Method of processing biomass into cellulose and solution of low-molecular weight oxidation products (versions)

FIELD: chemistry.

SUBSTANCE: invention relates to methods of obtaining cellulose and low-molecular weight oxygen-containing compounds from processing biomass from forestry and agricultural wastes. The method of processing biomass involves heating water to 58-75°C, adding FeCl3 × 6H2O, holding the solution at 58-75°C for not less than 10 minutes while stirring continuously. After complete precipitation of Fe3+, the biomass is added with ratio of water to biomass of 10-20; the mixture is stirred and held for not more than 10 hours. Hydrogen peroxide is then added with ratio of hydrogen peroxide to biomass of 3.5:0.5; the mixture is stirred at temperature of 25-70°C until hydrogen peroxide is exhausted. The obtained oxidate is separated into a solid precipitate and a solution of water-soluble products. The solid precipitate is washed with water, which is then used in the next cycles and/or is added to the aqueous solution of water-soluble products. Versions of the method involve further addition of 1-10% lower alcohol to water and/or addition of soda to FeCl3 × 6H2O with weight ratio of iron chloride and soda of 1.5-80. Versions of the invention enable to combine synthesis of a catalyst and oxidative processing of biomass in a single cycle (reactor). Output of water-soluble products and solid precipitate (cellulose) can be controlled depending on the ratio of the catalyst and the biomass. The water-soluble products contain organic acids and polyphenols, which can be used as preservatives and biological additives in producing feedstuff in agriculture.

EFFECT: reducing water consumption by about an order, as well as consumption of energy and components.

15 cl, 1 tbl, 9 ex

 

The invention relates to the field of biotechnology, and in particular to methods for production of cellulose and low molecular weight oxygen-containing compounds with simultaneous utilization of waste as in the forestry industry and in agriculture.

Recycling of organic wastes and biomass at the present time is a vital issue and attracts great attention of researchers and practitioners. One of the widely used methods of biomass (wood and waste wood, straw, municipal solid waste, and others) is direct combustion, which is the most studied and commercially developed. Along with the direct burning of developing such technologies thermochemical processing of biomass, as gasification and pyrolysis. Biomass with high moisture content (waste water, waste products of hydrolysis of organic residues) may be processed by biochemical processes: anaerobic digestion, ethanol fermentation, azonaphthalene fermentation. As a result of these processes biogas (CH4, CO2), organic acids, ethanol, acetone, butanol. In recent years, large efforts are made to find and develop ways of chemical processing of biomass into biofuels. It is preferable to utilize biomass through direct combustion or processing it on the right in helices the om and pharmaceutical production of commodity products. Due to their low toxicity and relatively low cost catalysts based on iron oxides are widely used in various chemical processes. In recent years, in connection with the development and popularity of nanotechnology highly dispersed heterogeneous catalysts based on iron oxides, feel for the processes of oxidation and additional oxidation of organic pollutants in water as oxygen [3-5], and using environmentally friendly oxidant hydrogen peroxide [6-9]. In nature signosagencia biomass is converted by microorganisms for growth, reproduction and functioning of which a necessary condition is the presence of water containing metal ions [10-13]. The mechanism of the enzymatic oxidative cleavage involving hydrogen peroxide and oxygen [14,15]. The catalyst based on iron oxide nanoparticles (3) in combination with H2O2can purify water from phenol and ethylene glycol [16].

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15. Lesin VI, Pisarenko L.M., Kasaikina O.T. RF Patent 2425715 (2011)

16. Lesin VI, Pisarenko L.M., Kasaikina O.T. // number. Zhur. (2012) T No. 1. from 1-6.

The most promising catalytic methods for obtaining oxygen-containing compounds, based on the use as oxidant molecular oxygen and hydrogen peroxide, as both oxidant are environmentally friendly and inexpensive. Although the cost of hydrogen peroxide is higher than the cost of the oxygen in the small-capacity processes of fine organic synthesis using the first oxidizer is often preferable, because the cost of technological equipment for the oxidation of N2About2in General lower than for oxidation, which is usually carried out at elevated temperatures and pressures [R.A.Sheldon, J.Dakka. Heterogeneous catalytic oxidations in the manufacture of fine chemicals. Catalysis Today 19(1994)215].

