CN112876380B

CN112876380B - Method for preparing acetonitrile and coproducing propionitrile from biomass material

Info

Publication number: CN112876380B
Application number: CN202110108575.5A
Authority: CN
Inventors: 张颖; 贾挺挺
Original assignee: University of Science and Technology of China USTC
Current assignee: University of Science and Technology of China USTC
Priority date: 2021-01-27
Filing date: 2021-01-27
Publication date: 2022-04-19
Anticipated expiration: 2041-01-27
Also published as: CN112876380A

Abstract

The invention relates to a method for preparing acetonitrile and coproducing propionitrile from a biomass material, which comprises the following steps: reacting the biomass material at a temperature of 200 ℃ to 1000 ℃ in the presence of a biologically derived basic catalyst and a reactive nitrogen-containing compound, optionally in the presence of an inert gas, and obtaining a liquid product containing acetonitrile and propionitrile by condensation and separation. The method of the invention not only utilizes renewable biomass materials with wide sources as reaction starting materials, but also utilizes calcined products of waste animal bones which are completely different from the existing acid catalysts and are derived from domestic wastes as biological source alkaline catalysts, can prepare acetonitrile and coproduce propionitrile with high selectivity through a simple reaction process, has stable catalyst and can be repeatedly used for many times without inactivation, thereby providing a synthetic process which can realize the renewable, green and environment-friendly synthesis process, and obviously improving the economic benefit and social benefit of industrial scale production of target products.

Description

Method for preparing acetonitrile and coproducing propionitrile from biomass material

Technical Field

The invention relates to the field of organic and environmental protection, in particular to a method for preparing acetonitrile and coproducing propionitrile from a biomass material with high selectivity.

Background

Acetonitrile is widely applied to the fields of medicines, agricultural chemicals, fine chemical engineering and the like as a chemical with high added value, has excellent solvating power, low viscosity, low freezing point and low boiling point, and is one of the most important solvents in the chemical industry. However, acetonitrile is obtained industrially mainly as a by-product of acrylonitrile production, which is far from satisfying the demand for acetonitrile. The current process for the preparation of acetonitrile comprises: the acetonitrile is prepared by taking small molecular acid, alcohol, amine and synthesis gas as raw materials, but the methods need high-temperature and high-pressure operating conditions, and a virulent substance is generated in the preparation process. Similarly, propionitrile, another high value-added chemical, has the same problems as the existing synthetic methods.

Meanwhile, with the growing concern about environmental protection, there is also a need in the art for more environmentally friendly methods for the synthesis of acetonitrile and/or propionitrile. In this regard, the inventors of the present invention have made studies from the aspect of synthesizing raw materials. For example, the present inventor's patent application CN 109369451 a discloses a method for preparing acetonitrile using waste organic plastics as raw materials, wherein an acidic catalyst composed of a carrier and an active metal oxide is used, and wherein the carrier is selected from a molecular sieve-based carrier, a metal salt-based carrier, an oxide-based carrier, or a combination thereof, and the active metal oxide is an oxide selected from a group consisting of a IV period transition metal, a V period transition metal, an alkaline earth metal, or a group III main metal in the periodic table of elements.

With the diminishing fossil resources and the growing concern for environmental issues, biomass resources, as the only renewable bulk carbon source, are considered to be an important alternative source for the large-scale production of renewable fuels and chemicals. The biomass material can be a material consisting of cellulose, hemicellulose and lignin and can be divided into native biomass, waste biomass and energy crops. The native biomass comprises all native terrestrial plants in the nature, including trees, shrubs, weeds and the like; waste biomass is a low-value byproduct of each industrial part, such as corn straw, corn cob, bagasse, rice hull and the like generated in the agricultural production process, and a large amount of waste wood chips and paper are also generated in the wood sawing factory and the paper making factory in forestry; energy crops are a high-yielding type of lignocellulosic biomass that can be used to produce second generation biofuels such as switchgrass, elephant grass, and the like. Other biomass materials also include organic carbohydrates that are most abundant in nature, having a broad spectrum of chemical structures and biological functions, such as monosaccharides, oligosaccharides, starches, hemicelluloses, cellulose, complex polysaccharides, and sugar derivatives. Fast pyrolysis, which converts biomass resources into renewable fuels and chemicals in one step, is considered to be a promising biomass conversion technology. In this regard, the present inventor's patent application CN 106117082 a discloses a method for producing acetonitrile using a specific nitrogen-containing biomass material such as amino acids, proteins, algae, meals, activated sludge, etc. as a raw material, wherein the catalyst used is an acidic catalyst selected from the group consisting of solid acids, metal salts having acidity, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, etc. Further, the present inventor's patent application CN 108084053 a discloses a method for preparing acetonitrile from lignocellulosic biomass material, wherein an acidic catalyst selected from a solid acid, a metal salt having acidity, an inorganic acid, an organic acid or a combination thereof is also used.

