JP5129900B2 - Absorbent for impurities consisting of mercury, arsenic and sulfur and method for removing the same - Google Patents
Absorbent for impurities consisting of mercury, arsenic and sulfur and method for removing the same Download PDFInfo
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- JP5129900B2 JP5129900B2 JP2008217279A JP2008217279A JP5129900B2 JP 5129900 B2 JP5129900 B2 JP 5129900B2 JP 2008217279 A JP2008217279 A JP 2008217279A JP 2008217279 A JP2008217279 A JP 2008217279A JP 5129900 B2 JP5129900 B2 JP 5129900B2
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- 239000002250 absorbent Substances 0.000 title claims description 57
- 230000002745 absorbent Effects 0.000 title claims description 57
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims description 41
- 229910052753 mercury Inorganic materials 0.000 title claims description 41
- 239000012535 impurity Substances 0.000 title claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 29
- 239000011593 sulfur Substances 0.000 title claims description 29
- 229910052717 sulfur Inorganic materials 0.000 title claims description 29
- 229910052785 arsenic Inorganic materials 0.000 title claims description 26
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 42
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 40
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002131 composite material Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000012438 extruded product Nutrition 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003498 natural gas condensate Substances 0.000 description 2
- -1 oxide carrier Chemical compound 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- HTDIUWINAKAPER-UHFFFAOYSA-N trimethylarsine Chemical compound C[As](C)C HTDIUWINAKAPER-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- HBNBMOGARBJBHS-UHFFFAOYSA-N dimethylarsane Chemical compound C[AsH]C HBNBMOGARBJBHS-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- IDDBICIFODFKQO-UHFFFAOYSA-N methylarsane Chemical compound [AsH2]C IDDBICIFODFKQO-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- XAZAQTBGMXGTBD-UHFFFAOYSA-N tributylarsane Chemical compound CCCC[As](CCCC)CCCC XAZAQTBGMXGTBD-UHFFFAOYSA-N 0.000 description 1
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
本発明はナフサ留分や天然ガスコンデンセート等の炭化水素中の水銀、砒素、硫黄などの微量不純物を除去する吸収剤およびその除去方法に関するものである。 The present invention relates to an absorbent for removing trace impurities such as mercury, arsenic and sulfur in hydrocarbons such as naphtha fraction and natural gas condensate, and a method for removing the same.
天然ガスコンデンセートなどの炭化水素には、水銀、砒素、硫黄などの微量不純物が含まれることがある。これらのコンデンセート又はこれを蒸留したナフサなどは、エチレン原料、接触改質、水素化処理などに使用されるが、水銀、砒素、硫黄などが含まれていると、腐食を引き起こす、下流の貴金属触媒の被毒となるなど、多くの問題がある。従って、これらの炭化水素から水銀、砒素、硫黄などの微量不純物を除去する必要がある。 Hydrocarbons such as natural gas condensate may contain trace impurities such as mercury, arsenic, and sulfur. These condensates or naphtha obtained by distilling these condensates are used for ethylene raw materials, catalytic reforming, hydrotreating, etc., but if they contain mercury, arsenic, sulfur, etc., downstream precious metal catalysts that cause corrosion There are many problems such as being poisoned. Therefore, it is necessary to remove trace impurities such as mercury, arsenic and sulfur from these hydrocarbons.
炭化水素中の水銀や砒素を除去する各種の吸収剤が提案されている。例えば、モリブデンやコバルト、ニッケルなどの金属化合物を硫化した吸収剤（特許文献１、特許文献２）、活性炭に塩素含有化合物を添着した吸収剤（特許文献３）、酸化マンガンと酸化鉄の複合酸化物をアルミナなどの担体に担持した吸収剤（特許文献４）などがある。 Various absorbents for removing mercury and arsenic in hydrocarbons have been proposed. For example, an absorbent obtained by sulfurizing a metal compound such as molybdenum, cobalt, or nickel (Patent Documents 1 and 2), an absorbent obtained by adding a chlorine-containing compound to activated carbon (Patent Document 3), or a composite oxidation of manganese oxide and iron oxide There is an absorbent (Patent Document 4) in which an object is supported on a carrier such as alumina.
