FR2482867A1 - MEMBRANE FOR THE REGENERATION OF OILS - Google Patents

Abstract

FILTERING MEMBRANE FOR THE REGENERATION OF OILS IN HOUSEHOLD OR ARTISANAL USE. THIS MEMBRANE CONSISTS ESSENTIALLY OF 5 TO 95 PARTS OF A FIBROUS PAPER PULP MATERIAL AND 95 TO 5 PARTS OF AN ABSORBENT MATERIAL, BY WEIGHT, PER 100 PARTS BY TOTAL WEIGHT.

Description

The present invention relates to a filamentary membrane

  trante planned for the regeneration of oils and especially to

  a membrane for regenerating the oils in household use

  manages or artisanal, by adsorption and filtration of the resulting impurities.

  both of the degradation of a used oil. The invention will be described in more detail below with reference to the regeneration of edible oils, and in particular cooking oils. But it is clear that this is only a particular example of used oil, and that the invention applies

  obviously to the regeneration of many types of used oils.

  The edible oil used for frying

  gnets, fish, etc., is degraded by chemical modification

  such as oxidation, polymerisation, etc., and the repeated use of

  frying oil leads to a deterioration of the taste of

  fried duitings due to a transfer of odors from the oil to the materials

  fries, for example fish or meat.

  The currently commercially available devices for the regeneration of edible oils in household use, in particular for regenerating spent cooking oil containing impurities as described above, have been designed primarily for filtering out solids. contained in the waste oil, so that the products, degradation in solution

  in oil and odors are virtually not eliminated.

  As a result of extensive research, we have now discovered that a filter-adsorbent membrane obtained by combining pulp fibrous materials and adsorbent material solves the problems described above, and avoids adding to the oil a fine powder, thus allowing a

  purification of the used oil without agitation.

  The invention therefore relates to a filter membrane designed for the regeneration of oils, which membrane consists essentially of 5 to 95 parts by weight of a fibrous material for pulp and 5 parts by weight of an adsorbent substance, per 100 parts

by weight of the membrane.

  Other features and advantages of the invention

  more clearly from the detailed description given below.

  FIG. 1 and 2 show a trapezoidal filter according to the invention; and FIG. 3 represents in perspective the same filter,

open for use.

  It is known that oils commonly have a high viscosity so that their filtration on a filter membrane such as filter paper or filter cloth is extremely slow at ordinary temperature (eg, about 40 ° C or less). At elevated temperatures (e.g., about 60 ° C or more), however, the viscosity decreases and the filtration rate is higher. However, the tests carried out by the applicant have shown that the degree of purification of an oil by adsorption increases when the temperature of the oil increases. This relationship between temperature and adsorption rate may be due to the variation of the permeability of the oil with respect to

  the adsorbent, which is a function of the viscosity of the oil.

  The applicant has discovered that this improvement in the degree of purification by adsorption, obtained by increasing the temperature of the oil, made it possible to solve the problems posed by the increase in the filtration rate; thus, a hot oil, immediately after being used for frying, can be sufficiently purified by passing once through an adsorbent layer in the form of a membrane,

what constitutes the invention.

  In addition, when an adsorbent substance such as activated clay or diatomaceous earth is used, in powder form to purify an oil, it must be disposed of

  separately from a tank for used oil, an adsorption container

  a filter and a receiver for the purified oil, so

  that it is inevitably a large installation.

  Such a system is difficult to compact for the regeneration treatment of a relatively small amount of waste oil, such as

  this is the case in household or craft use.

  More particularly, when a degraded oil is used as a result of the use for the preparation of donuts in a funnel-shaped filter membrane, for example according to the invention, the oil enters the porous outer wall and is filtered but during this filtration, the degradation products contained in the oil and the odorous compounds are adsorbed; at the same time, solid substances such as particles of fried or carbonized material are separated by filtration

  and a purified oil is obtained in the filtrate.

