WO2014170250A1 - Verfahren zur aufarbeitung von abwasser aus der nitro-benzolherstellung - Google Patents
Verfahren zur aufarbeitung von abwasser aus der nitro-benzolherstellung Download PDFInfo
- Publication number
- WO2014170250A1 WO2014170250A1 PCT/EP2014/057488 EP2014057488W WO2014170250A1 WO 2014170250 A1 WO2014170250 A1 WO 2014170250A1 EP 2014057488 W EP2014057488 W EP 2014057488W WO 2014170250 A1 WO2014170250 A1 WO 2014170250A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wastewater
- alkaline
- nitrobenzene
- benzene
- organic phase
- Prior art date
Links
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002351 wastewater Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000012958 reprocessing Methods 0.000 title abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 122
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000012074 organic phase Substances 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 22
- 238000006396 nitration reaction Methods 0.000 claims abstract description 18
- 239000008346 aqueous phase Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000007717 exclusion Effects 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 13
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 16
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 238000005191 phase separation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- -1 aromatic nitro compounds Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000470 constituent Substances 0.000 description 6
- 238000010626 work up procedure Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- YPAKZCPHSZUMCR-UHFFFAOYSA-N benzene;nitrobenzene Chemical compound C1=CC=CC=C1.[O-][N+](=O)C1=CC=CC=C1 YPAKZCPHSZUMCR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- VMMLSJNPNVTYMN-UHFFFAOYSA-N dinitromethylbenzene Chemical class [O-][N+](=O)C([N+]([O-])=O)C1=CC=CC=C1 VMMLSJNPNVTYMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical group 0.000 description 1
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical class [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/025—Thermal hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
Definitions
- the invention relates to a process for the treatment of alkaline wastewater, which is produced in the washing of crude, obtained by nitration of benzene nitrobenzene, wherein
- Nitrobenzene is an important intermediate in the chemical industry, especially for the production of aniline and thus also for the production of diisocyanates and polyisocyanates
- the reaction product is first a crude nitrobenzene, which contains nitric acid as impurities and - if mixed with mixed acid - sulfuric acid, and as organic impurities dinitrobenzene and nitrated oxidation products of benzene, especially nitrated phenols (nitrophenols). It also contains organic compounds which are formed from the compounds which are contained as impurities in the benzene used (WO 2008/148608 Al).
- the crude nitrobenzene also contains metal salts which may be present dissolved in the acid residues or in the crude nitrobenzene (DE 10 2007 059 513 AI).
- the crude nitrobenzene has impurities as water, benzene and nitrophenols and dinitrobenzene and - if nitrated with mixed acid - sulfuric acid on. These impurities are undesirable because they can negatively impact downstream processes where nitrobenzene is used, such as the production of aniline.
- Suitable work-up procedures, which include washing and distillation stages are, for.
- EP 1 816 117 B1 describes the work-up of the crude nitrobenzene in an acidic wash, an alkaline wash with aqueous sodium hydroxide solution, a neutral wash and a final distillative purification.
- bases other than sodium hydroxide solution such as, for example, aqueous sodium carbonate solution or aqueous ammonia solution (WO 2011/082 977 A1) or potassium hydroxide or ammonia (DE 60 113 579 T2).
- the work-up of the alkaline wastewater from the alkaline wash can z. B. by thermal pressure decomposition (TDZ).
- TDZ thermal pressure decomposition
- EP 0 005 203 B1 describes a process for working up wastewaters containing nitrohydroxyaromatics, the effluents being treated under exclusion of air and oxygen at a pressure of 50 bar to 250 bar and at a temperature of 150.degree. C. to 500.degree.
- EP 0 503 387 B1 describes a similar process, which is characterized in that the said alkaline wastewater is worked up by addition of nitric acid and subsequent treatment in temperature ranges from 180 ° C. to 350 ° C. and a pressure range from 40 bar to 250 bar. Both methods, however, have considerable disadvantages: EP 0 005 203 B1 does not describe the removal of organic carbon, as it does
- EP 0 503 387 B1 complete decomposition of nitrobenzene is not possible, so that further treatment of the wastewater is necessary.
- the nitrobenzene contained in the wastewater is decomposed in the TDZ and therefore reduces the yield obtained.
