JPS63264106A - Method for removing and treating minute amount of dangerous hydrocarbon compound from aqueous stream - Google Patents
Method for removing and treating minute amount of dangerous hydrocarbon compound from aqueous streamInfo
- Publication number
- JPS63264106A JPS63264106A JP9215287A JP9215287A JPS63264106A JP S63264106 A JPS63264106 A JP S63264106A JP 9215287 A JP9215287 A JP 9215287A JP 9215287 A JP9215287 A JP 9215287A JP S63264106 A JPS63264106 A JP S63264106A
- Authority
- JP
- Japan
- Prior art keywords
- hydrocarbon compounds
- adsorbent
- aqueous
- hazardous
- aqueous stream
- 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.)
- Granted
Links
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 81
- 238000000034 method Methods 0.000 title claims description 23
- 239000003463 adsorbent Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000012156 elution solvent Substances 0.000 claims description 22
- 238000005201 scrubbing Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 239000002699 waste material Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 231100001261 hazardous Toxicity 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- -1 clays Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 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
- 239000013056 hazardous product Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 description 27
- 229930195733 hydrocarbon Natural products 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 13
- 239000012071 phase Substances 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- WBEJYOJJBDISQU-UHFFFAOYSA-N 1,2-Dibromo-3-chloropropane Chemical compound ClCC(Br)CBr WBEJYOJJBDISQU-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- BDEDPKFUFGCVCJ-UHFFFAOYSA-N 3,6-dihydroxy-8,8-dimethyl-1-oxo-3,4,7,9-tetrahydrocyclopenta[h]isochromene-5-carbaldehyde Chemical compound O=C1OC(O)CC(C(C=O)=C2O)=C1C1=C2CC(C)(C)C1 BDEDPKFUFGCVCJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009434 installation Methods 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（発明の利用分野）
本発明は水性の流れから微量の炭化水素化合物の除去に
関する。詳しくは、本発明は、危険又は存置な微量の炭
化水素化合物の除去に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to the removal of trace hydrocarbon compounds from aqueous streams. Specifically, the present invention relates to the removal of hazardous or residual trace hydrocarbon compounds.
（従来の技術）
米国特許第３．９１９．３９８号には、芳香族臭化物か
ら臭素を水素の臭化物として回収する方法が開示されて
いる。この方法は、芳香族臭化物を、パラジウム活性化
触媒の存在において約２００〜６００℃の範囲の温度に
おいて、水素と反応させることから成る。(Prior Art) US Pat. No. 3,919,398 discloses a method for recovering bromine from aromatic bromide as hydrogen bromide. The process consists of reacting an aromatic bromide with hydrogen in the presence of a palladium-activated catalyst at a temperature in the range of about 200-600<0>C.
米国特許第３．８９２．８１８号には、水素の存在にお
ける炭化水素塩化物の炭化水素と塩化水素への転化が開
示されている。この方法は、気相で、そしてロジウム含
有触媒の存在において行われる。U.S. Pat. No. 3,892,818 discloses the conversion of hydrocarbon chlorides to hydrocarbons and hydrogen chloride in the presence of hydrogen. The process is carried out in the gas phase and in the presence of a rhodium-containing catalyst.
（発明が解決しようとする問題点）
本発明は、水性の流れを吸着剤と接触して該水性の流れ
から微量の炭化水素化合物を除去し、廃吸着剤は堆積し
た炭化水素化合物の溶出溶剤による吸着剤からの除去に
よって再生し、次に、これらの炭化水素化合物を水素化
処理反応域において処理することによる、水性の流れか
ら微量の炭化水素化合物を除去する方法を提供するもの
である。(Problem to be Solved by the Invention) The present invention removes trace amounts of hydrocarbon compounds from an aqueous stream by contacting the aqueous stream with an adsorbent, and the waste adsorbent is used as an elution solvent for the accumulated hydrocarbon compounds. The present invention provides a method for removing trace hydrocarbon compounds from an aqueous stream by regenerating them by removal from an adsorbent by and then treating these hydrocarbon compounds in a hydrotreating reaction zone.
また、本発明゛は、炭化水素化合物の除去のため水素化
処理した溶出溶剤の廃吸着剤への再循環を意図するもの
である。The present invention also contemplates recycling of the hydrotreated elution solvent to the waste adsorbent for the removal of hydrocarbon compounds.
（問題点を解決するための手段）
本発明の広範な一興体例は、
（ａ）水性の流れを吸着剤と接触して水性の流れからｉ
ｔの炭化水素化合物を除去し、それによって炭化水素化
合物の濃度の減少した水性の流れを得、（ｂ）水性の流
れからの炭化水素化合物の堆積した廃吸着剤を溶出溶剤
と接触して、廃吸着剤から炭化水素化合物を除去し、そ
れによって吸着剤を再生し、
（ｃ）段階（ｂ）において廃吸着剤から除去された炭化
水素化合物と混合した溶出溶剤を、水素化処理反応域に
おいて水素の存在において、水素化触媒と接触し、
（ｄ）水素化処理反応域流出液を水性スクラビング溶液
と接触し、
（ｅ）反応域流出液と水性スクラビング溶液との混合液
を分離域に導入して水素化処理した溶出溶剤と廃水性の
流れとを得る
段階から成る水性の流れから微量の炭化水素化合物を除
去する方法を特徴とする。SUMMARY OF THE INVENTION Broad examples of the present invention include: (a) contacting an aqueous stream with an adsorbent to remove an aqueous stream from the aqueous stream;
(b) contacting waste adsorbent loaded with hydrocarbon compounds from the aqueous stream with an elution solvent; removing hydrocarbon compounds from the waste adsorbent thereby regenerating the adsorbent; (c) introducing the eluting solvent mixed with the hydrocarbon compounds removed from the waste adsorbent in step (b) in a hydroprocessing reaction zone; (d) contacting the hydrotreating reaction zone effluent with an aqueous scrubbing solution in the presence of hydrogen; (e) introducing a mixture of the reaction zone effluent and the aqueous scrubbing solution into the separation zone; A method for removing trace hydrocarbon compounds from an aqueous stream comprises the steps of: obtaining a hydrotreated elution solvent and a waste stream.
