PROCESS FOR CLEANING OF WASTE MATERIALS BY REFINING AND/OR ELIMINATION OF BIOLOGICALLY DIFFICULT TO DEGRADE HALOGEN-, NITROGEN- AND/OR SULFUR COMPOUNDS

Abstract: Liquid waste materials, contaminated with biologically dif­ ficult to degrade halogen, nitrogen and/or sulfur containing compounds and containing 0.1-60 WT.% halogen up to 10 WT% sulfur and/or small amounts of nitrogen, are cleaned or purified by conditioning these materials and passing them together with hydrogen over a guard column filled with absorbent, preferably granular alumina, under a hydrogen pressure of 30-80 bar and with an LHSV of 0.5-2.5H⁻¹ and subsequently passing the stream over a hydrogenating catalyst, preferably a catalyst comprising nickel or cobalt plus molybdenum supported on an inert carrier. The catalyst is preferably a sulfided catalyst.

Description: The invention concerns a process for cleaning liquid waste materials contaminated with difficult to degrade halogen-, nitrogen- and/or sulphur containing compounds by refining and/or elimination of halogen-, nitrogen-, and/or sulphur compounds in which the contaminated waste material together with hydrogen is passed over a hydrogenation catalyst at a temperature between 250 and 400°C and under increased pressure and the effluent is cooled and separated in a cleaned liquid hydrocarbon stream, a hydrogen halogenide, ammonia and/or hydrogen sulfide containing stream and a gaseous stream containing light hydrocarbons and hydrogen. There is a great variety of wastes containing biologically difficult to degrade halogen-, nitrogen- and/or sulphur compounds. A first classification can be made in solid and liquid waste materials. Liquid waste materials can be divided in water containing and wastes which are substantially water free. If halogen-nitrogen- and/or sulphur contained in an aqueous waste material are bounded to hydrocarbons. Those hydrocarbons can be separated from the water after which the separated hydrocarbons can be treated. Many liquid halogen-, nitrogen- and/or sulphur containing waste materials, like waste materials from the metal industry are treated by distillation, a process which leaves a solid halogen-, nitrogen- and/or sulphur containing waste material. Another part of the liquid fraction consists of all kinds of biologically difficult to degrade halogen-, nitrogen- and/or sulphur compounds which often are mixed with other organic compounds. Polychlorinated biphenyls (PCB's) e.g. have frequently been detected in waste oils;their origin is e.g. transformer oil. Nowadays most halogen-, nitrogen- and/or sulphur containing waste materials are disposed off by burning in special incinerators to prevent the formation of compounds like dioxines. Further it has been proposed to decompose halogen containing waste materials in halogen free compounds and hydrogen halogenide, by catalytic hydrogenolysis. According to Japanese Patent 7445043 polychlorinated biphenyls (PCB's) are decomposed by hydrogenation in the presence of a noble metal catalyst, e.g. a platinum metal catalyst. Japanese Patent, 7413155 also mentions this possibility. The Japanese Patent 7461143 describes the decomposition of PCB's by heating this compound in aqueous hydrazine in an inert solvent and in the presence of a palladium catalyst. Noble metal catalysts, however, are sensitive to poisoning and in practice show only a moderate conversion degree; the use of hydrazine in the latest method is problematic because of the toxicity of hydrazine. From US Patent 4400566 it is known that halogen containing waste materials in a protic solvent can be converted with hydrogen in the presence of a catalyst containing (a) nickel compounds with zero valent nickel, in which no N-O bonds are present, (b) triarylfosfines, (c) a reduction agent (e.g. a metal) maintaining the zero valent nickel state and (d) halogenide ions. The catalyst used is complex and necessitates a careful control of the process. From Japanese Patent 7413155 it is known that PCB's can be decomposed by hydrogenolysis in the presence of catalysts based on metals from the iron group (Fe, Ni, Co) plus molybdenum and in the presence of aqueous sodium hydroxide. It is known that in practice under