DD154713A1 - METHOD FOR HYDROLYZING CELLULOSE-CONTAINING ABPRODUCTS - Google Patents

Abstract

The invention relates to a process for the utilization of cellulose-containing waste products by way of hydrolysis and the purpose of eliminating the cellulose components without damaging the noncellulosic materials and without the need for expensive equipment. Their task is to work under atmospheric pressure and not in the strongly acidic medium. The hydrolysis is carried out in the presence of Zellulasen or Zellulasekombinationen in weakly acidic medium at a temperature of 40 - 50 degrees C. The solids content of the hydrolysis liquid is at most 10%.

Description

225234

Heidenau, 11. 11. 1980 021 P-212 / zi

Process for the hydrolysis of cellulose-containing waste products

Applicability of the invention

The invention relates to a method in which cellulosic waste products of the textile industry (eg mixed fibers of synthetics and cellulosics) and the paper industry (eg catching agents from the mechanical wastewater treatment) are degraded by hydrolysis of the polysaccharide portion to glucose. As a residue can be in the case of Fangstoff the respective filler (eg kaolin or titanium dioxide) or recover the degradation of mixed fabric residues of the synthetic fiber content.

Characteristic of the known technical solutions

The complex use of wood has received more and more attention in recent times, as it allows significant reserves for the economy to be developed in this way. The application-oriented research is less directed to the wood than to HoIz- and in particular cellulose waste of various origins, where for years the sputtering and deepening of hexoses and pentoses from sulfite liquors of the pulp industry known. Processes that have the advantage of already existing monomers (simple sugars) that were originally highly poly-organic in the biomaterial, go directly to alcohol (ethanol)

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and single-cell protein (feed yeast) «

Not always for waste products whose polysaccharide content one wants to use, so favorable conditions are given.

Fibers of the paper and board industry fall as partially dewatered, fibrous residues, which are recovered from the residual wastewater treatment plant, after decantation with a water content of about 70 % . The proportion of filler (inorganic pigment, expressed as ash, which can be determined by annealing at 575 ⁰ C to constant weight) varies between 30 ... 60%.

Currently, a large part of the * catching catchment is deposited, which causes high transport costs and is rejected in terms of environmental protection. Lower proportions are used as aggregate in the cement, construction and brick industries. To recover the filler is also worked in various countries by the Zimmermann method, ie by way of Naßoxydation the organic ingredients are energetically used by combustion to carbon dioxide and water. The inorganic filler can be recovered, not free from contamination. This process, which was developed by ZIMMERMANN and DIDDAMS (Tappi A3 (1960) 8, 710-715), operates at temperatures between 250 ... 300 ⁰ C and pressures of 5000 ... 15000 kPa, which are corrosion-resistant reactors condition. Therefore, this process makes significant investments necessary, which is considered to be particularly disadvantageous.

The direct reuse of unaltered catch for the production of paper products depends on the respective filler content and the resulting fiber composition (long, short and fine fiber content). Due to the high variety specificity in the paper mills, direct reuse is therefore only possible for subordinate assortments with lower quality standards.

requirements possible.

The high value of various inorganic pigments makes their technologically simple regeneration appear as a highly desirable goal.

For the reuse of waste of the textile industry, especially the bleached cellulose blended fabrics, no methods are known, according to which there is a satisfactory solution and after which these waste can be extensively used for economic use, although they represent a considerable potential · In a reprocessing of old textiles arise through High proportions of mixed fabrics problems, since the recycling of valuable synthetic fibers requires a separation of the cellulosic part.

The acidic hydrolysis of cellulosic waste has been carried out on a large scale for years, but the attack of the acid on the cellulosic material is non-specific, the sugar solution must be neutralized before further processing, numerous by-products, such as furfural, formic acid, etc., require additional separation processes. As a disadvantage, high demands were placed on the apparatus material (corrosion) by using increased pressure and elevated temperature, which are process conditions, making the only advantage of this method, the relatively short residence time, practically meaningless.

Object of the invention

The purpose of the invention is to eliminate the cellulose components from the by-products without damaging the noncellulosic recyclables and without the need for expensive equipment.

Explanation of the essence of the invention

The invention has for its object to develop a working under atmospheric pressure and not in the strongly acidic medium process method.

