3816106 - EP18924058A1 - EPO
Application Jun 28, 2018 - Publication May 05, 2021
Disclosed is a method for producing silicon dioxide from a cellulose-containing material using acid hydrolysis of a feedstock before burning same in order to produce silicon dioxide. The method makes it possible not only to produce silicon dioxide, but also to isolate carbonaceous materials such as monosaccharides and lignin as additional products, while expending less energy.
The invention relates to a technology for deep conversion of agricultural waste, waste of municipal facilities and other types of waste (sawdust, wheat straw, paddy straw etc., rice husk and sunflower husk, bagasse of fast-growing grass, residual sludge of the urban treatment facilities etc.), namely, to the field of conversion of cellulose-containing materials in order to extract silicone dioxide and organic substances contained in such materials for subsequent use thereof in various technical fields. Thus, the silicon dioxide extracted in this process can find application in the tire industry (as a filler), the production of industrial rubber goods and plastics, chemical and food industry, machine-building industry, electronics and electrical engineering industry.Background of the inventionRice husk is used as the most common vegetable source raw material for producing silicon dioxide. In this case, two different technologies are used - without pretreatment of source material (rice husk) and with pretreatment.Methods for producing silicon dioxide without the pretreatment of source raw material involve simple roasting of rice husk at high temperatures. Examples for this method are the Patent of Germany No.2416291, Cl. C04 B and British Patent No.150 8825, Int.Cl C01B 33/12, where rice husk is roasted with the roasting temperature varying in the range of 200°C - 900°C. The main disadvantages of such a method for producing silicon dioxide are the fact that the produced product has a low degree of purity and the fact that up to 80% and more of the mass of husk are discharged into the atmosphere in the form of gases.The second type of technology uses pretreatment of a source raw material before the stage of roasting with dilute solutions mineral or organic acids, water wash and, afterwards, stepped annealing of the residue in the temperature range of 300°C - 1100°C (US Patent 7998448 B2andUS Patent 118 9403688 B1). However, when it used there is a large mass of waste (at the preliminary stage of processing, lignin is not removed, but only partially cellulose and hemicellulose) and one type of product is obtained, silicon dioxide, which is in the amorphous phase.Thus, though preliminary preparation of the source raw materials when producing silicon dioxide by the method of roasting yields better results compared to the methods that do not involve prepreparing the source raw material, however, it has two significant disadvantages. First, the multistage processes use large volumes of liquids and a variety of equipment, which leads to high energy costs. Second, they do not allow to process and use all potentially possible useful related substances of cellulose-containing materials in an integrated fashion. Rice husk contains only about 15% - 20% of silicon dioxide (like many other cellulose-containing materials and waste), while in the existing technologies 80% - 85% of the remaining substances included in the material, namely cellulose, polysaccharides, lignin and a number of other valuable substances are lost irretrievably and destroyed.The most effective is the method for producing silicon dioxide (US Patent 8178067 B2) from the waste of forest raw material, agricultural raw material or materials containing hexose and/or pentose and SiO2, where acid hydrolysis of the source cellulose-containing material is performed in two steps using high pressure in order to produce silicon dioxide before the process of roasting (in the presence of mineral or organic acid). At the same time, it is possible to decrease the content of the components containing hexose and pentose in the source material up to 10 weight % and 20 weight % respectively. At the same time, the content of polyphenols (in particular, lignin) in the residue after the stage of hydrolysis reaches 40 weight %, which makes the process of roasting the residue difficult and expensive. The residue is annealed after hydrolysis at a temperature from 400°C to 1200°C.Summary of the inventionThe purpose of the invention is to develop a method for producing silicon dioxide by burning a cellulose-containing material that has undergone preliminary preparation aimed at removing (maximum reduction) of its carbon part before the combustion process. Another