these conditions the catalyst is deactivated after a short while. It is assumed that the use of the sodium hydroxide solution, to bind the hydrogen halogenides, hydrogen sulfide and hydrogen cyanide formed, leaves insufficient hydrogen sulfide to keep the Ni-Mo-Catalyst in the sulfided state. From DE-A-34 05 858 it is known that spent oil can be re-refined. By this process an oil which has been contaminated in use, is refined so that it is suitable for re-use. The feedstocks used in this process are predominantly lube oils with small amounts of sulphur, nitrogen and only faint amounts of hazardous biologically difficult to degrade halogen compounds. According to this document (page 13, lines 25-27) the spent oils are relatively free of PCB's. Typical feedstocks of the known process have (according to table 1 of this document) sulphur contents of 0,49 % or 0,39 %, halogen contents of 770 ppm or 2500 ppm and PCB contents of 0,1 ppm or 0,4 ppm. Higher amounts of those contaminants are not mentioned. The process of DE-A-34 05 858 may comprise the following steps: a) filtering the spent oils, b) removal of water and fuel by treating said oils in a wiped-film-evaporator, c) heat soak of said oils at 250-340°C for 15-120 min. for removal of phosphorus and sludge, d) distillation of said oils, e) passing the distillate over a bed of activated material (adsorbent), f) mixing the distillate with hydrogen, g) treating said mixed distillate under hydrogenating conditions. It is further described in this document (page 47, lines 11-17) that the use of hydrogen as process gas for the adsorption step is preferred instead of an inert gas. Therefore mixing step f may be carried out before step e. It is important to establish that there is no hint in this document as to mixing spent oils with hydrogen before the heat soak step c. Therefore undesired forming of heavy compounds is possible during the heat soak step of the known process. The heart of the invention is the finding that a waste material containing biologically difficult to degrade halogen-, nitrogen- and/or sulphur and containing between 0.1 and 60 wt.% halogen and up to 10 wt.% sulphur and/or small amounts of nitrogen compounds can be cleaned by refining and/or elimination by catalytic hydrogenolysis of halogen-, nitrogen- and/or sulphur compounds which are decomposed with formation of hydrogen halogenide, ammonia, hydrogen sulfide resp. besides the formation of a cleaned hydrocarbon stream containing less than 10 mg/kg halogen, less than 1 ppm wt. PCB's, less than 0.15 wt. % sulfur and traces of nitrogen, and which waste material after fractionation gives a useful hydrocarbon product, without problems of catalyst fouling, if the waste stream contaminated with biologically difficult to degrade halogen-, nitrigen-, and/or sulfur containing compounds, and containing 0.1-60 wt.% halogen, up to 10 wt.% sulfur and/or small amounts of nitrogen containing compounds is cleaned by refining and/or elimination of said contanimating compounds by the combination of following steps: a) conditioning said contaminated waste stream by filtering or by filtering, heating to 100-200°C and subsequent vacuum distillation, b) mixing said conditioned waste stream with hydrogen, c) heating said mixed waste stream to a temperature of 250-400°C by passing said waste stream through a heat exchanger, such heating carried out as a heat soak being excluded, d) passing said heated mixed waste stream of step c under a pressure of 30-80 bar with a LHSV of 0,5-2,5 h⁻¹ over a column filled with adsorbent in order to guard a subsequent hydrogenating catalyst, e) passing said waste stream of step d over said hydrogenating catalyst at a temperature of 250-400°C and a pressure of 30-80 bar and with a LHSV of 0,5-2,5 h⁻¹, f) cooling the effluent of said hydrogenolysis of step e and separating it into a cleaned liquid hydrocarbon stream, a hydrogen halogenide, ammonia and/or hydrogen sulfide containing stream and a gaseous stream of light hydrocarbons and hydrogen. The catalytic hydrogenolysis is sensitive to the presence of metals and metal salts that might be present (inhibition or fouling of the catalyst). For this reason well defined feed