本発明の他の具体例は、
（ａ）水性の流れを吸着剤と接触して水性の流れから微
量の炭化水素化合物を除去し、それによって炭化水素化
合物の濃度の減少した水性の流れを得、（ｂ）水性の流
れからの炭化水素化合物の堆積した廃吸着剤を溶出溶剤
と接触して、廃吸着剤から炭化水素化合物を除去し、そ
れによって吸着剤を再生し、
（ｃ）段階（ｂｌにおいて廃吸着剤から除去された炭化
水素化合物と混合した溶出溶剤を、水素化処理反応域に
おいて水素の存在において、水素化触媒と接触し、
（ｄ）水素化処理反応域流出液を水性スクラビング溶液
と接触し、
（ｅ）反応域流出液と水性スクラビング溶液との混合液
を分離域に４人して水素化処理した溶出溶剤と廃水性の
流れとを得、
（ｆ）段階（ｅ）からの水素化処理した溶出溶剤の少な
くとも一部分を再循環して段階（ｂ）において利用され
る溶出溶剤の少なくとも一部分を得る
段階から成る水性の流れから微量の炭化水素化合物を除
去する方法を特徴とする。Other embodiments of the invention include: (a) contacting an aqueous stream with an adsorbent to remove trace amounts of hydrocarbon compounds from the aqueous stream, thereby obtaining an aqueous stream with a reduced concentration of hydrocarbon compounds; , (b) contacting the waste adsorbent loaded with hydrocarbon compounds from the aqueous stream with an elution solvent to remove hydrocarbon compounds from the waste adsorbent, thereby regenerating the adsorbent; and (c) step ( contacting the leaching solvent mixed with hydrocarbon compounds removed from the waste adsorbent in the bl with a hydrogenation catalyst in the presence of hydrogen in a hydroprocessing reaction zone; (d) aqueous scrubbing the hydroprocessing reaction zone effluent; (e) transferring the mixture of reaction zone effluent and aqueous scrubbing solution to a separation zone to obtain a hydrogenated eluent and wastewater stream; (f) step (e) a method for removing trace hydrocarbon compounds from an aqueous stream comprising the step of recycling at least a portion of the hydrotreated elution solvent to obtain at least a portion of the elution solvent utilized in step (b). do.
本発明のその他の具体例は、炭化水素化合物汚染物、水
性スクラビング溶液、水素化処理触媒、吸着剤、溶出溶
剤及び操作条件のごとき詳細を包含し、それらは以下に
記載する。Other embodiments of the invention include details such as hydrocarbon contaminants, aqueous scrubbing solutions, hydroprocessing catalysts, adsorbents, elution solvents, and operating conditions, which are described below.
例えば、廃水及び飲料水のごとき水性の流れから微量の
炭化水素化合物を無くすることのできる技術に対して間
断なく増大する要求がある。有機相が水相からデカンテ
ィションされた場合、残留する水は、例えば炭化水素化
合物のごとき有機化合物の微量を潜在的に含むかもしれ
ない、廃水が環境中に放出される前に、これらの微量の
炭化水素化合物は減少させるか、或いは無くされねばな
らない。これらのＷＩＮの炭化水素化合物が毒性、発癌
性、或いは危険性である場合、炭化水素化合物は水相か
ら除去されるだけではなく、毒性のより少ない化合物に
転化されることが好ましい。したがって、当業者は、水
相から微量の炭化水素化合物を除去することの実行可能
な技術を発見することを求めて来た。概念としては簡単
ではあるけれども、従来の液−液抽出は、ＰＰＭレベル
、或いはそれ以下の濃度の炭化水素化合物の除去に対し
ては、しばしば実際的ではない。For example, there is an ever-increasing need for technologies that can eliminate trace amounts of hydrocarbon compounds from aqueous streams such as wastewater and drinking water. When the organic phase is decanted from the aqueous phase, the remaining water may potentially contain trace amounts of organic compounds, such as hydrocarbon compounds, and these trace amounts are removed before the wastewater is released into the environment. hydrocarbon compounds must be reduced or eliminated. If these WIN hydrocarbon compounds are toxic, carcinogenic, or otherwise dangerous, it is preferred that the hydrocarbon compounds not only be removed from the aqueous phase, but also converted to less toxic compounds. Therefore, those skilled in the art have sought to find a viable technique for removing trace amounts of hydrocarbon compounds from the aqueous phase. Although simple in concept, conventional liquid-liquid extraction is often impractical for removing hydrocarbon compounds at concentrations at or below PPM levels.
本発明は、水性の流れから微量の炭化水素化合物を除去
する改良された方法を堤供するものである０本発明の方
法に依れば、広範な種類の炭化水素化合物が水性の流れ
から除去され得るものと考えられる。本発明の方法によ
る処理に対して適当な化合物の例は、ハロゲン化炭化水
素である。顕在的、或いは潜在的毒性を有するハロゲン
化炭化水素は、ケボン、ハロゲン化ビフェニル類、アル
ドリン、シールドリン及びヘキサクロロサイクロペンタ
ジェン類のごときハロゲン化サイクロジエン類、ジブロ
モクロロプロパン、ポリブロモ無水フタル酸のごときハ
ロゲン化無水フタル酸、テトラクロロエチレン、テトラ
クロロジベンゾジオキシンのごときポリクロロジオキシ
ン類、２．２ジクロロビニルジメチルホスフエートのご
ときハロゲン化有機ホスフェート類を包含する。但し、
これらに限定されるものではない。処理に適当な化合物
の追加の例は、有機金属化合物、特に、鉛、水銀、コバ
ルト、砒素、バナジウム及びクロムのごとき金属を含む
化合物である。汚染炭化水素化合物は、硫黄、酸素、金
属、又は窒素成分から成ることもある。本発明に依れば
、一般に、どんな炭化水素化合物でも水性の流れから除
去され得る。The present invention provides an improved method for removing trace amounts of hydrocarbon compounds from an aqueous stream. According to the process of the present invention, a wide variety of hydrocarbon compounds can be removed from an aqueous stream. It is considered to be something that can be obtained. Examples of compounds suitable for treatment by the method of the invention are halogenated hydrocarbons. Halogenated hydrocarbons that are overtly or potentially toxic include kebones, halogenated biphenyls, halogenated cyclodienes such as aldrin, shieldrin, and hexachlorocyclopentagenes, halogenated hydrocarbons such as dibromochloropropane, and polybromophthalic anhydride. phthalic anhydride, polychlorodioxins such as tetrachloroethylene and tetrachlorodibenzodioxin, and halogenated organic phosphates such as 2.2 dichlorovinyl dimethyl phosphate. however,
It is not limited to these. Additional examples of compounds suitable for treatment are organometallic compounds, especially those containing metals such as lead, mercury, cobalt, arsenic, vanadium and chromium. Contaminant hydrocarbon compounds may also consist of sulfur, oxygen, metals, or nitrogen components. According to the present invention, generally any hydrocarbon compound can be removed from an aqueous stream.
