CN105316034A - Method for processing phenol-containing oil in coal tar - Google Patents
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Abstract
The invention provides a method for processing phenol-containing oil in coal tar. The method comprises the following steps: fractioning and cutting coal tar to obtain a phenol-containing oil fraction with the boiling range from an initial boiling point to 220DEG C and other fractions with the distillation temperature being greater than 220DEG C; allowing the phenol-containing oil fraction and at least one alcohol to be in contact with an etherification catalyst under etherification reaction conditions to obtain an ether-containing mixture; and removing alcohol in the ether-containing mixture to obtain etherified oil. The etherified oil obtained through the method has high octane number, and is suitable for being used as a gasoline blending component to improve the octane number of the gasoline. Extraction of the phenol-containing oil is not needed by the method in the invention, so the problems of increased cost and hidden environmental protection trouble caused by generation of a large amount of waste acid solutions and waste alkali solutions of present phenol-containing oil dephenolization quality improvement methods are avoided. The method can simultaneously realize increase of the added values of the phenol-containing oil and clean utilization of the phenol-containing oil.
Description
Technical field
The present invention relates to the working method of carbolic oil in a kind of coal tar.
Background technology
The coal tar that the volatile constituent that pyrolysis of coal process produces comprises coke(oven)gas and evaporates under pyrolysis temperature, by chilling process, volatile constituent is divided into coke(oven)gas and coal tar component, coal tar can segment further in secondary fractionator, wherein, the cut being equivalent to kerosene boiling point separated is commonly referred to as carbolic oil, and the feature of carbolic oil is containing a large amount of monohydric phenol.
Because carbolic oil contains a large amount of monohydric phenol, if therefore carbolic oil is carried out hydrotreatment, on the one hand phenol is transformed by deoxidation, cause being worth and reduce, also significantly add the hydrogen consumption (mass percentage of the oxygen in raw material often increases by 1%, corresponding hydrogen consumption increase by 0.125 quality %) of hydrogenation process simultaneously; The water that phenol deoxidation generates on the other hand can cause the active metal centre of cracking catalyst to assemble, and affects the activity of catalyzer.Therefore, carbolic oil be not suitable for adopting the method for hydrogenation directly to process.
At present, conventional carbolic oil upgrading mode is that carbolic oil is carried out dephenolize, and the phenolic compound obtained is for the preparation of fine chemicals, and remaining dephenolize oil carries out hydrotreatment.General employing alkaline aqueous solution extracts carbolic oil, phenolic compound is transformed into phenates, extracts from carbolic oil, and then neutralize with acid, thus obtain phenolic compound.Such dephenolize process can produce a large amount of spent acid solution and waste lye, and a large amount of spent acid solution and waste lye need to carry out cleaning process, and this not only can increase the burden of enterprise, and there is serious pollution hidden trouble.
Therefore, how while the added value increasing carbolic oil, carbolic oil is utilized to be of great practical significance cleanly.
Summary of the invention
The object of the present invention is to provide a kind of working method of carbolic oil, the method not only increases the added value of carbolic oil, and clean environment firendly.
The invention provides the working method of carbolic oil in a kind of coal tar, the method comprises:
Fractionation cutting coal tar, obtains other cut that the carbolic oil cut of boiling range within the scope of initial boiling point to 220 DEG C and recovered temperature are greater than 220 DEG C;
Under etherification reaction condition, described carbolic oil cut is contacted with catalyst for etherification with at least one alcohol, obtain containing ether mixture;
Remove described containing the alcohol in ether mixture, obtain etherificate and generate oil.
According to carbolic oil working method of the present invention, coal tar is carried out distillation cutting thus the carbolic oil cut separated wherein, and carbolic oil cut is contacted with alcohol carry out etherificate dexterously, phenol is wherein transformed into ether, and the transformation efficiency of phenol is high, the etherificate generation oil obtained has higher octane value and (is generally more than 90, can more than 95 be reached under optimum condition, even can reach more than 110), be suitable for as gasoline blending component, to improve the octane value of gasoline.Further, method of the present invention, without the need to extracting carbolic oil, avoids existing carbolic oil dephenolize method for upgrading owing to producing a large amount of spent acid solution and waste lye and the cost up caused and environmental protection hidden danger.Therefore, method of the present invention can realize, while increase carbolic oil added value, utilizing carbolic oil cleanly.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is for illustration of a kind of embodiment of the inventive method.