is necessary and this is attained by analysing the impurities present in the feed and conditioning of the feed on the basis of these analysis data. In many cases, e.g. in the case of gasoil contaminated with halogen- and/sulfur compounds it is sufficient to filter the waste stream, in order to separate sludge-like contaminants (metal, carbon). Optimum conditioning is obtained by filtration and vacuum distillation of the hydrocarbon stream, in which the top product of the vacuum distillation after separation of gaseous components, serves as the feed for the hydrogenation step. Preferably the vacuum distillation is performed in two wiped film evaporators in series, in which the bottom product of the first film evaporator is the feed material for the second one. This gives the best results. Subsequently the conditioned feed is mixed with hydrogen in such a way that a ratio of hydrogen to halogen-, nitrogen- and/or sulfur compounds to hydrocarbons is obtained suitable for hydrogenolysis, and by passing these through a column filled with absorbent in which potential catalyst poisons are effectively absorbed, by which way the hydrogenation catalyst obtains a longer lifetime and the process is suitable for application on a technical scale. The adsorbents can be active carbon or preferably an active metal oxide with a large specific area. Very suitable is granular aluminium oxide with a large porosity which perfectly guards the catalysts in such a way that the catalyst has a long lifetime. All possible types of hydrogenating catalysts may be applied as catalyst according to the process. Noble metal catalysts, like catalysts based on metals from the platinum group are, however, not preferred, because, like mentioned before, they give a moderate conversion and are rapidly deactivated. Very suitable is a catalyst consisting of an inert carrier (e.g. silica, alumina, or a mixture of silica and alumina, aluminium silicate or similar materials), impregnated with an activating metal in the oxide or salt form, e.g. nickel oxide, magnesium sulfate, barium chloride. Excellent results are obtained particularly with catalysts based on metals from the iron group (Fe,Ni,Co) together with tungsten or rhenium or in particular molybdenum. Therefore preferably catalysts of that type are used. The metal from the iron group and molybdenum, tungsten or rhenium are preferably deposited on an inert carrier (e.g. silica, alumina, aluminium silicate) and are generally present in the oxidic state. Before the use the catalysts are preferably conditioned with sulfur containing compounds until the sulfidic state is reached. Such a sulfided catalyst gives the best results. When using a sulfided catalyst the feed has to contain such an amount of sulfur compounds, that the catalyst remains sulfided during the hydrogenolysis. The temperature in the hydrogenolysis reactor has to be at last 250°C, because otherwise the reaction with certain types of organic compounds is too slow and incomplete. An optimum result is obtained at temperatures between 250°C and 400°C;the conversion of waste materials is then over 99% at an LHSV between 0.5-2.5 H⁻¹. The effluent of the hydrogenolysis reaction is cooled directly or indirectly, in order to separate the hydrogen fraction and the aqueous phase, with the by-products formed like HCl, H₂S and NH₃, from the main stream. When indirect cooling is applied the usual cooling agents may be applied. When using direct cooling, water is an excellent cooling agent; it has a good heat capacity. The use of water as a coolant necessitates, however, special measures, because water is also a solvent for the by products of the reaction like HCl, H₂S.and water vapour formed with HCl and H₂S may give corrosion problems. Another suitable cooling agent is a cold hydrocarbon. HCL and H₂S do not or hardly solve in such hydrocarbons and HCl and H₂S in a hydrocarbon atmosphere are not or hardly corrosive. The gaseous effluent of the hydrogenolysis reaction after cooling is separated in a hydrogen and possibly lighter hydrocarbons containing phase, a liquid hydrocarbon phase and a hydrogen halogenide(s), nitrogen-, sulfur compounds and similar compounds containing phase. Hereto