WATER PURIFICATION PROCESS

Abstract: A process for the purification of acid aqueous effluents contaminated with organic materials thereby a) bringing the aqueous effluent in contact with an iron-containing material in the form of pieces or a powder, wherein the iron at least partially is present in a metallic state; b) subjecting said material to mechanic processing in contact with the aqueous effluent while dissolving at least part of the metallic iron; c) increasing the pH of the aqueous effluent after said mechanical processing to an essentially neutral pH; d) causing precipitation of three-valent iron under oxidizing conditions; and e) separating the precipitate from d) the aqueous phase.

Description: Water purification process. The present invention relates to a process for the purification of sewage water which is contaminated with orga- nic materials and which has a pH lower than neutral. The in¬ vention is particularly directed to the purification of in¬ dustrial effluents from pulp bleaching, particularly chlo- rine/chlorinedioxide bleaching of chemical pulp. Industrial effluents of this type are presently puri- fied only insu iciently, whereby the recipients used are subjected to large loads with concomitant ecologic problems. To the extent that the requirements on the environment have been increased the need for effective purification processes therefore arise, and such processes must also be acceptable from an economic point of view. Presently satisfactory puri¬ fication processes for industrial effluents are needed, par¬ ticularly for effluents originating from the bleaching of chemical pulp. The present invention has for its object to provide a simple and effective process for the purification of such industrial water effluents. Another object is to provide a process which is acceptable from an economic point of view but also results in highly effective purification so as to reduce the load on the recipient to a minimum. For these and other objects which will be clear from the following description the present invention provides a purification process for acid aqueous effluents, said process comprising the steps of : a) bringing the aqueous effluent in contact with an iron- -containing material in the form of pieces or a powder, wherein the iron at least partially is present in a metallic state; b) subjecting said material to abrasive mechanic proces¬ sing in contact with the aqueous effluent while dissolving at least part of the metallic iron; c) increasing the pH of the aqueous effluent after said mechanical processing to an essentially neutral pH; d) causing precipitation of three-valent iron under oxi¬ dizing conditions; and e) separating the precipitate from d) from the aqueous phase . It is preferred in the above-defined step a) to intro¬ duce also magnetite in the form of pieces or a powder, where¬ by better mechanical processing and better precipitation will be obtained. The pH-adjustment carried out in step c) above is suitably performed in two stages with a first addition of limestone, i.e. unburnt lime, in the form of pieces or a pow¬ der with mechanical treatment, and then in a second stage the pH will be further increased by adding a strong base. The strong base can be constituted by sodium hydroxide, potassium hydroxide or another suitable base. In this neutralization in two stages the pH-ad ustment in the first stage is suitably to a pH of from about 5.5 to about 6.5, such as about 6.0, and in stage two the pH is further increased to an interval lying within the range about 7 to about 8, for example about 7.5. Before precipitating three-valent iron under oxidizing conditions according to step d) above it is preferred to per¬ form magnetic precipitation of excess of metallic iron and, optionally excess of magnetite, and this excess is suitably returned to step a) of the process. The oxidizing conditions in step d) can be provided by a suitable oxidant , and it is preferred to use air, optional¬ ly enriched in oxygen, or hydrogenperoxide . The abrasive mechanical processing of solid materials in contact with the aqueous effluent that shall be purified is suitably carried out in some sort of grinding mill. It is particularly preferred to use a ballmill operating with iron or steel balls as grinding bodies. During the abrasive mecha¬ nical processing that is carried out in such mill the grin- ding bodies contribute with iron ions in that the acid efflu¬ ent dissolves iron from the grinding bodies in connection with the processing. Generally, the aqueous effluent in which the abrasive mechanical processing takes place has a pH of less than about 3. The invention will in the following be further descri¬ bed by non-limiting embodiments in conjunction with the ap- pended drawing which shows a diagrammatic sketch in the form of a flow sheet on a preferred industrial process for the purification of an aqueous effluent from bleaching of chemi¬ cal