The known method of synthesis of a multifunctional catalyst for self-tuning W is dataseg low-temperature oxidative cracking of organic raw materials, including natural biomass, which is dissolved or suspended salt of iron in water containing a surface-active substance (surfactant), usually selected from a lower alcohol and a lower organic acid, at concentrations required for the formation capable of peptization of the colloidal system, when heated to a temperature not exceeding 100°C. and constant stirring. The result is a colloidal suspension of solid particles of iron oxide containing organic impurities, which has the ability to alter their activity depending on the type of organic feedstock and oxidant and has the properties of enzymes in the cracking of natural biomass containing lignin. As iron salts used FeCl3x 6H2O, and as a surfactant use ethyl alcohol and the process is conducted at a temperature of 65°C and stirring for 15 minutes. When it is desired concentration of alcohol, and salts of iron, necessary for formation capable of peptization of the colloidal system is 1%(vol.)10 ml/l and 0.05 g/l, respectively. There is also known a method of liquid-phase low-temperature oxidative cracking of organic raw materials, including natural biomass in the presence of a catalyst at atmospheric pressure (patent No. 2425715), which involves the dissolution of iron salts in water, the content is overall lower alcohol concentrations necessary for formation capable of peptization colloidal mass when heated to a temperature not exceeding 100°C. and constant stirring, as the oxidant used hydrogen peroxide, the process is conducted at a temperature from 20°C to 80°C (prototype).

The disadvantage is using only tap water of medium hardness (2-10°F, degrees of hardness) in the process.

The known method requires a separate stage of obtaining a colloidal dispersion of the catalyst.

The disadvantage of this method is the consumption of large amounts of water and the uncertainty of the quantity and quality of water consumed during biomass processing.

The present invention is:

- getting from biomass cellulose and organic acids in a continuous process with a closed water cycle.

- improvement of the known method of producing pulp from natural biomass through the implementation process in one cycle, while the synthesis of the catalyst is associated with oxidative processing of biomass.

- implementation of process without pre-treatment, i.e. the possibility of using water of any degree of hardness and any pH;

In the proposed method, the water consumption is reduced by about an order. Consumed amount of water not submitted the deadweight loss as in alternative ways, and can be 90-80% re-used.

In the proposed method of obtaining a cellulose solution of low molecular weight oxidation products use a colloidal suspension of the catalyst, which is based on iron oxides containing organic impurities. Necessary for the functioning of the catalyst pH 6.0-7.0 water environment is created by addition of soda ash (Na2CO3), contributing to the formation of microaggregates, well communicating with the surface of the biomass to be processed. The number of added soda is determined by the amount of biomass and iron salts. The mass ratio of ferric chloride (3) and soda is in the range of 1.5-4, depending on the water hardness.

As a result of implementation of the method of producing pulp and solution of low molecular weight oxidation products are colloidal suspension of the catalyst, which is based on iron oxides containing organic impurities. The catalyst has the ability to alter their activity depending on the type of organic feedstock and oxidant exhibiting the properties of enzymes in the cracking of natural biomass containing lignin.

The invention relates to variants of the method of producing pulp and solution of low molecular weight oxidation products (solution of water-soluble products), zakluchalsya, that

- water containing 1-10% of a lower alcohol, heated to 58-75°C, add FeCl3x 6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, and the resulting mixture was stirred at a temperature of 25-70°C until complete consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

- heat the water to 58-75°C, add FeCl3x 6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, per mesilat the resulting mixture at a temperature of 25-70°C until complete consumption of hydrogen peroxide share received oxidat solid precipitate and a solution of water-soluble products, wash the solid residue with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

- heat the water to 58-75°C, add FeCl3x 6N2Oh, withstand aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe+3make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, stir the resulting mixture at a temperature of 25-70°C until complete consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

- water containing 1-10% of a lower alcohol, heated to 58-75°C, add FeCl3x 6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, the resulting mixture was stirred and kept not the Sabbath. m ore than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, the resulting mixture was stirred until total consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

that can heat the water to 58-75°C, add PeCl3x 6N2Oh and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, and the resulting mixture was stirred until total consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

- heat the water to 58-75°C, add PeCl3x 6H2O maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes PR is continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, and the resulting mixture was stirred until total consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

- flushing of sediment carried out n times, where n≥1.

- heated sea water or ocean water or river water or a mixture of water from the flushing of sediment.

a solution of a water-soluble product is a mixture of organic acids, esters, polyphenols and oligosaccharides.

- additions of hydrogen peroxide exercise dosage in the n-tricks, where n≥1

The solid residue is a cellulose. If necessary (to obtain high-quality cellulose) repeat washing the solid product. Water from washing washing (single, double, etc. flushing of sediment can be used in subsequent cycles of oxidative processing of biomass, i.e. water from washing the solid residue containing n is schie alcohols and water-soluble products can be used as part of the required amount of water to obtain a catalyst (implementation methods biomass), i.e. used in subsequent cycles

As organic raw materials can be used tow (bast crops), natural biomass, including straw (rice, rice, reed, cane, etc.)., peat, waste products of the production of vegetable oils - olive, palm, linseed etc. (bagasse), wood waste (e.g., sawdust pine, eucalyptus and other tree species), technical lignin, fire (linen, cotton, and others).

Mixture to the total consumption of hydrogen peroxide is not less than 2 hours.

Hydrogen peroxide can be served immediately (the required number is served at once), and metered in n-receptions (n≥1), which leads to a more efficient use of hydrogen peroxide.

