PROCESS FOR CONTROLLING THE SODIUM AND SULFUR BALANCE IN A PULP MILL

Abstract

The present invention relates to a process for the controlling the sodium and sulfur levels in a pulp mill, comprising the steps of: a) providing a pulp mill stream comprising sulfide and having a total alkali concentration of at least 2 Molar; b) supplying a portion of the pulp mill stream to a reactor comprising sulfide oxidizing bacteria and removing sulfide from the pulp mill stream by subjecting said stream to sulfide oxidizing bacteria in the presence of oxygen, and at a pH in the range 8 to 11, to oxidize the sulfide to elemental sulfur, c) withdrawing from the reactor a treated pulp mill stream comprising sulfur, wherein the portion of the pulp mill stream is mixed with a portion of the sulfide oxidizing bacteria present in the reactor prior to supplying the pulp mill stream to the reactor in step b).

Claims

1. A process for the controlling the sodium and sulfur levels in a pulp mill, comprising: (a) providing a pulp mill stream comprising sulfide and having a total alkali concentration of at least 2 Molar, (b) supplying a portion of the pulp mill stream to a reactor comprising sulfide oxidizing bacteria, and subjecting the stream to sulfide oxidizing bacteria in the presence of oxygen, and at a pH in the range 8 to 11, to oxidize the sulfide to elemental sulfur, thereby removing sulfide from the pulp mill stream, (c) withdrawing from the reactor a treated pulp mill stream comprising the elemental sulfur, (d) separating the elemental sulfur from the treated pulp mill stream to provide a desulfurized pulp mill stream, wherein the portion of the pulp mill stream is mixed with a portion of the sulfide oxidizing bacteria present in the bioreactor prior to supplying the pulp mill stream to the reactor in (b).

2. The process according to claim 1, wherein the desulfurized pulp mill stream is reused in a process at the pulp mill.

3. The process according to claim 1, wherein at least a portion of the separated elemental sulfur is reused in a process at the pulp mill.

4. The process according to claim 1, wherein the pulp mill stream has a conductivity of at least 70 mS/cm.

5. The process according to claim 1, wherein the total alkali concentration is between 2 to 6 Molar.

6. The process according to claim 5, wherein the total alkali concentration is between 3 to 5 Molar.

7. The process according to claim 6, wherein the total alkali concentration is between 2.5 to 4.5 Molar.

8. The process according to claim 1, wherein pulp mill stream comprises, in addition to sulphide, other sulfur compounds selected from the group consisting of sulfate, sulfite, thiosulfate and mixtures thereof.

9. The process according to claim 1, wherein the pulp mill stream comprises at least 15 g/L sulfide.

10. The process according to claim 1, wherein pulp mill stream has a carbonate concentration of at least 50 g/L.

11. The process according to claim 10, wherein pulp mill stream has a carbonate concentration of at least 60 g/L.

12. The process according to claim 1, further comprising supplying a pH adjustment agent during (c) to maintain a pH in the range of 8 to 11 at 30° C.

13. The process according to claim 12, wherein the pH is maintained in the range of 9 to 10.5 at 30° C.

14. The process according to claim 13, wherein a pH is maintained in the range of 9.2 to 10.2 at 30° C.

15. The process according to claim 12, wherein the pH adjustment agent is an acid.

16. The process according to claim 15, wherein the pH adjustment agent is carbon dioxide gas.

17. The process according to claim 1, wherein the sulfide oxidizing bacteria belongs to the group of Thioalkalimicrobi and/or Thioalkalivibrio .

18. The process according to claim 1, wherein the amount of oxygen present in (c) is in the range of 0.5-1.25 mole of oxygen (O.sub.2) per mole of H.sub.2S/HS.

19. The process according to claim 1, wherein the pulp mill stream is a white liquor and/or green liquor.

20. The process according to claim 19, wherein the pulp mill stream is a green liquor.

21. The process according to claim 1, wherein the pulp mill stream is not diluted with water prior to contacting the sulfide oxidizing bacteria.

22. The process according to claim 1, wherein the process further comprises: (e) converting the elemental sulfur to sulfuric acid or using the elemental sulfur as feedstock to local production of SO.sub.2 gas.

23. The process according to claim 1, wherein the portion of the total stream that is treated in the bioreactor is in the range of 1 to 40% by weight of total available stream.

