CN203833630U - Heat integration device - Google Patents
Heat integration device Download PDFInfo
- Publication number
- CN203833630U CN203833630U CN201320823490.6U CN201320823490U CN203833630U CN 203833630 U CN203833630 U CN 203833630U CN 201320823490 U CN201320823490 U CN 201320823490U CN 203833630 U CN203833630 U CN 203833630U
- Authority
- CN
- China
- Prior art keywords
- ammonia
- hcn
- tower
- prussic acid
- desorption tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000010354 integration Effects 0.000 title claims abstract description 10
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 397
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 381
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 189
- 238000003795 desorption Methods 0.000 claims abstract description 90
- 238000010521 absorption reaction Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910001868 water Inorganic materials 0.000 claims abstract description 46
- 239000002918 waste heat Substances 0.000 claims abstract description 28
- 239000012530 fluid Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 73
- 239000006096 absorbing agent Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000007670 refining Methods 0.000 abstract description 29
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 65
- 239000001301 oxygen Substances 0.000 description 65
- 229910052760 oxygen Inorganic materials 0.000 description 65
- 239000000047 product Substances 0.000 description 51
- 239000007789 gas Substances 0.000 description 48
- 239000000203 mixture Substances 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000011084 recovery Methods 0.000 description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 21
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000003016 phosphoric acids Chemical class 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 150000002825 nitriles Chemical class 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 238000007600 charging Methods 0.000 description 9
- 238000005669 hydrocyanation reaction Methods 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 235000011089 carbon dioxide Nutrition 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- -1 sulphur compound Chemical class 0.000 description 5
- 239000004254 Ammonium phosphate Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 4
- 235000019289 ammonium phosphates Nutrition 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910000629 Rh alloy Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005844 autocatalytic reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001262 Ferralium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000566 Platinum-iridium alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000001970 hydrokinetic effect Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The utility model relates to a heat integration device for recycling ammonia and hydrogen cyanide from crude hydrogen cyanide product containing 25-50vol% of water. The heat integration device comprises an ammonia absorption tower, an ammonia desorption tower, a waste heat boiler, a washing tower, a hydrogen cyanide absorption tower, a hydrogen cyanide desorption tower and a pipeline, wherein the waste heat boiler is used for enabling the flow at the tower top of the desorption tower to flow through the waste heat boiler to generate steam with pressure smaller than 400kPa and partially condensing the flow at the tower top of the ammonia desorption tower to form liquid flow; the hydrogen cyanide desorption tower is used for separating at least part of the tail flow of the hydrogen cyanide absorption tower to obtain an HCN fluid; the hydrogen cyanide desorption tower comprises a discharging pipe; the pipeline is used for adding the steam from the waste heat boiler into the discharging pipe; when the heat recycled from the ammonia desorption tower exists in a form of low-pressure steam, the steam can be integrated and used for refining the hydrogen cyanide.
Description
The cross reference of related application
The application requires to enjoy in the right of priority of U. S. application 61/738,830 of submitting on December 18th, 2012, the full content of this application and disclose incorporated herein.
Technical field
The utility model is about a kind of heat integration device, for by the heat integration reclaiming from Ammonia recovery system in HCN refining system.
Background technology
Traditionally, prussic acid (HCN) carries out plant-scale production (for example, referring to Ullman ' s Encyclopedia of Indusrial Chemistry by Andrussow method or BMA method, Volume A8, Weinheim1987, P.161-163).For example, in Andrussow method, can under applicable catalyzer exists, in reactor, make ammonia and contain the gas of methane and oxygen-containing gas and at high temperature react commercialization and prepare HCN (United States Patent (USP) 1,934,838 and 6,596,251).The higher homologue of sulphur compound and methane may affect the parameter of the oxidation ammonia solution of methane.For example, referring to Trusov, Effect of Sulfur Compounds and Higher Homologues of Methane on Hyfrogen Cyanide Production by the Andrussow Method, Russian J.Applied Chemistry, 74:10 (2001), pp.1693-1697.By making reactor effluent stream contact unreacted ammonia is separated with HCN with ammonium phosphate solution in ammonia absorber.By the ammonia purifying separating and concentrated, for being recycled to the conversion of HCN.Conventionally from reactor effluent stream after treatment, reclaimed HCN by absorbing in water.The HCN reclaiming can process by further refinement operation, to prepare the HCN of purifying.Document Clean Development Mechanism Project Design Document Form (CDM PDD, Version3), has explained to 2006 n-lustrative Andrussow HCN manufacturing process.The HCN of purifying can be used for hydrocyanation reaction, as the hydrocyanation of the hydrocyanation of the group that contains alkene or 1,3-butadiene and pentenenitrile, and above-mentioned hydrocyanation can be used for manufacturing adiponitrile (" ADN ").In BMA method, HCN substantially there is no oxygen and under the condition of platinum catalyst by methane and ammonia synthesis, HCN, hydrogen, nitrogen, residual ammonia and residual methane are consequently produced (as referring to Ullman ' s Encyclopedia of Industrial Chemistry, Volume A8, Weinheim1987, P161-163).Business operator requires process safety management, to control the dangerous character of prussic acid (referring to people such as Maxwell, Assuring process safety in the transfer of hydrogen cyanide manufacturing technology, JHazMat142 (2007), 677-684).In addition, the abidance by rule possibly of the discharge from production unit in HCN manufacturing process, this may affect the economy that HCN produces.(referring to Crump, Economic Impact Analysis For The Proposed Cyanide Manufacturing NESHAP, EPA, in May, 2000).
United States Patent (USP) 2590146 has been described by methane, ammonia and air are reacted to the method for producing prussic acid under platinum-iridium catalyst exists.From the gas that contains 23 volume % water vapour, reclaim HCN, it is by contacting described gas with the aqueous solution of acid boron poly-hydroxy organic complex, to dissolve and to evaporate prussic acid.
United States Patent (USP) 3718731 has been described a kind of for reclaim the method for ammonia from the gaseous mixture that contains prussic acid.Described ammonia reclaims and enters two fluid streams in desorption tower, the per share temperature with 40-70 DEG C, and be all back to uptake zone.
United States Patent (USP) 4530826 has been described a kind of high-temperature product gas of discharging from HCN reactor and in waste heat boiler, has been accepted effective utilization of heat and reduce its temperature, is passed into subsequently the method on ammonia absorption tower.Described ammonia absorption column is maintained to quite high temperature and be dissolved in the aqueous sulfuric acid of the circulation of flowing from top to bottom in adsorption column to prevent prussic acid, therefore, the temperature of the aqueous sulfuric acid of described circulation is raised to and is not less than 60 DEG C.Absorptionmachine is arranged near the position for discharge the hole of described aqueous sulfuric acid from described ammonia absorber bottom, and thus by using described aqueous sulfuric acid to produce refrigeration agent, its temperature is raised as drive source.