Although the above documents provide improved environmentally friendly processes, acidic catalysts are used in these processes, and such acidic catalysts are easily deactivated in the fast pyrolysis of biomass and are difficult to reuse, which increases the cost of these processes in industrial scale production and affects the economics of their industrial mass production. Further, the acid catalysts used in these prior art methods are chemicals derived from industrial synthesis, and are high in cost and disadvantageous from the viewpoint of environmental friendliness.

Accordingly, there remains a need in the art for improved, novel, environmentally friendly processes for the preparation of acetonitrile and/or propionitrile.

Disclosure of Invention

In view of the above, it is an object of the present invention to provide an improved process for the preparation of acetonitrile with concomitant production of propionitrile.

The object of the present invention is achieved by using biomass material as a reaction raw material and using a bio-derived basic catalyst which is reusable and is derived from calcined powder of waste animal bones as a domestic waste.

To this end, the present invention provides a process for the preparation of acetonitrile from a biomass material in combination with propionitrile, the process comprising:

reacting a biomass material at a temperature of 200 ℃ to 1000 ℃ in the presence of a biologically derived basic catalyst and a reactive nitrogen-containing compound, optionally in the presence of an inert gas, and obtaining a liquid product containing acetonitrile and propionitrile by condensation and separation,

wherein the content of the first and second substances,

the biomass material is one or more selected from the group consisting of cellulose, hemicellulose, lignin, glucose, fructose, galactose, sucrose, lactose, maltose, trehalose, sorbitol, mannitol, raffinose, stachyose, fructooligosaccharides, cellobiose, xylose, xylan, maltodextrin, pectin, starch, bagasse powder, birch powder, pine powder, corn cob powder, corn straw powder, bamboo powder, arbor powder, shrub powder, oak powder, straw powder, wood chips, soybean straw powder, cotton stalk powder, rapeseed cake, wheat straw powder, waste paper scraps, and switchgrass powder;

the biogenic basic catalyst is a calcined product of waste animal bones; and is

The reactive nitrogen-containing compound is one or more selected from ammonia gas, methylamine, ethylamine, dimethylamine, urea, ammonium chloride, ammonium acetate, ammonium sulfate, ammonium bicarbonate and diammonium hydrogen phosphate.

In a preferred embodiment, the animal bone is selected from one or more of chicken bone, fish bone, sheep bone, pig bone, cattle bone, duck bone, goose bone, dog bone, horse bone, donkey bone and mule bone.

In a preferred embodiment, the animal bone is comminuted and washed with water prior to calcination; in a further preferred embodiment, the water washing is to stir the crushed animal bones in hot water at 50-100 ℃ for 4-48 h.

In a preferred embodiment, the animal bone is calcined in a muffle furnace to a powder or granules.

In a preferred embodiment, the calcining temperature is 450-700 ℃, and the calcining time is 4-12 h.

In a preferred embodiment, the biogenic alkaline catalyst is regenerated for reuse after each use by calcination again.

In a preferred embodiment, the feed mass ratio of the biomass material to the biogenic alkaline catalyst is from 1:0.1 to 1: 1000.

In a preferred embodiment, the inert gas is one or more selected from the group consisting of nitrogen, helium, neon, argon, krypton, xenon, radon, and carbon dioxide.

In a preferred embodiment, a carrier gas is formed from an inert gas and an ammonia gas from the reactive nitrogen-containing compound, and the volume ratio of the ammonia gas to the inert gas in the carrier gas is 1:20 to 20: 1.

