CN110437031B - Wood vinegar hydrogenation process - Google Patents
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
The invention discloses a wood vinegar hydrogenation process. The process combines reduced pressure distillation and hydrogenation for the first time to treat the pyroligneous liquor, and finds that the process can effectively convert most of organic matters in the pyroligneous liquor into biomass alcohols such as bio-based methanol, fuel ethanol, bio-based propanol, bio-based butanol and the like, the biomass alcohols contain few other components, the content of acetic acid in a hydrogenation product is not more than 1 wt%, and after the content of heavy components in the pyroligneous liquor is controlled, the stability of a hydrogenation catalyst is greatly improved, so that the pyroligneous liquor has commercial value; after the previous reduced pressure distillation and hydrogenation treatment, various biomass alcohols can be easily obtained by separating hydrogenation products, the process can be continuously and stably operated for thousands of hours or even thousands of hours, and the pressure drop of the reactor is maintained in a reasonable range.
Description
Technical Field
The invention belongs to the technical field of hydrogenation, and particularly relates to a wood vinegar hydrogenation process, in particular to a hydrogenation process for preparing bio-based products such as bio-based methanol, fuel ethanol, bio-based propanol, bio-based butanol and the like by wood vinegar hydrogenation.
Background
During pyrolysis of biomass, char, tar, and gaseous products are produced. The water-soluble substances obtained by condensing the gas products are generally called as wood vinegar, the appearance is brown, the pH value is acidic, the wood vinegar is crude wood vinegar, the yield is high, the main component of the wood vinegar is water, and the wood vinegar also contains acids, alcohols, phenols and aldehydes. In recent years, the research and application of wood vinegar have advanced to a new stage, and wood vinegar has begun to be applied to the fields of medicines, foods, agricultural chemicals, etc., as bacteriostatic agents, insecticides, antioxidants, plant growth regulators, etc. However, crude wood vinegar prepared by pyrolysis of biomass contains tar and harmful substances, and refined vinegar with different purposes can be obtained by refining. The common refining method of the pyroligneous mainly comprises the following steps: standing, distilling, extracting, adsorbing with activated carbon, and filtering with membrane.
Among the above-mentioned purification methods, the standing method is a method of purifying and separating the wood vinegar liquid by utilizing instability of a part of components in the wood vinegar liquid, which is likely to precipitate by oxidation, polymerization or the like. The standing method is simple and easy to operate, simple in equipment and low in cost, but the influence of the standing method on the performance of vinegar liquid is related to the standing time, so that the time is consumed; distillation methods are generally classified into atmospheric distillation methods and vacuum distillation methods, and are methods for separating components of vinegar by utilizing their different boiling points. The extraction method is a method for separating and purifying target components by utilizing the principle of similarity and intermiscibility; the activated carbon adsorption method is to treat the pyroligneous liquor by utilizing the huge specific surface area, rich pore structure and excellent adsorption performance of the activated carbon so as to achieve the refining purpose; the membrane filtration method is a technology for treating the pyroligneous liquor by adopting a combined integrated membrane of microfiltration, ultrafiltration, nanofiltration, reverse osmosis and the like.
The conventional refining method is difficult to effectively separate components in the wood vinegar, such as phenols can be generally separated by a distillation method, but the ketone substances and the aldehyde substances are difficult to separate, the ketone substances, the aldehyde substances and the residual phenol substances can influence the chromaticity and the thermal stability of the wood vinegar, and the biomass alcohol recovery is influenced by the existence of the substances, so that the refining method is difficult to effectively utilize the wood vinegar; particularly, in the long term, the demand scale is small whether the bactericide or the plant regulator is used; particularly, in the process of rapidly developing the preparation of the biochar-based fertilizer by biomass pyrolysis in recent years, a large amount of pyroligneous liquor is gathered, so that the large-scale application of the pyroligneous liquor becomes one of the bottlenecks in the development of the biochar-based fertilizer.
Fuel ethanol, butanol, or the like has attracted considerable attention as an important means for reducing vehicle pollution, particularly fuel ethanol obtained from renewable resources. The common method for producing fuel ethanol by using straws as raw materials is an enzyme catalysis method, but the straw conversion is difficult and the cost is extremely high, so the actual implementation range is small and the difference from the expected requirement is large. The method also comprises the steps of preparing biological butanol, propanol and the like, and how to reduce the cost of the biomass alcohol and realize large-scale production is a technical problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
Therefore, the technical problems to be solved by the invention include that the prior art can not treat the pyroligneous liquor on a large scale, so that the downstream application of the pyroligneous liquor is lacked, and novel downstream utilization needs to be developed; organic matters in the pyroligneous liquor are converted into biomass alcohol, and the market demand of the biomass alcohol can be matched with the development of the pyroligneous liquor. After a detailed examination, the technical solution for solving the above technical problems is adopted in the present application,
a pyroligneous hydrogenation process comprises the following steps:
refining: distilling the wood vinegar solution under reduced pressure, and collecting refined wood vinegar solution;
hydrogenation: mixing the refined pyroligneous with hydrogen in the presence of a hydrogenation catalyst to carry out hydrogenation reaction, and collecting a hydrogenation product;
separation: and separating the hydrogenation product, and collecting the biomass alcohol in the hydrogenation product.
