CN106701158B - The desulfuration processing method and desulfurization carbolic oil of carbolic oil - Google Patents

Abstract

The invention relates to the field of oil refining, and discloses a desulfurization treatment method for phenolic oil and desulfurized phenolic oil prepared by the method. The method comprises: contacting phenol-containing oil with a desulfurization and non-removing phenol catalyst to perform desulfurization and non-removal phenol treatment under hydrogen-facing conditions, and the desulfurization and non-removal phenol catalyst contains a carrier and an active metal component loaded on the carrier , the carrier is one or a combination of at least two of zinc oxide, aluminum oxide and silicon oxide, and the active metal component is at least one of nickel, copper, palladium, platinum and ruthenium, wherein the Based on the total weight of the desulfurization and non-removing phenol catalyst, the content of the carrier is 80-98% by weight, the content of the active metal component is 2-20% by weight, and the hydrogen-facing condition refers to the reaction under normal pressure conditions. carried out in a hydrogen atmosphere. Adopting the method of the invention can reduce the sulfur content to the greatest extent on the premise of reducing the phenol content as little as possible, thereby improving the economic benefit to a greater extent.

Description

Desulfurization treatment method of phenolic oil and desulfurized phenolic oil

technical field

The invention relates to the field of oil refining, in particular to a method for desulfurizing phenol-containing oil and the desulfurized phenol-containing oil prepared by the method.

Background technique

Coal tar contains a large amount of phenolic compounds. If the coal tar is directly hydrogenated and upgraded, on the one hand, the phenolic compounds will be hydrodeoxygenated, resulting in a decrease in added value, and at the same time, it will increase the hydrogen consumption of the hydrogenation process; on the other hand, The water generated by the deoxygenation of phenolic compounds may lead to the aggregation of the active metal center of the catalyst, affecting the activity of the catalyst. It can be seen that the rational utilization of phenolic compounds in coal tar is of great significance.

At present, the conventional way to upgrade phenolic compounds in coal tar is to dephenolize coal tar to obtain crude phenols or further purify them into refined phenols, and the remaining dephenolized oil is subjected to hydrogenation treatment. This dephenolization process will produce a large amount of waste acid and waste alkali, which has serious potential pollution hazards. Cleaning them will greatly increase the burden on enterprises.

Among them, the phenol content is the most abundant in the phenolic oil fraction of coal tar (initial boiling point -210 ° C distillate), and 40-50% of the phenolic compounds in the tar are concentrated in this fraction, mainly phenol and formaldehyde base phenol. The yield of phenolic oil is about 5-7% of anhydrous tar. Compared with the traditional phenol extraction method, converting phenolic compounds in phenolic oil into high-octane components to prepare high-octane gasoline blending oil is a cleaner and broader market upgrading method. However, the presence of sulfur in phenolic oil is one of the obstacles to the upgrading process. Since the sulfur compounds in gasoline are likely to cause sulfur emission pollution during use, the limitation of sulfur content is an important indicator in gasoline standards. In order to respond to the call of the country and maximize the benefits of enterprises, it is an inevitable trend to develop desulfurization technologies with low energy consumption and low pollution.

CN103695030A discloses a method for hydrogenating anthracene oil in coal tar to produce diesel oil, and specifically discloses that anthracene oil is first reacted in a hydrogenation reaction zone containing a first catalyst, and then the product oil obtained in the hydrogenation reaction zone is put into The finished product of diesel component is produced by reaction in the hydrocracking reaction zone containing the second catalyst. In the hydrorefining catalyst of this prior art, additive potassium is added, which suppresses the coking and clogging of the reactor easily coked in coal tar, improves the stability of the catalyst, and adjusts the addition ratio of titanium dioxide and cerium dioxide in the carrier , effectively control the acidity of the carrier, which is conducive to improving the activity and selectivity of hydrocracking; at the same time, titanium dioxide has a strong adsorption capacity for sulfur, which is beneficial to desulfurization, and the melting point of ceria is high, which improves the stability of the carrier. The service life of the catalyst is improved, but the hydrorefining catalyst will simultaneously remove oxygen during hydrodesulfurization and denitrogenation.

