KR960015653B1 - Animal hair solvent treatment process - Google Patents

Abstract

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Description

[Name of invention]

Refining method of animal hair such as wool using organic solvent

[Brief Description of Drawings]

1 is a process flow diagram of the present invention.

2 is a schematic diagram of the method of the present invention using a batch process.

3a, 3b, 3c are schematic diagrams of the method of the present invention using a continuous process.

4 is a schematic diagram illustrating the method of the present invention using an optional continuous process for the process shown in FIGS. 3a, 3b, 3c.

5 shows a schematic of the recycling process for the purification of the solvent used in the process of the invention.

[Detailed name of invention]

The present invention relates to a method for refining animal hair such as wool and the like, and to a new method for refining using an organic solvent.

In general, the most common method of removing the dirt, sut and grease of raw wool is to add surfactant to neutral or alkaline cold / hot water while using raking type agitation of wool. There were aqueous refining methods.

These conventional aqueous refining methods are known to cause entanglement of fibers resulting from slumping of wool, which entangles the fibers during the next carding and combing process step. Generates.

The average fiber length of the finished wool top is 70% -80% of the average fiber length of raw or greasy wool, which reduces the production and quality of wool.

Recent advances in the aqueous refining apparatus described in Soviet Union Patent No. 1,183,575 have been to reduce the consumption of refining agents.

Another advance described in US Pat. No. 3,708,262 to Kanegafuchi Spinning Company Limited, Japan, uses a method of pre-refining raw wool by reducing fiber damage.

In this characteristic, the refining fluid is smoothly pulled out of the fleece by inhalation and at least fat and dirt are removed from the wool.

Soviet Union Patent No. 996,532 describes the use of ultrasonic agitation of the refining solution to reduce physical damage to wool fibers, and recommends ultrasonic vibrating of the refining fluid between 100 kHz and 250 kHz. This is not completely eliminated, and at frequencies above 250 kHz, wool fibers are twisted, adversely affecting spinning.

Although the methods described in the patents show significant improvements over conventional hot water refining methods, all of the above methods result in a slight reduction in the fiber length at the wool top relative to the fiber length of the raw wool.

This reduction in fiber length is generally known to be caused by the use of an aqueous refining apparatus that causes slumping of wool fibers.

Several solvents and solvent-related methods for wool refining have been proposed as alternatives to aqueous refining and for the purpose of overcoming the inherent problems associated with aqueous refining.

For example, British Patent No. 1,233,901 and U.S. Patent No. 3,619,116 suggest using trichloroethylene or perchlorethylene as a refining liquid, and the usual vigorous stirring is performed. Extracted with alcohol and distilled to recover solvent and purified lanolin.

Other advances using solvent refining include the refining described in Australian Patent No. 40379/85 related to cleaning with water / alcohol solutions, followed by a process of rinsing wool in a hydrocarbon solvent. .

US Patent No. 3,600, 124 describes methods using hydrophilic solvents or solvent mixtures (such as acetone) as further refinements to conventional aqueous refining.

Similarly, US Pat. No. 4,343,619 proposes the use of additional solvent refining to reduce the residual fat content of wool.

In contrast, Japanese Patent No. 138,032 / 76 describes a method of using an initial solvent refining using petroleum with a high flash point prior to aqueous refining, whose purpose is to reduce water consumption while increasing the recovery of wool fat. As a result, the resulting refined wool will have the same properties as the wool refined by conventional techniques.

South African Patent No. 5106/73 proposes to use an emulsion refining comprising a modified solvent and a nonvolatile solvent selected from nonionic surfactants and animal and vegetable oils.

And this method has inherent properties of aqueous refining.

The above are also incorporated by reference in the wool refining method described in US Pat. No. 4,343,619 and Australian Pat. No. 533,117.

These methods include the following steps:

(i) treating the fatty wool using an organic solvent comprising 1,1,1-trichloroethane and methylene chloride; And (ii) after step (i), the treated wool is subjected to an aqueous cleaning or refining process as described above.

The above methods used organic solvents only as preliminary refining according to the conventional aqueous refining process, and thus the method had disadvantages as described above with aqueous refining. However, the method also describes the use of 1,1,1-trichloroethane only as a preliminary washing step prior to the application of the quartz cleaning or refining step.