Although some patents and documents refer to the conversion of carboxylic acid, aldehyde into alcohol, hydroxy ketone into diol, and phenol into cyclohexanol, the respective reaction conditions are different, and the kinds of catalysts are different, the inventors have surprisingly found that almost 100 kinds of substances of pyroligneous liquor are converted into alcohols, which are monohydric alcohols, under the same conditions under the action of the hydrogenation catalyst.
Further, the heavy boiling substance with an atmospheric boiling point higher than 250 ℃ in the refined pyroligneous liquor is not more than 1.0%, preferably the heavy boiling substance with an atmospheric boiling point higher than 250 ℃ in the refined pyroligneous liquor is not more than 0.5%, more preferably the heavy boiling substance with an atmospheric boiling point higher than 250 ℃ in the refined pyroligneous liquor is not more than 0.2%.
Further, the temperature of the reduced pressure distillation is 40-90 ℃ and the absolute pressure is 0-95Kpa, preferably the temperature of the reduced pressure distillation is 50-70 ℃ and the absolute pressure is 30-90Kpa, more preferably the temperature of the reduced pressure distillation is 60-70 ℃ and the absolute pressure is 30-50 Kpa.
The discovery of the reduced pressure distillation is crucial to the stable operation of the hydrogenation catalyst, the pyroligneous liquor which is not subjected to the reduced pressure distillation is directly hydrogenated and is completely inactivated in only tens of hours after being continuously hydrogenated, while the conversion process of the invention can be continuously and stably operated for thousands of hours or even tens of thousands of hours, and the pressure drop of the reactor can be stabilized in a reasonable range, for example, the pressure drop can be maintained in a range of 0.1-0.3 kilopascal/meter of the height of the catalyst bed, and the great improvement can not occur along with the reaction, and meanwhile, the control of the reduced pressure distillation parameters is critical, namely, the reduced pressure distillation under the specific parameters in the invention is discovered by the inventor after hundreds of experiments.
Further, before the hydrogenation reaction, the mixture formed by the refined pyroligneous and the hydrogen is subjected to heat exchange for at least two times, the temperature of the mixture subjected to the first heat exchange is 100-220 ℃, the mixture subjected to the first heat exchange is subjected to gas-liquid separation, heavy components are separated and removed in a liquid phase mode, gas-phase substances are collected, and the gas-phase substances are subjected to the second heat exchange until the temperature is 170-280 ℃. Through heating step by step and setting up gas-liquid separation, the stability of catalyst can last, and subsequent separation process also can get higher quality biomass alcohol simultaneously.
Further, the temperature of the hydrogenation reaction is 170-280 ℃, the pressure is 1-5MPa, preferably the temperature is 170-200 ℃, and the pressure is 1-1.5 MPa; preferably, the temperature is 200 ℃ and 280 ℃ and the pressure is 1-1.5 MPa.
The molar ratio of unsaturated substances to hydrogen in the refined wood vinegar is 1: (2-100), preferably 1: (8-40);
the volume space velocity of the refined pyroligneous liquor is 0.1-10 h-1Preferably 1-3h-1。
Further, the hydrogenation catalyst comprises an active component and an auxiliary agent, wherein the active component comprises at least one of copper, cobalt and ruthenium, and the auxiliary agent comprises at least one of oxides of zinc, chromium, tin, manganese, zirconium, calcium, magnesium, silicon and aluminum.
Further, the mass ratio of the active component to the auxiliary agent is (0.1-50): (10-90).
Further, the content of the active component is 0.1-50 wt% based on the total weight of the hydrogenation catalyst;
the content of the auxiliary agent is 10-90 wt%;
the sum of the content of the active component and the content of the auxiliary agent is not more than 100 wt%.
Further, when the active component is copper and/or cobalt, the content of the active component is 5-50 wt%;
when the active component is ruthenium, the content of the active component is 0.1-5 wt%.
Further, the hydrogenation catalyst comprises an active component and an auxiliary agent, wherein the active component is copper and/or cobalt, the auxiliary agent comprises a first auxiliary agent and a second auxiliary agent, the first auxiliary agent is an oxide of silicon and/or an oxide of aluminum, the second auxiliary agent is at least one of zinc, chromium, tin, manganese, zirconium, calcium and magnesium, the content of the active component is 10-50 wt%, and the content of the auxiliary agent is 50-90 wt%.
