CN115466627B - Method for alcoholysis hydrogenation treatment of papermaking black liquor lignin - Google Patents

Method for alcoholysis hydrogenation treatment of papermaking black liquor lignin Download PDF

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CN115466627B
CN115466627B CN202211247347.7A CN202211247347A CN115466627B CN 115466627 B CN115466627 B CN 115466627B CN 202211247347 A CN202211247347 A CN 202211247347A CN 115466627 B CN115466627 B CN 115466627B
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alcoholysis
hydrodeoxygenation
hydrogenation
black liquor
catalyst
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CN115466627A (en
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柴永明
徐彦琳
刘宾
孙亚伟
董斌
潘原
李奕川
于英民
刘晨光
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China University of Petroleum East China
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The invention discloses a method for alcoholysis hydrogenation treatment of lignin in papermaking black liquor, and relates to the technical field of lignin conversion. The method disclosed by the invention converts the papermaking black liquor lignin into hydrocarbon products after fluidized bed alcoholysis hydrogenation and fixed bed hydrodeoxygenation, realizes the continuous operability of the process of converting the papermaking black liquor lignin into chemical raw materials, recovers inorganic alkali in the papermaking black liquor, and solves the problems of difficult lignin treatment and serious lignin and inorganic alkali resource waste of the current papermaking black liquor. The method adopts the coupling mode of catalytic alcoholysis and catalytic hydrogenation to treat the papermaking black liquor, effectively converts the lignin of the papermaking black liquor into high-value hydrocarbon products, and improves the conversion rate of the lignin of the papermaking black liquor by using the method, so that the yield of the hydrocarbon products is high.

Description

Method for alcoholysis hydrogenation treatment of papermaking black liquor lignin
Technical Field
The invention relates to the technical field of lignin conversion, in particular to a method for alcoholysis and hydrotreatment of lignin in papermaking black liquor.
Background
The paper industry is one of the most serious industries in China. The discharge of paper products and pulping and papermaking wastewater above county and county level in China is inferior to annual discharge of chemical raw materials and chemical product manufacturing industries. The papermaking production process comprises two basic processes of pulping and papermaking. The pulping process generally takes plants such as wood, grass and the like as raw materials, and the main components of the pulping process are cellulose, hemicellulose and lignin. Due to the color and anti-yellowing properties of lignin, for the production of high whiteness The pulp is prepared by dissociating plant wood fiber raw materials by a mechanical pulping method, a chemical pulping method or a semi-chemical pulping method, removing lignin in the raw materials, and retaining cellulose and hemicellulose solids. The most common modern pulping process in the world is a chemical pulping process, and the most important is an alkaline pulping process. The alkaline pulping process comprises adding wood chip into NaOH alkaline solution (or Na) 2 S is an auxiliary agent), and the pH value of the cooking liquid is more than 13. In the alkaline pulping process, a plurality of ether bonds in lignin macromolecules are subjected to nucleophilic reagent OH - The ionic action breaks the macromolecular lignin which is randomly crosslinked with cellulose, so that the macromolecular lignin is dissociated from the lignocellulose raw material, and the lignin macromolecules are deeply degraded into phenolic micromolecules and are dissolved into alkaline aqueous solution. Because the structures of cellulose and hemicellulose are not damaged basically in the pulping process flow, papermaking black liquor and paper pulp are obtained after the pulping process products are separated, and the paper pulp enters the papermaking process. The main components of the papermaking black liquor are lignin, inorganic alkali and water, and the main components of the paper pulp are cellulose and hemicellulose solids.
The pollution produced by the black liquor of industrial papermaking accounts for about 90% of the total pollution of industrial papermaking. Treatment of papermaking black liquor is one of the problems which are solved at home and abroad. In the traditional alkaline pulping process, lignin dissolved into pulping black liquor accounts for about 30% of the mass of wood raw materials, and is also a main source of COD content of papermaking black liquor. However, because the structure of the papermaking black liquor lignin is complex, the treatment difficulty is high, meanwhile, the requirement on the treatment method of the black liquor lignin is very harsh due to the strong alkalinity of the papermaking black liquor, only 5% of papermaking black liquor lignin in the market is consumed as low-value commodities such as low-grade fuel, concrete admixture (lignosulfonate) and the like, and more than 90% of papermaking black liquor is directly discharged, so that a great amount of lignin resources are wasted. Therefore, the recovery and utilization of lignin in papermaking black liquor for conversion to prepare high-value chemicals has important practical significance.
Common treatment methods of lignin in papermaking black liquor comprise alkali recovery by a high-temperature incineration method, lignin extraction by an inorganic acid precipitation method,separating lignin by membrane separation method, extracting lignin by oxidation method, depolymerizing lignin by pyrolysis method, decomposing lignin by biodegradation method. Although the traditional methods have certain results and experience, the COD of the black liquor wastewater can be effectively reduced cr The values, however, still suffer from a number of drawbacks, principally summarised as follows: firstly, the high-temperature incineration of black liquor lignin causes serious lignin carbon resource waste; secondly, lignin obtained by an inorganic acid precipitation method, a membrane separation method and an oxidation method is macromolecular lignin sulfonate, the industrial application range is narrow, the high value degree of lignin is low, and a large amount of inorganic alkali is wasted; thirdly, the main components of the biological oil produced by the pyrolysis method are hundreds of oxygen-containing compounds of phenols, ketones, alcohols and aldehydes, the separation difficulty is high, and the biological oil is difficult to be efficiently separated into chemical raw materials for large-scale utilization; and thirdly, the biological degradation method has long treatment time, large occupied area and unstable treatment effect, and is easily influenced by natural factors such as seasons, air temperature, illumination and the like. These factors limit the large-scale application and industrial development of lignin conversion from black liquor to high-value chemicals.