The use of the pretreatment process of submerging fatty wool in organic solvents in a quip zone facility or equipment using a quartz refining step is problematic and costly in retrofitting existing equipment or equipment. Could not.

Moreover, the method still involves the use of a final aqueous cleaning or refining step, which can result in slumping of the wool fibers during the coaming and / or carding process resulting in fiber entanglement and the resulting fiber breaks.

In addition, US Pat. No. 4,343,619 and Australian Pat. No. 533,117 disclose that 0.1 to 10% of the animal is extracted from animal hair during the organic solvent process during the initial stages of fatty wool cleaning using the organic solvent described above. It is described as including the simulated fat.

U.S. Pat. No. 4,343,619 and Australian Pat. No. 533,117 relate to the production of refined bristles having 1-3% by weight of residual soap and 0.3-5.0% by weight of residual fat.

And also the inclusion of foreign matters is not essential to the present invention.

U. S. Patent No. 4,343, 619 and Australian Patent No. 533, 117 also mention the inclusion of an additional step of moving one or both of the bristles or refining fluid at a relative speed of 3 to 60 m / min for each.

This additional step is not essential to the invention, particularly in batch processes. However, the reflow of these refiners and wool fleece during the continuous process in the belt conveyor is desirable, but the state flow is not critical to this refining performance.

It is an object of the present invention to provide a wool refining method which at least eliminates some of the problems associated with the prior art and also significantly improves fiber strength.

This, in turn, leads to an increase in fiber lengths and an increase in the value of wool and saw products for making textiles.

This increase in fiber strength also increases the ratio of wool to wool at low fiber cuttings.

Another object of the invention is to provide a suitable device for use in the method.

The method includes treating the wool with an organic solvent, optionally comprised of halogenated hydrocarbons, halogenated ethers, or mixtures thereof for optimum contact time to improve fiber strength.

With regard to the present invention, it has been found that there is an optimum connection time between organic solvents which are halogenated hydrocarbons including trichloroethane and methylene chloride.

That is, there is an upper limit time for the contact time which depends on various factors such as the stirring method, the special solvent and the special hair treated.

In addition, factors such as fiber diameter, inherent fiber strength and fiber morphology may be the quality of the hair.

As a result, it was found that the upper limit time for the connection time is about 15 minutes, about 10 minutes is more suitable for the conventional stirring method, and about 5 minutes or less for the severe stirring method (for example, ultrasonic vibration). .

Furthermore, in the case of severe stirring methods (ultrasound and vibration), it has been found that after the upper limit time, the fiber strength decreases with time and ultimately reaches its original value.

As the strength of the fiber decreases over the upper limit time, the fiber gradually becomes weak.

This fiber fragility has been a disadvantage of wool that has been conventionally refined with a solvent.

The present invention not only increases the fiber strength but also stops the solvation process to the extent that it does not damage any other fibrous materials.

When wool is treated with normal agitation methods (including submerging wool and immersing the wool into low pressure, high solvent spraying), the fiber strength gradually increases during the first 10 minutes, but after 10-15 minutes The actual fiber strength is changeable and unpredictable as the fiber strength can continue to increase or decrease or even remain constant.

Preferably new or unused organic solvents have been employed in the present invention, which flow in countercurrent to wool in a scouring bath.

The contact time between the submerged wool and the organic solvent is preferably 6 to 10 minutes, and the residual fat content of the solvent consumed from the refining process is suitably 3% or less (preferably 1.5% to 1%) to obtain the required refining conditions. 2.0%).

If necessary, a rinse step can be used where fresh organic solvent is applied to the refined or washed wool to remove the residual amount of detergent added to the solvent in the refinery.

If desired, wool may be initially treated in an initial aqueous or organic solvent based refining step.

More preferably, however, the minimum adhesion time with the organic solvent can be applied as a refining step, especially when processing raw or fatty wool.

The initial aqueous refining step consists of a suitable conventional aqueous refining step known in the prior art, which has been extensively described above.

The initial quartz refining step also includes tip scouring to minimize wool slumping.

Initial refining using an organic solvent is particularly desirable when the organic solvent can increase the strength of the fiber. The initial refining step is very suitable and does not cause entanglement and / or cleavage of the fibers.

A preferred solvent for the refining step of the present invention is 1,1,1-trichloroethane (TCE) because of the relative cost and ease of recovery.