pulp. The effluent referred to in the following specific examples originates from the bleaching of pine sulphate pulp having a kappa number of about 30, said pulp being bleached according to the sequence oxygen gas<0>-<chlorine+chlorinedi- o ide)-(C35+Di5>-alkali extrac io CE^)-chlorinedioxide(Dι>- -alkali extractions(E2>-chlorinedioxide(D2> . Thus, the se- quence is O-CCQS+DIS>-E1-D1-E2-D2. The acid effluents from the steps are admixed as well as the effluents of the alkaline steps. These two effluents are thus mixed at the cite of release. The flows from the acid of the alkaline steps are 20m^ per ton pulp and 5 ^ per ton pulp, respectively. The mixed bleach effluent has a pH of 2.1-2.2. The purification procedure according to the inven¬ tion starts from such acid water effluent. Description of the flow sheet of the drawing The apparatus used comprises cylindric ball mills 1,3 made of iron and having the dimensions length 30 cm, inner diameter 20 cm, corresponding to a volume of 9.4 1. The ball mill 1 is operated at a rotational speed of 67 revolutions per minute, whereas the identical ball mill 3 is operated at a rotational speed of 77 revolutions per minute. Device 2 is constituted by a magnet separator, wherein excess iron and magnetite are separated and recirculated to the process. Limestone in the form of pieces are added to a ball mill 3. In a mixing vessel 4 strong base or alkali is supplied, for example sodium hydroxide for increasing the pH before ente¬ ring flotation cells 5, where oxidation of the iron from Fe^ + to Fe 3+ takes place by the supply of air, which results in precipitation of iron hydroxide while co-precipitation of the organic material takes place in the effluent. The precipitate formed is separated in lamellae thickeners 6 and filtration takes place in suitable filters 7 that may be constituted by press filters, band filters or drum filters. The solid mate¬ rial precipitated and separated may either be deposited or may be destructed in a special destruction furnace 8. Alter¬ natively the separated solid materials are supplied to a blast furnace for complete destruction while utilizing the iron present therein. Between devices 5 and 6 there may be added a mixing vessel for the supply of precipitating and flocculating agents. Chemicals used In ball mills 1,3 the iron balls contained therein have a size of about 3 g per ball. As magnetite there is used finely ground magnetite powder, and the limestone is consti¬ tuted by dolomite in the form of pieces . As a strong base there is used sodium hydroxide, 1-molar (Labasco puru ) . The coagulation agent is CDM 1597 50% and the flocculation agent © is constituted by CDM 333, 0.5%, Magnafloc, non-ionic. The present invention is based on the principle that acid effluents dissolve iron in the mechanical processing in the mill and this dissolution takes place under the formation of hydrogen gas and increase of pH. The dissolved iron forms complexes with organic substances found in the effluent, and the excess of dissolved iron in two-valent form is precipita¬ ted by the adjustment of pH using limestone and alkali to form iron< 11)hydroxide. By neutralization to a pH of about 7.5 and oxidation with air two-valent iron is converted to three-valent iron which precipitates as FeO(OH) . The precipi¬ tation process is facilitated by the addition of coagulation agent and flocculation agent and compact and large flocks are formed which are rapidly deposited on the bottom of the ves- sel used. Flocks can be effectively separated in thickeners and de-watered in a suitable device, for example a band fil¬ ter, and can then be destructed for example in a blast fur- nace, suitably after briquetting or pelleting of the precipi¬ tated material. By using the techniques of the present inven¬ tion there will be obtained a purification degree with regard to the water effluent of about 85% based on organic bound chlorine and about 65% based on COD (Chemical Oxygen Demand) . Remaining dissolved iron in the water is only about 1 mg per liter. Aromatic chloro compounds, such as polychlorinated phenols, cannot be detected at all in the purified effluent. EXAMPLE 1 2 1 of bleaching effluent having a pH of about 2.15 are added to mill 1 containing 15.3 kg iron balls. Then 16 g of magnetite are added. The mill is rotated for 15 sec., the pH increasing to about 3.8. The treated effluent is transfer- red to mill 3 containing 4.3 kg of limestone. This mill is rotated for 3 i . , pH increasing to about 5.85. 