In a preferred embodiment, the process further comprises subjecting the liquid product obtained to chromatography or distillation to yield an acetonitrile product and a propionitrile product, respectively.

The method of the invention not only utilizes renewable biomass materials with wide sources as reaction starting materials, but also uses a biological source alkaline catalyst which is completely different from the existing acidic catalyst and is derived from calcined products (usually in a powdery or granular form and also in other forms) of waste animal bones as domestic wastes, and can prepare acetonitrile and coproduce propionitrile with high selectivity through a simple reaction process, thereby providing a synthetic process which can realize the renewable, green and environment-friendly effects, and obviously improving the economic benefit and the social benefit for industrial scale production.

In addition, the biological basic catalyst used in the method is derived from domestic waste, so that the catalyst is wide in source and low in cost, waste utilization is realized, and the preparation process is simple; meanwhile, the biological source alkaline catalyst in the method can be recycled for multiple times, so that the economic benefit and the industrial significance of the method are further highlighted.

In addition, by the process of the present invention, only the desired target products, i.e., acetonitrile and propionitrile products, are contained in the liquid product obtained after the reaction, which makes it possible to omit complicated post-treatment processes caused by the presence of other by-products such as benzene in the conventional processes, on the one hand, and to obtain pure acetonitrile and propionitrile products, respectively, by simple treatments such as column chromatography or distillation, fractional distillation, and the like, if necessary.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) photograph of waste chicken bones for a bio-derived basic catalyst before (left) and after (right) water washing according to the present invention;

fig. 2 is SEM photographs of waste fishbone for a bio-derived basic catalyst before (left) and after (right) water washing according to the present invention;

fig. 3 is SEM photographs of waste sheep bones for a bio-derived basic catalyst before (left) and after (right) water washing according to the present invention;

fig. 4 is a Gas Chromatography (GC) plot of an unseparated liquid organic product obtained according to an embodiment of the present invention, using dicyclohexyl as an internal standard.

Detailed Description

The present inventors have conducted intensive and extensive studies with respect to the problems occurring in the existing processes for producing acetonitrile and/or propionitrile, such as the use of non-renewable raw materials, the use of an acid catalyst which is not recyclable, and the use of a non-environmentally friendly acid catalyst as a synthetic chemical. Surprisingly, the present inventors have found that acetonitrile can be produced with co-production of propionitrile using biomass material as a reaction substrate in the presence of a reactive nitrogen-containing compound and a biologically derived basic catalyst at a reaction temperature with high selectivity (typically close to 100% selectivity for both acetonitrile and propionitrile in the liquid product).

Based on the discovery, the method for preparing acetonitrile and coproducing propionitrile from biomass material provided by the invention comprises the following steps: reacting the biomass material at a temperature of 200 ℃ to 1000 ℃ in the presence of a biologically derived basic catalyst and a reactive nitrogen-containing compound, optionally in the presence of an inert gas, and obtaining a liquid product containing acetonitrile and propionitrile by condensation and separation.

As used herein, the term "acetonitrile co-production of propionitrile" means that the target products of the process of the invention are acetonitrile as the major or first product and propionitrile as the minor or second product. Generally, in the process of the present invention, after the reaction, a liquid product containing the desired target product (both acetonitrile and propionitrile) is obtained by conventional condensation and separation means well known in the art. The liquid product may be isolated without isolation or may be separated, for example, by conventional chromatography or distillation, to provide the individual acetonitrile and propionitrile products.

In the method of the present invention, the biomass material as the reaction substrate may be one or more selected from the group consisting of cellulose, hemicellulose, lignin, glucose, fructose, galactose, sucrose, lactose, maltose, trehalose, sorbitol, mannitol, raffinose, stachyose, fructo-oligosaccharide, cellobiose, xylose, xylan, maltodextrin, pectin, starch, bagasse powder, birch powder, pine powder, corn cob powder, corn stalk powder, straw powder, bamboo powder, arbor powder, shrub powder, oak powder, straw powder, wood chips, soybean stalk powder, cotton stalk powder, rapeseed cake, wheat straw powder, waste paper scraps, and switchgrass powder. Preferably, these biomass materials are derived from biomass of renewable biological origin. Optionally, these raw materials may be formed into a desired feed form, for example, a powder or a granular form, by grinding, mechanical crushing, etc. with a conventional grinder or pulverizer, as necessary, before use, and wherein there is no particular requirement for a specific particle size or particle size thereof, as long as the desired reaction can be accomplished, for example, about 20 mesh.

