阅读说明：本技术 抗氧化的生物油的生产方法 (Method for producing antioxidant bio-oil ) 是由 王娜 于 2020-12-22 设计创作，主要内容包括：本发明提供了一种抗氧化的生物油的生产方法,该方法包括：从垃圾高温蒸馏处理得到的生物油获得多酚提取物,将该多酚提取物加入到该高温蒸馏处理自身获得的经提质的生物油中,从而获得具有良好氧化安定性的生物油。(The invention provides a production method of antioxidant bio-oil, which comprises the following steps: obtaining polyphenol extract from the bio-oil obtained by the high-temperature distillation treatment of the garbage, and adding the polyphenol extract into the upgraded bio-oil obtained by the high-temperature distillation treatment, thereby obtaining the bio-oil with good oxidation stability.)

1. A method for producing an antioxidant bio-oil, the method comprising: obtaining polyphenol extract from a mixture of bio-oil and water obtained by the high-temperature distillation and carbonization treatment of garbage, upgrading and separating the bio-oil after polyphenol extraction to obtain upgraded bio-oil, and adding the polyphenol extract into the upgraded bio-oil to obtain the antioxidant bio-oil.

2. The method of claim 1, the upgrading comprising hydro upgrading.

3. The method of claim 2, wherein the upgraded biooil has an oxygen content of less than 5 weight percent.

4. The process according to any one of the preceding claims, the polyphenol extract is used in the form of a concentrate of its dichloromethane solution to prepare an antioxidative bio-oil.

5. The method of claim 1, the mixture of bio-oil and water being derived from waste.

6. The method of claim 5, wherein the waste is municipal solid waste.

7. The method of claim 6, wherein the municipal biological waste is organic-rich waste.

8. The process according to any one of the preceding claims, wherein the proportion of phenolic substances having a boiling point of 200-300 ℃ at atmospheric pressure in the polyphenolic substance is 60-80% by weight.

Technical Field

The invention belongs to the technical field of waste resource utilization, relates to a production method of antioxidant bio-oil, in particular to a production method of antioxidant bio-oil, and more particularly relates to a preparation method of bio-oil added with a phenol antioxidant derived from the same process.

Background

Oxidation stability (oxidation resistance) is a very important indicator of bio-oils. Compared with the traditional fossil fuel, the biological oil has poor oxidation stability due to the characteristics of the components of the biological oil. How to improve the oxidation resistance is usually achieved by adding antioxidant additives.

The phenolic antioxidants are phenolic compounds with certain space obstruction, have obvious thermal oxidation resistance effect and good stability, do not pollute products, and are widely concerned and applied. In contrast, conventional aromatic amine antioxidants are toxic, produce color contamination, are poorly compatible with many substrates such as polyolefins, and are gradually replaced by hindered phenolic antioxidants. In addition, the phenolic antioxidants have significantly improved efficacy due to the ortho and para alkyl and electron donating substituents. Such antioxidants are mainly used in plastics, synthetic fibers, latex, petroleum products, food, pharmaceuticals and cosmetics.

Along with the rapid development of economy, the urbanization process is continuously accelerated, so that the quantity and the scale of cities are continuously changed and expanded, and the total quantity of urban domestic garbage is greatly increased along with the rapid increase of the population and the urban area of the cities. The current garbage disposal is mainly incineration disposal. In recent years, the study of the distillation or gasification of waste to obtain high value fuels and other by-products has received attention.

The present phenolic antioxidants are basically obtained by synthesis or natural product extraction methods, and have higher cost. The inventor finds that in the high-temperature distillation and carbonization treatment of the garbage, the biological oil product contains higher amount of phenols, particularly hindered phenols, and if the phenols can be extracted, the biological oil product can be used as a high-value antioxidant, so that the economic benefit of the high-temperature distillation and carbonization treatment of the garbage is greatly improved.

CN105585454A discloses a preparation method of a hindered bisphenol antioxidant, which comprises the following process steps: adding 2, 6-di-tert-butylphenol and a catalyst into a reaction vessel, adding 3-8mL of the catalyst into 1mol of 2, 6-di-tert-butylphenol, stirring the mixture at the temperature of 40-60 ℃ until the mixture is molten, adding a formaldehyde solution, wherein the molar ratio of formaldehyde to 2, 6-di-tert-butylphenol is 1: 2.0 to 2.2, heating to 60 to 80 ℃ after the addition, reacting for 2 to 5 hours, carrying out suction filtration, washing for 3 to 5 times by using hot water with the temperature of 40 to 50 ℃, carrying out vacuum drying on a filter cake, recrystallizing a crude product, adding 0.5 to 5mL of recrystallization solvent into each 1g of the crude product, and carrying out vacuum drying to obtain a yellow needle-shaped crystal.

