CN114736713A

CN114736713A - Device and method for producing solvent oil by poor-quality cracking carbon nine hydrogenation

Info

Publication number: CN114736713A
Application number: CN202210370510.2A
Authority: CN
Inventors: 张笑剑; 柴平平; 陈小斌; 罗继刚; 罗如麟; 崔益鹏; 罗杰; 罗继庆
Original assignee: Liaoning Xinrui Environmental Protection Industry Co ltd
Current assignee: Liaoning Xinrui Environmental Protection Industry Co ltd
Priority date: 2022-04-10
Filing date: 2022-04-10
Publication date: 2022-07-12
Anticipated expiration: 2042-04-10
Also published as: CN114736713B

Abstract

The application provides a device and a method for producing solvent oil by poor-quality cracking carbon nine hydrogenation. Device of nine hydrogenation production solvent oil of inferior schizolysis carbon includes: the system comprises a degumming tower, a first-stage hydrogenation reactor, a first-stage oil-gas separator, a second-stage pre-hydrogenation reactor, a second-stage main hydrogenation reactor, a second-stage oil-gas separator and a fractionating tower. The method for producing the solvent oil by poor cracking carbon nine hydrogenation comprises the following steps: the poor-quality cracking carbon nine raw material is subjected to degumming, first-stage hydrogenation reaction, first oil-gas separation, second-stage pre-hydrogenation reaction, hydrofining reaction, second oil-gas separation and fractionation to obtain solvent oil containing mixed xylene, mixed trimethylbenzene and mixed tetramethylbenzene. The device and the method for producing the solvent oil by poor-quality cracking carbon nine hydrogenation have the advantages of low energy consumption, no polymerization coking problem, high yield, long-period operation realization and low production cost.

Description

Device and method for producing solvent oil by poor-quality cracking carbon nine hydrogenation

Technical Field

The application relates to the field of petroleum deep processing, in particular to a device and a method for producing solvent oil by poor-quality cracking carbon nine hydrogenation.

Background

The cracking carbon nine is a byproduct generated in the process of producing ethylene, the yield of the cracking carbon nine is about 12 percent of that of an ethylene raw material, and the cracking carbon nine has a dark color and a quick darkening color when exposed to air and has an irritant smell because the cracking carbon nine contains a large amount of unstable diene and olefin and a certain amount of impurities such as sulfur, nitrogen and the like. The partially cracked carbon nine was previously used to produce resins, most of which were considered as poor fuel burn points. Along with the increasing environmental protection and the increasing shortage of resources, the content of aromatic hydrocarbon in the cracking carbon nine is very high, and the octane number can reach about 98, so that the gasoline blending component is produced by hydrogenating the carbon nine in China in recent years. However, due to the particularity of cracking carbon nine, the existing domestic carbon nine hydrogenation device has various phenomena of short start-up period and unstable product quality.

In addition, at present, main products of the cracking carbon nine after hydrogenation mainly comprise gasoline blending components, but due to the appearance of new gasoline standards and new energy automobiles, the cracking carbon nine hydrogenation products have great impact on being used as the gasoline blending components.

The existing carbon nine hydrogenation devices in China all adopt two-stage hydrogenation, but in recent years, because a large amount of crude oil is imported from various domestic refineries and raw materials are deeply cracked in various ethylene plants, the quality of cracked carbon nine is increasingly poor, and the existing carbon nine hydrogenation devices and processes are difficult to meet the requirement of processing inferior carbon nine. For example, the dry point of the hydrogenation section materials of the domestic existing carbon nine hydrogenation device is controlled to be about 180 ℃, the dry point of the hydrogenation feeding material is controlled to be 205 ℃ as described in patent CN102627980A, but the dry point of domestic enterprises controls to be 210-230 ℃, which results in that the operation cycle of the devices does not exceed 6 months at most.

Disclosure of Invention

The application aims to provide a device and a method for producing solvent oil by hydrogenating carbon nine through poor-quality cracking, so as to solve the problems.

In order to achieve the purpose, the following technical scheme is adopted in the application:

a device for producing solvent oil by poor-quality cracking carbon nine hydrogenation comprises:

the degumming tower is used for pretreating inferior cracking carbon nine;

the primary hydrogenation reactor is used for carrying out primary hydrogenation reaction;

the primary oil-gas separator is used for separating the output of the primary hydrogenation reactor;

the second-stage pre-hydrogenation reactor is used for carrying out second-stage pre-hydrogenation reaction;

the second-stage main hydrogenation reactor is used for carrying out second-stage main hydrogenation reaction;

the second-stage oil-gas separator is used for separating the output of the second-stage main hydrogenation reactor;

the fractionating tower is used for fractionating to obtain a target product;

the degumming tower, the first-stage hydrogenation reactor, the first-stage oil-gas separator, the second-stage pre-hydrogenation reactor, the second-stage main hydrogenation reactor, the second-stage oil-gas separator and the fractionating tower are communicated in sequence.