Embodiment
The invention provides the working method of carbolic oil in a kind of coal tar, the method comprises:
Fractionation cutting coal tar, obtains other cut that the carbolic oil cut of boiling range in initial boiling point to 220 DEG C (preferably 200 DEG C) scope and recovered temperature are greater than 220 DEG C (being preferably greater than 200 DEG C);
Under etherification reaction condition, described carbolic oil cut is contacted with catalyst for etherification with at least one alcohol, obtain containing ether mixture;
Remove described containing the alcohol in ether mixture, obtain etherificate and generate oil.
In the present invention, boiling range adopts true boiling point distillation method to measure.
In described carbolic oil cut, the total amount of monohydric phenol is preferably greater than 10 % by weight, and such etherificate generates oil and has higher octane value, is suitable for as gasoline blending component to improve the octane value of gasoline.More preferably, in described carbolic oil cut, the content of monohydric phenol is 45-70 % by weight.Further preferably, in described carbolic oil cut, the content of monohydric phenol is 50-70 % by weight.
Method of the present invention can carry out processing and utilization to the carbolic oil cut in the coal tar in various source.Particularly, described coal tar can be coalite tar, coal-tar middle oil, coal-tar heavy oil or liquefied coal coil.
Described alcohol can be C
1-C
3fatty alcohol in one or more, can be such as one or more in methyl alcohol, ethanol, n-propyl alcohol and Virahol.From improving the angle that etherificate generates the octane value of oil further, described alcohol is preferably methyl alcohol and/or ethanol.
Ratio between described carbolic oil cut and described alcohol can be selected according to the phenol content in carbolic oil cut.Usually, the phenol in described carbolic oil cut and the mol ratio of described alcohol can be 1:1-5, are preferably 1:2-5, are more preferably 1:3-5.
Described catalyst for etherification can be the material that the various etherification reaction to phenol has katalysis, is preferably solid acid alkali catalytic agent, can generates separating of oil by catalyzer and etherificate easily like this, simplifies the aftertreatment flow process that etherificate generates oil.Described solid acid alkali catalytic agent refers to the solid matter with acid sites and/or basic center.
Described catalyst for etherification is specifically as follows but is not limited to Al
2o
3, Al
2o
3-SiO
2one or more in composite oxides, solid supported acid catalyst and solid supported alkaline catalysts.Described Al
2o
3-SiO
2in composite oxides, Al
2o
3and SiO
2between ratio can be conventional selection, usually, with Al
2o
3-SiO
2the total amount of composite oxides is benchmark, described SiO
2content can be 20-80 % by weight.
Described solid supported acid catalyst refers to that load has the solid of acidic substance.Usually, described solid supported acid catalyst comprises carrier and load acidic substance on the carrier.Described acidic substance can be one or more in phosphoric acid, sulfuric acid and heteropolyacid.Preferably, described acidic substance are phosphoric acid.
The content of described solid supported acid catalyst middle acid substance is as the criterion can realize catalysis.Usually, with the total amount of described solid supported acid catalyst for benchmark, the content of described acidic substance can be 5-40 % by weight, is preferably 15-25 % by weight.
Described solid supported alkaline catalysts refers to that load has the solid of alkaline matter.Usually, described solid supported alkaline catalysts comprises carrier and load alkaline matter on the carrier.Described alkaline matter can be an alkali metal salt of alkalimetal oxide and/or phosphoric acid, and the basic metal in an alkali metal salt of described alkalimetal oxide and phosphoric acid can be the one in lithium, sodium, potassium, rubidium and caesium separately.Described alkalimetal oxide is preferably Cs
2o and/or K
2o, is more preferably Cs
2o.An alkali metal salt of described phosphoric acid can be an alkali metal salt of its aqueous solution various in the phosphoric acid of alkalescence, can be sodium phosphate and/or potassiumphosphate.
The content of described solid supported alkaline catalysts neutral and alkali material is as the criterion can realize catalysis.Usually, with the total amount of described solid supported alkaline catalysts for benchmark, can be 5-70 % by weight with the content of the described alkaline matter of elemental metal, be preferably 6-35 % by weight.More preferably, with the total amount of described solid supported alkaline catalysts for benchmark, with the content of the described alkaline matter of elemental metal for 10-15 % by weight.