United States Patent (USP) 7785399 has been described and has been utilized one or more that system and the technique of tower top used heat with the method for the feeding temperature in the hot solvent desorption and regeneration loop in raising sour gas removal process are provided.These techniques are suitable for optionally removing hydrogen sulfide, carbonyl sulfide (COS) and other sulfide, remove in a large number carbonic acid gas, mercaptan, ammonia, prussic acid (HCN) and metal carbonyl.
Therefore, be necessary to improve the efficiency that reclaims ammonia and refining prussic acid.
Utility model content
In a specific embodiment of the present utility model, a kind of heating integrated device is provided, comprise: ammonia absorber, thus it produces the rich ammonia fluid that comprises ammonia and water and the ammonia absorber overhead streams that comprises prussic acid for the thick prussic acid product that comprises prussic acid, ammonia and water is contacted with absorption liquid; Ammonia desorption tower, at least part of described rich ammonia fluid is separated, so that ammonia and water evaporation are formed to ammonia desorption tower overhead streams and lean stream; Waste heat boiler, for described ammonia desorption tower overhead streams is flowed through to described waste heat boiler and produced steam, the pressure of wherein said steam is less than 400kPa, and described ammonia desorption tower overhead streams is partially condensated as to liquid stream; Washing tower, for removing residual ammonia to produce ammonia stripping tower exhaust flow from least part of described ammonia absorber overhead streams; Absorption tower, for contacting described part exhaust flow the prussic acid absorption tower wake flow that forms prussic acid absorption tower exhaust flow and include prussic acid with diluted acid water; Prussic acid desorption tower, for separating of at least part of described prussic acid absorption tower wake flow, to obtain a prussic acid stream, wherein said prussic acid desorption tower has comb; And pipeline, for passing into described comb from the steam of described waste heat boiler.The length of described pipeline, for being less than 50 meters, is preferably less than 25 meters.Described device also can further comprise reactor, for by ternary gas mixture is contacted to produce described thick prussic acid product with catalyzer.Described catalyzer can contain platinum and rhodium.Described device also can further be included in the condenser of the tower top of described prussic acid desorption tower, for described prussic acid fluid section being condensed into liquid-phase reflux stream and vapour stream.Described device can further include prussic acid rectifying column, obtains prussic acid product for vapour stream described in purifying.Described device can further include technique to process heat interchanger, for heat is transferred to described rich ammonia stream from described lean stream.Described absorption liquid can comprise the aqueous solution of phosphoric acid hydrogen mono-ammonium and Secondary ammonium phosphate salt.Described device can further include fractional distillating tube, and for described exhaust flow being condensed into liquid stream and vapour stream, the two passes into described prussic acid absorption tower from different positions.Described device can further include ammonia rectifying column, for the desorption tower overhead streams of distilling described partial condensation to reclaim ammonia.
The utility model provides a kind of heat integration device, it is characterized in that, comprising: for the ammonia absorber that the thick prussic acid product that comprises prussic acid, ammonia and water is contacted with absorption liquid; Ammonia desorption tower, it is connected with the bottom of ammonia absorber; Waste heat boiler, it is connected with the top of ammonia Analytic Tower; Washing tower, it is connected with the top of ammonia absorber; Prussic acid absorption tower, it is connected with the top of washing tower; Be used for obtaining prussic acid fluid prussic acid desorption tower, it is connected with the bottom on prussic acid absorption tower, and wherein said prussic acid desorption tower contains comb; And pipeline, for connecting waste heat boiler and comb.The length of described pipeline is less than 50 meters.The length of described pipeline is less than 25 meters.Described device also comprises that it is connected with ammonia absorber for the preparation of the thick product reactor of described prussic acid.Described device is also included in the condenser of the tower top that connects described prussic acid desorption tower.Described device also comprises the prussic acid rectifying column being connected with condenser.Described device also comprises that technique is to process heat interchanger, and described technique is arranged on to the pipeline for connecting ammonia absorber and ammonia Analytic Tower to process heat interchanger.Described device also comprises fractional distillating tube, and it is connected with the different positions on prussic acid absorption tower.Described device also comprises ammonia rectifying column, and it is connected with the tower top of ammonia desorption tower.
Brief description of the drawings
Fig. 1 is the simple flow schematic diagram of the HCN production system of an embodiment of the present utility model.
Fig. 2 is that an embodiment of the present utility model a kind of has and the schematic flow sheet of the integrated ammonia recovery system of HCN refining system heat.
Embodiment
Term used herein only, for the object of describing particular, is not intended to limit the utility model.Unless clearly shown other situation in context, singulative " " and " being somebody's turn to do " also comprise plural form as used herein.It should also be understood that, the term using in this manual " comprises " and/or has illustrated when " including " and have described feature, entirety, step, operation, parts and/or member, but do not hinder existence or the interpolation of one or more other features, entirety, step, operation, parts group, member and/or member group.
For example " comprise ", term and the variant thereof of " comprising ", " having ", " containing " or " relating to " should understand widely, and comprises listed main body and equivalent, also has unlisted other main body.In addition, when " being comprised " by transitional term, " comprising " or " containing " while drawing component, parts group, technique or method steps or any other statement, be to be understood that and also considered identical component, parts group, technique or method steps herein, or there is any other statement of transitional term before the record of this component, parts group, technique or method steps or any other statement " substantially by ... composition ", " by ... composition " or " choosing freely ... the group of formation ".
If applicable words, the device of corresponding structure, material, action and all functions in claim or the equivalent of step comprise that the miscellaneous part for specifically stating with claim carries out any structure, material or the action of function in combination.Specification sheets of the present utility model for introduce and describe object and provide, but be not exhaustive or the utility model is restricted to disclosed form.Do not departing under the prerequisite of scope and spirit of the present utility model, many changes and variant are apparent for the person of ordinary skill of the art.Here select and described some embodiments, object is that principle of the present utility model and practical application are carried out to best explanation, and other those of ordinary skill that make this area can be understood different embodiments of the present utility model and have multiple variation, as being suitable for this specific end use.Correspondingly, although the utility model is described according to embodiment, but those skilled in the art will recognize that, the utility model can change to some extent ground and implement within the spirit and scope of claims.
Now with detailed reference to specific disclosed theme.Although disclosed theme is described in connection with cited claim, however be appreciated that they not by disclosed subject matter restricted in these claims.On the contrary, disclosed theme has covered all replacement schemes, change and equivalent, within these can be contained in the scope of disclosed theme defined by the claims.
According to Andrussow method or BMA method with industrial-scale production prussic acid (" HCN ").In Andrussow method, methane, ammonia and containing reacting and prepare the thick prussic acid product that comprises prussic acid, hydrogen, carbon monoxide, carbonic acid gas, nitrogen, residual ammonia, residual methane and water at the temperature of oxygen raw material 1000 DEG C or more and under catalyzer exists.Described catalyzer is generally silk screen platinum rhodium or is silk screen platinum iridium alloy.Other spendable catalyst composition includes but not limited to, the platinum metals of platinum metals, platinum-group metal alloy, load or the platinum-group metal alloy of load.Can use other structures of catalyzer to include but not limited to, vesicular structure, silk screen, lamellar body, spheroid, block, foam, Dipping and coating cleaning.In BMA technique, as described in United States Patent (USP) 7429370, adopt platinum catalyst methane and ammonia are reacted, this patent full content by reference and in conjunction with the utility model in.