Chinese patent CN107286006a discloses a method for preparing vanillyl ethanone and acetosyringone by catalytic alcoholysis of lignin, which uses lignin as raw material, and carries out microwave alcoholysis in alcohol solvent containing supported metal catalyst, and then liquid product mainly comprising vanillyl ethanone and acetosyringone is obtained through cooling, filtering and washing. The catalytic alcoholysis method can economically and effectively depolymerize lignin macromolecules into micromolecular oxygen-containing compounds, but is not suitable for preparing chemical products by a papermaking black liquor system. This is because the papermaking black liquor contains a large amount of water, so that the oxygen-containing compound cannot be separated from the alcohol-water system with high efficiency; meanwhile, al under the strong alkaline condition of papermaking black liquor 2 O 3 The framework structure of the acid carrier is seriously damaged, so that the stability of the catalyst is low, and the catalyst is difficult to apply in large-scale industrial application.
Chinese patent application CN201510464008.8 discloses a method for preparing hydrocarbons by efficient deoxidization and hydrogenation of guaiacol, which adopts a mixture of guaiacol and alcohol as raw materials, and under the catalysis of an HZSM-5 molecular sieve, gas-solid catalytic cracking reaction is carried out at 500-600 ℃ to obtain the product hydrocarbons with the yield of 20.68%. Because of the low solubility of hydrocarbons in water, the method is characterized in that the reaction product is condensed, stood and layered, and the water phase and the oil phase are respectively collected, and the hydrocarbons are in the oil phase. However, the method has the advantages that the aromatic ring of the lignin compound is easy to polymerize and coke due to higher operating temperature, and the catalyst surface lacks metal for activating hydrogen, so that the hydrogenation efficiency of the catalyst is low and the hydrocarbon yield is low.
Therefore, a method for treating papermaking black liquor lignin is needed, which can take the strongly alkaline papermaking black liquor as a raw material to prepare hydrocarbon chemical products by utilizing the papermaking black liquor lignin in a large scale.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for alcoholysis and hydrotreatment of papermaking black liquor lignin, which not only solves the problems of resource waste, poor catalyst stability, difficult separation of reaction products and the like caused by acidizing the papermaking black liquor, but also can efficiently convert the papermaking black liquor lignin into hydrocarbon chemical raw materials under milder conditions.
In order to achieve the above object, the invention provides a method for alcoholysis and hydrotreatment of lignin in papermaking black liquor, which comprises the following operation steps:
carrying out catalytic alcoholysis hydrodeoxygenation reaction on papermaking black liquor, low-carbon alcohol and an organic solvent to obtain an alcoholysis hydrodeoxygenation product;
standing and layering an alcoholysis hydrodeoxygenation product, and separating to obtain an organic solvent phase and an alcohol water phase;
distilling and separating the obtained organic solvent phase to obtain alcoholysis hydrogenated biological oil and tail oil;
the obtained alcoholysis hydrogenation biological oil is further subjected to hydrodeoxygenation reaction to obtain hydrodeoxygenation biological oil;
and distilling and separating the hydrodeoxygenation biological oil to obtain hydrocarbons, water and an organic solvent.
And (3) recycling part of hydrocarbons obtained by distilling and separating the hydrodeoxygenation biological oil obtained by the method into the catalytic alcoholysis hydrodeoxygenation reaction.
Standing and layering the alcoholysis hydrodeoxygenation product obtained by the method, separating an obtained alcohol water phase, distilling to obtain methanol and the water phase, recycling the obtained methanol into a catalytic alcoholysis hydrodeoxygenation reaction to supplement low-carbon alcohol, and evaporating the water phase at a high temperature to recover inorganic alkali;
recycling tail oil obtained by distilling and separating the organic solvent phase obtained by the method into catalytic alcoholysis hydrodeoxygenation reaction to supplement the organic solvent; and (3) recycling the organic solvent and part of hydrocarbons obtained by distilling and separating the hydrodeoxygenation biological oil into catalytic alcoholysis hydrodeoxygenation reaction to supplement the organic solvent.
The mass ratio of the papermaking black liquor, the low-carbon alcohol and the organic solvent in the method is 1:0.1-5:0.2-5; preferably, the mass ratio of the papermaking black liquor to the low-carbon alcohol to the organic solvent is 1:3:3.
the steps for obtaining the alcoholysis hydrodeoxygenation product in the method are as follows:
firstly, placing papermaking black liquor, low-carbon alcohol, an organic solvent and an alcoholysis hydrogenation catalyst into a first alcoholysis hydrogenation device, and carrying out catalytic alcoholysis hydrogenation reaction under the condition of introducing hydrogen to obtain an alcoholysis hydrogenation product;
and then placing the alcoholysis hydrogenation product and an alcoholysis hydrodeoxygenation catalyst in a second alcoholysis hydrogenation device, and carrying out deep catalytic alcoholysis hydrodeoxygenation reaction under the condition of introducing hydrogen to obtain the alcoholysis hydrodeoxygenation product.
Wherein the reaction temperature in the first alcoholysis hydrogenation device is 200-300 ℃, the pressure is 8-25MPa, and the hydrogen-oil volume ratio is 100-1000:1, the reaction space velocity is 1.0-10.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature in the second glycolysis hydrogenation device is 280-350 ℃, the pressure is 10-30MPa, and the volume ratio of hydrogen to oil is 100-1000:1, the reaction space velocity is 1.0-10.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature for further hydrodeoxygenation reaction is 280-350 ℃, the operating pressure is 10-30MPa, and the hydrogen-oil volume ratio is 100-1500:1, the reaction space velocity is 1.0-10.0h -1 。
The carrier of the alcoholysis hydrogenation catalyst is one of magnesium oxide, magnesium aluminum hydrotalcite, zirconium oxide, silicon nitride, silicon carbide and carbon material, one or more metals selected from vanadium, molybdenum, bismuth, nickel, iron, antimony, tungsten, copper, iron, niobium, chromium, magnesium, zinc and aluminum are loaded on the surface of the carrier, and the total atom loading of the metals is 1-80%.
