JPS60150832A - Absorbent of organic liquid - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to absorbents for organic liquids, especially oils. The absorbents of the present invention are non-dust explosive, ie they do not tend to pose a dust explosion hazard and have a low fire hazard.

In the past, sawdust was almost always used to remove waste oil from, for example, factory floors. Sawdust has good absorption capacity, but its use has the disadvantage that it forms fine combustible dust, which under unfavorable conditions can cause fires and dust explosions. Accidents with sawdust have thus occurred. Swedish National Commission for Occupational Safety and Health Act AFS
1981:5 "Dust Explosions" lists wood powder as a substance with a dust explosion hazard.

In view of fire hazards as well as dust explosion hazards, sawdust is increasingly being replaced by absorbents consisting 100% of inorganic materials such as volcanic ash and crushed stone or crushed rock.

It is true that there is no risk of fire or dust explosion when using such materials. However, such materials have low absorption capacity, low permeation rates, and are susceptible to leaching and infiltration when deposited. When distributing such absorbents, dust from the absorbents can damage machine bearings and irritate the skin and eyes. Inorganic products generally have a greater tendency to form dust.

The object of the present invention is therefore an absorbent for organic liquids, in particular oils, which does not have the above-mentioned disadvantages and which has a low tendency to ignite and is not prone to dust explosion hazards, i.e. is dust non-explosive. An object of the present invention is to provide an absorbent having an absorbing capacity fully comparable to that of bonito sawdust, and which can be destroyed by a simple method.

Absorbents possessing a combination of such properties are the most attractive from a commercial point of view. In particular, the present invention relates to an absorbent of the above type, which is non-explosive to dust, has a ignition tendency of 15 to 50 It is a composite material mainly composed of a mixture with % by weight of inorganic materials. The absorbent of the present invention is characterized in that the inorganic material is hydrophobized and bonded to hexagonal fibers by precipitating chemicals commonly used for wastewater purification.

The cellulose fibers used in the absorbent of the present invention are mechanically
Suitably, the chemical-mechanically or semi-chemically treated fibers include sulfate fibers, sulfite fibers or mixtures thereof.

Particularly preferred #: Fibers disposed of in the t'M paper and board industry.

This cellulose fiber is hydrophobized. This hydrophobization is carried out using hydrophobizing chemicals such as rosin sizes, starch sizes, and neutral sizes (ketene dimers) commonly used in silk mills and board mills.

Cellulose fibers can also be made hydrophobic by sizing agents based on acrylates, alkyds or polyesters, by melting polyethylene or polypropene on the fiber surface, or by adding wax emulsions to the fibers. can do.

The advantage of combining different hydrophobization methods is that all possible 10 individual fiber fragments can be treated uniformly.

The inorganic materials present in the absorbent of the invention are preferably kaolin (clay), Merck, calcium carbonate, etc., commonly used as materials or coating materials in the silk and board industry, such as Fuller's earth (Kieselguhr). The inorganic material used. The precipitating chemicals that combine the hydrophobized fibers and the inorganic materials are the usual precipitating chemicals used in so-called chemical processes in purification plans. - Examples include Human VB (iron-containing aluminum sulfate) and FaCZ=.

(ferric chloride). However, it is also advantageous to use sodium tripolyphosphate and purified aluminum sulfate. A preferred precipitation chemical is Boliden (B
It is an AVR obtained from (olid6n) and has the following analytical values.

Particle size 1~3 ■ Aluminum 7% (AI!2 (S04) 3.16~1
7H20) Iron 3% (Fe2(S04)3・9H20)
Sulfuric acid deficiency 2% Water immiscible substances 2.5% Silicate mineral active substances 3.2 mol/kp Aluminum content approximately 95% Particularly preferred absorbents of the invention are conventional sizing agents with rosin, starch plus latex from about 70% by weight of hydrophobized cellulose fibers, the hydrophobization of which has been carried out by a mixture of about 30% by weight of inorganic materials commonly used for water purification and bonded by a chemical AVH of about 5% by weight. It is configured. , such absorbents are produced by mixing the sediment obtained from the pre-sedimentation plant of the purification plant of the cardboard mill with the sediment obtained from the chemical precipitation process (see Examples below for details). 1). Depending on the manufacturing/method parameters of the cardboard mill, chemically precipitated sediment may be
It is necessary to supplement this by adding common precipitation chemicals such as AVH and inorganic materials such as kaolin in the pre-sedimentation step to obtain a suitable ratio of organic to inorganic phases.

