TW546288B - Process for reducing the amount of nitrification-inhibiting sulfur compounds - Google Patents
Process for reducing the amount of nitrification-inhibiting sulfur compounds Download PDFInfo
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- TW546288B TW546288B TW089123218A TW89123218A TW546288B TW 546288 B TW546288 B TW 546288B TW 089123218 A TW089123218 A TW 089123218A TW 89123218 A TW89123218 A TW 89123218A TW 546288 B TW546288 B TW 546288B
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- 150000003464 sulfur compounds Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000002351 wastewater Substances 0.000 claims abstract description 16
- 239000011541 reaction mixture Substances 0.000 claims abstract description 13
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- 238000006396 nitration reaction Methods 0.000 claims description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 7
- 239000001530 fumaric acid Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 238000007689 inspection Methods 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910001869 inorganic persulfate Inorganic materials 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical class SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims 1
- 241001327638 Cimex lectularius Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000007812 deficiency Effects 0.000 abstract 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 abstract 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000010865 sewage Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGMPVYSXXIOGJY-UHFFFAOYSA-N Fusaric acid Chemical compound CCCCC1=CC=C(C(O)=O)N=C1 DGMPVYSXXIOGJY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 thio Naphthylamine Chemical compound 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 244000125380 Terminalia tomentosa Species 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RHMZKSWPMYAOAZ-UHFFFAOYSA-N diethyl peroxide Chemical compound CCOOCC RHMZKSWPMYAOAZ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CYEBJEDOHLIWNP-UHFFFAOYSA-N methanethioamide Chemical compound NC=S CYEBJEDOHLIWNP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical compound C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- IHRLABACBKPYLT-UHFFFAOYSA-N prop-2-enethioamide Chemical compound NC(=S)C=C IHRLABACBKPYLT-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000008886 xiangdan Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/903—Nitrogenous
