CN104209089A - Preparation method of copper-containing zeolite adsorbent used for separating olefin from alkane - Google Patents
Preparation method of copper-containing zeolite adsorbent used for separating olefin from alkane Download PDFInfo
- Publication number
- CN104209089A CN104209089A CN201410481695.XA CN201410481695A CN104209089A CN 104209089 A CN104209089 A CN 104209089A CN 201410481695 A CN201410481695 A CN 201410481695A CN 104209089 A CN104209089 A CN 104209089A
- Authority
- CN
- China
- Prior art keywords
- zeolite
- adsorbent
- cupric
- copper
- preparation
- 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.)
- Pending
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 164
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 131
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000010457 zeolite Substances 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 title claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 title abstract description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 title abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract 5
- 238000005342 ion exchange Methods 0.000 claims abstract description 74
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000926 separation method Methods 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 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 2
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 54
- 229910001431 copper ion Inorganic materials 0.000 description 38
- 238000000034 method Methods 0.000 description 29
- 239000001294 propane Substances 0.000 description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 27
- 239000007789 gas Substances 0.000 description 22
- 238000001179 sorption measurement Methods 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 19
- 238000001816 cooling Methods 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000011148 porous material Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 235000013844 butane Nutrition 0.000 description 15
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000001273 butane Substances 0.000 description 10
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- -1 alkene alkane Chemical class 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a copper-containing zeolite adsorbent used for separating olefin from alkane. The preparation method of the copper-containing zeolite adsorbent used for separating olefin from alkane is capable of preparing relatively high content of cuprous active site with relatively low energy consumption in relatively short time, so that the separation performance of the copper-containing zeolite adsorbent during separation of olefin and alkane is improved. The preparation method of the copper-containing zeolite adsorbent used for separating olefin from alkane comprises the following steps: exchanging ions of a bivalent copper salt solution and a carrier zeolite, filtering reaction liquid to obtain solid, drying the solid to obtain bivalent cupric ion exchange zeolite, putting the obtained bivalent cupric ion exchange zeolite and a reducing agent in a sealed reaction kettle, separating the bivalent cupric ion exchange zeolite from the reducing agent by using an open container, enabling the zeolite to not be in direct contact with the reducing agent, introducing reducing agent steam and carrying out reduction reaction to obtain a zeolite adsorbent containing a cuprous active component.
Description
Technical field
The present invention relates to a kind of preparation method of adsorbent, more specifically to a kind of preparation method for alkene-alkane separation cupric zeolite adsorbents, belong to chemical gases separation technology field.
Background technology
Output in Petro-chemical industry of alkene and alkane and demand all larger, be most important raw material.Owing to having similar physical property, the separating difficulty of alkene and alkane is comparatively large, industrial main employing cryogenic distillation process, and the investment of this separating technology equipment needed thereby is large, energy consumption is high.Adsorption method of separation, because it is efficient, energy-conservation and the advantage such as low cost, is considered to method comparatively suitable in current numerous separation method.Especially, some transition metal (Cu is utilized
+, Ag
+deng) being separated of the alkene alkane of high selectivity can be realized with the complex reaction between unsaturated hydrocarbons.
Monovalence copper, as active component, is widely used in adsorbing separation.But in currently available technology, obtained by two kinds of approach reduction cupric on zeolite adsorbents: (1) will the cupric that exchange on carrier zeolite long-time (>6h) heat treatment of high temperature (>450 DEG C) under an inert atmosphere, the method exists that reduction temperature is high, the time long, the percent reduction of copper is low, the shortcoming of extremely unstable; (2) cupric (the H under reducing atmosphere will exchanged on carrier zeolite
2, CO or C
2h
4) heat treatment, the method existence is difficult to control, and easy over reduction is the shortcoming of elemental copper.Therefore, solve prior art in-problem key, being to research and develop new method prepared by a kind of cupric zeolite adsorbents, utilizing the shorter time at a lower temperature cupric to be controllably reduced into monovalence copper to realizing.
Summary of the invention
Technical problem to be solved by this invention is: for prior art Problems existing, provides a kind of preparation method for alkene-alkane separation cupric zeolite adsorbents.The preparation method of this cupric zeolite adsorbents can realize, compared with low energy consumption, the monovalence copper activity position obtaining high level in the short period, improve the separating property of this cupric zeolite adsorbents in alkene-alkane separation.