The carrier of described solid supported acid catalyst and described solid supported alkaline catalysts can be Al separately
2o
3and/or SiO
2, be preferably SiO
2.The most probable pore size of described carrier is preferably 9-12nm, and pore volume is preferably 0.5-1mL/g, and specific surface area is preferably 100-300m
2/ g, such catalyzer can demonstrate higher catalytic activity.Described most probable pore size, pore volume and specific surface area adopt nitrogen adsorption methods to measure.
In the preferred embodiment of the present invention, described catalyst for etherification is solid supported alkaline catalysts, and the carrier of described solid supported alkaline catalysts is SiO
2, alkaline matter is Cs
2o, and with the total amount of solid supported alkaline catalysts for benchmark, the content of Cs is 10-15 % by weight.This catalyzer have very high while transform the ability of phenol, ortho-cresol, meta-cresol and p-cresol, thus when all the other conditions are identical, can obtain higher phenol transformation efficiency, etherificate generates oil and has higher octane value.
In another preferred embodiment of the present invention, described catalyst for etherification is Al
2o
3or Al
2o
3-SiO
2composite oxides, even if now carry out etherification reaction at a lower temperature, also can obtain higher high-octane number component yield.
The size of described solid acid alkali catalytic agent can be selected according to the type of reactor of carrying out etherification reaction, is not particularly limited.Such as, when etherification reaction carries out in fixed-bed reactor, the particle diameter of described solid acid alkali catalytic agent is preferably in the scope of 1-3mm.
Described solid acid alkali catalytic agent is shaping catalyzer, can have different shape, such as spherical, bar-shaped and cloverleaf pattern.
Described solid acid alkali catalytic agent can be commercially available, and ordinary method also can be adopted to prepare, such as pickling process, spraying process or liquid phase deposition.
The consumption of described catalyst for etherification can be selected according to the type of reactor of carrying out etherification reaction, is as the criterion can realize catalysis.Particularly, described carbolic oil cut and described alcohol and described catalyst for etherification contact carry out in fixed-bed reactor time, the volume space velocity of described carbolic oil cut can be 0.2-2h
-1.
The present invention is not particularly limited for described etherification reaction condition, can be conventional selection.Usually, described etherification reaction can carry out at the temperature of 220-450 DEG C.When described catalyst for etherification is previously described solid supported acid base catalysator, preferably at the temperature of 350-450 DEG C, carry out etherification reaction; More preferably at the temperature of 380-400 DEG C, carry out etherification reaction, the phenol transformation efficiency that can obtain like this, and the coke content formed on a catalyst is few, longer catalyzer work-ing life can be obtained, the parallel-adder settle-out time of extension fixture.Be Al at described catalyst for etherification
2o
3or Al
2o
3-SiO
2during composite oxides, etherification reaction can be carried out at a lower temperature, preferably 220-350 DEG C, more preferably at the temperature of 220-260 DEG C, carry out etherification reaction.
According to method of the present invention, described carbolic oil cut and described alcohol and described catalyst for etherification contact carry out in fixed-bed reactor time, at least one non-active gas can also be passed into as carrier gas in fixed-bed reactor.Described non-active gas refers to and with reactant, catalyzer and resultant, chemically interactive gas does not occur under etherification reaction condition, can be neutral element gas (as argon gas) and/or nitrogen, is preferably nitrogen.The amount of described non-active gas is not particularly limited.Usually, the volume ratio of described non-active gas and described carbolic oil cut can be 5-600:1.
According to method of the present invention, hydrogen can also be passed in the reactor carrying out etherification reaction, the trend that catalyst surface forms carbon deposit can be reduced in so further.The amount of described hydrogen can be selected according to concrete etherification reaction condition.Usually, the volume ratio of described hydrogen and described carbolic oil cut can be 200-1500:1.
According to method of the present invention, etherification reaction can carry out in conventional various reactors, preferably carries out in fixed-bed reactor.When carrying out in fixed-bed reactor, by after carbolic oil cut and alcohol vaporization, can mix with optional non-active gas and optional hydrogen, and send in reactor, react with filling catalyst exposure in the reactor.