24. The process according to claim 23, wherein the portion of the total stream that is treated in the bioreactor is in the range of 3 to 30% by weight of total available stream.

25. The process according to claim 24, wherein the portion of the total stream that is treated in the bioreactor is in the range of 5 to 25%, by weight of total available stream.

Description

SHORT DESCRIPTION OF DRAWINGS

[0021] The present invention will be discussed in more detail below, with reference to the attached drawings:

[0022] FIG. 1 shows a process diagram according to the present invention.

[0023] FIG. 2 shows a graph of sodium concentration and conductivity in the bioreactor. The black circles are the conductivity in mS/cm (primary y axis (left)). The white circles are the sodium concentration in mol (secondary y axis (right)). The time course of the process is plotted in months (date-month label) on the x axis.

[0024] FIG. 3 shows a graph of sulfate and sulfate & sodium, alkalinity in the bioreactor. The white triangles are the sulphate concentration and the black circles are the thiosulphate concentration.(primary y axis (left)). The black diamonds are the alkalinity in mmol (secondary y axis (right)) and the white squares are the sodium concentration (secondary y axis (right)). The time course of the process is plotted in months (date-month) label on the x axis.

DESCRIPTION OF EMBODIMENTS

[0025] 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 and white liquor.

[0026] 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 (Na.sub.2CO.sub.3), sodium sulfide (Na.sub.2S) and sodium hydroxide (NaOH) as the main compounds. Typically, such a liquor has total alkali concentration of more than 2 M.

[0027] The term “white liquor” as used herein means a liquor comprising sodium sulfide and sodium hydroxide as the main components used as a delignification agent for wood chips in kraft pulping. Typically, such a liquor has total alkali concentration of more than 2 M.

[0028] “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.

[0029] The term “sulfur compounds” as used herein means compounds comprising sulfur, for example metal salts of sulfide, sulfide, sulfate, sulfite, thiosulfate, said metal being sodium or potassium.

[0030] 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.

[0031] 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 Na.sub.2O basis) by the weight of sodium hydroxide plus sodium sulfide (also expressed in g/l on Na.sub.2O basis) multiplied by 100.

[0032] The term “total alkali” as used herein means all Na.sup.+, and equivalents such as K.sup.+, containing compounds.

[0033] The term “carbonate” as used herein relates to carbonate in any form of carbonate, including carbonate anions, sodium hydrogen carbonate, sodium carbonate, Burkeite (Na.sub.6(SO.sub.4).sub.2(CO.sub.3)).

[0034] The stream supplied to the bioreactor is only a part of the total stream available in the pulp mill, i.e. only a part of the total stream is fed to the bioreactor. It has surprisingly been found that it is sufficient to only treat a first part of the stream from the pulp mill with the process according to the present invention. This is due to that the process is very efficient and it often is sufficient to only treat a first part of the total stream in order to achieve the desired balance of the sodium/sulfur ratio of the mill.

[0035] Preferably, the portion of the total stream that is treated in the bioreactor may be in the range of 1 to 40% by weight of the provided stream (i.e. by weight of the total available stream), preferably in the range of 3 to 30%, even more preferably 5 to 25%, by weight of the provided stream.

[0036] All streams from a pulp mill that comprises sulfide can be used in the process according to the invention. Preferably, the pulp mill stream is a stream from a Kraft pulp mill, such as green or white liquor. It has been found especially suitable to treat part of a green liquor stream with the bacteria according to the invention. Green liquor comprises large amounts of sulfide and despite the high salt concentration of the green liquor, it has been found that such a feed can be used without adding large volumes of aqueous diluents.

[0037] The pulp mill 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 the green liquor caustic strength.

2HS.sup.−+2 O.sub.2−.fwdarw.S.sub.2O.sub.3.sup.2−+H.sub.2O   Equation 1

[0038] 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.sub.2].sup.0.6   Equation 2

[0039] with the concentrations in mol/l and k equals 1 (L.sup.0.6/mol.sup.0.6/s)

[0040] 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:

S.sub.x+2.sup.2−+1.5 O.sub.2.fwdarw.S.sub.2O.sub.3.sup.2−+S.sub.x   Equation 3

[0041] The inventors have found that when a portion of the sulfide oxidizing bacteria is removed from the bioreactor and mixed with the pulp mill stream prior to supplying the pulp mill stream to the bioreactor in step b), the production of thiosulphate is reduced and the production of elemental sulfur is increased.