Further, the hydrogenation catalyst comprises an active component and an auxiliary agent, wherein the active component is cobalt, the auxiliary agent comprises a first auxiliary agent, a second auxiliary agent and a third auxiliary agent, the first auxiliary agent is an oxide of zirconium, the second auxiliary agent is an oxide of silicon and/or an oxide of aluminum, the third auxiliary agent is at least one of zinc, tin, manganese, calcium and magnesium, the content of the active component is 10-50 wt%, and the content of the auxiliary agent is 50-90 wt%.
Further, the separation is one or the combination of two of rectification separation and membrane dehydration.
Further, the method also comprises the step of collecting the wood tar separated in the reduced pressure distillation and the wood tar separated after the gas-liquid separation;
before the separation, the method also comprises a step of condensing the hydrogenation product;
during the separation, the method also comprises the steps of recovering steam with the temperature of 80-110 ℃ in the separation process and using the steam for the reduced pressure distillation and/or heat exchange.
Further, the content of acetic acid in the hydrogenated product is not more than 1 wt%, preferably not more than 0.5 wt%, and more preferably not more than 0.2 wt%, based on the total weight of the hydrogenated product.
The technical scheme of the invention has the following advantages:
1. according to the wood vinegar hydrogenation process provided by the invention, the reduced pressure distillation and hydrogenation are combined for the first time to treat the wood vinegar, and the process is found to be capable of effectively, efficiently, stably and economically converting most of organic matters in the wood vinegar into biomass alcohols such as bio-based methanol, fuel ethanol, bio-based propanol and bio-based butanol, wherein other components in the biomass alcohols are few, and the content of acetic acid in a hydrogenation product is not more than 1 wt%; after the content of heavy components in the pyroligneous liquor is controlled, the stability of the hydrogenation catalyst is greatly improved, so that the pyroligneous liquor has a commercial value; after the preceding reduced pressure distillation and the hydrogenation treatment, various biomass alcohols can be easily obtained by separating hydrogenation products, the process can be continuously and stably operated for thousands of hours or even thousands of hours, the pressure drop of the reactor is maintained in a reasonable range, and the obtained biomass alcohols are monohydric alcohols.
2. According to the pyroligneous hydrogenation process provided by the invention, impurities in the pyroligneous can be well removed, the content of biomass alcohol can be improved, the chromaticity of the pyroligneous can be reduced, the stability of the pyroligneous can be improved, and meanwhile, the selection of the parameters of the reduced pressure distillation process can ensure that the process can continuously and stably run for thousands of hours or even tens of thousands of hours, and the pressure drop of a reactor is maintained in a reasonable range; by selecting a specific type and proportion of hydrogenation catalyst, the pyroligneous liquor containing nearly 100 substances can be mostly converted into alcohols under the same condition to generate more biomass alcohols, so that other non-biomass alcohols are prevented from being generated, particularly more methanol, ethanol, propanol and butanol can be generated, the biomass alcohols are monohydric alcohols, the selectivity of the monohydric alcohols is improved, and the catalyst can resist the influence of moisture and impurities in the pyroligneous liquor.
3. According to the wood vinegar hydrogenation process provided by the invention, before hydrogenation reaction, a mixture formed by refined wood vinegar and hydrogen is subjected to heat exchange for at least two times, the temperature of the mixture can be slowly raised through the heat exchange reaction for two times, and the influence on the properties of the wood vinegar is avoided; meanwhile, gas-liquid separation is carried out between two heat exchanges, and gas-phase substances are collected, so that other impurities are removed, and the subsequent hydrogenation and conversion are facilitated;
the cost for preparing the biomass alcohol is greatly reduced compared with the cost for preparing the alcohol by other methods, for example, the cost for preparing the ethanol by the enzyme catalysis method can be reduced by more than 60 percent, and remarkable economic benefit is obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of the structure of a pyroligneous acid hydrogenation process in the example of the present invention;
wherein the reference numerals are represented as:
1-a distillation column; 2-a heat exchanger; 2-1-a first heat exchanger; 2-2-a second heat exchanger; 3-a hydrogenation reaction device; 4-a condenser; 5-a separation device; 6-a separator.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a pyroligneous hydrogenation process, as shown in fig. 1, comprising the following steps:
1) performing Gas Chromatography (GC) measurement on organic matters in the wood vinegar with pH value of 4.2, brown color, suspended matters in the wood vinegar and water content of 79.7 wt%, wherein the contents of all components in the organic matters are as follows based on the total weight of the organic matters: 11.8% for methanol, 3.4% for hydroxyacetone, 1.0% for acetaldehyde, 40.0% for acetic acid, 8.6% for propionic acid, 2.2% for furfural, 2.6% for cyclopentanone, 1.3% for furanone, 1.7% for butyric acid, 1.44% for valeric acid, 5.5% for phenol, 5.2% for methylphenol, 2.1% for ethylphenol, 3.8% for methoxyphenol, and 3.96% for other undetected components;
