FI59016B - FOERFARANDE FOER AVLAEGSNANDE OCH AOTERVINNING AV FAELLNINGSMEDEL FRAON UTFAELLT PROTEINHALTIGT MATERIAL - Google Patents

Description

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Norway-Norway (NO) 7 ^ 2703 (71) A / S Apothekernes Laboratorium for Specialpreeparater, Harbitzalleen 3,

Oslo 2, Norway-Norway (NO) (72) Per Oscar Nettli, Asker, Norway-Norway (NO) (71 *) Oy Kolster Ab (5U) Method for removing and recovering precipitants from a doped proteinaceous material - Förfarande för avlägsnande och ätervinning av fällningsmedel fr & n utfällt proteinhaltigt material

It is well known to use certain substances as precipitants on an industrial scale in the recovery of protein substances from wastewater, such as process water. The main group of precipitants used is probably lignin sulfonic acids and their derivatives. Many plants based on the use of lignin sulphonic acids have been built in several countries and are used for the treatment of industrial waste while recovering significant amounts of protein, cf. U.S. Patent 3,390,999. Other organic materials used as precipitants include organic sulfonates, for example aryl or arylalkyl sulfonic acids described in CA Patent 882,398, and organic sulfates such as sulfuric acid esters of monohydric and polyhydric alcohols such as lauryl sulfate. glyceryl trisulphate and sulphated hexahydric alcohols and sulphated hexahydric carbohydrates, here reference is made to N0 patent 117 339 and CA patent 887 899 · Most of these organic sulphonic acids and sulphates give very good purification efficiencies, but their use in water purification at industrial scale results in relative scale industrial purification. It is further known that proteins precipitated with these precipitants can be used as feed. However, it would be advantageous if the concentration of these precipitants could be reduced. Namely, by lowering the content of precipitant in the precipitated substance, it is possible to simultaneously increase the protein content and thus increase the commercial value of the substance as feed.

In known methods for precipitating proteins, and in particular from industrial effluents, the precipitate is separated from the aqueous phase by some mechanical method, for example by foaming, to obtain a slurry with a dry matter content of 5-15%.

This sludge can often be further concentrated before final treatment. The concentration can be carried out, for example, by filtration or centrifugation after it has been pretreated, for example by heat and / or by the addition of lime, in a manner known per se, as disclosed, for example, in CH patent publication 552 5 ^ 1. This appears to be a relatively efficient method of concentration, but most of the precipitant remains in the slurry phase and a relatively large proportion of the proteins go with the liquid phase.

The invention is characterized in that alkaline earth metal compounds are added to the precipitated proteinaceous substance as an aqueous slurry in an amount sufficient to bind the proteins, and if the pH is still below 7 after the addition, the base is added in the form of alkaline earth metal or alkali metal hydroxide until pH 9, after which the substance is heated to a temperature higher than the coagulation point of the proteins present, and in this case the separating aqueous phase containing the precipitant is separated, for example as a filter or a suitable centrifuge, optionally rinsing with water, after which the precipitated aqueous phase can be re-used. . When rinsing the coagulated substance, it is possible to recover the precipitants almost quantitatively. If an alkaline earth metal hydroxide, for example Ca (OH) 2, is used alone before the heat treatment of the protein slurry, a smaller part of the precipitant enters the solution and thus less precipitant is recovered, probably because the calcium salts of these precipitants are less soluble. However, one advantage of using lime alone is that the coagulated material has a firmer consistency and better resolution, for example filtration is easier.

When a sufficient alkaline earth metal salt is used to form the alkaline earth metal protein and a sufficient amount of alkali metal hydroxide for neutralization, the precipitant enters the solution as a high solubility alkali metal salt, thus making it possible to recover a nearly quantitative precipitant.

Example 1

A lignoprotein slurry separated by precipitation of protein 5 5901 6 from slaughterhouse effluent with a dry matter content of 14.5 & was used for the experiment.

To the slurry having a pH of 4.1 was added lime to raise the pH to 8, Forehead. The slurry was then heated to 95 ° C where the slurry coagulated. After a sufficient standing and reaction time, the slurry was centrifuged. Lincoane was then used as a precipitant in a protein solution for which the optimal dosage of pure lignosulfonic acid was known. A certain amount of lincosanis solution was added to the protein solution along with various amounts of lignosulfonic acid. The proteinaceous material in solution precipitated and the organic matter in the resulting decantation solution was measured by determining COD. (COD - oxygen consumption).