The advantage of the proposed invention is the ability to combine in a single process (reactor) synthesis of catalyst and the oxidation processing of biomass. This reduces the consumption of water (approximately)), energy and catalyst components.. depending on the ratio of catalyst and biomass it is possible to regulate the release of water-soluble products and a solid residue. Water-soluble products are a valuable product for agriculture. They contain organic acids and polyphenols, which may find application in to the amount of preservatives and dietary supplements in feed production in agriculture.

Because as the oxidant is hydrogen peroxide, the resulting products are sterile, i.e. safe from the point of view of bacterial contamination. A virtually waste-free process, because the resulting solid precipitate is a pulp.

Oxidation of lignin in the lignin-cellulosic biomass using as the oxidant hydrogen peroxide and received in the process of catalyst leads to the production of pulp and valuable organic, easily recyclable and is the preferred process than the currently used processes using acid and alkali, resulting in huge amounts of troublesome, dangerous waste. In the catalytic mechanism of oxidative cleavage involving hydrogen peroxide and oxygen. Thus in the proposed invention simulates natural enzymatic processes of decomposition of organic natural materials.

The advantage of the newly proposed method is the use of cheap raw materials in a one-step process., however, depending on the weight proportions of iron salt/surfactant/water achieved by obtaining catalysts of oxidative cracking with various catalytic and physico-chemical characteristics, which allows creci the guy, leading to a different composition of products and in different reaction media from water to hydrocarbon. While colloidal particles of the catalyst accelerates the reaction of oxidative cracking when replacing the water environment on carbohydrate (alcohols) and hydrocarbon, and when applied to a surface such as a glass substrate, depending on the environment type catalysts exhibit radical and molecular types of catalysis.

The method in accordance with the present invention carried out by the following procedure:

Fill the reactor water containing 1-10% of a lower alcohol, heated to 58-75°C, add PeCl3x 6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75 With not less than 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe+3then the resulting suspension is used as a catalyst. An indicator of the formation of the catalyst is the absence of ions Fe3+that determine, for example, in the absence of pink color when added to water of potassium thiocyanate (KSCN). Make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, and the resulting mixture was stirred at which the temperature 25-70°C until complete consumption of hydrogen peroxide, divide the resulting oxidate solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

Pour into the reactor water, which is heated to 58-75°C, add PeCl3x 6N2Oh and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, and the resulting mixture was stirred at a temperature of 25-70°C until complete consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

Pour into the reactor water, heat it up 58-75°C, add FeCl3x 6H2O maintain the aqueous solution at a temperature 58-75 With not less than 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe+3make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, and the resulting mixture was stirred at a temperature of 25-70°C until complete consumption of hydroperoxides, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

Pour in the reactor water containing 1-10% of a lower alcohol, heated to 58-75°C, add FeCl3x 6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3.5:0.5, and the resulting mixture was stirred until total consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

N is liveout in the reactor water, heat it up 58-75°C, add FeCl3x 6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide hydrogen at a ratio of hydrogen peroxide to the biomass 3.5:0.5, the resulting mixture was stirred until total consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, which, after washing use in the following cycles and/or added to aqueous solution of water-soluble products.

Pour into the reactor water, heat it up 58-75°C, add FeCl3×6N2Oh, withstand aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3,5:0,5, the resulting mixture was stirred for 2-25 hours to the total consumption of hydrogen peroxide share received oxidat solid residue with water, after rinsing, use the following cycles and/or added to aqueous solution of water-soluble products.

Flushing of sediment carried out n times, where n≥1.

For a process can use any water - tap, distilled, sea water or ocean water or river water, a mixture of water from washing the solid residue, the mixture of water or distilled or sea or ocean or river water with water from the flushing of sediment, the water from washing the solid residue.

The resulting solution of low molecular weight products (solution of water-soluble products) is a mixture of organic acids, esters, polyphenols and oligosaccharides.

Additions of hydrogen peroxide dosed exercise in several techniques. The quantity of additives and the size of the dose depends on the quality and kind of the used organic materials, including biomass.

Examples of the application of the method of processing biomass

Example 1.

Oxidative cracking of sawdust pine (rough grinding, the particle size 1-3 mm)

In a glass reactor placed 220 ml of water containing 2% ethanol, and heated to 70°C, was added 0,149 g FeCl3×6N2Oh, stood at this temperature for 10 min and left to the time required for maturation of sediment. Then, with stirring, was added 10 g of sawdust, peroxide water the ode (34 g). Oxidative cracking was carried out at 70°C for 18 h; the content of catalyst in the reactor in terms of Fe3+was 0,083%.

Separation of the products was performed by centrifugation. The output of the cellulose 0.5 g, 5%.

The release of organic acids: 0.1 mol.

Water-soluble products - 2.8 g (28%).

Range of IR solid product is shown in figure 1. Range IR water-soluble products shown in figure 2.

Example 2.

