DE1658043A1 - Process for the purification of wastewater using the contaminants contained therein, in particular the proteins and similar organic substances - Google Patents

Description

1 BSßUii ä "j ίV \ .; UIM)

HüTTENWteö 15 69/12 729 DB. ItLfcrGN 76I5U5 ' *

November 10, 1967

Patent application

of the company

A / S Apothekernsa Laboratorium for Specialpraepatarc'jfe

Sköyen,

OSLOj Norway Procedure for cleaning Abwaeeer underneath

the impurities contained therein, in particular

of proteins and similar organic substances, ^

The present invention relates to a process of cleaning waste water using the contaminants it contains, in particular proteins and similar organic substances the content of slurried and .Tulgeiüstem material is quite low and includes proteins, and especially a

Cleaning and material utilization of organic materials in so-called glue water bucks _u d> h. Wass ?? where sr * licha, auflösüchar usually small amounts of proteins and similar Substansen ^ such polypeptides are dissolved in different ,, As If * games such stick water can ^ Hwater "from dairies MaUgsreien, Kartoffelmehifabrikeri, Fiechmehlfabriken _u canneries and factories and3iraru for in-possession «protein-containing foods and feed materials are cirwishat,

BATH ORIGINAL

The discharge of such wastewater to water courses, lakes _t ponds and other partially closed bodies of water, even small bodies of water in direct connection with the sea * see e.g. Fjords and Sunde, has a number of disadvantages. On the one hand are the recordings? directly contaminated, so that the water ils bath water ,; Drinking water u <«'. it even becomes unsuitable for many Izidustffieswscke. On the other hand, the sensors are indirectly contaminated because the wastewater, suction- *? with low concentrations of impurities, a significant growth of more or less harmful bacteria, υ D> Coli bacteria, cause the water to be directly harmful to health. Said indirect damage can also arise "in that the wastewater serves as a food substrate for a large number of microorganisms and other organisms" harmful and harmless "so that a huge pile" develops in the transducer, mainly of microorganisms, especially bacteria and green and blue-green algae ₍ . but possibly also of sponges and larger size green algae and crane needle algae, the microflora has a significant Saueratoffverbrauch "the aog. biological or biochemical ψ Oxygen consumption which can become large «the β sr sum damage

the usual flora and especially fauna can be found in the transducer, because too little sauce for the shop or desired * Crustacean is suggestive, and the whole thing becomes biological Equilibrium in the transducer due to high biological oxygen * wastewater consumption slightly disturbed «for a short or long period Sight can be very damaging * although the specific damage often occurs difficult or impossible to overlook, ledaniall can be a se high biological oxygen consumption in wastewater means that, for example, the fish population sugrunde g-sht.

BAD ORIGfNAL

ν. The organic substances contained in wastewater have in

(usually a certain value «if they are, for example, for lining materials

i. can be processed * and the use of this .Vertes

^(/ improves the profitability of the wastewater-supplying activity.

It is known to purify wastewater by biological treatment with suitable biological filters. In general a good reduction in biological oxygen consumption of the treated wastewater achieved »The process has the disadvantage« that biological filters have both high system costs and ™

They require operating costs and that the substances retained in the filter cannot or almost not be removed ₂ and possibly N _{2 are} converted, so that organically bound nitrogen is even returned to inorganic form.

It was officially proposed «waste water by filing out the like

proteins and similar substances contained therein. like polypeptides, clean with lignin sulfone & ure su. You can do that the biological oxygen consumption of the wastewater to a certain extent but not satisfactorily reduced, and the nitrogenous substances in the wastewater can be reduced to a certain extent as Sows the lining on the outside.

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909840/1373
BAD ORfGINAi.