In the process of the present invention, the biogenic basic catalyst used is a calcined product of waste animal bones, which is usually in the form of powder, granules or other calcined form. In the present invention, there is no particular limitation on the form of the calcined product of waste animal bones, the size thereof, the form used, and the like, and the present inventors have found that any such calcined product of waste animal bones can be used in the present invention. In the practice of the present invention, the powder or granules obtained after calcination may be used directly as the catalyst of the present invention, or such calcined product may be further processed, for example, pressed into pellets or larger-sized particles for use.

In the present invention, the waste animal bones typically refer to common animal bones that are discarded, discarded or useless as household garbage in daily life. It is to be noted herein that although waste animal bones are generally mentioned in the present invention, in practice, animal bones in any form or at any stage may be used as long as the calcined product of animal bones required in the present invention can be obtained by calcination. Typically, animal bones that may be used in the present invention include, but are not limited to, chicken bones, fish bones, sheep bones, pig bones, cow bones, duck bones, goose bones, dog bones, horse bones, donkey bones, mule bones, and the like.

In the method of the present invention, preferably, the animal bone is first comminuted, for example mechanically, prior to calcination, such comminution being effected by any comminuting device or means known in the art. The invention has no special requirement on the particle size of the crushed bone, and only needs to be convenient for washing the surface of the crushed bone with water in the subsequent process. After the pulverization, the pulverized animal bone is washed with water. Preferably, the water washing is carried out by stirring the crushed animal bones in hot water of 50-100 ℃, for example 80 ℃, for 4-48 hours, for example 24 hours.

Optionally or preferably, after being washed with water, it is subjected to a drying step, for example in an oven at 80 to 160 ℃, for example 105 ℃, for 4 to 48 hours, for example 24 hours.

In the method of the present invention, preferably, after the above-mentioned treatment step, the animal bone or its pulverized particles are calcined into powder or granules in, for example, a muffle furnace. Preferably, the calcination temperature is 450-700 ℃, for example 550 ℃, and the calcination time is 4-12 h, for example 6 h.

In the method of the present invention, the basic catalyst of biological origin may be used by being directly put into a reactor, or may be used by being fixed in, for example, a fixed bed reactor, a quartz tube reactor or the like, or may be used by, for example, a solid carrier such as a support.

In the method of the present invention, the basic catalyst of biological origin used can be regenerated by placing it in a muffle furnace and calcining it again after each use, and can be reused. The inventors have found that in the present invention, the basic catalyst of biological origin used can be reused at least 10 times or more.

In the process of the present invention, although not particularly limited, preferably, the feed mass ratio of the biomass material as the reaction substrate to the biologically-derived basic catalyst may be 1:0.1 to 1:1000, more preferably 1:0.5 to 1:10, for example 1: 1.

In the process of the invention, the reaction temperature in the reactor is in the range of 200 ℃ to 1000 ℃, for example 500 ℃ to 900 ℃. The present inventors have found that in such a temperature range, the process of the present invention enables acetonitrile to be obtained and propionitrile to be co-produced stably and with high selectivity.

In the method of the present invention, the heating means or apparatus is not particularly limited, and examples thereof include oil bath heating, resistance heating, and heating by a heating apparatus provided in the reactor itself.

In the process of the present invention, the reaction time or residence time is not particularly limited, and depends mainly on the raw material and/or carrier gas feed rate.

Without being bound to a particular theory, in the process of the present invention, the reactive nitrogen-containing compound participates in the reaction therein and provides a nitrogen atom to the target product. In the method of the present invention, the reactive nitrogen-containing compound which can be used is one or more selected from the group consisting of ammonia gas, methylamine, ethylamine, dimethylamine, urea, ammonium chloride, ammonium acetate, ammonium sulfate, ammonium bicarbonate and diammonium hydrogen phosphate. It is to be noted that, as will be understood by those skilled in the art, with respect to the above-mentioned reactive nitrogen-containing compounds, in addition to ammonia gas itself, other reactive nitrogen-containing compounds used herein are converted to ammonia gas at the reaction temperature (200 ℃ to 1000 ℃) of the process of the present invention. Therefore, for convenience, only ammonia is generally referred to in the following description.