Oxidative cracking of sawdust pine (rough grinding, the particle size 1-3 mm)

In a metal reactor was placed 800 ml of water containing 2% ethanol, and heated to 70°C; added 0.75 g FeCl3×6N2Oh, stood at this temperature for 10 min and left to the time required for maturation of sediment. Then with stirring, added 61 g of sawdust, hydrogen peroxide (90 g). The total volume of water - 1100 ml. of Oxidative cracking was carried out at 70°C for 15 h; the content of catalyst in the reactor in terms of Fe3+was 0,278%.

Separation of the products was performed by centrifugation. Pulp output 18 g, 29.5 per cent. The release of organic acids: 0.51 mol. Water-soluble products - 13 g (22%).

Range of IR solid product shown in figure 3. Range IR water-soluble products is shown in Fig.4.

Example 3.

Oxidation of oat straw (collectively, stems, seeds, leaves, cut into pieces 15-20 mm)

In metal the mini-reactor was placed 850 ml of water and heated to 70°C; added 0,77 g FeCl3×6N2O and 0.02 g of sodium (Na2CO3), held at this temperature for 10 min and left to the time required for maturation of sediment. Then, with stirring, was added 55 g of straw, hydrogen peroxide (94 g). The total volume of water - 1100 ml.

Oxidative cracking was carried out at 70°C for 28 h, the content of catalyst in the reactor in terms of Fe3+was 0,286%.

Separation of the products was performed by centrifugation. Pulp output 11 g, 20%.

Water-soluble products - 9.5 g (17%).

Range of IR solid product is shown in figure 5. Range IR water-soluble products is shown in Fig.6.

Example 4.

Oxidation of stems of oat straw (chopped pieces of 15-20 mm)

In a glass reactor placed 310 ml of water used for washing the pulp from previous experience, and was heated to 60°C, was added 0,147 g FeCl3×6N2Oh and, 0,012 g of sodium (Na2CO3), held at this temperature for 10 min and left to the time required for maturation of sediment. Then under stirring was added 29 g of straw, hydrogen peroxide 90 ml (36 g). Oxidative cracking was carried out at 60°C for 38 h, the content of catalyst in the reactor in terms of Fe3+amounted to 0.15%.

Separation of the products was performed by centrifugation. Pulp output 7 g, 24%.

The release of organic acids: 0.1 mol.

Odorant arimah products 5.5 g (19%).

Range of IR solid product is shown in Fig.7. Range IR water-soluble products is shown in Fig.8.

Example 5.

Oxidation of stems of oat straw (chopped pieces of 15-20 mm)

In a glass reactor was placed 160 ml of water containing 2% ethanol, and heated to 67°C, was added 0,147 g FeCl3×6N2Oh and, 0,012 g of sodium (Na2CO3), held at this temperature for 10 min and left to the time required for maturation of sediment. Then under stirring added to 5.1 g pre-swollen straw, hydrogen peroxide (12 g) was introduced fractional (see table). Oxidative cracking was carried out at 60°C for 43 h.

During oxidation was controlled by the consumption of hydrogen peroxide, selecting microsamples in the course of oxidation. Analysis of peroxide was performed by the method iodometric titration. This experience was carried out by fractional flow of hydrogen peroxide (H2O2). Each of the next portion of H2O2 was injected after using up the previous portion. The number and duration expenditure of each portion are shown in table 1. The last portion of H2O2 was also trashdolls to end.

Table 1.
Characteristics of the consumption of H2O2 at fractional add in rectional mixture of 5.1 g of cut straw, the catalyst is received from 0.14 g FeCl 3×6N2About 160 ml of water
№ p/pQty H2O2, g(ml)The initial H2O2 concentration,mol/lReaction time, hoursInitial rate of consumption of H2O2, 105, mol/(l s)
10.16(0.4)0,02560,31
20.16(0.4)0,02140.1
30.8 in(2)0,1160,26
41,8(4,5)0,2982,3
52,48(6)0,2351,18
61,6(4)0,1160,4
72,48(6)0,25 43,0
82,48(6)0,1140,83
Only12(29)43

Separation of the products was performed by centrifugation. Pulp output 1.2 g, 23.5 per cent. The release of organic acids: 0,007 mol. Water-soluble products of 0.85 g (17%).

Example 6.

Oxidation of woody debris of eucalyptus (thin branches with bark) (scissored pieces 4-8 mm)

In the glass vessel was placed 200 ml of distilled water, added 0,137 g of sodium (Na2CO3), 7 ml of ethanol, was heated to 65°C, was added 0,188 g FeCl3×6N2Oh, stood at this temperature for 10 min (pH 11).

After deposition of sediment added to 10.5 g of dry eucalyptus pieces and left for the night. Then added 50 ml of a 19%solution of hydrogen peroxide, mixed and raised the temperature to 70°C. Oxidative cracking was carried out for 18 h.

Separation of the products was performed by centrifugation. Pulp output 4.1 g,39%. The release of organic acids: 0.18 mol.

