JP2018515330A - ポリスルフィド蒸解液の製造用に使用された触媒を再生する方法 - Google Patents
ポリスルフィド蒸解液の製造用に使用された触媒を再生する方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 16
- 239000005077 polysulfide Substances 0.000 title claims abstract description 16
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000010411 cooking Methods 0.000 title claims abstract description 12
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000004140 cleaning Methods 0.000 claims abstract description 66
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 58
- 238000005406 washing Methods 0.000 claims abstract description 58
- 229910052742 iron Inorganic materials 0.000 claims abstract description 36
- 230000002378 acidificating effect Effects 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 27
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 15
- 235000019253 formic acid Nutrition 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 12
- 239000004571 lime Substances 0.000 claims description 12
- 239000002023 wood Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 8
- 239000010802 sludge Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 239000002803 fossil fuel Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001875 compounds Chemical group 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000008237 rinsing water Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 10
- 238000010306 acid treatment Methods 0.000 description 7
- HEDOODBJFVUQMS-UHFFFAOYSA-N n-[2-(5-methoxy-1h-indol-3-yl)ethyl]-n-methylpropan-2-amine Chemical compound COC1=CC=C2NC=C(CCN(C)C(C)C)C2=C1 HEDOODBJFVUQMS-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019988 mead Nutrition 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- -1 poly (tetrafluoroethylene) Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/20—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
- B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/34—Polysulfides of sodium or potassium
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- D—TEXTILES; PAPER
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- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
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- D—TEXTILES; PAPER
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- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
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Abstract
Description
第二鉄イオンが今度はスルフィドを式Iにしたがって元素イオウへと酸化する:
a-b; b-a; a-a-b; b-b-a; a-b-b; b-a-a; a-b-a-b; b-a-b-a; a-b-a-b-a-b; 及び b-a-b-a-b-a
MOXY触媒を精製するために、ギ酸と塩酸を用い、また白液とEDTA溶液を用いて実験室試験を行った。試験における変数は化学品の量と温度であった。一連の試験において、酸性化又は触媒の他の処理を毎回三回繰り返し、各回ごとに新しい洗浄溶液を用いた。白液は洗浄中取り替えなかった。