US5730860 discloses a desulfurization method for gasoline and hydrocarbon feedstocks. This prior art is the IRVAD technology jointly developed by Black & Veatch Pritchard Inc and Alcon Industrial Chemicals, which is a breakthrough in the low-cost removal of sulfur-containing or other heteroatom compounds from hydrocarbons technology. This technology adopts multi-stage adsorption method, uses alumina-based selective solid adsorbent to treat liquid hydrocarbons, operates under low pressure, and has a desulfurization rate of over 90%. However, the method in the prior art uses a polar adsorbent to remove sulfur and nitrogen compounds in a segmented adsorber in a hydrogen-free state, which belongs to a physical adsorption method, and has disadvantages such as insufficient adsorption capacity.

US6350422, US6346190 and US6338794 are S-Zorb unique sulfur removal technology adsorbents of Phillips Petroleum Company. The adsorbent is composed of Zn and other metals carried on the carrier. The carrier adopts a mixture of zinc oxide, silica and aluminum oxide. In the carrier The content of zinc oxide is 10-90%, that of silica is 5-85%, and that of aluminum oxide is 5-30%. The metal component can be Co and Ni or Ni and Cu. The weight ratio of Ni and Co is 1:1, and the weight ratio of Ni and Cu is about 3:1. The adsorbent is made by mixing, granulating, drying and calcining. The adsorbent can adsorb sulfur-containing compound molecules and remove sulfur atoms, so that the sulfur atoms in the molecules can remain on the adsorbent, while the hydrocarbons are partially released and returned to gasoline. The adsorbent can carry out reactive adsorption desulfurization under low hydrogen consumption, but the octane number of the product gasoline is significantly lost, the sulfur capacity is not large enough, and the life of the single-stage reaction is short.

Therefore, the traditional desulfurization technology is mainly hydrodesulfurization. However, the hydrodesulfurization on the traditional hydrodesulfurization catalyst also deoxidizes the phenolic hydroxyl groups, which fails to achieve the purpose of desulfurization while retaining phenolic compounds. Therefore, a new desulfurization method was developed to achieve The purpose of oil desulfurization without dephenolization is of great significance to the utilization of phenolic oil.

Contents of the invention

The purpose of the present invention is to overcome the defects of the prior art, reduce the sulfur content to the greatest extent on the premise of reducing the phenol content as little as possible, and provide a desulfurization treatment method for phenol-containing oil and the desulfurized phenol-containing oil prepared by the method .

In order to achieve the above object, the present invention provides a desulfurization treatment method for phenol-containing oil, the method comprising: under the condition of hydrogen, contacting the phenol-containing oil with a desulfurization and non-removal phenol catalyst to perform desulfurization and non-removal phenol treatment, the desulfurization The non-phenol removal catalyst contains a carrier and an active metal component loaded on the carrier, the carrier is one or a combination of at least two of zinc oxide, aluminum oxide and silicon oxide, and the active metal component is nickel , copper, palladium, platinum and ruthenium, wherein, based on the total weight of the desulfurization and non-dephenolization catalyst, the content of the carrier is 80-98% by weight, and the content of the active metal component is 2-20% by weight, the hydrogen-facing condition means that the reaction is carried out in a hydrogen atmosphere under normal pressure.

The present invention also provides a desulfurized phenol-containing oil prepared by the above-mentioned desulfurization treatment method for phenol-containing oil of the present invention.

Adopting the above-mentioned desulfurization treatment method for phenol-containing oil of the present invention can reduce the sulfur content to the greatest extent on the premise of reducing the phenol content as little as possible, thereby improving economic benefits to a greater extent.

It can be seen from the results of the examples of the present invention that when the desulfurization treatment method of the present invention is used to desulfurize the phenolic oil, the sulfur therein can be selectively removed, and the phenols therein can be removed in a very small amount or not substances; and when the method of the prior art is used to desulfurize the phenol-containing oil, most of the phenolic substances are also removed while removing the sulfur in the phenol-containing oil, which is not conducive to the subsequent processing of the product. Significantly reduces the economic value of the product.

Moreover, the method of the present invention only needs to be carried out under the condition of hydrogen at normal pressure, which greatly saves the production cost.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

In one aspect, the present invention provides a method for desulfurization of phenol-containing oil, the method comprising: contacting the phenol-containing oil with a catalyst for desulfurization without dephenolization under hydrogen-facing conditions to perform desulfurization without dephenolization treatment, the desulfurization without dephenolization The dephenolization catalyst contains a carrier and an active metal component loaded on the carrier, the carrier is one or a combination of at least two of zinc oxide, aluminum oxide and silicon oxide, and the active metal component is nickel, At least one of copper, palladium, platinum and ruthenium, wherein, based on the total weight of the desulfurization and non-dephenolization catalyst, the content of the carrier is 80-98% by weight, and the content of the active metal component is 2 -20% by weight, the hydrogen-facing condition means that the reaction is carried out in a hydrogen atmosphere under normal pressure.