The carrier of the alcoholysis hydrodeoxygenation catalyst is one of magnesium oxide, magnesium aluminum hydrotalcite, zirconium oxide, silicon nitride, silicon carbide and carbon material, and one or more metals selected from cobalt, molybdenum, nickel, iron, tungsten, copper, iron, niobium and chromium are loaded on the surface of the carrier, and the total atom loading of the metals is 1-80%.
The total acid amount on the surface of the alcoholysis hydrodeoxygenation catalyst is 1-6mmol/g.
The alcoholysis hydrogenation biological oil obtained in the method further comprises a catalyst in the hydrodeoxygenation reaction, wherein a carrier of the catalyst is selected from one of alumina, molecular sieve, magnesia, magnalium hydrotalcite, zirconia, silicon nitride, silicon carbide and carbon material, the surface of the catalyst is loaded with one or more metals selected from platinum, palladium, ruthenium, cobalt, molybdenum, nickel, iron, tungsten, copper, iron, niobium and chromium, and the total atom load of the metals is 1-80%.
The preparation methods of the alcoholysis hydrogenation catalyst, the alcoholysis hydrodeoxygenation catalyst and the catalyst are as follows: weighing active metal salt, dissolving in deionized water, and stirring at room temperature to form clear and transparent solution to obtain metal precursor solution; and loading the metal precursor on a carrier by adopting an isovolumetric co-impregnation method or a deposition precipitation method, and then reducing, vulcanizing or phosphating the metal precursor to obtain the catalyst.
Wherein, the treatment conditions of the reduction, vulcanization or phosphating treatment are as follows:
the reduction treatment conditions are as follows: the reduction temperature is 150-500 ℃, and the reduction atmosphere is H 2 Or H 2 The mixed gas of Ar and the reduction time is 1-6h, and the reduced catalyst is obtained after treatment;
the vulcanization treatment conditions are as follows: the vulcanizing temperature is 250-500 ℃, and the vulcanizing agent is thiourea and H 2 S, DMDS and CS 2 The sulfuration time is 1-6h, and the sulfuration catalyst is obtained after treatment;
the phosphating conditions are as follows: the phosphating temperature is 250-500 ℃, the phosphating agent is one of triphenylphosphine, phosphoric acid, ammonium dihydrogen phosphate, diamine hydrogen phosphate and urea phosphate, the phosphating time is 1-6h, and the phosphating catalyst is obtained after treatment.
The hydrocarbon in the method comprises circulating hydrocarbon and external throwing hydrocarbon, wherein the circulating hydrocarbon is used for supplementing organic solvent, and the volume ratio of the circulating hydrocarbon to the external throwing hydrocarbon is 0.1-10:1.
The operation procedure for recovering inorganic alkali by high-temperature evaporation of the water phase is as follows: concentrating at 80-130deg.C until the concentration of the solution is 25-30%, and burning in a recovery furnace at 1000-1200deg.C.
The method disclosed by the invention converts the papermaking black liquor lignin into hydrocarbon products after fluidized bed alcoholysis hydrogenation and fixed bed hydrodeoxygenation, realizes the continuous operability of the process of converting the papermaking black liquor lignin into chemical raw materials, recovers inorganic alkali in the papermaking black liquor, and solves the problems of difficult lignin treatment and serious lignin and inorganic alkali resource waste of the current papermaking black liquor. The method adopts the coupling mode of catalytic alcoholysis and catalytic hydrogenation to treat the papermaking black liquor, effectively converts the lignin of the papermaking black liquor into high-value hydrocarbon products, and improves the conversion rate of the lignin of the papermaking black liquor by using the method, so that the yield of the hydrocarbon products is high.
In the implementation process, a catalyst with alkali resistance is preferably used, papermaking black liquor is taken as a raw material, lignin in the papermaking black liquor is depolymerized into hydrocarbon micromolecules by an alcoholysis hydrotreating method, and meanwhile, inorganic alkali is recovered by high-temperature evaporation. Compared with the traditional alcoholysis treatment or hydrotreatment method, the alcoholysis hydrotreatment method provided by the invention has the advantages that the lignin conversion rate is higher, the hydrocarbon yield is higher, and meanwhile, the waste of inorganic alkali resources is avoided.
Compared with the prior art, the invention at least comprises the following beneficial effects:
firstly, the papermaking black liquor lignin alcoholysis hydrogenation process provided by the invention can be operated continuously and for a long period;
secondly, the papermaking black liquor lignin alcoholysis hydrogenation process provided by the invention can directly take the papermaking black liquor as a raw material without pre-acidification, so that the waste of inorganic alkali resources is avoided;
thirdly, the catalytic alcoholysis and catalytic hydrogenation coupling treatment method is adopted in the papermaking black liquor lignin alcoholysis hydrogenation process, so that the lignin conversion rate is high and the hydrocarbon yield is high;
fourth, the papermaking black liquor lignin alcoholysis hydrogenation process provided by the invention has the advantages of mild operation conditions, stable effect and high feasibility of industrial application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of one embodiment of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
It should be noted that, without conflict, the following embodiments and features in the embodiments may be combined with each other; and, based on the embodiments in this disclosure, all other embodiments that may be made by one of ordinary skill in the art without inventive effort are within the scope of the present disclosure.
The external dodecane mentioned in the examples below is the dodecane added in step one.