[0042] The pulp mill stream may comprise, in addition to sulfide, other sulfur compounds.

[0043] 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 SO.sub.4/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.

[0044] 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 pulp mill 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 pulp mill stream comprises at least 15 g/L sulfide, preferably at least 20 g/L sulfide even more preferably at least 25 g/L sulfide.

[0045] Preferably, the present invention comprises step d) of separating the elemental sulfur from the treated pulp mill stream to provide a desulfurized pulp mill stream, wherein said desulfurized pulp mill stream is preferably reused in a process at the pulp mill, and preferably wherein at least a portion of the separated elemental sulfur is reused in a process at the pulp mill.

[0046] In a preferred embodiment, the desulfurized pulp mill stream, that is the treated pulp mill stream from which sulphide and sulfur have been removed, is supplied to the pulp mill to be used in a process at the pulp mill. In other words, the treated stream leaves the bioreactor and is fed to a suitable solid/liquid separator where the elemental sulfur is separated and a sulfide depleted stream is removed, which sulfide depleted stream is optionally fed back into a process in the pulp mill.

[0047] The pulp mill stream preferably comprises carbonate. Preferably, the pulp mill stream has a carbonate concentration in the range of at least 50 g/L, preferably at least 60 g/L.

[0048] The pulp mill 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 streams having a high conductivity can be tolerated in the bioreactor.

[0049] Preferably, the pulp mill stream has a total alkali concentration in the range of 2 to 6 Molar, preferably 3 to 5 Molar, more preferably 2.5 to 4.5 Molar.

[0050] 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.

[0051] The chemical reaction carried out by the bacteria is shown below.

HS−+½ O.sub.2.fwdarw.S+OH.sup.−  Equation 4

HS−+2 O.sub.2.fwdarw.SO.sub.4.sup.2−+H.sup.+  Equation 5

[0052] It is apparent from this reaction scheme that the bacteria produce hydroxide ions, and consequently the pH will increase over time. Therefore, it is preferable to add a pH adjustment agent to the bioreactor.

[0053] Preferably, 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.

[0054] The pH may be controlled by any suitable pH controlling or reducing agent, e.g. 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 pH may not be too low since problems with scaling will occur.

[0055] The conversion of sulfide to element sulfur takes place in the presence of oxygen. Preferably, the amount of oxygen present in step c) in the range of 0.5-1.25 mole of oxygen (O.sub.2) per mole of H.sub.2S/HS.sup.−. Preferably, the oxygen supplied to the reactor 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.

[0056] The molecular-oxygen containing gas is preferably supplied to the reactor 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.

[0057] The sulfide-oxidising reaction in the reactor is preferably carried out at a temperature in the range of from 20 to 45° C.

[0058] The skilled person understands that the portion of sulfide oxidizing bacteria that is mixed with the portion of pulp mill stream prior to supplying the pulp mill stream to the reactor in step b), is provided as part of a solution/slurry of the reactor contents.

[0059] In another preferred embodiment, the process further comprises: step e) converting the elemental sulfur to sulfuric acid. The removed elemental sulfur that is separated from the stream during the process may be reused in any suitable process in the pulp mill, e.g. to production of sulfuric acid to be either sold or reused at the mill. It may also be externally sold as such, used as feedstock for local production of SO.sub.2 gas, used to produce polysulfide cooking liquor, utilized in certain processes for the production of chloride dioxide (ClO.sub.2) and/or used to enhance the quality (concentration) of bisulfite produced at the mill. Due to its hydrophilic nature and very fine and porous particle structure it can also be used in several commercial applications such is as fertilizer, rubber vulcanizing agents and as pesticide production, where elemental sulfur is used today.

[0060] 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 nutrients as is known to the skilled person.

[0061] 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.