微量の炭化水素化合物は約１０．０００ ＰＰＭより少
ない量、より好ましくは約５．０００ ＰＰＭより少な
い量で水性の流れ中に存在することが好ましい。Preferably, trace hydrocarbon compounds are present in the aqueous stream in an amount of less than about 10.000 PPM, more preferably less than about 5.000 PPM.
本発明に依れば、微量の炭化水素化合物を含む水性の流
れは、微量の炭化水素化合物を選択的に保持し炭化水素
化合物の濃度の減少した水性の流れを生ずる適当な吸着
剤と接触させる。適当な吸着剤は、炭化水素化合物選択
性の一次的要件を発揮し、そして使用に便利な物質から
選ばれる。適当な吸着剤は、例えばモレキュラーシーブ
、非晶質シリカ−アルミナゲル、シリカゲル、活性炭、
活性アルミナ及び粘土を包含する。勿論、ある場合には
、特定の吸着剤が他のものより良好な結果を与えること
が認められる。According to the invention, an aqueous stream containing trace amounts of hydrocarbon compounds is contacted with a suitable adsorbent that selectively retains trace amounts of hydrocarbon compounds and produces an aqueous stream with a reduced concentration of hydrocarbon compounds. . Suitable adsorbents are selected from materials that exhibit the primary requirements of hydrocarbon compound selectivity and are convenient to use. Suitable adsorbents include, for example, molecular sieves, amorphous silica-alumina gel, silica gel, activated carbon,
Includes activated alumina and clay. Of course, it is recognized that in some cases certain adsorbents will give better results than others.
選択された吸着剤は、吸着域において微量の炭化水素化
合物を含む水性の流れと接触させる。吸着剤は任意の適
当な方法で吸着域に設置される。The selected adsorbent is contacted with an aqueous stream containing trace amounts of hydrocarbon compounds in the adsorption zone. The adsorbent is placed in the adsorption zone in any suitable manner.
吸着剤の設置の好ましい方法は、固定床設置においてで
ある。吸着剤は一つ、又はそれ以上の容器に、そして直
列、又は並列の流れに設置される。The preferred method of installing the adsorbent is in a fixed bed installation. The adsorbents are placed in one or more vessels and in series or parallel flow.
吸着域を通る水性の流れの流れは、好ましくは、平行の
態様で行われ、したがって吸着剤床（又は室）の一つが
炭化水素化合物の堆積によって効果が無くなった時、廃
吸着剤域は迂回され、平行する吸着剤域を通って中断す
ることの無い操作が続けられる。The flow of the aqueous stream through the adsorption zone is preferably carried out in a parallel manner so that when one of the adsorbent beds (or chambers) becomes ineffective due to the accumulation of hydrocarbon compounds, the waste adsorbent zone is bypassed. and continued uninterrupted operation through parallel adsorbent zones.
吸着中、吸着域は、好ましくは、はぼ大気圧から約１５
００ｐｓｉｇ （１０３４２Ｋ Ｐａゲージ）の圧、約
３２〜３００’Ｆ（０〜１４９℃）の温度、及び約０．
１〜５００ｈｒ−’の液体時間空間速度に維持される。During adsorption, the adsorption zone is preferably about 15 m above atmospheric pressure.
00 psig (10342 K Pa gauge), a temperature of about 32 to 300'F (0 to 149 C), and about 0.
A liquid hourly space velocity of 1 to 500 hr-' is maintained.
吸着域を通る微量の炭化水素化合物を含む水性の流れは
、上旬流れ、下向流れ、或いは放射状流れの態様で行わ
れる。吸着域の温度および圧は、好ましくは、水性の流
れを液相に維持するように選ばれる０本明細書において
“本質的に炭化水素フリー”と言う用語は、約１１０Ｐ
Ｐ以下の炭化水素化合物濃度を示す。The flow of aqueous water containing trace amounts of hydrocarbon compounds through the adsorption zone may be in the form of a head-flow, a downward flow, or a radial flow. The temperature and pressure of the adsorption zone are preferably selected to maintain the aqueous stream in the liquid phase.
Indicates the concentration of hydrocarbon compounds below P.
吸着剤の廃滅は、廃吸着域を隔離し、吸着剤を溶出溶剤
と接触して炭化水素化合物を除去し、それによって吸着
剤を再生することによって再生される。一般に、吸着剤
に吸着される炭化水素化合物に対して高い溶剤吸着性を
有し、吸着剤の性能を低下させる効果を有しない溶出溶
剤が利用される。好ましい溶出溶剤は、ナフサ、灯油、
ジーゼル燃料、軽油、或いはその混合物から成る。吸着
剤の再生中、吸着域は、好ましくは、はぼ大気圧から約
１５００ ｐｓｉｇ （１０３４２Ｋ Ｐａゲージ）の
圧及び約３２〜３００’Ｆ（０〜１４９℃）の温度に維
持される。再生中吸着域を通る溶出溶剤の流れは、上向
流れ、下向流れ、或いは放射状流れの態様で行われる。Decommissioning of the adsorbent is regenerated by isolating the waste adsorption zone and contacting the adsorbent with an elution solvent to remove hydrocarbon compounds and thereby regenerate the adsorbent. Generally, an elution solvent is used that has high solvent adsorption properties for the hydrocarbon compounds adsorbed on the adsorbent and does not have the effect of reducing the performance of the adsorbent. Preferred elution solvents are naphtha, kerosene,
Consists of diesel fuel, light oil, or a mixture thereof. During regeneration of the adsorbent, the adsorption zone is preferably maintained at a pressure from about atmospheric to about 1500 psig (10342 K Pa gauge) and a temperature of about 32-300'F (0-149C). The flow of elution solvent through the adsorption zone during regeneration may be in an upward flow, downward flow, or radial flow manner.