Example 1
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a high-pressure reaction kettle of a first alcoholysis hydrogenation device filled with a Ni/AC catalyst for alcoholysis hydrogenation reaction to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the catalyst is 1:3:3:0.17, the catalyst uses active carbon as a carrier and Ni as an active component, wherein the active component and the carrierThe mass ratio of the body is 0.18:1, a step of; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operating temperature is 300 ℃, the operating pressure is 20MPa, and the volume space velocity is 1.0h -1 ；
Step two, transferring the alcoholysis hydrogenation product obtained in the step one into a catalyst filled with Ni 2 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the P/AC catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses active carbon as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 300 ℃, the operating pressure is 19MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the obtained alcoholysis hydrogenation products is shown in table 1;
thirdly, standing and layering the alcoholysis hydrodeoxygenation product obtained in the second step, and separating to obtain a dodecane phase product and an alcohol water phase product;
step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into Ni-filled bio-oil 2 P/γ-Al 2 O 3 Hydrodeoxygenation reaction is carried out in a fixed bed reactor of the catalyst, so as to obtain hydrodeoxygenation biological oil; the catalyst uses gamma-Al 2 O 3 As a carrier, ni was used as an active component, wherein the mass ratio of active component to carrier was 0.18:1, a step of; the operating temperature is 320 ℃, the operating pressure is 7MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, and the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase; the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device, and the obtained hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, wherein the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of; wherein, the distribution and the element composition of the hydrocarbon products are shown in tables 2 and 3;
and step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, the obtained methanol is partially recycled into a first alcoholysis hydrogenation device to replace raw material methanol, the water phase product is concentrated and evaporated at the high temperature of 1000 ℃ to recover inorganic alkali, and the material accounting is shown in the table 4.
Example 2
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a high-pressure reaction kettle of a first alcoholysis hydrogenation device filled with a CoMoS/AC catalyst for alcoholysis hydrogenation reaction to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the catalyst is 1:3:3:0.17, wherein the catalyst uses active carbon as a carrier and Co and Mo as active components, and the mass ratio of an active substance to the carrier is 0.18:1, the mass ratio of Co to Mo calculated by oxide is 1:0.36; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operating temperature is 300 ℃, the operating pressure is 20MPa, and the volume space velocity is 1.0h -1 ；
Step two, transferring the alcoholysis hydrogenation product obtained in the step one into a catalyst filled with Ni 2 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the P/AC catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses active carbon as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 300 ℃, the operating pressure is 19MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the obtained alcoholysis hydrogenation products is shown in table 1;
thirdly, standing and layering the alcoholysis hydrodeoxygenation product, and separating to obtain a dodecane phase product and an alcohol water phase product;
step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into a reactor filled with CoMoS/gamma-Al 2 O 3 Hydrodeoxygenation reaction is carried out in a fixed bed reactor of the catalyst, so as to obtain hydrodeoxygenation biological oil; the catalyst uses gamma-Al 2 O 3 As the carrier, co and Mo were used as active components, wherein the mass ratio of Co and Mo as oxides was 1:0.36, the mass ratio of the active component to the carrier is 0.18:1, a step of; wherein the operating temperature is 320 ℃, the operating pressure is 7MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase, the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device, the obtained hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace an organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of; wherein, the distribution and the element composition of the hydrocarbon products are shown in tables 2 and 3;
and step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, recycling part of the methanol into a first alcoholysis hydrogenation device to replace raw material methanol, concentrating the water phase product, evaporating at the high temperature of 1000 ℃ to recover inorganic alkali, and carrying out material accounting as shown in the table 4.
Example 3
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a reactor filled with Ni 2 Alcoholysis hydrogenation reaction is carried out in a high-pressure reaction kettle of a first alcoholysis hydrogenation device of the P/AC catalystObtaining an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the catalyst is 1:3:3:0.17, wherein the catalyst uses active carbon as a carrier and Ni as an active component, and the mass ratio of the active component to the carrier is 0.18:1, a step of; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operating temperature is 300 ℃, the operating pressure is 20MPa, and the volume space velocity is 1.0h -1 ；
Step two, transferring the alcoholysis hydrogenation product obtained in the step one into a catalyst filled with Ni 2 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the P/AC catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses active carbon as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 300 ℃, the operating pressure is 19MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the obtained alcoholysis hydrogenation products is shown in table 1;
and thirdly, standing and layering the alcoholysis hydrodeoxygenation product, and separating to obtain a dodecane phase product and an alcohol water phase product.
Step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into a reactor filled with Pt/gamma-Al 2 O 3 Hydrodeoxygenation reaction is carried out in a fixed bed reactor of the catalyst, so as to obtain hydrodeoxygenation biological oil; the catalyst uses gamma-Al 2 O 3 Pt was used as the active component for the support, wherein the mass ratio of active component to support was 0.18:1, a step of; wherein the operating temperature is 340 ℃, the operating pressure is 9MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, and the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase; the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device; the hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, wherein the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of; wherein, the distribution and the element composition of the hydrocarbon products are shown in tables 2 and 3;
Step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range temperature of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, recycling part of the methanol into a first alcoholysis hydrogenation device to replace raw material methanol, concentrating the water phase product, and evaporating at the high temperature of 1000 ℃ to recover inorganic alkali; the material accounting is shown in Table 4.