- the presence of nitric acid in the TDZ required according to the teaching of EP 0 503 387 B1 also increases the process costs in two respects: on the one hand by the consumption of nitric acid and on the other hand by the high material load due to the corrosivity of the nitric acid and the resulting associated high investment costs, such as a corrosion resistant titanium-lined tubular reactor.
- EP 1 593 654 A1 describes a process for working up alkaline wastewaters, which are produced during the scrubbing of crude nitrobenzene, wherein the crude nitrobenzene is prepared by adiabatic nitration of benzene with nitrating acid and then washed in an acidic scrub and then in an alkaline scrubber, wherein an alkaline waste water containing benzene is obtained in concentrations of 100 ppm to 3000 ppm and nitrobenzene in concentrations of 1000 ppm to 10000 ppm, wherein the benzene and / or nitrobenzene subsequently separated from the alkaline wastewater is separated and optionally from the alkaline waste water Subsequently, residual benzene and / or nitrobenzene is removed by stripping, and the alkaline waste water is then heated under exclusion of oxygen to temperatures of 150 ° C to 500 ° C under pressure. The thus treated wastewater can therefore be fed without dilution directly to a biological treatment plant
- EP 0 953 546 B1 describes a process for the degradation of an aromatic nitro compound or a mixture of two or more thereof in waste waters having a pH value of 7 to 14, wherein the effluents to temperatures of 150 ° C to 350 ° C below be heated to a pressure of 10 to 300 bar, wherein at least one aromatic nitro compound carries no hydroxyl group on the aromatic ring.
- aromatic nitro compounds are nitrohydroxyaxomaten such as mono-, di- and trinitrophenols, mono-, di-. Trinitrocresols, mono-, di- and trinitric resorcinols and mono-di-, trixylenols.
- Aromatic nitro compounds which do not bear a hydroxy group on the aromatic ring are, for example, nitrobenzenes, nitrotoluenes and dinitrotoluenes.
- EP 0 953 546 B 1 states that the wastewaters treated in this way can easily be biologically cleaned.
- step (a) single-stage or multi-stage washing of the crude aromatic nitro compound to obtain at least one organic phase and at least one aqueous phase and separation of the aqueous phase or phases, wherein step (a) comprises the addition of a base (b) optionally removing organic constituents from at least part of the aqueous phase or aqueous phases obtained in step (a) by stripping preferably with steam, then (c) removing organic compounds from at least part of the from step (a) or step (b) resulting aqueous phase or aqueous phases by thermal and / or oxidative degradation, then (d) distillative depletion of ammonia from at least a portion of the resulting from step (c) aqueous phase or aqueous phases, and subsequently (e) optional Supplying at least a portion of the resulting from step (d) aqueous phase or aqueous phases to a biological wastewater treatment.
- step (d) the ammonia content in the wastewater should be reduced in step (d), which results from the nitration of aromatic compounds and subsequent removal of organic constituents.
- WO 2012/025393 AI speaks of free ammonia and not of dissolved ammonium ions in
- an object of the present invention is a process for the treatment of alkaline wastewater, which results from the scrubbing of crude, preferably adiabatic nitration of benzene obtained nitrobenzene, wherein
- the nitrobenzene which passes with the alkaline wastewater in step (i) is at least partially converted to aniline there, so that the resulting organic phase can be advantageously fed to an aniline production process.
- the overall process comprises the following steps: a) nitration of benzene with nitric acid or, preferably, a mixture of nitric acid and sulfuric acid (hereinafter also referred to as mixed acid) and separation of the aqueous phase; b) washing the organic process product obtained in step a); c) alkaline washing of the washed organic process product obtained in step b), preferably obtaining an alkaline waste water containing benzene at a concentration of 100 ppm to 3,000 ppm and nitrobenzene at a concentration of 1,000 ppm to 10,000 ppm; d) optional deposition of benzene and / or nitrobenzene from the alkaline wastewater obtained in step c); e) work-up of the alkaline wastewater obtained in step c) or step d) comprising the above-described steps (i) to (iii).
- step a) The nitration of benzene to nitrobenzene with nitric acid or a mixture of nitric acid and sulfuric acid (mixed acid) in step a) takes place according to any of the known in the skilled worker from the prior art, such.
- EP 0 436 443 B1 EP 0 771 783 B1, US Pat. No. 6,562,247 B2 or in EP 0 156 199 B1. Since a crude nitrobenzene containing excess acid, unreacted benzene, water and organic minor components is obtained in all prior art processes, the purification according to the invention of the crude nitrobenzene obtained in step a) is basically applicable to all processes.