the effluent is e.g. separated in a liquid (hydrocarbon) phase and a gaseous phase, and subsequently the gaseous phase is e.g. passed through a absorbence for the hydrogen halogenide(s), nitrogen-, or sulfur compounds. Water is preferred as an absorbent, since it is cheap and easily available and forms an excellent solvent for the compounds aimed. The hydrogen and possible lighter hydrocarbons containing phase remaining is recycled and after completion with fresh hydrogen, mixed with the conditioned feed. The invention is elucidated in but not restricted to the following examples and by the following figures. Figure 1 shows schematically an installation for the process according to the invention, in which filtration is used as conditioning treatment and in which the separation yields an aqueous solution of hydrogen halogenides. Figure 2 shows schematically an installation, in which the conditioning treatment is a filtration followed by vacuum distillation in two wiped film evaporators in series. Figure 3 shows schematically a mode of operation of the hydrogenolysis, proceeded by a column with adsorbents, in which the hydrogenolysis proceeds in 2 steps with separation of formed by-products in between. In the figures corresponding parts are indicated with the same reference numbers. Apparatus like pumps, valves, control systems etc. are not indicated. The installation of figure 1 is very suitable for the clean-up of lightly contaminated hydrocarbon mixtures. The contaminated hydrocarbon mixtures, e.g. gasoil contaminated by halogen-, nitrogen- and/or sulfur compounds supplied by line 1, is filtered in filter 2 and subsequently mixed with hydrogen from line 14 (as described later on), is passed to heat exchanger 4 via line 3. Herein the mixture is heated to a temperature of 250-400°C, which temperature gives the best results in the subsequent adsorption and hydrogenolysis steps. Subsequently the mixture is passed through a vertical column 5 filled with adsorbent (e.g. alumina of high porosity), in which way effectively catalyst poisons are adsorbed. The mixture of contaminated hydrocarbon feed and hydrogen cooled slightly during absorption is passed subsequently via heat exchanger 5A in which it is heated and by line 6 to a hydrogenolysis reactor 7, where the mixture at a temperature between 250 and 400°C and under a pressure of 30-80 bar is contacted with a hydrogenating catalyst. The effluent from the hydrogenolysis reactor 7 is cooled to a temperature of about 50°C in cooler 9 by mixing the effluent with a coolant (e.g. water). Subsequently the mixture of water and effluent from the hydrogenolysis reaction enters separator 11, where, at a pressure of about 50 bar and a temperature of about 50°C gaseous components (hydrogen and traces methane, ethane and other hydrocarbons in the vapour state) are separated and discharged by line 12. Part of this gaseous stream is recycled by line 14 and after suppletion with hydrogen from line 15 fed in line 3. The remainder leaves the installation by line 13. The liquid phase, consisting of liquid hydrocarbons and an aqueous phase in which hydrogen halogenide, ammonia and/or hydrogen sulfide are dissolved, is drained from the bottom of separator 11 via line 17 to expansion vessel 18, in which the pressure is lowered to about 2-10 bar. Hereby part of the hydrocarbons and traces water and hydrogen sulfide evaporate. The vapour phase is discharged by line 20. The remaining liquid phase goes to a separator 19 where phase separation occurs. The hydrocarbon phase is discharged as a product by line 22. The bottom, aqgueous phase is discharged by line 23. The hydrocarbon vapour escapes by line 13 and is discharged. In figure 2 a hydrocarbon mixture contaminated by halogen-, and nitrogen- and/or sulphur compounds is supplied by line 3, filtered in filter 2 and passed through a heat exchanger 4 where it is preheated to a temperature of about 100-200°C. Subsequently it is fed to a wiped film evaporator 26, where a top product of light organic components (hydrocarbons, halogen, nitrogen and/or sulfur compounds), and possibly present traces of water are separated, which are discharged by line 35. The bottom fraction from film