2) introducing the pyroligneous liquor into a distillation tower 1, carrying out reduced pressure distillation at the temperature of 60 ℃ and under the absolute pressure of 40Kpa, collecting condensate, namely refined pyroligneous liquor, and ensuring that the normal pressure boiling point in the refined pyroligneous liquor is higher than 0.2% of a reboiler above 250 ℃;
3) refining pyroligneous acid for 2 hr-1The volume space velocity of the gas phase is introduced into a heat exchanger 2, specifically, the gas phase is sequentially introduced into a first heat exchanger 2-1 and a second heat exchanger 2-2 for heat exchange until the temperature of the gas phase is 250 ℃, wherein the outlet temperature of the first heat exchanger 2-1 is 190 ℃;
4) introducing the gas-phase substances and hydrogen into a hydrogenation reaction device 3 for hydrogenation reaction, wherein the temperature of the hydrogenation reaction is 250 ℃, the pressure is 3Mpa, and the molar ratio of unsaturated substances to hydrogen in the refined pyroligneous is 1: 30, active components in the hydrogenation catalyst are cobalt and copper, an auxiliary agent is silicon oxide, wherein the cobalt content is 22 wt%, the copper content is 2 wt%, and the silicon oxide content is 73 wt%, the hydrogenation product is collected, and based on the total weight of components except water in the hydrogenation product, the methanol content in the hydrogenation product is 17.45%, the ethanol content is 53.93%, the n-propanol content is 14.86%, the n-butanol content is 4.99%, the pentanol content is 2.38%, the cyclopentanol content is 1.34%, the cyclohexanol content is 1.4%, and the phenol content is 3.65%, wherein the contents of isopropanol and isobutanol are extremely low and almost undetectable, which shows that the hydrogenation process has selectivity for n-propanol and n-butanol, and simultaneously generates monohydric alcohol and monohydric alcohol, and the hydrogenation product is a transparent and clear liquid;
the hydrogenation process can be continuously operated for 3800 hours, and the content of outlet acetic acid is less than 0.1 percent; the pressure drop of the reactor is stabilized at 0.2 kilopascal/meter of the height of the catalyst bed layer;
5) condensing and rectifying the hydrogenation product to collect biomass alcohol, and recovering steam and hot water at 80-110 deg.c for vacuum distillation.
Example 2
The embodiment provides a pyroligneous acid hydrogenation process, which comprises the following steps:
1) performing Gas Chromatography (GC) measurement on organic matters in the wood vinegar with pH value of 4.3, brown color, suspended matters in the wood vinegar and water content of 65.7 wt%, wherein the contents of all components in the organic matters are as follows based on the total weight of the organic matters: 11.6% for methanol, 3.2% for hydroxyacetone, 1.2% for acetaldehyde, 40.0% for acetic acid, 8.8% for propionic acid, 2.2% for furfural, 2.6% for cyclopentanone, 1.3% for furanone, 1.7% for butyric acid, 1.44% for valeric acid, 5.5% for phenol, 5.2% for methylphenol, 2.1% for ethylphenol, 3.8% for methoxyphenol, and 3.96% for other undetected components;
2) introducing the pyroligneous liquor into a distillation tower 1, carrying out reduced pressure distillation at 70 ℃ and 50Kpa absolute pressure, collecting condensate, namely refined pyroligneous liquor, and ensuring that the normal pressure boiling point in the refined pyroligneous liquor is higher than 0.16% of the heavy boilers of more than 250 ℃;
3) adding refined wood vinegar for 1 hr-1The volume space velocity of the gas phase is introduced into the heat exchanger 2, specifically, the gas phase is introduced into the first heat exchanger 2-1 and the second heat exchanger 2-2 in sequence for heat exchange until the temperature of the gas phase is 200 ℃, wherein the outlet temperature of the first heat exchanger 2-1 is 170 ℃;
4) introducing the gas-phase substances into a hydrogenation reaction device 3 for hydrogenation reaction, wherein the temperature of the hydrogenation reaction is ensured to be 200 ℃, the pressure is 1Mpa, and the molar ratio of unsaturated substances to hydrogen in the refined pyroligneous is 1: 40, the active component in the hydrogenation catalyst is cobalt, the auxiliary agents are manganese oxide, tin oxide, zirconium oxide and silicon oxide, wherein the cobalt content is 30 wt%, the manganese oxide content is 15 wt%, the tin oxide content is 15%, the zirconium oxide content is 2 wt%, and the silicon oxide content is 10 wt% based on the total weight of the hydrogenation catalyst, and the hydrogenation product is collected, wherein the methanol content in the hydrogenation product is 17.35%, the ethanol content in the hydrogenation product is 54.03%, the n-propanol content is 18.86%, the n-butanol content is 4.99%, the pentanol content is 2.38%, the cyclopentanol content in the cyclopentanol content is 1.34%, the cyclohexanol content in the cyclohexanol content is 1.4%, and the phenol content in the hydrogenation product is 2.65% based on the total weight of the components except water in the hydrogenation product; meanwhile, monohydric alcohol is generated, the monohydric alcohol has selectivity to the monohydric alcohol, and the hydrogenation product is transparent and clear liquid;
the continuous operation of the hydrogenation process is 4000 hours, and the content of outlet acetic acid is less than 0.1 percent; the pressure drop of the reactor is stabilized at 0.2 kilopascal/meter of the height of the catalyst bed layer;
5) and (3) rectifying the hydrogenation product to collect the biomass alcohol.
