CN109595878A - A method of synthesis ammonia, urea co-production liquid CO 2 - Google Patents
A method of synthesis ammonia, urea co-production liquid CO 2 Download PDFInfo
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- CN109595878A CN109595878A CN201811504776.1A CN201811504776A CN109595878A CN 109595878 A CN109595878 A CN 109595878A CN 201811504776 A CN201811504776 A CN 201811504776A CN 109595878 A CN109595878 A CN 109595878A
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- Prior art keywords
- ammonia
- liquid
- carbon dioxide
- urea
- gas
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 241
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 116
- 239000007788 liquid Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 70
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000004202 carbamide Substances 0.000 title claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 201
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 107
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 96
- 230000008569 process Effects 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 238000009833 condensation Methods 0.000 claims abstract description 12
- 230000005494 condensation Effects 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000002309 gasification Methods 0.000 claims description 16
- 238000005057 refrigeration Methods 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 238000009434 installation Methods 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 5
- 229910052756 noble gas Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000003795 desorption Methods 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- 238000012806 monitoring device Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 2
- 229960004424 carbon dioxide Drugs 0.000 description 76
- 239000000047 product Substances 0.000 description 13
- 239000003245 coal Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 206010051640 Ammoniuria Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010017577 Gait disturbance Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SQXFNEDZVPHSPV-UHFFFAOYSA-N carbon dioxide;urea Chemical compound O=C=O.NC(N)=O SQXFNEDZVPHSPV-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/067—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- 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
- C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Of Gases By Adsorption (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
The present invention provides a kind of method for synthesizing ammonia, urea co-production liquid CO 2, the technique is on the basis of existing synthesis ammonia, urea technique, utilize the surplus capacity of equipment component in synthesis ammonia, urea plant, the technique that a by-product liquid carbon dioxide is derived on primary routing, it is main to prepare liquid CO 2 by processes such as CO 2 raw material gas taking-up, dehydration, condensations.The present invention sufficiently recycles the carbon dioxide more than needed discharged in technical process, to reduce process costs, solves the problems, such as that environment is polluted in CO2 emission.
Description
Technical field
The invention belongs to synthesize ammonia, field of urea production, and in particular to titanium dioxide of having more than needed in synthesis ammonia, urea production process
The recycling of carbon gas.
Background technique
Synthesis ammonia refers to the ammonia directly synthesized in the presence of the catalyst at elevated temperature and pressure by nitrogen and hydrogen, is a kind of substantially inorganization
Work process.In modern chemical industry, ammonia is the primary raw material of chemical fertilizer industry and basic organic chemical industry.As a kind of neutral fertilizer,
Urea is suitable for various soil and plant.It is easy to maintain, easy to use, small to the destruction of soil, be current usage amount compared with
A kind of big chemical nitrogen fertilizer.Industrially use liquefied ammonia and carbon dioxide urea synthesis under certain condition.Due to ammonia and carbon dioxide
Reaction is reversible reaction, therefore is produced in the technical process for synthesizing ammonia, urea by raw material of coal at present, and the carbon dioxide of generation is rich
Surplus is more, this part carbon dioxide more than needed is directly discharged to atmosphere.In long-term production process, the discharge of carbon dioxide
Environmental pollution is caused, while making that the production cost increases, influences Business Economic Benefit and social benefit.Currently, for titanium dioxide
Carbon recycling is usually to build independent device, using techniques such as pressure-variable adsorption, chemical absorbings, but invests big, production cost recovery
It is very high.Carbon dioxide recovery and the storage technology of a kind of low-cost high-efficiency are studied to reduce synthesis ammoniuria element process costs tool
It is significant.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of synthesis ammonia, urea co-production liquid titanium dioxide
The method of carbon, co-producing carbon dioxide on the basis of synthesizing ammonia, urea technique sufficiently discharge in recycling technical process more than needed
Carbon dioxide solves the problems, such as that environment is polluted in CO2 emission to reduce process costs.