CN104725664A discloses a compound antioxidant and its application, the compound antioxidant comprises antioxidant and toner, wherein the weight ratio of toner to antioxidant is (0.01-1): (99-100).

CN104342228A an antioxidant composition and its use, the antioxidant composition comprises the following components by weight: a) 10-80 parts of thioester; b) 20-90 parts of at least one of arylamine antioxidants or phenolic antioxidants.

CN103709438A discloses a method for synthesizing a bisphenol antioxidant, which comprises the following steps: 1) carrying out acylation reaction on p-cresol and alkyl acyl chloride under the catalysis of a catalyst to prepare 2-alkyl acyl p-cresol; 2) reducing the 2-alkyl acyl-p-cresol to obtain 2-alkyl-p-cresol; 3) then the 2-alkyl acyl-p-cresol is processed by a methylene reaction to prepare the product.

CN101805245A discloses a method for synthesizing a polysubstituted hindered phenol antioxidant, which comprises the steps of synthesizing an intermediate product by using a tertiary amine and secondary amine composition as a catalyst, evaporating a solvent and the catalyst after the reaction is finished to obtain an intermediate crude product, and adding the intermediate into a halogenated alkane solution containing organic ether, sulfuric acid and a mesitylene reaction substrate at room temperature in one step or in batches to synthesize the polysubstituted hindered phenol antioxidant.

CN101475806A discloses a method for preparing a hindered phenol type antioxidant taking 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate as a monomer, wherein a methanol solution of a used methoxyl alkali metal catalyst is filtered to remove insoluble substances by a filtering device with a filter pore size of less than 50 micrometers, then used for the ester exchange reaction procedure of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate and n-octadecyl alcohol as reactants, the procedure can obtain the crude product of the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate with high conversion rate and low color, then obtaining the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate product with high purity and low hue through crystallization, filtration, drying and other purification procedures.

CN101988001A discloses an antioxidant additive for lubricating grease, which is prepared from base oil; a sterically hindered phenol; alkyl succinic acid derivatives; bis-salicylidene propylenediamine; alkyl phosphate esters and salts; lead naphthenate; a borate metal salt; polyisobutylene. The weight percentages of the components are as follows: 42-45% of hindered phenol; 3-5% of alkyl succinic acid derivative; 3-5% of bis-salicylidene propane diamine; alkyl phosphate esters and salts 6-8%; 4-6% of lead naphthenate; 3-5% of borate metal salt; 5-7% of polyisobutene.

KR20110084323A discloses a food waste treatment and bio-oil extraction apparatus, wherein food waste is thrown into a fermentation dryer and a fermentation chamber into which microorganisms have been thrown, and is fermented, dried and decomposed for 24 hours to reduce the amount of the organic matter, the dried and decomposed organic matter is pulverized into small particles by a pulverizer, the pulverized particles are heated at a low temperature under a low pressure environment in a distillation tank, vapor and oil gasified by thermal decomposition are separated and discharged, the discharged gas is cooled and liquefied in a distillation column and is separated into moisture and oil, and the separated oil is collected in a vacuum storage tank and supplied to a centrifugal separator to be refined.

In the above-mentioned documents and other prior arts, phenolic antioxidants in biodiesel or fossil fuels are basically obtained by synthetic methods, and the cost is relatively high. In addition, in the high-temperature distillation and carbonization treatment of the garbage, the extraction and utilization of phenolic substances are not concerned. The inventor finds that the bio-oil product oil contains higher amount of phenols, particularly hindered phenols, in the high-temperature distillation carbonization treatment of the garbage, the phenols are effectively extracted, and the bio-oil product oil can be effectively used in the bio-oil produced by the same process with higher requirements on oxidation stability to effectively replace the current artificially synthesized antioxidant, and the comprehensive utilization can obviously improve the economic benefit of the high-temperature distillation carbonization treatment of the garbage. Therefore, there is a need in the art for a method of obtaining bio-oil with high oxidation resistance in a comprehensive utilization manner.

Disclosure of Invention

In order to solve the problems, the inventor of the invention carries out intensive and systematic research, fully combines the composition of the biological oil obtained by high-temperature distillation and carbonization of garbage and the antioxidant characteristics of phenolic substances (polyphenol) in the biological oil, combines the specific requirements of the biological oil on antioxidation, carries out intensive research on a polyphenol extraction method and biological oil quality improvement, and provides the following technical scheme, thereby obtaining the biological oil with good antioxidation in a very effective recycling mode.

