CN109952384A

CN109952384A - Olive mill waste water leather tanning industry in purposes

Info

Publication number: CN109952384A
Application number: CN201780061329.0A
Authority: CN
Inventors: 马西米利亚诺·弗兰切斯基; 贾科莫·帕基; 毛里齐奥·马拉维利亚
Original assignee: Donald Co Ltd
Current assignee: Donald Co Ltd
Priority date: 2016-08-03
Filing date: 2017-08-03
Publication date: 2019-06-28
Also published as: IT201600081688A1; EP3494237A1; PL3494237T3; PT3494237T; WO2018025210A1; EP3494237B1; ES2880083T3

Abstract

Describe olive mill waste water (OMW) tanning industry in leather tanning process at least one step in purposes.Preferably, olive waste water of milling is used as bactericide, tanning agent or tanning adjuvant and/or antioxidant, to prevent from forming chromium (VI) during retanning step.Advantageously, a kind of tanning composition is described, which includes that the olive is milled waste water (OMW) and suitable additive.

Description

Olive mill waste water leather tanning industry in purposes

Invention field

The present invention relates to for evaluating the olive in (requalification) tanning industrial (tanning industry) again Olive oil is milled the technique of waste water (olive oil mill waste water).

The prior art

Olive oil mill waste water (OMW) be organic substance and minerals aqueous solution, olive oil mill waste water also include by The suspension plant solid material that the separation of the necessary step (oily must step) of oiliness generates.Their composition is extremely variable , and depend on a number of factors, degree, soil, extraction process and the guarantor of type and its maturation including olive growing kind Deposit method.

Olive oil mill waste water include Multiple components, such as organic substance, nitrogen substance, sugar, tannin, phenolic compound, Polyalcohol, pectin, lipid, minerals and polyphenol.

Sugar is main organic substance, especially fermentable sugar, such as glucose (70%), mannitol (14%), fruit Sugared (10%), sucrose (5%), galactolipin (1%) and cellulose.

In nitrogen substance, it was found that whole amino acid, especially glutamic acid and proline.

The pH value typically comprised between 4 and 6 is determined by the content of organic acid, such as malic acid, citric acid, winestone Acid, succinic acid and oxalic acid.These pH oscillation (pH oscillation) is attributable to olive kind, maturity period and storage life.

The mill organic fraction of waste water of olive oil determines their high pollution ability (polluting power), usually its Very high COD (COD) and BOD (BOD5) are characterized in that, for being originated from most modern centrifugation factory Water, COD and BOD are respectively in 90 grams of O₂/ L and 30 gram of O₂Between/L, and for being originated from tradition The water of factory, COD and BOD even 150 grams of O₂/ L and 90 gram of O₂/L。

In addition, stopped in wherein waste water in the holding vessel for continuing more time or less time during storage, it is certain to hold The concentration of organic component easy to ferment can also be significant by the effect of aerobe present in it and anaerobe Reduce, aerobe and anaerobe can decompose the organic component that can be easy fermentation.

Even if OMW is actually extremely complex matrix from the viewpoint of microbiology, wherein there are a variety of micro- lifes Object, yeast and mold, even up to 10⁵-10⁶Concentration value.

Therefore, olive oil mill waste water generation and characteristic with for olive oil production olive production and olive spy Property and directly related with used extraction process and both subsequent condition of storage and storage time.

The waste water in general, olive oil that the olive of the processing of every 100kg obtains 70kg-100kg is milled.Since olive oil is milled The very high pollution potential of waste water and the significant volume of generation, it will therefore be apparent that in view of there is no effective processing sides Method, olive oil waste water of milling is main waste water to be disposed now.

Over time, it has had attempted to olive oil to mill the various methods of wastewater treatment, from the removing toxic substances with fungi Technique is tactful to using ozone treatment and biological value to promote (biovalorization).No one of these systems by Be proved to be really effective and industrially applicable, so current olive oil is milled waste water be still used as non hazardous waste or pass through by They are dispersed on farmland and are disposed.

In recent years, many effort have been made to evaluate olive oil again and mill waste water, they have been converted from the waste of disposition At available product, to obtain the value promotion of this waste, while its environmental impact is reduced.

Therefore, the main object of the present invention is to evaluate to be milled waste water by the olive oil that the technique of olive processing generates again.

Summary of the invention

Purpose above mills purposes of the waste water in leather tanning industry by offer olive oil to realize.

Particularly and surprisingly, waste water can be in processing animal hides the inventors have discovered that olive oil is milled For in leather tanning process at least three different steps in technique.

Therefore, in the first embodiment, the present invention relates to any stages in the process for tanning for needing bactericidal effect In, olive oil is milled purposes of the waste water (OMW) as bactericide preferably in soaking step.

In this second embodiment, the present invention relates to especially olive oil is milled waste water (OMW) conduct in tanning step The purposes of tanning agent or tanning adjuvant (tanning adjuvant agent).

Preferably, in the embodiment described in which, the mill use of waste water (OMW) of the olive oil combines hair with other tanning agents It is raw.

Tanning agent is more preferably selected from the group being made up of: natural gallotannin, such as tower draws (tara), sensitive plant, chestnut, scolds Sub (myrobalan)；Syntannin, for example, hydroxyl diphenyl sulphone (DPS), belong to phenolic resin family compound, belong to naphthalene resin family Compound；Aldehyde or its precursor, such as glutaraldehyde, isoxazole alkane, oxazolidine；Metal salt, such as chromic salts, zirconates or titanium salt；With And acrylic resin, such as by acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylamide it is equal The resin of poly- or free-radical polymerized acquisition, preferably at the acrylic resin of salt, such as Sodium Polyacrylate (PA).

Even further preferably, in the embodiment described in which, olive oil waste water of milling is combined with polyacrylic resin (PA) It uses.

In the third embodiment, the present invention relates to olive oil to mill waste water (OMW) as antioxidant to prevent multiple The purposes of chromium (VI) is formed in tan step.