Example 3
The embodiment provides a pyroligneous acid hydrogenation process, which comprises the following steps:
1) performing Gas Chromatography (GC) measurement on organic matters in the wood vinegar with pH value of 4.2, brown color, suspended matters in the wood vinegar and water content of 79.7 wt%, wherein the contents of all components in the organic matters are as follows based on the total weight of the organic matters: 11.8% for methanol, 3.4% for hydroxyacetone, 1.0% for acetaldehyde, 40.0% for acetic acid, 8.6% for propionic acid, 2.2% for furfural, 2.6% for cyclopentanone, 1.3% for furanone, 1.7% for butyric acid, 1.44% for valeric acid, 5.5% for phenol, 5.2% for methylphenol, 2.1% for ethylphenol, 3.8% for methoxyphenol, and 3.96% for other undetected components;
2) introducing the pyroligneous liquor into a distillation tower 1, carrying out reduced pressure distillation at the temperature of 70 ℃ and the absolute pressure of 20Kpa, collecting condensate, namely refined pyroligneous liquor, and ensuring that the normal pressure boiling point in the refined pyroligneous liquor is higher than 0.02% of the heavy boilers with the temperature of more than 250 ℃;
3) adding refined wood vinegar for 3 hr-1The volume space velocity of the second heat exchanger 2 is introduced into the heat exchanger 2, specifically, the volume space velocity of the second heat exchanger 2 is introduced into the first heat exchanger 2-1 and the second heat exchanger 2-2 in sequence for heat exchange until the temperature of the gas phase substance is 280 ℃, wherein the outlet temperature of the first heat exchanger 2-1 is 245 ℃;
4) introducing the gas-phase substances into a hydrogenation reaction device 3 for hydrogenation reaction, wherein the temperature of the hydrogenation reaction is 280 ℃, the pressure is 4.5Mpa, and the molar ratio of unsaturated substances to hydrogen in the refined pyroligneous is 1: the hydrogenation catalyst comprises cobalt, copper and ruthenium as active components, chromium oxide, tin oxide, zirconium oxide and silicon oxide as auxiliary agents, wherein the cobalt content is 20 wt%, the copper content is 0.5 wt%, the ruthenium content is 0.1 wt%, the chromium oxide content is 10 wt%, the tin oxide content is 10 wt%, the zirconium oxide content is 10 wt% and the silicon oxide content is 30 wt% based on the total weight of the hydrogenation catalyst, the hydrogenation product is collected, and the hydrogenation product comprises 15.2% of methanol, 56.18% of ethanol, 15.51% of n-propanol, 4.99% of n-butanol, 2.38% of pentanol, 1.34% of cyclopentanol, 1.4% of cyclohexanol and 3.00% of phenol based on the total weight of components except water, wherein the propylene glycol content is less than 0.1%, and monohydric alcohol is generated at the same time, so that the hydrogenation catalyst has selectivity to monohydric alcohol; the hydrogenation product is transparent and clear liquid;
the hydrogenation process is continuously operated for 12000 hours, and the content of the outlet acetic acid is less than 0.3 percent; the pressure drop of the reactor is stabilized at 0.14 kilopascal/meter of the height of the catalyst bed layer;
5) and (3) performing membrane dehydration on the hydrogenation product to collect the biomass alcohol.