In one aspect of the invention, a polyphenol extract is obtained from a mixture of bio-oil and water obtained by high-temperature distillation and carbonization treatment of garbage, the bio-oil after polyphenol extraction is subjected to quality improvement and separation to obtain quality-improved bio-oil, and the polyphenol extract is added into the quality-improved bio-oil, so that antioxidant bio-oil is obtained.

The biological oil after polyphenol extraction is preferably subjected to hydrogenation upgrading. The hydro-upgrading process is defined in further detail below.

The polyphenol extract can be directly added into the upgraded bio-oil in a blending mode; alternatively, the polyphenol extract is incorporated into an additive package and added to the upgraded bio-oil.

Preferably, the polyphenol compound in the polyphenol extract is present in the bio-oil in an amount of 0.01 wt.% to 0.2 wt.%, preferably 0.02 wt.% to 0.05 wt.%, based on the total weight of the bio-oil.

In the existing garbage treatment, basically no attention is paid to phenolic substances and extraction thereof in the biological oil produced in the treatment process, and the biological oil is usually subjected to hydrodeoxygenation treatment as an unexpected product because detailed study on the structure and characteristics of the phenolic compounds in the biological oil is lacked, and adjustment and selection on distillation carbonization treatment conditions for generation of the phenolic substances are lacked. The inventor finds that in the high-temperature distillation and carbonization treatment of the garbage, the bio-oil product oil contains higher amount of phenols, particularly hindered phenols, and the phenols are effectively extracted and can be effectively used as antioxidants, so that the economic benefit of the high-temperature distillation and carbonization treatment of the garbage is greatly improved.

Preferably, the polyphenol comprises a phenolic compound and/or an oligomer thereof.

The phenolic compounds include compounds represented by the following formulas (I) to (IV):

in the above preferred phenolic compounds, methoxy groups are electron donors, and in addition to providing steric hindrance, the antioxidant effect of the antioxidant can be significantly improved. In addition, it has been unexpectedly found that under the specific conditions of high temperature distillation and carbonization, the mixture of bio-oil and water can contain phenolic substances in an amount of 5-10 wt%, preferably 10 wt%.

Preferably, the weight ratio of the formulas (I) to (IV) is (5.0-10.0): (1.0-3.0): (0.5-1.0). When the ratio is within this range, the antioxidant prepared can have a good balance of antioxidant effects because different antioxidants have different antioxidant effects and stabilities in different antioxidant application environments, and a single compound antioxidant is difficult to adapt to various antioxidant requirements of bio-oil because the oxidative instability of bio-oil is caused by various impurity factors and composition characteristics. The ratio can be adjusted by the choice of the waste material and the choice of the distillation process conditions.

The oligomers may include terpolymers, tetramers, pentamers, or higher polymers.

The phenolic compound may comprise monomethoxyphenol.

The phenolic compound may include dimethoxyphenol.

In a preferred embodiment, the polyphenol extract is used as a concentrate of its methylene chloride solution for addition to the base oil.

Obtaining the polyphenol extract from the mixture of biological oil and water is preferably carried out by: distilling and carbonizing garbage at high temperature to obtain mixture of bio-oil and water (usually in the form of emulsion), adding dichloromethane, sufficiently shaking to obtain organic layer, water layer and intermediate emulsion layer, taking out the organic layer, adding 8-12 wt% NaCl aqueous solution with KOH concentration of 0.5-1.5mol/L into the organic layer, thereby transferring phenols into the aqueous phase, and optionally, combining the organic phase with the intermediate emulsion layer for other use (the combined mixture is marked as mixture M); removing the aqueous phase, adjusting pH of the aqueous phase to 3-7, preferably 5, with 1-3mol/L HCl, extracting the aqueous phase with 1-3 times volume of dichloromethane, and combining dichloromethane organic phases to obtain polyphenol extract. Preferably, the polyphenol extract may be concentrated under reduced pressure to obtain a concentrated polyphenol extract.

More specifically, obtaining the polyphenol extract from the mixture of bio-oil and water is preferably carried out by: distilling and carbonizing garbage at high temperature to obtain mixture of bio-oil and water (usually in the form of emulsion), adding 1-2 times volume of dichloromethane, sufficiently shaking to obtain organic layer, water layer and intermediate emulsion layer, taking out the organic layer, adding 8-12 wt% NaCl solution with KOH concentration of 1mol/L and NaCl solution volume of 5-10 times, preferably 8 times, of the organic layer to the organic layer, transferring the phenolic substances into water phase, and optionally combining the organic phase with the intermediate emulsion layer for other use (the combined mixture is marked as mixture M); removing the aqueous phase, adjusting pH of the aqueous phase to 3-7, preferably 5, with 1-3mol/L HCl, extracting the aqueous phase with 1-3 times volume of dichloromethane, and combining dichloromethane organic phases to obtain polyphenol extract. Preferably, the polyphenol extract may be concentrated under reduced pressure to obtain a concentrated polyphenol extract. Particularly preferably, the methylene chloride can be completely or substantially removed by concentration.

