Patent Application
20210130209
The present invention relates to a process for the biological treatment of industrial alkaline streams.
Many industrial processes result in alkaline streams that pose environmental processing challenges due to the mix of salts and contaminants, and if the alkaline stream is no longer needed there can be issues with safe disposal of such streams. An example of an industrial alkaline stream is spent caustic, which is an industrial caustic solution that has become exhausted and is no longer useful (i.e. spent).
Different spent caustics are known. Ethylene spent caustic comes from the caustic scrubbing of cracked gas from an ethylene cracker. This liquor is produced by a caustic scrubbing tower. Ethylene product gas is contaminated with H2S(g) and CO2(g), and those contaminants are removed by absorption in the caustic scrubbing tower to produce NaHS(aq) and Na2CO3(aq). The sodium hydroxide is consumed and the resulting wastewater (ethylene spent caustic) is contaminated with the sulfides and carbonates and a small fraction of organic compounds.
Refinery spent caustic comes from multiple sources: the Merox processing of gasoline; the Merox processing of kerosene/jet fuel; and the caustic scrubbing/Merox processing of LPG. In these streams sulfides and organic acids are removed from the product streams into the caustic phase. The sodium hydroxide is consumed and the resulting wastewaters (cresylic for gasoline; naphthenic for kerosene/jet fuel; sulfidic for LPG -spent caustics) are often mixed and called refinery spent caustic. This spent caustic is contaminated with sulfides, carbonates, and in many cases a high fraction of heavy organic acids.
Another industrial alkaline stream is pulp mill liquor from the paper making process. Alkaline streams at pulp mills include streams commonly referred to as white, black and green liquors. Green liquor is produced from dissolving a smelt from a Kraft recovery furnace. Green liquor normally comprises sodium carbonate (Na2CO3), sodium sulfide (Na2S) and sodium hydroxide (NaOH) as the main compounds. White liquor comprises sodium sulfide and sodium hydroxide as the main components, and is contaminated by carbonate. Black liquor comprises lignin derivatives as the main components and sodium sulfide, as well as carbonate.
Typically, industrial alkaline streams are contaminated by carbonate. The presence of carbonate in the industrial alkaline streams complicates the processing of industrial alkaline streams due to the occurrence of undesirable carbonate precipitation in reactors and supply lines.
Processes for the biological treatment of a spent caustic containing sulfides are known in the art and for example described in WO9804503. In the process described in WO9804503 a spent caustic solution is introduced into a single aerobic reactor containing sulfide-oxidizing bacteria, and the sulfides are partly converted to elemental sulfur and partly to sulfate by controlling the redox potential in the reactor at a value below -300 mV against an Ag/AgCl electrode. A disadvantage of the described process is that a very large reactor is needed in order to convert the spent caustic to levels low enough to meet modern regulatory requirements for discharge into the environment.
WO2005044742 discloses relates to the treatment of sulfur-containing salts using biological oxidation with the possibility of recovering dissolved salts. The sole example discloses a process in which an aqueous solution is treated, which contained about 75 g/l of sodium (3 M) and 45 g/l of dissolved sulfide. The solution was fed together with a nutrient solution containing among other a nitrogen and a phosphorous source to a continuously operating 5 liter bioreactor at a temperature of 30° C. containing Thio(alkali)vibrio strains comprising strain DSM 13738. A gas recycle over the bioreactor ensured mixing. Oxygen was added to the gas recycle in order to maintain the redox potential in solution to a value between-100 and-450 mV, preferably-360 to-430 mV measured with a platinum electrode against an Ag/AgCl reference electrode. The pH was measured with a glass electrode. It was controlled at a value between 9 and 12, in particular at about 10.5 through the injection of CO2 gas in the gas recycle. Thio(alkali)vibrio bacteria converted the dissolved sulfide to elemental sulfur. Effluent from the bioreactor was led through a settler where the sulfur was separated from the liquid.