evaporator 26 goes through line 24 to a second wiped film evaporator 28, where this fraction is redistilled under a pressure between 0.005 bar and 0.15 bar (in particular 0.05-01 bar) in which way a tarry (sediment) fraction is obtained as bottom fraction which is discharged via line 30. The top product from this column discharged by line 29 consists of hydrocarbons and halogen-, nitrogen-, and/or sulfur containing compounds. The top product stream from the first film evaporator 26 is passed via line 35 and condensor 36 to separator 37, in which a hydrocarbon and halogen-, nitrogen-, and/or sulfur compounds containing phase is separated which is partly recycled by line 39 and partly goes to the hydrogenolysis reactor by line 40 and line 34. The aqueous phase from separator 37 is passed via line 41 to scrubber 42, in which an additional fraction for the hydrogenolysis is obtained. The top product from film evaporator 28 is supplied via line 29 and condensor 31 also to a separator 32 in which a phase comprising hydrocarbon and halogen-, nitrogen-and/or sulfur compounds is separated and discharged by line 33. Part of this phase is recycled to the film evaporator;the remainder is supplied to the hydrogenolysis reactor by line 34. The volatile phase from separator 32 is discharged and supplied to scrubber 42, in which valuable components suitable for the hydrogenolysis are obtained and fed via line 34. Gaseous components are separated and discharged. The product streams destinated for the hydrogenolysis e.g. from line 34 are mixed with hydrogen and subsequently passed to the hydrogenolysis system as shown in figure 1 The product streams in line 34 originating from the conditioning system of figure 2, however often contain a higher content of halogenide, nitrogen- and/or sulfur compounds and therefore can be treated advantageously in a two-stage hydrogenolysis. A suitable embodiment of such a two-stage hydrogenolysis has been depicted schematically in figure 3. The product stream from line 1 or 34, after mixing with hydrogen, is heated in heat exchanger 4 to a temperature of about 250 to 400°C, and the mixture is subsequently passed through column 5 filled with adsorbent. Via heat exchanger 5A in which the mixture, slightly cooled during adsorption, is reheated it is passed through line 6 to a first hydrogenolysis reactor 7, in which the mixture at 250-400°C and under a pressure of 30-80 bar is contacted with hydrogenating catalyst. The effluent from the hydrogenolysis reactor 7 is cooled and the hydrogen halogenide, ammonia and/or hydrogen sulfide formed are separated in separator 36 and discharged by line 37. The remaining mixture of hydrogen, hydrocarbons and remaining halogen-, nitrogen- and/or sulfur compounds is discharged from separator 36, heated to 250-400°C in heat exchanger 36 and supplied to a second hydrogenolysis reactor 39, where the mixture is contacted with a hydrogenating catalyst and the hydrogenolysis of the halogen-, nitrogen- and/or sulfur compounds is completed. The effluent of this second hydrogenolysis reactor is cooled to about 50°C, by mixing of the effluent with a cooling agent, after which the cooled stream is separated in a similar way as discussed before when describing figure 1. The hydrogen halogenide (S), ammonia and/or hydrogen sulfide separated in separator 36 are discharged via line 37 and fed to flash vessel 18 where they are mixed with the liquid phase from the separator 11 consisting of hydrocarbons, hydrogen halogenide (S), ammonia and/or hydrogen sulfide and together with this liquid phase are subjected to the same separation unit operations. Example 1 An installation as shown in figure 1 is used for the dechlorination and desulfurization of a contaminated gas oil. This gasoil has the following specifications: This gasoil is dechlorinated and desulfurized in hydrogenolysis reactor 7 at 300°C and a pressure of 50 bar (hydrogen pressure). The catalyst consists of alumina supported nickel and molybdenum presulfided with H₂-. The following results are obtained under these conditions: 1. Starting material, gas oil with above mentioned Specifications 2500 KG/HR Hydrogen 65 NM³/HR 2. Product diesel oil 2120 KG/HR (quality according to ASTM D975 for diesel fuel) total chlorine max. 10 MG/Kg; PCB Max 1 MG/KG Temp. 50°C Pressure 2 BAR Sulfur content 0.15 weight % maximum. 