Cleaning agents are used to improve TCE performance when cleaning dirty fiber tops, which can be combined with organic solvents such as aliphatic hydrocarbons.

Refining with solvents can be carried out in batch or continuous processes, depending on the scale of the process, in which batch processes are more appropriate in terms of equipment cost, and in large industrial installations, continuous processes are likely to be chosen.

Where the batching process is used, the wool is conveniently placed in dip baskets in a refining bath containing solvent.

In particular, it is particularly desirable to place the fleece wool in a carrying basket in which the outer part of the fleece faces downward.

Where continuous processing is used, fleece is placed on the fleece on the belt, such as plastic or metal mesh belts, perforated so that the fleece begins to partially submerge, with the hair tip down, and move completely through the solvent smelting tank. Is preferably placed.

Such belts require ribs or cleats to maintain the movement of the fleece with countercurrent trichloroethane (TCE) solvent flow.

If necessary, the wool may be placed in a flexible net or perforated container to provide easy access to the trichloroethane and to remove trichloroethane from the wool.

Washing steps using trichloroethane (TCE), methylene chloride or mixtures thereof also show good drying performance of wool.

Like other refining methods, the wool is conveniently dried prior to deburring, carding and combing after refining by the method of the present invention.

It is essential to use centrifugal or other spin drying steps to remove the maximum amount of solvent from the wool, in which the top of the wool is removed from the solvent to achieve drainage for the final removal of impurities. It should be carried out in an oriented outward or upward direction in the flow direction.

The wool is then dried to an optimal level for the required deburring or effective carding ming coaming.

Wool is suitably washed in TCE or other organic solvents in centrifuges or spin dryers to maximize removal of contaminants or other impurities and trace residues.

In one embodiment of the present invention, after submersion in quartz refining, the wool leaves the final cleaning process and passes through a ringer or other suitable mechanical dehydration step prior to drying.

High temperature wool can be taken out of the dryer immediately and submerged in trichloroethane. The soaking time is at least 2 minutes and is not longer than 15 minutes by stirring.

The wool is then taken out of the trichloroethane refinery and placed in a spin dryer.

The relatively high specific gravity of trichloroethane and the relatively open coordination of wool fibers make it fast and effective to remove the solvent from the yum.

Residual solvents of levels up to 2% based on the dry wool weight can be obtained.

Spin dryers and g force sizes are typically between 200 and 400 but may range from 50 to 1000.

Optionally, wet aqueous refined wool can be processed, wherein the water from the aqueous refinement can be separated from the TCE solvent by conventional techniques using specific gravity differences between TCE and water.

By doing so it enables the recycling of the TCE to be performed with minimal loss but this procedure is not described here.

It is desirable to recover the solvent from all steps of the process in order to minimize costs and to meet environmental regulations and to minimize solvent recirculation throughout the process.

This solvent is recovered by distillation, which is left as a wax wax roll, which is further refined into a valuable lanolin product.

Solvent refining typically yields 95% recovery to maximize recovery of wool wax.

An unexpected advantage given to the wool refined by the method of the present invention lies in the actual initial increase in the tensile sensitivity of the wool over conventional aqueous refined wool.

This increase in refined wool's fiber tension results in increased wooltop fiber lengths (ie, more valuable wooltop products) after further processing.

The structure causing this fiber strength is related to the internal change of the fiber after solvent penetration.

Proper solvent treatment is likely to cause biochemical reactions with keratin's cell membrane complex (CMC), but these changes require biochemical explanations.

This complex is the harmony of the outer layer and epidermal cells.

This gives the matrix the weakest component of keratin.

The complex consists of protein material that is weakly crosslinked with fat, which represents only a small percentage of keratin (6%), but it is nevertheless important because it primarily determines the tensile strength of keratin.

Exposure of this membrane membrane complex (CMC) to a suitable solvent resulted in an increase in tensile strength, which advantageously led to changes leading to the removal of fats (eg cholesterol triglycerides and free fatty acids) from the fibers in the initial contact period. Bring.

Ultimately, spongolipids and phospho lipids can be extracted under severe agitation conditions of ultrasonic vibrations and often under normal agitation conditions, which can reduce fiber strength after an initial period of strength increase. will be.