Said mixture M is subjected to a gas phase hydrotreatment, i.e. hydrodeoxygenation upgrading, by the method described hereinafter.

In the extraction method, the characteristic that phenolic substances in the product are weakly acidic is fully utilized, reverse extraction and phase transfer are realized through pH adjustment, so that the extraction selectivity is very high, and the phenolic substances are separated from acids (acidity is usually obviously stronger than that of the phenolic substances), aldehydes, ketones, alcohols and other substances. In addition, the method has high extraction effect, and the extraction rate of phenols can reach more than 90%, preferably more than 95%.

In a particularly preferred embodiment, the mixture of bio-oil and water is derived from waste, particularly preferably from the high temperature distillation carbonization of waste.

Preferably, the garbage is municipal domestic garbage. The municipal solid waste contains high content of organic matters, and is particularly suitable for the generation of phenolic substances. For example, in municipal solid waste, lignin-rich kitchen waste and wood waste are particularly advantageous for the production of polyphenols

Preferably, the temperature of the high-temperature distillation carbonization treatment is 425-475 ℃, preferably 450 ℃, and the time is 3-8h, preferably 5 h.

In the existing high-temperature distillation and carbonization treatment of garbage, the adjustment of process conditions for generating phenolic compounds is not realized. For example, in many high-temperature steam distillation charring, a temperature of about 350 ℃ is preferred, which hardly decomposes lignin contained in the refuse to produce phenolic substances, and in conventional high-temperature steam distillation charring, the distillation charring time is as long as 9 hours, which easily decomposes the phenolic substances produced. The inventor determines the upper distillation carbonization temperature and time through intensive research and a large number of experiments, the temperature and time conditions are particularly favorable for the generation of phenolic substances, particularly, the middle distillate (200-.

Particularly preferably, the proportion of phenolic substances having a boiling point of 200-300 ℃ (middle distillate) at atmospheric pressure in the polyphenol is 60-80 wt%, preferably 70 wt%. The inventor of the invention finds that the middle-fraction phenolic substance has good antioxidant effect and good stability compared with high-fraction (above 300 ℃, preferably above 350 ℃) and light-fraction (below 200 ℃). This finding has been reported for the first time in the prior art.

The mixture of bio-oil and water used to obtain the polyphenol extract is preferably obtained by a process comprising the steps of: the waste is subjected to high temperature distillation carbonization to obtain a gas stream containing bio-oil and water vapor, and the gas stream is condensed to obtain a mixture (i.e. liquid mixture) containing bio-oil and water vapor. The mixture can be used directly for carrying out the extraction of polyphenols to obtain the above-mentioned polyphenol extract.

Optionally, after the polyphenol extract, the extraction residue (i.e. the combined mixture previously labelled mixture M) is subjected to a gas phase hydrotreatment to hydro-upgrade the bio-oil (crude bio-oil) therein, and the hydrotreated gas stream is condensed and then passed through a membrane separation process to obtain upgraded bio-oil.

After condensing the hydrotreated gas stream, condensing to obtain a mixture of upgraded bio-oil and water, and obtaining upgraded bio-oil by a membrane separation process.

The polyphenol extract can be directly added into the upgraded bio-oil by a blending mode; alternatively, the antioxidant bio-oil of the present invention is obtained by incorporating the polyphenol extract into an additive package and adding to the upgraded bio-oil.

Preferably, the polyphenol compound in the polyphenol extract is present in the bio-oil in an amount of 0.01 wt.% to 0.2 wt.%, based on the total weight of the bio-oil.

Typically, the water content in the upgraded mixture of bio-oil and water is 5-30 wt.%, preferably 5-10 wt.%.

More specifically, in the high-temperature distillation carbonization treatment, the garbage is loaded into the garbage conveying device, and the garbage conveying device passes through the high-temperature distillation carbonization device to perform high-temperature distillation carbonization on the garbage.

Preferably, in the hydroprocessing, the gas stream is passed through the catalyst bed in gaseous form. The catalyst bed is preferably a hydrogenation catalyst bed.

Preferably, the garbage is municipal domestic garbage.

In a preferred embodiment, the high temperature distillation charring apparatus is heated by high temperature oxygen-free steam.