As one of ordinary skill in the art can understand, the source of methane may be different, and may be from as garbage loading embeading district, farm, in renewable raw materials from the biogas fermenting, obtain, or from as Sweet natural gas, oil field gas, in the fossil oil of coal gas and gas hydrate, obtain, as VN Parmon, " Source of Methane for Sustainable Development ", P.273-284 with Derouane chief editor's Sustainable Strategies for the Upgranding of Natural Gas:Fundamentals, Challenges, in and Opportunities (2003), describe further.In some embodiments, described containing methane source can comprise 90 volume % methane and can be purified and reclaim the methane of purifying.
In Andrussow technique, conventionally adopt air as oxygen source preparation HCN.In order to improve the production efficiency of system and to reduce costs and energy consumption, as described herein, preferably use oxygen-rich air or purity oxygen.But, in the time using oxygen-rich air or purity oxygen, in reaction and separation processes step, all can produce multiple problems that merit attention.Particularly, it has changed the composition of thick prussic acid product to use oxygen-rich air or pure oxygen.Table 1 shown in the time containing the oxygen of at least 25 volume % in ternary gas mixture described in the exemplary composition (with volume % agent) of thick prussic acid product.
The thick prussic acid product of table 1 oxygen Andrussow technique
| Composition | Scope (volume %) | Scope (volume %) |
| HCN | 10-40 | 12-20 |
| NH 3 | 3-25 | 5-15 |
| CH 4 | 0.1-10 | 0.5-3 |
| CO 2 | 0.1-10 | 0.5-3 |
| H 2 | 10-60 | 20-50 |
| N 2 | 0.5-10 | 1-5 |
| CO | 0.1-10 | 1-5 |
| Ar | 0.01-1 | 0.05-0.5 |
| H 2O | 25-50 | 30-40 |
| Other nitrile | ＜1 | ＜1 |
Except table 1 data, the oxygen concentration in thick prussic acid product is very low, preferably lower than 0.5 volume %, because content may trigger shut-down event or necessary emptying when higher.As shown in table 1, in the time adopting oxygen Andrussow method, increase the concentration of HCN, can be accompanied by increase and the unreacted ammonia of water concentration, the concentration of for example residual ammonia increases.From described thick prussic acid product, separate described residual ammonia and reclaim.But the water concentration increasing in described thick prussic acid product has changed separation and the recovery process of described ammonia.Using the thick prussic acid product of air explained hereafter different from separation, is not concentrated but concentrated together with ammonia together with HCN from the water in described thick prussic acid product.In air technique, concentrated together with HCN from the water in crude product, therefore the water in ammonia sepn process is to less.Use the thick prussic acid product in the utility model, water need to be removed from ammonia.Due to the water concentration increasing, in ammonia sepn process, need higher temperature, and therefore increased the possibility that ammonia tripping device is corroded.Unexpectedly, have been found that in the time using oxygen-rich air or purity oxygen Andrussow method, have the temperature of rising from ammonia desorption tower overhead streams, it can be used for described fluid to flow through waste heat boiler and produce a fluid streams.The described fluid waste heat boiler of flowing through has reduced corrosion simultaneously, and allows to reclaim heat to be integrated into the refining district of prussic acid in technique from this fluid.Especially, the utility model can reclaim low-pressure steam, and for example, containing pressure is the steam that is less than 400kPa, for example, lower than 315kPa.Be gauge pressure except as otherwise noted, described pressure all refers to absolute pressure.In some embodiments, described steam has the pressure of 180-400kPa, for example 180-380kPa, 180-310kPa or 200-280kPa.Be construed as described low-pressure steam and there is the pressure lower than 400kPa higher than normal atmosphere.Conventionally preferably low-pressure steam is applicable in heat integral process, wherein by described ammonia desorption tower and the close setting of HCN refining system.Need to be used for the length of the pipeline that transmits described low-pressure steam of the present utility model, can be less than 50m or be less than 25m, be applicable near the ammonia desorption tower and the HCN refining system that arrange.
Term " air " refers to the gaseous mixture that composition is roughly the same with the original composition of gas of taking from atmosphere (conventionally at ground place) as used herein.In some instances, air is taken from surrounding environment.Air has following composition, comprises oxygen, the argon gas of approximately 1% volume and the carbonic acid gas of approximately 0.04% volume of the nitrogen of approximately 78% volume, approximately 21% volume, and other a small amount of gas.
Term " oxygen-rich air " refers to that composition comprises than the gaseous mixture of existing more oxygen in air as used herein.Oxygen-rich air has following composition, comprise be greater than 21% volume oxygen, be less than 78% volume nitrogen, be less than the argon gas of 1% volume and be less than the carbonic acid gas of 0.04% volume.Oxygen-rich air can comprise the oxygen that is greater than 21-100 volume %, be for example greater than 21-99.5 volume % oxygen, be greater than the oxygen of 21-95 volume % or be greater than the oxygen of 21-80 volume %.
The formation of HCN in Andrussow method is typically expressed as following general reaction:
2CH
4+2NH
3+3O
2→2HCN+6H
2O
But, it will be appreciated that, what above-mentioned reaction represented is the simplification of a more complicated dynamic process, and in described dynamic process, a part of hydrocarbon is first oxidized, and to produce necessary heat energy, to support remaining hydrocarbon and the ammonia to carry out the heat absorption of HCN synthetic.
Between the synthesis phase of HCN, also can there are three basic side reactions:
CH
4+H
2O→CO+3H
2
2CH
4+3O
2→2CO+4H
2O
4NH
3+3O
2→2N
2+6H
2O
Except the amount of the nitrogen that produces, according to oxygen source, in thick product, may there is extra nitrogen in side reaction.Although suggestion can be used oxygen-rich air or purity oxygen as oxygen source in prior art, use the advantage of oxygen-rich air or purity oxygen not developed completely.In the time using air as oxygen source, the thick aeriferous component of prussic acid product bag as the nitrogen of 78 volume %, and has produced nitrogen in the side reaction of ammonia and oxygen.
Due to airborne a large amount of nitrogen, therefore in HCN synthetic, use oxygen-rich air (nitrogen containing with air ratio is few) is favourable, this is because use air can cause described synthesizing in a large amount of rare gas element (nitrogen) to be carried out as oxygen source in the production of HCN, this need to use larger equipment in synthesis step, and causes the lower concentration of HCN in product gas.In addition, due to the existence of inert nitrogen, for the temperature of ternary gas mixture component is increased to and can maintains the synthetic temperature of HCN, the more methane that need to burn (in the time using air, comparing with oxygen-rich air).Therefore, in the production of HCN, use oxygen-rich air or pure oxygen to replace air that several benefits are provided, comprise the raising of Sweet natural gas to the transformation efficiency of HCN, and be attended by reducing of processing unit size.Therefore, the inert compound that uses oxygen-rich air or pure oxygen to enter synthesis technique by minimizing has reduced the size of reactor, and has reduced at least one parts of gas downstream treatment facility.The use of oxygen-rich air or pure oxygen has also reduced heating and has contained oxygen feed gas to the desired energy expenditure of temperature of reaction.