Synthesis ammonia of the present invention, urea co-production liquid CO 2 technique are in existing synthesis ammonia, urea technique basis
On, using the surplus capacity of equipment component in synthesis ammonia, urea plant, a by-product liquid is derived on primary routing
The technique of body carbon dioxide, it is main to prepare liquid CO 2 by processes such as CO 2 raw material gas taking-up, dehydration, condensations.
The method of synthesis ammonia provided by the invention, urea co-production liquid CO 2, including from the two of apparatus for urea synthesis
Carbonoxide compressor second stage exit takes the carbon dioxide for having been subjected to desulfurization, dehydrogenation as unstripped gas, unstripped gas successively pass through transformation,
After temp.-changing adsorption dehydration, condensation obtains liquid carbon dioxide product.
Further, in temp.-changing adsorption process, regeneration gas is synthesis ammonia liquid nitrogen washing device regenerating molecular sieve nitrogen, utilizes heat
Regeneration nitrogen make to have adsorbed the adsorbent of the moisture in unstripped gas and be desorbed again, so that the adsorbent after desorption be made to enter next round
Absorption, nitrogen emptying.
Further, in temp.-changing adsorption process, dewatered unstripped gas dew point is less than -70 DEG C.
Further, the condensation procedure is to be carried out using the liquid ammonia gasification of synthetic ammonia installation refrigeration system to carbon dioxide
Condensation liquefaction.
Co 2 liquefaction is a kind of typical physics liquefaction process, is not related to any chemical reaction.In certain pressure
Under, when temperature is reduced to the dew point of carbon dioxide corresponding pressure, atmospheric carbon dioxide starts to liquefy, complete until liquefying.Liquid
Change is an exothermic process, so cold source is needed to remove condensation heat, the present invention relies on original synthesis ammonia, urea technique, using liquid
Ammonia removes carbon dioxide condensing heat as cold source, by liquid ammonia gasification.
Further, after condensation procedure, then air-liquid separation is carried out, liquid CO 2 meets industrial carbon dioxide
Product standard is sent into carbon dioxide basin, and not solidifying noble gas is vented after re-heat, and the ammonia after gasification returns to synthetic ammonia installation ammonia pressure
One section of entrance of contracting machine.
Further, by adding carbon dioxide recovery process equipment on existing synthesis ammonia, urea technique line tower foundation
And route, coproduction liquid carbon dioxide is carried out, the carbon dioxide recovery process equipment includes pressure swing adsorber, temp.-changing adsorption
Device, thermal energy recoverer, co 2 liquefaction device, co 2 liquefaction device level tank and liquid carbon dioxide storage tank；It is closed in urea
Interconnected pressure swing adsorber and temperature swing adsorbers are set gradually at the carbon-dioxide gas compressor second stage exit of device, alternating temperature is inhaled
The outlet of adnexa is connected to the raw material gas inlet of thermal energy recoverer, the carbon dioxide gas outlet of thermal energy recoverer and carbon dioxide liquid
Change device inlet communication, the outlet of co 2 liquefaction device is sequentially connected co 2 liquefaction device level tank and liquid carbon dioxide storage again
Tank；Meanwhile the thermal energy recoverer and ammonia device refrigeration system constitute circuit, the co 2 liquefaction device and ammonia device freeze
System constitutes circuit.
Further, the thermal energy recoverer is heat exchanger, for by unstripped gas and from ammonia device refrigeration system CO2
The part cold air of liquefier carries out raw material CO2 cooling, to recycle cooling capacity.Realize that this process is needed thermal energy recoverer and two
Connection is between carbonoxide liquefier with pipeline.
Further, the co 2 liquefaction device be U-tube heat exchanger, be provided with gaseous carbon dioxide entrance,
The carbon dioxide gas of liquid carbon dioxide outlet, the outlet of liquefied ammonia entrance, gas ammonia, gaseous carbon dioxide entrance and thermal energy recoverer goes out
Mouth connection, liquid carbon dioxide outlet are connected to carbon dioxide liquid level slot, and the carbon dioxide after making liquefaction enters carbon dioxide liquid
Change device and carry out gas-liquid separation, liquefied ammonia entrance is connected to ammonia cooler, and gas ammonia outlet is connected to ammonia cooler carries out gas ammonia recycling.