For protein extraction, the slaughter experiment vaxten used slaughterhouse effluent of the same quality as that used to precipitate the lignoprotein sludge studied.

The test results are shown in the following table.

Table I

Dosages (500 none COD # CODtn Curve of protein solution decantation no.

Lignoeulfophyclic acid Lincoamlsnesic acid, a * / i tete, ng / l ^ ml__wgcyi I_

° O. O 4690 O

O 600 0 3886 17.14 O 700 5 1259 73.15 50 "" 1178 74.89 100 "" 1189 74.64 χ 150 * · m 1239 73.59 200 »· h 1276 72.79? 5Q" «1300 · 72.29 O 600 O. 3886 17.14 0 700 5 1259 73.15 2 0 "10 1341 71.41 _ °" 15 1706 63.64 250 600 O 1036 77.91 300 · 'O 1016 78.34 3,350 "O 1022 78.20 4Q0" O 1075 77.07 4 59016

The table and curves clearly show that the centrifugal solution contains a large amount of recovered precipitant. The best result in precipitating the protein solution with the centrifugation solution alone was obtained by adding 5 ml of the centrifuge solution to the 500 basin protein solution. The COD reduction in this case is 73.15 verrattuna ° compared to 17.14 # »with the addition of sulfuric acid alone.

Curve 2 shows that the optimal amount of centrifugation fluid to precipitate the protein class would be about Θ ml / 500 ml, giving a COD value of about 1.90 mg Og / l in the decantation fluid, which corresponds to a COD reduction of about 74.6.

If this is compared with the extrapolated part of curve 5, the amount of precipitant recovered could be estimated to correspond to a dosage of about 175 mg / l, i.e. about 87 mg / 500 ml. This means that the concentration of the precipitant in the centrifugation medium would be about 82 mg / ml, i.e. about 10 g / l · 8 added more, precipitation of the protein solution, due to overdose, becomes less effective. This effect of overdose is also clearly seen in curve 3, which shows an optimal lignosulfonate dose of 300 mg / l. When amounts of lignosulfonate greater than about 70 mg / l plus 5 no centrifugation fluid give a better COD reduction (ke. Curve 1), it can be assumed that the recovered precipitant in the centrifuge anise would correspond to a dose of 300-70 to 230 mg / l, i.e. about 115 mg / 500 ml. According to this assumption, the added centrifuge fluid would contain 115 mg / ml, i.e. about 20 g / l.

5

Example II

To the same slurry used in Example I was added a certain amount of calcium chloride, followed by pH adjustment with sodium hydroxide to pH -8.0. The slurry was heated after 95 Olsen, after which coagulation occurred, and after a mowing standing and reaction time at this temperature, the sample was centrifuged. The centrifugation fluid was analyzed and used as a source of ligiosulfate, then that a certain amount was added to the protein solution and then a varying amount of lignosulfonic acid was added. Surprisingly, it turned out that using this centrifugation liquid as a precipitant gave a much better precipitation of proteins, so that the resulting liquid phase becomes clear and pure. The liquid phases of the products were analyzed for COD to provide a reference for protein precipitant recovery.

The test results are shown in the following table.

. ; ·.) 'F 5 59016

Tiu l Akko II

Dosages (500 so-called protail solution COD de- COStn Curve carrier reduction no.

—— new

Llgnosnlfo- Sulfuric acid Lincoane · -seaeate sodium mg / ml solution,.

Mg / l_l __ «X | j mg tyl _ [___

O O O 4690 O

O 600 O 3886 17.14 O 700 5 1126 75.99 50 * "1084 '76, 88 100" "1117 76.18 4 150 ·· ·· 1148 75.52 200 ·· 1173 74.98 250" »· 1210 * 74.20 «O 700 5 1126 75.99 O · '10 1146 75.56 5 O ·· 15 1312 72.02

It is best to compare the results of the B-mark II with the results of Example I by comparing curve 4 (e.g. XX) with curve 1 (e.g. I) and curve 5 (e.g. II), curve 2 (e.g. I).