Have been found that partly oxygen-containing gas by enough oxygen enrichments are provided and the mol ratio by adjusting ammonia/methane, to sufficiently high level, can make the throughput of HCN and production efficiency all improve significantly, keep stable operation simultaneously.In one embodiment, in described ternary gas mixture, the mol ratio of ammonia and oxygen is 1.2-1.6, and the mol ratio of ammonia and methane is 1-1.5, for example 1.1-1.45, and the mol ratio of methane and oxygen is 1-1.25, for example 1.05-1.15.For example ternary gas mixture can have mol ratio and 1.2 methane and the mol ratio of oxygen of 1.3 ammonia and oxygen.In another exemplary embodiment, described ternary gas mixture can have mol ratio and 1.15 methane and the mol ratio of oxygen of 1.5 ammonia and oxygen.Oxygen concentration in described ternary gas mixture can be according to these mol ratios and difference.Be construed as all excess temperature and pressure compensations of described mol ratio.Further, the oxygen that described ternary gas mixture comprises at least 25 volume %, for example oxygen of at least 28 volume %.In some embodiments, the oxygen that described ternary gas mixture comprises 25-32 volume %, for example oxygen of 26-30 volume %.
In general, Fig. 1 has shown HCN production system 10.Conventionally in reaction unit 12, ammonia recovery system 14 and HCN refining system 16, produce HCN.To comprise oxygenous incoming flow 18, contain methane feed stream 20 and pass into described reaction unit 12 containing the reactant gases of ammonia incoming flow 22.On the one hand, the described gas containing methane can be obtained by the raw material containing lower than 90% methane, and can carry out as required purifying and obtain.Reaction unit can have the mixing device that comprises one or more static mixers, and for the production of the ternary gas mixture of mixing completely, this ternary gas mixture is passed through catalyst bed.
The thick prussic acid product 24 of withdrawing from from reaction unit 12 is introduced into ammonia recovery system 14.Preferably, use oxygen-rich air or pure oxygen as reactant gases to form thick prussic acid product 24.Due to the oxygen concn that is at least 25 volume % in ternary gas mixture, therefore in thick prussic acid product 24, also produce the water of higher concentration.In an embodiment, can for example, containing the water of at least 25 volume %, the water of at least 30 volume % in thick prussic acid product 24.If with Range Representation, in thick prussic acid product 24, can contain the water of 25-50 volume %, be for example the water of 30-40 volume %.On the contrary, in the time having formed thick prussic acid product 24 with air as reactant gases, water to exist lower than the amount of 25 volume %, for example, is 20-24 volume %.Higher water concentration during due to oxygen-rich air or the production of purity oxygen method in waste gas, makes ammonia recovery system 14 under higher temperature, move to reclaim ammonia, and described ammonia is back in reaction unit 12 through pipeline 26.Do not retrained by theory, think that ammonia can raise and increase along with temperature the infection of production unit.In order to prevent the corrosion of ammonia recovery system 14, can carry out cooling heated fluid by catching unnecessary heat.Can use waste heat boiler to reclaim the heat using in ammonia recovery system 14, and set it as steam and pass in HCN refining system 16 via pipeline 28.In order to realize the purpose of this utility model, the steam of recovery is to have the low-pressure steam that is less than 400kPa pressure, for example pressure of 180-380kPa, 180-310kPa or 200-280kPa.Due to Infrastructure and the expenditure of the low pressure of this steam and low this low-pressure steam of transport, described steam-energy is closely integrated and is used in HCN refining system 16.
Advantageously, the heat reclaiming from ammonia recovery system can be used for refining HCN incoming flow 30 to refine the HCN product 32 into purifying.HCN is refining to carry out at a certain temperature, in order to avoid fouling or the obstruction of the equipment of the HCN refining system 16 causing because of nitrile and polymerization.Maintaining HCN refines in suitable temperature and can reduce or stop HCN autocatalysis polymerization.Further, can be captured in efficiently in ammonia desorption tower except anhydrating the heat of required increase in the multiple positions recycling by HCN purification system, therefore improve the economy of producing HCN.
Conventionally in reaction unit 12, carry out rapidly cooled product gas to avoid the decomposition of HCN with waste heat boiler.This reaction is carried out at the temperature of 1000-1200 DEG C, product gas need to be quickly cooled to the temperature lower than 600 DEG C, for example, lower than 400 DEG C or lower than 300 DEG C.The utility model reclaims the heat in ammonia recovery system 14 with another waste heat boiler.The heat of described recovery, is preferably the form of low-pressure steam, can integrate to reduce with HCN refining system 16 cost of energy of preparation HCN product 32.
In order to realize the purpose of this utility model, can with waste heat boiler come partial condensation come from ammonia recovery system 14 containing ammonia fluid.But, when being less than the pressure of 400kPa in pipeline 28, for example, be 180-380kPa, while deriving from ammonia recovery system 14 under the pressure of 180-310kPa or 200-280kPa, can obtain comparatively ideal heat energy and integrate.According to the needs of the consumption in HCN refining system 16, the pressure of steam can be reduced to lower pressure.In one embodiment, the described steam reclaiming from ammonia recovery system 14 can provide 40～60% energy for driving the separation of HCN refining system 16, in particular for driving described HCN desorption tower.
Described reactant gases is sent to a reaction unit, preferably delivers in a stirred vessel, so that a kind of ternary gas mixture that contains at least 25 volume % oxygen to be provided.The ternary gas mixing completely for the purpose of this utility model has the variation factor (CoV) that is less than 0.1 on the diameter of catalyst bed, or is more preferably less than 0.05 and be even more preferably less than 0.01 variation factor.Aspect scope, CoV can be formed as 0.001 to 0.1, or more preferably from 0.001 to 0.05.Low CoV has advantageously increased reactant and has been converted to the productive rate of HCN.CoV is defined as the ratio of standard deviation and average deviation μ.CoV is low as much as possible ideally, for example, be less than 0.1, as 0.05.HCN unit can be operation on 0.1 at CoV, and CoV is 0.2 also unrare, in 0.01 to 0.2 or 0.02 to 0.15 scope.But at CoV higher than 0.1 o'clock, running cost is higher and HCN productive rate is lower, for example low by 2% to 7%, this is equivalent to the loss of annual millions of dollars in service of continous way business.
Can regulate reacting gas flow by various control system.For example, can use and can measure flow velocity, the temperature and pressure of reactant gases feedstream and allow Controlling System to provide the under meter feeding back through " in real time " of the flow velocity of pressure and temperature compensation for operator and/or control device.