In the present invention, the hydrogen-facing condition means that the reaction is carried out in a hydrogen atmosphere under normal pressure.

The desulfurization and non-phenol removal treatment of the present invention can be carried out in various conventional reactors, and the number of catalyst beds in the reactor is not particularly limited, and can be one or more, as long as it can realize The above object of the present invention is sufficient.

When the above-mentioned method of the present invention is used to carry out desulfurization and non-removal treatment of phenol-containing oil, the sulfur in the phenol-containing oil can be selectively removed without even removing the phenolic substances in a small amount, thereby, the above-mentioned method of the present invention Can improve the economic benefits to a greater extent.

Preferably, in the present invention, the carrier is further zinc oxide and/or aluminum oxide. That is to say, in the method of the present invention, it is preferred that the carrier can be zinc oxide, aluminum oxide or zinc oxide and aluminum oxide.

In the present invention, based on the total weight of the desulfurization and non-removing phenol catalyst, preferably, the content of the carrier is 80-98% by weight, and the content of the active metal component is 2-20% by weight.

According to the first preferred embodiment of the present invention, the carrier of the present invention is zinc oxide and aluminum oxide, based on the total weight of the desulfurization and non-removing phenol catalyst, the content of the zinc oxide is 40-90 wt. %, the content of the alumina is 8-58% by weight, and the content of the active metal component is 2-20% by weight. When the desulfurization and no dephenolization catalyst of the first preferred embodiment of the present invention is used for the desulfurization and no dephenolization treatment, the sulfur content in the phenolic oil can be significantly reduced and the removal rate of phenolic substances therein can be reduced .

According to the second preferred embodiment of the present invention, the carrier of the present invention is alumina, based on the total weight of the catalyst for desulfurization without dephenolization, the content of alumina is 80-97% by weight, so The content of the active metal component is 3-20% by weight. When the desulfurization and no dephenolization catalyst of the second preferred embodiment of the present invention is used for the desulfurization and no dephenolization treatment, the sulfur content in the phenolic oil can be significantly reduced and the removal rate of phenolic substances can be reduced. .

In the present invention, preferably the active metal component is nickel and/or copper, particularly preferably the active metal component is nickel or copper. The inventors of the present invention have found that when a single non-noble metal nickel or copper is used as the active metal component in the desulfurization and non-removal catalyst of the phenol-containing oil of the present invention, it can significantly reduce the Reduce the sulfur content in phenolic oils and minimize the removal rate of phenolic substances in phenolic oils.

According to a third preferred embodiment of the present invention, the carrier is zinc oxide and aluminum oxide, the active metal component is nickel, and based on the total weight of the desulfurization and non-removing phenol catalyst, the zinc oxide The content is 70-90% by weight, the content of the aluminum oxide is 8-27% by weight, and the content of the nickel is 2-15% by weight.

According to a fourth preferred embodiment of the present invention, the carrier is zinc oxide and aluminum oxide, the active metal component is copper, and based on the total weight of the desulfurization and non-dephenolization catalyst, the zinc oxide The content is 70-90% by weight, the content of the aluminum oxide is 8-15% by weight, and the content of the copper is 2-15% by weight.

According to the fifth preferred embodiment of the present invention, the carrier is alumina, the active metal component is nickel, and the content of alumina is 85% based on the total weight of the catalyst for desulfurization and non-removal of phenols. -97% by weight, the nickel content is 3-15% by weight.

In particular, the inventors of the present invention have found that the desulfurization without dephenolization catalysts provided in the above-mentioned third, fourth and fifth preferred embodiments of the present invention are used to carry out the desulfurization without dephenolization treatment described in the present invention When, the sulfur content in the phenol-containing oil can be reduced more significantly, and the phenolic substances in the phenol-containing oil can be reduced to the greatest extent or even not removed, so that the production cost can be reduced more significantly to improve economic benefits.

Preferably, in the present invention, the inventors have found that when the reaction conditions for controlling desulfurization without dephenolization treatment are within the following ranges of the present invention, the removal rate of sulfur in the phenol-containing oil is higher, and the desulfurization does not The conditions of the dephenolization treatment include: the temperature is 280-400°C, the hydrogen flow rate is 5-50mL/min, and the liquid hourly volume space velocity is 0.1-4h ^-1 .