Ferae r ^: .3t es ϊ-efennf ₀ fvcfceifsorte » in abwüsces ¹ fen να raw β with vinterschißdl ^ cheis mit -'- rucrorganisms« in particular G & rschw & mmen sand used ■ / related Sdwifiramer nu g & ven «but also because of this no two things can Herobeetaen Ue ε biologiach-sE. Pig? fabric raue before β ev »ile

A particularly difficult both for biological treatment of sewage proteinhaltigezn and in the utilization of sugar, "" locate in the wastewater at Gftvimg * as aRgegebem _e liagt fact that ,,

wl the meage of the N-haHeirbinduiigen versus the amount of

Carbohydrates in Liimvwsccr, alco in with different frequency " t "ceät occurring piroteinhaitigcn Abv / aseertyp, often far above the Optimal for the organisms in the biological filter, which cause the decomposition of the organic matter in the wastewater, or for the Gfirschworm ^ which use the carbohydrates "lies" This means "that the organisms do not grow as well" as they do at a smaller relative amount of relevant compounds would do " such, that the decomposition of organic matter is either too slow goes or is not fully carried out. Either the plant must

ψ be disproportionately large, or the wastewater becomes

iKnglich cleaned «whereby this is done by the cleaning system or goods installation The water diverted away continues to have a much higher biological oxygen consumption Has.

Has it been surprising now? can be g "seigt" that avoid the disadvantages described and equilateral a reduction of the biological Sauerstoffverbre-uches the wastewater au very lesser price _0! Aner.iitznng et- as the valuable products

909840/1373

from the wastewater before the ProtsSae vtztti ühf & i & chev substance "and possibly also other, mainly nitrogen-containing organic substances, in particular carbohydrates ₀ wsua mass eirfindmBgs · vegetable proteins, polypeptides and similar substances by means of ligmirisulphonic acids or their salts first gana © that · partially precipitates Substances filled in afterwards sur further » Ai separates and the residual residue © liquid coo with Dine or similar organism! dL that the mitigation

the biological oxygen consumption is stronger & ls the sum ™

or the product of the diminution by means of each sätssefosc-m of the two Steps for yourself "

Precipitation of the proteins with lignin sulfonates or their salts takes place practically at acidic pH values, preferably at pH 4-5 and particularly smoothly at pH 4 "5. In practice , precipitation takes place normally with the free lignin sulfones, even if they are in the form of salts of which are included. The pH is regulated by adding acid, especially strong mineral acid. In general, sulfuric acid or saline acid is used, and the choice will mainly depend on the price. mineral sow .te mixed with the Ligninsuifonsämren zu8 <3ts3si _r so that the relative contents of the two Kompoüiente of * Mischimg controlled to and discharged the. amount of waste water of the mixture, is metered in such a way., that the © rwlimechte pH "value is obtained, and the SwgeaetEte amount of the mixture so.gross iet "that the amount of lignosulfonic acids the eggialt from. Proteins

909840/1373 " ⁶ ~

BATH ORIGINAL

«■ 4 -

and similar Subctam-sn in wastewater. In doing so, it essentially covers the entire Psrataisviieag * on the Ab i use of a lignosulfonate * or mineral

u83es is filled in, Esa iierajitige:, * Excess does not harm the siiedsrgeoclilageaen Prc-ffckt, as long as he b'Sgreast JaS ₀ bfiiigi jsdirch iu ^ hf: eino yöi .- '.':?. ^r ie aiit sici: nsid thus means an unnecessary increase in costs. Daa ^ iedergaachisgene product is a complex of proteins and Ligssisssulfonssäuren and can with ashx good Ergabnfxssen ,, beispielev / else ssash drying ,, used as animal feed It can be separated into beictEnier manner from the wastewater ,, for example by simple Bodensatsbildungv FÜtrierung o'ler Zeniriiungserung. In the first process step, a high-quality fatter preparation is thus obtained, whereby the wastewater is largely freed from protein constituents at the same time, which form the predominant impurity in certain wastewater and, as mentioned; even have the disadvantage £ n _V 'that they impede biological purification in a customary manner and utilization of other organic component such as carbohydrates during fermentation,

The lignisulphones are relatively high molecular weight substances which, however, have somewhat varying molecular weights. In j molecule, however, »u? The acid function and the molar weight thus have a certain significance for the precipitate. AOgemeiroesn are lig ^ disfosized with a *) medium molecular weight of about 500 preferred »If the molecular weight is significant