WO2009101090A1 provides a method and apparatus for biologically treating a spent caustic to provide a treated spent caustic, said method comprising the steps of: (a) passing a spent caustic stream (25) comprising water, alkali metal hydroxide and sulfide to a first bioreactor (30); (b) biologically oxidizing sulfide in the first bioreactor (30) with sulfide-oxidizing bacteria to form sulfur (S0) and sulfate to provide a partially oxidized spent caustic comprising sulfur (S0) and sulfate; (c) passing the partially oxidized spent caustic to a second bioractor (40) where at least a portion of the partially oxidized spent caustic is further oxidized with sulfide-oxidizing bacteria to generate sulfate from sulfur (S0) to provide a treated spent caustic comprising sulfate.
There remains a need for an improved method for treating industrial alkaline streams comprising sulfide and carbonate.
The present invention seeks to provide an improved method for treating industrial alkaline streams comprising sulfide and carbonate, comprising the steps of:
According to the present invention, a process as defined above is provided, in which sulfur (present for example as sulfide) is removed from an industrial alkaline stream comprising sulphide and carbonate in the form of elemental sulfur by contacting the waste stream with sulfide oxidizing bacteria. This results in a treated waste stream that is less prone to undesirable carbonate precipitation, for example pirssonite precipitation, and consequently less blocking of supply lines results.
Without wishing to be bound by theory, it is believed that by removing the sulfur from the industrial alkaline stream, by oxidizing the sulfide to elemental sulfur, the sulfidity of the alkaline waste water decreases resulting in an increase in solubility of carbonate salts, such as pirssonite.
It has been found that it is possible to efficiently and specifically reduce the amount of undesirable carbonate precipitation in industrial alkaline streams by reducing the sulfidity of the industrial alkaline stream.
A further advantage of the present invention is that by mixing the industrial alkaline stream with a portion of the sulfide oxidizing bacteria prior to supplying the industrial alkaline stream to the bioreactor, conditions are maintained in the bioreactor that stimulate the sulfide oxidizing bacteria. The process of the present invention does not require costly, energetically inefficient dilution of the high salt concentration of industrial alkaline streams. For example, the process according to the invention can be used for regenerating NaHS containing caustic liquids back to NaOH e.g in various scrubbing processes where H2S scrubbing is done by using NaOH as agent, therefore this invention can be used as a replacement for NaOH capturing processes from waste streams.
The present invention will be discussed in more detail below, with reference to the attached drawings:
The term “industrial alkaline stream” as used herein means a melt, liquid or aqueous process fluid having a pH>8.
The term “spent caustic” as used herein in means an aqueous NaHS solution. Typically, such a solution is obtained from the reaction of sodium hydroxide and hydrogen sulphide in the refinery and chemical industries. Typically, spent caustics have a pH of more than 12 and a sulphide concentration exceeding 2 wt. %.
The term “pulp mill stream” as used herein means a melt, liquid or aqueous process fluid originating from a pulp mill, for example green liquor, white liquor and black liquor.
The term “green liquor” as used herein means the liquor produced from dissolving a smelt from a Kraft recovery furnace. Green liquor normally comprises sodium carbonate (Na2CO3), sodium sulfide (Na2S) and sodium hydroxide (NaOH) as the main compounds. Typically, such a liquor has total alkali concentration of more than 2 M.
The term “white liquor” as used herein means a liquor comprising sodium sulfide and sodium hydroxide as the main components. Typically, such a liquor has total alkali concentration of more than 2 M
“Chemical oxygen Demand” (COD) refers to organic material that can be oxidised to smaller molecules, ultimately to carbon dioxide and water, and the term expresses the amount of oxygen that would be needed to oxidise the organic material in a litre of wastewater.
The term “black liquor” as used herein means a liquor comprising lignin degradation products and other dissolved wood components as the main components and sodium sulfide originating from a pulping process. Typically, such a liquor has total sodium concentration of more than 15% on dry solids content. and preferably a total alkali concentration of more than 1M.
The term “sulfur compounds” as used herein means compounds comprising sulfur, for example metal salts of sulfide, sulfide, sulfate, sulphite, thiosulfate, said metal being sodium or potassium.