More preferably, in the present invention, when the reaction conditions for controlling desulfurization without dephenolization treatment are within the following ranges of the present invention, the removal rate of sulfur in the phenol-containing oil is higher, and the phenol-containing oil of the present invention The removal rate of phenolic substances in the product is lower, and the conditions for the desulfurization without dephenolization treatment include: the temperature is 320-380°C, the hydrogen flow rate is 10-30mL/min, and the liquid hourly volume space velocity is 0.2-2h ^-1 .

In the present invention, the preparation method of the desulfurization without dephenolization catalyst is not particularly limited, and the desulfurization without dephenolization catalysts prepared by those skilled in the art using various conventional preparation methods in the field that meet the above requirements of the present invention are all The purpose of selective desulfurization can be achieved. However, the inventors of the present invention have found that the desulfurization and non-removal of phenol catalyst prepared by preparing the carrier first, and then using the solution containing the active metal component element and the carrier to prepare the same volume impregnation method can have better selective desulfurization Effect. In the present invention, the solution containing the active metal component element is directed at the aforementioned active metal component of the present invention, and the solution containing the active metal component element of the present invention is in the process of preparing the catalyst, by The aforementioned active metal components of the present invention can be obtained after subsequent drying and reduction steps.

The method of the present invention has no special limitation on the preparation method of the carrier. In the process of preparing the carrier, various additives that need to be added conventionally, such as scallop powder, acidic binder, etc., can be added, and the amount of the additive is not particularly limited. Those skilled in the art can determine the amount of additives added according to actual needs.

The method of the present invention is not particularly limited to the concentration of the solution containing the active metal component elements, as long as the content of the active metal component of the desulfurization and non-removing phenol catalyst prepared by using the solution containing the active metal component elements It only needs to meet the aforementioned scope of the present invention. The method of the present invention has no special limitation on the type of the solution containing the active metal component elements, for example, it may be in the form of an aqueous solution of nitrate, sulfate and halide of the active metal component.

According to the sixth specific preferred embodiment of the present invention, the desulfurization without dephenolization treatment method of the present invention further includes equal volume impregnation of the carrier with a solution containing active metal component elements, and the obtained The solid product is dried, calcined and reduced in sequence to prepare the desulfurization and non-dephenolization catalyst.

In the present invention, the specific operation method of the equal-volume impregnation method is well known to those skilled in the art. Specifically, the equal-volume impregnation method is to dissolve the catalyst precursor with deionized water whose volume is just saturated and absorbed by the carrier, and then Add carrier and stir well to impregnate.

Preferably, in the present invention, the reducing step includes: reducing the dried solid product at a temperature of 300-500° C. for 4-36 hours in the presence of a reducing gas.

The method of the present invention can use various reducing gases to reduce the dried solid product, preferably, hydrogen is used to reduce the dried solid product.

The method of the present invention has no special requirements on the properties of the raw material phenolic oil, and the method of the present invention is suitable for processing phenolic oils of various properties. Preferably, when the sulfur content in the phenol-containing oil is 500-3800 mg/L and the phenol content is 100-700 g/L, the selective desulfurization effect of the desulfurization without dephenolization treatment method of the present invention is better.

In the present invention, the phenol is the aforementioned phenolic substances, including phenol, methylphenol and dimethylphenol.

The present invention also provides a desulfurized phenol-containing oil prepared by the above-mentioned desulfurization and non-dephenol-containing treatment method of the phenol-containing oil.

In the present invention, the sulfur content in the desulfurized phenolic oil is preferably lower than 100 mg/L, and the dephenolization rate is lower than 10% by weight; more preferably, the sulfur content in the desulfurized phenolic oil is lower than 50 mg/L.

Particularly preferably, in the present invention, the sulfur content in the desulfurized phenolic oil is 0-30 mg/L, and the dephenolization rate is lower than 5% by weight.

The present invention will be described in detail below by way of examples.

In the following preparation examples, examples and comparative examples, unless otherwise specified, all materials used are commercially available.

In the following examples and comparative examples, gas chromatography was used to detect the content of phenolic substances in phenol-containing oil and desulfurized phenol-containing oil, and an elemental analyzer was used to measure the sulfur content in phenol-containing oil and desulfurized phenol-containing oil. Adopt XRF method to detect the component content of the prepared desulfurization non-removal phenol catalyst, described dephenolization rate=(phenol content in phenol-containing oil-desulfurization phenol content in phenol-containing oil)/phenol content in phenol-containing oil ×100%.