9098AO / 1373

BATH ORIGINAL

Hch less ? .At? v * ar «? ert the particles« tee gisbalicter. Koroplexeo sw klein "nd lticH, - cc 'it-ss filing out causes difficulties, If the Molefcülgeverricht on the other hand is wQffctslEch larger, the consumption cu large," ben far only a S &"iro £ uElct £ o <n £ üs" every lignin · Sulfbneüurernolekftl bsctehtc For «aSreracaiieditei: ® Pro4ei2i® can however be 3twao tintcrsc7LiedI; .f: I * -e MfisJiiÜgewii ^ te der JLigninsullfanei & ure optimni, and irine rv / ecka? <2agnfirs The invention shows that the precipitation is carried out in two or more steps with sulfonyl groups of different molecular weights. This wi? D another advantage ersielt, Ee has ervsacen »<£ AA 0 proteins with high verhttltnismücoig Moleiciiigewiciit at best with vel & tively high molecular weight lignosulfonic acids 'been v.iegefüllt ,, while zsiedermolekulare proteins vcrr.ugcweiae with niedermoHekulsren Ijigainsulfonafaui-cn auegeifil!'. wesrtüea, Γη of the specified Weierersiel one therefore sine grabe Fi'f.It ^ iomertmg the proteins ₅ vr & a for their A \ xtmV '&: t, g can be of importance,

The next filing? with the LignirtculionsKuren and separation of the protein "complex remaining liquid usually contains a few Vs:.. * i r * a £ conditions, before sllero in dtr form of stick * otoff .i'mer or etickstof £ reieu?. Organic compounds such as vitamins and, if necessary, some fatty substance. According to the invention, these substances can be prepared either with a suitable medium or with a suitable medium . Give way to the two further - & * rd! U! K £ e :? S ',. vy.vr ^ r «ict. UfiEigt v-sf a!. "« M of the kind of ab- ρα: ί * Ί zk ₍ ie rcr uqt Msnigfl of the remaining organic

909840/1373
BATH ORIGINAL

and thus when directed into natural water, oxygen-consuming Substansea. If the remaining content of organic substances is low, "one will prefer biological cleaning in many cases." Is subjected to biological purification without prior removal of the proteins as described »where the amount of complex-bound proteins does not inhibit the active microflora of the biological filter. Even if the residual content of organic substances in the freed of proteins wastewater low Ut ₀ can be a treatment subject with a suitable Gftrungsorganiemus the wastewater ,, wherein the G & consumed approximately organism the organics after which it is dried and used as a lining material or for example as a vitamin supplement for animal feed materials.

If, on the other hand, the original and thus also the mainly protein-free wastewater has a relatively high content of other organic substances * in particular types of sugar and other carbohydrates *, it is generally preferable! to expose the wastewater to a pre-fermentation with a suitable microorganism. There are several different microorganisms known "is particularly suitable Torulopsis utilie = It should be noted that the invention is not to use this type limits or other organisms, the taxonomic botany in" meaning of the word Gäir sponges eind _s

909840/1373

BATH ORIGINAL

but that other "green organisms" also rerweaaiilet can * which assimilate the Kohlsnhydraia and asideirg residual ice-fan sewage.

The choice of the LigninsuÜEonsäuretyp can also be the tfTaml of the process - biological filter or Gämmg - in de? further Bo action affect β level. JüignineuAfcneäuren are available in very large quantities because they make up an essential part of the sulphite liquor. The lignin sulphurous structures can be in the form of sulphite liquor or in the form of refined or more or less A

Purified Li gnineulfons cures can be used. Di® refined or more or less highly purified! »Igninsulphonic acids differ from sulphite liquor mainly because of their content of sugars (Perothoeen, Hexogen) and carbohydrates is mainly or completely removed * The amounts of such substances in the sulphite liquor can be large and, if sulphite liquor, precipitate the protein is used "it can happen" that the wastewater after the first step of the inventive process has a higher biological oxygen consumption than before Failure of the proteins. Yes, in this case one will be erfämdumgegemäse the second step of the procedure in the manner

zuiührsn _d that the liquid freed from the precipitated product is put on fermentation with a "GttruaigsorganimTius". In diessm case, it may also be particularly swcckinässig, aussusetcen the fermented off * and befrsite of the Gärungsorgasiiemen liquid of a biological treatment. As a result, the biological oxygen consumption of the wastewater is reduced to a very low level, while at the same time a valuable product, namely the fermenting swamra, is obtained, which is used as fodder

can be. 909840/1373

"Io '*

BATH ORIGINAL '