- nitration can be carried out with removal of the heat of reaction (i.e., isothermal or approximately isothermal) or even without removal of the heat of reaction in preferentially isolated reactors (i.e., adiabatic).
- heat of reaction i.e., isothermal or approximately isothermal
- preferentially isolated reactors i.e., adiabatic
- the crude nitrobenzene prepared in step a) is finally separated in a separation tank of excess acid (using mixed acid substantially sulfuric acid).
- step b) The organic phase obtained in step a) after the phase separation, which usually still contains traces of acid, is washed in step b) in one to two, preferably one wash (s) and then separated from the acidic aqueous phase by phase separation (in the case of several Washes after every single wash).
- step b) the acid residues containing the crude nitrobenzene are washed out; Therefore, this process step is also referred to as acidic laundry. It is preferred to proceed in such a way that a pH ⁇ 5 (measured at 20 ° C.) is established in the aqueous phase obtained after the phase separation.
- washing liquid can in step b) any kind of water, eg. B. demineralized water or steam condensate can be used.
- the water can also contain dissolved salts.
- aqueous streams which are obtained during operation are preferably recycled.
- the organic phase thus obtained is then in step c) in preferably one to two, more preferably an alkaline wash (s) with a base, preferably an aqueous solution of a base selected from the group consisting of sodium hydroxide, sodium carbonate and sodium bicarbonate, washed and then separated from the alkaline wash water by phase separation (for several washes after each wash).
- Sodium hydroxide is preferably used as the aqueous base solution.
- the alkaline wash is described below with reference to caustic soda; it is easy for the skilled person to make appropriate modifications if necessary, if other bases are used.
- the sodium hydroxide solution used preferably has a pH of 9.0 to 14 (measured at 20 ° C.).
- the mass ratio of sodium hydroxide solution to organic phase depends on the benzene excess used in step a) and is preferably between 1:80 and 1: 500.
- the pH of the sodium hydroxide solution used and its mass ratio to the organic phase are adjusted so that that acid impurities (for example nitrophenols formed as by-products and acid residues not completely removed in step b) in step c) are largely or completely, preferably completely, neutralized.
- the base in step c) is preferably used in an excess of from 0.5% to 5.0% of theory, more preferably from 1.0% to 3.0% of theory and most preferably from 1.5% to 2%, 5% of theory, in each case based on the nitrophenols contained in the wastewater according to step b) used.
- the relevant value for the nitrophenol content is that determined by gas chromatography.
- step d) the unreacted benzene and / or nitrobenzene still present are separated from the alkaline wastewater from step c). The thus separated benzene and / or nitrobenzene is then preferably again the nitration process, particularly preferably the crude nitrobenzene fed.
- the separation of the non-dissolved nitrobenzene can be carried out by separators, settling tanks or other Pliasentrennapparatiiren.
- a settling tank is used.
- an alkaline wastewater is obtained in step d)
- Benzene in a concentration of 100 ppm to 1000 ppm and nitrobenzene in a concentration of 1200 ppm to 3000 ppm contains. It is preferred to carry out step d).
- step e) (i) (of the TDZ) the alkaline wastewater, which is still laden with organic salts of the nitrohydroxyaromatics, obtained from steps c and d), with the exclusion of oxygen at a pressure increased against atmospheric pressure, preferably at a absolute
- inert gases z. As nitrogen and / or argon suitable. Depending on the temperature and, where appropriate, the inert gas inlet pressure, the heating of the Wastewater prefers the aforementioned pressures.
- the heating of the alkaline waste water and thermal pressure decomposition of the organic constituents such as benzene, nitrobenzene and nitrohydroxyaromatics is usually carried out for 5 minutes to 120 minutes, preferably 1 5 minutes to 30 minutes.
- the alkaline waste water is then cooled so that it leaves the TDZ at a temperature of 60 ° C to 100 ° C.
- the cooling is preferably carried out in countercurrent to the input ström under relaxation.
- Steps d) and e) (i) can be carried out according to the prior art, preferably according to the disclosure of EP 1 593 654 A1.
- step e (i) it is particularly preferred to match the residence time in step e (i) and the excess of base used in step c) to one another. So is with a short residence time in
- Step e) (i) a larger base excess in step c) advantageous.