purpose of the invention is to develop such a method that would allow to extract from the source raw material other useful products, monosaccharides (hexose and pentose), as well as pure unsulphated lignin, in addition to producing silicon dioxide as a final target product.These and other accompanying purposes, in particular, reduction of costs of raw material pretreatment and a decrease in the quantity of generated gas products during the step ofroasting a pretreated raw material when producing silicon dioxide are achieved by the invention using raw material pretreatment technique including:acid hydrolysis of raw material under pH < 5, at a temperature of 140°C - 240°C and under elevated pressure, separation of lignin and monosaccharides from the reaction products. Silicon dioxide is extracted by burning the solid part of the hydrolysis residue at a temperature of 350°C - 750°C.To increase the yield of monosaccharides as one of useful by-products in addition to silicon dioxide, it is advisable to perform hydrolysis in the presence of at least one of the protectors protecting monosaccharides from high temperatures and pressure. Ketones or oxygen-containing heterocycles can be used as such protector.It is also advisable to perform additionally the following operations: washing the hydrolysis residue with a solvent to reduce the carbon content; treating the hydrolysis residue with IN hydrochloric acid to reduce the content of metal oxides; subjecting the lignin (raw material) to alkaline pulping in the event of high content of lignin in the source raw material.It is advisable, but not necessary, to use rice husk as a source raw material.If the raw material is pretreated in accordance with the invention, it becomes possible to extract to the fullest extent the carbon component in the form of industrially useful products (lignin, monosaccharides) from the main mass of the source raw material in an amount of up to 80% of the total mass. The hydrolysis (mineral) residue is about 20% of the source raw material and contains mainly silicon dioxide with impurities of metal oxides and insignificant residues of carbon.The above characteristics and advantages of the invention will be more clear from the following detailed description of the invention, which is given in the embodiments of the invention, is not limiting and is provided by reference to the accompanying drawing.Brief description of the drawingFig.1shows a variant of the technological scheme for implementing the method in accordance with the invention.Detailed description of the inventionReferring now toFig. 1, there is shown a flow diagram of realization of the method.The source material enters the "grinder" - dispenser M (or without preliminary grinding, just like in the case of, for example, using primary residual sludge of the treatment facilities). From the dispenser M, solid material with particles with the size of 0.5 - 1.0 mm is fed to a mixer 2. The solution for hydrolysis (HS) is also fed to the mixer through the dispenser 1. The reaction mass is fed from the mixers 2 and 1 in sequence through the dispensing pump 3 and a check valve K to a reactor 4. The reactor 4 is provided with a heating jacket (not shown in the diagram), temperature sensors, pressure sensors, a safety valve, a siphon connected to an upper valve (a throttle) to discharge reaction products, a lower valve (a throttle) to discharge reaction products, (as well as a valve to inject steam directly to the apparatus 4, if necessary, to heat the reaction mass quickly and to inject a portion of the necessary amount of water for a hydrolyzing solution or for preliminary steaming of the source raw material before treating with hydrolyzing solutions, if necessary), which are not shown on the diagram. The reaction mass is heated and the reaction products are discharged from the reactor 4 through the valves (the throttles) of the apparatus 4 into a hydrocyclone 5, where they are quickly cooled and the volatile by-products are separated, which, in their turn, are discharged through the valve 6 from the cyclone 5 to an accumulator tank (not shown). Then, through the filters 7 and 15, in which the solid components of the reaction mass are separated, the solution of the reaction products enters the distiller 8, where the protectors (or at least one) are separated. The protectors are returned to measuring tank - dispenser 1 for preparation of HS. The residue is fed to the filter (or the hydrocyclone) 9, where the lignin is separated, and then enters the "neutralizer" 10, equipped with a pH-meter (11), a gauging dispenser for a neutralizing solution (12). The neutralized products (the aqueous solution of sugars) through a filter 13 are collected