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In general, however, one will become in accordance with the invention the Lignineulfons & uren or their Salse in refined Foirxn see below use »d, h. become from sulphite liquor and essentially freed from sugars and other carbohydrates. In. the There can be a wide range of wastewater from a farm with one Fermentation organism, which is often necessary «if the content of organic substances other than proteins and the like, des original wastewater is relatively high »or biologically safe Purification, which is preferred in certain cases »when the contents ™ of such organic substances is low,

It can happen that the wastewater freed from proteins and the like is so poor in nutrition "that it is useful to increase the" food "content by further treatment with a yogurt easily aug & ngliche stick material source for the organism and its growth is hindered if it is not used in proper amounts, ammonia is aueserdem to ^ the liquid has a suitable pH su hire en ₀ often about 6 or 6-7,

^w On the other hand, you can optionally contain sugary waste «»

as s.B · molasses, aumn feeders of the growth of the organism add «If ammonia is sugesetst» and the wastewater with Sulfuric acid or Salss & us · «has been made acidic« will turn out to be Ammonia sulfai or chloride form, which also easily useful S4iic3coto £ fqu'ßHon are which promote the growth of the sponges ».

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909840/1373

BATH ORIGINAL

1858043

As mentioned, the treatment according to the invention, i.e. first Precipitation with Ligninsulfonsfiuren and cooking on it or biologi ' sch «cleaning or both ·» a synergistic effect, like out the following appears.

The cleaning effect on the wastewater is here by BODg ₀

i.e. the biological saturation consumption in 5 days (normal

Calculation method), explained and printed out in mg consumed Oxygen per liter of wastewater. Daa is the result of a typical experiment BOD. before treatment 316O rag / l BOD. after 24 hours of previous cooking Torulopttis utilis 180 mg / l BOD. after precipitation with refined Lignin sulfonic acids. 2OOO ro g / l

BOD. after precipitation with refined lignin sulfonic acid and subsequent fermentation with Torulopsis utilis 240 mg / l for 24 hours

This results in "that" the reduction in BOD. after cooking alone 135O mg / l. or about 42 %, and in the case of precipitation with lignin * sulfonic acid alone U60 mg / l or 3? % is "79 % (251O mg / l) if the values are added" or real only about 63 % if the calculation is correct "which consists of" multiply the prosent amounts for BOD ₅ after the treatment and get the result of 100% . * subtract u. In a combination of the two treatments in sequence, however, a reduction of 2920 mg / l CDER 9Z% e? Twiddles "d _r h. Much more than was to be expected if only an additive effect was present * A clear synergistic pocket of effect is thus achieved.

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909840/1373 BAOORIQINAL

This effect erkläs-t probably so ₀ daee the ouch * precipitation deir Psfoteinstoffe and polypeptides microorganisms better NahrungebediRguHagen gives, Ee is known that · many microorganisms in Nahrungseubstiraten su groaaen amounts came plexgebutidenen nitrogen o'der & not u much nitrogen do well flourish »Ea has shown» that the best conditions for Gttrschwatnm are achieved «when the ratio between BODg, which is a function of the amount of organic matter« and the nitrogen content, both expressed in mg / l or parts / million »17 : 1, which corresponds to a BODg / protein ratio of about 6: 1. In the wastewater before precipitation, the BOD / N ₂ ratio (in mg / l or parts / million) can be on the order of 6: 1 or 8: 1 to 12: 1, and it changes to the desired value when filing from about 17: 1 or 18sl or maybe 2O; l.