Example 4
The embodiment provides a pyroligneous acid hydrogenation process, which comprises the following steps:
1) performing Gas Chromatography (GC) measurement on organic matters in the wood vinegar with pH value of 4.2, brown color, suspended matters in the wood vinegar and water content of 79.7 wt%, wherein the contents of all components in the organic matters are as follows based on the total weight of the organic matters: 11.8% for methanol, 3.4% for hydroxyacetone, 1.0% for acetaldehyde, 40.0% for acetic acid, 8.6% for propionic acid, 2.2% for furfural, 2.6% for cyclopentanone, 1.3% for furanone, 1.7% for butyric acid, 1.44% for valeric acid, 5.5% for phenol, 5.2% for methylphenol, 2.1% for ethylphenol, 3.8% for methoxyphenol, and 3.96% for other undetected components;
2) introducing the pyroligneous liquor into a distillation tower 1, distilling at 40 ℃ and 0Kpa absolute pressure, collecting condensate to obtain refined pyroligneous liquor, and ensuring that the heavy boiling substance with the normal pressure boiling point higher than 250 ℃ in the refined pyroligneous liquor is less than or equal to 0.2%;
3) refining pyroligneous acid for 2 hr-1The volume space velocity of (2) is introduced into a heat exchanger (2), specifically, the volume space velocity of (2) is introduced into a first heat exchanger (2-1) and a second heat exchanger (2-2) in sequence for heat exchange until the temperature of a gas phase substance is 220 ℃, wherein the outlet temperature of the first heat exchanger (2-1) is 120 ℃, and a separator is arranged between two heat exchanges for gas-liquid separation;
4) introducing the gas-phase substances and hydrogen into a hydrogenation reaction device 3 for hydrogenation reaction, wherein the temperature of the hydrogenation reaction is 220 ℃, the pressure is 5Mpa, and the molar ratio of unsaturated substances to hydrogen in the refined pyroligneous is 1: 100, the active component in the hydrogenation catalyst is cobalt, the auxiliary agents are calcium oxide, aluminum oxide and tin, wherein the total weight of the hydrogenation catalyst is 35 wt%, the content of the calcium oxide is 20 wt%, the content of the aluminum oxide is 35 wt%, the content of the tin is 5%, the hydrogenation product is collected, the content of methanol in the hydrogenation product is 15.2%, the content of ethanol is 50.0%, the content of n-propanol is 14.51%, the content of n-butanol is 4.99%, the content of pentanol is 3.38%, the content of cyclopentanol is 2.34%, the content of cyclohexanol is 3.4%, the content of phenol is 5.18%, the generated monohydric alcohol is selective to the monohydric alcohol, and the hydrogenation product is a transparent and clear liquid;
the hydrogenation process can be continuously operated for 6000 hours, and the content of outlet acetic acid is less than 0.2 percent; the pressure drop of the reactor is stabilized at 0.25 kilopascal/meter of the height of the catalyst bed layer;
5) and (3) performing membrane dehydration on the hydrogenation product to collect the biomass alcohol.
Example 5
The embodiment provides a pyroligneous acid hydrogenation process, which comprises the following steps:
1) performing Gas Chromatography (GC) measurement on organic matters in the wood vinegar with pH value of 4.2, brown color, suspended matters in the wood vinegar and water content of 79.7 wt%, wherein the contents of all components in the organic matters are as follows based on the total weight of the organic matters: 11.8% for methanol, 3.4% for hydroxyacetone, 1.0% for acetaldehyde, 40.0% for acetic acid, 8.6% for propionic acid, 2.2% for furfural, 2.6% for cyclopentanone, 1.3% for furanone, 1.7% for butyric acid, 1.44% for valeric acid, 5.5% for phenol, 5.2% for methylphenol, 2.1% for ethylphenol, 3.8% for methoxyphenol, and 3.96% for other undetected components;
2) introducing the pyroligneous liquor into a distillation tower 1, distilling at 65 ℃ and under the absolute pressure of 45Kpa, collecting condensate to obtain refined pyroligneous liquor, and ensuring that the heavy boiling substance with the normal pressure boiling point higher than 250 ℃ in the refined pyroligneous liquor is less than or equal to 0.5%;
3) adding refined wood vinegar for 6 hr-1The volume space velocity of the gas phase is introduced into a heat exchanger 2 for heat exchange until the temperature of the gas phase substance is 190 ℃;
4) introducing the mixture into a hydrogenation reaction device 3 for hydrogenation reaction, wherein the temperature of the hydrogenation reaction is 190 ℃, the pressure is 1.6Mpa, and the molar ratio of unsaturated substances to hydrogen in the refined pyroligneous is 1: 38, the active component in the hydrogenation catalyst is cobalt, the auxiliary agents are zirconia, silica, tin and calcium, wherein the total weight of the hydrogenation catalyst is 20 wt%, the zirconia content is 20 wt%, the silica content is 10 wt%, the tin content is 10 wt% and the calcium content is 25 wt%, the hydrogenation product is collected, and the methanol content, the ethanol content, the n-propanol content, the n-butanol content, the pentanol content, the cyclopentanol content, the cyclohexanol content, and the phenol content are respectively 17.45%, 56.58%, 15.86%, 3.99%, 2.38%, 1.34%, 1.4% and 1.00%, and meanwhile, the generated monohydric alcohol is selective to the monohydric alcohol, and the hydrogenation product is a transparent and clear liquid;
the hydrogenation process is continuously operated for 3800 hours, and the content of outlet acetic acid is less than 0.3 percent; the pressure drop of the reactor is stabilized at 0.21 kilopascal/meter of the height of the catalyst bed layer;
5) and (3) rectifying the hydrogenation product to collect the biomass alcohol.