Water-soluble products 2.1 g (22%).

Range of IR solid product is shown in Fig.9.

Example 7. Oxidation fires (large enough ragment different sizes).

Fire is the woody part of the stalk of the flax, obtained from primary processing, it is up to 70% of the mass of the stem.

In a glass reactor was placed 200 ml of tap water was added 0.11 g of sodium (Na2CO3), 7 ml of ethanol, was heated to 65°C, added to 0.19 g FeCl3×6H2O, held at this temperature for 10 min (pH 8). After deposition of the catalyst in the reaction vessel was placed 11,35 g dry fragments of fires of different sizes and left for the night. Then added 50 ml of a 19%solution of hydrogen peroxide, mixed and raised the temperature to 70°C. Oxidative cracking was carried out for 20 hours.

Separation of the products was performed by centrifugation.

Pulp output - 6,55 g, 57,7%.

The release of organic acids: 0.24 mol.

Water-soluble products of 1.88 g (16,5%).

Example 8. Oxidative cracking of rice straw

In a glass reaction vessel was placed 170 ml of tap water (pH 6.5)was added 0.08 g of sodium (Na2CO3), 6 ml of ethanol, was heated to 70°C, was added 0,144 g FeCl3×6N2Oh, stood at this temperature for 10 min (pH 8; when added to 1 ml of the aqueous phase of potassium thiocyanate no krasivaya).). After deposition of the catalyst in the reaction vessel was placed 3.5 g cut straw, pre-soaked in 30 ml of water, and thoroughly mixed. Then added 4.6 g of hydrogen peroxide. Oxidative cracking of n is bodily for 25 hours under stirring without additional heating.

Separation of the products was performed by centrifugation.

Pulp output - 1,36 g (38.8 per cent).

The release of organic acids: 0.14 mole.

Water-soluble products to 0.63 g (18%).

Example 9. Oxidative cracking of rice straw

In a glass reaction vessel was placed 200 ml of water (pH 6.5), used for washing the pulp from previous experience (pH 6.5)was added 0.08 g of sodium (Na2CO3), was heated to 70°C, was added 0.16 g FeCl3×6N2Oh, stood at this temperature for 10 min under stirring and left to complete deposition of sediment (pH 7.5). After deposition of the catalyst in the reaction vessel was placed 4.1 g of cut straw, carefully mixed, was added hydrogen peroxide (2.7 g). The following portions of hydrogen peroxide (2.7 g) was added after 8 hours and after 16 hours. In total, the oxidation was carried out for 24 hours under stirring (without additional heating)

Pulp output - 1.64 g (40%), acid - 0.2 mol, of water-soluble products - 0.74 g (18%)

1. A method of processing biomass, namely, that water containing 1-10% of a lower alcohol, heated to 58-75°C, add FeCl3×6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+make a biome is su when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3,5:0,5, stirred the mixture at a temperature of 25-70°C until complete consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

2. The method according to claim 1, characterized in that the washing of the solid precipitate is carried out n times, where n≥1.

3. The method according to claim 1, characterized in that the heated sea water, or ocean water, or river water, or a mixture of water from the flushing of sediment.

4. The method according to claim 1, characterized in that a solution of a water-soluble product is a mixture of organic acids, esters, polyphenols and oligosaccharides.

5. The method according to claim 1, characterized in that the additive of hydrogen peroxide implement metered in n tricks, where n≥1.

6. A method of processing biomass, namely, that heat the water to 58-75°C, add FeCl3×6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution until complete precipitation of Fe3+introducing the biomass when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3,5-0,5, stirred the mixture at a temperature of 25-70°C until complete consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

7. The method according to claim 6, characterized in that the washing of the solid precipitate is carried out n times, where n≥1.

8. The method according to claim 6, characterized in that the heated sea water, or ocean water, or river water, or a mixture of water from the flushing of sediment.

9. The method according to claim 6, characterized in that a solution of a water-soluble product is a mixture of organic acids, esters, polyphenols and oligosaccharides.

10. The method according to claim 6, characterized in that the additive of hydrogen peroxide implement metered in n tricks, where n≥1.

11. A method of processing biomass, namely, that heat the water to 58-75°C, add FeCl3×6H2O and soda when the mass ratio of ferric chloride and sodium 1,5-80, maintain the aqueous solution at a temperature 58-75°C for at least 10 minutes with continuous stirring, leave the aqueous solution to precipitation of Fe3+make a biome is su when the ratio of water to biomass 10-20, stir the mixture and incubated for no more than 10 hours, add hydrogen peroxide at a ratio of hydrogen peroxide to the biomass 3,5-0,5, stirred the mixture at a temperature of 25-70°C until complete consumption of hydrogen peroxide, share received oxidat solid precipitate and a solution of water-soluble products, the solid residue is washed with water, after which rinse is used in the following cycles and/or added to aqueous solution of water-soluble products.