Preferably, it is additionally provided with pressure gauge, interface of the level gauge above co 2 liquefaction device, is supervised at any time convenient for operator
Control the liquid level of equipment pressure and internal liquid.
Gaseous state CO2Carried out in the device with liquefied ammonia it is cold and hot exchange, by CO2Cooling is liquefied as liquid, and then liquefied ammonia is risen
Wet is melted into gas ammonia, sends original system back to.
Further, the co 2 liquefaction device level tank is vertical autoclave body, carries out gas-liquid using sedimentation theory
Separation.
Process flow: carbon-dioxide gas compressor second stage exit from apparatus for urea synthesis has been subjected to desulfurization, dehydrogenation
CO 2 raw material gas is successively dehydrated by pressure swing adsorber, temperature swing adsorbers, and the temp.-changing adsorption stage uses from synthesis ammoniacal liquor
Nitrogen cleaning device regenerating molecular sieve nitrogen is desorbed again using the adsorbent that the regeneration nitrogen of heat makes to have adsorbed the moisture in unstripped gas,
To make the adsorbent after desorption enter next round absorption, nitrogen emptying, dewatered carbon dioxide gas enters thermal energy recycling
Device utilizes the liquid ammonia gasification pair from ammonia device refrigeration system (Ammonia United Chiller With, to synthesize ammonia, urea technique existing equipment)
Feed carbon dioxide gas tentatively cool down, and the ammonia of liquid ammonia gasification returns ammonia device refrigeration system, preliminary original after cooling
Material carbon dioxide gas enters co 2 liquefaction device, also with from synthetic ammonia installation refrigeration system (Ammonia United Chiller With)
Liquid ammonia gasification carries out condensation liquefaction, gaseous state CO to carbon dioxide2Carried out in co 2 liquefaction device with liquefied ammonia it is cold and hot exchange, will
CO2Cooling is liquefied as liquid, and then liquefied ammonia, which is warmed, is gasificated into gas ammonia, sends former synthetic ammonia installation refrigeration system (ammonia compressor one back to
Section entrance).After condensation procedure, liquefied carbon dioxide enters co 2 liquefaction device level tank, carries out air-liquid separation, liquid
Body carbon dioxide meets industrial carbon dioxide product standard, is sent into carbon dioxide basin, and not solidifying noble gas is directly vented.Obtain liquid
State carbon dioxide product can be used as product direct marketing, also can be used as raw material and further refines, and obtain that purity is higher, food
Grade carbon-dioxide product.
In actual production, the carbon-dioxide gas compressor amount of inflating of existing apparatus is far below design value, therefore utilizes titanium dioxide
The carbon dioxide gas of the decrement more than needed recycling emptying of carbon compressor is (by entering pressure-variable adsorption, alternating temperature after compressor compresses
Absorption), as the raw material of production liquid carbon dioxide product, the setting of compressibility is saved, liquefaction process uses existing dress
The liquefied ammonia for setting production liquefies as cold source, and liquefied ammonia is generated from the ammonia compressor compression of existing apparatus, refrigeration, at present ammonia compressor
Payload is lower than Design cooling load, and so there is no need in addition increase refrigerating plant, most of equipment for consuming energy, doing work all depends on status
The expansion energy of device.Therefore, present invention process is obtaining pure carbon dioxide product simultaneously, has saved the energy, and improving equipment has
Utilization rate is imitated, utilization of resources value maximization is increased, is suitble to plant layout application.
Synthesis ammonia of the present invention, urea technique are prior art, including coal water slurry gasification, CO transformation, sour gas are de-
Remove, low-temp methanol is washed, gas purification, sulfur recovery, ammonia synthesis, urea synthesizing, low pressure separation and recovery, absorb and parsing etc. processes.