Comparative example 1
The comparative example provides a pyroligneous acid hydrogenation process, comprising the following steps:
1) performing Gas Chromatography (GC) measurement on organic matters in the wood vinegar with pH value of 4.2, brown color, suspended matters in the wood vinegar and water content of 79.7 wt%, wherein the contents of all components in the organic matters are as follows based on the total weight of the organic matters: 11.8% for methanol, 3.4% for hydroxyacetone, 1.0% for acetaldehyde, 40.0% for acetic acid, 8.6% for propionic acid, 2.2% for furfural, 2.6% for cyclopentanone, 1.3% for furanone, 1.7% for butyric acid, 1.44% for valeric acid, 5.5% for phenol, 5.2% for methylphenol, 2.1% for ethylphenol, 3.8% for methoxyphenol, and 3.96% for other undetected components;
2) mixing the wood vinegar solution for 2 hr-1The volume space velocity of the gas phase is introduced into a heat exchanger 2, specifically, the gas phase is sequentially introduced into a first heat exchanger 2-1 and a second heat exchanger 2-2 for heat exchange until the temperature of the gas phase is 250 ℃, wherein the outlet temperature of the first heat exchanger 2-1 is 190 ℃;
3) introducing the gas-phase substances and hydrogen into a hydrogenation reaction device 3 for hydrogenation reaction, wherein the temperature of the hydrogenation reaction is 250 ℃, the pressure is 3Mpa, and the molar ratio of unsaturated substances to hydrogen in the pyroligneous liquor is 1: 30, active components in the hydrogenation catalyst are cobalt and copper, an auxiliary agent is silicon oxide, wherein the cobalt content is 22 wt%, the copper content is 2 wt%, the silicon oxide content is 73 wt%, the balance is water and a forming auxiliary agent, a hydrogenation product is collected, the acetic acid content in the hydrogenation product obtained in the 5 hours before operation is 20%, the methanol content is 8.62%, the ethanol content is 30.12%, the propanol content is 8.95%, the butanol content is 2.13%, the hydrogenation product contains a large amount of aldehydes, phenols and ketones, the propylene glycol content in the reaction product is 2.2%, and the sampling color is red, wherein the total weight of the components except water in the hydrogenation product is calculated;
after the hydrogenation catalyst is continuously operated for 36 hours, the activity of the hydrogenation catalyst is reduced by more than 60 percent, and the pressure drop of the bed layer is increased by 6 times to 0.96 kilopascal per meter of the height of the catalyst bed layer.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (15)
1. A pyroligneous hydrogenation process comprises the following steps:
refining: distilling the wood vinegar solution under reduced pressure, and collecting refined wood vinegar solution;
hydrogenation: mixing the refined pyroligneous with hydrogen in the presence of a hydrogenation catalyst to carry out hydrogenation reaction, and collecting a hydrogenation product;
separation: separating the hydrogenation product, and collecting biomass alcohol in the hydrogenation product;
the hydrogenation catalyst comprises an active component and an auxiliary agent,
when the active component is at least one of copper, cobalt and ruthenium, the auxiliary agent is at least one of chromium oxide, tin oxide, manganese oxide, zirconium oxide and silicon oxide; or the like, or, alternatively,
when the active component is copper and/or cobalt, the auxiliary agent consists of a first auxiliary agent and a second auxiliary agent, wherein the first auxiliary agent is an oxide of silicon and/or an oxide of aluminum, and the second auxiliary agent is tin; or the like, or, alternatively,
when the active component is cobalt, the auxiliary agent consists of a first auxiliary agent, a second auxiliary agent and a third auxiliary agent, wherein the first auxiliary agent is an oxide of zirconium, the second auxiliary agent is an oxide of silicon and/or an oxide of aluminum, and the third auxiliary agent is at least one of tin and calcium;
the temperature of the hydrogenation reaction is 170-280 ℃, and the pressure is 1-5 Mpa.