in the receiving tank 14 and subsequently sent to fermentation.The solid residue from the filters 15 and 7 is sent to an accumulator tank 16, where (if necessary) it is treated with acetone to remove the residues of lignin, is treated with 1N HC1 solution and afterwards washed with water in a filter 17. The solid residue is fed to a drier 18, and from there to the zone furnace 19, where the zones with certain temperatures for combustion of the solid residue are determined depending on the quality of silicon dioxide that needs to be obtained for a specific application. The produced silicon dioxide contains total carbon in an amount of< 0.02 weight %, which shows that carbon is exhaustivelyremoved from the source cellulose-containing material in the form of useful related products.For some cellulose-containing materials, where the quantity of lignin is sufficiently high, it is possible that raw material can be pretreated, for example, by "alkaline pulping" in a solution of dilute alkali, for example, in a 4% aqueous solution of NaOH. In this case, a pretreatment unit is added to the technological scheme (Scheme 1, position 20). The grinded product is fed through the dispenser M to the"boiling tank" (not shown) in this case, where it is treated with an alkaline solution (T = 95°C - 100°C; 2 hours) and the main part of lignin contained in the source substrate is boiled down. Afterwards, alkali is washed away from the solid substrate in the filter, and the solid substrate is fed to the process chain of Scheme 1 through reference position 2, and the alkaline solution of lignin is sent to a settler (not shown), where lignin is set down. Alkali is returned to the process cycle, and the precipitation of lignin is removed from the process through a centrifuge (or a hydrocyclone).The scheme also allows for multiple processing of a dose of the source material with new portions of the hydrolyzing liquid. In this case, the reaction mix with a sample of cellulose-containing material in the first instance is fed from the mixer 2 through the dispensing pump to the reactor and, after curing, the liquid reaction products are discharged through the upper valve (the throttle) to the cyclone 5. In this case, the solid in-process sample remains in the autoclave. The fresh hydrolyzing liquid is fed from the mixer 1 by the dispensing pump 3, which switches (possibly, automatically) to this mixer. 2 withdrawals of the pure hydrolyzing solution from the mixer 1 take place per one withdrawal with a sample from the mixer 2. The valves for "discharging" the products also operate in sequence: one "discharge" through the lower valve (the throttle) takes place per 2 discharges through the upper valve (the throttle), a third treatment of the residues of the sample of the material takes place in this case.Below examples of implementation of the invention using various source materials (including those based on rice husks) and various monosaccharide protectors are provided. The overall results are presented in Table 1.Example 1The reactor was loaded with 130 g of primary sedimentary sludge from the city's treatment facilities with a humidity of 30% (100 g of dry source material), which was treated three times for 5 minutes each at T = 180 ° C and pH = 1.87 with a hydrolyzing solution (HS), at the ratio of the source material / hydrolysis solution of 1:10 and the ratio of the protector / water in the hydrolysis solution of 4:1 (protector - acetone). HS was introduced through a check valve with a dispensing pump, and the reaction products were removed through the upper and lower throttles of the autoclave into hydrocyclones, as described above (Scheme 1).The hydrolysis residue of source sludge was dried to constant weight (32 g) after filtering. The protector was removed from the combined hydrolyzing solutions by distillation in the water jet pump vacuum after filtering. The precipitated lignin was separated by filtering. The laid-down lignin was washed off from the walls of the distillation flask and dried. The total yield of lignin was 28.6 g. The residue (the aqueous solution of sugars) was neutralized up to pH = 6.1 with "calcium milk" (CaO), the precipitate was filtered out. The concentration of sugars in the aqueous solution was determined according to the saccharimeter. The yield of sugars was 32.5 g. The volatile reaction products were collected to the accumulation tanks through the valves of the cyclones. Their approximate content was 6.9 g (Table 1, item 1).The hydrolysis residue containing silicon dioxide is treated with acetone to dissolve the remaining traces of lignin, which remained in the solid residue after filtration. In this case, the content of total carbon is