The technical scheme that the present invention solves its technical problem is as follows:
Preparation method for alkene-alkane separation cupric zeolite adsorbents of the present invention, comprises the following steps:
After cupric salt solution and carrier zeolite are carried out ion-exchange, filtering reacting liquid obtains solid, after solid drying, obtain bivalent cupric ion exchanging zeolite, the bivalent cupric ion exchanging zeolite obtained and reducing agent are placed in closed reactor and also separate with open container, zeolite does not directly contact with reducing agent, introduces reducing agent steam, carry out reduction reaction, obtain the zeolite adsorbents containing monovalence copper activity component.
Preparation method for alkene-alkane separation cupric zeolite adsorbents of the present invention, its further technical scheme is described introducing reducing agent steam is under being heated to 150 ~ 250 DEG C of conditions, reducing agent volatilization produces steam, diffuse to and bivalent cupric ion exchanging zeolite occurs redox reaction obtain zeolite adsorbents containing monovalence copper activity component, wherein the mass ratio of bivalent cupric ion exchanging zeolite and reducing agent is 0.1 ~ 1:1, and the reaction time is 3 ~ 10h.Further technical scheme is described reducing agent is formaldehyde, methyl alcohol, formic acid, acetaldehyde, ethanol, hydrazine hydrate or N, one or more of N '-dimethyl formamide.
Preparation method for alkene-alkane separation cupric zeolite adsorbents of the present invention, its further technical scheme can also be described cupric salt solution is 2 ~ 10 times with the ion exchange capacity ratio of carrier zeolite, the temperature of ion-exchange is 25 ~ 100 DEG C, and the time is 12 ~ 48h.
Preparation method for alkene-alkane separation cupric zeolite adsorbents of the present invention, its further technical scheme one or more compositions that can also to be described carrier zeolite be in A type, X-type, Y type, ZSM type molecular sieve, modenite or clinoptilolite.
Preparation method for alkene-alkane separation cupric zeolite adsorbents of the present invention, its further technical scheme can also be described cupric salt is Schweinfurt green, copper sulphate, copper nitrate or copper chloride.
Compared with prior art the present invention has following beneficial effect:
The adsorbent utilizing above-mentioned preparation method to be prepared into also is applied in being separated of alkene and alkane by the present invention, obtains good separating effect.The present invention is the redox reaction utilizing cupric in zeolite and reducing agent steam, prepares a kind of cupric zeolite adsorbents at a lower temperature, and is effectively applied to the separation of alkene alkane.Preparation method's service condition provided by the invention is gentle, and in obtained sample, monovalence copper content is high, has higher adsorbance, substantially increase olefine selective to alkene.
Detailed description of the invention
The following examples will be further described the present invention, but content of the present invention is not limited thereto.
Embodiment 1
The preparation of adsorbent: take 10g Schweinfurt green and be dissolved in 500mL deionized water, the zeolite ZSM-5 taking 1g is dissolved in above-mentioned 50mL Schweinfurt green solution, ion-exchange 24h at 30 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL formaldehyde in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 5h in 180 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of (following examples all adopt the method to measure) adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.57mmol/g to the adsorbance of propylene, is 1.36mmol/g to the adsorbance of propane, and separation selectivity is 2.62.
Embodiment 2
The preparation of adsorbent: take 12.5g copper sulphate and be dissolved in 500mL deionized water, the zeolite ZSM-5 taking 1g is dissolved in above-mentioned 50mL copper-bath, ion-exchange 12h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL methyl alcohol in container that 0.8g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 210 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of ethene, ethane, and the ethylene/ethane separation calculating adsorbent is selective.Under normal temperature and pressure, adsorbent is 3.78mmol/g to the adsorbance of ethene, is 1.26mmol/g to the adsorbance of ethane, and equilibrium selective is 3.01.
Embodiment 3
The preparation of adsorbent: take 12.1g copper nitrate and be dissolved in 500mL deionized water, the zeolite ZSM-5 taking 1g is dissolved in above-mentioned 50mL copper nitrate solution, ion-exchange 24h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL hydrazine hydrate in container that 0.8g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 200 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of butylene, butane, and calculate the butenes/butanes separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.14mmol/g to the adsorbance of butylene, is 1.28mmol/g to the adsorbance of butane, and equilibrium selective is 2.44.
