CS251514B1 - A method of thermolytic saccharification of polysaccharide-containing raw materials - Google Patents

Abstract

The solution falling within the field of chemical technology relates to a method of thermolytic saccharification of lignocellulosic materials. The essence of the method is that - the raw material treated by dehydration and subsequent extraction is thermolyzed in a vibrofluid bed at a temperature of 250 to 800 ° C and a pressure of 0.025 to 80 kPa, volatile products are tractionally condensed, while a condensate fraction - with a content of 60 to 95% of glycosans is captured. Glyccetanes can be further hydrolyzed with 1 to 4% phosphoric acid or with the help of Ikatex in the H + cycle.

Description

251514

The present invention relates to a method for thermolytic drying of polysaccharide-containing raw materials, such as cellulose, hemicellulose, starch, to monosaccharide monomeric products, respectively. monosaccharide anhydrides. As described in U.S. Patent No. 1,163,595, the thermolytic sarification of air-dried ligno-cellulosic material is carried out in a reaction vessel at a temperature of 350 to 900 ° C and a pressure of less than 100 Pa. The lignocellulosic material, which may be wood, wood waste, agricultural wastes, peat and the like, is conditioned by the addition of a cobalt-containing catalyst prior to reacting. The above conditions yield up to 66% of the oil fraction which contains as the main component a levoglucosane.

Similarly, according to the process disclosed in U.S. Patent Application Serial No. 58 / 152,001, cellulose saccharification is carried out at temperatures of 350-500 ° C under a stream of nitrogen. The resulting condensate is hydrolyzed with 2 N H 2 SO 4 at 100 ° C for 4 h to give a glucose solution. Polkia! the charcoal conditions for thermolysis are not adhered to, charcoal is produced as described in Brazilian Patent Application No. 82/05742.

Thermolytic saccharification can be effected in a fluid bed apparatus (sand) as described in U.S. Pat. 4,448,589, wherein steam is used as the carrier gas. Similarly, the hot air circulation system described in EP 70 710 or EP 69 159 can be used.

The process of thermolytic saccharification can also be used for the conversion of lignified vegetable raw materials, whereby it is suitable to pretreat such, for example, by the explosive definition described in Canadian Patent No. 1,119,033. water vapor to 160-240 ° C and the raw material defiibrates when the pressure is suddenly released. Next, lignin is extracted from the defibrated feed using aqueous NaOH, NH 4 OH or organic solvents such as chloroethanol (AO number 220 999, 1982. Also known as lignin extraction from prehydrolyzed feedstocks is disclosed in Canadian Patent 1 147105). but this procedure is not recommended as a raw material treatment prior to thermolysis, but for enzymatic hydrolysis of these raw materials.

A disadvantage of the previously known processes is that certain catalysts are needed (Canadian Patent No. 1,163,595), and that sulfuric acid (Japanese Patent No. 58 / 152,002) is used in the hydrolysis and that the materials in the reactors it is present in a certain compact layer which prevents uniform heat transfer and at the same time slows the flow of reaction products from the reactor, thereby reducing product yields.

The aforementioned drawbacks are eliminated by the method of thermolytic saccharification according to the invention, characterized in that the treated raw material is thermolysed in a vibrofluid layer at a temperature of 250 to 800 ° C and a pressure of 0.025 to 80 kPa, the volatile products are condensed while collecting the fraction condensate with a content of 60 to 95% glycosanes. The thermolysis is preferably carried out at a temperature of 300 to 400 ° C and a pressure of 0.250 to 15 kPa.

The defibrillated feed and subsequent extraction is fed to a vibrofluidic reactor where thermolysis takes place, the volatile products formed are fed to a condenser where they are condensed and the glycosane-containing condensate fraction is further hydrolyzed to mono-saccharides or directly used to cure microorganisms.

Such conditions are attained at thermodynamic decomposition in a vacuum, respectively. in pyrolysis in a suitable device. The thermolysis products are captured by fractional coupling and the condensate is used for biochemical treatment or without dilution with water, the monosaccharide anhydrides are hydrolyzed with a strong acid-latex (in the H + cycle) of the monosaccharides.