reduced approximately by 3.5 weight %. After washing the residue with 1N HC1 solution, the total content of metal oxides is reduced up to 0.80 weight %. Subsequently, after drying in the air, the residue is submitted to the zonal kiln. Annealing the residue at T= 600°C leads to production of silicon dioxide with the content of total carbon< 0.02 weight %. The yield of amorphous silicon dioxide was 96.5 weight %. The yield of silicon dioxide was 29.5 % of the source raw material based on absolutely dry source raw material.Example 2Bagasse in the amount of 146 g with a humidity of the source sample of 46% (100 g of dry sample) at pH = 2.5, at a temperature of 150° C - 190°C (preferably, 180°C) was subjectedto a three-time autoclave treatment, the duration of each treatment being 5 minutes. The HS/sample ratio and the protector/water ratio are similar to Example 1. The protector was a mixture of methyl(ethyl)ketone and acetone with a ratio of 1:1. The procedure is similar to Example 1. The residue of the sample after autoclave hydrolysis was 18 g. The yield of sugars and lignin was 62 g and 18 g respectively (Table 1, item 2). The contents of volatile products is 2 g. The residue after hydrolysis is treated in a similar way to Example 1 and is fed to the zonal kiln afterwards to be burnt. Silicon dioxide obtained at T = 750°C contains< 0.02 weight% of total carbon. The yield of amorphous silicon dioxide was 96.1% (purity of silicon dioxide was 98%). The yield of silicon dioxide was 16.7% of the source raw material in absolutely dry source raw material equivalent.Example 3A sample of wheat straw of 110 g with a humidity of 4.82% was placed in the autoclave and treated three times, the duration of each treatment being 4 minutes, at T = 190°C; pH = 1.6. The HS/sample ratio and the protector/water ratio is similar to Example 1. The protector was methyl(ethyl)ketone. The treatment methods are similar to Example 1. The residue of the sample after hydrolysis was 18.2 g. The yield of sugars and lignin was 62.66 g and 20.2 g respectively (Table 1, item 3). The contents of volatile products is 3.64 g. After washing with acetone to remove the residues of lignin and with the aqueous solution of hydrochloric acid (1N) to reduce the total content of metal oxides in the residue up to 0.88 weight %, the hydrolysis residue was annealed in the zonal kiln at T = 750°C. The produced silicon dioxide contained< 0.02 weight % of total carbon and had a purity of 97%. The yield of amorphous silicon dioxide was 96.5% and 17.0% of the source raw material in absolutely dry source raw material equivalent.Example 4A sample of wheat straw was subjected to a preliminary treatment by a 4% solution of NaOH at a temperature of 97°C - 100°C for two hours ("alkaline pulping"). Afterwards, the sample was filtered from the solution, was washed in the filter with the residues of the alkaline solution being removed and was dried. Most of lignin and a part of hemicellulose is released from the sample of straw in such a treatment (the residue of lignin in straw may beabout 11%). The residue of straw after treatment is 41.7% of the treated source sample on average. A quantity of pentose sugars can be extracted from the filtrates, if necessary.The treated sample of straw (as described above) with a weight of 110 g with a moisture content of 10% was placed in the autoclave, where it was treated three times (for 4 minutes each time) at T = 180°C; pH = 2.1; HS with a ratio of protector : water =1:1 (the protector - methyl(ethyl) ketone) and with a ratio of the sample : HS = 1:10. The combined hydrolysates were placed in a "titrator" (as described above for the second embodiment of the process), pH was brought up to 10, and the solution was allowed to settle for a lignin precipitation to be formed.The lignin was separated by filtration and dried (10 g). Methyl ethyl ketone was removed from the filtrate after neutralization by distillation in a vacuum water-jet pump. The yield of sugars was 64.2 g. The residue of the sample of straw after hydrolysis was 17.68 g, and the residue was 17.0 g after treating with a solvent and an acid aqueous solution (Table. 