The term “sulfide” as used herein relates to sulfide is to any form of sulfide, including sulfide anions, mono-hydrogen sulfide ions, hydrogen sulfide, polysulfide, and organic sulfides such as lower alkyl mercaptans and carbon disulfide.
The term “sulfidity” as used herein means the sodium sulfide/sodium hydroxide ratio. Sulfidity is calculated by dividing the weight of sodium sulfide (expressed in g/l on Na2O basis) by the weight of sodium hydroxide plus sodium sulfide (also expressed in g/l on Na2O basis) multiplied by 100.
The term “total alkali” as used herein means all Na+, and equivalents such as K+, containing compounds.
The term “carbonate” as used herein relates to carbonate in any form of carbonate, including carbonate anions, sodium hydrogen carbonate, sodium carbonate, Burkeite (Na6(SO4)2(CO3)) and pirssonite (Na2CO3.CaCO3.2H2O).
The present invention is not limited to any particular industrial alkaline stream. It has been found that industrial alkaline streams comprising significant amounts of sulfide and carbonate can subjected to sulphide oxidizing bacteria without dilution. In addition, a treated industrial alkaline stream is provided that is less prone to carbonate precipitation.
Preferably, the industrial alkaline stream is an ethylene spent caustic, refinery spent caustic or pulp mill stream. In a preferred embodiment, the industrial alkaline stream is a waste stream from a Kraft pulp mill, such as green, white liquor or black liquor.
The industrial alkaline stream typically contains a high concentration of sulphide, for example above 10 g/l. In case the autotrophic sulphide oxidizing bacteria are directly exposed to this, their aerobic activity has to compete with the abiotic (non-biological oxidation) reaction producing thiosulphate as shown in Equation 1. The thiosulphate production does not regenerate caustic strength.
2HS−+2 O2−→S2O32−+H2O Equation 1
Without wishing to be bound by theory, thiosulphate production depends on both the (poly)sulphide concentration as well as the oxygen concentration. The reaction rate can be described with
dHS/dt=−k [Sx][O
2]0.6 Equation 2
with the concentrations in mol/l and k equals 1 (L0.6/mol0.6/s)
Due to the presence of sulphur in the solution, polysulphides are largely present in the bioreactor. The pH of the bioreactor is preferably in the range of 8 to 11 at 30° C., and the polysulphide dissociation constant is ˜9. Hence almost all sulphide is present as polysulphide, as summarized in Equation 3:
Sx+22−+1.5 O2→S2O32−+Sx Equation 3
The inventors have found that when a portion of the sulfide oxidizing bacteria is removed from the bioreactor and mixed with the industrial alkaline stream prior to supplying the industrial alkaline stream to the bioreactor in step b), the production of thiosulphate is reduced and the production of elemental sulfur is increased.
The alkaline waste steam may comprise, in addition to sulfide, other sulfur compounds. Sulfur compounds that may be present include any sulfur species, such as sulfate, sulfite, sulfide, thiosulfate, etc. Levels of sulfur compounds may vary widely e.g. between 0.05 and 50 g of the sulfur compounds (on elemental sulfur basis) per L, in particular between 0.1 and 40 g sulfur per L. On sulfate basis, the weight amounts are three times the amount on elemental sulfur basis because of the molar weight ratio SO4/S° of 96/32. Thus at least 0.05 g (50 mg) of sulfur compounds per L on elemental sulfur basis corresponds to at least 150 mg of sulfate per L. The present invention has the advantage that the process does not require diluting of the total amount of sulfur compounds prior to mixing with the sulfide oxidizing bacteria.
The sulfide concentration in the aqueous solution to be treated is not critical in the process according to the invention. Feed streams with sulfide concentrations (expressed as by weight of sulfur) as high as 30 grams per litre or even higher may be used. Preferably, the sulfide concentration in the industrial alkaline stream is in the range of from 10 mg/L to 100 g/L, more preferably of from 20 mg/L to 80 g/L, even more preferably of from 0.1 g/L to 60 g/L, still more preferably of from 0.5 g/L to 30 g/L. For example, in a preferred embodiment, the industrial alkaline stream comprises at least 15 g/L sulfide, preferably at least 20 g/L sulfide even more preferably at least 25 g/L sulfide.