It has been found that paper pulps and cellulose-containing waste textiles can be degraded to glucose by enzymatically hydrolysing schwachеі weak acidic pH in the temperature range of 40-50 С Ъеі concentrations up to $ 10 of secondary raw material depending on the duration of exposure of cellulases or cellulase combinations ,

A particularly advantageous embodiment of the invention consists in that a cellulase combination preparation is used for the hydrolysis, which is produced from Zellulasesystemen two different organisms, the Zellulasepräparat from the cellulase system of the organism endo- and exoglukanasereichem, but ß-glucosidasearm and the Zellulasepräparat from the Zellulasesystem the other organism is β-glucosidase, but it is endo-and exoglukanasearm.

The degree of degradation, based on the ashless cellulose contained in the waste, can be increased to nearly $ 100, which means that as a residue in the case of Fangstoff the Killstoff and in the case of used textiles remain the synthetic fiber.

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The regenerated enzymatically filler may be used in the Cardboard, packaging and wallpaper industry.

The hydrolyzate contains up to $ 4 glucose and serves as a starting point for the production of ethanol and / or single-cell protein and other derived products that can be synthesized from glucose.

embodiments

The invention will be explained below with reference to the embodiments,

example 1

Batches of 80 ml of Trichoderma culture filtrate are added to 100 ml of total pH adjusting liquid to pH 5.0, and in this solution 1 g of dry paper pulp with a filler content of 53.6 fo and an ashless cellulose content of 41, 5 % suspended

At a temperature of 40 ⁰ C, the degree of degradation after

6 h - 36 fo 12 h - 63 fo 24 h - 76 ° fo 48 h - 96 1o

Example 2

A 7.5 $ by weight suspension of the characterized in Example 1 was catching substance for 24 hours at pH 4.6 and a temperature of 45 ⁰ C with 2.5 mg / ml of a Zellulasekombinationspräparates whose I ¹ P-type: CMC activity: β-glucosidase activity = 1: 30: 15. The achieved degree of degradation was 63.2 fi. After 48 h of incubation, the degree of degradation after renewal of the enzyme solution increased to 93 ^.

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Example 3

In 100 ml of 0.05 M acetate buffer solution of pH 4.6 were suspended at 45 C 10 g of characterized in Example 1, dry imaginary catch. After 24 h incubation with 2.5 mg / ml of the cellulase combination preparation used in Example 2, the degree of degradation was already 67.5 fo.

Example 4

To pH 0.05 0.05 M acetate buffer solution was added 2.5 mg / ml of two cellulases whose IP activity: CMC activity: β-glucosidase activity was 1: 58: 0.14 and 1:: 120, respectively behaved, given in the ratio of 3: 2. To 100 ml of this tempered to 45. ⁰ C solution 10 g of mixed fibers (polyester regenerated fibers) were added with a cellulose content of 33 fo and incubated for 24 h at this temperature. With 3.5 Dinitrosalizylsäure agent 1.63 reducing sugars were detected, which corresponded to a degree of degradation of 44.8 fo . After Eesuspension of the remaining residue in 50 ml of cellulase solution and 24 h re-incubation at 45 ⁰ C and pH 4.6 1.74 g of reducing sugars were detected, whereby the degree of degradation increased to 92.8 $>.

The synthetic fiber content (polyester fiber) was retained as unchanged residue.

Claims (3)

2 5 2 3 Invention sanction 1. A process for the hydrolysis of cellulose-containing waste products, characterized in that the hydrolysis is carried out in the presence of cellulases or Zellulasekombinationen in a slightly acidic medium at a temperature of 4-0 50 ⁰ C v; Ird, robei the solids content in the hydrolysis liquid is not more than $ 10 , 2. The method according to item 1, characterized in that as ZellulasekomMnation a combination preparation is used, which is made of Zellulasesystemen two different organisms, the Zellulasepräparat from the Zellulasesystem of the organism endo- and exoglukanasereich, but ßglukosidasearm and the Zellulasepräparat from the Zellulasesystem of the other organism is β-glucosidase, but is endo- and exoglucan-poor. 3. The method according to item 1 or 2, characterized in that the glucose solution formed is separated from the residue and the further processing to ethanol and / or protozoan protein and / or other products can be produced from glucose.