Fig. 1 shows a kind of embodiment of carbolic oil working method in coal tar of the present invention, in this embodiment, carbolic oil and alcohol are mixed with nitrogen and/or hydrogen after vaporization with sending in vaporizer, gas mixture is sent in reactor and contacts with catalyst for etherification, carry out etherification reaction, the gas mixture exported from reactor obtains etherificate generation oil after cooling and isolate alcohol.
Method of the present invention is adopted to carry out processing and utilization to carbolic oil cut, in carbolic oil cut, the transformation efficiency of phenol is high, and the etherificate obtained generates in oil and contains a large amount of ether compound, has higher octane value, be suitable for the blend component as gasoline, to improve the octane value of gasoline.
According to the present invention, in coal tar, recovered temperature is can carry out hydrogenation higher than other cut of 220 DEG C to produce petrol and diesel oil.
Describe the present invention in detail below in conjunction with embodiment, but therefore do not limit the scope of the invention.
In following examples, gas-chromatography and makings method for combined use is adopted to measure carbolic oil cut and etherificate generation oil composition.
In following examples, catalyst for etherification adopts the preparation of iso volumetric impregnation method, and the composition of obtained catalyst for etherification is calculated by charging capacity and obtains.Adopt the most probable pore size of nitrogen adsorption methods mensuration catalyst for etherification carrier, pore volume and specific surface area, adopt method of sieving to measure the particle diameter of catalyst for etherification.
In following examples, adopt the model purchased from the prosperous Science and Technology Ltd. of Beijing Sai Borui be LAB130 octane value cetane test instrument measure etherificate generate oil octane value.
Following examples, the cut that the carbolic oil cut of use is the boiling range that cuts out from From Shenmu Coal tar within the scope of initial boiling point to 200 DEG C, its composition is listed in Table 1.
Table 1
| Composition | % by weight |
| Phenol | 15.4 |
| Ortho-cresol | 11.7 |
| Meta-cresol+p-cresol | 25.9 |
| 2,6-xylenol | 0.01 |
| 2,4-xylenol | 6.5 |
| Other component | 40.49 |
Wherein, other component comprises alkane, alkene, aromatic hydrocarbon, ketone, indenes, naphthalene, sulfocompound and nitrogenous compound and other phenols on a small quantity.
In following examples, high-octane number component yield refers to the total recovery of methyl-phenoxide, 2-methylanisole, 3-methylanisole, 4-methylanisole, 2,6-dimethylanisoles and 2,4-dimethylanisole.
Embodiment 1-10 is for illustration of method of the present invention.
Embodiment 1
(1) preparation of catalyzer
20 grams of spherical SiO are added to containing in the aqueous solution (concentration is 21.6 % by weight) of 3.87 grams of cesium acetates
2(in the scope of 1-3mm, most probable pore size is 10.5nm to particle diameter to particle, and pore volume is 0.75mL/g, and specific surface area is 200m
2/ g), and at room temperature stir 0.5 hour.Then, will the mixture that obtains be flooded after room temperature is dried, be placed in dry 12 hours of the baking oven of 120 DEG C, then roasting 12 hours in air atmosphere at the temperature of 500 DEG C in retort furnace.As calculated, in this catalyzer, the content of Cs is 11.8 % by weight.
(2) catalyst loading 10mL step (1) obtained, in micro fixed-bed reactor, forms beds.Be mixed 1.1 (methyl alcohol is about 5:1 with the mol ratio of phenol in carbolic oil) by volume by methyl alcohol and carbolic oil, then pump in reactor, carry out etherification reaction.Wherein, temperature of reaction is 400 DEG C, and nitrogen flow rate is 20mL/min, and during liquid, volume space velocity is 0.5h
-1.After measured, the yield of high-octane number component is 79.5%; After removing methyl alcohol, the octane value that etherificate generates oil is 120.5.
Embodiment 2
(1) the method Kaolinite Preparation of Catalyst identical with embodiment 1 is adopted, unlike, add 20 grams of spherical SiO to containing in the aqueous solution (concentration is 12.2 % by weight) of 1.94 grams of cesium acetates
2particle (with embodiment 1), thus obtain catalyzer.As calculated, the theoretical content of caesium is 6.3 % by weight.