- step e) (ii) the wastewater obtained in e) (i) is further purified by stripping and then the stripping gas stream loaded with impurities is heated to a temperature of 10 ° C to 60 ° C, preferably from 20 ° C to 50 ° C, more preferably from 25 ° C to 45 ° C, most preferably from 30 ° C to 40 ° C, cooled. In this case, any remaining organic constituents are removed.
- the stripping preferably takes place in countercurrent in a stripping column, the gas stream preferably emerging from the stripping gas (preferably water vapor) and the stripped volatile constituents at the top of the stripping column (vapors) and the stripped wastewater preferably at the bottom of the stripping column is removed.
- the gas withdrawn at the top of the stripping column (vapor) is very particularly heated in a condenser to a temperature of from 10.degree. C. to 60.degree. C., preferably from 20.degree. C. to 50.degree. C., more preferably from 25.degree. C. to 45.degree preferably cooled from 30 ° C to 40 ° C.
- Stopped, gaseous residual ammonia is preferably fed to a technical exhaust air purification.
- the stripping column is preferably a tubular device with several internals (e.g.
- step e) (ii) at an absolute pressure of 0.1 bar to 5 bar, more preferably 0.5 bar to 2 bar, and preferably at a temperature of 40 ° C to 160 ° C, particularly preferred 80 ° C to 120 ° C, performed.
- step e) (iii) the liquid stream obtained in step e) (ii) by cooling the gas stream from the stripping gas (preferably water vapor) and the stripped volatile constituents is separated into an aqueous and an organic phase. This is done in a phase separation apparatus, from which the separating organics are discharged. The thus largely freed from organics stream (in the preferred form imple mentation with
- the organic phase discharged from the phase separation apparatus obtained in step (iii) is fed to an aniline production process. It is preferably a process for producing aniline by catalytic hydrogenation of nitrobenzene.
- the catalytic hydrogenation of nitrobenzene is preferably carried out in the gas phase with recycling of unreacted hydrogen (cycle gas procedure).
- the supply of the organic phase from step (iii) can take place at various points:
- step (iii) it is possible to deliver the organic phase from step (iii) to a reactant stream from an aniline production plant.
- a reactant stream from an aniline production plant contains in large-scale operation with recycling of unreacted hydrogen, the feed hydrogen, a mixture of freshly supplied hydrogen and recirculated hydrogen, anyway shares in after the reaction is not completely separated aniline.
- Nitrobenzene was prepared in an adiabatic process as described in EP 2 168 942 A1.
- the wastewater produced during the last alkaline wash was used in the following examples.
- Example 1 (according to the invention)
- the waste water from the alkaline wash was taken to a settling tank where undissolved benzene and nitrobenzene were separated.
- 3.5 tonnes per hour of alkaline wastewater containing 2870 ppm of nitrobenzene, 409 ppm of benzene and 1 1809 ppm of nitrophenols, and a pH of 12.8 (1.8% excess of NaOH) the starting content of nitrophenols before the alkaline wash) were treated from there with a residence time of 20 min, a temperature of 290 ° C and an absolute pressure of 90 bar.
- the resulting wastewater was cooled to 80 ° C (step (i)).
- the conversion of nitrobenzene in the TDZ is 99%.
- step (ii) the wastewater was stripped with direct steam (step (ii)).
- the stripping column was operated at an absolute pressure of 1.05 bar.
- a flow of 3.9 tons per hour was obtained, which contained essentially water, ammonia and organics.
- the top product of the stripping column was condensed, separated into an aqueous and an organic phase (step (iii)), and 280 kg per hour of the aqueous stream was recycled as reflux to the column.
- the lower organic phase in the phase separation apparatus was run for further processing in the Rohanilintank an aniline plant.
- the organic phase contained per hour 2.6 kg aniline, 0.2 k nitrobenzene, 1, 5 kg benzene and 1 kg phenol.
- the yield of aniline recovered in the TDZ, based on nitrobenzene, was 22%.
- Tonnes per hour which contained essentially water, ammonia and organics.
- the top product of the stripping column was condensed, separated into an aqueous and an organic phase (step (iii)), and 280 kg per hour of the aqueous stream was recycled as reflux to the column.
- the lower organic phase in the phase separation apparatus is run for further processing in the Rohanilintank an aniline plant.
- the organic phase contains 5.9 kg of aniline per hour, 0.01 kg of nitrobenzene, 1.2 kg of benzene and 0.8 kg of phenol.