The industrial alkaline stream comprises carbonate. Preferably, the industrial alkaline stream has a carbonate concentration in the range of at least 50 g/L, preferably at least 60 g/L.
The industrial alkaline stream preferably has a conductivity of at least 70 mS/cm, preferably at least 80 mS/cm, more preferably at least 90 mS/cm, most preferably at least 100 mS/cm. It has been found that the process of the present invention has the advantage that waste streams having a high conductivity can be tolerated in the bioreactor.
Preferably, the industrial alkaline stream has a sodium concentration in the range of 1 to 6 Molar, preferably 2 to 5 Molar, more preferably 2.5 to 4.5 Molar.
In the process according to the invention any suitable autotrophic sulfide-oxidising bacteria may be used. Suitable sulfide-oxidising bacteria are known in the art. The autotrophic sulfide oxidizing bacteria preferably belong to the group of Thioalkalimicrobium, and/or Thioalkalivibrio. Preferably autotrophic sulfide-oxidising bacteria of the genera Halothiobacillus, Thioalkalispira, Thioalkalibacter, Thiobacillus or Thiomicrospira and related bacteria are used. The bacteria may be used as such, or may be supported on a dispersed carrier or may be immobilised on a solid carrier.
The chemical reaction carried out by the bacteria is shown below.
HS−+1/2 O2->S+OH− Equation 3
HS−2 O2->SO42−+H+ Equation 4
It is apparent from this reaction scheme that the bacteria produce hydroxide ions, and consequently the pH will increase over time. Therefore, it a pH adjustment agent is added to the bioreactor.
A pH adjustment agent is supplied during step b) to maintain a pH in the range of 8 to 11 at 30° C., preferably in the range of 9 to 10.5 at 30° C., even more preferably in the range of 9.2 to 10.2 at 30° C., even more preferably 9.4 to 10.0 at 30° C.
The pH adjustment agent is preferably a gas, for example carbon dioxide or sour gas, or any other suitable acid, for example hydrochloric acid, nitric acid and phosphoric acid. Preferably, the pH adjustment agent is carbon dioxide.
The conversion of sulfide to element sulfur takes place in the presence of oxygen. Preferably, the amount of oxygen present in step c) in in the range of 0.5-1.25 mole of oxygen (O2) per mole of H2S/HS−. Preferably, the oxygen supplied to the bioreactor is provided by a molecular-oxygen comprising gas. Preferably, the molecular-oxygen comprising gas is air or oxygen-depleted air, i.e. air having less than 20% (by volume) of oxygen, e.g. between 2 and 15 vol. % of oxygen.
The molecular-oxygen containing gas is preferably supplied to the bioreactor in such amount that an optimum amount of oxygen reactant is present for the required oxidation reaction (sufficient for the oxidation to sulfur; not too much in order to avoid sulfate formation) and that sufficient mixing of feed stream with aqueous medium takes place in order to quickly dilute the inlet sulfide concentration.
The sulfide-oxidising reaction in the bioreactor is preferably carried out at a temperature in the range of from 20 to 45° C.
In another preferred embodiment, the process according to the present invention comprise step d) of separating elemental sulfur from the treated industrial alkaline stream to provide an sulfur depleted alkaline stream. The sulfur depleted alkaline stream can be further processed/recycled in an industrial process with a lower risk of carbonate precipitation due to the lower sulfidty, compared to the sulfidity of the industrial alkaline stream prior to treatment by the process described herein. Preferably, said sulfur depleted alkaline stream is reused in an industrial process.
Preferably, the sulfur depleted alkaline stream has a sulfidity of less than 20%, preferably less than 15%, even more preferably less than 10%.
The sulfide oxidizing bacteria require nutrients for their growth and maintenance. Therefore a balanced solution of the essential minerals is dosed to the bioreactor. The concentration of the bacteria is kept at the desired level by supplying the right amount of nutrients.