The temperature of the high-temperature oxygen-free steam is preferably 320-560 ℃, more preferably 360 ℃.

Preferably, the high temperature oxygen-free steam comprises nitrogen.

In a particularly preferred embodiment of the present invention, the present inventors have conducted extensive studies to develop a catalyst capable of efficiently hydro-upgrading bio-oil in the residue after polyphenol extraction (i.e., mixture M)The agent comprises a carrier and an active ingredient loaded on the carrier, wherein the carrier can be zeolite or molecular sieve, and the catalytic active component can be Fe₂O₃With at least two transition metals and at least one noble metal. The transition metal is selected from Ni, Cu, Fe, Ce, etc., and the noble metal is selected from Pt, Pd, Ru, etc.

In a particularly preferred embodiment, the catalyst may be of the formula: Ni-Cu-Pd-Fe₂O₃/MCM-41, wherein the molar ratio of Ni, Cu, Pd, Fe is (1-2): 5-10): 0.1-0.5: (10-20), based on the total weight of the catalyst, Ni-Cu-Pd-Fe₂O₃The content of active ingredient is 1-10%, preferably 2-8%, more preferably 5%. MCM-41 is carrier. Preferably, MCM-41 is a low silica to alumina ratio MCM-41, e.g., silica to alumina ratio less than 15, more preferably less than 10, because it was found that highly acidic MCM-41 is more favorable for cracking of heavy components of bio-oil with minimal bio-oil distillation residue.

The composition of bio-oils is generally complex and can include mainly acids, aldehydes, ketones, alcohols, furans, esters, ethers and small amounts of nitrogen-containing compounds as well as other multifunctional compounds. Because of the characteristics of poor thermal stability, strong acidity and corrosivity, high water content, low calorific value, difficulty in mutual solubility with petroleum-based products and the like, the bio-oil can only realize primary application, such as being used for thermodynamic equipment such as industrial kilns and oil-fired boilers and the like, cannot replace petroleum products to be directly applied to combustion of internal combustion engines or turbines, and cannot meet the modern high-grade industrial application. In order to improve the applicability of the bio-oil, the bio-oil needs to be converted into high-grade liquid fuel to meet the requirement of transportation fuel so as to realize replacement or partial replacement of petroleum products, and therefore the bio-oil needs to be modified and upgraded to convert chemical components of the bio-oil from hydrocarbon oxides into hydrocarbons. One of the keys to how to effectively upgrade bio-oil is the development of catalysts.

It was found that, in the above-mentioned catalyst of the present invention, Ni^δ+Mo more conventional than^δ+Has higher activity, can obtain C6-C12 hydrocarbon (preferably alkane) with high selectivity by using Ni, and can obtain CuThe simultaneous use of Ni and Cu, which are highly selective to C16 hydrocarbons (preferably alkanes), was surprisingly found to ensure that a certain amount of C18 and C19 hydrocarbons was also obtained, and the use of Ni and Cu on the surface enabled efficient hydrogenolysis of the C — O bonds in the bio-oil.

The biological oil of the gas stream contains more non-aromatic hydrocarbons, and the acid centers on the MCM-41 molecular sieve can effectively convert the non-aromatic hydrocarbons into aromatic compounds. Most of carboxylic acid in the biological oil is derived from acetyl of hemicellulose, a pyrolysis product of the biological oil is mainly acetic acid, the MCM-41 molecular sieve has good decarboxylation capability, and the carboxylic acid in the biological oil is subjected to decarboxylation reaction and deoxidation reaction under the catalytic action of the molecular sieve, so that the content of the carboxylic acid in the upgraded biological oil is greatly reduced.

The above-mentioned particularly preferred catalysts have not been reported in the prior literature, and it is specifically designed according to the specific composition characteristics of the gas stream and bio-oil recovered from the waste, and a good upgrading effect is achieved.

The catalyst can be prepared by adopting an impregnation calcining method which is conventional in the field. Specifically, a certain amount of precursor salt such as Ni (NO) is weighed according to the proportion₃)₂、Cu(NO₃)₂、Pd(NO₃)₂、Fe(NO₃)₃(or their hydrate forms) and citric acid, adding deionized water to dissolve, stirring uniformly to prepare a solution with the concentration of 0.5-1.5mol/L, weighing a certain amount of MCM-41 molecular sieve and placing into a reaction container, pouring the prepared solution into the reaction container, placing into a constant-temperature heating oil bath device with a stirrer to heat, stirring for 1-10H at the temperature of 60-120 ℃, then placing into a drying box to dry for 12H at the temperature of 100-150 ℃, then placing the obtained catalyst precursor into a muffle furnace to calcine for 1-6H at the temperature of 500-800 ℃, and then placing into H₂Reducing and activating at 200-300 ℃ in the presence of the catalyst to prepare Ni-Cu-Pd-Fe₂O₃A/MCM-41 catalyst.