- the yield of aniline recovered in the TDZ, based on nitrobenzene, was 49%.
- the waste water from the alkaline wash was taken to a settling tank where undissolved benzene and nitrobenzene were separated.
- 3.6 tonnes per hour of alkaline wastewater containing 2420 ppm of nitrobenzene, 220 ppm of benzene and 11234 ppm of nitrophenols, and a pH of 13.0 (1.8% excess of NaOH compared to Starting content of nitrophenols before the alkaline wash) were treated at a residence time of 41 minutes, 280 ° C. and an absolute pressure of 106 bar.
- the resulting wastewater was then cooled to 80 ° C (step (i)).
- the conversion of nitrobenzene in the TDZ is 99.9%. Subsequently, the wastewater was stripped with direct steam.
- the stripping column was operated at an absolute pressure of 1.03 bar (step (ii)).
- a stream of 4.0 tons per hour was obtained, which contained essentially water, ammonia and organics.
- the top product of the stripping column was condensed, separated into an aqueous and an organic phase (step (iii)), and 680 kg per hour of the aqueous stream were recycled as reflux to the column.
- the lower organic phase in the phase separation apparatus was run for further processing in the Rohanilintank an aniline plant.
- the organic phase contained per hour 10 kg of aniline, 0.04 kg of nitrobenzene, 0.01 kg of benzene and 0.02 kg of phenol.
- the yield of aniline recovered in the TDZ, based on nitrobenzene, was 99%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Water Treatments (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016508110A JP6356219B2 (ja) | 2013-04-18 | 2014-04-14 | ニトロベンゼン製造からの廃水の後処理方法 |
CN201480021668.2A CN105263865B (zh) | 2013-04-18 | 2014-04-14 | 后处理来自硝基苯制备的废水的方法 |
KR1020157032658A KR102243717B1 (ko) | 2013-04-18 | 2014-04-14 | 니트로벤젠 제조로부터의 폐수의 후처리 방법 |
US14/784,699 US9771291B2 (en) | 2013-04-18 | 2014-04-14 | Process for working up waste water from nitrobenzene preparation |
EP14717751.3A EP2986562B1 (de) | 2013-04-18 | 2014-04-14 | Verfahren zur aufarbeitung von abwasser aus der nitro-benzolherstellung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13164307.4 | 2013-04-18 | ||
EP13164307 | 2013-04-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014170250A1 true WO2014170250A1 (de) | 2014-10-23 |
Family
ID=48142661
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2014/057488 WO2014170250A1 (de) | 2013-04-18 | 2014-04-14 | Verfahren zur aufarbeitung von abwasser aus der nitro-benzolherstellung |
Country Status (8)
Country | Link |
---|---|
US (1) | US9771291B2 (de) |
EP (1) | EP2986562B1 (de) |
JP (1) | JP6356219B2 (de) |
KR (1) | KR102243717B1 (de) |
CN (1) | CN105263865B (de) |
PT (1) | PT2986562T (de) |
TW (1) | TW201509833A (de) |
WO (1) | WO2014170250A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104671304A (zh) * | 2015-01-13 | 2015-06-03 | 青岛双桃精细化工(集团)有限公司 | 一种精馏塔塔顶气相潜热的综合利用方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8639782B2 (en) | 2006-08-23 | 2014-01-28 | Ebay, Inc. | Method and system for sharing metadata between interfaces |
CN110683701B (zh) * | 2019-10-30 | 2022-03-04 | 江苏扬农化工集团有限公司 | 一种硝基苯胺类废水资源化利用的方法 |
CN115197345B (zh) * | 2022-07-14 | 2024-06-25 | 湖南百利工程科技股份有限公司 | 一种合成橡胶生产中凝聚工艺的节能方法 |
Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2256999A (en) | 1939-03-08 | 1941-09-23 | Du Pont | Nitration of organic compounds |
US2739174A (en) | 1951-09-08 | 1956-03-20 | Eastman Kodak Co | Nitrating aromatic hydrocarbons with only nitric acid |