しかしながら、モリブデンやコバルト、ニッケルなどの金属化合物を硫化した吸収剤は、硫化物が炭化水素中に流出する可能性があることのほかに水銀については、除去率が充分でなく、水銀含有量が極微量の場合には吸収性能が極端に低下する問題を有している。また、活性炭に塩素含有化合物を添着した吸収剤も炭化水素中に塩素分の流出する恐れがあること、砒素、硫黄の除去はできないことなどが問題とされる。一方、酸化マンガンと酸化鉄の複合酸化物は水銀、砒素、硫黄など多種の不純物を吸収除去できるが、特に、水銀については、除去の能力が充分ではなく、より大きな吸収能力が求められている。 However, an absorbent that is sulfided with a metal compound such as molybdenum, cobalt, or nickel has an insufficient removal rate for mercury in addition to the possibility of sulfides flowing into hydrocarbons, and the mercury content is low. In the case of a very small amount, there is a problem that the absorption performance is extremely lowered. Further, there are problems that an absorbent in which a chlorine-containing compound is impregnated with activated carbon may cause chlorine to flow out into the hydrocarbon, and that arsenic and sulfur cannot be removed. On the other hand, composite oxides of manganese oxide and iron oxide can absorb and remove various impurities such as mercury, arsenic, and sulfur. In particular, mercury is not sufficiently capable of removing it, and a larger absorption capacity is required. .
従って、本発明の課題は、従来の水銀、砒素、硫黄などの微量不純物の吸収剤の問題点を解決し、かつ、効率的に水銀、砒素、硫黄などの微量不純物を除去する吸収剤を提供することにある。 Accordingly, an object of the present invention is to solve the problems of conventional absorbents of trace impurities such as mercury, arsenic and sulfur, and to provide an absorbent which efficiently removes trace impurities such as mercury, arsenic and sulfur There is to do.
そこで、本発明者らは、上記課題を解決するために鋭意検討を行ったところ、酸化マンガンと酸化鉄の複合酸化物を酸化物担体に担持した基材に銀を添加した吸収剤が、水銀、砒素並びに硫黄の除去能力が非常に大きいことを見出した。 Therefore, the present inventors have conducted extensive studies to solve the above-mentioned problems. As a result, an absorbent in which silver is added to a base material in which a composite oxide of manganese oxide and iron oxide is supported on an oxide carrier is a mercury. It has been found that the ability to remove arsenic and sulfur is very large.
すなわち、本発明は、
（１）銀と酸化鉄と酸化マンガンとそれらを坦持する酸化物担体を含有することを特徴とする炭化水素を含んだガスに含まれる水銀、砒素、硫黄からなる不純物の吸収剤である。
（２）吸収剤全体に対し、銀が０．０１〜５重量％、酸化鉄が４０〜６５重量％、酸化マンガンが２０〜４０重量％、酸化物担体が１０〜２０重量％の組成比であることを特徴とする（１）記載の水銀、砒素、硫黄からなる不純物の吸収剤である。
（３）酸化物担体がアルミナ、シリカ、チタニアからなる群から選択される酸化物であることを特徴とする（１）または（２）記載の水銀、砒素、硫黄からなる不純物の吸収剤である。
（４）上記（１）乃至（３）のいずれかに記載の吸収剤と、炭化水素を含んだガスを接触させ、炭化水素を含んだガスに含まれる水銀、砒素、硫黄からなる不純物を除去する方法である。
That is, the present invention
(1) An absorber of impurities composed of mercury, arsenic, and sulfur contained in a gas containing hydrocarbon , characterized by containing silver, iron oxide, manganese oxide, and an oxide carrier that supports them.