吸着剤の再生中の溶出溶剤は、液相、或いは気−液混合
相で存在する。The eluting solvent during regeneration of the adsorbent exists in a liquid phase or a gas-liquid mixed phase.
炭化水素から成る群から選ばれたを含む得られた溶出溶
剤は、水素化処理、或いは水素化域に導入され、水素リ
ッチの（水素分を多く含む）ガス相及び水素化触媒と接
触する。接触水素化域は、固定触媒床、エビュレイテッ
ド触媒床、又は流動触媒床を含む。この反応域は、好ま
しくは、約１００ｐｓｉｇ （６８９Ｋ Ｐａゲージ）
〜２０００ｐｓｉｇ（１３７９０Ｋ Ｐａゲージ）の圧
、より好ましくは、約２００ｐｓｉｇ （１３７９Ｋ
Ｐａゲージ） 〜１８００ｐｓｉｇ（１２４１１Ｋ Ｐ
ａゲージ）の圧に維持される。適当には、この反応は、
炭化水素化合物の望ましくない特性、或いは成分を減少
させ、或いは無くすように所望の転化を行うように選ば
れた約３５０〜８５００Ｆ （１７７〜 ４５４℃）
の範囲において最高触媒床温度で行われる。さらに、好
ましい操作条件は、約０．２〜１０ｈｒ−’の範囲の液
体時間空間速度及び約２００〜１０．０００５ＣＦＢ（
標準Ｆｔ”／バレル）（３５，６〜１７７８＋ｓ３／ｍ
３）、好ましくは約３００〜８０００５ＣＦＢ （５３
，３〜１４２２ａ＋３／ｗ３）の水素循環速度である。The resulting eluting solvent comprising a selected from the group consisting of hydrocarbons is introduced into a hydrotreating or hydrogenation zone and contacted with a hydrogen-rich gas phase and a hydrogenation catalyst. The catalytic hydrogenation zone includes a fixed catalyst bed, an ebulated catalyst bed, or a fluidized catalyst bed. This reaction zone is preferably about 100 psig (689K Pa gauge)
~2000 psig (13790K Pa gauge), more preferably about 200 psig (1379K Pa gauge)
Pa gauge) ~1800psig (12411K P
The pressure is maintained at a pressure of A gauge). Suitably, this reaction is
about 350-8500F (177-454C) selected to effect the desired conversion to reduce or eliminate undesirable properties or components of the hydrocarbon compound.
is carried out at a maximum catalyst bed temperature in the range of . Additionally, preferred operating conditions include a liquid hourly space velocity in the range of about 0.2 to 10 hr-' and a liquid hourly space velocity of about 200 to 10.0005 CFB (
Standard Ft”/barrel) (35,6~1778+s3/m
3), preferably about 300 to 80005 CFB (53
, 3 to 1422a+3/w3).
上記の水素化域内に配置される好ましい触媒組成物は、
天然産、又は合成された適当な耐火性無機酸化物担体物
質と結合された水素化活性を有する金属成分を含むこと
を特徴とする。担体物質の精細な組成及び製造方法は、
本発明に本質的なものとは考えられない。好ましい担体
物質は、アルミナ、シリカ、及びその混合物である。水
素化活性を有する適当な金属成分は、周期律表の第ＶＩ
−Ｂ族及び第１層の金属から成る群から選ばれたもので
ある。かくして、触媒組成物は、モリブデン、タングス
テン、クロム、鉄、コバルト、ニッケル、白金、イリジ
ウム、オスミウム、ロジウム、ルテニウム、及びその混
合物の群からの一つ、又はそれ以上の金属成分から成る
。触媒活性金属成分の濃度は、主として、特定の金属、
並びに特定の炭化水素供給原料の物理的及び／又は化学
的特性に依存する。例えば、第ＶＩ−Ｂ族の金属成分は
、一般に、約１〜２０重量％の範囲の量で、鉄族金属は
約０．２〜１０重量％の範囲の量で存在するが、第１層
の貴金属は、好ましくは、約０．２〜５重量％の範囲の
量で存在する。但しこれらの成分が元素の状態で触媒組
成物内に存在するとして計算したものである。さらに、
窒素及び硫黄を除去するため水素化処理中間留出炭化水
素化合物に対して商業的に使用される任意の触媒は、本
発明の水素化域において有効に作用する。A preferred catalyst composition disposed within the above hydrogenation zone is:
It is characterized by containing a metal component having hydrogenation activity combined with a suitable naturally occurring or synthetic refractory inorganic oxide support material. The precise composition and manufacturing method of the carrier material are as follows:
It is not considered essential to the invention. Preferred support materials are alumina, silica, and mixtures thereof. Suitable metal components with hydrogenation activity are listed in VI of the periodic table.
- selected from the group consisting of Group B and first layer metals; The catalyst composition thus comprises one or more metal components from the group of molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, iridium, osmium, rhodium, ruthenium, and mixtures thereof. The concentration of catalytically active metal components mainly depends on the specific metal,
and the physical and/or chemical properties of the particular hydrocarbon feedstock. For example, the Group VI-B metal component is generally present in an amount ranging from about 1 to 20% by weight, and the iron group metal is present in an amount ranging from about 0.2 to 10% by weight; The noble metal is preferably present in an amount ranging from about 0.2 to 5% by weight. However, these calculations are based on the assumption that these components exist in the catalyst composition in their elemental state. moreover,
Any catalyst commercially used on hydrotreated middle distillate hydrocarbon compounds to remove nitrogen and sulfur will work effectively in the hydrogenation zone of the present invention.