In fact, the present inventor is it has surprisingly been found that OMW can be used for leather tanning industry at least In one step, it is enable to only be doomed the product value promotion of disposition up to now.

Detailed description of the invention

Therefore, the present invention relates to olive oil mill waste water tanning industry in leather tanning process in purposes.

Olive oil mill waste water (OMW) be by olive oil processing generate waste water, and they during the separation of water from Oil must operate neutralization and obtain from washed plant operation.

Preferably, it includes pH between 2 and 8, between more preferably 3 and 5 that OMW used in the present invention, which has,；Including Suspended solid between 10,000mg/L and 100,000mg/L, more preferably between 20,000mg/L and 70,000mg/L contains Amount；Including the dried residue (dry residue) by weight between 1% and 12%, between more preferably 2% and 8%； Including total phenols content between 100 and 15,000, between more preferably 500 and 10,000 (according to according to Folin What Ciocalteau method determined, it is expressed as gallic acid mg equivalent/L OMW)；Be included in 25mg/L and 5,000mg/L it Between, the hydroxytyrosol content between more preferably 500mg/L and 3,000mg/L (as determined by HPLC-UV DAD).

It is highly preferred that the olive oil according to the present invention used in process for tanning is milled, waste water is that previous experience passes through use The olive oil of the antihunt means of nitrogen processing is milled waste water.Specifically, the olive oil mills waste water rich in one or more of more Phenol such as hydroxytyrosol is handled in the nitrogen by way of liquid or gas, preferably gas.

Waste water is milled optionally by the olive oil of the antihunt means handled with nitrogen even further preferably, previously undergoing The more early step being enriched with lactic acid bacteria is provided.

Process for tanning usually carries out in various ways, depending on the type of original rawhide and the class of product to be made into Type.

In the present invention, when using following statement:

" leather processing water " means the liquid of rawhide processing to be used for, and adds various inorganic agents to the liquid；Its amount is logical Often it is represented as the Kg of the liquid compared to the Kg to processed rawhide；

" network water (network water) " means the water supplied by general industry water system, and is often used as skin Remove from office the processing water in process for tanning.

In the present invention, and as by from being detailed below it will be evident that processing water include network water and given percentage Olive oil is milled waste water (OMW), which is represented as the percentage by weight of the total weight based on processing water.

Due to occur at each step in the process chemical-biological reaction property and diversification (plurality), Entire process for tanning is extremely complex.The purpose of process for tanning is to provide the leather of tanning, and the leather of the tanning has simultaneously There are high hydrothermal stability, good chemical resistance, to the resistance of bacterium and enzymatic agent, and is commercialized related permitted with it More properties, such as flexibility, flexibility, richness, solidness (firmness), tightness, stainability (dyeability) and good Good physical-mechanical properties.

Therefore, the whole chemical agents for being conventionally used to each step of process for tanning should ensure wherein to use the agent simultaneously Specific steps in the acquisition of property pursued, without damaging or changing the fine reaction balance of subsequent step, or do not damage The performance that evil obtains after the processing of previous steps.

Soaking step allows to bring back to rawhide the initial condition when just peeling, removes the salt used during storage, Dirt is cleaned, and is adsorbed on rawhide and saves the water that processing is lost later.

Present inventors have surprisingly discovered that OMW itself, i.e., it does not suffer from mentioning for any purifying and/or its component Take, can be used as bactericide process for tanning any stage especially during rawhide soaking step or tanning step, it is excellent Selection of land is added in soaking step.

Therefore, in the first embodiment, the present invention relates to the process for tanning for needing bactericidal effect at least one Olive oil is milled purposes of the waste water (OMW) as bactericide in step, preferably in soaking step.

Preferably, rawhide is immersed in the processing water-bath being made of the network water at 25 DEG C and carries out, wherein for removing decontamination The detergent and biocide of dirt, globular protein and blood are added, and to prevent bacterium charge from being formed, bacterium charge is formed Generate odorant and leather of degrading.Surprisingly, and such as will from hereafter experimental section it is evident that OMW The excellent bactericide being proved to be in use environment, and therefore advantageouslyed allow for reducing significantly or even replace The amount of usually used biocide during soaking step, biocide such as chlorophenol (chloreresol, trichlorophenol, 2,4,6,-T etc.), two sulphur For carbamate (sodium salt) and thiocyanomethylthio benzothiazole (thiocyanomethylthiobenzothiazole).

Typically, in soaking step, every kg waits for that processed rawhide use is included between 0.5kg and 2.5kg, preferably Between ground 0.7kg and 1.5kg, even more preferably about 1kg processing water amount, processing water be usually network water.

In this embodiment, OMW with based on processing water by weight from 50% to 100% amount, preferably with from 75% to 100% amount, even more preferably with 100% amount i.e. they replace network water to be used completely.

In this second embodiment, the present invention relates in leather tanning step olive oil mill waste water (OMW) as tan The purposes of agent or tanning adjuvant.

It is known that tanning is the operation for stablizing crosslinking that one group of permission obtains collagenous fibres in the intradermal of skin.? In tanning step, stable crosslinking is formed in collagen polypeptide chain, the result is that solidification, solidification protection corium substance was from degrading Journey, and provide with mechanical strength and the tan leather to humidity, temperature and chemical agent resistance.

Olive oil is milled both excellent tanning agent that waste water (OMW) is found to be in process for tanning and excellent adjuvant, such as It will be apparent from experimental section.

Therefore, in a second embodiment of the present invention, the present invention relates to the olives in the tanning step of leather tanning process Olive oil is milled purposes of the waste water (OMW) as tanning agent or tanning adjuvant.

Advantageously, in tanning step, it is included in 0.5kg and 2kg using what the dry rawhide of every kg was represented as the water of kg Between, the amount of processing water between preferably 0.8kg and 1.5kg.