12. The method according to claim 11, characterized in that the washing of the solid precipitate is carried out n times, where n≥1.

13. The method according to claim 11, characterized in that the heated sea water, or ocean water, or river water, or a mixture of water from the flushing of sediment.

14. The method according to claim 11, characterized in that a solution of a water-soluble product is a mixture of organic acids, esters, polyphenols and oligosaccharides.

15. The method according to claim 11, characterized in that the additive of hydrogen peroxide implement metered in n tricks, where n≥1.



 

Same patents:

FIELD: textiles, paper.

SUBSTANCE: method of production of cellulose lies in cooking wood chips at a temperature of 90-98°C, thorough mixing and at atmospheric pressure of 740-760 mm Hg in a mixture containing 3.9-5.6 wt % hydrogen peroxide, 25.2-26.7 wt % acetic acid in the presence of 2.0 % by weight of sulfuric acid catalyst chips with a duration of cooking of 2.5-3.5 hours, and irrigation modulus of 5-10 with subsequent isolation of the target product.

EFFECT: simplifying the method of production of cellulose, increase in target product yield, improvement of quality characteristics of the target product by increasing the content in it of holocellulose and reduction of residual lignin.

1 tbl, 11 ex

FIELD: textile, paper.

SUBSTANCE: method includes two stages of rice straw boiling. The first boiling stage is carried out in the alkaline medium with subsequent separation of cellulose-containing product, the second stage of boiling is carried out in the acid medium by mixture of peracetic acid (PAA), acetic acid and hydrogen peroxide in presence of a stabiliser, such as a mixture of organic phosphonates. At the same time the second stage of boiling is carried out in presence of ozone with a flow rate of 2-4 g/hr.

EFFECT: reduced flow of composition based on PAA, higher yield of finished product, reduced content of lignin and increased whiteness indices.

2 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: detection is carried out by treating the intermediate product with sulphuric acid. The intermediate product is then undergoes successive nitration with concentrated nitric acid, alkalisation and amount of lignin is photometrically determined.

EFFECT: simple and fast process.

2 tbl, 24 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: invention is directed to manufacture fibrous intermediate products from agricultural wastes originating from groats and grain crop (straw and fruit coats) processing. Cellulose manufacturing process is conducted in two steps. In the first step, preliminarily milled annual plants are treated with NaOH solution having concentration 20-60 g/L at temperature not lower than 70°C during at least 20 min. Cellulose-containing raw material is then separated from alkali solution. In the second step, pulping is conducted with mixture of peracetic acid, acetic acid, and hydrogen peroxide at weight ratio (1.25-1.75):1.0:(0.25-0.75), respectively, used in amount 0.3-1.0 g per 1 g bone-dry raw material in presence of stabilizer selected from organic phosphonate series, namely organophosphonate mixture containing sodium nitrilotrimethylenephosphonate and sodium methyliminodimethylenephosphonate salts as major components. Stabilizer is added in amount 0.005-0.02% based on the weight of bone-dry raw material.

EFFECT: extended resource of raw materials, improved quality of desired product, and thereby enabled manufacture of high-quality cellulose products and reduced expenses on industrial-scale cellulose manufacture.

6 cl, 4 tbl

FIELD: pulp-and-paper industry, in particular, production of sulfite cellulose.

SUBSTANCE: method involves mixing fir tree and hardwood chip; performing sulfite pulping of mixture and washing resulted pulp, with young thin birch wood being used as hardwood chip produced after wood care cuttings in an amount making 10-60% by total amount of raw wood material.

EFFECT: simplified method for producing of cellulose, wider range of raw material base and reduced cellulose production costs.

1 tbl, 8 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: invention relates to production of fibrous intermediate products from annual plants, in particular from rice husks and/or rice straw. raw materials are first treated with NaOH solution, 20-60 g/L, at temperature not lower than 70°C for at least 20 min in order to remove silica. Resulting pulp is then washed to neutral reaction and then subjected to delignification process in ice acetic acid-hydrogen peroxide mixture in presence of sodium molybdate.

EFFECT: improved quality of cellulose material and extended resource of raw materials.

2 tbl

FIELD: pulp-and-paper and food-processing industry.

SUBSTANCE: fibrous product contains grain-based fibrous material treated with acid and having full coefficient of cellulose of at least 50% and coefficient of hemi-cellulose of at least 5%. Described are fibrous product used for obtaining preferably paper products, food products, food mixture with additive based on fibrous product, method for treating of grain-based fiber, and methods for manufacturing paper and food product.

EFFECT: increased strength of paper without increasing of main weight, increased functional properties, improved structure, coagulation and taste of food product obtained with the use of grain-based fibrous material.

36 cl, 31 dwg, 10 tbl, 20 ex

FIELD: pulp-and-paper industry, in particular, production of cellulose from cellulose semi-finished products.