Example 4
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a reactor filled with Ni-Cu/ZrO 2 Performing alcoholysis hydrogenation reaction in a high-pressure reaction kettle of a first alcoholysis hydrogenation device of the catalyst to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the catalyst is 1:3:3:0.17; the catalyst uses ZrO 2 As the carrier, ni and Cu are used as active components, wherein Ni: the atomic ratio of Cu is 1:1, the mass ratio of the active component to the carrier is 0.3:1, a step of; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operation temperature is 200 ℃, the operation pressure is 8MPa, and the hydrogen-oil volume ratio is 100:1, volume space velocity of 10.0h -1 ；
Transferring the alcoholysis hydrogenation product obtained in the step one into a high-pressure reaction kettle of a second alcoholysis hydrogenation device filled with a NiMoS/SiC catalyst for alcoholysis hydrodeoxygenation reaction to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses SiC as a carrier and Ni and Mo as active components, wherein Ni: mo atomic ratio 1:0.6, the mass ratio of the active component to the carrier is 0.2:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 280 ℃, the operating pressure is 10MPa, and the hydrogen-oil volume ratio is 100:1, empty volume The speed is 10.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the obtained alcoholysis hydrogenation products is shown in table 1;
and thirdly, standing and layering the alcoholysis hydrodeoxygenation product, and separating to obtain a dodecane phase product and an alcohol water phase product.
Step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into a reactor filled with CoMoS-Nb 2 O 5 Carrying out hydrodeoxygenation reaction in a fixed bed reactor of the HZSM-5 catalyst to obtain hydrodeoxygenation biological oil; the catalyst uses HZSM-5 as a carrier and Co, mo and Nb as active components, wherein the Co is calculated by oxide: mo: the mass ratio of Nb is 1:0.36:0.06, the mass ratio of the active component to the carrier is 0.18:1, a step of; wherein the operating temperature is 350 ℃, the operating pressure is 30MPa, and the hydrogen-oil volume ratio is 1500:1, volume space velocity of 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, and the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase; the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device; the hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, wherein the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of; wherein, the distribution and the element composition of the hydrocarbon products are shown in tables 2 and 3;
Step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range temperature of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, recycling part of the methanol into a first alcoholysis hydrogenation device to replace raw material methanol, concentrating the water phase product, and evaporating at the high temperature of 1000 ℃ to recover inorganic alkali; the material accounting is shown in Table 4.
Example 5
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a high-pressure reaction kettle of a first alcoholysis hydrogenation device filled with a Ni/MgAlLDH catalyst for alcoholysis hydrogenation reaction to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the catalyst is 1:3:3:0.17; the catalyst uses magnesium aluminum hydrotalcite as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operating temperature is 300 ℃, the operating pressure is 25MPa, and the hydrogen-oil volume ratio is 1000:1, volume space velocity of 1.0h -1 ；
Step two, transferring the alcoholysis hydrogenation product obtained in the step one into a reactor filled with FeNi/ZrO 2 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses SiC as a carrier and Fe and Ni as active components, wherein Fe: ni atomic ratio is 1:2, the mass ratio of the active component to the carrier is 0.2:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 350 ℃, the operating pressure is 30MPa, and the hydrogen-oil volume ratio is 1000:1, volume space velocity of 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the obtained alcoholysis hydrogenation products is shown in table 1;
and thirdly, standing and layering the alcoholysis hydrodeoxygenation product, and separating to obtain a dodecane phase product and an alcohol water phase product.
Step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into a reactor filled with RuMoO 3 Carrying out hydrodeoxygenation reaction in a fixed bed reactor of the USY catalyst to obtain hydrodeoxygenation biological oil; the catalyst uses USY as a carrier and Ru and Mo as active components, wherein Ru is calculated by oxide: the mass ratio of Mo is 1:36, the mass ratio of the active component to the carrier is 0.18:1, a step of; wherein the operating temperature is 280 ℃, the operating pressure is 10MPa, and the hydrogen-oil volume ratio is 100:1, volume space velocity of 10.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, and the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase; the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device; the hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, wherein the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of; wherein, the distribution and the element composition of the hydrocarbon products are shown in tables 2 and 3;
Step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range temperature of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, recycling part of the methanol into a first alcoholysis hydrogenation device to replace raw material methanol, concentrating the water phase product, and evaporating at the high temperature of 1000 ℃ to recover inorganic alkali; the material accounting is shown in Table 4.
Example 6
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a high-pressure reaction kettle of a first alcoholysis hydrogenation device filled with a Ni-Al/AC catalyst for alcoholysis hydrogenation reaction to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the catalyst is 1:5:5:0.17, wherein the catalyst uses active carbon as a carrier and uses Ni and Al as active components, and the atomic ratio of Ni to Al is 1:0.3, the mass ratio of the active component to the carrier is 0.18:1, a step of; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operating temperature is 300 ℃, the operating pressure is 20MPa, and the volume space velocity is 1.0h -1 ；
Step two, transferring the alcoholysis hydrogenation product obtained in the step one into a catalyst filled with Ni 2 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the P/AC catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalysis is that The agent uses active carbon as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 300 ℃, the operating pressure is 19MPa, and the hydrogen-oil volume ratio is 1000:1, volume space velocity of 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the obtained alcoholysis hydrogenation products is shown in table 1;
thirdly, standing and layering the alcoholysis hydrodeoxygenation product obtained in the second step, and separating to obtain a dodecane phase product and an alcohol water phase product;
step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into Ni-filled bio-oil 2 Carrying out hydrodeoxygenation reaction in a fixed bed reactor of the P/H beta catalyst to obtain hydrodeoxygenation biological oil; the catalyst uses an H beta molecular sieve as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the operating temperature is 320 ℃, the operating pressure is 7MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, and the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase; the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device, and the obtained hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, wherein the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of; wherein, the distribution and the element composition of the hydrocarbon products are shown in tables 2 and 3;
and step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, the obtained methanol is partially recycled into a first alcoholysis hydrogenation device to replace raw material methanol, the water phase product is concentrated and evaporated at the high temperature of 1000 ℃ to recover inorganic alkali, and the material accounting is shown in the table 4.