2. The process of claim 1, wherein the refined pyroligneous acid contains 1% or less of reboilers having an atmospheric boiling point of 250 ℃ or higher.
3. The process of hydrogenating pyroligneous acid according to claim 2, wherein the hydrogenation step comprises the steps of,
the heavy boiling substance with the normal pressure boiling point higher than 250 ℃ in the refined pyroligneous is less than or equal to 0.5 percent.
4. The process of claim 3, wherein the refined pyroligneous acid has an atmospheric pressure boiling point of not less than 0.2% and not more than 250 ℃.
5. The process of claim 1, wherein the distillation under reduced pressure is carried out at a temperature of 40 to 90 ℃ and an absolute pressure of 0 to 95 Kpa.
6. The process of hydrogenating pyroligneous acid according to claim 5, wherein the hydrogenation step,
the reduced pressure distillation temperature is 50-70 deg.C, and the absolute pressure is 30-90 Kpa.
7. The pyroligneous hydrogenation process of claim 1, wherein before the hydrogenation reaction, the mixture of the refined pyroligneous and hydrogen is subjected to at least two heat exchanges, the temperature of the mixture after the first heat exchange is 100-220 ℃, the mixture after the first heat exchange is subjected to gas-liquid separation, heavy components are separated and removed in a liquid phase, gas-phase substances are collected, and the gas-phase substances are subjected to a second heat exchange to a temperature of 170-280 ℃.
8. The pyroligneous acid hydrogenation process according to claim 1, wherein the hydrogenation reaction is carried out at a temperature of 200 ℃ and a pressure of 2 to 4 Mpa;
the molar ratio of unsaturated substances to hydrogen in the refined wood vinegar is 1: (2-100); the volume space velocity of the refined pyroligneous liquor is 0.1-10 h-1。
9. The pyroligneous acid hydrogenation process according to claim 8, wherein,
the molar ratio of unsaturated substances to hydrogen in the refined wood vinegarIs 1: (8-40); the volume space velocity of the refined pyroligneous liquor is 1-3h-1。
10. The pyroligneous hydrogenation process according to claim 1, wherein when the active component is at least one of copper, cobalt and ruthenium, and the auxiliary agent is at least one of chromium oxide, tin oxide, manganese oxide, zirconium oxide and silicon oxide, the mass ratio of the active component to the auxiliary agent is (0.1-50): (10-90).
11. The pyroligneous hydrogenation process according to claim 10, wherein when the active component is at least one of copper, cobalt and ruthenium, and the auxiliary agent is at least one of chromium oxide, tin oxide, manganese oxide, zirconium oxide and silicon oxide, the content of the active component is 0.1 to 50 wt% based on the total weight of the hydrogenation catalyst; the content of the auxiliary agent is 10-90 wt%; the sum of the content of the active component and the content of the auxiliary agent is not more than 100 wt%.
12. The pyroligneous hydrogenation process according to claim 11, wherein when the active ingredient is copper and/or cobalt and the auxiliary agent is at least one of chromium oxide, tin oxide, manganese oxide, zirconium oxide, and silicon oxide, the content of the active ingredient is 5 to 50 wt%;
when the active component is ruthenium and the auxiliary agent is at least one of chromium oxide, tin oxide, manganese oxide, zirconium oxide and silicon oxide, the content of the active component is 0.1-5 wt%.
13. The pyroligneous hydrogenation process according to claim 1, wherein when the active ingredient is copper and/or cobalt, the assistant is composed of a first assistant and a second assistant, the first assistant is an oxide of silicon and/or an oxide of aluminum, and the second assistant is tin, the content of the active ingredient is 10 to 50 wt%, and the content of the assistant is 50 to 90 wt%.
14. The pyroligneous hydrogenation process according to claim 1, wherein when the active ingredient is cobalt, the auxiliary agent is composed of a first auxiliary agent, a second auxiliary agent and a third auxiliary agent, the first auxiliary agent is an oxide of zirconium, the second auxiliary agent is an oxide of silicon and/or an oxide of aluminum, and the third auxiliary agent is at least one of tin and calcium, the content of the active ingredient is 10 to 50 wt%, and the content of the auxiliary agent is 50 to 90 wt%.
15. The pyroligneous hydrogenation process according to claim 7, wherein the separation is one or a combination of both of distillation separation or membrane dehydration; or the like, or, alternatively,
the method also comprises the step of collecting the wood tar separated in the reduced pressure distillation and the wood tar separated after the gas-liquid separation;
before the separation, the method also comprises a step of condensing the hydrogenation product;
during the separation, the method also comprises the step of recovering steam and hot water with the temperature of 80-110 ℃ in the separation process and using the steam and the hot water for the reduced pressure distillation and/or the heat exchange.
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