If the precipitation is combined with a subsequent biological purification »corresponding results are obtained. A typical one; Example is, ¹

BOD. before treatment 3OOO m BODg after 10 hours of biological cleaning 18OO mg / l

after precipitation with refined Lignmstaifonsfiure 16OO tng / l

BODg after precipitation with lignin & fons & ure "and after"

the following ten-hour biological protection lOO mg / l,

Ten hours of biological cleaning aBefe resulted in an EOD _K "reduction of IZOO mg / l or 40 fo to & Ό% of the initial level ^ o.

909840/1373

BATH

Precipitation alone resulted in a reduction of 14OO mg / l or 46 % and the two treatments combined in the correct order resulted in a reduction of 2900 mg / l or 96 _U 7 %, i.e. to 3.3 % of the initial level, where you konntec} expect in a non-* syn <ergiotisehen- effect only a reduction of 18 "4% to 18» 6% of Anfangsaiveaus (or 13% for Addiemrag the absolute values, the cause is probably the same as above "because the microorganisms on biological filters thrive best »when the protein cold of the wastewater is not as high» but close to what is biologically desirable for BOD g / N, »w & s five · biological cleaning is about 18: 1.

It should be added that in the above-mentioned treatment "where the BOD _g amount when filled with refined Ligninsulfone & ure fell from 3OOO to 16OO mg / l, when using sulphite liquor an increase to 4200 mg / l would be obtained,"

In further experiments a solution of 50 g of blood albumin in 5 liters of water was treated. The BOD _S / N ₂ ratio was very unfavorable here, actually 6: L The data obtained were;

BOD »before treatment

BOD »after 24 ** hours of biological cleaning with active mud

BOD> after precipitation with refined lignin » sulfonic acid

Precipitation with refined lignin suIfonsSure and subsequent? 24 stündi ^u ger biological treatment

6OOO mg / l 46OO mg / 1 9OO mg / l

SO mg / l ..

909 8 4 0/1373 BADORlQlNAt.

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After the precipitation, the BOD _g / N ₂ ratio was 18: 1, which is favorable for the organisms in the active sludge. It's herVOi ₀ that the biological treatment alone NOD within 24 hours only? Won 6 _O decrease 7% of Auegangswertes "which meant that the plant has a very high capacity must have to for this type of waste water can be used below. On the other hand, the ligninsulphoneaure _{treatment alone could reduce BOD 5} to 15 % of the initial value. If the effect of the two treatments had been additive, "we would expect" that BODe would have been around 11 * 5 % after both treatments (namely 15% of 76 "7 f ») Or about 690 rag / l . In fact, however, the amount was only 50 mg / i ie «8 % of the original amount» or much lower than expected »'The effect is therefore clearly synergistic.

It is to be noted by BU “that wastewater” which was examined in the specified experiments with only one form of treatment “d. h> either precipitation or biological purification or fermentation, see _{below high BOD 5} values (900 * 2OOO mg / l), so that they could not generally run out into natural water, wastewater that had been treated by the process according to the invention * could however, in all three cases (BOD ₅ 5O - 24O mg / l) are passed readily Vfasserstrume, lakes' bays or fjords.

The inventive method is hereinafter based on a Implementation example explains, '

984071373
BAD ORlQlNAJL

-15 -B EISPIE L

In an experiment on a semi-technical scale, 6 m Treated wastewater from a potato starch factory. The sewage contained 3 g nitrogenous compounds and 3 g redusable gambler per liter and was totaled with 2700 g lignin sulfono & ure-sodium corn, i.e. 450 g per m and such a large amount Sulfuric acid that the pH was about 4.5 »treated. The nitrogenous compounds consist predominantly or exclusively (detailed analysis was not carried out) Proteins and their preparation products, i.e. polypeptides with larger or smaller chain length and amino acids. at Adding the liigninsulfons & uresalBes the proteins were almost momentarily precipitated and a slurry thereof formed. The * slurry was passed through a sand filter where the sand was with Silica was coated and a small amount of the clear filtrate was swung back through the filter. whereby an essentially concentrated slurry was formed, from which the knocked down proteins in known? Way and could then be used.

The clear filtrate still contains 1.7 g of nitrogen-containing compounds per liter, namely dissolved peptides and amino acids. Of the The treatment did not affect sugar content.