水素化域からの炭化水素流出液は水性スクラビング溶液
と接触させ、得られた混合物は、廃水性スクラビング溶
液、水素化処理した溶出溶剤と先に廃水供給原料を汚染
した水素化処理した炭化水素化合物とから成る水素化炭
化水素相、及び水素リッチのガス相を分離するため、分
離域に導入する。水素化域からの炭化水素流出液と水性
スクラビング溶液との接触は任意の便利な方法で行われ
るが、好ましくは、固有乱流、混合オリフィス、又は他
の適当な混合手段によって促進されるコーカレント（同
向流れ）インライン混合によって行われる。水性スクラ
ビング溶液は、好ましくは、水素化域からの炭化水素流
出液の約１〜４０容量％の量で導入される。水性スクラ
ビング溶液は、汚染した廃水供給原料に同伴される炭化
水素化合物の特性に依って選択される。例えば、炭化水
素化合物がハロゲン化化合物から成る廃水供給原料中に
存在する場合は、水性スクラビング溶液は、好ましくは
、ハロゲン化合物の水素化中に生成される酸を中和する
ため、水酸化カルシウム、水酸化カリウム、又は水酸化
ナトリウムのごとき塩基性化合物を含む。炭化水素化合
物汚染物が硫黄化合物及び窒素化合物のみを含む場合は
、純水が適当な水性スクラビング溶液である。得られた
水素化処理炭化水素相は回収され、水素リッチのガス相
は、所望ならば、水素化域に再循環される。本発明の好
ましい具体例においては、回収された炭化水素相の少な
くとも一部分は上記の溶出溶剤の少なくとも一部分とし
て再循環される。分離域において回収された水性スクラ
ビング溶液の一部分は再循環されて水素化域からの炭化
水素流出液と接触する。廃水性スクラビング溶液は、中
和、又はその他の処理をされて環境的により受容性の流
出液を提供する。The hydrocarbon effluent from the hydrogenation zone is contacted with an aqueous scrubbing solution, and the resulting mixture contains the wastewater scrubbing solution, the hydrotreated leaching solvent and the hydrotreated hydrocarbon compounds that previously contaminated the wastewater feedstock. A hydrogenated hydrocarbon phase consisting of and a hydrogen-rich gas phase are introduced into a separation zone for separation. Contacting the hydrocarbon effluent from the hydrogenation zone with the aqueous scrubbing solution may be carried out in any convenient manner, but is preferably a cocurrent facilitated by inherent turbulence, mixing orifices, or other suitable mixing means. (co-current flow) performed by in-line mixing. The aqueous scrubbing solution is preferably introduced in an amount of about 1 to 40% by volume of the hydrocarbon effluent from the hydrogenation zone. The aqueous scrubbing solution is selected depending on the characteristics of the hydrocarbon compounds entrained in the contaminated wastewater feedstock. For example, if hydrocarbon compounds are present in the wastewater feedstock consisting of halogenated compounds, the aqueous scrubbing solution preferably contains calcium hydroxide, Contains basic compounds such as potassium hydroxide or sodium hydroxide. If the hydrocarbon compound contaminant contains only sulfur and nitrogen compounds, pure water is a suitable aqueous scrubbing solution. The resulting hydrotreated hydrocarbon phase is recovered and the hydrogen-rich gas phase is recycled to the hydrogenation zone, if desired. In a preferred embodiment of the invention, at least a portion of the recovered hydrocarbon phase is recycled as at least a portion of the elution solvent. A portion of the aqueous scrubbing solution recovered in the separation zone is recycled into contact with the hydrocarbon effluent from the hydrogenation zone. The wastewater scrubbing solution is neutralized or otherwise treated to provide a more environmentally acceptable effluent.
次に、添付図面のフローシートによって、本発明のプロ
セスを説明する。図において、ポンプ、計器類、熱交換
器及び熱回収回路、コンプレッサー、サージタンク及び
同様のハードウェアは、本発明の技術の理解に不可欠の
ものではないので、省略されている。このような種々の
付属器具は当業者に周知の範囲内のものである。Next, the process of the present invention will be explained with reference to the flow sheet of the accompanying drawings. Pumps, instrumentation, heat exchangers and heat recovery circuits, compressors, surge tanks, and similar hardware have been omitted in the figures, as they are not essential to an understanding of the technology of the present invention. A variety of such accessories are within the purview of those skilled in the art.
図において、微量の炭化水素化合物で汚染された水性供
給原料は、導管１を通ってプロセス中に導入され、導管
２、バルブ３及び導管４を通って吸着域５に入る。また
、この汚染した廃水供給原料は、導管６、バルブ７及び
導管８を通って吸着域５と平行に置かれた吸着域９に導
入される。炭化水素化合物の濃度の減少した水性の流れ
は、導管１０．導管１１、バルブ１２、導管１３を通っ
て吸着域５から取り出され、回収される。また一方、炭
化水素化合物の濃度の減少した水性の流れは、導管１４
、バルブ１５、導管１６、導管１３を通って吸着域９か
ら取り出され、回収される。In the figure, an aqueous feedstock contaminated with trace amounts of hydrocarbon compounds is introduced into the process through conduit 1 and enters adsorption zone 5 through conduit 2, valve 3 and conduit 4. This contaminated wastewater feedstock is also introduced through conduit 6, valve 7 and conduit 8 into adsorption zone 9, which is placed parallel to adsorption zone 5. The aqueous stream with reduced concentration of hydrocarbon compounds is transferred to conduit 10. It is removed from the adsorption zone 5 through conduit 11, valve 12 and conduit 13 and recovered. On the other hand, the aqueous stream with a reduced concentration of hydrocarbon compounds is
, valve 15, conduit 16, and conduit 13, and are removed from the adsorption zone 9 and collected.