  Among the adsorbents that can be used in the

  porous mineral solid adsorbents such as activated clay, acidic clay, diatomaceous earth, aluminum hydroxide gel, activated alumina, silica gel,

  zeolite, calcium oxide or activated carbon. We can use them

  read alone or in combination of two or more of them. The

  particle size of the granular adsorbent substance or pulp

  is not a particularly critical factor but

  usually substances with a parti-

  average (average diameter) 500, u or less.

  Among the adsorbents described above, those of the montmorillonite class such as activated clay and acidic clay are the most advantageous because they have a high capacity for regeneration of oils and are inexpensive. However, they have a special smell and in some cases the smell is transferred to the oil. However, it has now been found that this smell was

  frequently due to acidic substances such as hydrogen sulphide

  gene, which can be removed by treating the clays with an aqueous solution of an alkaline substance. Therefore, the adsorbents of the class montmorillonites used in the invention are

  preferably treated with an alkaline substance in aqueous solution.

  Among these alkaline substances, mention may be made, for example, of hydroxide

  potassium hydroxide, sodium hydroxide, calcium hydroxide, car-

  sodium carbonate, potassium carbonate, potassium bicarbonate

  sium and sodium bicarbonate. They can be used alone or

  combination between them. The pH of treatment is not a factor

  particularly critical, but preferably the pH of the filter cake obtained by neutralizing an aqueous suspension of a montmorillonite grade substance with an aqueous alkaline solution and filtering the suspension (and when it is necessary, a new neutralization with an acid, for example hydrochloric acid, followed by washing with water)

  is preferably 7.0 or below and more preferably 3.0 to 6.0.

  In the case where an alkali is added to a clay and then an acid, the alkali addition pH will preferably not exceed 9.0. If the pH

  the addition of alkali is 7 or less, it is not

  first necessary to neutralize by. an acid.

  The fibrous materials for paper pulp to be used in the invention consist of natural or synthetic fibers and their nature is not a particularly critical factor as long as the fibers have a sufficient resistance to heat and meet the requirements of the invention. food hygiene. However, high purity and high tenacity plant fibers such as cotton, hemp, viscose rayon fibers, etc., are preferred. Thin, long and hydrophilic fibers are preferred. The fibrous material for pulp for use in the invention is not necessarily of a single type and can be

  use in combination two or more

paper pulp.

  The filter membrane used for the regeneration of oils according to the invention is composed of 5 to 95 parts by weight of fiber material for pulp and 95 to 5 parts by weight

  of adsorbent substance. In general, membrane membranes are preferred.

  20 to 40 parts by weight of fibrous material for pulp and 80 to 60 parts by weight of adsorbent substance because they have a good oil regeneration efficiency, although this efficiency depends on the nature of the fibrous materials

and the adsorbent substance.

  The filter membranes for regeneration of the oils according to the invention are prepared generally by mixing

  fibrous materials for pulp and adsorbents

  bantes in water, thus forming a dispersion that is filtered in a porous metal mold or on a wire cloth; thus obtaining a membrane, and the type of membrane thus prepared is not limited to those formed of a uniform layer of fibrous material for pulp and adsorbent substance; membranes can be formed

  having a stratified structure with two or more different layers

  the relative proportions of fibrous material and adsorbent substance. For example,. membranes having an upper layer which contains a large amount of adsorbent and a lower layer containing the fibrous materials alone, membranes having upper and lower layers containing a large amount of fibrous material and separated by an intermediate layer of adsorbent substance, membranes further comprising an outer layer of fine paper, with an intermediate layer of fibrous material and adsorbent to prevent escape of the adsorbent contained in the membranes

  during transport or use.

  The filter membrane for regeneration of the oils according to the invention can be used in sheet form as

  filter medium to be placed on the porous bottom plate of a filter.