The solvent proposed in the present invention has a higher vapor pressure than water and has a low specific heat and latent heat of evaporation. Therefore, less time and less energy is required to dry the refined wool.

Furthermore, when the solvent of the present invention is used in wet wool after a quartz preliminary operation, the drying time and drying energy are significantly reduced by the formation of perfume substances (solvent / water) when using special detergents in trichloroethane solvents. .

This facilitates the removal of water in the spin drying step of the solvent recovery method for water extraction.

This water component of the perfume material is then recovered with the wool wax product in a solvent recovery distillation step.

Another advantage of the present invention is an improvement in the average color of the refined wool, where an off-white color is obtained in aqueous refined wool and a very white color in wool refined according to the present invention.

Experiment related matters

Lipids were refined to test 25 staples forming each group to be tested in an AWTA (Australian Wool Testing Authority) certified test apparatus.

According to the attached Table 1, samples were averaged for the purpose of providing average tensile strength for each treatment group.

Table 1 shows the degree to which trichloroethane (TCE) solvents and various treatment regimes can affect the tensile strength of aqueous refined wool.

The unit of tensile strength is given in newtons per kilotex.

A pair of staples were then tested after varying the bedtime in TCE, and the test results were given as shown in Table 1.

Here samples were immersed in a lidless container and then dried prior to the measurement of tensile strength as described above.

All wool staples were initially refined using conventional aqueous refining methods as described below.

These samples were processed as individual staples so that the tensile strength could be measured after refining (aqueous control in Table 1).

The Wool School at TAFE University in Brisbane kindly made it possible to use conventional aqueous refining equipment using KLEENIT cleaners (obtained from Campbell Broze Limited), which is designed for the process of small test batches.

After aqueous refining, the wool is dried in a forced hot air stream and conditioned by about half of the staples to regain moisture.

All staples were then submerged in 1,1,1-trichloroethane for various times (Table 1), air dried, conditioned, and then subjected to tensile strength testing.

Prior to testing, the samples were spin dried in a centrifuge with a force of about 300 g.

The centrifuge used here was a LIGHTBUN spin dryer of serial number 6504.

Thus, Table 1 describes conventional aqueous refining samples (aqueous control) and similar samples that had been further processed by submersion in TCE.

All of these samples were measured for tensile strength, and the following summarizes the main findings of treating aqueous refined wool with solvents to increase tensile strength.

1. TCE treatment increases the tensile strength of refined wool.

2. This effect occurs after a minimum of two minutes of bedtime.

3. Preferred bedtimes are 2 to 3 minutes in severe agitation (ultrasound) and 6 to 10 minutes in gentle normal stirring.

4. The same results were also obtained when submersed in methylene chloride or TCE methylene chloride mixture.

5. Direct submersion of aqueous refined wool from the oven showed a slightly improved tensile strength compared to wool that was dry and conditioned at room temperature.

Optionally, the wet wool taken out of the final bath of aqueous refining can be squeeze dried and treated in TCE as above to obtain a similar result (Table 2) in mind.

Therefore an increase in tensile strength can be obtained by the use of TCE immersion treatment after this final flush or after the drying process.

Also shown in the attached figures 1a, 2b, 2b, 3 and 4a are the reactions described above of the wool treated according to the invention.

Thus, Figure 1a shows wool treated with severe ultrasonic agitation, Figures 2a and 2b show wool treated with normal agitation, and Figure 3 shows an increase in wool top quality obtained by the method of the present invention. And FIG. 4a shows a graphical analysis of the fiber test results.

Reference may also be cited in Table 3 relating to the testing of wool samples already shown in FIGS. 2A, 2B and 3.

TABLE 1

** The figures in this column represent the result of subtraction of the staples from the oven (70 ° C.) and submersion in TCE immediately.

TABLE 2

The temperature measurement relates to the temperature of the final cleaning bath.

Wool samples used for TCE Solvent Refining Fiber Hardness Tests according to FIGS. 2a, 2b, and 3 (AWTA Test Results for Lots Used)

TABLE 3

In the case of refining fatty wool using a solvent, wool samples with an initial tensile strength of 35 N / ktex with ultrasonic vibration at 25 kHz increased to a peak of 56 N / ktex after 2-3 minutes and then 50 N after 20 minutes. reduced to / ktex.

It is also pointed out that other halogenated hydrocarbons such as brominated or iodide derivatives can be used in addition to the chlorinated hydrocarbons preferably used in the present invention.