As understood by one of ordinary skill in the art, aforementioned function and/or method may be embodied as system, method or computer program.For example, function and/or method may be embodied as the executable programmed instruction of computer, this instruction is recorded in computer-readable memory device, and in the time retrieving and carry out this instruction by computer processor, it controls computer system to carry out function and/or the method for above-mentioned embodiment.In one embodiment, computer system can comprise one or more central processing unit, computer memory (for example read-only storage, random access storage device) and data storage device (for example hard disk drive).The executable instruction of computer can be used any applicable computer programming language (such as C++, JAVA etc.) to encode.Correspondingly, the form (comprise firmware, resident software, microcode etc.) of entirety for the embodiment of software can be taked in aspects more of the present utility model, or combines the embodiment of software aspect and hardware aspect.
The suitable catalyzer using in the catalyst bed of Andrussow technique contains VIII family metal.VIII family metal comprises platinum, rhodium, iridium, palladium, osmium or ruthenium, and described catalyzer can be the plural alloy in mixture or these metals of these metals, these metals.Producing in a lot of examples of HCN, use the catalyzer that contains the platinum based on catalyzer total mass 50-100 quality %.A kind of metal or be that the metal mixture that contains 90wt% platinum and 10wt% rhodium or 85wt% platinum and 15wt% rhodium or alloy are conventionally preferred catalyzer based on this total catalyst weight.This catalyzer can comprise one or more layers silk screen, gauze or other filler or guide frame that is suitable for carrying out this reaction.Described catalyzer is essential enough strong, the speed that may increase while using oxygen-rich air or pure oxygen preparation to contain the three-element mixed gas that is greater than 25 volume % oxygen bearing.Therefore, can in plane support of the catalyst, use 85/15 platinum/rhodium alloy.Also can in the corrugated load than plane support of the catalyst with larger surface-area, use 90/10 platinum/rhodium alloy.
The composition of thick prussic acid product can change according to the difference of the mol ratio of incoming flow and reaction conditions.In the purpose of this utility model, the concentration that contains higher water in thick prussic acid product compared with conventionally only using the prussic acid production technique of air.In fact, as shown in table 1, in thick prussic acid product, contain HCN, can also contain by product hydrogen, methyl hydride combustion by product (for example carbonic acid gas, carbon monoxide and water), nitrogen, residual methane and residual ammonia.In the time operating under top condition, described Andrussow method has the potential callable residual ammonia in thick prussic acid product.Due to well known to those skilled in the art, the rate of polymerization of HCN, along with pH value raises and raises, therefore must be removed residual ammonia to avoid the polymerization of HCN.HCN polymerization has not only shown process efficiency problem, has also shown that operation is arduous, and this is to cause the obstruction of process pipeline due to the HCN of polymerization, thereby causes pressure to increase and relevant technology controlling and process problem.Conventionally, in the first step of purifying technique, ammonia is separated from thick prussic acid product 107, and by by thick prussic acid product immediately with excessive acid (for example H
2sO
4or H
3pO
4) react and suppress HCN polymerization, remaining free ammonia is caught and is become the pH of ammonium salt and solution maintenance acidity by acid like this.Formic acid and oxalic acid in thick prussic acid product are all formed formate and oxalate by the aqueous solution capture in ammonia recovery system.In an embodiment, described in United States Patent (USP) 6872296, use electrolyzer formate can be converted into carbonic acid gas and hydrogen, this patent institute full content two is incorporated in the utility model by reference with open.
When HCN is used for hydrocyanation as incoming flow, for example 1,3-butadiene (being sometimes referred to as " divinyl " here) and pentenenitrile hydrocyanation, to produce in adiponitrile, will require low water and highly purified HCN time, need the HCN of the non-inhibition of production and preparation.Term " non-inhibition " is used for representing that HCN does not have stable polymerization inhibitor substantially here.HCN being used in to for example hydrocyanation, as the hydrocyanation of the hydrocyanation by 1,3-butadiene and pentenenitrile is produced adiponitrile, and before other conversion process well known by persons skilled in the art, this inhibitor need to be removed.
Fig. 2 represents the schema of ammonia recovery system 14 and HCN refining system 16 in the utility model.Heat produces in ammonia recovery system 14, and transfers to HCN refining system 16 by pipeline 28.Ammonia recovery system 14 comprises ammonia absorber 100, HCN/ phosphoric acid salt desorption tower 110, ammonia desorption tower 120 and ammonia rectifying column 130.In reaction unit 12, this thick prussic acid product can be cooled to the temperature higher than group and thing dew point, for example, higher than 150 DEG C or higher than 200 DEG C.Thick prussic acid product 24, from ammonia absorber 100 lower position chargings, for the absorption liquid 104 of dilute phosphoric acid salt incoming flow contacts, produces rich ammonia phosphoric acid salt flowage 102 and absorption tower tower top stream with for example, and this overhead streams is also referred to as the refining incoming flow 30 of HCN.In an embodiment, compared with thick prussic acid product 24, rich ammonia phosphoric acid salt flowage 102 have reduction prussic acid concentration.As described here.Absorption tower tower top stream 30 comprises prussic acid, is passed into HCN refining system 16 to produce the HCN product 32 of purifying.
In an embodiment, poor phosphate solution is stored in the charging stock tank 106 of ammonia absorber, here, before entering the top of ammonia absorber 100 as poor phosphoric acid salt incoming flow 104, can in poor phosphate solution, add and supplement phosphoric acid stream.Charging stock tank 106 enough goes stockization ability and provide technique kinetics buffer zone between ammonia desorption tower 120 and ammonia absorber 100 can hold all ammonium phosphate solutions in ammonia recovery system 14, to provide thus greatly.Ammonia absorber charging stock tank 106 can be heated or cooled to maintain described poor phosphate solution and be in the ideal temperature that in ammonia absorber 100, ammonia adsorbs.The surface contacting with ammonium phosphate solution in ammonia absorber charging stock tank 106 can be constructed by 304SS.The pH value of described poor phosphoric acid salt incoming flow 104 in the scope of 5-6.1, for example 5.3-6.0.
Poor phosphoric acid salt charging 104 comprises mono phosphoric acid ester ammonium salt (NH
4h
2pO
4) and di(2-ethylhexyl)phosphate amine salt ((NH
4)
2hPO
4) the aqueous solution, wherein NH
4 +/ PO
4 -3ratio be 1.2-1.7.In some embodiments, poor phosphoric acid salt charging 104 is from different positions and/or with different N H
4 +/ PO
4 -3than introducing in ammonia absorber 100, describe in detail and see United States Patent (USP) 3718731, its full content and open by reference and in conjunction with the utility model in.In an embodiment, the temperature of poor phosphoric acid salt incoming flow 104 is the 50-60 DEG C of good absorption with realization ammonia from thick prussic acid product 24, forms the phosphoric acid salt flowage 102 of rich ammonia.