Preferably, the industrial alkaline stream is not diluted with aqueous diluents, such as water, prior to contacting the sulfide oxidizing bacteria.
The present invention has been described above with reference to a number of exemplary embodiments as shown in the drawings. Modifications and alternative implementations of some parts or elements are possible, and are included in the scope of protection as defined in the appended claims.
The calculated sodium concentrated is shown in
In
Measurement Methods
The alkalinity of the industrial alkaline stream is determined by bringing sample of said stream to pH 4.0 with hydrochloric acid. The amount of acid needed indicates the alkalinity (buffering capacity) of the liquid. A 100 mL sample of centrifuged or filtered waste stream was pipetted in to a glass beaker and 100 ml demineralized water was added. pH electrode was placed in the solution. The solution in the beaker was titrated with 0.1 M hydrochloric acid to pH 4.0, while the solution is continuously stirred. The volume of titrated hydrochloric acid solution (═Z) was noted and the alkalinity determined by equation 3:
Oxidation—reduction potential in the bioreactor was monitored using an ORP-sensor (Endress+Hauser).
Anions: SO3, SO4, S2O5 were measured according to SFS-EN ISO 10304-1.
Cation concentrations were measured by ICP analysis.
Sulfide (HS−) was measured by titration according to standard method SCAN-N 5:83,
Scandinavian Pulp, Paper and Board Testing Committee, Revised 1983.
Carbonate (CO3) was measured according to standard method SCAN-N 32:1998,
Scandinavian Pulp, Paper and Board Testing Committee, Revised 1998.
A bioreactor (5L) is fed with a sulfide rich stream (influent) from a holding tank under N2 atmosphere. Prior to supplying the sulfide rich stream to the bioreactor, the stream to the bioreactor it is mixed with a portion of the bioreactor contents.
A continuously fed system consisting of one bioreactor series was used. The system was operated under sulfide oxidizing conditions (pH 9.5; Na+>4 M) using autotrophic sulphide oxidising bacteria originating from soda lakes. The reactor have a maximum wet volume of 5 L (Ø=100 cm). The temperature was maintained at 30° C. by using a water-jacket and a thermostat bath (Shinko, Japan). The influent was fed to the bioreactor using peristaltic pumps (Watson-Marlow), and the effluent from the reactor was controlled by overflow. The sulfide rich stream (influent) was mixed with a portion of the contents of the bioreactor prior to addition to the bioreactor. The pH was monitored using a pH sensor (Endress+Hauser The Netherlands). The oxygen supply was done with air dosing controlled with an ORP-sensor (Endress+Hauser, the Netherlands)
The sulfide oxidizing bacteria present in the bioreactor is a species adapted to an increased salt concentration, but not adapted to the high salt concentration of the green liquor.
After a gradual build-up in about 6 weeks, the conductivity was maintained well above 100 mS/cm. Despite that some periods of precipitation of NaHCO3 the bacteria were still active, even at sodium concentration above 4.5M. This is advantageous, as the current full scale commercial desulfurization (e.g. Thiopaq process) plant will operate at a sodium concentration up to 1.5 M and a maximum operating pH of 9.
The calculated sodium concentrated is shown in
The composition of the influent and effluent is shown in Table 1.
1 Influent pulp mill stream—green liquor
2 Isolated from the effluent
Premixing the highly concentrated industrial alkaline stream (green liquor) needs to be done in order to produce sulphur and regenerate the caustic. In case no premixing is executed there are no savings in the caustic consumption of a pulp mill. When the described method is applied the savings are 2.6 kg NaOH/kg S removed. The reduction in total caustic consumption for a pulp mill will range between 10-40%.
| Number | Date | Country | Kind |
|---|---|---|---|
| 18184411.9 | Jul 2018 | EP | regional |
This application is a continuation of International Application No. PCT/EP2019/069138, filed Jul. 16, 2019, which claims the benefit of and priority to European Application No. 18184411.9, filed Jul. 19, 2018, both of which are hereby incorporated by reference herein in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP2019/069138 | Jul 2019 | US |
| Child | 17148472 | US |