吸着域９が再生されるべき場合は、バルブ７及び１５は
隔離のために閉鎖され、溶出溶剤が、導管１７、バルブ
２０、導管１７、導管１４を通って吸着域９に導入され
る。吸着域９から抽出された炭化水素化合物リッチの（
炭化水素化合物を多量に含む）溶出溶剤は、導管８、導
管２１、バルブ２２、導管２１を通って取り出され、水
素化処理反応域２５中に導入される。吸着域５が再生さ
れるべき場合は、バルブ３及び１２が隔離のため閉鎖さ
れ、溶出溶剤ＩＬＥ導管１７、導管１８、バルブ１９、
導管１８、導管１０を通って吸着域５中にｍ人される。If the adsorption zone 9 is to be regenerated, valves 7 and 15 are closed for isolation and eluting solvent is introduced into the adsorption zone 9 through conduit 17, valve 20, conduit 17, conduit 14. The hydrocarbon compound rich (
The elution solvent (containing a large amount of hydrocarbon compounds) is removed through conduit 8 , conduit 21 , valve 22 , conduit 21 and introduced into hydrotreating reaction zone 25 . If the adsorption zone 5 is to be regenerated, valves 3 and 12 are closed for isolation and the elution solvent ILE conduit 17, conduit 18, valve 19,
m people are introduced into the adsorption area 5 through the conduit 18 and the conduit 10.
炭化水素化合物リッチの溶出溶剤は、導管４、導管２３
、バルブ２４、導管２３、導管２１を通って吸着域５か
ら取り出され、水素化処理反応域２５中に導入される。The elution solvent rich in hydrocarbon compounds is contained in conduit 4 and conduit 23.
, valve 24 , conduit 23 and conduit 21 from the adsorption zone 5 and introduced into the hydrotreating reaction zone 25 .
後に記載の態様で引き出される水素リンチのガス状流れ
は、導管３２、導管２１を通って水素化処理反応域２５
中に導入される。補給の水素は、導管３３、導管３２、
導管２１を通って水素化処理反応域２５中に導入される
。溶出溶剤と炭化水素汚染物の混合物は、前記のごとき
水素化条件に維持された水素化触媒の存在において、水
素化処理反応域２５中で水素化される。得られた水素化
処理された溶出溶剤と炭化水素化合物及びガス相は、導
管２６を通って水素化処理反応域２５から取り出され、
導管２７を通って導入された水性スクラビング溶液と接
触する。この混合物は、導管２６を通って高圧分離器２
８中に導入される。水素リンチのガス相は、導管３２を
通って高圧分離器２８から取り出され、前記のごとく再
循環される。水素化処理された溶出溶剤から成る除毒さ
れた炭化水素の流れは、導管２９を通って高圧分離器２
８から取り出され、回収される。水素化処理された溶出
溶剤から成る除毒された炭化水素流れの少なくとも一部
分は、導管３１を通って再循環され、導管１７を通って
提供される溶出溶剤の少なくとも一部分となる。廃水性
スクラビング溶液は、４管３０を通って高圧分離器２８
から取り出され、回収される。The gaseous stream of hydrogen lynch withdrawn in the manner described hereinafter passes through conduit 32, conduit 21 to hydrotreating reaction zone 25.
introduced inside. Replenishment hydrogen is supplied through conduit 33, conduit 32,
It is introduced into the hydrotreating reaction zone 25 through conduit 21 . The mixture of leaching solvent and hydrocarbon contaminants is hydrogenated in the hydrotreating reaction zone 25 in the presence of a hydrogenation catalyst maintained at hydrogenation conditions as described above. The resulting hydrotreated eluting solvent and hydrocarbon compounds and gas phase are removed from the hydrotreating reaction zone 25 through conduit 26;
Contact is made with an aqueous scrubbing solution introduced through conduit 27. This mixture passes through conduit 26 to high pressure separator 2
It will be introduced during the 8th. The hydrogen lynch gas phase is removed from high pressure separator 28 through conduit 32 and recycled as described above. The detoxified hydrocarbon stream comprising the hydrotreated leaching solvent passes through conduit 29 to high pressure separator 2.
8 and collected. At least a portion of the detoxified hydrocarbon stream comprising the hydrotreated elution solvent is recycled through conduit 31 and becomes at least a portion of the elution solvent provided through conduit 17. The waste scrubbing solution passes through four pipes 30 to high pressure separator 28.
taken out and collected.
（実施例）
本発明のプロセスを、実施例に依って、さらに具体的に
説明する。しかしながら、本発明は実施例に依って限定
されるものではない。(Example) The process of the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to the examples.
この具体例は、吸着域における５００重量ＰＦ’Ｍのポ
リ塩素化ビフェニル（ＰＣＢ ）を含む水性の流れから
のＰＣＢの除去、吸着域に含まれた吸着剤からのＰＣＢ
の溶出、及び水素化処理に依る溶出ＰＣＢを転化して無
毒の炭化水素化合物の生成について説明する。A specific example of this is the removal of PCBs from an aqueous stream containing 500 wt PF'M of polychlorinated biphenyls (PCBs) in an adsorption zone, the removal of PCBs from an adsorbent contained in an adsorption zone.
The elution of PCBs and the conversion of eluted PCBs by hydrotreating to produce non-toxic hydrocarbon compounds will be explained.