(2) The composition ratio of silver is 0.01 to 5% by weight, iron oxide is 40 to 65% by weight, manganese oxide is 20 to 40% by weight, and the oxide carrier is 10 to 20 % by weight with respect to the entire absorbent. (1) An impurity absorbent comprising mercury, arsenic, and sulfur.
(3) The oxide absorber is an oxide selected from the group consisting of alumina, silica, and titania. (1) or (2) is an absorbent for impurities consisting of mercury, arsenic, and sulfur. .
(4) Contacting the absorbent according to any one of (1) to (3) above with a gas containing hydrocarbon, and removing impurities including mercury, arsenic, and sulfur contained in the gas containing hydrocarbon. It is a method to do.
本発明の吸収剤では、水銀、砒素、硫黄などの微量不純物の除去性能が大幅に向上することで、長期に運転可能であり、かつ、この吸収剤は硫化物や塩化物を含まないので、炭化水素中に流出する恐れもないため、工業的価値が大きく、公害防止の観点から有用である。 In the absorbent according to the present invention, the removal performance of trace impurities such as mercury, arsenic, sulfur and the like can be improved over a long period of time, and the absorbent does not contain sulfides or chlorides. Since there is no fear of spilling into hydrocarbons, it has great industrial value and is useful from the viewpoint of pollution prevention.
以下に本発明を詳述する。 The present invention is described in detail below.
本発明は酸化マンガンと酸化鉄の複合酸化物を酸化物担体に担持した基材に銀を添加した吸収剤に関するものである。 The present invention relates to an absorbent in which silver is added to a base material in which a composite oxide of manganese oxide and iron oxide is supported on an oxide carrier.
酸化マンガンと酸化鉄の複合酸化物について、特に、制限はないが、金属塩類を水溶液となした後、アルカリ化合物類水溶液との中和反応によって製造することもできる。アルカリ化合物類としてはナトリウム、カリウムの水酸化物、炭酸塩、或いはアンモニア水、等を使用するのが好ましい。中和反応によって得られた沈澱物は水洗した後、濾過、乾燥され、原料とされるが、場合によっては濾過物をそのまま原料として使用することもできる。ここで、複合酸化物は市販のもの、沈澱法によるもの共に単一化合物での使用のみならず、混合物となして使用してもよい。沈殿法による化合物類の場合、混合物としての使用においては化合物を単独で沈澱させたものを混合してもよいが、共沈法によって複数成分を含む沈澱物を得ることによる方が好ましい。 Although there is no restriction | limiting in particular about complex oxide of manganese oxide and iron oxide, After making metal salt into aqueous solution, it can also manufacture by neutralization reaction with alkaline compound aqueous solution. As the alkali compounds, it is preferable to use sodium, potassium hydroxide, carbonate, or aqueous ammonia. The precipitate obtained by the neutralization reaction is washed with water, filtered, dried, and used as a raw material. In some cases, the filtrate can be used as a raw material as it is. Here, the composite oxide may be used not only as a single compound but also as a mixture, both commercially available and precipitated. In the case of compounds by the precipitation method, in the case of use as a mixture, a compound obtained by precipitating the compound alone may be mixed, but it is preferable to obtain a precipitate containing a plurality of components by the coprecipitation method.
担体について、活性成分である酸化マンガンと酸化鉄の複合酸化物や銀を高分散にする、吸収剤の形状を実用に耐えうる強度で保持できるものであれば、特に、制限はないが、アルミナ、シリカ、チタニアなどが使用できる。酸化マンガンと酸化鉄の複合酸化物と物理混合することもできる。また、沈殿により酸化マンガンと酸化鉄を調製する際に、予め、水溶液中に担体成分を分散させて、調製することもできる。 The carrier is not particularly limited as long as it is capable of highly dispersing a composite oxide of manganese oxide and iron oxide, which is an active ingredient, and silver, and capable of maintaining the shape of the absorbent at a strength that can withstand practical use. Silica, titania, etc. can be used. It can also be physically mixed with a complex oxide of manganese oxide and iron oxide. In addition, when preparing manganese oxide and iron oxide by precipitation, the carrier component can be dispersed in an aqueous solution in advance.