Preparation Example 1

This preparation example is used to prepare the desulfurization and non-removal phenol catalyst of the present invention, and the specific method is as follows:

After mixing 450g of zinc oxide, 50g of aluminum oxide, and 15g of scallop powder evenly, add 3% by weight of dilute nitric acid to make the dry-mixed sample present a paste, and use a screw extruder to extrude the paste sample into strips, and then dry it in a blast dryer Dry at 120°C overnight, place in a muffle furnace and bake at 400°C for 6 hours to obtain a ZnO-Al ₂ O ₃ carrier. Then, prepare the supported catalyst for desulfurization without dephenolization by equal volume impregnation method: take 5 g of nickel nitrate and dissolve it in 7 ml of deionized water, add 20 g of the aforementioned ZnO-Al ₂ O ₃ carrier, stir for 30 minutes, and impregnate overnight at room temperature (25°C) . The solid product was dried at 120° C. for 6 hours to obtain a catalyst precursor for desulfurization without dephenolization. The desulfurization without dephenolization catalyst precursor was reduced under H ₂ atmosphere at 360°C for 20 hours to obtain the desulfurization without dephenolization catalyst C1.

After testing, based on the total weight of the desulfurization and non-dephenolization catalyst C1, the content of ZnO in the desulfurization and non-dephenolization catalyst C1 was 85.71% by weight, the content of _Al2O3 was 9.52% by weight, and the balance _was Ni.

Preparation example 2

This preparation example is used to prepare the desulfurization and non-removal phenol catalyst of the present invention, and the specific method is as follows:

After mixing 500g of alumina and 15g of turnip powder evenly, add 3% by weight of dilute nitric acid to make the dry-mixed sample present as a paste, use a screw extruder to extrude the paste sample into strips, and then place it in a blast dryer at 120°C Dry overnight, place in a muffle furnace and bake at 400°C for 6 hours to obtain an Al ₂ O ₃ support. Then, prepare the supported catalyst for desulfurization without dephenolization by equal-volume impregnation method: dissolve 5 g of nickel nitrate in 7 ml of deionized water, add 20 g of the aforementioned Al ₂ O ₃ carrier, stir for 30 minutes, and impregnate overnight at room temperature. The solid product was dried at 120° C. for 6 hours to obtain a catalyst precursor for desulfurization without dephenolization. The desulfurization without dephenolization catalyst precursor was reduced under H ₂ atmosphere at 360°C for 20 hours to obtain the desulfurization without dephenolization catalyst C2.

After detection, based on the total weight of the desulfurization and non-dephenolization catalyst C2, the content of Al ₂ O ₃ in the desulfurization and non-dephenolization catalyst C2 is 95.24% by weight, and the balance is Ni.

Preparation example 3

This preparation example is used to prepare the desulfurization and non-removal phenol catalyst of the present invention, and the specific method is as follows:

After mixing 450g of zinc oxide, 50g of aluminum oxide, and 15g of scallop powder evenly, add 3% by weight of dilute nitric acid to make the dry-mixed sample present a paste, and use a screw extruder to extrude the paste sample into strips, and then dry it in a blast dryer Dry at 120°C overnight, place in a muffle furnace and bake at 400°C for 6 hours to obtain a ZnO-Al ₂ O ₃ carrier. Then, the supported catalyst for desulfurization without dephenolization was prepared by equal-volume impregnation method: 4.062 g of copper nitrate was dissolved in 9 ml of deionized water, 20 g of the aforementioned ZnO-Al ₂ O ₃ carrier was added, stirred for 30 minutes, and soaked overnight at room temperature. The solid product was dried at 120° C. for 6 hours to obtain a catalyst precursor for desulfurization without dephenolization. The desulfurization without dephenolization catalyst precursor was reduced under H ₂ atmosphere at 360°C for 20 hours to obtain the desulfurization without dephenolization catalyst C3.

After testing, based on the total weight of the desulfurization and non-dephenolization catalyst C3, the content of ZnO in the desulfurization and non-dephenolization catalyst C3 was 85.39% by _weight , the content of _Al2O3 was 9.49% by weight, and the balance was Cu.