US3780116A (en) | 1972-06-15 | 1973-12-18 | Zaverchand & Co | Method for nitration of aromatic hydrocarbon compounds |
EP0005203B1 (de) | 1978-04-27 | 1981-04-29 | Bayer Ag | Verfahren zur Aufarbeitung von Nitro-hydroxy-aromaten enthaltenden Abwässern |
EP0078247B1 (de) | 1981-10-21 | 1985-11-27 | Monsanto Company | Katalysatoren und Verfahren zur Dampfphasen-Nitrierung von Aromaten |
EP0156199B1 (de) | 1984-03-16 | 1988-10-26 | Bayer Ag | Verfahren zur Herstellung von Nitrobenzol |
EP0503387B1 (de) | 1991-03-13 | 1993-12-22 | BASF Aktiengesellschaft | Verfahren zum Abbau von aromatischen Nitroverbindungen enthaltenden Abwässern |
EP0552130B1 (de) | 1992-01-15 | 1996-03-20 | Cu Chemie Uetikon Ag | Verfahren zur Herstellung von Nitrobenzol |
EP0436443B1 (de) | 1990-01-04 | 1996-04-17 | Nrm International Technologies C.V. | Nitrierungsverfahren |
EP0771783B1 (de) | 1995-10-22 | 2000-04-05 | JOSEF MEISSNER GMBH & CO | Verfahren zur Aromatennitrierung |
US6288289B1 (en) | 2000-01-27 | 2001-09-11 | Noram Engineering And Constructors Ltd. | Integrated effluent treatment process for nitroaromatic manufacture |
US6562247B2 (en) | 2000-03-02 | 2003-05-13 | Dow Global Technologies Inc. | Process for conducting liquid/liquid multiphase reactions in a tubular reactor having static mixing elements separated by coalescing zones |
EP0953546B1 (de) | 1998-04-08 | 2004-09-22 | Basf Aktiengesellschaft | Verfahren zum Abbau von aromatischen Nitroverbindungen in Abwässern |
EP1593654A1 (de) | 2004-04-10 | 2005-11-09 | Bayer MaterialScience AG | Verfahren zur Aufarbeitung von aromatische Nitroverbindungen enthaltenen Abwässern |
EP1816117B1 (de) | 2006-02-03 | 2008-11-05 | Bayer MaterialScience AG | Verfahren zur Herstellung von Nitrobenzol |
WO2008148608A1 (en) | 2007-06-06 | 2008-12-11 | Huntsman International Llc | Process for preparing mixtures of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates |
DE102007059513A1 (de) | 2007-12-11 | 2009-06-18 | Bayer Materialscience Ag | Verfahren zur Herstellung von Nitrobenzol durch adiabate Nitrierung |
DE102008048713A1 (de) | 2008-09-24 | 2010-03-25 | Bayer Materialscience Ag | Verfahren zur kontinuierlichen Herstellung von Nitrobenzol |
WO2011021057A1 (en) | 2009-08-18 | 2011-02-24 | Noram International Limited | Washing system for nitroaromatic compounds |
WO2011082977A1 (de) | 2009-12-16 | 2011-07-14 | Basf Se | VERFAHREN ZUR AUFARBEITUNG VON NOx-HALTIGEN ABGASEN AUS ABWASSERSTRÖMEN VON NITRIERANLAGEN |
WO2012025393A1 (de) | 2010-08-12 | 2012-03-01 | Basf Se | Verfahren zur aufreinigung von abwässern aus der aufarbeitung von rohen aromatischen nitroverbindungen |
US20120078015A1 (en) * | 2009-06-17 | 2012-03-29 | Huntsman International Llc | Chemical Installation |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL1993990T3 (pl) * | 2006-03-07 | 2011-12-30 | Basf Se | Sposób destylacyjnego wydzielania dinitrotoluenu ze ścieków procesowych z wytwarzania dinitrotoluenu przez nitrowanie toluenu mieszaniną nitrującą |
-
2014
- 2014-04-14 WO PCT/EP2014/057488 patent/WO2014170250A1/de active Application Filing
- 2014-04-14 CN CN201480021668.2A patent/CN105263865B/zh active Active
- 2014-04-14 EP EP14717751.3A patent/EP2986562B1/de active Active
- 2014-04-14 JP JP2016508110A patent/JP6356219B2/ja active Active
- 2014-04-14 KR KR1020157032658A patent/KR102243717B1/ko active IP Right Grant
- 2014-04-14 US US14/784,699 patent/US9771291B2/en active Active
- 2014-04-14 PT PT147177513T patent/PT2986562T/pt unknown
- 2014-04-16 TW TW103113790A patent/TW201509833A/zh unknown