５００１！ｔＰＰＭのＰＣＢを含む水の水性供給原料の
流れを、約１００°Ｆ （３８℃）の温度、約１０ｐｓ
ｉｇ（６９にＰａゲージ）の圧、及び約１０の液体時間
空間速度を包含する条件において、活性炭粒子を含む吸
着域中に導入した。吸着域から取り出された処理した水
性相ば、ＰＣＢの含有量がｌＰＰＭより少ないことが発
見された。廃活性炭粒子を含むもう一つの吸着域が上記
の吸着域と平行に置かれ、供給原料の先の処理によって
効果が無くなった。この廃吸着剤は、ＰＣＢを含む活性
炭を、約１００’Ｆ（３８℃）の温度、約Ｉ Ｑｐｓｉ
ｇ （６９Ｋ Ｐａゲージ）の圧を含む条件において、
活性炭吸着剤から実質的に全てのＰＣＢを溶出、或いは
除去するに充分な時間、ナフサの一部分、ヘプタンから
成る溶出溶剤と接触することによって、再生し、先に吸
着されたＰＣＢを除去した。次に、溶出溶剤と吸着剤か
ら除去されたＰＣＢとの混合物は、水素リッチのガス状
の流れと共に、アルミナ、コバルト及びモリブデンから
成る触媒を装填した水素化処理反応域中に導入した。
水素化処理反応は、７５０’Ｆ（３９９℃）の触媒ピー
ク温度、９００ｐｓｉｇ （６２０５Ｋ Ｐａ ゲー
ジ）の圧、新鮮な供給原料に基づき液体時間空間速度１
、及び水素循環速度２５００ＳＣＦＢ （４４４ｓｔｄ
ｍ３／ｍ３）で行われた。5001! The aqueous feedstock flow of water containing tPPM of PCBs was controlled at a temperature of about 100°F (38°C) and about 10 ps.
ig (69 Pa gauge) and a liquid hourly space velocity of about 10 was introduced into the adsorption zone containing activated carbon particles. The treated aqueous phase removed from the adsorption zone was found to contain less than 1 PPM of PCBs. Another adsorption zone containing waste activated carbon particles was placed parallel to the above adsorption zone, rendered ineffective by previous processing of the feedstock. This waste adsorbent absorbs activated carbon containing PCBs at a temperature of about 100'F (38C) and about IQpsi.
Under conditions including a pressure of g (69K Pa gauge),
The activated carbon adsorbent was regenerated and previously adsorbed PCBs were removed by contacting it with an eluting solvent consisting of a portion of naphtha, heptane, for a period of time sufficient to elute or remove substantially all of the PCBs from the activated carbon adsorbent. The mixture of eluting solvent and PCBs removed from the adsorbent was then introduced with a hydrogen-rich gaseous stream into a hydrotreating reaction zone loaded with a catalyst consisting of alumina, cobalt and molybdenum.
The hydroprocessing reaction was run at a catalyst peak temperature of 750'F (399°C), a pressure of 900 psig (6205 KPa gauge), and a liquid hourly space velocity of 1 on fresh feedstock.
, and hydrogen circulation rate 2500SCFB (444std
m3/m3).
水素化処理反応域からの流出液は、水素化処理域からの
炭化水素流出液に基づいて１０容量％の量において、水
性水酸化ナトリウム溶液と接触させた。水素化処理反応
域流出液と水性スクラビング溶液との混合物は分離域中
に導入され、廃水性の流れとＩ ＰＰＭより少ない量の
ＰＣＢを含む再循環に適する水素化処理した溶出溶剤が
得られた。The effluent from the hydrotreating reaction zone was contacted with an aqueous sodium hydroxide solution in an amount of 10% by volume based on the hydrocarbon effluent from the hydrotreating zone. A mixture of the hydrotreating reaction zone effluent and the aqueous scrubbing solution was introduced into the separation zone to yield a wastewater stream and a hydrotreated leaching solvent suitable for recycle containing less PCBs than I PPM. .
図は、本発明の一興体例のプロセスのフローシートであ
る。
特許出願人 ニーオービー インコーポレイテッ手続
争ｍ正書（自発）
昭和６２年 ５月２５日
特許庁長官 黒 １）明 ｍ 殴
１、事件の表示
昭和６２年特許願第０９２１５２号
２、発明の名称
水性の流れから微量の危険性炭化水素
化合物を除去及び処理する方法
３、補正をする者
事件との関係 特許出願人
住所 アメリカ合衆国イリノイ州６００１６−５０１７
デスプレインズ、
イースト アルゴンフィン ロード
２５番地
名称 ニーオーピー インコーホレイテンド４、代理人
住所 ０１０４東京都中央区銀座８丁目１５番１０号銀
座ダイヤハイツ４１０号The figure is a process flow sheet of an example of the present invention. Patent Applicant: N.O.B. Incorporated Procedural Dispute M (spontaneous) May 25, 1985 Commissioner of the Patent Office Black 1) Akira M Hit 1, Indication of the Case 1986 Patent Application No. 092152 2, Name of the Invention Aqueous Flow Method for removing and treating trace amounts of hazardous hydrocarbon compounds from 3. Relationship with the case of the person making the amendment Patent applicant address: Illinois, United States of America 60016-5017
25 East Algonfin Road, Des Plaines Name: N.O.P. Inc. Address: 410 Ginza Dia Heights, 8-15-10 Ginza, Chuo-ku, Tokyo 0104
Claims (1)
を吸着剤と、該吸着剤が効果が無くなるまで、接触して
炭化水素化合物の少なくとも一部分を除去し、それによ
って炭化水素化合物の濃度の減少した水性の流れを得、 （ｂ）段階（ａ）からの廃吸着剤を回収し、その後該廃
吸着剤を溶出溶剤と接触して、該廃吸着剤から該炭化水
素化合物を除去し、それによって該吸着剤を再生し、続
いて再生した吸着剤を段階（ａ）に戻し、（ｃ）段階（
ｂ）から回収された溶剤を含む炭化水素化合物と水素と
を、危険有害な炭化水素化合物を安全無害な生成物に転
化するように選ばれた条件において、水素化処理反応域
において、水素化触媒と接触し、 （ｄ）得られた水素化処理反応域流出液を水性スクラビ
ング溶液と接触し、 （ｅ）該反応域流出液と該水性スクラビング溶液との得
られた混合液を分離域に導入して水素化処理した溶出溶
剤と段階（ｃ）において生成した安全無害な生成物の水
溶性部分を含む水性生成物の流れとを得る 段階から成る水性の流れから微量の危険性炭化水素化合
物を除去及び処理する方法。 ２）該危険性炭化水素化合物は、ハロゲン化炭化水素、
又は有機金属化合物である第１項に記載の水性の流れか
ら微量の危険性炭化水素化合物を除去及び処理する方法
。 ３）該水素化処理条件は、約６８９〜１３７９０ＫＰａ
ゲージの圧、１７７〜４５４℃の最高触媒温度及び３５
．６〜１７７８ｓｔｄｍ＾３／ｍ＾３の水素循環速度で
ある第１項に記載の水性の流れから微量の危険性炭化水
素化合物を除去及び処理する方法。 ４）段階（ｄ）に使用される該水性スクラビング溶液は
、水酸化ナトリウム、水酸化カリウム、又は水酸化カル
シウムを含む第１項に記載の水性の流れから微量の危険
性炭化水素化合物を除去及び処理する方法。 ５）該吸着剤は、シリカゲル、活性炭、活性アルミナ、
シリカ−アルミナゲル、粘土、モレキュラーシーブ及び
これらの混合物から成る群から選ばれる第１項に記載の
水性の流れから微量の危険性炭化水素化合物を除去及び
処理する方法。 ６）段階（ｅ）において分離された該水素化処理された
溶出溶剤の少なくとも一部分は、段階（ｂ）に再循環さ
れそこで利用される該溶出溶剤の少なくとも一部分を与
える第１項に記載の水性の流れから微量の危険性炭化水
素化合物を除去及び処理する方法。 ７）該水素化触媒は、耐火性無機酸化物と、周期律表の
第VI−Ｂ族及び第VIII族の金属及びその化合物から選ば
れた水素化活性を有する少なくとも一つの金属成分とか
ら成る第１項に記載の水性の流れから微量の危険性炭化