When tested, the catalyst was used with an oxygen content of 5.0 wt.% in the upgraded bio-oil and a catalyst life of about 700 h. In contrast, conventional NiMo/Al is used₂O₃When the catalyst is used, the catalyst is added,the oxygen content in the upgraded bio-oil obtained was 19.7 wt.% and the catalyst life was about 120 h.

For the purposes of the present invention, the membrane used in membrane separation (i.e. separation membrane or filtration membrane) is a hydrophilic membrane.

Preferably, the membrane has an average pore size of about 0.5 to 0.7 μm and a maximum pore size of no more than 0.90 μm.

More preferably, the water contact angle of the membrane is substantially 0.

Further preferably, the elastic modulus of the film is 60.0 to 90.0 MPa.

In a particularly preferred embodiment, the membrane is a polyvinylidene fluoride-based separation membrane. Further preferably, the polyvinylidene fluoride-based separation membrane is a polyvinylidene fluoride-hexafluoropropylene separation membrane.

The inventor of the invention has further studied deeply, and modified polyvinylidene fluoride-hexafluoropropylene separation membrane is modified by adopting cellulose, so as to obtain a novel modified polyvinylidene fluoride-hexafluoropropylene separation membrane which is particularly suitable for separating bio-oil and water obtained by high-temperature distillation and carbonization of garbage in the invention.

In particular, the modification method is preferably as follows:

(1) dissolving polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) in a mixed solution of acetone and N-methylpyrrolidone (acetone: N-methylpyrrolidone in a volume ratio of 1:5 to 5:1, preferably 4:1) to make a solution having a concentration of 5 to 15 wt.%, preferably 10 wt.%;

(2) then electrospinning using an electrospinning apparatus (e.g., Nanon-01A, available from MECC of Japan) wherein the electrospinning chamber temperature is from room temperature to 40 deg.C, preferably room temperature, and the relative humidity is 40-70%; placing the solution in an electrospinning injector, wherein the diameter of the injector needle is 0.2-0.8mm, and preferably 0.5 mm; applying a voltage of 10-40kV, preferably 25kV between a needle and a rotating disc, maintaining the solution feed rate at 0.5-2.0ml/h, preferably 1.0ml/h, collecting a membrane consisting of electrospun fibers (i.e. an electrospun fiber membrane) and drying at 45 ℃ for 24h, and hot-pressing the obtained electrospun fiber membrane;

(3) cellulose (e.g., microcrystalline cellulose) and an ionic liquid represented by the following formula (I) were dried under reduced pressure, respectively:

wherein the reduced pressure drying temperature is 65-80 deg.C, and the drying time is 10-30 h;

(4) adding the dried cellulose into the ionic liquid to prepare a cellulose solution with the weight percentage of 2-8 percent, preferably 5 percent, then coating the cellulose solution on the electric spinning fiber membrane prepared in the step (1), allowing the cellulose solution to permeate through the electric spinning fiber membrane for 1-5 hours, preferably 3 hours, then immersing the electric spinning fiber membrane permeated with the cellulose into water to remove the ionic liquid, then rotating in boiling water for 1-3 hours, preferably 2 hours, and washing with deionized distilled water to prepare the separation membrane.

Of course, one skilled in the art will recognize that the above-described modified polyvinylidene fluoride-hexafluoropropylene separation membrane preparation method can be scaled up.

The large surface area of such nanofibers of the electrospun fiber membrane enables the cellulose to adhere strongly throughout the thickness of the electrospun fiber membrane. The reason for this is presumed to be that the use of the ionic liquid can effectively carry cellulose into the pores of the electrospun fiber membrane as compared with a general organic solvent.

The cellulose impregnated electrospun fiber membranes have an average pore size of 0.5-0.7 μm, preferably about 0.65 μm, with the largest pores not exceeding 0.90 μm, and the porosity decreases from the original 90% to 45% due to the impregnated packing of cellulose. The diameter of emulsion droplets formed by the mixture of the upgraded bio-oil and water of the invention is usually larger than 18 μm, so the separation membrane of the invention can play a good role in oil resistance.

The separation membrane of the invention has excellent hydrophilic performance because of the introduction of the cellulose, and the water contact angle is basically 0.