In the process of the present invention, optionally, the reaction may be carried out under an inert gas atmosphere. In other words, the process of the present invention may or may not have an inert gas present during the reaction. The inert gas used in the present invention may be one or more selected from the group consisting of nitrogen, helium, neon, argon, krypton, xenon, radon and carbon dioxide.

In the process of the present invention, preferably, when no inert gas is present, the carrier gas for the reaction is the formation of ammonia gas generated by the reactive nitrogen-containing compound; and when an inert gas is present, the carrier gas for the reaction is formed from the above-mentioned ammonia gas and the inert gas. More preferably, the reaction carrier gas is formed of an inert gas and an ammonia gas from the reactive nitrogen-containing compound, and the volume ratio of the ammonia gas to the inert gas may be 1:20 to 20: 1.

In the method of the present invention, as understood by those skilled in the art, the flow rate of the reaction carrier gas generally varies depending on the scale of the reaction, the amount of the fed material, and the like, and thus the present invention is not particularly limited to the flow rate of the carrier gas. Typically, on a laboratory feed scale, the flow rate of the reaction carrier gas may be 20-200mL/min, for example about 80 mL/min.

In the method of the present invention, preferably, the obtained liquid product containing acetonitrile and propionitrile is subjected to column chromatography on silica gel or distillation, for example, to obtain pure acetonitrile product and propionitrile product, respectively, and the obtained liquid product or separated acetonitrile/propionitrile product can be subjected to Gas Chromatography (GC) combined Mass Spectrometry (MS), for example, to detect the selectivity of acetonitrile and propionitrile in the product and calculate the yield of acetonitrile and propionitrile.

In the process of the present invention, the reactor is not particularly limited, and it may be, for example, a tubular reactor, a fixed bed reactor, a fluidized bed reactor, or the like. Preferably, the reactor used in the present invention is equipped with a condensing means and a gaseous product or off-gas collection means. Preferably, the reactor used in the present invention is also equipped with a gas inlet for the introduction of the desired gas stream or carrier gas stream. More preferably, the reactor used in the present invention is equipped with a flow meter for detecting or controlling the flow rate of the gas stream.

Examples

In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the specific embodiments. All raw materials are commercially available and used directly in the commercially available form, unless otherwise specified.

General Experimental procedure

Regarding the preparation of the basic catalyst of biological origin:firstly, crushing the collected waste animal bones by using a conventional crusher; then putting the crushed animal bones into hot water at 80 ℃ for stirring for 24 hours, and then drying in an oven at 105 ℃ for 24 hours; finally, the dried animal bones were calcined in a muffle furnace at 550 ℃ for 6 hours, and the resulting granular calcined product was used as a catalystThe reagent is used for reaction.

In the above catalyst preparation process, as an example, SEM characterization was performed on chicken bones, fish bones and sheep bones before and after water washing, respectively, and the results are shown in fig. 1 to 3, respectively, in which fig. 1 is Scanning Electron Microscope (SEM) photographs of waste chicken bones before (left) and after (right) water washing; fig. 2 is SEM photographs of waste fishbone before (left) and after (right) water washing; and fig. 3 is SEM photographs of the waste sheep bone before (left) and after (right) water washing. As can be seen from fig. 1 to 3, respectively, the particle size of the waste animal bones becomes smaller after water washing. Without being bound by any theory, the inventors believe that this may be due to the washing step described above washing away a portion of the inorganic salt content of the waste animal bones.

In the following examples, a quartz tube reactor (coquette instruments technologies ltd) having a diameter of 10mm x 280mm in length was used, in which a catalyst was supported by quartz wool, and the quartz tube reactor was inserted into a temperature-controlled zone in which a fixed-bed pyrolysis furnace (coquette physico-chemical equipment ltd) was located, and the temperature of the reactor was monitored by a thermocouple inserted into the interior of the temperature-controlled furnace.