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/908—Organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
546288
五、發明說明( /本發明係有關-種藉以使抑制硝酸化之硫化合物(其 係於α』·不飽和化成相對應之反式或順式之異構 物中作為異構化催化劑)之殘餘量被降至於生物污物處理 廠清理期間無硝酸化抑制作用產生之程度之方法。 ”於工業污垢處理中,實際上大部份各種不同型式之廢 料產生,其需以無環境污染者被棄置。處理廢水之棄置中 之-問題,除其它者外,係其因硫化合物之污染。例如, 硫代尿素已被美國環保局分類成有害物質。其已知於生物 污物處理廠之硝酸化處理巾作為抑制。特収於氮及碟 之移除中,硝酸化速率限制生物污物處理廠之性能。因此, 此等污物處理廠之反應易受卫業廢水中存在之特殊抑制劑 〜響但疋,因大部份硫化合物亦具有抑制硝酸化活性, 因此,於入生物流出物溝渠前需降低處理廢水中之此等化 合物之含量。為了此目的,抑制硝酸化作用之化合物可被 完全移除或使其含量降低至少至生物污物處理廠之環境可 容忍棄置之條件被符合之程度。除硫代尿素外,此情況中 之抑制硝酸化作用之硫化合物亦係諸如硫代醯胺化合物、 硫代氰酸鹽、噻唑或硫代半卡巴肼之硫化合物,其被廣泛 用於,除其它者定,合成樹脂之製備及改良、藥物之製備、 工業清理助劑、作為抗氧化劑及於不飽和羧酸轉化 成相對應之反式或順式之異構物中之異構化催化劑。 一種棄置以此方式污染之廢水之方法係焚化,於高溫 度時使用NaOH相當長時間(例如,4天)之熱分解或與次氣 酸鈉反應。此等方法之缺點係,首先,複雜之廢氤排放控 本紙張尺度適用中國國家標準(CNS)A4規格(2i〇x297公髮) (請先閱讀背面之注意事項再填寫本頁) --裝 I I I I ·11111111 AWI · 經濟部智慧財產局員工消費合作社印製
546288 五、發明說明(3 ) (/、係以刻崔化劑化合物為基準計)之氧化劑至該異構化作 用名口束後獲传之該反應混合物,然後,以已知方式隔離該 相對應之反式或順式之異構物,及將其檢查及使形成之處 理廢水供應至生物清理階段。 依據本务明,藉由使α,石·不飽和羧酸以硫化合物催 化轉化成相對應之反式或順式之異構物而獲得之反應溶液 中之抑制硝酸化作用之硫化合物之量可被降低,結果,此 反應中產生之處理廢水可無問題地被供應至生物清理。 於此清況之抑制硝酸化作用之硫化合物係諸如硫代醯 胺化合物、硫代氰酸鹽、噻唑或硫代半卡巴胼之硫化合物。 較佳者係硫代醯胺化合物。於此清況中之適當硫代醯胺化 合物係如下化學式之化合物:
S ii ,人 FT NR.R, 12 (Ο 其中R係Η、烷基或烯基、苯甲基、萘基或 NR!R2 ;
Ri及R2可為相同或相異,且係HSCi-Cio-燒基。 於此情況中之烷基或烯基係可為未分支、環狀或分支 之基’例如,甲基、乙基、異丙基、正丙基、正丁基、第 三丁基、己基、癸基、環戊基、環五伸甲基等。此等之例 子係硫代甲醯胺、硫代乙醯胺、硫代丙醯胺、硫代丁醯胺、 硫代戊醯胺、硫代十二碳醯胺、硫代苯醯胺、硫代萘醯胺、 硫代丙烯醯胺、硫基-N-甲基乙醯胺、硫-N,N-二甲基乙醯 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) ^--------^--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 6 經濟部智慧財產局員工消費合作社印製 546288 A7 ---~-----2L____ 五、發明說明(4 ) 胺、硫代-N,N-二乙基乙醯胺、硫基環五伸甲基苯醯胺、 硫代尿素等。 較佳者,R係NR】!^基。特別佳者,R係NRiR2*,且 心及1每一者係Η。因此,特別佳之硫代醯胺化合物係硫 代尿素。 本發明係用於使例如α,yj -不飽和羧酸之不飽和化合 物轉化成相對應之反式或順式之異構物。較佳者,本發明 方法被用於馬來酸轉化成福馬酸。 於檢查經由上述方法獲得之反應溶液中,例如,藉由 使反式異構物自受作為催化劑之硫化合物污染之反應混合 物隔離’此等抑制硝酸化作用之硫化合物經,例如,被分 離之母液通過處理廢水内。 為降低抑制硝酸化作用之硫化合物之量,適合之氧化 劑被添加至經由上述方法之一者獲得之反應混合物或溶 液。此添加較佳係於反應完成後但於反應溶液實際檢查前 直接施行。因此,例如,於自馬來酸製備福馬酸中,氧化 劑係於異構化作用完成後但於福馬酸隔離前直接添加至反 應溶液。不可預期地,於此情況中未發生對反應期間或產 物品質之不利作用。此外,無需使反應溶液呈鹼性及/或改 變個別反應混合物之溫度。 但是,若適當,此添加亦可於反應溶液檢查後至處理 廢水之生物清理前不久施行之。 因此,添加氧化劑之溫度可依添加時間而定,其係於 室溫與相對應處理之反應溫度間,且較高溫度有利地影響 Μ.--------^---------Awl (請先閱讀背面之注意事項再填寫本頁)
經濟部智慧財產局員工消費合作社印製