添加する銀について、特に、制限はないが、硝酸塩などの水溶性の銀塩を酸化マンガンと酸化鉄及び担体を含んだ基材にソーキング法やポアフィリングなどの方法により含浸することができる。また、含浸する際の形状は、粉体、成形体でもよい。 The silver to be added is not particularly limited, but a water-soluble silver salt such as nitrate can be impregnated into a base material containing manganese oxide, iron oxide and a carrier by a method such as soaking or pore filling. Moreover, the shape at the time of impregnation may be a powder or a molded body.
酸化鉄は、吸収剤全重量に対する含有量として示すと４０〜６５重量％の範囲であり、その含有量が４０重量％未満では水銀等の不純物の除去性能が不充分であり、また、その量が６５重量％を超えると性能が低下するだけでなく、吸収剤を成形した際の物理的強度が低下するなどの問題を有する。 Iron oxide is in the range of 40 to 65% by weight when expressed as a content with respect to the total weight of the absorbent, and if the content is less than 40% by weight, the removal performance of impurities such as mercury is insufficient. When the amount exceeds 65% by weight, not only the performance is lowered, but also the physical strength when the absorbent is molded is lowered.
酸化マンガンは、吸収剤全重量に対する含有量が２０〜４０重量％の範囲であり、その含有量が２０重量％未満では水銀等の不純物の除去性能が不充分であり、また、その量が３０重量％を超えると性能が低下するだけでなく、吸収剤を成形した際の物理的強度が低下するなどの問題を有する。 Manganese oxide has a content of 20 to 40% by weight with respect to the total weight of the absorbent, and if the content is less than 20% by weight, the removal performance of impurities such as mercury is insufficient, and the amount is 30%. When it exceeds wt%, not only the performance is lowered, but also the physical strength at the time of molding the absorbent is lowered.
酸化物担体は、吸収剤全重量に対する含有量が１０〜２０重量％の範囲であり、１０重量％未満では吸収剤を成形したときの強度が不充分であり、活性成分である酸化マンガンと酸化鉄の複合酸化物や銀の分散程度が不充分となる。また、その量が２０重量％を超えると活性成分の量が低下し、水銀等の不純物除去性能も低下する。 The content of the oxide carrier with respect to the total weight of the absorbent is in the range of 10 to 20% by weight. If the content is less than 10% by weight, the strength when the absorbent is molded is insufficient, and manganese oxide as an active ingredient is oxidized. The degree of dispersion of iron complex oxide and silver becomes insufficient. On the other hand, when the amount exceeds 20% by weight, the amount of the active ingredient is lowered and the performance of removing impurities such as mercury is also lowered.
銀は、吸収剤全重量に対する含有量として示すと０．０１〜５．０重量％の範囲であり、その含有量が０．０１重量％未満では水銀等の不純物の除去性能が不充分であり、またその量が５重量％を超えると一層の吸収性能向上効果が認められなくなるばかりでなく、添加成分は高価なので経済的に好ましくない。 Silver is in the range of 0.01 to 5.0% by weight as a content with respect to the total weight of the absorbent, and if the content is less than 0.01% by weight, the performance of removing impurities such as mercury is insufficient. Further, if the amount exceeds 5% by weight, not only the effect of further improving the absorption performance is not recognized, but also the added components are expensive, which is not economically preferable.