Directional air / water spray or solvent spraying (from side and bottom) may also be used for agitation methods that may be used in the aqueous refining step or organic solvent refining step as described above, for example in a bath apparatus or as described above. It can be used in preferably a large amount of low pressure solvent spray from submerged wool fibers.

This spraying can be used to replace conventional rake structure agitation used in aqueous refining methods, thereby simplifying the recommended apparatus or installation.

In another possible embodiment, the wool scouring process uses water or a solvent (+ cleaner) during the first cycle to remove contaminants and the like, followed by a gentle use of solvent in the soaking, washing, washing and spin drying cycles or any combination cycle. It can be performed in large scale automatic cleaning machines using stirring, soaking, washing, homemade and spin drying cycles.

Special cleaning machines designed with gentle agitation to minimize fiber entanglement are automatic valves that send solvent scouring liquor and debris to a standard scouring liquor processing process to remove debris by filtration or centrifugation, followed by solvent It has an automatic valve for distillation and lanolin recovery steps.

The method of the present invention can be applied not only to fatty wool which requires scouring but also to hydroponic dried or wet wool treatment.

Treatment with halogenated hydrocarbons may be after aqueous refining or may preferably be a practical refining process.

Also from the foregoing, the term `` wool '' generally relates to animal hair, and the method of the present invention relates to muskcat, weasel, American raccoon hair, astracan hair, fox hair, mink hair, chinchilla. It should be noted that it can be applied to hairs including wool, sable hair, angora / cashmere hair, camel hair and alpaca hair.

Therein, reference may be made to preferred embodiments of the present invention.

In FIG. 1, a flowchart illustrating the process is shown in FIG.

Each separately dried wool fleece is released before the tip is placed downwards in the man conveyor and subjected to a tip pretreatment procedure before being refined in an organic solvent.

This allows the separated fleece to be ground into wool clumps prior to drying of the refined wool.

The solvent used is then sent to a centrifuge to recover the spent solvent, which is then filtered to remove contaminants and anoline oxides.

The spent solvent is then distilled off and the recovered solvent is sent to the tip pretreatment unit.

Wool wax is recovered from the distillation process and sent to the refinery for use as a lanolin raw product.

In FIG. 2, a stake 10 of separated fleece (ie aqueous refined or fatty wool) is placed in the basket 11 with the tip facing down and the head roller 13, the tail roller 14 and A conveyor 12 having an intermediate idler roller 15 approaches and transports the tip preliminary treatment zone 16 of the refining tank 9, which is a downward ramp 17 and a hydroponic section 18. And bounded by an upward slope 19.

The tip of the fleece is subjected to gentle cleaning as described above.

The remainder of each fleece is not in contact with the refining liquid 20 and the refining liquid can also be applied to the fleece by the stirring spray 21 in the tip pretreatment zone 16.

After passing through the preliminary treatment zone, the fleece in the basket 11 passes through the horizontal zone 22, where the fleece is withdrawn from the refining fluid before entering the refining zone 23.

Also shown is a downward ramp 24 through which the basket 11 passes through area 23, where the fleece is completely submerged in the refining liquid 20 containing halogenated hydrocarbons retained in the refining tank 9. As described above, the contact time is preferably 6 to 10 minutes.

Outlets 26 and 27 may also be provided so that spent refinery may be discharged for filtration and purification. Also shown is a manifold 23 for applying the cleaning agent to the scouring liquid 20.

After passing through the refining zone 23, the basket 11 is moved upwards along the uphill slope 28, where the manifold 28A for rinsing with fresh solvent before the fleece 10 passes into the laid-down zone 29. ) Is included in the uphill slope 28, and for drying the fleece 10 is lowered from the basket 11 to the centrifuge 30 in the laid down area 29.

The fleece is then sent to a secondary conveyor (31) where the fleece (10) passes separately through the dryer (32) and into the cold bath (33), which is followed by crushing rolls (34). Will be processed.

The fleece 10 is then stacked on the table 35 for subsequent processing, including carding.

The conveyor 31 is controlled by the head roller 31A, the tail roller 31B and the middle idler roller 31C as shown.

3a, 3b, and 3c show a state in which a plurality of fleeces 10 (aqueous purified wool or fatty wool) are stacked and a layout table 36 adjacent to the refining tank 9.