表2 様々な試験ポイントでの触媒の外来物質パーセント
ギ酸は鉄を実質的に除去せず、元素イオウもまったく除去しない。
塩酸は鉄の70〜90%を除去するが、元素イオウは除去されない。
マンガン、カルシウム及びマグネシウムの除去はギ酸処理を用いることによっても、塩酸処理を用いることによっても十分に達成されるが、塩酸処理の方が常により良好な結果をもたらす。
工業スケール試験をMOXY触媒を精製するために行った。ポリスルフィドの製造プロセスを第一の時点で止め、その時点で二つの一連の酸洗浄ステップ(bステップ)をギ酸(その水溶液濃度は4.5%であった)を用いて行った。酸性化の前に水による洗浄を2回行った。水リサイクル時間は約25分であった。目的は、金属の除去のために酸性化の最終pHレベルを十分に下げる(<3)ために触媒から酸中性化液をできるだけ効率的に除去することであった。酸性化において酸再循環時間は60分であった。
Claims (20)
- 活性炭触媒の存在下で実質的な量の鉄を含有する白液の酸化によるポリスルフィド蒸解液の製造に用いられる該活性炭触媒を再生する方法において、該触媒に蓄積される沈殿物を除去するために洗浄液により該触媒が洗浄される上記方法であって、
使用される洗浄液が硫化ナトリウム含有洗浄液であることを特徴とする上記方法。 - ポリスルフィド蒸解液の製造に用いられる、酸化されるべき白液が、少なくとも1mg/l、特に少なくとも2ml/l、特に少なくとも4ml/lの鉄を含有することを特徴とする、請求項1に記載の方法。
- 活性炭触媒中に沈殿される元素イオウが硫化ナトリウム含有洗浄液を用いて溶解される、請求項1又は2に記載の方法。
- 前記使用される洗浄液が白液又は緑液又はそれらの混合液である、先行する請求項のいずれに記載の方法。
- 前記洗浄液が硫化ナトリウムを水酸化ナトリウム又は炭酸ナトリウム又はそれらの混合物とともに含有し、その中の活性アルカリの量が10〜200g/l、特に約100〜120g/lであり、その硫化度が約10〜50%、特に約30〜35%である、先行する請求項のいずれかに記載の方法。
- 硫化ナトリウム含有洗浄液がポリスルフィド蒸解液の製造用に用いられる白液であり、その白液は所望により水で希釈されることを特徴とする、先行する請求項のいずれかに記載の方法。
- 少なくとも一つの硫化ナトリウム洗浄ステップと酸性洗浄液で行なわれる少なくとも一つの洗浄ステップを含む多段式洗浄に、活性炭触媒を付すことにより該活性炭触媒を再生することを特徴とする、先行する請求項のいずれかに記載の方法。
- 少なくとも一つの硫化ナトリウム洗浄ステップの後に少なくとも一つの洗浄ステップを酸性洗浄液を用いて行うか、又は対応して、
酸性洗浄液を用いて行われる少なくとも一つの洗浄ステップの後に少なくとも一つの硫化ナトリウム洗浄ステップを行うことを特徴とする、請求項7に記載の方法。 - 酸性洗浄液を用いて行われる洗浄ステップに先立ち、イオウを含む化合物の残渣を除去するために活性炭触媒をすすぐ、特にすすぎ水の廃液のpH値が少なくともほとんど中性になるまで活性炭触媒をすすぐことを特徴とする、請求項7〜8のいずれかに記載の方法。
- 酸洗浄ステップにおいて、触媒に含有される沈殿した金属、例えば沈殿した鉄、マンガン、カルシウム、又はマグネシウム又はそれらの混合物が除去されることを特徴とする、請求項7〜9のいずれかに記載の方法。
- 使用される酸性洗浄液が有機又は無機酸、例えばギ酸若しくは同様のアルカン酸、又は塩酸若しくは同様の鉱酸、又はそれらの混合物であることを特徴とする請求項7〜10のいずれかに記載の方法。
- 使用される酸性洗浄液が無機酸、例えば塩酸又は同様の鉱酸であり、その量が触媒中に含有される鉄沈殿物を除去するのに適切であることを特徴とする請求項7〜11のいずれかに記載の方法。
- 使用される酸性洗浄液が有機又は無機酸の水溶液であり、その液の酸濃度が1〜15重量%、特に約4〜6重量%であることを特徴とする請求項7〜12のいずれかに記載の方法。
- 使用される洗浄液が硫化ナトリウムを含み、第一の時点で行われる少なくとも一つの洗浄ステップ、及び
酸性洗浄液が使用され、第一の時点の前か又はその後のいずれかの第二の時点で行われる一つの洗浄ステップ
を含む多段式洗浄に活性炭触媒を付すことにより該活性炭触媒を再生することを特徴とする請求項7〜13のいずれかに記載の方法。 - 複数の硫化ナトリウム洗浄ステップが順次行われ、その後に少なくとも一つの洗浄ステップが酸性洗浄液を用いて行われ;
複数の洗浄ステップが酸性洗浄液を用いて順次行われ、その後に少なくとも一つの硫化ナトリウム洗浄ステップが行われ;
洗浄シーケンスにおいて、少なくとも一つの硫化ナトリウム洗浄ステップと、酸性洗浄液を用いて行われる少なくとも一つの洗浄ステップとが交互に行われ、その後にこのような洗浄シーケンスが0〜5回繰り返される、請求項14に記載の方法。 - 第二の時点が第一の時点のすぐ後に続く、特に第一と第二の時点の間の時間が0.1〜24時間、特に0.5〜18時間である、請求項14又は15に記載の方法。
- 第一と第二の時点の間の時間が1日超、特に7日〜720日、最も適切には14日〜180日である、請求項14又は15に記載の方法。
- 使用される洗浄液が硫化ナトリウムを含む複数の洗浄ステップを含む多段式洗浄に活性炭触媒を付すことにより該活性炭触媒を再生し、酸性洗浄液が使用される洗浄ステップが硫化ナトリウムを含む最後の洗浄ステップの後に先立っては行われないことを特徴とする請求項7〜17のいずれかに記載の方法。
- 酸化される白液がスルフェート又はポリスルフィド製造装置の化学サイクルから得られ、そのサイクルにおいて非化石燃料が石灰スラッジ再燃焼に用いられ、特に樹皮又は木材チップ又は同様の木材燃料のような木材ベース燃料が石灰スラッジ再燃焼に用いられることを特徴とする先行する請求項のいずれかに記載の方法。