Curve 4 shows, compared to Curve 1, that Example II gives a better COS reduction than Example I, and that the optimal dosage is somewhat lower than in Example I. This means that the 1 aniano liquid obtained by coagulation with CaCl 3 and NaOH contains a higher amount of yield aid. as in Example I.

This relationship is further elucidated by comparing the results of protelinisaoe tests using centrifugal fluid alone. Curve 5 (e.g. II) is well below curve 2 (e.g. I), indicating that the specific COS reduction is better with the centrifugation fluid of Example II. Ideally, curve 5 shows a smaller increase than curve 2 as the amount of centrifugal anion is increased above the optimal dosage, which means that the proportion of substances without protein-accompanying properties in the centrifugation liquid of Example II is lower than the corresponding proportion in Example I.

6 59016

B «<Msric1rl III

To 5 portions of the word slurry used in Examples I and II were added different amounts of lime corresponding to pH 7 # 8 and 9 before coagulating at 95 ° C. Centrifugation was performed as in Precursor I and centrifugal fluids were examined as described in Precursors I and II.

The test results are shown in Hai from the following table.

Table III

pH co- Dosage (500 basins of progulogenin

Lignoeul- Ukki- Centrifuge- C09- dskaa- COD-sale- Curve phonate, acid sensory lean, no 1/1 1/1 S · * · * - u ~ k "*“.

tÄ mg 02A * ------.-------- ....... y | '——— · 7 O 700 5 1,372 70,74 8 O 700 5 1,259 73,16 6 9 O 700 5 1,168 75,09 7 50 .700 5 1,265 73,02 8 50 700 5 1,178 74,88 7 9 50 700 5 1,143 75,62 7 100 700 5 1,225 73,88 8 100 700 5 1,189 74,64 8 9 100 700 5 1,202 74,37 t _______ 1-

Labeling the results literally as in Examples I and II provides an indication of the pH dependence or role in the coagulation of the doped proteinaceous material.

Curve 6, which shows the protein precipitation assay with 1cocyanic liquid alone, clearly shows a better precipitation efficiency for the centrifugal liquid obtained with coafuloin acetate as the pH increases. Curves 7 and Θ, with 50 and 100 ng / l of excess lignin sulfonate, respectively, show that as an additional increase of 50 ngt / l in 5 basin centrifugation, an increase in COD area is obtained as a flow of centrifugation only 100, but the increase to 100 agsn / l slurry dosage gel, on the other hand, is obtained with poor COD reduction with centrifugal ascites from coagulase pH 9 * seä · This is illustrated in the curve. 9 »from which it is clear that the optical addition of lignin sulfonate when added to the 3 basin centrifugal fluid is n · 30 ag / l. If this result is judged verbally in the same way as eslaerklse I »it can be assumed that the amount of precipitant recovered in the centrifugal fluid in coagulation at pH 9> would correspond to a dosage of 300-50-250 g / l, i.e. l, which is 25 pounds greater than the concentration in the corresponding centrifugal fluid at coagulolal pH Sts (Example I) ·

Bsiaerkkl IT

4 portions, each 100 g, of the word lignoprotein slurry as in coaguloltin 95 ° C after the addition of CaCl 2 and HaOH in two portions and Ca (OH) 2 alone in two portions, the pH being adjusted to 9 ·

True removal from these doses occurred in two different ways, with one dose of treatment with CaCl 3 and HaOH and one dose of treatment with Ca (OH) IIIa alone being retrieved as in the previous eslaerkel, while the remaining two doses from different treatments were filtered through a glass gold filter, Threatened GP / C and washed twice with 50 alps of water · The centrifugal liquid and filtrate ends were anesthetized and the concentration of the precipitant was controlled in the protein precipitation experiments as in the previous eslaerkel ·

Table

Precipitate yield ‘r Treatment Dewatering- Hestepaa- Concentration Recovery- 8 Yield gene roll area Amount Dt.ttu ai * k ~ ------- rx-- * j ~ 1" r '“T -

CaCl 2 + centrifugate 58 35 2,030 66.6

NaOH

CaCl 2 + filtration 121 20 2.420 79.5

NaOH

Ca (OH) 2 centrifugate 72 · 25 1,800 59.1

Ca (0H) 2 filtration 150 15 2.250 73.9 5901 6

In addition, the filtration rate and volume yield were examined using cold (15 ° C) and warm (63 ° C) water for washing the coagulated material, respectively. Further experiments were performed by adding cold water (15 ° C) after coagulation and stirring to cool the material before separation.