Compared with thick prussic acid product 24, the rich ammonia phosphoric acid salt flowage 102 with reduction prussic acid concentration is passed into HCN/ phosphoric acid salt desorption tower 110, wherein heats described rich ammonia phosphoric acid salt flowage 102 to remove the residual prussic acid existing.In some embodiments, according to the concentration of HCN, rich ammonia phosphoric acid salt flowage 102 can enter ammonia desorption tower 120 by optional pipeline 103.
HCN/ phosphoric acid salt desorption tower 110 produces the HCN/ phosphoric acid salt desorption tower overhead streams 112 and the second rich ammonia phosphoric acid salt fluid 114 that comprise prussic acid.The second rich ammonia phosphoric acid salt fluid 114 has the prussic acid concentration of reduction, and it is less than the prussic acid concentration in rich ammonia phosphoric acid salt fluid 102.In an embodiment, can use particulate filter (not shown) that the HCN polymkeric substance existing in described the second rich ammonia phosphoric acid salt flowage 114 or other particulates are removed, the fluid that does not substantially contain polymkeric substance is provided thus.The second rich ammonia phosphoric acid salt flowage 114 passes into described ammonia desorption tower 120, is present in ammonia and water in the phosphoric acid salt fluid 114 of described the second rich ammonia separated at this, forms ammonia desorption tower overhead streams 124 and poor phosphoric acid salt fluid 122.
In an embodiment, poor phosphoric acid salt flowage 122 leaves ammonia desorption tower 120 under the pressure of the temperature of 160-165 DEG C and 580-620kPa.Poor phosphoric acid salt flowage 122 is back in ammonia absorber charging stock tank 106.In an embodiment, by technique to the poor phosphoric acid salt flowage 122 of technique heat exchanger cooling.For example, thus technique can be by heating cooling poor phosphoric acid salt flowage 122 to rich ammonia phosphoric acid salt flowage 102 and/or the second rich ammonia phosphoric acid salt flowage 114 of passing in ammonia desorption tower 120 to process heat interchanger.The further cooling of poor phosphoric acid salt flowage 122 is desirable, absorbs with the ideal that realizes ammonia in ammonia absorber 100.
Provide the heat to ammonia desorption tower 120 by heat transfer unit 180.Described heat transfer unit 180 can be natural circulation comb, for example, use the steam of 1300kPa at the shell-side of described comb.Described comb can be one way shell-and-tube binding type heat exchanger.The heat generation water vapour being provided by unit 180 impels the desorb of ammonia from rich ammonia phosphoric acid salt flowage 102 and/or the second rich ammonia phosphoric acid salt flowage 114.By this processing, rich ammonia phosphoric acid salt flowage 102 and/or the second rich ammonia phosphoric acid salt flowage 114 are turned round to the poor phosphate solution into ammonia desorption tower 120 bottoms.
The structured material of acceptable ammonia desorption tower 120 includes but not limited to, corrosion resistant metal, zirconium, DuPlex2205 and FERRALIUM substantially
tM255.At a lower temperature, 316 stainless steels are also acceptables.
Ammonia desorption tower 120 is by ammonia and water simmer down to overhead streams 124.By this overhead streams 124 being passed in waste heat boiler 126 and by its condensation.The steam producing in waste heat boiler 126, this steam is transferred to HCN refining system 16 via pipeline 28.By at high pressure and therefore and at high temperature operate ammonia desorption tower 120, by overhead streams 124 is carried out partial condensation make heat can be advantageously from wherein reclaiming, for example adopt the waste heat boiler 126 that produces steam to produce condensate stream 128 and vapour stream 129, the steam producing can be used for providing the heat that inputs to necessary at least a portion of other tower in one or more HCN refining systems 16.
The ammonia that comprises 5-20 volume %, be for example the overhead streams 124 of ammonia of 7-17 volume % under the pressure of 400-600kPa, for example, under the pressure of 550-600kPa, and at the temperature of 140-175 DEG C, for example, at the temperature of 155-170 DEG C, leave ammonia desorption tower 120.Under lower pressure, operation may cause phosphatic entrainment in described overhead streams 124.
Overhead streams 124 by partly condensation, and is discharged with liquid stream 128 in waste heat boiler 126.From this waste heat boiler 126, also can disengage vapour stream 129, and adopt water coolant or air to distinguish condensation to it.The vapour stream 129 of liquid stream 128 and condensation is combined and passes into ammonia rectifying column 130.In this ammonia rectifying column 130, the ammonia being present in overhead streams 124 forms through pipeline 26 and is back to the anhydrous ammonia stream of reaction unit and the current 132 that are discharged from through distillation.In an embodiment, ammonia rectifying column 130 reclaims 85-99% ammonia, and reclaimed ammonia is back to reaction unit through pipeline 26.
In an embodiment, air/nitrogen mixture can pass into ammonia desorption tower 120 and/or ammonia rectifying column 130 corrodes to reduce.This air/nitrogen mixture can contain the oxygen that is less than 9 volume %.
Get back to the exquisite incoming flow 30 of the HCN withdrawing from from described absorption tower tower top stream, this fluid is admitted in HCN refining system 16 to reclaim the HCN product 32 of purifying.HCN refining system 16 comprises ammonia stripping tower 140, HCN absorption tower 150, HCN desorption tower 160 and HCN rectifying column 170.Introduce the refining charging 30 of HCN at ammonia washing tower 140 lower position places, by the dilute acid streams 142 of one or more recycles, it is washed therein, to remove any residual Trace Ammonia coming from described ammonia absorber overhead streams.Diluted acid fluid 142 can comprise phosphoric acid or sulfuric acid.In the diluted acid fluid 142 of this circulation, adding acid makes the pH of washing tower wake flow 146 remain on 1.7-2.0.Before described washing tower tower top exhaust flow 144 enters described HCN absorption tower 150, ammonia stripping tower 140 is designed to removal to be present in nearly all free ammonia in described ammonia absorber overhead streams 30.Described ammonia stripping column overhead exhaust flow 144 should be substantially containing ammonia, because free ammonia (ammonia not being neutralized) by the pH value in rising HCN refining system 16, therefore improves the possibility of HCN generation polymerization.Through comprising except the ammonia stripping column overhead exhaust flow 144 after ammonia the ammonia that is less than 1000mpm, for example, be less than 500mpm or be less than 300mpm.Because along with the rising of pH, the rate of polymerization of HCN can raise, and therefore must remove residual ammonia to avoid the polymerization of HCN.HCN polymerization has not only shown process efficiency problem, has also shown that operation is arduous, and this is to cause the obstruction of process pipeline due to the HCN of polymerization, thereby causes pressure to increase and relevant technology controlling and process problem.