In addition, the inventors found that the cellulose soaked with the ionic liquid shown in formula (I) forms a three-dimensional hydrogen bond network compared with the cellulose soaked before, so that the structure of the cellulose is effectively improved and maintained, and the porosity, hydrophilicity and mechanical properties can be effectively controlled, which cannot be achieved by common solvents. In addition, the ionic liquid shown in the formula (I) is selected because nitrogen atoms in the ionic liquid can form hydrogen bonds with cellulose, and the molecular space structure defined by two ethyl groups is matched with the pores of the electrospun fiber membrane, so that compared with other ionic liquids, the ionic liquid can effectively bring the cellulose into the pores of the electrospun fiber membrane on one hand, and cannot be blocked in the pores of the electrospun fiber membrane to be difficult to remove on the other hand.

Preferably, the cellulose content in the separation membrane is 10-20 wt.%.

Preferably, the separation membrane has an elastic modulus of 60.0 to 90.0MPa, a tensile strength of 10.0 to 12.0MPa, and an elongation at break of 100-150%.

The cellulose is preferably carboxymethyl cellulose or hydroxymethyl cellulose.

In a particularly preferred embodiment, the cellulose is a modified cellulose, which is preferably modified by:

weighing 2.0g of cellulose (preferably carboxymethyl cellulose) and 4.0g of polyglutamic acid (the molar ratio of monomers is about 1:2.5-3), mixing, fully grinding for 30min under an infrared lamp to obtain uniform fine powder, using 20mL of dimethyl sulfoxide (DMSO) as a cosolvent, ultrasonically stirring for 30min to uniformly disperse the powder in a DMSO solvent system, heating the system to 120 ℃ through an oil bath, adding sulfuric acid as a catalyst under heating and stirring, reacting for 6h, filtering the reaction system, washing filter residues with ethanol and deionized water, washing with saturated sodium bicarbonate, washing with deionized water to be neutral, washing with ethanol and acetone sequentially, and drying at 80 ℃ to obtain the modified cellulose.

By adopting the chemical modification method, polyhydroxy on the surface of the cellulose can be modified, and carboxyl functional groups are grafted in modified cellulose molecules by introducing carboxyl, amino and other groups, so that the hydrophilicity of the modified cellulose is effectively improved. In addition, the use of polyglutamic acid effectively improves the hydrophilicity of cellulose without deteriorating the strength of cellulose and affecting the performance of cellulose characteristics, as compared with other modifiers.

The pressure of the high-temperature oxygen-free steam is preferably 0.2-1.0 MPa.

Preferably, wherein the high temperature oxygen-free steam comprises nitrogen. More preferably, the nitrogen content is 10-80 v.%, more preferably 20-60 v.%.

In the present invention, it is preferred that the waste is not subjected to any pretreatment. Alternatively, the inorganic substances in the garbage can be removed.

Compared with the simple dry distillation in the prior art, the nitrogen gas can prevent the garbage from burning in the carbonization process, so that the generated carbon has higher heat value. In addition, compared with pure steam gasification in the prior art, the existence of nitrogen can also increase the heating medium heat value, improve the heating efficiency and thus improve the carbonization efficiency, and can also save the steam consumption, and more importantly, through the addition of nitrogen, can provide the required catalytic conditions for the subsequent catalytic upgrading of distillate, such as adjusting the required steam partial pressure, because the excessive steam pressure can cause the catalytic upgrading to be difficult to be effectively carried out, and the addition of nitrogen can reduce the steam partial pressure in the gas stream, namely the distillate.

The inventor finds that in the existing garbage steam treatment technology, selective steam treatment conditions for garbage composition are often ignored, and the difference of the garbage composition is ignored, so that the garbage treatment efficiency is low. The inventor of the invention has conducted a great deal of research, and selects different steam treatment conditions according to different garbage compositions, thereby obtaining good steam treatment effect. In particular, the following conditions of the high-temperature distillation carbonization treatment are selected: (1) when the content of the organic substances in the garbage is more than or equal to 80 weight percent based on the total weight of the garbage, the temperature of the high-temperature oxygen-free steam is 300-450 ℃, and preferably 300-400 ℃; the nitrogen content in the high temperature oxygen-free steam is 10-30 v.%, preferably 10-20 v.%; the retention time in the high-temperature distillation carbonization device is 8-12 h; and (2) the temperature of the high temperature oxygen-free steam is between 450 ℃ and 600 ℃, preferably between 500 ℃ and 550 ℃, when the content of organic substances in the composition of the waste is less than 80% by weight and preferably the content of plastic rubber substances is less than 10% by weight, based on the total weight of the waste; the nitrogen content in the high temperature oxygen-free steam is 40-80 v.%, preferably 60-80 v.%; the retention time in the high-temperature distillation carbonization device is 5-8 h.