Embodiment 4
The preparation of adsorbent: take 8.5g copper chloride and be dissolved in 500mL deionized water, the zeolite ZSM-5 taking 1g is dissolved in above-mentioned 45mL copper chloride solution, ion-exchange 24h at 60 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL formaldehyde in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 180 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.81mmol/g to the adsorbance of propylene, is 1.30mmol/g to the adsorbance of propane, and equilibrium selective is 2.93.
Embodiment 5
The preparation of adsorbent: take 10g Schweinfurt green and be dissolved in 500mL deionized water, the zeolite NaY taking 1g is dissolved in above-mentioned 50mL Schweinfurt green solution, ion-exchange 24h at 50 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL formic acid in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 220 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of ethene, ethane, and the ethylene/ethane separation calculating adsorbent is selective.Under normal temperature and pressure, adsorbent is 4.30mmol/g to the adsorbance of ethene, is 1.26mmol/g to the adsorbance of ethane, and equilibrium selective is 3.41.
Embodiment 6
The preparation of adsorbent: take 12.5g copper sulphate and be dissolved in 500mL deionized water, the zeolite NaY taking 1g is dissolved in above-mentioned 50mL copper-bath, ion-exchange 12h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL methyl alcohol in container that 0.8g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 210 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of butylene, butane, and calculate the butenes/butanes separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.73mmol/g to the adsorbance of butylene, is 1.29mmol/g to the adsorbance of butane, and equilibrium selective is 2.89.
Embodiment 7
The preparation of adsorbent: take 12.1g copper nitrate and be dissolved in 500mL deionized water, the zeolite NaY taking 1g is dissolved in above-mentioned 50mL copper nitrate solution, ion-exchange 24h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL methyl alcohol in container that 0.8g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 5h in 220 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 4.14mmol/g to the adsorbance of propylene, is 1.32mmol/g to the adsorbance of propane, and equilibrium selective is 3.14.
Embodiment 8
The preparation of adsorbent: take 8.5g copper chloride and be dissolved in 500mL deionized water, the zeolite NaY taking 1g is dissolved in above-mentioned 45mL copper chloride solution, ion-exchange 24h at 60 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL formaldehyde in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 180 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 4.11mmol/g to the adsorbance of propylene, is 1.33mmol/g to the adsorbance of propane, and equilibrium selective is 3.07.
Embodiment 9
The preparation of adsorbent: take 12.1g copper nitrate and be dissolved in 500mL deionized water, the zeolite NaY taking 1g is dissolved in above-mentioned 50mL copper nitrate solution, ion-exchange 24h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL hydrazine hydrate in container that 0.8g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 220 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 4.18mmol/g to the adsorbance of propylene, is 1.30mmol/g to the adsorbance of propane, and equilibrium selective is 3.21.
Embodiment 10
The preparation of adsorbent: take 6.04g copper nitrate and be dissolved in 250mL deionized water, the 4A zeolite taking 1g is dissolved in above-mentioned 45mL copper nitrate solution, ion-exchange 48h at 30 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.To get in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening with 1mL acetaldehyde isolation in closed reactor, be placed in 5h in 180 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of butylene, butane, and calculate the butenes/butanes separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.81mmol/g to the adsorbance of butylene, is 1.28mmol/g to the adsorbance of butane, and equilibrium selective is 2.97.
Embodiment 11
The preparation of adsorbent: take 12.5g copper sulphate and be dissolved in 500mL deionized water, the zeolite 4A taking 1g is dissolved in above-mentioned 50mL copper-bath, ion-exchange 12h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL methyl alcohol in container that 0.8g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 210 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of butylene, butane, and calculate the butenes/butanes separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.87mmol/g to the adsorbance of butylene, is 1.49mmol/g to the adsorbance of butane, and equilibrium selective is 2.60.
Embodiment 12
The preparation of adsorbent: take 10g Schweinfurt green and be dissolved in 500mL deionized water, the zeolite 4A taking 1g is dissolved in above-mentioned 50mL Schweinfurt green solution, ion-exchange 24h at 30 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL formaldehyde in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 5h in 180 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of (following examples all adopt the method to measure) adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of ethylene-ethane, and the ethylene/ethane separation calculating adsorbent is selective.Under normal temperature and pressure, adsorbent is 3.95mmol/g to the adsorbance of ethene, is 1.25mmol/g to the adsorbance of ethane, and separation selectivity is 3.15.