As shown in Figure 2, ammonia stripping tower wake flow 146 can draw and be back in ammonia absorber 100 by the lower position from washing tower 140.Dilute acid streams 142 is preferably used phosphoric acid, and so washing tower wake flow 146 is recyclable to ammonia absorber 100.Except heat integration, by using identical acid to make described Ammonia recovery system 14 integrated with HCN refining system 16 in whole technique.For example, in described ammonia recovery system 14, use phosphoric acid (with ammonium hydrogen phosphate form) thereby and in HCN refining system 16, also use phosphoric acid to make logistics circulation (for example cleaning) more flexible, and produce the ammonium phosphate by product of comparing ammonium sulfate and have more value, but also without processing sulfide, and compare and use sulfuric acid, can also use the more structured material of low price.In one embodiment, described two steps of removing ammonia can be merged into a step.But in another embodiment, two different uses except ammonia step have reduced the risk that leaves residual ammonia in HCN reactor effluent leaving.With a kind of phosphoric acid of routine operate two different from ammonia step, in second step, fill into the phosphoric acid not used, it is the most useful adding stronger acid here, and the aqueous solution of the ammonium phosphate salt obtaining and excess phosphoric acid (being diluted acid) can return in first step.
Tower top exhaust flow 144 in ammonia stripping tower 140 comprises HCN, water, carbon monoxide, nitrogen, hydrogen, carbonic acid gas and methane.In one embodiment, described tower top exhaust flow 144 is passed in fractional distillating tube and therein and is cooled to 40 DEG C by cold water, to form the liquid stream of cooling vapour stream and condensation.Dilute phosphoric acid can be sprayed in this condenser and described cooling vapour stream in to suppress the polymerization of HCN.The liquid stream and the described cooling vapour stream that come from the described condensation of described tower top exhaust flow 144 can pass into from the lower position on HCN absorption tower 150 independently.Reclaim HCN by HCN being absorbed in generate HCN absorption tower wake flow 152 in diluted acid water.Tower top exhaust flow 154 is also discharged from HCN absorption tower 150.The HCN that HCN absorption tower wake flow 152 comprises sour water and such small concentrations, for example 2-8 volume %.In order to remove nearly all HCN, cooling HCN desorption tower wake flow 162 can pass into 150 tops, HCN absorption tower.In addition, also can pass into the discharge wake flow 174 of HCN rectifying column in HCN absorption tower 150, it is the tributary of HCN rectifying column wake flow 172.This tributary is recycled to HCN absorption tower 150, and so for example for these medium boiling point impurity of acetonitrile, propionitrile and vinyl cyanide can be removed with the form of HCN absorption tower tower top exhaust flow 154, otherwise it can be assembled among HCN desorption tower-upgrading tower.
Described HCN absorption tower tower top exhaust flow 154 can comprise carbon monoxide, nitrogen, hydrogen, carbonic acid gas, methane, argon and trace nitrile.Main fuel composition is hydrogen, carbon monoxide and some methane.If while having enough hydrogen, can adopt pressure-variable adsorption device recover hydrogen.Otherwise HCN absorption tower tower top exhaust flow 154 described in incendivity, or the boiler oil that sets it as steam generation boiler uses with recovered energy.The nitrile that comes from HCN rectifying column 170 can be discharged wake flow 174 and transfer in tower top exhaust flow 154 via HCN rectifying column.
It is 80-100 DEG C that HCN absorption tower wake flow 152 was preheated to temperature before adding HCN desorption tower 160.It is for example another fluid of HCN desorption tower wake flow 162 that operation is integrated process heat interchanger.This HCN desorption tower 160 comprises two bursts of feed fluid, the HCN absorption tower wake flow 152 being preheated and a part of HCN rectifying column wake flow 172, and both all add from the higher position of HCN desorption tower 160.HCN rectifying column wake flow 172 comprises a large amount of HCN, for example the HCN of about 30 % by weight-60 % by weight; A small amount of inhibitor, for example, be less than the phosphoric acid salt of 1wt%; And surplus is water.
Heat, via a steam-heated heat transfer unit, as comb 164, adds from the lower position of HCN desorption tower 160.For realizing the purpose of this utility model, discharge from waste heat boiler 126 for the steam that drives comb 164, and it can provide at least part of energy, be preferably the 40%-60% of institute's energy requirement, to drive the separation in HCN desorption tower 160.In some specific embodiments, extra energy is provided by waste heat boiler or the special facilities of reactor.Comb 164 can utilize the described low-pressure steam producing in waste heat boiler 126.In order to be suitable for the consumption in comb 164, the vapor pressure in pipeline 28 can highlyer also can be reduced to lower pressure.Low-pressure steam can via pipeline, for example, transfer to comb 164 from waste heat boiler 126 via pipeline 28.In one embodiment, this duct length is less than 50m, for example, be less than 25m.It is enough for transmission low-pressure steam.
In addition, the throughput rate of coupling ammonia desorption tower 120 and HCN desorption tower 160, the steam so producing in ammonia desorption tower 120 can be in HCN desorption tower 160.
HCN desorption tower wake flow 162 is to disengage from the lower position of HCN desorption tower 160 at 110 DEG C-120 DEG C in temperature.Described HCN desorption tower wake flow 162 is substantially not containing the sour water of HCN, and it is cooled to temperature is 30 DEG C-65 DEG C and is circulated in HCN absorption tower 150.In some specific embodiments, HCN desorption tower wake flow 162 can be drained as required.
HCN desorption tower exhaust flow 166 is central fluid of a kind of HCN of being rich in, it comprises a large amount of HCN, minor amount of water and nitrile, it is through using the described HCN desorption tower fractional distillating tube of water coolant, and the liquid that generation refluxes stream 167, large water gaging and HCN desorption tower vapor fraction stream 168.Therefore, the temperature of HCN desorption tower vapour phase cut 168, and then its purity is all controlled by the separating power of HCN rectifying column 170 always.The liquid stream 167 of described backflow is back to the top of HCN desorption tower 160.HCN desorption tower vapor fraction stream 168 flow to the lower position of HCN rectifying column 170.In one embodiment, the pressure of described control HCN desorption tower vapor fraction stream 168 is that 120kPa-140kPa and temperature are 45 DEG C-67 DEG C.The HCN that HCN desorption tower vapor fraction stream 168 comprises 70-99 volume %, for example HCN of 80-90 volume %.
Introduce described HCN desorption tower vapor fraction stream 168 at the lower position of HCN upgrading tower 170.Except the incoming flow as HCN upgrading tower 170, described HCN desorption tower vapor fraction stream 168 is returned HCN rectifying column 170 provides heat.Therefore the heat of, integrating from ammonia recovery system 14 can be used in HCN desorption tower 160 and HCN upgrading tower 170 via pipeline 28 simultaneously.Because described HCN rectifying column 170 is coupled on described HCN desorption tower 160, therefore distill the mixture of described HCN/ water without extra heat, the performance of described HCN upgrading tower 170 and described HCN desorption tower and described HCN desorption tower fractional distillating tube are all closely related.By acid, be preferably phosphoric acid, one or more position compared with upper part with the form of a kind of acid inhibitor stream 176 below the top position of described HCN upgrading tower 170 adds, further to suppress HCN polymerization.Easily there is autocatalysis (rapidly/blast) polymerization in the HCN of non-inhibition.The organism that HCN rectifying column wake flow 172 can comprise HCN, water and mix, it is returned to absorption tower 150 and desorption tower 160.