Compared with prior art, the invention has the following advantages:
1. the present invention utilizes traditional coal ammonia, urea plant some processes and equipment, by co 2 liquefaction technique
It is in combination, it using the surplus capacity of its equipment component, realizes the purpose of coproduction liquid CO 2, while energy saving, mentions
High utilization rate of equipment and installations reduces production cost.
2. being saved by the carbon dioxide recovery technology investment that present invention process is built, easy to operate, operating cost is cheap, production
Cost can be greatly lowered.
3. carbon dioxide is used as product after liquefying, convenient for storage and transport, the approach more recycled is provided,
To greenhouse gas emission is reduced, protection environment is highly beneficial.
4. the present invention depends on existing synthesis ammonia, urea technique and device are further improved and perfect, it is different from tradition
The carbon dioxide recovering apparatus and technique individually built, system have good safety and reliability.
It, can also be with 5. the high-pureness carbon dioxide product of the method for the invention production can be used as the raw material of soda manufacture
As the raw material of oil exploitation, at the same time it can also the carbon fertilizer as New-type green house crop, application is very extensive.
6. engineering can reduce 50,000 tons of greenhouse gases CO2 discharge amount every year.
Detailed description of the invention
Fig. 1 is the flow diagram of existing synthesis ammonia, urea technique described in embodiment.
Fig. 2 is carbon dioxide recovery process flow diagram of the present invention.
Fig. 3 is the process flow chart that ammonia, urea co-production liquid CO 2 are synthesized in embodiment.
In figure, 1- thermal energy recoverer, 2- co 2 liquefaction device, 3- ammonia cooler, 4- co 2 liquefaction device level tank, 5-
Pressure swing adsorber, 6- temperature swing adsorbers, 7- liquid titanium dioxide storage tank A, 8- liquid titanium dioxide storage tank B, 9- carbon dioxide dress
Vehicle pumps A, 10- carbon dioxide Loading Pump bis- sections of intersegmental coolers of B, 11-, 12- dehydrogenation reactor, 13- secondary vacuum seperator, 14- liquid
Nitrogen washes molecular sieve.
Specific embodiment
It does below by method of the specific embodiment to synthesis ammonia of the present invention, urea co-production liquid CO 2 into one
Walk explanation.As described below is only the embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize the present invention
Equivalent structure or equivalent flow shift made by specification and accompanying drawing content is applied directly or indirectly in other relevant technologies
Field is included within the scope of the present invention.
Embodiment 1
Synthesizing ammonia, the feed coal of urea production, boiler oil coal is Meng great mining company bituminous coal.Feed coal is big from covering
Mining industry is delivered to 2 10000 tons of raw coal silos of on-site using three conveyor belts by Automobile Transportation to coal yard, then
It is sent respectively to coal gasification apparatus and thermoelectric device.The flue gas that bituminous coal combustion generates uses the ammonia process of desulfurization.
Using coal as raw material, Coal Gasification Technology is starched using the more raw materials of Xibei Chemical Inst 6.5Mpa, water-coal-slurry is through high pressure coal
Being sent into gasification furnace after stock pump pressurization, violent gasification reaction does not occur for oxygen under conditions of 6.5MPa, 1400 DEG C or so, generates
After raw gas based on carbon monoxide, hydrogen, carbon dioxide, Quench and washing, CO resistant to sulfur change of stumbling after raw gas removing lime-ash
It changes, acid gas removal process, gas purification, synthesis gas compression, freezing are that ammonia synthesis process produces intermediate products liquefied ammonia, liquid
Ammonia and the CO come from acid gas removal2It send to urea plant and produces small particle urea.Ammonia synthesis uses KBR low pressure ammonia synthesis skill
Art, urea plant use the super excellent CO of 2000+TM of Stamicarbon company2Stripping process, final products are small particle urea.
Sulfur recovery uses three-level Crouse sulphur recovery technical matters.