Preferably, olive oil waste water (OMW) of milling is applied in combination with selected from other tanning agents of group being made up of: natural Tannin, such as tower drawing, sensitive plant, chestnut, myrobalan；Syntannin, such as hydroxyl diphenyl sulphone (DPS), the chemical combination for belonging to phenolic resin family Object, the compound for belonging to naphthalene resin family；Aldehyde or its precursor, such as glutaraldehyde, isoxazole alkane, oxazolidine；Metal salt, such as chromium Salt, zirconates or titanium salt；And acrylic resin, such as pass through acrylic acid such as Sodium Polyacrylate, methacrylic acid, metering system The resin of homopolymerization or the free-radical polymerized acquisition of sour methyl esters, ethyl acrylate, acrylamide and its mixture, preferably at salt Acrylic resin such as Sodium Polyacrylate (PA).

It is highly preferred that in the embodiment described in which, olive oil waste water of milling is applied in combination with acrylic resin, acrylic acid tree Rouge is the homopolymerization or freedom for example by acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylamide The resin that base copolymerization obtains, optionally preferably at the acrylic resin of salt, such as Sodium Polyacrylate (PA).

Even further preferably, in the embodiment described in which, olive oil waste water of milling is combined with polyacrylic resin (PA) It uses, polyacrylic resin passes through the homopolymerization or free-radical polymerized acquisition that carry out in OMW identical with reaction medium.

Advantageously, process for tanning (the so-called no chrome tanning that OMW is also used as process for tanning, does not use chromium preferably Technique processed) in tanning agent adjuvant.

Therefore, according to the present invention, OMW can be used in composition in chrome-free tanning technique with other tanning agents, such as example Such as oxazolidine, glutaraldehyde or dihydroxydiphenylsulisomer (DIDS), other tanning agents serve as the collaboration compound of known tanning compound (synergistic compound), such as will be apparent from experimental section.

In in terms of again other, the present invention relates to tanning composition (tanning composition), the tanning groups Closing object includes that olive oil is milled waste water (OMW) and suitable additive.

In other preferred embodiment, the present invention relates to tanning composition, the tanning composition includes olive oil Mill waste water (OMW) and one or more of tanning agents selected from the group being made up of: natural gallotannin, such as tower drawing, sensitive plant, Chestnut, myrobalan；Syntannin, for example, hydroxyl diphenyl sulphone (DPS), belong to phenolic resin family compound, belong to the change of naphthalene resin family Close object；Aldehyde or its precursor such as glutaraldehyde, isoxazole alkane, oxazolidine；Metal salt, such as chromic salts, zirconates or titanium salt；And propylene Acid resin, such as pass through acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylamide and its mixture Homopolymerization or free-radical polymerized acquisition resin, preferably at the acrylic resin of salt such as Sodium Polyacrylate (PA).

Preferably, the present invention relates to tanning composition, the tanning composition includes that olive oil is milled waste water (OMW) and extremely A kind of few acrylic resin, acrylic resin pass through acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, third The homopolymerization of acrylamide or free-radical polymerized acquisition, preferably at the acrylic resin of salt.

It is highly preferred that the acrylic resin is polyacrylic resin (PA).

Selectively, the acrylic resin passes through acrylic acid, methacrylic acid, methyl methacrylate, acrylic acid second The homopolymerization or free-radical polymerized acquisition that are carried out in OMW identical with reaction medium of ester, acrylamide, preferably at the third of salt Olefin(e) acid resin, such as Sodium Polyacrylate.

It preferably, is poly- by the acrylic resin obtained that polymerize carried out in OMW identical with reaction medium Sodium acrylate resin (PA).

Tanning composition of the invention be preferably included in from 2 to 20 in the range of, more preferably from 5 to 18 range Interior, the even more preferably ratio by weight between the OMW in the range of from 10 to 12 and one or more of tanning agents, institute It states one or more of tanning agents and is selected from the group being made up of: natural gallotannin, such as tower drawing, sensitive plant, chestnut, myrobalan；Synthesis Tannin, for example, hydroxyl diphenyl sulphone (DPS), belong to phenolic resin family compound, belong to the compound of naphthalene resin family；Aldehyde or its before Body, such as glutaraldehyde, isoxazole alkane, oxazolidine；Metal salt, such as chromic salts, zirconates or titanium salt；And acrylic resin, such as By the homopolymerization of acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylamide and its mixture or from The resin obtained by base copolymerization, preferably at the acrylic resin of salt, such as Sodium Polyacrylate (PA).

When OMW is used as the synergist (synergistic agent) of tanning compound or is used as unique tanning chemical combination When object, they additionally advantageously serve as the microorganism stabilizer of leather itself, that is, serve as the leather preservative in tanning step.

In fact, retanning is another step of leather tanning process, and it is by allowing to improve certain leather particulates Chemical treatment composition.In general, leather adsorbs other tanning substance or filler during retanning, so that it, which is provided, has It is expected that the final products of the richness of rank, flexibility, absorption of perspiration (sweat resistance) and more characteristic.In general, single Rather, chromic salts or other salt are used as retanning agent (retanning agent), and temperature condition and damp condition can be by chromium (III) be converted to chromium (VI), chromium (VI) be it is a kind of it has been known that there is agent toxic and carcinogenic, towards biosystem height aggressiveness, therefore It is impacted with high environmental pollution.

The waste water surprisingly, olive oil is milled is the result is that prevent the advantageous antioxygen for forming chromium (VI) in retanning step Agent, such as will be apparent from the experimental section of reported be-low.

Advantageously, in retanning step, it is included in 0.5kg and 2kg using what the dry leather of every kg was represented as the water of kg Between, the amount of processing water between preferably 0.8kg and 1.5kg.

Experimental section

Embodiment 1: assessment of the OMW as bactericide in the technique for impregnating rawhide

In order to confirm OMW anti-microbial effect, 6 Soak Tests are carried out in parallel to dry rawhide, compare experience to The performance (behavior) of the rawhide of lower immersion: only network water, the network water added with traditional antimicrobial or with it is variable The network water of the OMW mixing of amount.