The upgraded bio-oil is mixed or blended with the polyphenol extract described above.

For the purposes of the present invention, the gas stream is preferably substantially free of dioxins. Because the temperature is raised and the distillation is carried out under the anaerobic condition, harmful substances such as dioxin and the like are not generated, and the atmospheric environment can be protected. This has a great advantage over the conventional incineration method.

Preferably, wherein the high temperature oxygen-free steam used in the high temperature distillation carbonization unit is from a high pressure once-through steam furnace.

In another aspect of the invention, there is provided an upgraded bio-oil obtained according to the aforementioned method. Preferably, the oxygen content of the upgraded bio-oil is below 10 wt%, preferably below 5 wt%, more preferably below 2 wt%. Further, the upgraded bio-oil has a higher calorific value greater than 41 MJ/kg.

In another aspect of the invention, there is provided a carbonaceous material obtained by a process according to any one of the preceding claims.

Preferably, the carbonaceous material is activated carbon.

Drawings

FIG. 1 is a chromatogram obtained by simulated distillation of a polyphenol extract obtained according to example 2 of the present invention using GC-FID.

Detailed description of the preferred embodiments

The present invention will be described in further detail below with reference to the following examples and comparative examples, but the embodiments of the present invention are not limited thereto.

Example 1

Selecting domestic garbage from a main urban area in Beijing city, and carrying out high-temperature distillation carbonization on the garbage by the following steps: loading the garbage into a garbage conveying device, enabling the garbage conveying device to pass through a high-temperature distillation carbonization device, taking out gas material flow of bio-oil and water vapor from the upper part of the high-temperature distillation carbonization device, and condensing the gas material flow to obtain a mixture of bio-oil and water for extracting polyphenol. The high-temperature distillation carbonization device is heated by high-temperature oxygen-free steam, the temperature of the high-temperature oxygen-free steam is 450 ℃, the content of nitrogen in the high-temperature oxygen-free steam is 12 v.%, the pressure is 1.0MPa, and the average treatment time is 5.0 hours.

Example 2

Taking 100mL of the mixture of bio-oil and water obtained in example 1, adding 150mL of dichloromethane, sufficiently shaking to obtain an organic layer, an aqueous layer and an intermediate emulsion layer, taking out the organic layer, adding 10 wt% NaCl aqueous solution (added in 4 portions) to the organic layer, wherein the concentration of KOH in the aqueous solution is 1mol/L and the volume of the NaCl aqueous solution is 800mL, thereby transferring the phenolic substances to the aqueous phase, taking out the aqueous phase, simultaneously combining the organic phase with the previous intermediate emulsion layer to obtain a mixture (marked as mixture M, which is left for other purposes), adjusting the pH value of the aqueous phase to 5 by using 1mol/L HCl solution, then extracting the aqueous phase 3 times by using 800mL of dichloromethane, combining the dichloromethane organic phases, and concentrating to 30mL to obtain the polyphenol extract.

Example 3

The mixture M of example 2 was upgraded by hydrodeoxygenation with a catalyst bed of Ni-Cu-Pd-Fe₂O₃/HZSM-5, wherein the molar ratio of Ni, Cu, Pd, Co and Fe is 2:8:0.15:15, based on the total weight of the catalyst, Ni-Cu-Pd-Fe₂O₃The content of the catalytic active component is 5%, the hydrogenation upgrading conditions are 250 ℃, the hydrogen pressure is 8.0MPa, and the mixture of the upgraded bio-oil and the water is separated by using the separation membrane for 2 hours, so that the upgraded bio-oil is obtained. The oxygen content in the bio-oil was 4.9 wt.%.

Example 4

The polyphenol extract prepared in example 2 was used for the antioxidant performance test as follows: 100mL of the polyphenol extract obtained in example 2 was added to 100L of the upgraded biooil obtained in example 3, shaken well at 60 ℃ for 72h, and then the amount of peroxide formed therein was measured (measured according to GB25199-2015 method). The peroxide content was found to be 12.5 mmol/kg.

Comparative example 1

The peroxide content was tested in the same operation as in example 3, except that the polyphenol extract obtained in example 2 was not added. The peroxide content produced was found to be 67.1 mmol/kg.

It is clear from the above examples and comparative examples that the polyphenol antioxidant of the present invention has a particularly good antioxidant effect, so that the oxidation stability of bio-oil derived from the same process is significantly improved, and it has a good commercial application value, and at the same time, it can also make the resource treatment of garbage have a greater economic benefit.

This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. All citations referred to herein are incorporated herein by reference to the extent that no inconsistency is made.