(2) method identical with embodiment 1 step (2) is adopted to carry out etherification reaction, unlike, catalyst for etherification is catalyzer prepared by embodiment 2 step (1).After measured, the yield of high-octane number component is 59.4%.
Embodiment 3
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 2 and carry out etherification reaction, unlike, in step (2), 0.66 (methyl alcohol is about 3:1 with the mol ratio of phenol in carbolic oil) mixed by volume for methyl alcohol and carbolic oil.After measured, the yield of high-octane number component is 45.1%.
Embodiment 4
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 2 and carry out etherification reaction, unlike, in step (2), 0.22 (methyl alcohol is about 1:1 with the mol ratio of phenol in carbolic oil) mixed by volume for methyl alcohol and carbolic oil.After measured, the yield of high-octane number component is 35.6%.
Embodiment 5
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 2 and carry out etherification reaction, unlike, in step (2), temperature of reaction is 450 DEG C, and nitrogen flow rate is 50mL/min.After measured, the yield of high-octane number component is 64.9%.
Embodiment 6
(1) the method Kaolinite Preparation of Catalyst identical with embodiment 2 is adopted.
(2) catalyst loading 10mL step (1) obtained, in micro fixed-bed reactor, forms beds.Be mixed 1.1 (methyl alcohol is about 5:1 with the phenol amount mol ratio that contains in carbolic oil) by volume by methyl alcohol and carbolic oil, then pump in reactor, carry out etherification reaction.Wherein, temperature of reaction is 450 DEG C, and nitrogen flow rate is 5mL/min, and during liquid, volume space velocity is 1.5h
-1.After measured, the yield of high-octane number component is 37.6%; After removing methyl alcohol, the octane value that etherificate generates oil is 111.9.
Embodiment 7
(1) the method Kaolinite Preparation of Catalyst identical with embodiment 1 is adopted, unlike, add 20 grams of spherical SiO to containing in the aqueous solution (concentration is 54.5 % by weight) of 19.15 grams of cesium acetates
2particle (with embodiment 1), thus obtain catalyzer.As calculated, the theoretical content of caesium is 39.9 % by weight.
(2) catalyst loading 10mL step (1) obtained, in micro fixed-bed reactor, forms beds.Be mixed 0.22 (methyl alcohol is about 1:1 with the mol ratio of phenol in carbolic oil) by volume by methyl alcohol and carbolic oil, then pump in reactor, carry out etherification reaction.Wherein, temperature of reaction is 350 DEG C, and nitrogen flow rate is 5mL/min, and during liquid, volume space velocity is 0.5h
-1.After measured, the yield of high-octane number component is 3.7%; After removing methyl alcohol, the octane value that etherificate generates oil is 91.7.
Embodiment 8
(1) the method Kaolinite Preparation of Catalyst identical with embodiment 1 is adopted, unlike, add 20 grams of spherical SiO to containing in 4.97 grams of phosphorus aqueous acids (concentration is 27.2 % by weight)
2particle (with embodiment 1).Then, will the mixture that obtains be flooded after room temperature is dried, be placed in dry 12 hours of the baking oven of 120 DEG C, thus obtain catalyzer.As calculated, H in this catalyzer
3pO
4content be 19.6 % by weight.
(2) catalyst loading 10mL step (1) obtained, in micro fixed-bed reactor, forms beds.Be mixed 0.44 (methyl alcohol is about 2:1 with the mol ratio of phenol in carbolic oil) by volume by methyl alcohol and carbolic oil, then pump in reactor, carry out etherification reaction.Wherein, temperature of reaction is 400 DEG C, and nitrogen flow rate is 50mL/min, and during liquid, volume space velocity is 0.2h
-1.After measured, the yield of high-octane number component is 15.7%; After removing methyl alcohol, the octane value that etherificate generates oil is 98.9.
Embodiment 9
By 10mLAl
2o
3be seated in micro fixed-bed reactor, form beds.Be mixed 0.44 (methyl alcohol is about 2:1 with the mol ratio of phenol in carbolic oil) by volume by methyl alcohol and carbolic oil, then pump in reactor, carry out etherification reaction.Wherein, temperature of reaction is 220 DEG C, and nitrogen flow rate is 50mL/min, and during liquid, volume space velocity is 0.5h
-1.After measured, the yield of high-octane number component is 37.2%.