OMW used in the embodiment has characteristic shown in following table 1:

Table 1

It tests as follows:

Test 1: the network water of dry rawhide+100% (kg rawhide/kg bath raio), at 25 DEG C, at jar mill (jar mill) Middle rotation lasts 2 hours (skip test)；

Test 2: dry rawhide+100% (kg rawhide/kg bath raio) resists added with commercially available dithiocarbamate The network water of microorganism agent, at 25 DEG C, rotation lasts 2 hours in jar mill；

Test 3: the network water+25%OMW of dry rawhide+75% (kg rawhide/kg bath raio), at 25 DEG C, in jar mill Rotation lasts 2 hours；

Test 4: the network water+50%OMW of dry rawhide+50% (kg rawhide/kg bath raio), at 25 DEG C, in jar mill Rotation lasts 2 hours；

Test 5: the network water+75%OMW of dry rawhide+25% (kg rawhide/kg bath raio), at 25 DEG C, in jar mill Rotation lasts 2 hours；

Test 6: the OMW of dry rawhide+100% (kg rawhide/kg bath raio), at 25 DEG C, rotation lasts 2 are small in jar mill When.

After the completion of the technique, opens tank and stay in the sample of the rawhide impregnated in this way in closed container (polybag) It stands to moisten and continues 24 hours, then in second day inspection sample.

Significant stench has been shown when tank is opened in the rawhide (test 1) individually impregnated in water.

Based on include between 0 and 3 number index evaluation rawhide bacterial degradation Olfactive evaluation (specifically: 0- without Smell；1- faint odor；2- moderate smell；3- overpowering odor) it summarizes in table 2 below:

Test No.	Olfactive evaluation index
		1	3
2	0
		3	3
4	2
		5	1
6	0

Table 2

As it will be evident that in the process the use of OMW allow stench to substantially reduce, be in high OMW concentration it is significant, especially It is the ratio (test 5 and test 6) between network water and OMW for 1:3 or bigger, i.e., for from 75% to 100% In the range of processing water OMW concentration.

Particularly, it in soaking technology, replaces network water (test 6) to allow to obtain use completely with OMW and is dispersed in network The usual performance (test 2) that traditional antimicrobial in water obtains.

In addition, carrying out tanning to test by the possible hide degradation effect for the microorganism charge induction being likely to form In industry typically with test, i.e., hair present in assessment rawhide is to the resistance of pulling.

This simply by hair is pulled out from rawhide the order of magnitude of applied power by using from 0 to 3 model Interior qualitative number index is enclosed to determine that (specifically: actually without applied force, hair is easy to be drawn out 0-；1- needs slight Power；2- needs the power of moderate；3- needs high intensity).

When rawhide is by microorganism attack, rawhide undergoes the dipping of corium, so that hair is easily removed (low resistance to drawing Value).

Exist to the result obtained from the pulling test that the 6 rawhide samples obtained in above-mentioned soaking technology carry out It is shown in following table 3.

The rawhide sample obtained from test No.	Resistance to pull index
		1	0
2	3
		3	0
4	1
		5	2
6	3

Table 3

The result obtained in the assessment of these test results and stench is completely the same.

Resistance to drawing property (the hair pull of higher hair is shown with the rawhide that the 50%OMW in processing water impregnates Resistance), more consistent for higher concentration, and for 100%OMW concentration, i.e., when network water is completely by OMW generation For when, or even it is suitable with the resistance to drawing property of hair realized with traditional immersion process.

Therefore, these test demonstrate based on always handled used in soaking step water preferably with by weight from 50% to 100% concentration, more preferably from 75% to 100%, even more preferably with the OMW of 100% concentration in rawhide Possibility and effective purposes in soaking step.

The assessment of embodiment 2:OMW tanning ability (OMW Tanning Capacity)

In order to assess the ability of OMW tan leather, using and modify in rawhide and leather industry typically use as follows Chambort-Jamet standardized method, Chambort-Jamet standardized method be based on absorption by German Forschungs What Institut f ü r Leder und Kunststoffbahneng GmbH was bought is named as Freiberg rawhide powder The determination of the ability of the tanning substance of standard rawhide.

According to this method, the measurement for being represented as the tanning ability of percentage is determined according to following formula:

Wherein Ci and Cf is initially and in the aqueous solution with tanning effect after being absorbed by standard rawhide respectively Tanning product concentration.

In order to assess the tanning effect of OMW, it is contemplated that they are typically used in " pure " product, such as tannery Commercially available tannin, using the solution of the identical total phenol concentration with business tanning solution of the product design in 4g/L.In this way Initial total phenol concentration be 2g/L.Therefore, the assessment of OMW tanning effect is not represented as the concentration of the dried residue in solution Variation, and be expressed as the variation of the concentration of total phenol.

According to the method for modification, the measurement for being represented as the tanning ability of percentage is determined according to following formula:

Wherein Pi and Pf is total initially and in the aqueous solution with tanning effect after being absorbed by standard rawhide Phenol concentration.In order to compare, the determination of total phenol is also carried out about business tanning solution.

By the amount of the phenol absorbed by rawhide, fixed output quota is raw really for the measurement of tanning ability (tanning power).It absorbs The percentage of phenol is higher, and the tanning ability of the agent used is bigger.

Test is carried out by following: the sample for preparing the identical initial concentration of the total phenol with about 2g/L (passes through Folin Ciocalteau method determine), and by the sample be committed to OMW or with tradition tannin (tower drawing, myrobalan, chestnut and Sensitive plant) tanning processing.

The result obtained in test is shown in following table 4.

Tanning agent	The phenol (%) of absorption
		OMW	82.94
Tower is drawn	91.71
		Myrobalan	86.75
Chestnut	90.20
		Sensitive plant	91.32

Table 4

It can be seen that the very high tanning ability that OMW shows about 83% from the result obtained, i.e., be equivalent to use completely The tanning ability of the vegatable tannin of vegetable tanning is made comparisons and is conventionally used to, vegatable tannin is showed about 87% and 92% Between tanning ability.