Part HCN rectifying column wake flow 172 can be used as HCN rectifying column discharge wake flow 174 and is recycled in HCN absorption tower 150, so for example can not assemble among HCN desorption tower-rectifying column for the medium boiling point impurity of acetonitrile, propionitrile and vinyl cyanide is removed.Be not bound by any theory, from ammonia recovery system 14 and the additional integration heat coming can be by the medium boiling point impurity producing in the concentrated nitrile impurity of HCN rectifying column 170 lower positions reduces HCN rectifying column 170.Can continous way or intermittent type ground discharge nitrile, for remove medium boiling point impurity from described HCN upgrading tower wake flow 172.In another embodiment, thus the pump-around stream (not shown) shifting out from the arbitrary height of HCN rectifying column 170 or HCN desorption tower 160 can provide enough nitrile rates of discharge prevent nitrile assemble.
The HCN product 32 of purifying disengages from tower top, can reflux as required.The HCN product 32 of this purifying can be collected in (not shown) in pump groove, and the gas existing in this pump groove can be discharged as required.This HCN rectifying column overhead streams comprises almost pure HCN and trace water, and preferably water content is by weight for being less than 100ppm, and more preferably it is by weight for being less than 10ppm.
Distillation tower of the present utility model can use filler and/or column plate, for example, be bubble cap plate, valve tray or sieve tray.Bubble cap plate, valve tray and sieve tray are contents known of the prior art.Valve tray is well known in the art, and tray designs is and reaches a good circulation, prevents stagnant area and prevention polymerization and corrosion.In entrainment trap, generally include the use of following technology, comprise and underspeed, centrifugation, demist, block or load, or its combination.
Should be appreciated that, multiple towers can be used for being connected ammonia recovery system 14 and HCN refining system 16 with relevant device, and this does not depart from essence of the present utility model.Should also be appreciated that; structure with the graphic tower showing in schema can be used various design, internal structure, building material, hydrokinetics etc.; as long as the function of described tower is in a mode that is enough to double or at least do not have tangible difference, described method or technique are all within the protection domain of the utility model claim.
In sum, the utility model adopts technique means as above to realize the purpose of this utility model and obtains advantage of the present utility model according to the disclosed technical scheme of the utility model.Preferred embodiment of the present utility model, just to setting forth better the utility model, is construed as the change completing according to the apparent training centre of the utility model essence to those skilled in the art and also belongs to protection domain of the present utility model.
Can further understand the utility model with reference to the following examples.
Embodiment 1
Use pure oxygen, form a kind of ternary gas mixture containing ammonia gas and methane-containing gas.In ternary gas mixture, the mol ratio of ammonia and oxygen is 1.3:1, and the mol ratio of methane and oxygen is 1.2:1 in ternary gas mixture, the ternary gas mixture that comprises 27～29.5 volume % oxygen is reacted and is generated a kind of component thick prussic acid product as shown in table 2 under platinum/rhodium catalyst existence condition.
Described thick prussic acid product shifts out and is admitted to the ammonia recovery system that contains ammonia absorber and ammonia desorption tower from reactor.First described thick prussic acid product contacts with ammonia absorption agent and generates a kind of rich ammonia phosphoric acid salt fluid that contains ammonia and water and flow containing the absorption tower tower top of HCN.Described absorption tower tower top stream separates to be further purified described HCN product subsequently in a HCN desorption tower.Described rich ammonia phosphoric acid salt fluid is admitted to described ammonia desorption tower subsequently so that ammonia and water evaporation are formed to a kind of desorption tower overhead streams and one lean stream.Described desorption tower overhead streams is formed and contains the steam that pressure is 180～380KPa by partial condensation in a waste heat boiler.Described delivery of steam, to the exquisite system of HCN, and provides 40～60% energy for operating described HCN desorption tower.
Comparative example A
Use air, form a kind of ternary gas mixture containing ammonia gas and methane-containing gas.In described ternary gas mixture, comprise the oxygen that is less than 25 volume %.Except steam does not reclaim, all the other separation methods that use as described in Example 1.The disposable reason of its steam is that the moisture content in described thick prussic acid product is too low, and vapor recovery is not calculated from cost.
The thick prussic acid product of table 2
| ? | Embodiment 1 | Comparative example A |
| H 2 | 34.5 | 13.3 |
| N 2 | 2.4 | 49.2 |
| CO | 4.7 | 3.8 |
| Ar | 0.1 | ? |
| CH 4 | 0.8 | 0.3 |
| CO 2 | 0.4 | 0.4 |
| NH 3 | 6.6 | 2.3 |
| HCN | 16.9 | 7.6 |
| Other nitrile | ＜0.1 | ** |
| H 2O | 33.4 | 23.1 |
Claims (9)
1. a heat integration device, is characterized in that, comprising:
For the ammonia absorber that the thick prussic acid product that comprises prussic acid, ammonia and water is contacted with absorption liquid;
Ammonia desorption tower, it is connected with the bottom of ammonia absorber;
Waste heat boiler, it is connected with the top of ammonia Analytic Tower;
Washing tower, it is connected with the top of ammonia absorber;
Prussic acid absorption tower, it is connected with the top of washing tower;
Be used for obtaining prussic acid fluid prussic acid desorption tower, it is connected with the bottom on prussic acid absorption tower, and wherein said prussic acid desorption tower contains comb; And
Pipeline, for connecting waste heat boiler and comb.
2. device as claimed in claim 1, is characterized in that, the length of described pipeline is less than 50 meters.
3. device as claimed in claim 1, is characterized in that, the length of described pipeline is less than 25 meters.
4. device as claimed in claim 1, is characterized in that, also comprises that it is connected with ammonia absorber for the preparation of the thick product reactor of described prussic acid.
5. device as claimed in claim 1, is characterized in that, is also included in the condenser of the tower top that connects described prussic acid desorption tower.
6. device as claimed in claim 5, is characterized in that, also comprises the prussic acid rectifying column being connected with condenser.
7. device as claimed in claim 1, is characterized in that, also comprises that technique is to process heat interchanger, and described technique is arranged on to the pipeline for connecting ammonia absorber and ammonia Analytic Tower to process heat interchanger.
8. device as claimed in claim 1, is characterized in that, also comprises fractional distillating tube, and it is connected with the different positions on prussic acid absorption tower.
9. device as claimed in claim 1, is characterized in that, also comprises ammonia rectifying column, and it is connected with the tower top of ammonia desorption tower.
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| US201261738830P | 2012-12-18 | 2012-12-18 | |
| US61/738,830 | 2012-12-18 |
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| TW (1) | TWM499253U (en) |
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