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1557528A (en) * 2004-01-18 2004-12-29 成都天立化工科技有限公司 Process for removing CO2 from conversion gas by three-stage pressure swing adsorption device
CN101095996A (en) * 2006-06-30 2008-01-02 山东联合化工股份有限公司 Transformed gas recycling technics through pressure swing adsorption process
CN105967184A (en) * 2016-05-10 2016-09-28 杨皓 Process for combined production of ammonia and sodium carbonate by using shift gas
CN106139820A (en) * 2016-07-18 2016-11-23 杨皓 The technique that a kind of conversion gas pressure-variable adsorption combines decarburization with ammonia after-purification

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1557528A (en) * 2004-01-18 2004-12-29 成都天立化工科技有限公司 Process for removing CO2 from conversion gas by three-stage pressure swing adsorption device
CN101095996A (en) * 2006-06-30 2008-01-02 山东联合化工股份有限公司 Transformed gas recycling technics through pressure swing adsorption process
CN105967184A (en) * 2016-05-10 2016-09-28 杨皓 Process for combined production of ammonia and sodium carbonate by using shift gas
CN106139820A (en) * 2016-07-18 2016-11-23 杨皓 The technique that a kind of conversion gas pressure-variable adsorption combines decarburization with ammonia after-purification

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