During the reaction, separate NH is introduced into the quartz tube reactor₃Or NH₃/N₂、NH₃/Ar or NH₃The mixed gas of/He is used as carrier gas, and the flow rate of the gas is controlled to be 20-200mL/min by a rotameter. The reaction raw material and the carrier gas enter through a feed inlet of a quartz reaction tube together, and then contact with the catalyst to react at the temperature of 200-1000 ℃. A glass tube was connected below the quartz reaction tube to collect liquid products and condense the liquid products with liquid nitrogen, while collecting gas products (mainly including carbon dioxide, carbon monoxide, methane) collected by the reaction in a gas sampling bag (7#, shanghai ramon instruments ltd) and analyzing the liquid and gas products with a gas chromatograph (GC1690, dawn chemical instruments ltd).

Further, the acetonitrile and propionitrile products were further separated and purified by silica gel chromatography, as necessary.

Unless specifically noted in the examples, the experimentally relevant reaction conditions and procedures are as described above.

In the following examples, the total yield of liquid product, the yields of acetonitrile and propionitrile, and the selectivity of acetonitrile and propionitrile were calculated by the following formulas:

total yield (%) of liquid product, which is the sum of the carbon moles of each product in the liquid organic product/carbon moles in the raw material × 100%;

the acetonitrile yield (%) ═ mole amount of carbon in acetonitrile/mole amount of carbon in raw material × 100%;

propionitrile yield (%) ═ molar carbon of propionitrile/molar carbon in the raw material × 100%;

selectivity (%) of acetonitrile ═ yield of acetonitrile/total yield of liquid organic product × 100%;

selectivity (%) of propionitrile ═ yield of propionitrile/total yield of liquid organic product × 100%,

the liquid organic products mentioned therein are organic substances in the liquid products obtained from the pyrolysis reaction.

Example 1: influence of different kinds of biological basic catalysts on selectivity and yield of acetonitrile coproduction propionitrile

In this example, granular calcined products obtained by calcining various waste animal bones shown in Table 1 were used as the bio-derived basic catalyst by the above-mentioned catalyst preparation procedure and reaction process, and fixed in a quartz tube reactor for reaction.

Reaction conditions are as follows: the used biomass raw material is 0.5g of cellulose powder; the mass of the catalyst used was 1.0 g; the carrier gas consisted of 100% ammonia (i.e., no inert gas present) and a flow rate of 80 mL/min; the reaction temperature is 650 ℃; the reaction time was 30 min.

The liquid organic product obtained after the reaction was directly analyzed by gas chromatography, wherein the liquid product distribution obtained in the case of using the sheep bone catalyst is shown in fig. 4. As can be seen from fig. 4, in addition to the peak of the internal standard (dicyclohexyl), only the acetonitrile peak around 3.7min and the propionitrile peak around 4.2min appear in the gas chromatogram, indicating that the liquid product obtained by the method of the present invention contains only the target product, which makes it possible to obtain pure acetonitrile and propionitrile products subsequently by very simple, e.g. column chromatography or fractional distillation. Furthermore, it can be seen from FIG. 4 that acetonitrile is the major product and propionitrile is the minor product in the liquid product obtained by the process of the present invention.

Acetonitrile yield (%), propionitrile yield (%), total yield of liquid organic product (%), acetonitrile selectivity (%) and propionitrile selectivity (%) obtained by detection and calculation are shown in table 1.

TABLE 1

As can be seen from Table 1, acetonitrile can be produced from biomass material with co-production of propionitrile with high selectivity by using calcined products of waste animal bones from different sources as catalysts.

Example 2: influence of different kinds of biomass on selectivity and yield of acetonitrile coproduction and propionitrile preparation

In this example, a granular calcined product obtained by calcining waste sheep bones was used as a bio-derived basic catalyst for reaction by the above-mentioned catalyst preparation procedure and reaction process.

Reaction conditions are as follows: the raw materials are biomass raw materials of different types after being ground into powder: cellulose, hemicellulose, lignin, glucose, fructose, sucrose, lactose, maltose, xylan, starch, xylose, cellobiose, bagasse, birch, pine, corn cob, corn stover, straw, bamboo, arbor, shrub, oak, straw, wood chip, soybean stover, cotton stalk, rapeseed cake, wheat straw, waste paper shredder, switchgrass powder, and used in an amount of 0.5g, respectively; the mass of the catalyst used was 1.0 g; the carrier gas consists of 100% ammonia gas and the flow rate is 80 mL/min; the reaction temperature is 650 ℃; the reaction time was 30 min.