  But we can also give the membrane the shape of a funnel for filtration and purification on the entire wall of the funnel. In addition, a funnel can be formed by combining several membrane sheets. In this case, the materials for joining the sheets are preferably themselves oil-impermeable and flexible sheets such as regenerated cellulose films, polyamide resin films, polycarbonate films, and the like. In the case where the sheet-shaped membrane is placed

  at the bottom of a filter, it is extremely difficult to prevent

  leaks of oil around the membrane even when the

  The latter's shape is such that it avoids openings, and part of the oil leaks around the membrane instead of crossing it, resulting in insufficient adsorption and purification results. When the membrane is funneled, an oil introduced into the funnel necessarily passes through the membrane which constitutes the wall, so that the oil is fully regenerated. However, these funnels are bulky and therefore have the disadvantage of requiring a lot of space for transportation, shopping and marketing. This disadvantage can be remedied by folding the funnels obtained by association

  more leaves by means of a flexible sheet, less

  binder, as shown in the figures of the accompanying drawing.

  The capacity of the funnel for regeneration of

  oils can range from 0.5 to 10 liters; however, for the use

  As a housewife, a size of 1.5 to 1.2 liters is preferable from the point of view of ease of handling. For reasons of efficiency

  regeneration and mechanical resistance, the

  funnel with the capacity, and the thickness is usually

0.1 to 3.0 mm.

  The shape of the oil regeneration funnel is not a particularly critical factor, but the opening of the funnel is preferably wide enough that the used oil contained in a frying pan can be easily poured. For example, forms of conical circular cone, inverted elliptical cone, inverse pyramid, or the same shapes.

  wrinkled, inverted trunk or trunk

  mide inverted bottom, cylinder bottom or relangled conduit

  thoroughly, or other arbitrary forms can be used.

  The optimum temperature of the puri fi ed oil

  proud using the membrane according to the invention may vary according to Ies

  characteristics of the adsorbent substance and the nature of huiie.

  However, in general, a higher temperature leads to better regeneration efficiency as long as the oil does not undergo decomposition or chemical modification.

  best results are obtained at temperatures of 80 160Q C.

  Since the temperature used for frying is usually used

  of about 180 ° C, the frying oil is preferably immnd.a

  in the funnel after use, taking into account that the oil

  cools down and then goes into the temperature range cp-

  when it is poured into a filter or an enton-

  regenerating black. If it is desired to regenerate a degraded oil after cooling, it is preferable to maintain it at a temperature of 60 ° C. or above because the viscosity of the oil is then decreased, the filtration speed and the efficiency of the oil are increased. 'adsorption

and purification.

  A filter comprising the oil regeneration funnel

  according to the invention does not always have a container (for example the

  funnel can be arranged on a ring-shaped support but the filter can be maintained for use on the oil receiver

  regenerated (preservation container), so as to avoid trans-

  regenerated oil in another container and to facilitate

the manipulations of the oil.

  It is also possible to improve the adsorption efficiency and filtration rate by maintaining the temperature of the oil to be regenerated to a defined level which can be achieved by equipping the support itself with a heater or by placing the support in a Dewar vase. The examples which follow illustrate the invention without, however, limiting its scope; in these examples the indications of

  parts and percentages are by weight unless otherwise indicated.

Example 1

  1.5 g of capacity are introduced into a mixer and 10 g of cotton pulp and 30 g of activated clay are mixed for 5 minutes (commercial product Galleon earth V2R from the firm Mizusawa).

  Industrial Chemicals Ltd.) and 1200 g of demineralized water.

  -We then place on a vacuum container a mold

  porous metal in the shape of an inverted trunk (greater diameter

  120 mm, bottom diameter 100 mm, height 110 mm, pore diameter 1 mm) and the mixture described above is dehydrated on the metal mold by applying the vacuum with a pump on the part outer porous metal mold. We thus form a

  funnel in the shape of an inverted trunk, open to the upper part

  pool. The funnel (still in place on the porous metal mold) is dried at 110C for 30 minutes in a dryer and then

  cooled to room temperature; it is then removed from the metal mold

  lic; the article obtained is a funnel for regeneration of oils

  edible, weighing about 30 g, at an average thickness of 0.8 mm.

  160 g of oil which was used for frying (salad oil used for the preparation of donuts of vegetables, fish and meat, to reason

  twice for each of these constituents).

  The light transmission coefficient and the odor of the original oil, the oil sent to the regeneration (degraded oil) and the regenerated oil are shown in Table I below.