SUBSTANCE: method involves cooking ground larch wood in mixture having 37 wt% of hydrogen peroxide and 30 wt% of acetic acid used in mole ratio of 0.3-0.5 in the presence of molybdic acid catalyst used in an amount of 0.5-0.7% by weight of perfectly dry wood; providing cooking at liquor ratio of 7.5:1 - 10:1 and at temperature of 110-140°C for 2-3 hours.

EFFECT: improved quality of cellulose semi-finished product, reduced consumption of reactants and catalyst, wider range of available raw materials owing to utilization of larch wood, and manufacture of cellulose semi-finished product without preliminarily providing of arabinogalactane extraction stage.

3 tbl, 22 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: process of producing high-refined cellulose for manufacture of man-made fibers and films comprises water or acid pre-hydrolysis of disintegrated vegetable material followed by delignification of pre-hydrolyzed wood by way of catalyzed peroxide pulping and alkali extraction of oxidized lignin at atmospheric pressure. Final operations are bleaching and alkali refining of cellulose.

EFFECT: improved quality of cellulose, improved environmental safety of process, and reduced power consumption.

1 tbl, 4 ex

FIELD: textiles, paper.

SUBSTANCE: production processes of mechanical wood pulp using refiners are disclosed, and more particularly, the wood-pulp plant is disclosed which is integrated with the neutral-alkaline processes of paper production, generating printing paper from mechanical wood pulp. The waste products are treated with hydrogen peroxide, alkali and an organic stabilising additive immediately before or during refining, that provides improved optical and physical properties of the refined waste products and uses electrical energy more efficiently to achieve the desired quality of the fiber after bleaching for cost-effective production of a wide variety of coated and uncoated printing paper from mechanical wood pulp.

EFFECT: improvement of quality of rejected material.

4 cl, 2 tbl, 12 dwg

FIELD: textiles, paper.

SUBSTANCE: method for producing sulphate pulp from a mixture of chips from different species of wood includes the use of three batch cookers sequentially interconnected by liquid phases, their loading with a mixture of chips from different species of wood, including wood of larch, pine, spruce, birch, aspen, preliminary two-stage treatment of the mixture with water extraction at the first stage and black liquor at the second, removal of the extract from the cooker, supply to the cooker of cooking liquor, recycling the extract to obtain arabinogalactan. Both extraction treatments are carried out in three cookers interconnected by liquid phases by their sequential filling with each of the liquid phases with the removal of the aqueous extract by its replacement from the cookers by black liquor and the removal of the black liquor by its displacement by the cooking liquor.

EFFECT: alignment of the characteristics of chips from all types of wood and increase in the concentration of arabinogalactan in the aqueous extract.

4 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: material is fed into a mixer 1 and treated with steam from a pipe 10. The treated material is then fed into a screw feeder 2 which is provided with valve locking device. The reactor 3 is in form of a vertical cylindrical vessel which is provided with means of loading and unloading material and a means of intensifying agitation of the reaction mass, having a pulsation chamber 4, which encloses the reactor 3, and a pulsator - pulse generator 12. Cooking liquor is fed into the reactor 3 through pipe 5. Spent cooking liquor is removed from the reactor 3 through pipe 6. Steam is fed into the reactor 3 through pipe 7, which is fitted with steam injectors. The reaction mass is subjected to acoustic energy pulses with frequency of 5-70 pulsations per minute with energy density of 3-100 MJ/mol. The pulsator - pulse generator 12 consists of a compressor 13, a receiver 14, a pipe 16 and a pulse generator 15. The reaction mass is moved into the top part of the reactor 3 and, using a blade or scrapping device 8 of a screw device 9, the ready product is separated from the cooking liquor to obtain the end product - edible cellulose.

EFFECT: simple reactor design and delignification technology, low power consumption, while improving quality of the cellulose mass.

3 cl, 3 dwg

FIELD: textiles, paper.

SUBSTANCE: method includes cooking of cellulose containing raw material in the presence of hydrogen peroxide, followed by alkali extraction and washing off. Carbon dioxide in the supercritical state is used as a medium, and the hydrogen peroxide is added in the form of a solution containing at least 30% hydrogen peroxide. Consumption of hydrogen peroxide for cooking is at least 65% by weight of oven-dry wood.

EFFECT: invention enables to produce cellulose wood pulp which has high mechanical strength, to improve the environmental situation near the manufacturing enterprises.

5 cl, 6 ex, 1 tbl

FIELD: textiles, paper.