Such an absorbent FiALFOB® 80 (
granular structure, ) and ALFOB 800 (shredded structure) (primarily for industrial decontamination) and ALFOBW
It will be sold under the trade name (for removing oil pollution from waterways). Carlfors
During tests in Bruk), the absorbent was found to pose no risk of dust explosion hazards, regardless of whether the material was in granular or shredded form (see Example 2). . Additionally, tests at the National Feed Testing Laboratory (see Example 5 below) have shown that the absorbent of the present invention carbonizes when heated and that it is extremely difficult to burn the absorbent in an open flame. It has become clear. Thus, the absorbent of the present invention has approximately 10.5 MJ
It burns even though it has a heat capacity of / kg. The used absorbent material is therefore easily disposed of, for example by burning it in a waste incinerator.

It is impossible to give a clear and accurate explanation for the fact that the oil absorbent of the present invention is not dust explosive and has extremely low flammability. When cellulose fibers are sized with a sizing agent such as ketene dimer, the cellulose chains are divided into two fatty acids: the cellulose fiber and the ketene dimer.
It is known that polyester is formed between J and J. Two fatty acids, silver and ketene dimer, make cellulose @ hydrophobic or water repellent. Similarly, a possible explanation for the nature of the absorbent of the present invention is that the precipitating chemical, e.g.
Since the aluminum therein is a well-known anchoring agent for cellulose, the AVR binds the inorganic material to the cellulose chains. The effects of the present invention, namely the combustion tendency, are clearly explained in the examples. The extremely low combustibility of the absorbent of the present invention means that cellulose 9.
This can be explained by the inorganic phase covering the fibers.

The absorbent of the present invention that has absorbed oil burns, which can be extinguished by sprinkling it with ALFOB. Sprinkling ALFOB on top of it appears to extinguish the fire.

Example 1 The oil absorption capacity of the absorbent of the present invention was evaluated in comparison with the absorption capacity of two conventional oil absorbents.

A preferred absorbent of the present invention is made as follows = 2
one cardboard making machine, namely a groundwood mill (C.I.T.M.
The waste water obtained from P.P. is purified by the conventional method by first passing it through a coarse filter and then through a large settling tank (Al).
It contained % by weight cellulose fibers and about 20% by weight inorganic materials, primarily kaolin. The stock solution from this settling pond was pumped to a conventional biological bed where aeration, settling and thickening were performed to obtain biological sludge. The p-liquid obtained from this biological process is further pumped to a chemical purification process where precipitated chemicals (flocculants)
AVR was added as a. The purified flocs were sent to a settling tank (B) where they were e-condensed by settling. The transparent phase obtained from this sedimentation is microscreened and
The clear filtrate thus obtained was pumped into a container. The sediment obtained from the settling basin (Bl) and the microscreen were concentrated together into a so-called chemical sludge, which contained almost entirely inorganic substances.

Sediment A and this chemical sludge are mixed in the following proportions, i.e., this mixture is about 70% by weight of cellulose fibers (in this case a conventional fiber mixture of mechanical fibers and sulfate fibers rosin-sized with Hercules T sizing agent). , 50% by weight of inorganic material (the main part of this inorganic material is kaolin and A
(consisting of 20-40% VR-containing chemical sludge)
were mixed in such proportions as to contain

The absorbent of the present invention therefore contains about 70% by weight of a conventional fiber mixture of mechanical fibers and sulfate fibers sized with a rosin sizing agent such as Hercules T-size cut, and about 50% by weight of an inorganic material, the major part of which is kaolin. Including weight percent, 20-40 weight percent of the inorganic material is composed of AT/R-containing chemical sludge, and A V, R is about 5 percent relative to the inorganic material. This material is available in two forms: granular structure (AL
FOB 80) and shredded structure (ALFOB 800)
I tested it thoroughly. For comparison, sawdust and a crushed rock product sold under the trade name ABSOL were tested.

Test Method: Weigh 5 g of the absorbent to be tested and then place it in a 1-e beaker containing 400 g of the oil to be absorbed. Next, mix the oil and absorbent mixture using a magnetic stirrer for 50 min.
Stir for 5 minutes at 0 rpm.

The mixture is allowed to stand for 5 minutes and then poured through a screen. Leave the absorbent collected on the screen for 5 minutes to drain the oil. In other words, it does not push out oil. The oil retained on the screen mesh is absorbed using a regular paper towel.

The oil-containing absorbent retained on the screen is weighed, and the drying chamber z (sy) of the absorbent is subtracted from the weight obtained to determine the amount of oil absorbed (oil weight).

Absorption capacity refers to the ratio of oil weight to dry weight.
The higher this value is, the better the absorption capacity is.