Assessment of the embodiment 3:OMW as preservative and tanning adjuvant

Certain leather tanning tests are carried out, it is (decomposed to eliminate as the microorganism stabilizer for rawhide to assess OMW Degree) and as the adjuvant in chrome-free tanning technique purposes.

It is tested by the way that OMW is used alone or is applied in combination by OMW with several chrome-free tanning agents.

Each test carries out four calf-skin rawhides in 50L volume drum；4 rawhides respectively have the instruction of 10Kg Weight.

Assessment for the anti-microbe ability of bath, the parameter of assessment are the control of the formation of stench and mould, and right In the active assessment of tanning, the parameter of assessment is the determination of shrinkage temperature (contraction temperature) Tg.It should examine Consider, in the case where the process for tanning carried out with tannin or aldehyde, this second parameter is usually in the range of from 70 DEG C to 80 DEG C.

Test 1: microorganism is stablized

Rawhide is taken out from wet work drum and is discharged from pickling bath (Pickle ' s bath), and is then shifted To the drum comprising tanning bath, tanning bath based on rawhide weight 100%OMW by being made and being heated to 30 DEG C.By 5% washing Sea salt is added to OMW, to bathe band of density to about 6 ° of Be.Then, make rawhide rotation lasts 2 hours in drum, then check The thickness of rawhide, and and the result is that permeated completely by OMW.As the confirmation for penetrating through skin thickness completely, bath color is shallower, This instruction rawhide has absorbed a certain amount of bath component.Since the technique for fixing of the tanning program for these types needs long Time, therefore rawhide is stood in horse back and is taken several days.

Following test is carried out to the rawhide so obtained:

A) climatic chamber (climate chamber) continues 7 days in 40 DEG C and 60% regulation of relative humidity.

As a result: there is no moulds or stench to be formed, and does not have organized degradation (decomposed) sign.

B) determination (the UNI EN ISO3380 of shrinkage temperature or gelatinization point (gelatinization temperature) Method).

As a result: Tg=60 DEG C.

Test (a) is shown, and OMW processing is effective in the microorganism of rawhide is stablized.

Test (b) shows 60 DEG C of shrinkage temperature, it means that the interested tanning activity of OMW.

Test 2: the microorganism stabilization and synergistic adjuvant of known tanning agent

Rawhide is discharged from taking-up in wet work drum and from pickling bath, and is then transferred to comprising tanning bath Drum, 5% oxazolidine that tanning bath is mixed by 100%OMW and previously with OMW are made and homogenize lasting 10 minutes.Then, make Rawhide rotation lasts 2 hours in drum, then check the thickness of rawhide, and and the result is that are permeated completely by OMW.

In parallel, in the case where replacing OMW using water, similar preparation is carried out.Continue standing rawhide in horse back After several days, following test is carried out:

C) climatic chamber continues 7 days in 40 DEG C and 60% regulation of relative humidity.

As a result: OMW bathes no mould or stench is formed, and does not have organized degradation (decomposed) sign.On the contrary, in water In the case where bath, from the point of view of microorganism viewpoint, observes that rawhide is not stablized, mould region occur.

D) determination (3380 method of UNI EN ISO) of shrinkage temperature or gelatinization point.

As a result: in the case where OMW bath, Tg=70 DEG C, in the case where water-bath, Tg=65 DEG C.

Test 2 is shown, and other than microorganism is stablized, OMW and Researches on Tanning of Oxazolidines act synergistically, the tanning energy of this enhancing bath (the test d) that power, such as 5 DEG C of the increase in the case where OMW is bathed through Tg prove.Particularly, OMW, which exists, allows to obtain and have There is the completely comparable Tg value of Tg value of the conventional tanning bath of aldehyde or tannin.

Test 3: the synergistic adjuvant of known tanning agent

In this test, we want to test tanning of the OMW in different OMW concentration values of the synergistic adjuvant as known tanning agent Ability.

Rawhide is discharged from taking-up in wet work drum and from pickling bath, and is then transferred into two bathed comprising tanning In a drum, 5% oxazolidine that tanning bath is mixed by 100%OMW and previously with OMW is made and homogenizes lasting 10 minutes.

Make rawhide rotation lasts 2 hours in drum, then check the thickness of rawhide, and and the result is that is permeated completely by OMW.

Then, with dihydroxydiphenylsulisomer (DIDS) tannin of the amount addition synthesis of the initial weight 40% based on rawhide, make They are rotating slowly lasting 1h, and then leave automatic rotation overnight.

Check again for them in the morning；Tanning agent has been absorbed in the whole thickness of rawhide, and rawhide is fully filled (tanning).

The pH of bath is 3.7, and instruction tannin and other tanning compounds are at least partly fixed by rawhide.

After rawhide to be rested on to horse back and is taken several days, shrinkage temperature is determined, as a result,

E) with the bath of 50%OMW, 5% oxazolidine, 40%DIDS: Tg=74 DEG C

F) with the bath of 100%OMW, 5% oxazolidine, 40%DIDS: Tg=77 DEG C

Test 3 also shows that OMW is synergistically acted on oxazolidine and DIDS tanning agent, as proved by the high tg values obtained, It is generally suitable with Tg value obtainable in conventional process for tanning, Tg value with tanning bathe in OMW concentration increase and increase.

Test 4: it is tested in tanning with the Chrome-free plant sample tanning of OMW adjuvant

Tanning test is carried out on pickling rawhide, that is, is acidified until the pH that tanning is bathed is in 2.8-2.9.

Acidification is compulsory for any kind of tanning in bath, because of previously alkaline matter used in epilation phase It must remove from rawhide fiber to modify rawhide isoelectric point, to help tanning molecule (natural gallotannin, chromium) to enter, then lead to It crosses modification isoelectric point again to react tanning molecule with rawhide, in fact this rises the pH (and therefore pH of rawhide itself) of bath Up to about 3.8-4.0.

Test is by the way that tanning agent to be added directly to carry out in pickling bath.

In these tests, using both OMW and the OMW added with polyacrylic resin.