SUBSTANCE: reactor vessel has an inlet to enter the cellulosic material and an outlet for discharging cellulosic material, and the cellulosic material flows through the reactor vessel from the inlet for the material to the outlet to unload the material; extracting sieve for hydrolysate and liquid; hydrolysis zone between the inlet for the material and extracting sieve for hydrolysate and liquid. Hydrolysis zone is maintained at a temperature of hydrolysis or above the temperature of hydrolysis at which the reaction of hydrolysis of the cellulosic material takes place. The reactor vessel contains the flush zone between the extracting sieve for hydrolysate and liquid and extracting sieve for flushing fluid, where hydrolysis is suppressed; an inlet pipe for flushing fluid to enter the flushing fluid in the flush zone. At least a part of flushing fluid flowing into the inlet pipe for flushing fluid flows through the flushing zone and is extracted with extracting sieve for hydrolysate and liquid, and the flushing fluid is entered into the flushing zone at a temperature below the temperature of hydrolysis. The reactor vessel contains a pulping area between the flushing zone and unloading zone for release of material, and the said pulping area includes a pipe for injecting of cooking liquor; and extracting sieve for cooking liquor in the pulping area or under the pulping area, and over the unloading release for the material, and the flushing fluid is a mixture of water and at least one of the substances, such as sodium hydroxide and white liquor, essentially free of sulfur.

EFFECT: reduction of risk of precipitation of lignin and other dissolved wood components, and reduction of consumption of alkali during the chemical pulping of cellulosic material.

40 cl, 1 dwg

FIELD: textiles, paper.

SUBSTANCE: whiteness of paper products of natural colour is 35-60% ISO, and for their production unbleached straw cellulose is used with a tensile strength of 230-280 mN, fracture strength with multiple bends of 40-90 times and permanganate index of 16-28. The composition of natural-coloured paper products includes sanitary and hygienic natural-coloured paper, paper towel of natural colour, paper for wipe of natural colour, paper for photocopies of natural colour, paper box for food of natural colour, natural-coloured wrapping paper for food products, and printing paper of natural colour.

EFFECT: strength of the above mentioned paper products is high, and when control over the content of harmful substances dioxin and adsorbable organic halides are not detected.

24 cl, 20 ex

FIELD: textiles, paper.

SUBSTANCE: method of delignification of wood chips is carried out in the digester during turbulisation of the pulp. For this a limited along the length fragment of the area of the brewing process in the digester is chosen, which is over the entire cross section of the stream of pulp is divided into a series of parallel and independent streams, in each of which turbulisation is created. The latter is carried out by periodic changes in the volume of each of the streams, which is implemented due to changes in cross-sectional area of these streams.

EFFECT: significant acceleration of delignification process, decrease in temperature of technological zones and pressure in them, and the reduced specific energy consumption of pulping, increased productivity of plants, weight and size characteristics of the digester are reduced several times.

3 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: raw material undergoes steam treatment before the cooking step. Cellulose obtained by cooking, undergoes cold caustic extraction (CCE) during subsequent treatment.

EFFECT: invention enables to obtain cellulose with high output and purity of the product, and avoid accumulation of hemicellulose in the bleaching filtrate.

21 cl, 7 ex, 9 tbl, 13 dwg

FIELD: oil and gas industry.

SUBSTANCE: synthesis method of multi-purpose self-adjusting catalyst for liquid-phase low-temperature oxidation cracking of organic raw material, including natural biomass, is described, and it consists in the fact that iron salt FeCl3 x 6H2O is dissolved in water containing lower alcohol in concentrations required for formation of colloid system capable of peptisation, at heating up to the temperature not exceeding 100°C and constant mixing so that suspension of colloid solid particles of iron oxides containing organic impurities is obtained. The above suspension can change its activity depending on type of organic raw material and oxidiser, and at cracking of natural biomass and in case the latter represents lignine or lignine-containing biomass it has properties of ferments in relation to lignine. Method of liquid-phase low-temperature oxidising cracking of organic raw material, including natural biomass, in presence of catalyst at atmospheric pressure is described. At that, air oxygen and/or hydrogen peroxide is used as oxidiser and the above catalyst is used as catalyst.

EFFECT: high-activity catalyst of liquid-phase oxidising cracking.

8 cl, 7 dwg, 11 ex

FIELD: chemistry.

SUBSTANCE: water suspension of crushed aspen wood is put into a flow reactor and ozonised. Ozonation is carried out with concentration of ozone in the ozone-oxygen mixture equal to 90 mg/l, gas flow rate equal to 2-4 l/h and temperature of 20°C and hydromodulus between 0.1:1.0 and 1.6:1.0.

EFFECT: high quality of the cellulose intermediate product, low consumption of reagents, high ecological cleanness of the process.

5 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: present invention describes a method of producing hydrocarbon raw material for synthesis of biofuel from lignin. The method involves hydrotreatment of lignin-containing raw material to obtain raw material for biofuel. The lignin-containing raw material contains lignin which is separated from black liquor from a pulping method. The lignin is separated from black liquor from a pulping method by injecting carbon dioxide (CO2) gas. The lignin-containing raw material further contains still residues from an oil refining plant.

EFFECT: as a result of hydrotreatment of lignin contained in raw material for biofuel, oxygen content and average molecular weight of the latter decreases compared to lignin.

8 cl, 6 dwg

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