Example 7
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a high-pressure reaction kettle of a first alcoholysis hydrogenation device filled with a Ni/AC catalyst for alcoholysis hydrogenation reaction to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the catalyst is 1:0.1:0.2:0.17, wherein the catalyst uses active carbon as a carrier and Ni as an active component, and the mass ratio of the active component to the carrier is 0.18:1, a step of; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operating temperature is 300 ℃, the operating pressure is 20MPa, and the volume space velocity is 1.0h -1 ；
Step two, transferring the alcoholysis hydrogenation product obtained in the step one into a catalyst filled with Ni 2 P/Si 3 N 4 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses silicon nitride as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 300 ℃, the operating pressure is 19MPa, and the hydrogen-oil volume ratio is 1000:1, volume space velocity of 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the obtained alcoholysis hydrogenation products is shown in table 1;
thirdly, standing and layering the alcoholysis hydrodeoxygenation product obtained in the second step, and separating to obtain a dodecane phase product and an alcohol water phase product;
step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into Ni-filled bio-oil 2 Carrying out hydrodeoxygenation reaction in a fixed bed reactor of the P/AC catalyst to obtain hydrodeoxygenation biological oil; the catalysis is that The agent uses active carbon as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the operating temperature is 320 ℃, the operating pressure is 7MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, and the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase; the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device, and the obtained hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, wherein the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of; wherein, the distribution and the element composition of the hydrocarbon products are shown in tables 2 and 3;
and step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, the obtained methanol is partially recycled into a first alcoholysis hydrogenation device to replace raw material methanol, the water phase product is concentrated and evaporated at the high temperature of 1000 ℃ to recover inorganic alkali, and the material accounting is shown in the table 4.
The yields of the products, elemental compositions and material accounting for all examples 1-7 below are shown in tables 1-4 below; wherein the yield is calculated based on the lignin quality in the black liquor.
TABLE 1 distribution of alcoholysis hydrogenation products
TABLE 2 distribution of hydrocarbon products
TABLE 3 elemental composition of hydrocarbon products
Project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
C 91.6 86.1 85.5 86.2 89.9 91.4 91.5
H 8.5 13.9 14.5 18.8 10.1 8.6 8.5
S -- -- -- -- -- -- --
N -- -- -- -- -- -- --
O -- -- -- -- -- -- --
TABLE 4 accounting for materials
As can be seen from tables 1 to 4, the process provided by the invention is used for converting papermaking black liquor into hydrocarbon products finally, and effectively recovering inorganic alkali in the papermaking black liquor, thereby realizing the process of converting papermaking black liquor into chemical products.
Comparative example 1
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a high-pressure reaction kettle of a first alcoholysis hydrogenation device filled with a Ni/AC catalyst for alcoholysis hydrogenation reaction to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the alcoholysis hydrogenation catalyst is 1:3:3:0.17, wherein the catalyst uses active carbon as a carrier and Ni as an active component, and the mass ratio of the active component to the carrier is 0.18:1, a step of; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operating temperature is 300 ℃, the operating pressure is 20MPa, and the volume space velocity is 1.0h -1 。
Step two, transferring the alcoholysis hydrogenation product obtained in the step one into a catalyst filled with Ni 2 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the P/AC catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses active carbon as a carrier and Ni as an active component, wherein the mass ratio of the active component to the carrier is 0.18:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 300 ℃, the operating pressure is 19MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Thirdly, standing and layering the alcoholysis hydrodeoxygenation product, and separating to obtain a dodecane phase product and an alcohol water phase product;
step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into Ni-filled bio-oil 2 P/γ-Al 2 O 3 Hydrodeoxygenation reaction is carried out in a fixed bed reactor of the catalyst, so as to obtain hydrodeoxygenation biological oil; the catalyst uses gamma-Al 2 O 3 As a carrier, ni was used as an active component, wherein the mass ratio of active component to carrier was 0.18:1, a step of; wherein the operating temperature is 320 ℃, the operating pressure is 7MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase, and the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device;
and step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, the obtained methanol is partially recycled into the first alcoholysis hydrogenation device to replace raw material methanol, and the water phase product is concentrated and evaporated at the high temperature of 1000 ℃ to recover inorganic alkali. The material accounting is shown in Table 5.
TABLE 5 accounting for materials
As can be seen from tables 4 and 5, in the comparative example 1 and the comparative example 1, in the example 1 of the present invention, hydrocarbon products are used to replace part of the solvent, and when the raw material of the black liquor is the same as the hydrogen, the material balance of the comparative example 1 and the material balance of the example 1 are similar, and the use ratio of lignin in the black liquor can be improved by less supplementing the solvent through the circulation of the hydrocarbon products.
Comparative example 2
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a reactor filled with Ni 2 P/γ-Al 2 O 3 Performing alcoholysis hydrogenation reaction in a high-pressure reaction kettle of a first alcoholysis hydrogenation device of the catalyst to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the catalyst is 1:3:3: 0.17, said catalyst using gamma-Al 2 O 3 As a carrier, ni was used as an active component, wherein the mass ratio of active component to carrier was 0.18:1, a step of; the first alcoholysis hydrogenation device is a boiling bed reactor; the reaction operating temperature is 300 ℃, the operating pressure is 20MPa, and the volume space velocity is 1.0h -1 。
Step two, transferring the alcoholysis hydrogenation product obtained in the step one into a catalyst filled with Ni 2 P/γ-Al 2 O 3 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses gamma-Al 2 O 3 As a carrier, ni was used as an active component, wherein the mass ratio of active component to carrier was 0.18:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 300 ℃, the operating pressure is 19MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the alcoholysis hydrogenation products and the distribution of the dodecane phase products are shown in tables 6 and 7;
thirdly, standing and layering the alcoholysis hydrodeoxygenation product obtained in the second step, and separating to obtain a dodecane phase product and an alcohol water phase product;
step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
Step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into a reactor filled with Pt/gamma-Al 2 O 3 Hydrodeoxygenation reaction is carried out in a fixed bed reactor of the catalyst, so as to obtain hydrodeoxygenation biological oil; the catalyst uses gamma-Al 2 O 3 Pt was used as the active component for the support, wherein the mass ratio of active component to support was 0.18:1, a step of; wherein the operating temperature is 340 ℃, the operating pressure is 9MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase, the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device, the obtained hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace an organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of;
and step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range temperature of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, recycling part of the methanol into a first alcoholysis hydrogenation device to replace raw material methanol, concentrating the water phase product, and evaporating at the high temperature of 1000 ℃ to recover inorganic alkali.