Example 2

  We operate as in Example 1 but we form the enton-

  black with 10 g of cotton pulp, 20 g of the same activated clay as in Example 1, 10 g of diatomaceous earth (from Kanto Chemical Co., Inc.) and 1200 g of demineralised water. Regeneration

  is carried out with the same degraded oil as in Example 1.

  The results of the regeneration are reported in Table I below.

Example 3

  The procedure is as described in Example 1 but using

  8 g of cotton pulp, 2 g of viscose rayon pulp (from Toyo Spinning Co., Ltd.), 28 g of the same activated clay as in Example 1, 7 g of bentonite (hydrated aluminosilicate of the

  Kanto Chemical Co., Ltd.) and 1200 g of demineralized water.

  The same degraded oil is regenerated as in Example 1.

  The results of the regeneration are reported in

- Table I below.

Example 4

  The procedure is as in Example 1 but using 8 g of cotton pulp, 23 g of the same activated clay as in Example 1, 8 g of alumina gel (Kyowa Chemical Industry Co., Ltd. .) and 1200 g of demineralised water. We regenerate the same degraded oil

than in Example 1.

  The results of the regeneration are reported in

Table I below.

Example 5

  We put a high quality paper (from Mitsu

  bishi Paper Mills, Ltd., thickness 40, u, basis weight 9.2 g / m 2) under

  the funnel shape inside a porous metal mold iden--

to that of example 1.-

  Inside this paper without wood, we throw and dehydrate a mixture of 10 g of cotton pulp, 30 g of the same

  activated clay as in Example 1 and 1200 g of demineralized water.

  The other operations are carried out in the same manner as in Example 1. With the funnel obtained, the degraded oil is regenerated.

of Example 1.

  The results of the regeneration are reported in

Table I below.

Example 6

  The procedure is as in Example 1 but using 10 g of cotton pulp and 1200 g of demineralized water; we thus form a funnel. In this funnel, a mixture of 10 g of cotton pulp, 30 g of the activated clay of Example 1 and 1200 g of demineralized water is discarded and is dehydrated, thus forming a two-layer funnel which weighs 25 g. but has an average thickness of

1.5 mm.-

  Oil regeneration results are reported

in Table I below.

  Comparative Example 1 60 g of the activated clay of Example 1 are introduced into 800 g of the same oil as in Example 1 (cooled to 1600 ° C.) which was used for the preparation of donuts and mixed

  for 2 minutes using a stirrer.

  The mixture was then filtered on filter paper (qualitative analysis filter paper n02 from Toyo Roshi Co., Ltd.) placed on a glass funnel; the results obtained in this

  example are reported in Table I below.

  A funnel is formed by operating as described in Example 1 but using 10 g of cotton pulp and 1200 g of demineralised water. The same regeneration tests are carried out.

  degraded oil as in Example 1.

  The results obtained are reported in Table I below.

TABLE I

  Example 1 light transmission coefficient,% odor Example 2 light transmission coefficient,% _ odor Example 3 light transmission coefficient,% odor Example 4 light transmission coefficient,% odor Example 5 transmission coefficient - light,% odor Example 6 light transmission coefficient,% odor Example comparative coefficient 1 light transmission,% odor Example comparative coefficient 2 light transmission,% odor oil of origin 87.9 no 87.9 no 87, 9 no 87.9 no 87.9 no 87.9 no 87.9 no 87.9 no oil degraded oil regenerated

37.0 76.2

  yes 37.0 yes 37.0 yes 37.0 yes 37.0 yes 37.0 yes 37.0 yes 37.0 yes no 82, 8 no 84.5 no 89.2 no 79.0 no 87.5 no 93.3 no 51.2 yes The light transmission coefficients given in Table I are those corresponding to light at 450 m, measured with the aid of an automatic recording spectrophotometer from Hitachi, Ltd, on a sample and a standard (distilled water) in a quartz cell of 10 x 10 x 30 mm; the odor is appreciated at room temperature; when the oil sample has an odor different from that of the original oil, the existence of

of this smell by "yes".