Particularly, I is tested in two kinds of tannings described below comprising the OMW or OMW with polyacrylic resin itself It is related to forming in detail below with II:

I) 60% pickling bath+70%OMW+ acrylic resin Sodium Polyacrylate

II) 60% pickling bath+70%OMW

The formula that I and II is tested for two kinds is as follows: for pickling rawhide, OMW is added with pickling bath (tanning bath)；For The glutaraldehyde of by weight 6% modification and by weight 1.5% long-chain alcohol sulfosuccinate are also added in the bath (long chain alcohol sulfosuccinate), then makes tank rotation lasts 180 minutes.

Then, the modified dihydroxydiphenylsulisomer of addition 2.0%, and make tank rotation lasts other 180 minutes.

Finally, especially polyacrylic resin is added to test I and test II by 5.0% tanning acrylic resin Bath, and then by they leave rotation overnight (8 hours).

Tanning is bathed and is discharged, and washed with 100% cold water and 1.0% sodium acetate by morning, by rawhide It is cleaned from any residue of used product.

Then, make to be wrapped in stand in Nylon Bag to avoid over-drying rawhide and continue a few houres, measure its Tg later (shrinkage temperature, according to UNI EN ISO 3380:2015).

Rawhide needs to stand at high humidity, primarily to the chemicals of absorption is homogenized, this allows them uniformly Ground is distributed in entire rawhide thickness.Within the time period, allow the completion chemically reacted, which actually exhausts glue Still loose any residual chemicals in former albumen.

The weight for being all based on the pickling rawhide being discharged from pickling bath of percentage above.

The Tg result (the Tg result measured three times/every rawhide) tested three times is as follows:

I) Tg=82 DEG C, 82 DEG C, 83 DEG C-average value: 82 DEG C；

II) Tg=78 DEG C, 79 DEG C, 77 DEG C-average value: 78 DEG C；

First observation of the test result extremely positive to these is considered based on following: the typical Tg values of chrome tanning are 100 DEG C, the maximum value of vegetable tanning (natural gallotannin) is 80 DEG C, and for aldehyde tannage system, is worth typically from 70 DEG C -77 DEG C In range, thus it is evident that with the OMW acquisition comprising acrylic resin and not comprising both acrylic resins from 78 DEG C Tg value in the range of to 82 DEG C have been shown it is substantially uniform with the Tg value obtained by other chrome-free tannings, sometimes even more It is excellent.

Then, OMW allows to obtain extremely high performance tanning bath as the purposes of tanning adjuvant.

Best Tg value obtains in test I, wherein there is also the acrylic resins polymerizeing in OMW, such as under previous occasion, When being used together with other traditional chrome-free tanning agents, the OMW that test I is shown in tanning step assists ability.

Embodiment 4: the assessment of the tanning ability of the OMW composition of the acrylic resin comprising various amounts

As being described in detail in example 2 above, Chambort-Jamet standardized method is for assessing the propylene mixed with OMW The tanning ability of acid resin.

Then, fixed output quota is raw really for the dry matter content for the tanning agent that the measurement of tanning ability is absorbed by standard rawhide.

The test by preparing there is the tanning solution of the dry matter of the identical initial concentration of whole of about 4g/L to carry out.

Test 1

For this test, two kinds of differences comprising OMW and polyacrylic resin (PA) in two kinds of various concentrations are prepared Solution, that is:

Mixture 1- is prepared in room temperature by stirring by using common mechanical agitator or magnetic stirring apparatus, and 80% (w/w) OMW of PA and 20% (w/w)；

Mixture 2- is prepared in room temperature by stirring by using common mechanical agitator or magnetic stirring apparatus, and 42% (w/w) OMW of PA and 58% (w/w).

The characteristic of the OMW used is shown in following table 5.

Table 5

And the characteristic of used polyacrylic resin is listed in following table 6.

Table 6

Mixture 1 and mixture 2 and in order to compare individually PA resin, are used for tanning hide sample according to UNI EN ISO 3380:2015 method also determines Tg shrinkage temperature.

Specifically, tanning test is carried out to pickling rawhide in jar mill, acidification is in 2.8- until the pH that tanning is bathed 2.9.It is tested by the way that the tanning agent of 5% concentration is added directly to pickling bath, and rotates it overnight (8 hours).

Tanning is bathed and is discharged, and washed with 100% cold water and 1.0% sodium acetate by morning, by rawhide It is cleaned from any residue of the product used.

By comparing with individually polyacrylic resin (PA) and with two kinds of mixtures 1 and 2 obtain a series of senses The property of interest such as tanning ability and Tg value are come the test result listed in the following table 7 that collects.

Table 7

According to these tests, compared to what is observed for individually resin, it is blended the OMW's for having polyacrylic resin Use the increase that highly significant is both generated in tanning ability and Tg.Particularly, feature is the mixture 2 of the OMW of higher amount Seem that optimum performance is presented.

Be conducive to OMW in view of the amount for reducing PA resin, this is interested aspect, in both cost and reduction environmental impact The significant consequence of aspect and both the disposition of OMW and the generation of PA resin are related.

Test 2

In order to prepare the mixture of denseer acrylic resin and OMW, especially in terms of polyphenol, such as allusion quotation in tanning industry It needs to type, prepares two kinds of other mixtures.

Mixture 3- is prepared in room temperature by stirring by using common mechanical agitator or magnetic stirring apparatus, and 30% (w/w) OMW of PA and 70% (w/w)；

Mixture 4- is prepared in room temperature by stirring by using common mechanical agitator or magnetic stirring apparatus, and 20% (w/w) OMW of PA and 80% (w/w).

Two kinds of mixtures are concentrated on a rotary evaporator in 70 DEG C and 500 millibars, until the drying for obtaining about 40% is residual Excess.

Similar to previous test, the identical method of sequence is abided by, using 4 tanning hide of mixture 3 and mixture, to determine Tg。

It is shown in following table 8 with the result of these mixtures 3 and 4 processing rawhide, always and individually at PA resin The result that reason obtains is compared.