On the basis of above-mentioned process flow, carbon dioxide recovery process equipment and route are added, carries out coproduction liquid dioxy
Change carbon, the carbon dioxide recovery process equipment includes pressure swing adsorber 5, temperature swing adsorbers 6, thermal energy recoverer 1, carbon dioxide
Liquefier 2, co 2 liquefaction device level tank 4 and liquid carbon dioxide storage tank (7,8)；In the titanium dioxide of apparatus for urea synthesis
Carbon compressor second stage exit sets gradually interconnected pressure swing adsorber and temperature swing adsorbers, the outlet and heat of temperature swing adsorbers
The raw material gas inlet connection of energy recover, the outlet of feed carbon dioxide gas and the import of co 2 liquefaction device of thermal energy recoverer connect
Logical, the outlet of co 2 liquefaction device is sequentially connected co 2 liquefaction device level tank and liquid carbon dioxide storage tank again；Meanwhile institute
It states thermal energy recoverer and ammonia device refrigeration system constitutes circuit, the co 2 liquefaction device and ammonia device refrigeration system are constituted back
Road.
The thermal energy recoverer be heat exchanger, using from ammonia device refrigeration system (Ammonia United Chiller With, for synthesis ammonia,
Urea technique existing equipment) liquid ammonia gasification feed carbon dioxide gas is carried out tentatively cooling, the ammonia of liquid ammonia gasification returns
Ammonia device refrigeration system, it is preliminary cooling, while making full use of the cooling capacity more than needed of ammonia cooler.
The co 2 liquefaction device is U-tube heat exchanger, is provided with gaseous carbon dioxide entrance, liquid titanium dioxide
Carbon outlet, the outlet of liquefied ammonia entrance, gas ammonia, the carbon dioxide gas outlet of gaseous carbon dioxide entrance and thermal energy recoverer, liquid
State carbon dioxide outlet is connected to carbon dioxide liquid level slot, and the carbon dioxide after making liquefaction enters co 2 liquefaction device and carries out gas
Liquid separation, liquefied ammonia entrance are connected to ammonia cooler, and gas ammonia outlet is connected to ammonia cooler carries out gas ammonia recycling.On co 2 liquefaction device
Face is additionally provided with pressure gauge, interface of the level gauge, convenient for operator monitoring device pressure and the liquid level of internal liquid at any time.
The co 2 liquefaction device level tank is vertical autoclave body, carries out gas-liquid separation using sedimentation theory.
Process flow chart is shown in Fig. 3, wherein ammonia cooler, two sections of intersegmental coolers, dehydrogenation reactor, secondary vacuum seperator, liquid nitrogen
Washing molecular sieve is existing synthesis ammonia, the equipment on urea technique route.
The carbon dioxide gas temperature extracted out from urea plant carbon-dioxide gas compressor second stage exit is about 36 DEG C, and pressure is about
For 2.66MPaG, flow: 4800m3/ h successively passes through pressure-variable adsorption and temp.-changing adsorption, removes moisture and impurity, enters back into thermal energy
Recover, unstripped gas with come from CO2The part cold air of liquefier carries out heat exchange for unstripped gas CO2It is cooling, to recycle cooling capacity.
The temp.-changing adsorption stage uses from synthesis ammonia liquid nitrogen washing device regenerating molecular sieve nitrogen (pressure: 0.4MPa, temperature: 205 DEG C), benefit
It is desorbed again with the adsorbent that the regeneration nitrogen of heat makes to have adsorbed the moisture in unstripped gas, thus under entering the adsorbent after desorption
One wheel absorption, nitrogen emptying, while noble gas re-heat will be vented.
Then, carbon dioxide gas enters co 2 liquefaction device and is condensed.Condensing cold source used is from synthesis ammonia
The liquefied ammonia (pressure: 0.4MPa, temperature: -3.5 DEG C) of device, liquefied ammonia gasifies under micro-positive pressure, and gasification temperature is -29 DEG C or so, gas
One section of entrance of ammonia compressor is returned after change.Condensed carbon dioxide temperature is -25 DEG C or so, into co 2 liquefaction device
Level tank carries out gas-liquid separation, and liquid phase obtains liquid carbon dioxide product, do not coagulate noble gas by entering carbon dioxide basin from force feed
(pressure 2.3MPa) is vented after thermal energy recoverer re-heat after pressure-regulating valve is depressured, and product carbon dioxide is through Loading Pump
(9,10) it is sold outside entrucking.