Preparation Example 4

This preparation example is used to prepare the desulfurization and non-removal phenol catalyst of the present invention, and the specific method is as follows:

After mixing 500g of zinc oxide and 15g of scallop powder evenly, add 3% by weight of dilute nitric acid to make the dry-mixed sample present as a paste, and use a screw extruder to extrude the paste sample into strips, and then place it in a blast dryer at 120°C. Dry overnight, place in a muffle furnace and bake at 400° C. for 6 hours to obtain a ZnO carrier. Then, prepare the supported catalyst for desulfurization without dephenolization by equal-volume impregnation method: take 5 g of nickel nitrate and dissolve it in 7 ml of deionized water, add 20 g of the aforementioned ZnO carrier, stir for 30 minutes, and impregnate overnight at room temperature. The solid product was dried at 120° C. for 6 hours to obtain a catalyst precursor for desulfurization without dephenolization. The desulfurization without dephenolization catalyst precursor was reduced under H ₂ atmosphere at 360°C for 20 hours to obtain the desulfurization without dephenolization catalyst C4.

After detection, based on the total weight of the desulfurization and non-dephenolization catalyst C4, the content of ZnO in the desulfurization and non-dephenolization catalyst C4 is 95.24% by weight, and the balance is Ni.

Preparation Example 5

This preparation example is used to prepare the desulfurization and non-removal phenol catalyst of the present invention, and the specific method is as follows:

After mixing 250g of zinc oxide, 250g of aluminum oxide, and 15g of scallop powder evenly, add 3% by weight of dilute nitric acid to make the dry-mixed sample present a paste, and use a screw extruder to extrude the paste sample into strips, and then dry it in a blast dryer Dry at 120°C overnight, place in a muffle furnace and bake at 400°C for 6 hours to obtain a ZnO-Al ₂ O ₃ carrier. Then, the supported catalyst for desulfurization without dephenolization was prepared by equal-volume impregnation method: 5 g of nickel nitrate was dissolved in 7 ml of deionized water, and 20 g of the aforementioned ZnO-Al ₂ O ₃ carrier was added, stirred for 30 minutes, and impregnated overnight at room temperature. The solid product was dried at 120° C. for 6 hours to obtain a catalyst precursor for desulfurization without dephenolization. The desulfurization without dephenolization catalyst precursor was reduced under H ₂ atmosphere at 360°C for 20 hours to obtain the desulfurization without dephenolization catalyst C5.

After testing, based on the total weight of the desulfurization and non-dephenolization catalyst C5, the _content of ZnO in the desulfurization and non-dephenolization catalyst C5 was 47.62% by weight, the content of _Al2O3 was 47.62% by weight, and the balance was Ni.

Preparation Example 6

This preparation example is used to prepare the desulfurization and non-removal phenol catalyst of the present invention, and the specific method is as follows:

After mixing 450g of zinc oxide, 50g of aluminum oxide, and 15g of scallop powder evenly, add 3% by weight of dilute nitric acid to make the dry-mixed sample present a paste, and use a screw extruder to extrude the paste sample into strips, and then dry it in a blast dryer Dry at 120°C overnight, place in a muffle furnace and bake at 400°C for 6 hours to obtain a ZnO-Al ₂ O ₃ carrier. Then, the supported catalyst for desulfurization without dephenolization was prepared by equal-volume impregnation method: 2.52 g of nickel nitrate and 2.01 g of copper nitrate were dissolved in 7 ml of deionized water, and 20 g of the aforementioned ZnO-Al ₂ O ₃ carrier was added, and impregnated overnight at room temperature. The solid product was dried at 120° C. for 6 hours to obtain a catalyst precursor for desulfurization without dephenolization. The desulfurization without dephenolization catalyst precursor was reduced under H ₂ atmosphere at 360°C for 20 hours to obtain the desulfurization without dephenolization catalyst C6.

After testing, based on the total weight of the desulfurization and non-dephenolization catalyst C6, the content of ZnO in the desulfurization and non-dephenolization catalyst C6 is 85.55% by _weight , the content of _Al2O3 is 9.51% by weight, and the content of Ni is 2.38% by weight %, the balance is Cu.