酸化鉄と酸化マンガンと酸化物担体、銀を含む水銀等の不純物吸収剤は、既知の一般的な手段により混合成形して本発明の吸収剤とすることができる。その形状及びサイズは、その使用形態により様々であり、一般的には直径が１〜６ｍｍで長さが３〜２０ｍｍ程度の円柱状ペレットが好適に用いられるが、種々のサイズの異形状のペレット、錠剤形状、顆粒状及び破砕粒、また噴霧乾燥による微粒子など、特に制限はない。 Impurity absorbers such as iron oxide, manganese oxide, oxide carrier, and silver-containing mercury can be mixed and molded by known general means to form the absorbent of the present invention. The shape and size vary depending on the form of use. In general, cylindrical pellets having a diameter of 1 to 6 mm and a length of about 3 to 20 mm are preferably used. There are no particular restrictions on the shape of tablets, granules, crushed particles, and fine particles by spray drying.
一般的な押出し円柱状ペレットの製造方法であるが、水銀等の不純物吸収剤の粉体をニーダーあるいはマーラー等の混合混練装置で充分に乾式混合した後、混合粉末に対して１６〜４０重量％、好ましくは２５〜３０重量％の範囲で水を添加して混練する。水を添加する際には混練物の不均質が生じないように分割投入するのが望ましい。得られた混練物を押出し成型機あるいはペレタイザーで所定の形状のダイスを用いて円柱状ペレットに成型する。これを、１００〜５００℃、好ましくは２５０〜４００℃の温度で乾燥した後、必要であれば所望の長さに粉砕する。得られた乾燥物を篩分けし、吸収処理に使用する。 This is a general method for producing extruded cylindrical pellets. After sufficiently dry-mixing a powder of an impurity absorbent such as mercury with a mixing and kneading apparatus such as a kneader or Mahler, it is 16 to 40% by weight based on the mixed powder. Preferably, water is added in a range of 25 to 30% by weight and kneaded. When water is added, it is desirable to divide and add so that the kneaded material does not become inhomogeneous. The obtained kneaded product is molded into cylindrical pellets using a die having a predetermined shape by an extrusion molding machine or a pelletizer. After drying this at a temperature of 100 to 500 ° C., preferably 250 to 400 ° C., if necessary, it is pulverized to a desired length. The obtained dried product is sieved and used for absorption treatment.
本発明の吸収剤は、乾式混合工程を省略して湿式混練のみでも製造可能である。この場合、分散し難い粘土などは、混練前に充分分散した状態にしてから添加する必要がある。このためには、予め多量の水に充分分散させる方法が有効である。分散が不完全だと、均一な混合物が得られず、圧壊強度が低下する。 The absorbent of the present invention can be produced by only wet kneading without the dry mixing step. In this case, clay or the like that is difficult to disperse needs to be added after being sufficiently dispersed before kneading. For this purpose, a method of sufficiently dispersing in a large amount of water in advance is effective. If the dispersion is incomplete, a uniform mixture cannot be obtained and the crushing strength is reduced.
得られた吸収剤の比表面積は、およそ９０ｍ２／ｇ以上であり、好ましくは、１２０〜２５０ｍ２／ｇ、細孔容積０．１〜０．９ｍｌ／ｇ、好ましくは０．２〜０．５ｍｌ／ｇである。 The specific surface area of the obtained absorbent is about 90 m 2 / g or more, preferably 120 to 250 m 2 / g, pore volume 0.1 to 0.9 ml / g, preferably 0.2 to 0.00. 5 ml / g.
本発明による吸収剤を使用して炭化水素中の水銀、砒素、硫黄からなる不純物の除去方法は、不純物を含有する炭化水素を吸収剤に接触させることにより行う。なお、接触方法は任意であるが、特に固定床流通方式が好ましく、この固定床流通方式を採用することにより連続運転が可能となる。 The method for removing impurities consisting of mercury, arsenic and sulfur in hydrocarbons using the absorbent according to the present invention is carried out by bringing hydrocarbons containing impurities into contact with the absorbent. In addition, although a contact method is arbitrary, a fixed bed circulation system is particularly preferable, and continuous operation is possible by adopting this fixed bed circulation system.