[0062] FIG. 1 shows an installation for carrying a process according to the present invention. A pulp mill stream comprising sulfide generated by pulp mill 1 is provided via supply line 2 to bioreactor 3. A portion of the bioreactor contents 4 is supplied via supply line 5 to blend with the stream prior to the stream being supplied to the bioreactor 3. Line 6 feeds gas (air, oxygen) to the bioreactor and line 7 feeds a pH adjustment agent 7 to the bioreactor. The spent air is removed via 8. In the bioreactor sulfide is oxidized to elemental sulfur by autotrophic sulfide-oxidizing bacteria. The treated stream leaves the bioreactor by line 9 and may optionally be stored in a storage tank 10 before being fed to via line 11 to separator 12. The separated elemental sulfur slurry is removed via line 13 and the sulfide depleted stream is removed via line 14 and optionally fed back into a process in the pulp mill. The separated elemental sulfur slurry is supplied via line 13 to a processing unit 15, for example to be dried. The elemental sulfur is then fed via line 16 back into a process in pulp mill 1, or removed via line 17.

[0063] The calculated sodium concentrated is shown in FIG. 2 (sodium equals 2×[sulphate+thiosulphate]+alkalinity). All concentrations follow the same pattern of increasing and decreasing pattern. In FIG. 3 the concentration of both sulfate and thiosulfate concentration are shown, as well as the measured alkalinity. Sulphate was measured with Hach-Lange (LCK153), sulphide with Hach-Lange (LCK653) and thiosulphate as COD with Hach-Lange (LCK154).

EXAMPLES

[0064] Measurement Methods

[0065] The alkalinity of the pulp mill 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 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 at room temperature. The volume of titrated hydrochloric acid solution (=Z) was noted and the alkalinity determined by equation 3:

[00001]$\begin{array}{cc}\mathrm{Alkalinity}=0.1\times \frac{Z}{V}& \left(3\right)\end{array}$

[0066] Key: Alkalinity Alkalinity of the sample (mol/l) [0067] Z Titrated volume of 0.1 M hydrochloric acid (ml) [0068] V Sample volume (ml)

[0069] Oxidation-reduction potential in the bioreactor was monitored using an ORP-sensor (Endress+Hauser)

[0070] Anions: SO.sub.3, SO.sub.4, S.sub.2O.sub.5 were measured by ionic chromatography using standard methods. Cation concentrations were measured ICP-OES analysis. Samples were prepared using standard methods by wet digestion, lithium-carbonate melt, and hydrochloric acid dissolution.

[0071] Sulfide (HS.sup.−) was measured by titration according to standard method SCAN-N 5:83, Scandinavian Pulp, Paper and Board Testing Committee, Revised 1983.

[0072] Carbonate (CO.sub.3) was measured according to standard method SCAN-N 32:1998, Scandinavian Pulp, Paper and Board Testing Committee, Revised 1998.

Example 1

[0073] A continuously fed system consisting of one bioreactor series was used. The system was operated under sulfide oxidizing conditions (pH 9.5; Na.sup.+>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)

[0074] 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

[0075] 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 NaHCO.sub.3 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.

[0076] The complete composition of the influent and effluent is shown in Table 1.

TABLE-US-00001 TABLE 1 Influent pulp mill stream-green liquor Effluent 1 Effluent 2.sup.1 Cations in mg/l Sodium 85497 99579 98579 Potassium 10754 12491 13045 Calcium 26 9.9 5.9 Magnesium 4.2 7.2 12 Aluminium 3.8 1.9 1.7 Copper 0.042 0.031 0.045 Iron 1.3 1 0.92 Manganese 4.2 12 7.2 Zinc 0.29 0.17 0.13 Anions in mg/l Sulphate 5500 17000 20000 Sulphite 2500 n.d. n.d. Thiosulphate 5200 23000 24000 Carbonate 65000 120000 110000 Sulfide.sup.2 19943 Biologically produced 1:1 1:1 sulfur compounds (elemental sulfur): thiosulphate .sup.1Effluent 2 was taken 7 days after effluent 1

Example 2

[0077]

TABLE-US-00002 TABLE 2 Savings in caustic consumption.sup.3 2-A: without premixing.sup.2 Negligible < 0.6 kg NaOH/kg S removed 2-1 with premixing.sup.2 2.6 kg NaOH/kg S removed .sup.2Influent pulp mill stream-green liquor .sup.3Isolated from the effluent

[0078] Example 2-1 shows that premixing the pulp mill stream with bioreactor contents increases sulphur production and regeneration of caustic (NaOH) compared to example 2-A (comparative) when no premixing takes place.