1 to 4% H 3 PO 4 can also be used for the hydrolysis, with which the glycosanes can be hydrolysed in a non-pressurized manner and the phosphoric ions left in the hydrolyzate. If used further for biochemical treatment, the pH hydro the amylate is still treated with ammonium hydroxide or ammonia.

The process according to the invention can be treated with a defocellulosic feedstock by defibrillation and subsequent extraction, whereby the reduction of the feedstock pretreatment and the extracbis is prepared by the cellulosic fraction suitable for thermolysis and the extract suitable for the production of 2-furaldehyde. Thermolytic sucrification takes place in the vibrofluid reactor, thereby shortening the saccharification time and increasing the yield of reaction products to improve heat transfer.

Another advantage of this process is that the prepared reaction product is hydrolyzed with phosphoric acid, or an appropriate acidic ion exchanger, and then used to cultivate the microorganisms, since the reaction product is used directly for the cultivation of microorganisms without treatment with hydrolysis. The solid-residue from the reactor can be used as an energy source. Example 1

The recovered paper (100 g / s and fractionated fraction (below 0.2 mm) containing 65% cellulose) is extracted with 1000 ml of 0.7% HCl and washed with water The solid residue (88 gj is metered into a vibrofluid reactor where it is mixed with vibrating pre-heated inert spherical particles

Claims (5)

251514 and thermolysed at 3.25 ° C. Volatile products are aspirated to a backfill system at a pressure of 0.3 kPa where they are cooled to a temperature. The fraction, and the corroding at 20-15 ° C, formed 31 g. After dilution and addition of nutrients, it was directly used for the culture of microorganisms. Similar good-growth parameters of the yeast used were observed, although the use of levogluicosan as a single carbon source was observed. Example 2 Corn chips (100 g pulp) are extracted with chloroethanol containing 1% HCl at 130 ° C for 5 minutes. The extract is used to produce 2-furaldehyde. The extracted pulp is metered into a vibro-fluidized bed reactor at a pressure of 75 kPa, preheated to 325 ° C. The volatile products are fed to fractional condensation apparatus as in Example 1. The condensate is hydrolyzed with 90 ml of 3% H3PO4 at boiling point for 1 h. The D-glucose content of 81% is calculated in the hydrolyzate, calculated on the weight of the cellulose contained therein. components. The hydro-lysate is adjusted to pH 6.5 with NH 4 OH and used for culturing microorganisms. EXAMPLE 3 Aspen wood pulped by steam and pressure (at 240 [deg.] C.) with explosive defibrillation is extracted with chloroethanol at 85 [deg.] C., with a yield of 67% of the pre-extracted residue. thermolysed in a fibrobluidic reactor at 350 ° C. The fractional condensate is boiled with water (300 ml) with acidic ion-xu (Dowex 50) after dilution with water of 300. After hydrolysis 1 h, Sav hydrolyzate determined D-glucose, the amount of which after conversion to cellulose the component contained in the pulped raw material increased to 31% by further hydrolysis after one hour. A process for thermolytic saccharification of polysaccharide-containing substrates, characterized in that the conditioned raw material is hydrolysed in a vibrofluid layer at a temperature of 250 to 800 ° C and a pressure of 0.0 to 25 kPa, the volatile products are fractionally condensed, with a condensate fraction of 60 to 95% glycosanes being collected. 2. The method of thermolytic saccharification according to claim 1, wherein the thermolysis is carried out at a temperature of 300 to 400 degrees C and a pressure of 0.250 to 15 kPa. 3. The method of thermolytic saccharification of items 1 and 2, characterized in that the annealed raw material is defibrated and subsequently delignified by extraction. 4. The method of thermolytic saccharification according to claim 1, characterized in that the glycosanes are further hydrolyzed with 1 to 4% phosphoric acid, the pH being adjusted to 3.5 to 7 with ammonia or ammonium hydroxide. 5. Calculate the thermolytic saccharification according to items 1 to 4, characterized in that the glycosanes are hydrolyzed by means of a cation exchange H + cycle.