Preparation Example 7

This preparation example is used to prepare the desulfurization and non-removal phenol catalyst of the present invention, and the specific method is as follows:

After mixing 50g of zinc oxide, 450g of aluminum oxide, and 15g of scallop powder evenly, add 3% by weight of dilute nitric acid to make the dry-mixed sample present a paste, and use a screw extruder to extrude the paste sample into strips, and then dry it in a blast dryer Dry at 120°C overnight, place in a muffle furnace and bake at 400°C for 6 hours to obtain a ZnO-Al ₂ O ₃ carrier. Then, the supported catalyst for desulfurization without dephenolization was prepared by equal-volume impregnation method: 5 g of nickel nitrate was dissolved in 7 ml of deionized water, 20 g of the aforementioned ZnO-Al ₂ O ₃ carrier was added, stirred for 30 minutes, and impregnated overnight at room temperature. The solid product was dried at 120° C. for 6 hours to obtain a catalyst precursor for desulfurization without dephenolization. The desulfurization without dephenolization catalyst precursor was reduced under H ₂ atmosphere at 360°C for 20 hours to obtain the desulfurization without dephenolization catalyst C7.

After testing, based on the total weight of the desulfurization and non-dephenolization catalyst C7, the _content of ZnO in the desulfurization and non-dephenolization catalyst C7 was 9.52% by weight, the content of _Al2O3 was 85.71% by weight, and the balance was Ni.

Comparative example 1

In this comparison, a commercial NiMo/Al ₂ O ₃ catalyst was used as the catalyst D1 for desulfurization without dephenolization.

After testing, based on the total weight of the desulfurization and non-dephenolization catalyst D1, the contents of NiO and _MoO3 components in the desulfurization and non-dephenolization catalyst D1 are respectively 5% by weight _and 25% by weight, and the content of _Al2O3 70% by weight.

Comparative Preparation Example 2

In this comparative preparation example, a catalyst for desulfurization without dephenolization was prepared by equal-volume impregnation. The metal active components were Ni and Mo, and the carrier was silicon oxide. Silica was purchased from Qingdao Sichuang Fine Chemical Co., Ltd. Take 5g of nickel nitrate and ammonium molybdate and dissolve in 22ml of deionized water, add 20g of the aforementioned silicon oxide carrier, stir for 30 minutes and then dry it at room temperature. The solid product was dried at 120° C. for 6 hours to obtain a catalyst precursor for desulfurization without dephenolization. The desulfurization without dephenolization catalyst precursor was reduced under H ₂ atmosphere at 360°C for 20 hours to obtain the desulfurization without dephenolization catalyst D2.

After testing, based on the total weight of the desulfurization and non-removing phenol catalyst D2, the contents of NiO and _MoO3 components in the desulfurization and non-removal of phenol catalyst D2 are respectively 4.7% by weight and 25.5% by weight, and the content of _SiO2 is 69.8% by weight. weight%.

Example 1

Take 5 mL of the catalysts for desulfurization without dephenolation prepared in Preparation Examples 1-7 above and fill them in a fixed-bed reactor to form a catalyst bed. Then the phenolic oil is pumped into the reactor for desulfurization without dephenolization. Wherein, the reaction temperature is 360° C., the hydrogen flow rate is 20 mL/min, and the liquid hourly volume space velocity is 1 h ⁻¹ . A liquid product, desulfurized phenolic oil, is obtained at the outlet of the reactor.

Wherein, the properties of the phenol-containing oil and the desulfurized phenol-containing oil are shown in Table 1.

Table 1

Comparative example 1

This comparative example is carried out by a method similar to that of Example 1. The difference is that the types of desulfurization and non-removal of phenol catalysts used are different. This comparative example adopts the desulfurization and non-removal of phenol catalyst D1 prepared in Comparative Preparation Example 1 as this pair. The desulfurization in the method of ratio does not remove phenolic catalyst, and all the other are identical with embodiment 1.

Wherein, the properties of the phenol-containing oil and the desulfurized phenol-containing oil are shown in Table 1.

Example 2

The desulfurization without dephenolization catalyst used in this example is the desulfurization without dephenolization catalyst described in Preparation Example 1. The difference is that the reaction temperature and liquid hourly space velocity of Example 1 are changed, and the rest are the same as in Example 1.

Among them, the reaction conditions, liquid hourly space velocity and properties of phenol-containing oil and desulfurized phenol-containing oil are shown in Table 2.

Table 2

Example 3

The desulfurization without dephenolization catalyst used in this example is the desulfurization without dephenolization catalyst described in Preparation Example 1, the difference is that the sulfur content in the phenolic oil is different, and the rest are the same as in Example 1.