Patent Citations (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2256999A (en) | 1939-03-08 | 1941-09-23 | Du Pont | Nitration of organic compounds |
US2739174A (en) | 1951-09-08 | 1956-03-20 | Eastman Kodak Co | Nitrating aromatic hydrocarbons with only nitric acid |
US3780116A (en) | 1972-06-15 | 1973-12-18 | Zaverchand & Co | Method for nitration of aromatic hydrocarbon compounds |
EP0005203B1 (de) | 1978-04-27 | 1981-04-29 | Bayer Ag | Verfahren zur Aufarbeitung von Nitro-hydroxy-aromaten enthaltenden Abwässern |
EP0078247B1 (de) | 1981-10-21 | 1985-11-27 | Monsanto Company | Katalysatoren und Verfahren zur Dampfphasen-Nitrierung von Aromaten |
EP0156199B1 (de) | 1984-03-16 | 1988-10-26 | Bayer Ag | Verfahren zur Herstellung von Nitrobenzol |
EP0436443B1 (de) | 1990-01-04 | 1996-04-17 | Nrm International Technologies C.V. | Nitrierungsverfahren |
EP0503387B1 (de) | 1991-03-13 | 1993-12-22 | BASF Aktiengesellschaft | Verfahren zum Abbau von aromatischen Nitroverbindungen enthaltenden Abwässern |
EP0552130B1 (de) | 1992-01-15 | 1996-03-20 | Cu Chemie Uetikon Ag | Verfahren zur Herstellung von Nitrobenzol |
EP0771783B1 (de) | 1995-10-22 | 2000-04-05 | JOSEF MEISSNER GMBH & CO | Verfahren zur Aromatennitrierung |
EP0953546B1 (de) | 1998-04-08 | 2004-09-22 | Basf Aktiengesellschaft | Verfahren zum Abbau von aromatischen Nitroverbindungen in Abwässern |
US6288289B1 (en) | 2000-01-27 | 2001-09-11 | Noram Engineering And Constructors Ltd. | Integrated effluent treatment process for nitroaromatic manufacture |
DE60113579T2 (de) | 2000-01-27 | 2006-06-22 | Noram International Ltd. | Integriertes Abwasserbehandlungsverfahren für die Herstellung von Nitroaromaten |
US6562247B2 (en) | 2000-03-02 | 2003-05-13 | Dow Global Technologies Inc. | Process for conducting liquid/liquid multiphase reactions in a tubular reactor having static mixing elements separated by coalescing zones |
EP1593654A1 (de) | 2004-04-10 | 2005-11-09 | Bayer MaterialScience AG | Verfahren zur Aufarbeitung von aromatische Nitroverbindungen enthaltenen Abwässern |
EP1816117B1 (de) | 2006-02-03 | 2008-11-05 | Bayer MaterialScience AG | Verfahren zur Herstellung von Nitrobenzol |
WO2008148608A1 (en) | 2007-06-06 | 2008-12-11 | Huntsman International Llc | Process for preparing mixtures of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates |
DE102007059513A1 (de) | 2007-12-11 | 2009-06-18 | Bayer Materialscience Ag | Verfahren zur Herstellung von Nitrobenzol durch adiabate Nitrierung |
DE102008048713A1 (de) | 2008-09-24 | 2010-03-25 | Bayer Materialscience Ag | Verfahren zur kontinuierlichen Herstellung von Nitrobenzol |
EP2168942A1 (de) | 2008-09-24 | 2010-03-31 | Bayer MaterialScience AG | Verfahren zur kontinuierlichen Herstellung von Nitrobenzol |
US20120078015A1 (en) * | 2009-06-17 | 2012-03-29 | Huntsman International Llc | Chemical Installation |
WO2011021057A1 (en) | 2009-08-18 | 2011-02-24 | Noram International Limited | Washing system for nitroaromatic compounds |
WO2011082977A1 (de) | 2009-12-16 | 2011-07-14 | Basf Se | VERFAHREN ZUR AUFARBEITUNG VON NOx-HALTIGEN ABGASEN AUS ABWASSERSTRÖMEN VON NITRIERANLAGEN |
WO2012025393A1 (de) | 2010-08-12 | 2012-03-01 | Basf Se | Verfahren zur aufreinigung von abwässern aus der aufarbeitung von rohen aromatischen nitroverbindungen |
Non-Patent Citations (2)
Title |
---|
"Nitrobenzene fact sheet: support document", OPPT CHEMICAL FACT SHEETS, 1 February 1995 (1995-02-01), XP055081053, Retrieved from the Internet <URL:http://www.epa.gov/chemfact/nitro-sd.pdf> [retrieved on 20130925] * |