Table 8

In addition in the case, being blended has the use of the OMW of polyacrylic resin in the tanning ability and rawhide of solution Tg in generate it is significant increase, in the case where mixture 4 of higher OMW content, significant increase is maximum value.

Therefore from these tests, can be inferred that OMW largely confirms to increase the tanning of traditional tanning agent The ability of ability is enable to acutely reduce the amount used in the technique, and wherein cost and environmental impact substantially reduces It is related with both OMW disposition and the generation of chemicals.

Test 3

Two kinds of other OMW and resin compound, mixture 5 and mixture 6 are prepared, wherein current polyacrylic resin Pass through the directly free radical polymerization acquisition in identical OMW (being used as polymerisation medium).

Particularly, using two different OMW, referred to as OMW1 and OMW2, their characteristic is listed in following table 9.

Characteristic	OMW1	OMW2
			pH	4.68	4.71
Suspended solid (mg/L)	69,025	5,893
			Dried residue (%)	9.09	3.13
Total polyphenols (mg/L)	2,058.33	5,283.33
			Hydroxytyrosol (mg/L)	514.46	1,834.70
Tanning ability (%)	79.03	47.73

Table 9

According to previously described method, by the solution of the resin in the OMW so obtained, referred to as mixture 5 (is wherein set Rouge is obtained by the direct polymerization in OMW1) and mixture 6 (wherein resin is obtained by the direct polymerization in OMW2), for true Determine their tanning ability and for tanning hide to determine Tg.

It is shown in following table 10 with the result of these mixtures 5 and 6 processing rawhide, always and individually at PA resin The result that reason obtains is compared.

Characteristic	PA	Mixture 5	Mixture 6
				Dried residue (%)	30.08	38.20	41.00
In 10% pH	5.69	5.43	5.43
				Brook viscosity (cPs)	8,020	5,030	3,486
Total polyphenols (mg/L)	0	11,067	12,083
				Hydroxytyrosol (mg/L)	0	1,894	2,861
Tanning ability (%)	11.47	21.04	35.99
				Tg(℃)	67	70	72

Table 10

Excellent performance of the OMW mixture in terms of tanning ability is also shown in these tests, it is characterised in that resin is current It is obtained by the direct polymerization in OMW.

This evidence is extremely important, because preparing both relevant production cost and environmental impact to resin by reducing, it The reduction of many techniques needed for the tanning mixture for allowing to assume to obtain OMW and resin, it is contemplated that in identical OMW directly A possibility that being polymerize.

Embodiment 5:OMW prevents the assessment of the oxidation resistance of the formation of chromium VI in the leather of chrome tanning

Presence or absence of the acrylic resin Sodium Polyacrylate obtained by the polymerization technique carried out in identical OMW (PA) under, using chrome tanning wet-blue leather (chromium tanned wet-blue leather) and standard will be used The result that retanning formula obtains carries out this test, the standard retanning formula compared with the result obtained by using retanning step Fish oil as tannin and using fatting agent as sulfiting is drawn using vegatable tannin tower, in the retanning step, place Reason water-bath is replaced by OMW (150%, the weight based on leather) and the drawing of vegatable tannin tower is eliminated.Handle whole works of leather Skill is described in following table 11.

Particularly, it by forming typical formula to obtain the product of vegetalization type, is carried out on the leather of chrome tanning Retanning step (wet-blue), wherein looks similar to the leather of vegetable tanning in terms of leather.

In retanning process, the fish oil of sulfiting is used during fatliquoring steps, it is contemplated that the unsaturation of high-content point Sub- site, the fish oil of sulfiting are the strong promotions by environmental condition such as temperature and humidity triggering of radical ion process Agent, this leads to be typically secured to the fixation of the chromium III in the collagenous fibres of leather by being oxidized to chromium VI, chromium VI be released and It can be determined according to international method UNI EN ISO 17075 by spectrometer.

Table 11

Thus obtained leather is left into standing and continues one day, to allow product to be evenly distributed on entire leather thicknesses In；Then, many drying processes are carried out, including use vacuum machine, hot-rolling machine, and be then displayed in top-type conveyer For being further dried in (overhead conveyor).However, in the case, it is contemplated that chromium VI is formed, and leather will Serious damp condition and heat condition are undergone, is displayed in top-type conveyer and only carries out continuing half a day, be followed by for chromium VI The adjusting program of test.

In order to help the formation of Cr VI, the leather of acquisition is committed to following adjusting technique:

Adjust 1: (iron halide UV lamp, JELOSIL HG200L emit 300W/ for 24 hours under the UV irradiation far from source 30cm m², power in the range of 320nm-400nm), T30 DEG C, relative humidity 55%；

Adjust 2: in 60 DEG C, the climatic chamber of relative humidity 90% (the big condition of more pressure) for 24 hours.

The determination of Cr VI in leather sample is carried out according to UNI EN ISO 17075:2008 method.As a result in following table It is shown in 12.

Table 12

As from it can be inferred that in table 12, there are under tanning acrylic resin Sodium Polyacrylate and be not present tanning Both under acrylic resin Sodium Polyacrylate, OMW inhibits the formation of chromium VI excellently under two kinds of experiment conditions, thus proves It is the highly effective antioxidant of the retanning step for leather tanning process.

Embodiment 6: the Cr by means of the tanning resin with different antioxidant properties polymerizeing in OMW, in aqueous solution (VI) assessment of ability is reduced.

It is carried out using three kinds obtained by direct polymerization in OMW different types of resins (resin 1, resin 2 and resin 3) This test；The characteristic of these three resins is shown in following table 13.

Resin properties	Resin 1	Resin 2	Resin 3
				Dry (%)	35.70	35.06	33.00
In 10% pH	5.25	4.70	5.04
				Brook viscosity (cPs)	2,862	3,180	3,547
Polyphenol (mg/L) on TQ	21,583	33,300	23,647
				Oxidation resistance (mg GA/L)	6,894	22,310	19,490

Table 13

To the K of Cr (VI) concentration with about 30mg/L₂Cr₂O₇Solution add different amounts of three kinds of resins, carry out multiple Test, so that their initial concentrations in the potassium dichromate aqueous solution are 10%, 5% and 1% (w/w).