Take 5 mL of the catalyst for desulfurization without dephenolization prepared in the above Preparation Example 1 and fill them in a fixed-bed reactor to form a catalyst bed. Then the phenolic oil is pumped into the reactor for desulfurization without dephenolization. Wherein, the reaction temperature is 320° C., the hydrogen flow rate is 20 mL/min, and the liquid hourly volume space velocity is 0.2 h ⁻¹ . A liquid product, desulfurized phenolic oil, is obtained at the outlet of the reactor.

Wherein, the properties of the phenol-containing oil and the desulfurized phenol-containing oil are shown in Table 3.

table 3

As can be seen by comparison, when adopting the desulfurization treatment method of the present invention to carry out desulfurization and no dephenolization treatment to phenol-containing oil, the sulfur therein can be selectively removed, and the phenolic substances therein can be removed in a very small amount or not; and When the method of the prior art is used to desulfurize and not dephenolize the phenol-containing oil, most of the phenolic substances in the phenol-containing oil are removed while the sulfur in the phenol-containing oil is removed, which is not conducive to the subsequent processing of the product. Significantly reduces the economic value of the product.

Moreover, the method of the present invention only needs to be carried out under the condition of hydrogen at normal pressure, which greatly saves the production cost.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (13)

1. a kind of desulfuration processing method of carbolic oil, including：Under hydro condition, carbolic oil and desulfurization not dephenolize catalyst are connect It touches to carry out desulfurization not phenol removal, it is characterised in that：The desulfurization not dephenolize catalyst contains carrier and is supported on the load Active metal component on body, the carrier are the combination of one kind or at least two in zinc oxide, aluminium oxide and silica, institute It is at least one of nickel, copper, palladium, platinum and ruthenium to state active metal component, wherein with the gross weight of the desulfurization not dephenolize catalyst The content of gauge, the carrier is 80-98 weight %, and the content of the active metal component is 2-20 weight %, described to face hydrogen Condition refers to being carried out in the hydrogen atmosphere of reaction in atmospheric conditions.

2. according to the method described in claim 1, wherein, the carrier is further zinc oxide and/or aluminium oxide.

3. according to the method described in claim 2, the carrier is further zinc oxide and aluminium oxide, wherein with the desulfurization The total weight of not dephenolize catalyst, the content of the zinc oxide are further 40-90 weight %, the content of the aluminium oxide into One step is 8-58 weight %, and the content of the active metal component is further 2-20 weight %；Or

The carrier is aluminium oxide, and with the total weight of the desulfurization not dephenolize catalyst, the content of the aluminium oxide is further Content for 80-97 weight %, the active metal component is further 3-20 weight %.

4. according to the method described in claim 1, wherein, the active metal component is nickel and/or copper.

5. according to the method described in claim 1, wherein, the active metal component is nickel, is catalyzed with the desulfurization not dephenolize The content of the total weight of agent, the zinc oxide is further 70-90 weight %, and the content of the aluminium oxide is further 8-27 The content of weight %, the nickel are further 2-15 weight %.

6. according to the method described in any one of claim 1-3, wherein the condition of the desulfurization not phenol removal includes： Temperature is 280-400 DEG C, hydrogen flow rate 5-50mL/min, and volume space velocity is 0.1-4h when liquid^-1。

7. according to the method described in claim 6, wherein, the condition of the desulfurization not phenol removal includes：Temperature is 320-380 DEG C, hydrogen flow rate 10-30mL/min, volume space velocity is 0.2-2h when liquid^-1。

8. according to the method described in any one of claim 1-3, wherein the method further include by by the carrier with Solution containing active metal component element carries out incipient impregnation, and obtained solid product after dipping is done successively Dry, roasting and reduction are to prepare the desulfurization not dephenolize catalyst.

9. according to the method described in claim 8, wherein, the step of reduction, includes：It, will in the presence of reducibility gas Solid product after drying restores 4-36h under conditions of temperature is 300-500 DEG C.

10. according to the method described in claim 1, wherein, the sulfur content in the carbolic oil is 500-3800mg/L, phenol content For 100-700g/L.

11. containing phenol by the desulfurization that the desulfuration processing method of the carbolic oil described in any one of claim 1-10 is prepared Oil.

12. desulfurization carbolic oil according to claim 11, wherein sulfur content is less than 100mg/L in the desulfurization carbolic oil, takes off Phenol rate is less than 10 weight %.

13. desulfurization carbolic oil according to claim 12, wherein sulfur content is 0-30mg/L in the desulfurization carbolic oil, Dephenolize rate is less than 5 weight %.