546288 五、發明說明( 反應動力學。 適當氧化劑係,例如,臭氧、無機可溶性過硫酸鹽、 過氧化氫、冑機過氧化物及氫過氧化物、過酸,例如,過 硫酸錄、過硫酸納、過硫酸鉀、過硫酸鐘、過硫酸舞、過 硫酸鎂、過氧化苯醯、環己酮過氧化物、過氧化乙酿、過 氧化月桂醯、第三丁基過氧化物、第三丁基氫過氧化物等。 較佳者,過氧化氫或無機過硫酸鹽(特別較佳之過氧化氫) 被作為氧化劑。 添加之氧化劑之量係依處理廢水中之抑制硝酸化作用 之所欲還原度而定。於處理廢水中被容忍之抑制硝酸化作 用可依各國而定。依清理處理廢水之污水處理廠之規定而 定,有時其另外足以僅降低抑制硝酸化作用之硫化合物之 量至即使抑制硝酸化作用之完全移除未被達成,不再被容 忍之峰值係相對應被降低之程度。 基於此理由,依抑制硝酸化作用之硫化合物之殘餘量 之所欲降低程度而定,氧化劑係以關於抑制硝酸化作用之 硫化合物而言係莫耳量不足至最高達莫耳量兩倍添加。較 佳者’氧化劑係以每莫耳之抑制硝酸化作用硫化合物係〇· i 莫耳至1莫耳之量添加之。 藉由添加氧化劑,抑制硝酸化作用之硫化合物被氧化 至生物污物處理廠内之硝酸化處理之抑制作用足以完全除 去之程度。 特別較佳地,此方法係被用於使用化學式⑴之硫代醯 胺化合物作為異構化催化劑自馬來酸製備福馬酸。於化學 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) .·* 裝--------訂---------^91 (請先閱讀背面之注意事項再填寫本頁) 546288 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(6 式⑴之硫代醯胺化合物中,特別較佳者係硫代尿素。 氧化劑(較佳係過氧化氫或無機過硫酸鹽,特別較佳係 過氧化氫)被添加至反應混合物,較佳係於異構化反應完成 後直接添加,且反應混合物被攪拌。 添加溫度較佳係異構化溫度,即,約8〇_9(rc。若適當, 反應混合物亦可已被冷卻,但是,係於添加氧化劑前。氧 化劑之較佳量係每莫耳催化劑化合物係〇 ·丨至1莫耳。 攪拌時間係依添加溫度而定且較佳係LUO分鐘,特別 較佳係10與30分鐘之間。 但是,其亦可能至其後(於移除反式異構物後)再直接 添加氧化劑至處理廢水。此添加可於污物處理廠之處理廢 水檢查前不久被為之。 藉由本發明方法(以簡單及經濟之方式),抑制硝酸化 作用之硫化合物之殘餘量之降低於廢水中被降低至預定 值。於此情況中直接添加氧化劑至個別反應混合物或溶液 對於反應期間或產物品質無不利作用。 範例1 (標準) 20%強度(克/克)水溶液形式之220克(1·9莫耳)之馬來 酸(其已於S太酸酐生產期間以洗滌水產生)被置於配以攪拌 器、加熱器、溫度計及迴流冷凝器之反應容器内。除馬來 酸外,溶液亦含有1%(克/克)之苯甲酸、1.4%(克/克)之酞酸 及小量之固態及被溶解之焦油狀之組份(其未被進一步研 究)。福刀酸含量係低於0.2%。馬來酸溶液之抑制硝酸化作 用係以傳統方式藉由製備稀釋系列(被指定為Din εν (請先閱讀背面之注意事項再填寫本頁) -1 ---- II---------Ψ.
546288 A7
請 先 閱 讀· 背 面 之-注 意 事 I# 重裝
本 _ 頁I 訂 546288
五、發明說明(8 ) 範例3 (化學計量之H2〇2處理) 以相似於範例1之方式,220克(1.9莫耳)之馬來酸(20% 強度(克/克)之水溶液之形式)被加熱至如前範例般, 7.9克(104亳莫耳)之硫代尿素被以33%強度(克/幻之熱水 性溶形式添加,且混合物於9(rc攪拌2小時。於添加118 克之30%強度(克/克)之過氧化氫(1〇4毫莫耳之私⑻且進 一步攪拌15分鐘後,負過氧化物測試指示過氧化氫已與硫 代尿素完全反應。反應溶液被過濾且濾液之抑制硝酸化作 用以相似於範例1之方式決定。1:680之值(EC2〇)被測量。 濾餅以相似於範例1般被檢。於福馬酸之產量(丨92克) 或品質上無不同於範例i之差異被發現(HPLC分析及過氧 化物測試)。 (請先閱讀背面之注意事項再填寫本頁) -I w am· am 經濟部智慧財產局員工消費合作社印製 11 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐)
Claims (1)
- 546288 '公.告.4 'ds 申請專利範圍 第89丨232丨8號專利申請案申請專利範圍修正本92年3月28曰 1 · 種降低藉由α,/5 _不飽和羧酸之以硫化合物催化轉化 成相對應之反式或順式之異構物而獲得之反應溶液内 之抑制硝酸化作用之硫化合物之含量之方法,其包含以 莫耳數不足至最高達莫耳含量兩倍之最大值(其係以該 催化劑化合物為基準計)添加氧化劑至該異構化反應終 結後獲得之該反應混合物,然後,以已知方式隔離該相 對應之反式或順式之異構物及對其檢查,及使該形成之 處理廢水供應至生物清理階段,其中存在於該反應.溶液 内之η亥抑制硝酸化作用之硫化合物係選自硫代醯胺化 合物、硫代氰酸鹽、噻唑或硫代半卡巴肼之化合物。 2.如申請專利範圍第旧之方法,其中存在之該抑制石肖酸 化作用之硫化合物係如下化學式之硫代醯胺化合物: S ii R Μ ⑴〜 其中R係Η、Ci-C2〇-烷基或烯基、苯甲基、萘基或 NRjR2 ; R1及R2可為相同或相異,且係H*Ci-Ci〇-烷基。 3·如申请專利範圍第^員之方法,其中該被使用之氧化劑 係臭虱、無機可溶性過硫酸鹽、過氧化氫、有機過氧化 物及氫過氧化物或過酸。 4·如申清專利範圍第3項之方法,其中該被使用之氣化劑 係過氧化氫或無機過硫酸鹽。 ^ Ui〇x297 公釐) 本紙張尺度巾規格- 12 546288 A8 Βδ 一 . C8 ___. * D8 _ 一1 1 1 —— _ _ 一 ~ ---------- 六、申請專利範圍 5·如申請專利範圍第1項之方法,其中該順式不餘 和叛酸之硫化合物催化轉化成相對應之反式異構物係 — 與使用化學式⑴之硫代醯胺化合物作為異構化催化劑 自馬來酸製備福馬酸有關。 6·如申請專利範圍第1項之方法,其中該氧化劑係以每莫 耳催化劑化合物係0.1至1莫耳之量使用。 7·如申請專利範圍第丨項之方法’其中該氧化劑係於該異 構化反應終結後直接於該異構化溫度時添加至該反應 混合物,該反應混合物被攪拌,然後,該反式或順式: 異構物自該反應混合物隔離。 本紙張尺·度適用中國國家標準(CNS ) A4規格Y2 1〇X297公發) 13
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AT0197399A AT408218B (de) | 1999-11-22 | 1999-11-22 | Verfahren zur reduktion der menge an schwefelhältigen nitrifikationshemmern in prozessabwässern |
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CN114314796A (zh) * | 2021-12-29 | 2022-04-12 | 北京师范大学 | 一种具有活化过硫酸盐和增溶氯代烃双重功能的材料 |
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GB719446A (en) * | 1951-12-29 | 1954-12-01 | Monsanto Chemicals | Production of fumaric acid |
JPS5394445A (en) * | 1977-01-31 | 1978-08-18 | Tokyo Yuuki Kagaku Kougiyou Kk | Method of treating waste water |
BE871436A (fr) * | 1978-10-20 | 1979-02-15 | Centre Rech Metallurgique | Procede pour epurer les eaux residuaires. |
JPS6018477B2 (ja) * | 1979-06-26 | 1985-05-10 | 三菱電機株式会社 | 過酸化水素添加オゾン廃水処理方法 |
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SU1028607A1 (ru) * | 1980-11-05 | 1983-07-15 | Государственный научно-исследовательский и проектный институт по обогащению руд цветных металлов "Казмеханобр" | Способ очистки сточных вод от тиомочевинных элюатов |
DE3125452C2 (de) | 1981-06-29 | 1985-09-12 | Degussa Ag, 6000 Frankfurt | Verfahren zum Entgiften und zum Absenken des CSB und des BSB in kontinuierlichen Abwasserströmen mit wechselnden Gehalten verschiedener oxidierbarer Inhaltsstoffe mit Wasserstoffperoxid |
JPS59189996A (ja) * | 1983-04-13 | 1984-10-27 | Denka Consult & Eng Co Ltd | 廃水中の難分解性cod除去方法 |
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JPS6256446A (ja) * | 1985-09-06 | 1987-03-12 | Mitsubishi Metal Corp | 2,2,2−トリフルオロエタノ−ルの精製方法 |
US5180500A (en) * | 1987-07-01 | 1993-01-19 | Dowell Schlumberger Incorporated | Chemical removal of thiourea from hydrochloric acid |
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IL139770A0 (en) | 2002-02-10 |
HUP0004645A3 (en) | 2003-04-28 |
CZ20004336A3 (cs) | 2001-08-15 |
US6387280B1 (en) | 2002-05-14 |
ATA197399A (de) | 2001-02-15 |
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