Subsequently, for each test, in the resin 1, resin 2 and resin 3 that will have 10%, 5% and 1% initial concentration It is added to after potassium bichromate solution 1 hour, 3 hours and 4 hours, evaluation is referred to as the percentage of red Cr (VI) the content reduction of % Than.

The result obtained from these tests is shown in following table 14.

Table 14

Such as the result shown in the table 14 it will be evident that all resins (1,2 and 3) polymerizeing in OMW show it is very high Reducing power.

As a result it also shows that by using the resin with the greater than about high anti-oxidation ability of 20,000mgGA/L, such as with tree Rouge 2 is also enough to realize the complete reduction of Cr (VI) to Cr (III) even if resin concentration is lower than 1%.

Claims

Purposes of the waste water (OMW) at least one step in the leather tanning process in tanning industry 1. olive is milled.
2. purposes according to claim 1, wherein the olive is milled, waste water (OMW) has in the range of from 2 to 8 PH, suspended solids content in the range of from 10,000mg/L to 100,000mg/L, by weight from 1% to 12% Dried residue in range, total phenol content in the range of from 100 to 15,000 are (according to according to Folin Ciocalteau What method determined, it is represented as gallic acid mg equivalent/L OMW) and in the hydroxyl in the range of from 25mg/L to 5,000mg/L Base tyrosol content (according to what is determined by HPLC-UV DAD).
3. purposes according to claim 1 or 2, wherein the olive is milled, waste water is previous experience by using nitrogen treatment The olives of antihunt means mill waste water.
4. purposes according to any one of claim 1 to 3, wherein the mill purposes of waste water of olive is as described Bactericide at least one step of the leather tanning process in tanning industry.
5. purposes according to claim 4, wherein the step of the leather tanning process is soaking step.
6. purposes according to claim 5, wherein the olive is milled, waste water (OMW) is with pressing based on total leather processing water The amount of poidometer from 50% to 100% is preferably made with from 75% to 100% amount, even more preferably with 100% amount With.
7. purposes according to claim 4, wherein the step of the leather tanning process is tanning step.
8. purposes according to any one of claim 1 to 3, wherein the mill purposes of waste water of olive is as described Tanning agent or tanning adjuvant in the tanning step of the leather tanning process in tanning industry.
9. purposes according to claim 8, wherein the olive is milled, waste water (OMW) is to press weight based on leather processing water The amount of meter from 50% to 100% is preferably made with from 75% to 100% amount, even more preferably with 100% amount With.
10. purposes according to claim 8 or claim 9, wherein the olive is milled waste water (OMW) with selected from being made up of Other tanning agents of group are applied in combination: natural gallotannin, such as tower drawing, sensitive plant, chestnut, myrobalan；Syntannin, such as hydroxyl hexichol Sulfone, the compound for belonging to phenolic resin family, the compound for belonging to naphthalene resin family；Aldehyde or its precursor, such as glutaraldehyde, different evil Oxazolidine, oxazolidine；Metal salt, such as chromic salts, zirconates or titanium salt；And acrylic resin, such as pass through acrylic acid for example poly- third Olefin(e) acid sodium, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylamide and its mixture homopolymerization or free radical It is copolymerized the resin obtained, preferably at the acrylic resin of salt, such as Sodium Polyacrylate (PA).
11. purposes according to claim 10, wherein the olive is milled, waste water (OMW) is combined with Sodium Polyacrylate (PA) It uses.
12. purposes described in 0 to 11 according to claim 1, wherein the acrylic resin passes through identical with reaction medium Olive is milled the homopolymerization or free-radical polymerized acquisition carried out in waste water (OMW).
13. the purposes according to any one of claim 8 to 12, wherein the leather tanning work in tanning industry The step of skill is chrome-free tanning step.
14. purposes according to any one of claim 1 to 3, wherein the mill purposes of waste water of olive is as anti- Oxidant, to prevent from forming chromium (VI) in retanning step.
15. purposes according to claim 14, wherein the olive is milled, waste water (OMW) is based on total leather processing water By weight from 50% to 100% amount, preferably from 75% to 100% amount, even more preferably made with 100% amount With.
16. a kind of bactericide composition, mill waste water (OMW) itself and suitable additive comprising olive.
17. a kind of tanning composition, mill waste water (OMW) and suitable additive comprising olive.
18. composition according to claim 17, wherein the composition also includes one selected from the group being made up of Kind or more tanning agent: natural gallotannin, such as tower drawing, sensitive plant, chestnut, myrobalan；Syntannin, such as hydroxyl diphenyl sulphone (DPS), category In phenolic resin family compound, belong to the compound of naphthalene resin family；Aldehyde or its precursor, for example, glutaraldehyde, isoxazole alkane, Oxazolidine；Metal salt, such as chromic salts, zirconates or titanium salt；And acrylic resin, such as pass through acrylic acid such as polyacrylic acid The homopolymerization or free-radical polymerized of sodium, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylamide and its mixture The resin of acquisition, preferably at the acrylic resin of salt, such as Sodium Polyacrylate (PA).
19. composition according to claim 18, waste water (OMW) and Sodium Polyacrylate (PA) group wherein the olive is milled It closes and uses.
20. composition described in any one of 7 to 19 according to claim 1, wherein the acrylic resin by with react The identical olive of medium is milled the homopolymerization or free-radical polymerized acquisition carried out in waste water (OMW).
21. composition according to claim 18, wherein olive is milled between waste water (OMW) and one or more of tanning agents Weight ratio in the range of from 2 to 20, preferably from 5 to 18, more preferably from 10 to 12.
22. a kind of anti-oxidant compositions, the anti-oxidant compositions prevent the formation of chromium (VI), institute during retanning step Stating anti-oxidant compositions includes oil mill waste water (OMW) and suitable additive.