TABLE 6 distribution of alcoholysis hydrogenation products
TABLE 7 dodecane phase product distribution
Comparative example 3 and comparative example 2 it can be seen from tables 1, 6 and 7 that when the catalyst supports selected in the first and second steps of the alcoholysis and hydrotreatment of the black liquor of paper manufacture are both gamma-Al which is not alkali-resistant 2 O 3 When the carrier is severely damaged, the depolymerization capability of the catalyst on lignin molecules of the papermaking black liquor is extremely weak, the yield of small molecules dissolved into a dodecane phase is not more than 1%, and extremely low hydrocarbon yield is obtained.
Comparative example 3
Step one, taking papermaking black liquor as a raw material, mixing the papermaking black liquor, dodecane and methanol, and transferring the mixture into a high-pressure reaction kettle of a first alcoholysis hydrogenation device filled with a Pt/AC catalyst for alcoholysis hydrogenation reaction to obtain an alcoholysis hydrogenation product; the mass ratio of the papermaking black liquor to the dodecane to the methanol to the alcoholysis hydrogenation catalyst is 1:3:3:0.17, wherein the catalyst uses active carbon as a carrier and Pt as an active component, and the mass ratio of the active component to the carrier is 0.01:1, a step of; the first alcoholysis hydrogenation device is an ebullated bed reactor, the reaction operating temperature is 300 ℃, the operating pressure is 20MPa, and the volume space velocity is 1.0h -1 ；
Step two, the alcoholysis hydrogenation product obtained in the step one enters a catalyst filled with Pt-Nb 2 O 5 Performing alcoholysis hydrodeoxygenation reaction in a high-pressure reaction kettle of a second glycolysis hydrogenation device of the AC catalyst to obtain an alcoholysis hydrodeoxygenation product; the catalyst uses active carbon as a carrier and Pt and Nb as active components, wherein the mass ratio of the Pt to the Nb to the carrier is 0.01:0.06:1, a step of; the second glycolysis hydrogenation device is a boiling bed reactor; the operating temperature is 300 ℃, the operating pressure is 19MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The distribution of the obtained alcoholysis hydrogenation products is shown in the following table 8;
thirdly, standing and layering the alcoholysis hydrodeoxygenation product, and separating to obtain a dodecane phase product and an alcohol water phase product;
step four, distilling and separating the dodecane phase product obtained in the step three, wherein the fraction with the distillation range of less than 300 ℃ is alcoholysis hydrogenation biological oil, the fraction with the distillation range of more than 300 ℃ is tail oil, and the obtained tail oil circularly enters a first alcoholysis hydrogenation device to continue to react;
step five, transferring the alcoholysis hydrogenated bio-oil obtained in the step four into a reactor filled with Pt/gamma-Al 2 O 3 Hydrodeoxygenation reaction is carried out in a fixed bed reactor of the catalyst, so as to obtain hydrodeoxygenation biological oil; the catalyst uses gamma-Al 2 O 3 Pt was used as the active component for the support, wherein the mass ratio of active component to support was 0.18:1, a step of; wherein the operating temperature is 340 ℃, the operating pressure is 9MPa, the hydrogen-oil volume ratio is 1000, and the volume airspeed is 1.0h -1 ；
Step six, distilling and separating the hydrodeoxygenation biological oil obtained in the step five, wherein the fraction with the distillation range of less than 120 ℃ is a hydrocarbon product, the fraction with the distillation range of more than 120 ℃ is a dodecane solvent phase, the obtained dodecane solvent phase circularly enters a first alcoholysis hydrogenation device, the obtained hydrocarbon product comprises circulating hydrocarbon and external throwing hydrocarbon, the circulating hydrocarbon enters the first alcoholysis hydrogenation device to partially replace an organic solvent, the external throwing hydrocarbon is thrown outwards, and the mass ratio of the external throwing hydrocarbon to the circulating hydrocarbon is 1:2, the ratio of external dodecane to recycle hydrocarbon is 1:3, a step of;
and step seven, distilling and separating the alcohol-water phase product obtained in the step three, wherein the fraction with the distillation range temperature of less than 76 ℃ is methanol, the residual product is the water phase product after the methanol is distilled, recycling part of the obtained methanol into a first alcoholysis hydrogenation device to replace raw material methanol, concentrating the water phase product, and evaporating at the high temperature of 1000 ℃ to recover inorganic alkali.
TABLE 8 distribution of alcoholysis hydrogenation products
From the results of table 8 above, it can be seen that in comparative example 3, when the active metal of the catalyst selected in the first and second steps of the alcoholysis and hydrotreatment steps of the black liquor is sulfur-intolerant noble metal Pt, the catalyst is rapidly deactivated, and lignin in the black liquor does not react.