The fleece 10 is separately mounted on a perforated or mesh conveyor 37 and sent to the tip reserve treatment area 38.

The fleece is conveniently separated by the ribs 37A (only a few ribs are shown here for clarity, but the ribs 37A are attached to the conveyor over the entire length of the conveyor 37).

The tip pretreatment zone 38 includes a skimmer box 39, a pump 40 and agitation sprays 41 as well as outlets 26 and 27. It is passed to outlets 26 and 27 for purification including filtration.

The skimmer box 39 and the pump 40 are useful for removing saw surface debris from the refining liquid 43, which also includes an idler roller 44.

The fleece 10 then enters the refining zone 45 where the refining liquid 43 consisting of halogenated hydrocarbons or halogenated ethers as described above is completely submerged, where the contact time is 6 to 10 minutes.

The refinery 45 also includes a skier box 39 and a pump 40.

Stir sprays 41 may also be used in scouring 45 including idler rollers 44 as well as manifold 45A for the action of the cleaner.

The fleece 10 is then passed to a rinse zone 46 bounded by an upward slope 47 of the conveyor 37.

Fresh solvent recycled in the rinse zone 46 is applied to the fleece 10 so that residual impurities are removed through the manifold 46A.

It also includes a separator 48, a head pulley or roller 49, and an idler roller 44 for crushing the fleece 10 into crumps.

The crumps are then sent through a chute 50 to a centrifuge 51 operated by a motor and gearbox assembly 52, where the fleece 10 is gathered to collect the aggregates. It becomes

Next, the wool containing the solvent is discharged from the centrifugal 51 and raised to the conveyor 53 and sent to the cyclone separator 54, where the solvent contained in the cyclone separator 54 is discharged onto the chimney 54.

The containing solvent passed over the chimney 55 is about 3% of the initial solvent used.

The washed wool is then lifted up with an pneumatic conveyor 57 to be inspected by a quality inspection at the inspection point 56 before entering the reservoir 58 including the baffle 59 and the dust accumulator 60. Is performed.

The final washed and refined wool is passed through the unloading site 61 for later transportation and storage.

Moreover, the electric motor 62, the suction fan 63 for the pneumatic conveyor 57, and the air discharge port 64 are prepared there.

4 shows an optional continuous process without the use of a tip pretreatment process, in which a conveyor is placed on the surface of the refiner 43 before the fleece 10 from the loading table 65 enters the refining zone 45. Passed to 66.

Subsequently, a continuous process as in FIGS. 3B and 3C was used. In FIG. 5, the solvent recycling step is shown, where a clean detergent or solvent is supplied to the refinery 9 via line 67. FIG.

The refinery 9 is provided with outlets 26, 27, through which pressure filter 69 is passed through line 68 before the spent or messy solvent exits the outlets 26, 27 and reaches the distillation vessel 70. Is sent).

This pressure filter 69 may be precoated with diatomaceous earth, benzoite, acid activated cray, carbon or montmorillonite.

It is also provided with a pump 71 as well as a condenser 72 for passing clean solvent through line 67.

If necessary also a stabilizer can be added as shown in the figure. There is also provided a line 73 for passing wool wax 74 or other adhesive from the midstream container for further purification.

Cooling water may pass through the capacitors 72 to lines 75 and 76.

Claims (3)

In a method of refining animal hair such as wool, the refining method comprises washing the animal hair with water; Contacting the animal hair with a halogenated hydrocarbon or halogenated ether for a predetermined contact time, and treating the animal hair with a detergent while stirring by ultrasonic waves during the contact time; Rinsing with the organic solvent without the animal hair; The animal hair is dehydrated by centrifugation or rotary dehydrogenation tank to remove organic solvents and dried; In the animal hair refining method comprising the process of recovering the used organic solvent, the animal hair grease (grease) component remaining in the organic solvent recovered after the use of the predetermined contact time is 2 minutes to 5 minutes A method for refining animal hair, characterized in that less than 3wt% based on the total amount. The method of refining animal hair according to claim 1, wherein the organic solvent is 1,1,1-trichloroethane. The method of refining animal hair according to claim 1, wherein the animal hair grease component remaining in the recovered organic solvent is 1.5-2.0 wt% based on the total amount of the organic solvent.