1, Item 4). In a similar manner to Examples 1 - 4, amorphous silicon dioxide with a yield of 98.8%, with the content of main substance of 98% and a yield of 17.0% of absolutely dry source raw material is produced in the zonal kiln.Example 5A weighed portion of sawdust of coniferous trees in the amount of 100 g(in terms of a dry sample) was subjected to three cycles of treatment in the autoclave (for 6 minutes each time) at T = 170°C - 190°C (preferably, 180°C), pH = 1.87 with a solution containing a mixture of acetone/water at a ratio of 4:1 with a dilution similar to the previous examples. The isolation of the reaction products was carried out according to a procedure similar to Example 1. The yield of volatile products was 6.2 g.The yield of monosaccharides was 35.6 g; that of lignin was 30 g. The conversion of the source sample reached 71.6% (Table 1, item 5). Before combustion in a zone furnace (750 ° C), the residue (28.4 g) was treated in the same way as in the above examples. The yield of amorphous silicon dioxide is 90%.Example 6The weighed portion of rice husk of 97.1 g (in terms of dry sample) was subjected to autoclaving similarly to Example 1. The yield of monosaccharides was 57.7% by weight of the source material (56.03 g) at a conversion of 80% (Table 1, item 6). The lignin yield was 14.6%, and for by-products it was 7.7%. The residue after hydrolysis is 19.42 g (20%). The residue was treated in a similar way to the above examples before being burnt in the zonal kiln. The yield of amorphous silicon dioxide was 97.1% in the event of annealing in the zonal kiln at 600°C.Example 7The weighed portion of rice husk of 100 g (on a dry sample basis) was treated in the autoclave in a similar way to the methods of Example 1. The yield of monosaccharides was 58.1% of the weight of the source material in the event of conversion in the amount of 81% (Table 1, item 7), the yield of the related products was 7.9%. The residue after hydrolysis was 19.0 g. The residue was treated in a similar way to the above examples before being burnt in the zonal kiln. The yield of amorphous silicon dioxide was 96.0% in the event of annealing in the zonal kiln at 750°C. The residual carbon content in silicon dioxide did not exceed 2% at a temperature of annealing the hydrolysis residue of 350°C and did not exceed 0.02% at the temperatures of 600°C and 750°C.Table 1No. Item No.Material type (dry weighed portion), gConversion (on a dry material basis), %The yield of sugars, %The yield of lignin,%The yield of the related products, %The residue after hydrolysis, %The yield of amorphous SiO2,%Temperature of roasting, °C1Primary sedimentarysludge (100)6832.528.66.932.096.56002Bagasse (100)8262182.018.096.17503Straw (104.7)82.659.719.23.717.496.57504Straw (99)82.164.9107.217.998.86005Sawdust of coniferous trees (100)71.635.6306.028.490.07506Rice husk (97.1)80.057.714.67.720.097.16007Rice husk (100)8158.115.07.91996.0750Industrial applicabilityThe method in accordance with the present invention makes it possible to obtain high quality silicon dioxide from various types of cellulose-containing materials, from woodworking industry waste and bagasse to primary sedimentary sludge of treatment facilities, that is, it is quite versatile.This provides a high yield of not only silicon dioxide, but also fuel monosaccharides, which are easily fermented by yeast into alcohol and lignin as a valuable product for industry. It allows for reduction the volume of flue gases emitted during the combustion of the hydrolysis residue, to practically use the heat of the latter in the technological process of hydrolysis and to significantly reduce the cost of silicon dioxide due to the production of industrially useful by-products. See more
A method of obtaining silicon dioxide from cellulose-containing material, including preliminary treatment of a source material by acid hydrolysis and subsequent isolation of silicon dioxide,characterized in thatacid hydrolysis is carried out at pH <5, temperature 140-240 ° C and elevated pressure in the presence of at least one protector of monosaccharides, protecting them from high temperatures and pressure, then lignin and monosaccharides are separated from the reaction products, the residue after removal of the liquid phase is burned at a temperature of 350 ° C -750 ° C to obtain silicon dioxide.The method according to claim 1, wherein the hydrolysis residue by using solvent is washed off the lignin residues before burning to reduce the carbon content.The method according to claim 1, wherein the hydrolysis residue is treated with IN solution of hydrochloric acid to reduce the content of metal oxides.The method according to any one of claims 1-3, wherein the raw material is subjected to alkaline pulping before hydrolysis in the event of high content of lignin in the source raw material.The method according to any one of claims 1-3, wherein at least one of chemical compounds chosen from ketones or oxygen-containing heterocycles is used as a protector of monosaccharides.The method according to any one of claims 1-5, wherein rice husk is used as a source raw material.See more
|12312075||16/08/2011||Amorphous Silica and Its Manufacturing Method|
|11991070||15/05/2012||Method of Making Amorphous Silicon Powder|