- 触媒が、その圧力の低下が少なくとも10%だけ、最も適切には少なくとも15%だけ、特に20%だけ減少するまで、硫化ナトリウムを含む洗浄液により処理されることを特徴とする先行する請求項のいずれかに記載の方法。
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PCT/FI2016/050271 WO2016174308A1 (en) | 2015-04-27 | 2016-04-27 | Method of regenerating catalysts used for production of polysulphide cooking liquors |
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CA814882A (en) * | 1969-06-10 | Worster Hans | Method for the preparation of polysulfide-kraft pulping liquor | |
US3460913A (en) | 1966-12-27 | 1969-08-12 | Universal Oil Prod Co | Regeneration of sulfur contaminated catalysts |
US4024229A (en) * | 1970-11-06 | 1977-05-17 | The Mead Corporation | Production of polysulfide with PTFE coated catalyst |
CA959628A (en) | 1970-11-06 | 1974-12-24 | Glen C. Smith | Production of polysulfide |
US4162187A (en) | 1974-05-09 | 1979-07-24 | The Mead Corporation | Process for production of sodium thiosulfate and sodium hydroxide |
NO150971C (no) * | 1981-04-10 | 1985-01-23 | Papirind Forskningsinst | Fremgangsmaate ved rensning av kondensater fra sulfatprosessen |
JPS62247812A (ja) * | 1986-04-18 | 1987-10-28 | Chiyoda Chem Eng & Constr Co Ltd | 加圧式上向流深層濾過方法及びそれに用いる濾過器 |
JPH07114959B2 (ja) | 1987-08-31 | 1995-12-13 | 千代田化工建設株式会社 | 活性炭触媒の再生方法 |
US5082526A (en) | 1989-01-23 | 1992-01-21 | Pulp And Paper Research Institute Of Canada | Process of producing kraft pulping liquor by the oxidation of white liquor in the presence of lime mud |
CN1018796B (zh) * | 1990-07-25 | 1992-10-28 | 湖北省化学研究所 | 用于钴-钼系催化剂硫化的固体硫化剂及制备 |
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DK172100B1 (da) | 1994-03-22 | 1997-10-27 | Smidth & Co As F L | Fremgangsmåde til varmebehandling af kalkslam, samt anlæg til udøvelse af fremgangsmåden |
SE507033C2 (sv) | 1995-07-04 | 1998-03-16 | Kvaerner Pulping Tech | Framställning av polysulfid genom oxidation av sulfid i grönlut |
JP4187826B2 (ja) * | 1998-05-29 | 2008-11-26 | 川崎化成工業株式会社 | 電解酸化による多硫化物の製造方法 |
RU2295386C2 (ru) * | 2003-03-07 | 2007-03-20 | Алексей Юрьевич Кочетков | Гетерогенный катализатор окисления неорганических и/или органических соединений на керамическом носителе |
JP4506085B2 (ja) | 2003-03-18 | 2010-07-21 | 日本製紙株式会社 | 白液酸化用の活性炭触媒の洗浄方法およびその洗浄機構を備えた白液酸化装置 |
WO2006029478A2 (en) | 2004-09-17 | 2006-03-23 | Orica Australia Pty Ltd | Effluent treatment process |
CN101368278A (zh) * | 2007-08-15 | 2009-02-18 | 贾建立 | 元素硫歧化电解制氢、铜、铅、锌、酸、氯碱的方法 |
RU2361026C1 (ru) * | 2008-04-07 | 2009-07-10 | Эдуард Львович Аким | Способ приготовления раствора для полисульфидной варки древесины |
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