Embodiment 13
The preparation of adsorbent: take 8.5g copper chloride and be dissolved in 500mL deionized water, the zeolite 4A taking 1g is dissolved in above-mentioned 45mL copper chloride solution, ion-exchange 24h at 60 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mLDMF in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 220 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.81mmol/g to the adsorbance of propylene, is 1.14mmol/g to the adsorbance of propane, and equilibrium selective is 3.35.
Embodiment 14
The preparation of adsorbent: take 12.5g copper sulphate and be dissolved in 500mL deionized water, the zeolite 13X taking 1g is dissolved in above-mentioned 50mL copper-bath, ion-exchange 24h at 60 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL formic acid in container that 0.8g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 200 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of ethene, ethane, and the ethylene/ethane separation calculating adsorbent is selective.Under normal temperature and pressure, adsorbent is 3.52mmol/g to the adsorbance of ethene, is 1.21mmol/g to the adsorbance of ethane, and equilibrium selective is 2.91.
Embodiment 15
The preparation of adsorbent: take 10g Schweinfurt green and be dissolved in 500mL deionized water, the zeolite 13X taking 1g is dissolved in above-mentioned 50mL Schweinfurt green solution, ion-exchange 24h at 30 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL formaldehyde in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 5h in 180 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of (following examples all adopt the method to measure) adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of ethylene-ethane, and the ethylene/ethane separation calculating adsorbent is selective.Under normal temperature and pressure, adsorbent is 3.70mmol/g to the adsorbance of ethene, is 1.16mmol/g to the adsorbance of ethane, and separation selectivity is 3.18.
Embodiment 16
The preparation of adsorbent: take 12.5g copper sulphate and be dissolved in 500mL deionized water, the zeolite 13X taking 1g is dissolved in above-mentioned 50mL copper-bath, ion-exchange 12h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL methyl alcohol in container that 0.8g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 210 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of butylene, butane, and calculate the butenes/butanes separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.94mmol/g to the adsorbance of butylene, is 1.40mmol/g to the adsorbance of butane, and equilibrium selective is 2.82.
Embodiment 17
The preparation of adsorbent: take 8.5g copper chloride and be dissolved in 500mL deionized water, the zeolite 13X taking 1g is dissolved in above-mentioned 45mL copper chloride solution, ion-exchange 24h at 60 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get and be isolated in closed reactor with 1mL hydrazine hydrate in container that 0.1g Copper Ion Exchange zeolite sample is placed on an opening, be placed in 6h in 220 DEG C of baking ovens, cupric zeolite adsorbents can be obtained after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.59mmol/g to the adsorbance of propylene, is 1.17mmol/g to the adsorbance of propane, and equilibrium selective is 3.06.
Comparative example 1
The preparation of adsorbent: adopt the method identical with embodiment 7 to prepare ion exchanged zeolite.Take 12.1g copper nitrate to be dissolved in 500mL deionized water, the zeolite NaY taking 1g is dissolved in above-mentioned 50mL copper nitrate solution, ion-exchange 24h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Getting 0.2g Copper Ion Exchange zeolite sample is filled in the middle part of quartz ampoule, and two ends quartz sand is fixed, and in inert gas argon gas atmosphere, 450 DEG C keep 6h, can obtain cupric zeolite adsorbents after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 4.08mmol/g to the adsorbance of propylene, is 2.51mmol/g to the adsorbance of propane, and equilibrium selective is 1.62.
Comparative example 2
The preparation of adsorbent: adopt the method identical with embodiment 7 to prepare ion exchanged zeolite.Take 12.1g copper nitrate to be dissolved in 500mL deionized water, the zeolite NaY taking 1g is dissolved in above-mentioned 50mL copper nitrate solution, ion-exchange 24h at 90 DEG C, through filtering, wash and after drying, obtaining Copper Ion Exchange zeolite sample.Get 0.2g Copper Ion Exchange zeolite sample to be filled in U-shaped quartz ampoule, utilize temperature programming device, in hydrogen/argon gas atmosphere, 350 DEG C keep 5h, can obtain cupric zeolite adsorbents after cooling.
Adsorption applications is tested: adopt volumetric method to measure the gas absorption performance of adsorbent.Get ASAP2020 specific surface and pore analysis instrument that above-mentioned adsorbent 500mg is placed in Merck & Co., Inc of the U.S., adsorb under certain pressure and temperature, finally measure adsorbent respectively to the adsorbance of propylene, propane, and calculate the propylene/propane separation selectivity of adsorbent.Under normal temperature and pressure, adsorbent is 3.87mmol/g to the adsorbance of propylene, is 2.73mmol/g to the adsorbance of propane, and equilibrium selective is 1.42.