この接触処理の際、本発明の吸収剤は、常温から５００℃の温度範囲で使用することができ、圧力は、通常、常圧〜５０ｋｇ／ｃｍ２の範囲で使用することができる。 At the time of this contact treatment, the absorbent of the present invention can be used in a temperature range from room temperature to 500 ° C., and the pressure can usually be used in the range of normal pressure to 50 kg / cm 2 .
また、本発明の吸収剤はオレフィン、パラフィンからなる炭化水素流で使用することができる。また、炭化水素流の炭素数は、Ｃ１からＣ１２で、ガス相もしくは液相で使用することができる。たとえばガス相で使用する場合、ガス時間空間速度(ＧＨＳＶ)が約２００〜５０，０００／ｈｒとなるような流量である。 The absorbent of the present invention can also be used in a hydrocarbon stream consisting of olefins and paraffins. Also, the hydrocarbon stream has carbon numbers from C1 to C12 and can be used in the gas phase or liquid phase. For example, when used in the gas phase, the flow rate is such that the gas hourly space velocity (GHSV) is about 200 to 50,000 / hr.
本発明の吸収剤により除去される炭化水素流中の不純物は、水銀、砒素、鉛、バナジウム、ニッケル、硫黄、金属水素化物等を挙げることができるが、特に水銀、砒素、硫黄などの微量不純物に適している。なお、水銀としては、単体水銀、無機水銀、有機水銀の形態として含有し、有機水銀としては、例えば、アルキル水銀等を挙げることができる。砒素は、通常ＲｎＡｓＨ３−ｎ（式中Ｒはアルキル、フェニル基等であり、ｎは０、１、２、３である。）で表わされる水素化物または有機化合物の形態で含有されている。このような砒素化合物として、具体的にはアルシン、モノメチルアルシン、ジメチルアルシン、トリメチルアルシン、トリブチルアルシンのようなアルキルアルシンおよびとりフェニルアルシン等を挙げることができる。硫黄は、硫黄単体、また硫黄化合物としては一般に硫化水素、二酸化硫黄、硫化カルボニル、二硫化炭素、及びこれらの二種又はそれ以上の混合物から成る種類である。 Impurities in the hydrocarbon stream removed by the absorbent of the present invention can include mercury, arsenic, lead, vanadium, nickel, sulfur, metal hydrides, etc., but in particular trace impurities such as mercury, arsenic, sulfur, etc. Suitable for Mercury is contained in the form of elemental mercury, inorganic mercury, or organic mercury, and examples of organic mercury include alkyl mercury. Arsenic is usually R n A s H 3-n ( wherein R is alkyl, phenyl group, n represents a 0,1,2,3.) Contained in a form of a hydride or an organic compound represented by Has been. Specific examples of such arsenic compounds include arsine, monomethylarsine, dimethylarsine, trimethylarsine, alkylarsine such as tributylarsine, and triphenylarsine. Sulfur is a kind consisting of simple sulfur or a sulfur compound generally composed of hydrogen sulfide, sulfur dioxide, carbonyl sulfide, carbon disulfide, and a mixture of two or more thereof.
また、本発明の不純物の除去方法に適用可能な炭化水素中の不純物の含有量は特に制限がなく、広範囲にわたって処理することができ、多量に含まれる不純物も極微量までほぼ完全に除去することができる。 In addition, the content of impurities in hydrocarbons applicable to the impurity removal method of the present invention is not particularly limited and can be treated over a wide range, and impurities contained in large amounts can be almost completely removed to trace amounts. Can do.
（炭化水素中の不純物の吸収性能試験）
２．５ｍｍのペレット状に成形した吸収剤を５００ｍｌの吸収塔に充填した。これを、ＧＨＳＶ：４０００ｈ~1、温度：５０℃、圧力：３０ｋｇ/ｃｍ２Ｇで連続試験を行なった。試験は３ヶ月間実施し、試験終了後、吸収剤により吸収された水銀、硫黄、砒素などの量を蛍光エックス線（リガク製ＲＩＸ２０００）で分析した。
(Absorption performance test of impurities in hydrocarbons)
The absorbent formed into a 2.5 mm pellet was packed in a 500 ml absorption tower. This was subjected to a continuous test at GHSV: 4000 h 1 , temperature: 50 ° C., pressure: 30 kg / cm 2 G. The test was conducted for 3 months, and after the test was completed, the amount of mercury, sulfur, arsenic and the like absorbed by the absorbent was analyzed with a fluorescent X-ray (Rigaku RIX2000).