Claims (10)
1. the method for synthesizing ammonia, urea co-production liquid CO 2, which is characterized in that including the titanium dioxide from apparatus for urea synthesis
Carbon compressor second stage exit takes the carbon dioxide for having been subjected to desulfurization, dehydrogenation as coproduction liquid CO 2 unstripped gas, unstripped gas
Successively after transformation, temp.-changing adsorption dehydration, condensation obtains liquid carbon dioxide product.
2. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 1, which is characterized in that temp.-changing adsorption
In process, regeneration gas is synthesis ammonia liquid nitrogen washing device regenerating molecular sieve nitrogen, and the regeneration nitrogen using heat makes to have adsorbed unstripped gas
In the adsorbent of moisture be desorbed again, so that the adsorbent after desorption be made to enter next round absorption, nitrogen emptying.
3. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 1, which is characterized in that temp.-changing adsorption
In process, dewatered unstripped gas dew point is lower than -70 DEG C.
4. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 1, which is characterized in that the condensation
Process is to carry out condensation liquefaction to carbon dioxide using the liquid ammonia gasification of synthetic ammonia installation refrigeration system.
5. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 1, which is characterized in that through condensing work
After sequence, then air-liquid separation being carried out, liquid CO 2 meets industrial carbon dioxide product standard, it is sent into carbon dioxide basin,
Not solidifying noble gas is vented after re-heat, and the ammonia after gasification returns to synthetic ammonia installation ammonia compressor.
6. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 1, which is characterized in that by existing
There is synthesis ammonia, on urea technique line tower foundation, add carbon dioxide recovery process equipment and route, carries out coproduction liquid titanium dioxide
Carbon；The carbon dioxide recovery process equipment includes pressure swing adsorber, temperature swing adsorbers, thermal energy recoverer, co 2 liquefaction
Device, co 2 liquefaction device level tank and liquid carbon dioxide storage tank；At two sections of carbon-dioxide gas compressor of apparatus for urea synthesis
Outlet sets gradually interconnected pressure swing adsorber and temperature swing adsorbers, the outlet of temperature swing adsorbers and the original of thermal energy recoverer
Expect gas inlet communication, carbon dioxide gas outlet and co 2 liquefaction device inlet communication, the co 2 liquefaction of thermal energy recoverer
Device outlet is sequentially connected co 2 liquefaction device level tank and liquid carbon dioxide storage tank again；Meanwhile the thermal energy recoverer with
Ammonia device refrigeration system constitutes circuit, and the co 2 liquefaction device and ammonia device refrigeration system constitute circuit.
7. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 6, which is characterized in that the thermal energy
Recover is heat exchanger, for by unstripped gas and from CO2The not solidifying inert gas of liquefier carries out raw material CO2It is cooling, to return
Receive cooling capacity.
8. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 6, which is characterized in that the dioxy
Change carbon liquefier be U-tube heat exchanger, be provided with gaseous carbon dioxide entrance, liquid carbon dioxide outlet, liquefied ammonia entrance,
Gas ammonia outlet, the carbon dioxide gas outlet of gaseous carbon dioxide entrance and thermal energy recoverer, liquid carbon dioxide outlet with
The connection of carbon dioxide liquid level slot, the carbon dioxide after making liquefaction enter co 2 liquefaction device and carry out gas-liquid separation, liquefied ammonia entrance
It is connected to ammonia cooler, gas ammonia outlet is connected to ammonia cooler carries out gas ammonia recycling.
9. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 6, which is characterized in that carbon dioxide
Pressure gauge, interface of the level gauge are additionally provided with above liquefier, convenient for operator monitoring device pressure and internal liquid at any time
Liquid level.
10. synthesizing the method for ammonia, urea co-production liquid CO 2 according to claim 6, which is characterized in that the dioxy
Change carbon liquefier level tank is vertical autoclave body, carries out gas-liquid separation using sedimentation theory.
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