Claims (6)
1., for a preparation method for alkene-alkane separation cupric zeolite adsorbents, it is characterized in that comprising the following steps:
After cupric salt solution and carrier zeolite are carried out ion-exchange, filtering reacting liquid obtains solid, after solid drying, obtain bivalent cupric ion exchanging zeolite, the bivalent cupric ion exchanging zeolite obtained and reducing agent are placed in closed reactor and also separate with open container, zeolite does not directly contact with reducing agent, introduces reducing agent steam, carry out reduction reaction, obtain the zeolite adsorbents containing monovalence copper activity component.
2. the preparation method for alkene-alkane separation cupric zeolite adsorbents according to claim 1, it is characterized in that described introducing reducing agent steam is under being heated to 150 ~ 250 DEG C of conditions, reducing agent volatilization produces steam, diffuse to and bivalent cupric ion exchanging zeolite occurs redox reaction obtain zeolite adsorbents containing monovalence copper activity component, wherein the mass ratio of bivalent cupric ion exchanging zeolite and reducing agent is 0.1 ~ 1:1, and the reaction time is 3 ~ 10h.
3. the preparation method for alkene-alkane separation cupric zeolite adsorbents according to claim 1 and 2, is characterized in that described reducing agent is formaldehyde, methyl alcohol, formic acid, acetaldehyde, ethanol, hydrazine hydrate or N, one or more of N '-dimethyl formamide.
4. the preparation method for alkene-alkane separation cupric zeolite adsorbents according to claim 1, it is characterized in that described cupric salt solution is 2 ~ 10 times with the ion exchange capacity ratio of carrier zeolite, the temperature of ion-exchange is 25 ~ 100 DEG C, and the time is 12 ~ 48h.
5. the preparation method for alkene-alkane separation cupric zeolite adsorbents according to claim 1 or 4, is characterized in that described carrier zeolite is one or more compositions in A type, X-type, Y type, ZSM type molecular sieve, modenite or clinoptilolite.
6. the preparation method for alkene-alkane separation cupric zeolite adsorbents according to claim 1, is characterized in that described cupric salt is Schweinfurt green, copper sulphate, copper nitrate or copper chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410481695.XA CN104209089A (en) | 2014-09-19 | 2014-09-19 | Preparation method of copper-containing zeolite adsorbent used for separating olefin from alkane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410481695.XA CN104209089A (en) | 2014-09-19 | 2014-09-19 | Preparation method of copper-containing zeolite adsorbent used for separating olefin from alkane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104209089A true CN104209089A (en) | 2014-12-17 |
Family
ID=52091232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410481695.XA Pending CN104209089A (en) | 2014-09-19 | 2014-09-19 | Preparation method of copper-containing zeolite adsorbent used for separating olefin from alkane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104209089A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573204A (en) * | 2017-09-11 | 2018-01-12 | 山东京博石油化工有限公司 | A kind of process for purification of pentane |
| CN111771078A (en) * | 2018-02-27 | 2020-10-13 | 松下知识产权经营株式会社 | Vacuum heat insulating material, heat insulating structure using the same, and household electrical appliance, house wall, and transportation equipment using the material or structure |
| CN112844319A (en) * | 2020-12-24 | 2021-05-28 | 南京工业大学 | Metal organic framework adsorbent with valence-sub metal nodes prepared by steam reduction method, and preparation method and application thereof |
| CN114937782A (en) * | 2022-04-24 | 2022-08-23 | 中国科学院长春应用化学研究所 | Supported metal-based catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101183A (en) * | 1983-12-30 | 1986-10-08 | Bp化学有限公司 | Select absorption and reclaim organic gas with the faujasite of ion-exchange |
| JP2005015267A (en) * | 2003-06-25 | 2005-01-20 | Taiyo Nippon Sanso Corp | Method of manufacturing copper ion exchange zeolite |
| CN103007874A (en) * | 2012-12-13 | 2013-04-03 | 南京工业大学 | Supported cuprous oxide adsorbent as well as preparation method, application and regeneration method thereof |
| CN103331139A (en) * | 2013-06-20 | 2013-10-02 | 南京工业大学 | Preparation method of copper-containing load-type adsorbent |
-
2014