試験における供給物の組成は、以下の通りである。 The composition of the feed in the test is as follows.
Ｈ2 :１５ｍｏｌ％
ＣＯ :０．０６ｍｏｌ％
ＣＨ４ :２５ｍｏｌ％
Ｃ２Ｈ２ :０．７ｍｏｌ％
Ｃ２Ｈ４ :３６ｍｏｌ％
Ｃ２Ｈ６ :７ｍｏｌ％
ＭＡＰＤ（メチルアセチレン／プロパジエン）:０．４ｍｏｌ％
Ｃ３Ｈ６ :１５ｍｏｌ％
Ｃ３’ｓ＋Ｃ４’ｓ :０．８４ｍｏｌ％（１００−Others＝０．８４）
H 2: 15mol%
CO: 0.06 mol%
CH 4: 25mol%
C 2 H 2 : 0.7 mol%
C 2 H 4: 36mol%
C 2 H 6: 7mol%
MAPD (methylacetylene / propadiene): 0.4 mol%
C 3 H 6: 15mol%
C3 ′s + C4 ′s: 0.84 mol% (100−Others = 0.84)
（実施例１）
イオン交換水２１ｋｇに１．６ｋｇの硫酸マンガンと４．８ｋｇの硫酸鉄を溶解した水溶液に、イオン交換水１７ｋｇに３．５ｋｇの炭酸ナトリウムを溶解した水溶液との中和反応により酸化マンガンと酸化鉄の沈殿物を得た。次いで水洗することによって不純物類を充分除去した後濾過、乾燥し、２ｋｇの酸化マンガンと酸化鉄の複合酸化物を調製した。得られた複合酸化物１ｋｇにアルミナ０．１ｋｇを乾式混合し、水分を添加した後に、２．５ｍｍの押し出し品に成型した。また、イオン交換水４０ｇに４．７ｇの硝酸銀に溶解し、この水溶液を、前記成型した押し出し品１５０ｇにポアフィリング法により含浸し、更に１２０℃で乾燥した。その後、５％ギ酸ソーダ水溶液１ｋｇにより吸収剤の銀を湿式還元し、純水で洗浄した後に、１２０℃で乾燥することによって実施例１の吸収剤を得た。得られた吸収剤の組成は、酸化鉄５９重量％、酸化マンガン２９重量％、アルミナ１０重量％、銀２重量％であった。得られた処理剤の水銀、硫黄の吸収性能結果を表１に示した。
Example 1
Manganese oxide and iron oxide by neutralization reaction of an aqueous solution in which 1.6 kg of manganese sulfate and 4.8 kg of iron sulfate are dissolved in 21 kg of ion-exchanged water and an aqueous solution in which 3.5 kg of sodium carbonate is dissolved in 17 kg of ion-exchanged water. A precipitate was obtained. Subsequently, impurities were sufficiently removed by washing with water, followed by filtration and drying to prepare 2 kg of a composite oxide of manganese oxide and iron oxide. 0.1 kg of alumina was dry-mixed with 1 kg of the obtained composite oxide, and after adding water, it was molded into a 2.5 mm extruded product. Further, 4.7 g of silver nitrate was dissolved in 40 g of ion-exchanged water, and this aqueous solution was impregnated into 150 g of the molded extruded product by a pore filling method and further dried at 120 ° C. Thereafter, the absorbent silver of the absorbent was wet-reduced with 1 kg of 5% sodium formate aqueous solution, washed with pure water, and dried at 120 ° C. to obtain the absorbent of Example 1. The composition of the obtained absorbent was 59% by weight of iron oxide, 29% by weight of manganese oxide, 10% by weight of alumina, and 2% by weight of silver. Table 1 shows the results of absorption performance of mercury and sulfur of the obtained treatment agent.