Acetonitrile yield (%), propionitrile yield (%), total yield of liquid organic product (%), acetonitrile selectivity (%) and propionitrile selectivity (%) obtained by detection and calculation according to the same procedure as in example 1 are shown in table 2.

TABLE 2

As can be seen from Table 2, acetonitrile can be produced with high selectivity and propionitrile can be produced from various kinds of biomass materials by using the bio-derived catalyst of the present invention.

Example 3: influence of different reaction temperatures on selectivity and yield of acetonitrile coproduction propionitrile

In this example, a powdery calcined product obtained by calcining waste chicken bones was used as a bio-derived basic catalyst for reaction by the above catalyst preparation procedure and reaction process, and the reaction was carried out using different reaction temperatures as shown in table 3 below.

Reaction conditions are as follows: the raw material is 0.5g of cellulose powder; the mass of catalyst used was 1.0 g; the carrier gas consists of 100% ammonia gas and the flow rate is 80 mL/min; the reaction temperature is 650 ℃; the reaction time was 30 min.

Acetonitrile yield (%), propionitrile yield (%), total yield of liquid organic product (%), acetonitrile selectivity (%) and propionitrile selectivity (%) obtained by detection and calculation according to the same procedure as in example 1 are shown in table 3.

TABLE 3

As can be seen from Table 3, the use of the basic catalyst of biological origin of the invention can prepare acetonitrile and coproduce propionitrile from biomass materials with high selectivity at the temperature of 200 ℃ and 1000 ℃.

Example 4: effect of carrier gases with different compositions on the yield and selectivity of acetonitrile co-production of propionitrile

In this example, by the above catalyst preparation procedure and reaction process, a powdery calcined product obtained by calcining waste fishbones was used as a bio-derived basic catalyst for the reaction, and the reaction was carried out using carrier gases having different compositions as shown in table 4 below.

Reaction conditions are as follows: the raw material is 0.5g of cellulose powder; the mass of the powdery catalyst used was 1.0 g; the flow rate of the carrier gas is 80 mL/min; the reaction temperature is 650 ℃; the reaction time was 30 min.

Acetonitrile yield (%), propionitrile yield (%), total yield of liquid organic product (%), acetonitrile selectivity (%) and propionitrile selectivity (%) obtained by detection and calculation according to the same procedure as in example 1 are shown in table 4.

TABLE 4

As can be seen from the results in Table 4, only the reactive nitrogen compounds (e.g., NH) were present in the alkaline catalyst derived from a living organism according to the present invention₃) Can produce acetonitrile and coproduce propionitrile from biomass materials with high selectivity.

Example 5: influence of mass ratio of different raw materials and catalyst on yield and selectivity of acetonitrile co-production propionitrile

In this example, a powdery calcined product obtained by calcining waste duck bones was used as a bio-derived basic catalyst for reaction by the above catalyst preparation procedure and reaction process, and the reaction was performed using different mass ratios of raw materials to catalyst as shown in table 5 below.

Reaction conditions are as follows: the raw material is cellulose powder; the carrier gas consists of 100% ammonia gas and the flow rate is 80 mL/min; the reaction temperature is 650 ℃; the reaction time was 30 min.

Acetonitrile yield (%), propionitrile yield (%), total yield of liquid organic product (%), acetonitrile selectivity (%) and propionitrile selectivity (%) obtained by detection and calculation according to the same procedure as in example 1 are shown in table 5.

TABLE 5

From the results in table 5, it can be seen that acetonitrile can be produced with propionitrile produced from a biomass material with high selectivity using the bio-based catalyst of the present invention in the range of the mass ratio of the biomass material to the bio-based catalyst of 1:0.1 to 1: 1000.

Example 6: influence of catalyst recycling on yield and selectivity of acetonitrile coproduction propionitrile

In this example, a powdery calcined product obtained by calcining waste sheep bones was used as a bio-derived alkaline catalyst for reaction by the above-mentioned catalyst preparation procedure and reaction process.