水素化合物を除去及び処理する方法。Claims: 1) (a) contacting an aqueous stream containing hazardous hydrocarbon compounds with an adsorbent to remove at least a portion of the hydrocarbon compounds until the adsorbent becomes ineffective; (b) recovering the waste adsorbent from step (a) and then contacting the waste adsorbent with an elution solvent to remove the waste adsorbent from the waste adsorbent; removing the hydrocarbon compounds thereby regenerating the adsorbent, subsequently returning the regenerated adsorbent to step (a) and (c) step (
The hydrocarbon compounds, including the solvent recovered from b), and hydrogen are combined with a hydrogenation catalyst in a hydroprocessing reaction zone at conditions selected to convert the hazardous hydrocarbon compounds into safe and non-hazardous products. (d) contacting the resulting hydrotreating reaction zone effluent with an aqueous scrubbing solution; and (e) introducing the resulting mixture of the reaction zone effluent and the aqueous scrubbing solution into a separation zone. to obtain a hydrotreated elution solvent and an aqueous product stream containing the water-soluble portion of the safe and non-hazardous product produced in step (c). Methods of removal and disposal. 2) The dangerous hydrocarbon compound is a halogenated hydrocarbon,
or an organometallic compound. 3) The hydrogenation treatment conditions are approximately 689 to 13790KPa.
gauge pressure, maximum catalyst temperature of 177-454°C and 35
．． A method for removing and treating trace amounts of hazardous hydrocarbon compounds from an aqueous stream according to paragraph 1, wherein the hydrogen circulation rate is between 6 and 1778 stdm^3/m^3. 4) The aqueous scrubbing solution used in step (d) removes traces of hazardous hydrocarbon compounds from the aqueous stream described in paragraph 1 containing sodium hydroxide, potassium hydroxide, or calcium hydroxide. How to process. 5) The adsorbent includes silica gel, activated carbon, activated alumina,
A method for removing and treating trace amounts of hazardous hydrocarbon compounds from an aqueous stream according to claim 1 selected from the group consisting of silica-alumina gels, clays, molecular sieves and mixtures thereof. 6) At least a portion of the hydrotreated elution solvent separated in step (e) is recycled to step (b) to provide at least a portion of the elution solvent utilized therein. method for removing and treating trace amounts of hazardous hydrocarbon compounds from streams. 7) The hydrogenation catalyst consists of a refractory inorganic oxide and at least one metal component having hydrogenation activity selected from metals of Group VI-B and Group VIII of the Periodic Table and their compounds. A method for removing and treating trace amounts of hazardous hydrocarbon compounds from an aqueous stream as described in paragraph 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9215287A JPS63264106A (en) | 1985-10-28 | 1987-04-16 | Method for removing and treating minute amount of dangerous hydrocarbon compound from aqueous stream |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/791,646 US4661256A (en) | 1985-10-28 | 1985-10-28 | Process for the removal of hydrocarbonaceous compounds from an aqueous stream and hydrogenating these compounds |
| JP9215287A JPS63264106A (en) | 1985-10-28 | 1987-04-16 | Method for removing and treating minute amount of dangerous hydrocarbon compound from aqueous stream |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63264106A true JPS63264106A (en) | 1988-11-01 |
| JPH0318481B2 JPH0318481B2 (en) | 1991-03-12 |
Family
ID=26433621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9215287A Granted JPS63264106A (en) | 1985-10-28 | 1987-04-16 | Method for removing and treating minute amount of dangerous hydrocarbon compound from aqueous stream |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63264106A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0326388A (en) * | 1989-06-22 | 1991-02-04 | Nippon Chem Ind Co Ltd | Method for removing halogenated hydrocarbon in waste water |
| US5068038A (en) * | 1989-09-27 | 1991-11-26 | Degussa Aktiengesellschaft | Method of lowering the AOX content in water |
| JPH0538431A (en) * | 1991-08-07 | 1993-02-19 | Toray Ind Inc | Method for baking zeolite adsorbent |
-
1987
- 1987-04-16 JP JP9215287A patent/JPS63264106A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0326388A (en) * | 1989-06-22 | 1991-02-04 | Nippon Chem Ind Co Ltd | Method for removing halogenated hydrocarbon in waste water |
| US5068038A (en) * | 1989-09-27 | 1991-11-26 | Degussa Aktiengesellschaft | Method of lowering the AOX content in water |
| JPH0538431A (en) * | 1991-08-07 | 1993-02-19 | Toray Ind Inc | Method for baking zeolite adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0318481B2 (en) | 1991-03-12 |
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