The pH of the clear filtrate was 4.5 and was through Addition of 180 g of liquid ammonia per m increased to 6

909840/1373
BATH ORIGINAL

36 -

■ »
per m FHtTRt O ₃ 5 kg Rufo'sinsiackerm © lasse

snoifc eisi-as-ti sugar content of about 50% and cime culture of fermentation = - i "?" Äi-warnsne "! Ta-rui-oppis utilis sugegen. Then a eubmers fermentation takes place in the liquid, at a temperature of 3O C for 8 hours with air supply of 3 m of air per hour "corresponding to about \ (Z m of air per m of liquid carried out per hour. After fermentation was complete, 4 * 8 m of the liquid were removed. From this, the slurried particles" So, practically only fermentation sponges were removed The isolation was carried out by means of centrifugation. In larger systems, however, a previous filtration is often necessary. With centrifugation, 8 g of compressed yeast per liter of liquid are obtained.

The remaining 1 »2 m were used as inoculating fluid for a new one Fermentation used which the latter was otherwise carried out in the same way and with similar results.

The fermentation is most appropriately submerged in as described suitable basins or rooms and provided with ventilation.

On the other hand, there is an obstacle to the process of fermentation as surface fermentation in open boxes in a manner known to all perform.

The following table shows the reduction in BODg wetias rz dem

treated wastewater,., gas lakes at Mucterm ναιτ detnn Ausffilleiß snift LigninstuLÜfoneüus · © "NatraalSf. lanmltfcslfosur after the fall and raaeh Gäsmag ·; during the iss ds ¹ : Ts.be! P; e

909840/1373 BATH ORIGINAL

EOD,

before your j. fall Hour » To to the Failures hours To m I hours ti It 3 hours ir 19th 6th hours 31 Il 9 hours Μ 12th «Ι IJ 18th

ZOlO 2140 143O

78O

57O

43O

98 ..

909840/1373 BAD OBtGtNAL

Claims (1)

69/12 729 EK lü. Ilovember 1967 j? a te η ta nriie ldung of the company h / l> pharmacists a! laboratory for üjpecialpraeparater, JD lü, Norway Claims I, process eur purification of sewage under Aaenutung in it vo.niegindsn impurities, in particular Protein « wnn. ähalsclae oi * g% ^: aisefo <a -Subetamse & i durck precipitation with Lilgidnsislfoneaur "jcd fermentation or biological purification" d ^ luffch gekesuuieicluiete that one first of all the proteins, polypeptides \ m <similar substances "uren" uren or whose Salsasi ganx οΔαν tiii.lwiise ^ usFäSHt, dmam ^ h the outer container; Liquid k @ jt @iAssr Cijrnng with iron Gäeßijhwamro or iisaEcheE. e * isr biolcyjiacfeeff Eehugesng c of the two parts Z, VEk-fahifuii according to claim 1, dasi »tue Awsfiilisiiig in swei or meharavea Staisia .with Lignineulfoiiii-; r. or dessin Salseii; "it tsntarachie ^ lSicibiira Mol" kiilgewlcht a ~ iol: * $. _ 909840/1373 BATH ORIGINAL 3e Move "li" sfc Anepirwcfe Ii or As a result, we apply that m & ut & um Axs.s £ & ll®n LignineuUone £ urs or salts thereof. 4. The method according to claim I ₀ Z or 3 “characterized in that one uses aiisfSSlfsu refined Iigninsulionsüuren or Salse dereclben and the liquid freed from the filled product ammonia or possibly sugary material, sB Met®ese _s susotst ,, before or after and naeii «. While this liquid is treated with a gauze, after which the hardened liquid! if desired, after separating the GKrsch ^ ammes, is subjected to biological cleaning. 5. The method according to claim 1 or 2, characterized marked that used as Ligninsulfons & ure SsiEfitlatage will * and that one freed from the gcg & ird product Exposing liquid to fermentation with an organic fermentation and if desired; the enriched liquid also according to Afetreixrang des Gäraagcos-gairiernue a biological cleaning 9O98A0 / 1373 BATH ORIGINAL