  The results reported in Table I clearly show that the results obtained in Examples 1 to 6 according to the invention are essentially identical to those obtained in Comparative Example 1 and greater than those obtained in the example

comparative 2.

  However, Comparative Example 1 requires complicated operations because the activated clay must be retained by filtration.

On paper.

  Other characteristics of the oils have been determined,

  namely the acid number (IA), the peroxide index (PI) and the

  foaming properties; the results obtained are reported in Table II below: it can be seen that the funnels according to the invention give results much higher than those obtained

  with commercial oil filters.

TABLE II

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example

comparative 1

Example

  comparative 2 IA IP foams IA IP foams IA IP foams IA IP

mousses-

  IA IP Foams IA IP Foams IA IP Foams IA IP Foams Original Oil 0, 04 1.66 0.04 1.66 0.04

- 1.66

  0.04 1.66 0.04 1.66 - 0.04 1.66 0.04 1.66 0.04 1.66 V 10 degraded oil 4, 56 78.50 4.56 78.50 4.56 78.50 4.56 78.50 4.56 78.50 4.56 78.50 4.56 - i 78.50 4.56 78.50 regenerated oil 0.88 2.50 1.00 3.65 0 , 95 3.80 0.65. 2.00 1.00 I6 0.35 2.30 0.68 2.30 4.50, 00 54: - Note The acid number, expressed in mg KOH / g, is measured by the

Shibsted method.

  The peroxide index, in meq./kg * is measured by the method

from Wheeler.

  The foam formations in mm are determined as follows: a 40 ml sample of the oil is placed in

  a graduated cylinder measuring 250 mm in height and 25 mm in diameter

  meter, we bring the temperature of the oil to 240'C, we immerse it

  a piece of potato of 10 x 10 x 10 mm to a depth of

  2 mm inriver and the height of the foam is measured.

  Moreover, when donuts are prepared using a regenerated oil according to the invention, the donuts obtained have the same color and the same taste as those prepared using a free-flowing oil. origin) this although in some

  case, there is a slight smell of activated clay.

Example 7

  Mix for 5 minutes in a mixer of 1.5 liters of capacity, 10 g of cotton pulp, 30 g of the clay

  activated from Example 1 and 1200 g of demineralised water.

  A sheet-shaped porous metal mold (300 cm long, 600 mm wide, diameter

  pore l mm) on a vacuum container, and the mixture is

  dehydrating top on the metal mold and forming sheet by applying vacuum on the bottom of the porous metal mold

using a vacuum pump.

  The wet sheet (always placed on the porous metal mold) is then held for 30 minutes by the dryer

  at 1100C then cooled to room temperature and removed from the mold.

  This sheet is cut into trap-shaped pieces

  zoldale 1 and 1 '(upper side 200 mm, lower side 100 mm, upper

  160 mm), the two pieces are glued at their sides and at the bottom by means of a ribbon 2 of regenerated cellulose (20 mm wide and 20 microns thick) using an aqueous methylcellulose solution. at 5%, thus forming a funnel as shown

in Figures 1 to 3.

  This funnel weighs 40 g and has an average thickness of

1.5 mm.

  600 g of an oil which has been used is cooled to 160.degree.

  used for the preparation of donuts and this oil is thrown into the regeneration funnel described above. The light transmission coefficient and the odor of the original oil, the oil sent to the regeneration (degraded oil) and the regenerated oil are shown in Table III below. Emple 8 A sheet is formed as described in Example 7 and a degraded oil is regenerated also as described in this example but in the present example, the sheet pieces are heat-welded using a film of polyamide resin

  (Nylon 6) 12 microns thick.

  The results of the regeneration are reported in

Table III below.

Example 9

  A sheet is formed as described in Example 7 and regenerated to a degraded oil also as described in this example but by welding the pieces of sheet by hot pressing.

  with a polyethylene terephthalate film of 12

thick crons.

  The results of the regeneration are reported in

Table III below.

Example 10

  A sheet is formed as described in Example 7 and a degraded oil is also regenerated as described in this example, but the pieces of sheet are welded by hot pressing using

  a polycarbonate film 12 microns thick.