- 2014-09-19 CN CN201410481695.XA patent/CN104209089A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101183A (en) * | 1983-12-30 | 1986-10-08 | Bp化学有限公司 | Select absorption and reclaim organic gas with the faujasite of ion-exchange |
| JP2005015267A (en) * | 2003-06-25 | 2005-01-20 | Taiyo Nippon Sanso Corp | Method of manufacturing copper ion exchange zeolite |
| CN103007874A (en) * | 2012-12-13 | 2013-04-03 | 南京工业大学 | Supported cuprous oxide adsorbent as well as preparation method, application and regeneration method thereof |
| CN103331139A (en) * | 2013-06-20 | 2013-10-02 | 南京工业大学 | Preparation method of copper-containing load-type adsorbent |
Non-Patent Citations (1)
| Title |
|---|
| 张霞艳等: "卤化亚铜的制备及催化应用研究进展", 《无机盐工业》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573204A (en) * | 2017-09-11 | 2018-01-12 | 山东京博石油化工有限公司 | A kind of process for purification of pentane |
| CN107573204B (en) * | 2017-09-11 | 2020-11-03 | 山东京博石油化工有限公司 | Refining method of pentane |
| CN111771078A (en) * | 2018-02-27 | 2020-10-13 | 松下知识产权经营株式会社 | Vacuum heat insulating material, heat insulating structure using the same, and household electrical appliance, house wall, and transportation equipment using the material or structure |
| CN112844319A (en) * | 2020-12-24 | 2021-05-28 | 南京工业大学 | Metal organic framework adsorbent with valence-sub metal nodes prepared by steam reduction method, and preparation method and application thereof |
| CN114937782A (en) * | 2022-04-24 | 2022-08-23 | 中国科学院长春应用化学研究所 | Supported metal-based catalyst and preparation method thereof |
| CN114937782B (en) * | 2022-04-24 | 2024-03-08 | 中国科学院长春应用化学研究所 | Supported metal-based catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | CO adsorption on activated carbon-supported Cu-based adsorbent prepared by a facile route | |
| CN103007874B (en) | Supported cuprous oxide adsorbent as well as preparation method, application and regeneration method thereof | |
| CN104209089A (en) | Preparation method of copper-containing zeolite adsorbent used for separating olefin from alkane | |
| CN103007885B (en) | A kind of adsorbent for alkene-alkane separation and its preparation method and application | |
| CN104492383A (en) | Metal organic framework adsorbent as well as preparation method and application thereof | |
| Qin et al. | Low-temperature fabrication of Cu (I) sites in zeolites by using a vapor-induced reduction strategy | |
| CN104525121A (en) | Adsorbent for olefin/alkane mixed gas separation and preparation method and application thereof | |
| CN104492375A (en) | Adsorbent for recovering CO from industrial exhaust gas as well as preparation method and application of adsorbent | |
| CN108569698A (en) | A kind of carbon dioxide purification device | |
| CN103213984A (en) | Method for preparing high thermal conductivity active carbon taking waste cotton cloth as raw material | |
| CN103331139B (en) | A kind of preparation method of cupric load type adsorbing agent | |
| CN104998631A (en) | Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof | |
| CN107442084A (en) | A kind of poly-dopamine pitch base composite porous carbon adsorbing material of Preferential adsorption ethane and preparation method and application | |
| CN110270303A (en) | A kind of efficient CO adsorbent and preparation method thereof | |
| CN102442878A (en) | Purification method of dichloromethane | |
| CN105536695B (en) | A kind of adsorbent and preparation method of adsorbing separation polycyclic aromatic hydrocarbon | |
| CN204034505U (en) | A kind of shell-and-tube organic waste gas purifying processing device | |
| CN103949206B (en) | A kind of metal salt molecular sieve type deep dehydration adsorbent and preparation method | |
| CN106622150A (en) | C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof | |
| CN102357366A (en) | Non-mercury catalyst used for acetylene hydrochlorination | |
| CN103933934B (en) | A kind of adsorbent for removing micro-moisture in gas and preparation method | |
| CN104402663B (en) | A kind of alkane impurity deep-purifying method | |
| CN106140263B (en) | It is a kind of using modified ZSM-5 as bromomethane preparing isobutene catalyst of carrier and preparation method thereof | |
| CN106140259B (en) | It is a kind of using modified zsm-5 zeolite as loaded catalyst of carrier and its preparation method and application | |
| CN103418164A (en) | Method for removing oxygen-containing compound in hydrocarbon stream |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141217 |