3. Petrol (Gasoline) fraction 330 KG/HR boiling trajectory 35-200°C, temperature 50°C Pressure 1.5 Bar 4. Waste streams; Sour fuel gas 35 KG/HR;sour waste water 261 KG/HR. Example 2 An experiment was conducted with an industrial waste stream of hydrocarbons contaminated with halogen containing compounds. Analysis of this waste stream gave the following results: Furthermore sodium is present (sodium and magnesium are insensitive to X-Ray analysis). Centrifugating at 1500 r.p.m. results in:an upper layer consisting of 25% of the original sample containing 15.5% water, density at 20°C is 1.115 Middle layer 65% - Density 1 .17 Residu 10%. This sediment layer has not been further examined. The following composition has been obtained from analysis results by means of column chromatography with carbon tetrachloride, tetrahydrofuran, methylethyl ketone and methanol as eluants: This waste stream is conditioned by filtering, followed by a 2-stage distillation in an apparatus according to figure 2 and the obtained stream 34 was subsequently hydrogenolysed in two stages in an apparatus according to figure 3. The conditions in and results from the distillation in the film evaporators were as follows: Conditions in and results from hydrogenolysis End Product

Claims: A process for cleaning liquid waste materials contaminated with 0,1-60 wt.% difficult to degrade halogen containing compounds, small amounts of nitrogen containing compounds and up to 10 wt.% sulphur containing compunds by refining and/or elimination of said contaminating compounds, characterized by the combination of following steps: a) conditioning said contaminated waste stream by filtering or by filtering, heating to 100-200°C and subsequent vacuum distillation, b) mixing said conditioned waste stream with hydrogen, c) heating said mixed waste stream to a temperature of 250-400°C by passing said waste stream through a heat exchanger, such heating carried out as a heat soak being excluded, d) passing said heated mixed waste stream of step c under a pressure of 30-80 bar with a LHSV of 0,5-2,5 h⁻¹ over a column filled with adsorbent in order to guard a subsequent hydrogenating catalyst, e) passing said waste stream of step d over said hydrogenating catalyst at a temperature of 250-400°C and a pressure of 30-80 bar and with a LHSV of 0,5-2,5 h⁻¹, f) cooling the effluent of said hydrogenolysis of step e and separating it into a cleaned liquid hydrocarbon stream, a hydrogen halogenide, ammonia and/or hydrogen sulfide containing stream and a gaseous stream of light hydrocarbons and hydrogen. A process according to claim 1, characterized by the vacuum distillation taking place in two wiped film evaporators in series, in which the bottom product of the first film evaporator forms the feed of the second one. A process according to one of the proceeding claims, characterized by granular alumina being the absorbent in the guard bed. A process according to the proceeding claims characterized by a hydrogenating catalyst based on metals of the iron group plus molybdenum, tungsten or rhenium being applied. A process according to claim 4, characterized by, a catalyst comprising nickel or cobalt plus molybdenum supported on an inert carrier. A process according to claim 5, characterized by, conditioning of the catalyst preceding the hydrogenation with a sulfur compound till the sulfided stage is reached. A process according to one of the proceeding claims, characterized by, recycling at least part of the gaseous stream separated from the effluent leaving the column filled with hydrogenating catalyst. A process according to claims 1 -6,characterized by the application of 2 columns with catalyst and by separation of the by-products formed in the first column with catalyst, before passing the mixture of hydrocarbons and hydrogen through the second column with catalyst.

Inventors: LAGHATE, ASHOK SHANKAR, VISSER, LEENDERT
Applicants: KINETICS TECHNOLOGY INTERNATIONAL B.V.
Application year: 1985
Main classification: C10G67
IPC codes: A62D3, A62D101, C10M175, C10G67