  The results of the regeneration are reported in

Table III below.

TABLE III

original oil

Example 7 coefficient of trans-

mission of light ,.

% odour

Example 8 transmission coefficient

mission of light,% odor

Example 9 coefficient of trans-

  mission of light,% 87,9 no 87,9 no 87,9

Example 10

odour

transmission coefficient

  mission of the light, smell smell Other characteristics of the oils were determined

  namely the acid number (IA), peroxide index (PI) and the

  foaming properties; it can be seen that the funnels according to the in-

  They give much better results than those obtained with commercial oil filters. These results are reported in

* Table IV below.

TABLE IV

Example 7

Example 8

Example 9

Example 10

  IA IP foams IA IP foams IA IP foams IA IP foams Original oil 0, 04 1.66 0.04 1.66 0.04 1.66 0.04 1.66 degraded oil 4.56, 50 4.56 , 50 4.56, 50 4.56, 50 regenerated oil 1.00 3.20 1.00 3.60 1.20 4.00 1.45 4.80 Note: The abbreviations IA, IP and foam have the following abbreviations: same meanings in Table II above, degraded oil 37.0 yes 37.0 yes 37.0 regenerated oil 83.6 no 81.6 no, 0 no 87.9 no yes 37.0 yes no 78.8 no

Example 11

  In order to remedy a transfer of the odor of the clay found in Examples 1 to 10, the activated clay is deodorized as described below: 500 g of the clay are placed in a 10-liter beaker.

  activated in Example 1 and 3 liters of demineralised water, the mixture is boiled.

  After cooling for 5 minutes, a 0.1 N solution of sodium carbonate in a quantity of 0.100, 400 O is added.

and 600 ml.

  The suspensions obtained on filter paper are filtered and the filter cakes are known for 3 hours at 120.degree. C. With

  the clays thus treated, funnels of 1.5 mm thick are formed.

  as described in Example 1 and degraded oil regenerations are carried out on these funnels also as described in

  Example 1. In regenerated oils, in order to control a trans-

  eventual fading of the clay smell to the fried products, we fry

  vegetables (burdocks and carrots). As the quantity

  added sodium carbonate increases, the transmission coefficient

  light mission decreases little by little as indicated in the ta--

  below, but the activated clay odor has practically

only disappeared.

  Moreover, with none of the oils, one observes

  smell reminiscent of fish and due to the oil itself.

TABLE V

  Quantity transfer of transmission coefficient of odor to

  Na2CO3 added, light,% products -

  ml - pR degraded oil fried regenerated oil 0 3.2 26.2 86.4 yes 3.7 26.2 81.3 light 200 4.1 26.2 79.8 no 400 5.0 26.2 - 76, 3 no 600 6,4 26,2 68, 8 no It is clear that the invention is in no way limited to the preferred embodiments described above as examples

  and that those skilled in the art can make modifications without

as far out of his frame. - - -

-. - .;

Claims (7)

  1. Membrane for the regeneration of oils, characterized in that it consists essentially of 5 to 95 parts by weight of fiber material for pulp and 95 to 5 parts by weight of   weight of adsorbent material per 100 parts by weight of the membrane.   2. Membrane according to claim 1, characterized in that it comprises several layers differing from each other by the relative proportions between the fibrous material for pulp and the adsorbent material.   3. Membrane according to claim 1 or 2 having a cutting shape.   4. Membrane according to claim 1 or 2, characterized in that it comprises several regenerative layers of leaf-shaped oils, associated with each other on the bor d a and down by means of flexible sheets impermeable to oil, to form a cup.   Membrane according to any one of claims 1 to   Characterized in that the adsorbent material is selected from the group consisting of activated clays, acid clays, diatomaceous earth, zeolites, silica gel, calcium oxide and   activated carbon, in the granular or powdery state.   6. Membrane according to claim 5, characterized in that the adsorbent material is an adsorbent material of the class montmorillonites which has been treated with an aqueous solution of a alkaline mineral matter.