As described above, the present invention includes at least the following effective benefits: firstly, the papermaking black liquor lignin alcoholysis hydrogenation process provided by the invention can be operated continuously and for a long period; secondly, the papermaking black liquor lignin alcoholysis hydrogenation process provided by the invention can directly take the papermaking black liquor as a raw material without pre-acidification, so that the waste of inorganic alkali resources is avoided; thirdly, the catalytic alcoholysis and catalytic hydrogenation coupling treatment method is adopted in the papermaking black liquor lignin alcoholysis hydrogenation process, so that the lignin conversion rate is high and the hydrocarbon yield is high; fourth, the papermaking black liquor lignin alcoholysis hydrogenation process provided by the invention has the advantages of mild operation conditions, stable effect and high feasibility of industrial application.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention may be suited, and further modifications may be readily made by one skilled in the art, and the invention is therefore not limited to the particular details and embodiments shown and described herein, without departing from the general concepts defined in the claims and the equivalents thereof.

Claims (7)

1. The method for alcoholysis and hydrotreatment of the lignin in the black liquor of paper making is characterized by comprising the following steps:
carrying out catalytic alcoholysis hydrodeoxygenation reaction on papermaking black liquor, low-carbon alcohol and an organic solvent to obtain an alcoholysis hydrodeoxygenation product;
standing and layering an alcoholysis hydrodeoxygenation product, and separating to obtain an organic solvent phase and an alcohol water phase;
distilling and separating the obtained organic solvent phase to obtain alcoholysis hydrogenated biological oil and tail oil;
the obtained alcoholysis hydrogenation biological oil is further subjected to hydrodeoxygenation reaction to obtain hydrodeoxygenation biological oil;
distilling and separating the hydrodeoxygenation biological oil to obtain hydrocarbons, water and an organic solvent;
the steps for obtaining the alcoholysis hydrodeoxygenation product are specifically as follows:
firstly, placing papermaking black liquor, low-carbon alcohol, an organic solvent and an alcoholysis hydrogenation catalyst into a first alcoholysis hydrogenation device, and carrying out catalytic alcoholysis hydrogenation reaction under the condition of introducing hydrogen to obtain an alcoholysis hydrogenation product;
placing the alcoholysis hydrogenation product and an alcoholysis hydrodeoxygenation catalyst in a second alcoholysis hydrogenation device, and carrying out deep catalytic alcoholysis hydrodeoxygenation reaction under the condition of introducing hydrogen to obtain an alcoholysis hydrodeoxygenation product;
the carrier of the alcoholysis hydrogenation catalyst is one of magnesium oxide, magnesium aluminum hydrotalcite, zirconium oxide, silicon nitride, silicon carbide and carbon material, one or more metals selected from vanadium, molybdenum, bismuth, nickel, iron, antimony, tungsten, copper, iron, niobium, chromium, magnesium, zinc and aluminum are loaded on the surface of the carrier, and the total atom loading of the metals is 1-80%;
The carrier of the alcoholysis hydrodeoxygenation catalyst is one of magnesium oxide, magnesium aluminum hydrotalcite, zirconium oxide, silicon nitride, silicon carbide and carbon material, and one or more metals selected from cobalt, molybdenum, nickel, iron, tungsten, copper, iron, niobium and chromium are loaded on the surface of the carrier, and the total atom loading of the metals is 1-80%;
and distilling the alcohol water phase to obtain methanol and a water phase, circularly feeding the obtained methanol into a catalytic alcoholysis hydrodeoxygenation reaction to supplement low-carbon alcohol, and evaporating the water phase at a high temperature to recover inorganic alkali.
2. The method according to claim 1, wherein a part of hydrocarbons obtained by distillation separation of hydrodeoxygenation bio-oil is recycled to the catalytic alcoholysis hydrodeoxygenation reaction.
3. The method as recited in claim 1, further comprising:
recycling tail oil obtained by distilling and separating an organic solvent phase into catalytic alcoholysis hydrodeoxygenation reaction to supplement the organic solvent; and (3) recycling the organic solvent and part of hydrocarbons obtained by distilling and separating the hydrodeoxygenation biological oil into catalytic alcoholysis hydrodeoxygenation reaction to supplement the organic solvent.
4. The method according to claim 1, characterized in that: the mass ratio of the papermaking black liquor to the low-carbon alcohol to the organic solvent is 1:0.1-5:0.2-5.
5. The process according to claim 1, characterized in that the reaction temperature in the first alcoholysis hydrogenation unit is between 200 and 300 ℃, the pressure is between 8 and 25MPa, and the hydrogen-to-oil volume ratio is between 100 and 1000:1, the reaction space velocity is 1.0-10.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature in the second glycolysis hydrogenation device is 280-350 ℃, the pressure is 10-30MPa, and the volume ratio of hydrogen to oil is 100-1000:1, the reaction space velocity is 1.0-10.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature for further hydrodeoxygenation reaction is 280-350 ℃, the operating pressure is 10-30MPa, and the hydrogen-oil volume ratio is 100-1500:1, reaction space velocity1.0-10.0h -1 。
6. The method according to claim 1, characterized in that: the total acid amount on the surface of the alcoholysis hydrodeoxygenation catalyst is 1-6mmol/g.
7. The method according to claim 1, characterized in that: the obtained alcoholysis hydrogenation biological oil is further subjected to hydrodeoxygenation reaction, wherein a catalyst is included in the catalyst, a carrier of the catalyst is selected from one of alumina, molecular sieve, magnesia, magnesium aluminum hydrotalcite, zirconia, silicon nitride, silicon carbide and carbon material, the surface of the catalyst is loaded with one or more metals selected from platinum, palladium, ruthenium, cobalt, molybdenum, nickel, iron, tungsten, copper, iron, niobium and chromium, and the total atom loading of the metals is 1-80%.
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