Preferably, the lower part of the degumming tower is provided with 3 feed inlets with different heights, and each feed inlet is different by 2 tower plates.

The feeding hole of the degumming tower is arranged at the lower part of the tower, so that the materials in the tower can be ensured to carry out mass transfer and heat transfer reflux through enough space, the colloid in the carbon nine raw material can be better removed, and the tower top effluent is ensured not to contain the colloid. The three feeding holes can be selected according to carbon nine raw materials with different colloid contents. When the raw material with high colloid content enters the tower from the feed inlet at the lowest part, the temperature of the feed inlet is highest, and the quality of the tower top effluent can be ensured by the longest reflux section at the upper part; when materials with low colloid content are fed from the feed inlet at the upper part, the temperature of the feed inlet is lowest, the reflux section at the upper part is shortest, and the running cost of the device can be saved on the premise of ensuring the product quality. The middle feed inlet can process raw materials within an index range. Therefore, the method not only is suitable for raw materials with different qualities on the premise of ensuring the product quality, but also can save energy.

Preferably, the first-stage hydrogenation reactor is a hot-wall bubbling bed reactor;

the bottom of one section hydrogenation ware is provided with liquid feed inlet and hydrogen inlet, the inside of one section hydrogenation ware is provided with many rings of annular, with the gas distributor of hydrogen inlet intercommunication, gas distributor is last to be seted up the exhaust hole of slope 45 degrees.

Circulating hydrogen and carbon nine materials of the first-stage hydrogenation reaction respectively enter the reactor from two openings at the bottom of the reactor, the degummed carbon nine is diluted by a first-stage hydrogenation product and then enters the reactor from the center of the bottom of the reactor, and the carbon nine overflows out of the reactor from bottom to top after entering the reactor; circulating hydrogen and new hydrogen are mixed and then enter the reactor from the bottom of the reactor slightly deviated, gas phase enters the reactor and then is uniformly distributed through a multilayer annular distributor in order to ensure that hydrogen participates in the whole section of the reactor, and small exhaust holes with the angle of 45 degrees are formed in the upper part of each circle of distribution disc.

Preferably, the outlet of the first segment of the hydrogenation reactor is arranged on the side wall of the upper part, the outlet of the first segment of the hydrogenation reactor is provided with a conical partition plate, and inert ceramic balls are filled around the conical partition plate;

the upper part of the first hydrogenation reactor is provided with a counterweight section consisting of inert ceramic balls.

The first-stage hydrogenation reactor adopts upper discharging, and because the flow rates of liquid-phase materials and gas-phase materials are high, a catalyst bed layer is easy to loosen, once the catalyst bed layer is loosened, the hydrogenation reaction is uneven, so that the local reaction is severe, and the catalyst is coked due to temperature runaway of the catalyst bed layer; the loosening of the catalyst bed can also cause catalyst particles to gradually move upwards and flow out of the material outlet, so that the device is forced to stop production, and in serious cases, the subsequent equipment can be damaged. Therefore, the discharge port is arranged on the side wall of the reactor, and the outlet is provided with the conical partition plate, so that the filler in the reactor is ensured not to flow out along with the material or block an outlet pipeline to cause the increase of the pressure difference of the device; the upper part of the discharge port is provided with a section of counterweight section which is filled with inert ceramic balls, and the purpose is to press the catalyst in the reactor, and the weight of the ceramic balls is used for overcoming the stirring force of materials on a catalyst bed layer, so that the catalyst in the reactor is ensured to be in a static state, thereby preventing the catalyst bed layer from being overturned by fast circulating gas and oil, leading the catalyst bed layer to be loosened to influence the reaction effect, and leading the catalyst to be taken out of the reactor to cause equipment damage more seriously.

Preferably, the second-stage pre-hydrogenation reactor and the second-stage main hydrogenation reactor are both fixed bed hydrogenation reactors.

Preferably, a heater is arranged between the second-stage pre-hydrogenation reactor and the second-stage main hydrogenation reactor;

and a stabilizing tower is arranged between the two-section oil-gas separator and the fractionating tower.

The heater mainly has the function of ensuring the temperature of the material entering the two-stage main hydrogenation reactor; the function of the stabilizing tower is to discharge the gas dissolved in the liquid phase output from the two-stage oil-gas separator, so that the material entering the fractionating tower is relatively stable.