Table ALFOB80 of the present invention ζ82.0 ALFOB800 of the present invention 5,0 3.6A B S
OL +, 0 0,9 Sawdust 5.4 3.4 The results shown in the table clearly demonstrate the superior absorption capacity of the absorbent of the invention compared to the conventional product ABSQL. Compared to sawdust, the shredded product of the invention ALFOB 800 has an equally good absorption capacity for hydraulic fluids, but an even better absorption capacity for lubricating oils. On the other hand, the granular product ALF of the present invention
OB 80 shows poor shingle absorption capacity for both hydraulic and lubricating oils. However, this somewhat lower absorption capacity is more than sufficed by the fact that this product does not form dust, apart from the lack of dust explosiveness and the low fire risk evident from Examples 2 and 3 below. It's so balanced.

Example 2 The dust explosive properties of the secondary class absorbents of the invention, namely the products ALFOB 80 and ALFOB 800 mentioned in Example 1, were tested in Karl Horspruck.

Two test methods were used, as described in Techniscutide Scrift-1970 Glue Print No. H4550055. This test was carried out at Karl Forsprück using a modified Hartmann apparatus and the pyrotechnic capsule test developed at Karl Forsprück. Both tests are intended to determine the tendency of dust to explode.

Both the Hartmann apparatus test and the flammable capsule test showed that neither products ALFOB 80 nor ALFOB 800 exhibited any tendency to dust explosion. This 2
It is concluded that the two products are completely harmless in terms of dust explosion hazard.

Example 3 Two products of the invention (ALFOB 80 and ALFOB8
The fire hazard of 00) was evaluated at the National Institute for Materials Testing.

Method Approximately 100 I of sample was weighed in a platinum dish. 100% of this sample
The mixture was kept in a heating chamber of C for 0.5 hours, and then taken out.
Inspected and weighed. This operation is performed at a temperature of 200.250.
Repeated in Matsufuru furnace at 300, 350, 400i and 500C.

After 05 hours at 110C ALFOB 80 No change 1.8 ALFOB800 3.1 After 0.5 hours at 200C ALFOB 80 No change Overall 2.4ALF
OB800 #57 After 0.5 hours at 250C ALFOB800 No change Overall 57300C
After 0.5 hours at ALFOB 80, the sample was carbonized. Overall, 494ALFOB 80% of this sample was carbonized. Overall Sfi, 8ALFOB800 This sample was carbonized. Overall, after 0.5 hours at 40,4400C, the ALFOB 80 sample charred. Overall 57.2ALFOB800 This sample was carbonized. Overall 45.6 ALFOB800 Same as above Overall 494 From the results shown in the table above, it can be seen that under normal test conditions with free entry and exit of air, neither flame nor red heat was detected in this sample. It can be seen that no combustion actually occurred, only thermal decomposition occurred. All tested products thus demonstrate a low fire risk.

The ALFOB absorbent of Comparative Experiment Example 1 was used in patent application 81
200 142.8 (Test 1) and the above Example with a higher kaolin content (Sample 2).

Test 1 50% by weight ground wood pulp + 4 layers! -% pine sulfate and 30% by weight kaolin were placed in an aqueous suspension, then drained in a Buchna funnel and dried. The ash content (1000C 1 hour) of this material was 29%.

Test 2 48% groundwood pulp 12% pine sulfate 40% kaolin ash; 42% Samples from Tests 1 and 2 were combined into ALFOB 80 (28% granular structure ash) and ALFOB 800 (34% shredded structure ash) ) was tested. The ash content of ALFOB is approximately 3
0%, ie this can vary within ±5%.

The samples for each ignition test were placed in a pile approximately 5 cm high and approximately 10 cm in base. Apply the Bunsen burner flame to this sample.
The contact was made for 0 minutes. After extinguishing the flame, the following results were obtained: ALFOB 80: No open flame.

ALFOBI300: Flame flame, which disappeared after 6 seconds.

Comment): ALFOB 80 if used in places where particularly high demands are made regarding fire safety, for example in steel factories.

Test 1: Open flame for 6 seconds, all material disappeared to ash.

Test 2: Open flame for 5 seconds or more, about 70% of the material disappeared and turned into ash.

+% (fir61oad) does not satisfy the requirement that it should not increase. As a result, sawdust disappeared from all major industries.

Agent Mitsuyoshi Ezaki Agent Mitsufumi Ezaki

Claims (1)

[Claims] t Hydrophobized cellulose fibers and a total of 15 to 50
In an absorbent for organic liquids, which is made of a composite material consisting essentially of an inorganic material constituting % by weight, is non-dust explosive, has extremely low ignitability, and is made of an inorganic material. The inorganic material is bonded to the cellulose fibers by an inder, which is a precipitating chemical commonly used for wastewater purification.
10% by weight of an absorbent. 2 The binder is AVR (iron-containing aluminum sulfate),
The absorbent according to claim 1, which is ferric chloride (Fe015) or purified aluminum sulfate.