Reaction conditions are as follows: the raw material is 0.5g of cellulose powder; the mass of the powdered catalyst used was 1.0 g; the carrier gas consists of 100% ammonia; the reaction temperature is 650 ℃; the reaction time was 30 min. Wherein, the catalyst is calcined again for 6h at 550 ℃ in a muffle furnace after each use for regeneration, and then is used for reaction again, and the catalyst is recycled for 10 times.

Acetonitrile yield (%), propionitrile yield (%), total yield of liquid organic product (%), acetonitrile selectivity (%) and propionitrile selectivity (%) obtained by detection and calculation according to the same procedure as in example 1 are shown in table 6.

TABLE 6

From the results in table 6, it can be seen that the basic catalyst derived from living beings of the present invention can be used for preparing acetonitrile and co-producing propionitrile from biomass materials with high selectivity after being recycled for 10 times, and no catalyst deactivation is found, indicating that the basic catalyst derived from living beings of the present invention has good stability and can be recycled.

As shown in the above examples, the present invention enables the production of high value-added chemical acetonitrile with co-production of propionitrile with high selectivity using waste animal bones as a catalyst source, wherein the total selectivity of both acetonitrile and propionitrile is about 100%.

The catalyst used in the invention is cheap and easy to obtain, nontoxic, green and environment-friendly, can realize waste utilization, has good stability, and still maintains good catalytic performance after 10-time cyclic regeneration. According to the knowledge of the inventor, the catalyst is the only biological basic catalyst with stable catalytic performance which is reported for the first time in the field of pyrolysis for preparing acetonitrile and/or propionitrile, and the catalyst reduces the cost for industrial mass production and provides a wide prospect.

The above embodiments are only intended to help the understanding of the method of the present invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims

1. A method for the co-production of acetonitrile from a biomass material and propionitrile, the method comprising:

wherein the content of the first and second substances,

the biomass material is one or more selected from the group consisting of cellulose, hemicellulose, lignin, glucose, fructose, galactose, sucrose, lactose, maltose, trehalose, sorbitol, mannitol, raffinose, stachyose, fructooligosaccharides, cellobiose, xylose, xylan, maltodextrin, pectin, starch, bagasse powder, birch powder, pine powder, corn cob powder, corn stover powder, straw powder, bamboo powder, arbor powder, shrub powder, oak powder, wood chips, soybean stover powder, cotton stalk powder, rapeseed cake, wheat straw powder, waste paper scraps, and switchgrass powder;

the biogenic basic catalyst is a calcined product of waste animal bones; and is

2. The method of claim 1, wherein the animal bone is selected from one or more of chicken bone, fish bone, sheep bone, pig bone, cow bone, duck bone, goose bone, dog bone, horse bone, donkey bone and mule bone.

3. The method as claimed in claim 2, wherein the animal bone is crushed and washed with water before calcination.

4. The method according to claim 3, wherein the water washing is performed by stirring the pulverized animal bone in hot water at 50-100 ℃ for 4-48 hours.

5. A method according to claim 3, wherein the animal bone is calcined in a muffle furnace to a powder or granulate.

6. The method according to claim 5, wherein the calcination temperature is 450-700 ℃ and the calcination time is 4-12 h.

7. The method according to claim 1, wherein the bio-derived basic catalyst is regenerated for reuse by re-calcination after each use.

8. The process according to any one of claims 1 to 7, characterized in that the feed mass ratio of the biomass material to the biologically derived basic catalyst is from 1:0.1 to 1: 1000.

9. The method of any one of claims 1-7, wherein the inert gas is one or more selected from the group consisting of nitrogen, helium, neon, argon, krypton, xenon, radon, and carbon dioxide.

10. The method according to any one of claims 1 to 7, wherein a carrier gas is formed from an inert gas and an ammonia gas from the reactive nitrogen-containing compound, and a volume ratio of the ammonia gas to the inert gas in the carrier gas is 1:20 to 20: 1.

11. The process of any one of claims 1-7, further comprising subjecting the obtained liquid product to chromatography or distillation to obtain acetonitrile product and propionitrile product, respectively.