（比較例１）
実施例１において、吸収剤調製を複合酸化物の押出し成型段階に留め、硝酸銀水溶液含浸を行わず、すなわち添加成分を全く含まない比較例１としての吸収剤を調製した。得られた吸収剤の組成は、酸化鉄６０重量％、酸化マンガン３０重量％、アルミナ１０重量％であった。得られた吸収剤の水銀、硫黄の吸収性能結果を表１に示した。
(Comparative Example 1)
In Example 1, the preparation of the absorbent was kept at the stage of extrusion of the composite oxide, and the absorbent as Comparative Example 1 was prepared without impregnation with an aqueous silver nitrate solution, that is, containing no additive components. The composition of the obtained absorbent was 60% by weight of iron oxide, 30% by weight of manganese oxide, and 10% by weight of alumina. The absorption performance results of mercury and sulfur of the obtained absorbent are shown in Table 1.
（比較例２）
市販のアルミナ１ｋｇを用い、ニーダー中で成型に適量のイオン交換水３００ｇを加えて充分混合した後、直径２．５ｍｍのサイズに押出し成型し、１２０℃で乾燥、４５０℃で焼成した。イオン交換水４０ｇに１１．８ｇの硝酸銀を溶解し、この水溶液を押し出し品１５０ｇにポアフィリング法により含浸し、更に１２０℃で乾燥した。その後、５％ギ酸ソーダ水溶液１ｋｇにより吸収剤の銀を湿式還元し、純水で洗浄した後に、１２０℃で乾燥することによって実施例１の吸収剤を得た。得られた吸収剤の組成は、銀５重量％であった。得られた処理剤の水銀、硫黄の吸収性能結果を表１に示した。
(Comparative Example 2)
Using 1 kg of commercially available alumina, 300 g of an appropriate amount of ion-exchanged water for molding was added in a kneader and mixed well, then extruded to a size of 2.5 mm in diameter, dried at 120 ° C., and fired at 450 ° C. 11.8 g of silver nitrate was dissolved in 40 g of ion-exchanged water, and this aqueous solution was impregnated into 150 g of an extruded product by the pore filling method and further dried at 120 ° C. Thereafter, the absorbent silver of the absorbent was wet-reduced with 1 kg of 5% sodium formate aqueous solution, washed with pure water, and dried at 120 ° C. to obtain the absorbent of Example 1. The composition of the obtained absorbent was 5% by weight of silver. Table 1 shows the results of absorption performance of mercury and sulfur of the obtained treatment agent.
表１より、酸化マンガンと酸化鉄の複合酸化物をアルミナなど担体に担持した基材に銀を添加した吸収剤は、銀を添加しない吸収剤に比較して、水銀、砒素、硫黄などの不純物全てに対する吸収効果が非常に高まったことが示された。 From Table 1, the absorbent with silver added to the base material supporting the composite oxide of manganese oxide and iron oxide on the carrier such as alumina is more impurities such as mercury, arsenic and sulfur than the absorbent without adding silver. It was shown that the absorption effect on all was greatly enhanced.
本発明によれば、従来の水銀、砒素、硫黄などの微量不純物の吸収剤の問題点を解決し、かつ、効率的に水銀、砒素、硫黄などの微量不純物を全て除去する吸収剤を提供することができ、その工業的価値は大きい。また硫化化合物および塩素化合物を使用しないため、公害防止の観点から有用である。 According to the present invention, there is provided an absorbent which solves the problems of conventional absorbents of trace impurities such as mercury, arsenic and sulfur and efficiently removes all trace impurities such as mercury, arsenic and sulfur. And its industrial value is great. In addition, since sulfur compounds and chlorine compounds are not used, it is useful from the viewpoint of pollution prevention.
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