These additional experiments showed that the filtration rate and volume yield were, as expected, the highest when using warm water to wash the coagulated material, but adding cold water and stirring before separation resulted in even higher filtration rate and liquid phase volume yield. Cooling the material to about 50 ° C before separation therefore appears to be an advantage.

The volume yield in centrifugation and filtration, respectively, shows that the separability is best for a slurry treated with Ca (OH) 2LLa alone, but the precipitate yield shows that treatment with CaCl 3 and NaOH before coagulation gives the best precipitation recovery from the protein material.

The used ligno-protein sludge with a dry matter content of 14 * 5 contains lignin sulphonate as a result of the use of lignin sulphonate in the preparation of the slurry and lignin sulphonate residue in the treated effluent. slurry. As shown in the table, after treatment with the coagulated slurry with CaCl 2 + NaOH or Ca (OH) 2 · Ha alone, respectively, it is possible to increase the recovery of the precipitation basin from 66.6 to 79.5, respectively, washing from 59 to 75 * with water.

Example V

To investigate the possibility of removing precipitants from the precipitated proteinaceous material, different types of protein slurries were prepared by mixing the following precipitants in the proteinaceous effluent with lauryl sulfate, glyceryl trisulfate, dodecylbenzenesulfonic acid, aluminum sulfate.

The same slaughterhouse waste with CO 4 - 4 * 990 mg O / l was used as wastewater as in the preparation of the lignoprotein slurry in the previous examples. Breast digestion was also performed with wastewater as slaughterhouse waste in a digestion plant (for the production of meat-and-bone meal and technical fat) and experiments with a diluted blood-water cycle on the slaughter of pigs.

To the separated slurry was added Ca (OH) 2 to pH 9, coagulated at 95 ° C and centrifuged. Centrifugal liquids from different types of sludge were subjected to the same protein precipitation test as in the previous examples using 5, 10 and 15 ml of precipitant for the same slaughterhouse effluent described in the previous examples. Sulfuric acid was added to give a pH of 3 in all precipitations, except for precipitation with a centrifugal slurry doped with aluminum sulfate, where the pH was adjusted to 6. Decan active liquids from the precipitation precipitation test were characterized by determining the COD used to calculate the precipitant recovery.

Score

Sapstus- Lincoanianes- COD decane- COD-decrease- Curve substance in tea dosing function- 500 nothing in tea g ng 02 / l

Lauryl-5 1> 426 68.9

sulfate 10 1.172 74.5 10

, 15 1,542 66.4, _ _’_ * - - «

Glyceryl, δ 2,380 48.1 trisulphate 10 1,438 68,7 11 15 1,567 65,8 _

Dodesyl 5 2,135 53.5 benzene 10 1,529 66,7 ^ 12 sulfonic acid 15 1,813 60,5

Aluminum 5 3.220 29.8 sulfate 10 3.072 33.0 13 15 3.030 34.0

Compared to the result from Example I, Curve 2, it is seen that the precipitant is removed from the doped proteinaceous material in the same manner. Recovery rates for organic sulfonates and sulfates are comparable when it is significantly lower for alunine sulfate. However, it is clear that the method according to the invention is generally useful for removing precipitants from a doped proteinaceous material in such a form that it can possibly be reused.

Claims (3)

10 5 901 6 A process for removing and recovering precipitants from a precipitated proteinaceous substance in the form of an aqueous slurry, characterized in that alkaline earth metal compounds are added to the precipitated substance in an amount sufficient to bind the proteins, and if the pH is still below 7 after addition of the alkali metal alkali. or in the form of an alkali metal hydroxide until the pH is 7-9> after which the substance is heated to a temperature higher than the coagulation point of the proteins present, and the separating aqueous phase containing the precipitant is separated, for example by filtration or suitable centrifugation, possibly rinsing with water the aqueous phase containing the resulting precipitant can be reused to precipitate proteins. Process according to Claim 1, characterized in that an alkaline earth metal salt, preferably calcium chloride, is used as the alkaline earth metal compound and alkali metal hydroxide, preferably sodium hydroxide, is used as the base. Process according to Claims 1 to 2, characterized in that an alkaline earth metal hydroxide, preferably calcium hydroxide, is used as the alkaline earth metal compound and the base.