Embodiment 10
(be 80wt%SiO by 10mL catalyzer
2-Al
2o
3+ 20wt%Al
2o
3, wherein, SiO
2-Al
2o
3in, SiO
2content be 40.9wt%) be seated in micro fixed-bed reactor, formed beds.Be mixed 0.44 (methyl alcohol is about 2:1 with the mol ratio of phenol in carbolic oil) by volume by methyl alcohol and carbolic oil, then pump in reactor, carry out etherification reaction.Wherein, temperature of reaction is 220 DEG C, and nitrogen flow rate is 50mL/min, and during liquid, volume space velocity is 0.5h
-1.After measured, the yield of high-octane number component is 20.5%.
The result of embodiment 1-10 confirms, adopts method of the present invention to process the carbolic oil cut in coal tar, effectively the phenol in carbolic oil cut can be transformed into corresponding ether, and can obtain higher phenol transformation efficiency.Wherein, the result of embodiment 1 and 6-8 confirms, the etherificate obtained by method of the present invention generates oil and namely has higher octane value without the need to being separated further, is suitable for use as gasoline blending component, to improve the octane value of gasoline.Therefore, method of the present invention can not only increase the added value of carbolic oil, and compared to traditional carbolic oil grading process clean environment firendly more.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. the working method of carbolic oil in coal tar, the method comprises:
Fractionation cutting coal tar, obtains other cut that the carbolic oil cut of boiling range within the scope of initial boiling point to 220 DEG C and recovered temperature are greater than 220 DEG C;
Under etherification reaction condition, described carbolic oil cut is contacted with catalyst for etherification with at least one alcohol, obtain containing ether mixture;
Remove described containing the alcohol in ether mixture, obtain etherificate and generate oil.
2. method according to claim 1, wherein, in described carbolic oil cut, the total amount of monohydric phenol is more than 10 % by weight, is preferably 45-70 % by weight, is more preferably 50-70 % by weight.
3. method according to claim 1 and 2, wherein, described alcohol is C
1-C
3fatty alcohol in one or more, be preferably methyl alcohol and/ethanol.
4. the phenol according to the method in claim 1-3 described in any one, wherein, in described carbolic oil cut and the mol ratio of alcohol are 1:1-5.
5. method according to claim 1, wherein, described catalyst for etherification is Al
2o
3, Al
2o
3-SiO
2one or more in composite oxides, solid supported acid catalyst and solid supported alkaline catalysts.
6. method according to claim 5, wherein, described solid supported acid catalyst comprises carrier and load acidic substance on the carrier, and described acidic substance are preferably phosphoric acid.
7. method according to claim 6, wherein, with the total amount of catalyzer for benchmark, the content of described acidic substance is 5-40 % by weight, is preferably 15-25 % by weight.
8. method according to claim 5, wherein, described solid supported alkaline catalysts comprises carrier and load alkaline matter on the carrier, and described alkaline matter is an alkali metal salt of alkalimetal oxide and/or phosphoric acid, be preferably alkalimetal oxide, be more preferably Cs
2o.
9. method according to claim 8, wherein, with the total amount of catalyzer for benchmark, with the content of the alkaline matter of elemental metal for 5-70 % by weight, is preferably 10-15 % by weight.
10. according to the method in claim 6-9 described in any one, wherein, described carrier is SiO
2.
11. according to the method in claim 6-10 described in any one, and wherein, the most probable pore size of described carrier is 9-12nm, and pore volume is 0.5-1mL/g, and specific surface area is 100-300m
2/ g.
12. methods according to claim 1, wherein, described etherification reaction condition comprises: temperature is 220-450 DEG C; Described contact is carried out in fixed-bed reactor, and the volume space velocity of described carbolic oil cut is 0.2-2h
-1.
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| CN109942383B (en) * | 2017-12-21 | 2020-10-30 | 中国科学院大连化学物理研究所 | Method for producing mixed ether by gas phase etherification of mixed phenol methanol |
| CN109749758A (en) * | 2019-03-11 | 2019-05-14 | 中国科学院过程工程研究所 | A kind of upgrading processing method of tar |
| CN109749758B (en) * | 2019-03-11 | 2021-04-30 | 中国科学院过程工程研究所 | Tar quality improvement treatment method |
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