W. MEIER; SULZER: "Kolonnen für Rektifikation und Absorption", TECHNISCHE RUNDSCHAU SULZER, vol. 2, 1979, pages 49 - 61, XP055262964 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104671304A (zh) * | 2015-01-13 | 2015-06-03 | 青岛双桃精细化工(集团)有限公司 | 一种精馏塔塔顶气相潜热的综合利用方法 |
CN104671304B (zh) * | 2015-01-13 | 2017-01-11 | 青岛双桃精细化工(集团)有限公司 | 一种精馏塔塔顶气相潜热的综合利用方法 |
Also Published As
Publication number | Publication date |
---|---|
JP6356219B2 (ja) | 2018-07-11 |
US9771291B2 (en) | 2017-09-26 |
EP2986562B1 (de) | 2017-04-05 |
CN105263865A (zh) | 2016-01-20 |
PT2986562T (pt) | 2017-04-24 |
US20160060152A1 (en) | 2016-03-03 |
KR102243717B1 (ko) | 2021-04-26 |
TW201509833A (zh) | 2015-03-16 |
KR20150143768A (ko) | 2015-12-23 |
CN105263865B (zh) | 2017-08-15 |
JP2016522803A (ja) | 2016-08-04 |
EP2986562A1 (de) | 2016-02-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2603461B1 (de) | Verfahren zur aufreinigung von abwässern aus der aufarbeitung von rohen aromatischen nitroverbindungen | |
EP1876142B1 (de) | Verfahren und Anlage zur Konzentrierung von Abfall-Schwefelsäuren aus Nitrierprozessen | |
EP1593654B1 (de) | Verfahren zur Aufarbeitung von aromatische Nitroverbindungen enthaltenen Abwässern | |
EP1496043B1 (de) | Verfahren zur Aufarbeitung des bei der Herstellung von Dinitroluol anfallenden Abwassers | |
EP2986562B1 (de) | Verfahren zur aufarbeitung von abwasser aus der nitro-benzolherstellung | |
EP2877443B1 (de) | Verfahren zur herstellung von nitrobenzol durch adiabate nitrierung | |
EP1493730B1 (de) | Verfahren zur Aufarbeitung von Nebenkomponenten der Dinitroluolherstellung | |
EP2719682B1 (de) | Verfahren zur kontinuierlichen Herstellung von Nitrobenzol | |
EP2751064B1 (de) | Verfahren zur kontinuierlichen herstellung von nitrobenzol | |
DE102015106617A1 (de) | Verfahren zur Entfernung von Verunreinigungen aus Dinitrotoluolen | |
DE102010038519A1 (de) | Verfahren zur Herstellung von Nitrobenzol durch adiabate Nitrierung | |
EP2844635B1 (de) | Verfahren zur behandlung eines ein aromatisches amin umfassenden stoffgemisches, insbesondere von roh-anilin | |
EP2986563B1 (de) | Verfahren zur aufarbeitung von abwasser aus der nitrobenzolherstellung | |
EP1993990B1 (de) | Verfahren zur destillativen abtrennung von dinitrotoluol aus einem prozessabwasser aus der herstellung von dinitrotoluol durch nitrierung von toluol mit nitriersäure | |
EP2841412A1 (de) | Verfahren zur wäsche von dinitrotoluol | |
WO2014177450A1 (de) | Verfahren zur herstellung von nitrobenzol durch adiabate nitrierung | |
EP2742003B1 (de) | Verfahren zur aufreinigung von abwässern aus der aufarbeitung von rohen aromatischen nitroverbindungen | |
WO2013020798A1 (de) | Verfahren zur aufreinigung von abwässern aus der aufarbeitung von rohen aromatischen nitroverbindungen | |
EP3592727B1 (de) | Verfahren zur herstellung von nitrobenzol | |
DE102018217955B4 (de) | Verfahren zur Aufarbeitung von Mischsäure und Abwasser aus der Nitrierung von Aromaten sowie Vorrichtung zur Durchführung des Verfahrens |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480021668.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14717751 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2014717751 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014717751 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14784699 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2016508110 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20157032658 Country of ref document: KR Kind code of ref document: A |