1 1 of water is withdrawn from mill 3 and transferred to mixer 4, wherein the pH is adjusted to about 7.5 using NaOH (15 ml). The water is then oxidized with air for 3 min. and transferred to a 2 1 beaker. In this beaker there is added 1 drop (0.05 ml) of coa¬ gulation agent with cautious stirring. This results in the formation of a course grained precipitate. Then there is ad- ® ded 1 drop (0.05 ml) of non-ionic Magnafloc with somewhat more intense stirring. The precipitate is quite quickly for¬ med and sinks to the bottom within a few minutes. The clear water is analyzed, as is the precipitate. EXAMPLE 2 A l l measuring glass is filled with the effluent treated according to Example 1. Precipitation is carried out in the same manner as in Example 1 but the stirring used therein is replaced with a procedure consisting in turning the measuring glass up-side-down repeatedly. After 15 min. the precipitate has deposited in the lower part of the measu¬ ring glass and takes a volume of about 50 ml (5%) . The water above the precipitate is clear. Below the principles of analysis carried out are briefly presented. Chloroorαanic substance Analysis using the AOX-method according to SCAN-W 9:89. The water is filtrated and activated carbon is added, stirring takes place and the water is filtered off. The car¬ bon is burnt in a quartz furnace and the HCl-gas formed is determined by coulometric titration. COD (Chemical Oxygen Demand) This is a measure of the quantity of organic substance in the water. COD is determined colorimetrically by the addi¬ tion of bichromate sulphuric acid. Organic materials are oxi- dized to carbondioxide and water. The reaction Co^ + ->Co 3+ is determined. Chlorophenols These are determined by gas chromatography. Iron Dissolved iron is determined using AAS atom absorption spektrophotometri. Chloride The quantity of chloride is determined using iron chromatography. Chlorate This is determined using ion chromatography. Results The appended Table 1 shows the results of analysis made on treated and untreated samples of water effluents and the degree of purification in percent. The values are consti¬ tuted by averages of three determinations . The reproducabi- lity of the precipitation tests is very good. The process according to the invention has been repeated tenths of times without noticable disturbances. The precipitate has a dry solids content of 3-5 g per liter depending on the quantity of magnetite that has been entrained in the water. TABLE 1 Results of analysis on untreated and treated samples and deg¬ ree of purification in percent. |Sample! AOX COD Chlorophenols Fe3 + Cl~ C10 3 I 1 |Un- | |trea- 110 606 0,15 - 107 123 | Ited |Trea- 17 215 _ *) 1 105 120 | I ed |Reduc- [ 85 65 >99 - 0 o 1 Ition % *' not detected

Claims: CLAIMS 1. A process for the purification of acid aqueous eff¬ luents contaminated with organic materials, characterized by the steps of: a) bringing the aqueous effluent in contact with an iron- -containing material in the form of pieces or a powder, wherein the iron at least partially is present in a metallic state; b) subjecting said material to abrasive mechanical pro- cessing in contact with the aqueous effluent while dissolving at least part of the metallic iron; c) increasing the pH of the aqueous effluent after said mechanical processing to an essentially neutral pH; d) causing precipitation of three-valent iron under oxi- dizing conditions; and e) separating the precipitate from d) from the aqueous phase. 2. A process according to claim 1, characerized by adding also magnetite in said form in step a) . 3. A process according to claim 1 or 2, characterized in that the pH-ad ustment in step c) is carried out in two stages by first adding limestone (CaC03> while performing mechanical processing and then adding a strong base. 4. A process according to claim 3, characterized in that the pH-adjust ent in the first stage is carried to a pH of from about 5.5 to about 6.5 and in stage two to a pH of about 7 to about 8. 5. A process according to claim 3 or 4, characterized in that the limestone is added in the form of pieces. 6. A process according to any preceding claim, charac¬ terized by performing magnetic precipitation of excess Fe+Fβ3θ4 before step d) , said excess being suitably recir¬ culated into the process. 7. A process according to any preceding claim, charac- terized by providing the oxidizing conditions of step d) by the supply of air or by adding H2O2. 8. A process according to any preceding claim, charac¬ terized in that the abrasive mechanical processing is carried out in a mill. 9. A process according to claim 8, characterized in that the mill is constituted by a ball mill operating with iron or steel balls as grinding bodies. 10. A process according to any preceding claim, cha¬ racterized in that the contaminated aqueous effluent origina¬ tes from the bleaching of chemical pulp. 11. A process according to claim 10, characterized in that the aqueous effluent originates from chlorine or chlo- rinedioxide bleaching of chemical pulp. 12. A process according to any preceding claim, cha¬ racterized by the further step of subjecting the precipitate resulting from step e) to destruction in a blast furnace.

Inventors: AXNAES ANDERS, AXNAES, ANDERS
Applicants: SOLVATOR PROCESS AB
Application year: 1990
Main classification: C02F1
IPC codes: C02F1, C02F9