The application also provides a method for producing the solvent oil by carrying out inferior cracking carbon nine hydrogenation, which is carried out by using the device for producing the solvent oil by carrying out inferior cracking carbon nine hydrogenation and comprises the following steps:

feeding the filtered poor-quality cracking carbon nine raw material into a degumming tower to remove colloid, then feeding the filtered poor-quality cracking carbon nine raw material and hydrogen into a first-stage hydrogenation reactor, and performing a first-stage hydrogenation reaction in the first-stage hydrogenation reactor by using a reduced-state catalyst;

inputting the first-stage hydrogenation reaction product from the first-stage hydrogenation reactor into a first-stage oil-gas separator for first oil-gas separation, inputting the liquid product into a second-stage pre-hydrogenation reactor for second-stage pre-hydrogenation reaction, and inputting gas into a first-stage circulating hydrogen compressor for compression and then returning to the first-stage hydrogenation reactor or inputting the gas into the second-stage pre-hydrogenation reactor;

the first-stage liquid product is subjected to a second-stage pre-hydrogenation reaction in the second-stage pre-hydrogenation reactor by using a vulcanized catalyst, and the second-stage pre-hydrogenation reaction liquid product is input into a second-stage main hydrogenation reactor and subjected to a hydrofining reaction under the action of a hydrofining catalyst;

inputting the product of the hydrofining reaction into a two-section oil-gas separator for second oil-gas separation, and inputting the liquid product into a fractionating tower for fractionation to obtain solvent oil containing mixed xylene, mixed trimethylbenzene and mixed tetramethylbenzene; and the gas is input into a second-stage circulating hydrogen compressor to be compressed and then returns to the second-stage pre-hydrogenation reactor.

The purpose of the filtration is to remove impurities of 20 μm or more. The primary purpose of the first-stage hydrogenation is to saturate the degummed carbon nine raw material with a large amount of very active components such as diolefin, olefin and the like under the action of a reduced catalyst. The temperature required for the saturated diolefins is much lower than that of the saturated olefins, and once the temperature for the saturation of olefins is reached, some very active diolefins in the carbon nine raw materials can be polymerized to generate the quality of colloid impression products; if the temperature of the first stage is too low, the diolefin is saturated, but part of the olefin is not saturated, so that the temperature runaway of the second-stage hydrofining is hidden. Therefore, a pre-hydrogenation reactor is arranged for the second-stage hydrogenation, the residual olefin in the first-stage hydrogenation can be fully saturated in the pre-hydrogenation reactor, and then the olefin enters a main hydrogenation reactor in the second stage for hydrogenation refining reactions such as desulfurization, denitrification and the like, so that the requirement of long-period stable operation of the device can be met. The pre-hydrogenation reactor carries out hydrogenation reaction at a lower temperature, and the main purpose of the pre-hydrogenation reactor is to remove the mono-olefin and colloid left in the first-stage hydrogenation, so as to ensure that the main reactor does not generate carbon deposition during the reactions of high-temperature desulfurization, denitrification and the like, thereby causing the coking of the device and being forced to stop production. The main function of the two-stage main hydrogenation reactor is to remove elements such as sulfur, nitrogen, oxygen and the like in the raw materials in the presence of a hydrofining catalyst to obtain a high-quality refined product.

Preferably, the reduction catalyst is a nickel-based hydrogenation catalyst and comprises an active component, an auxiliary agent and a carrier, wherein the active component is Ni, the auxiliary agent is one or more of Mg, Mo, Zn and Li, and the carrier is made of macroporous Al₂O₃Mixing with metal salt solution of assistant, molding, and roasting at 600-1200 deg.C; in the reduction catalyst, the content of nickel oxide is 25-65%; the sulfided catalyst takes alumina as a carrier, one or more of W, Mo and Ni in an oxidation state as an active metal, and vanadium, zirconium or lanthanide series metal asOne or more of the metal(s) is/are an auxiliary metal, the active metal accounts for 5-15% of the total mass of the vulcanized catalyst, and the auxiliary metal accounts for 0.5-5% of the total mass of the vulcanized catalyst; the hydrofining catalyst takes alumina as a carrier, one or more of W, Mo and Co in an oxidation state as active metal, and one or more of vanadium, zirconium or lanthanide series metal as auxiliary metal, wherein the active metal accounts for 15-45% of the total mass of the hydrofining catalyst, and the content of the auxiliary metal accounts for 0.1-0.5% of the total mass of the hydrofining catalyst.

Preferably, the preparation method of the reduced catalyst comprises the following steps:

loading a saturated salt solution of nickel into a catalyst carrier under a vacuum state by the carrier, and then discharging moisture in the nickel salt through reduced pressure evaporation to obtain a semi-finished product of the catalyst containing high-concentration nickel salt; controlling the furnace temperature of the semi-finished product in a roasting furnace to be 250-600 ℃ so that the nickel salt is completely converted into nickel oxide;

then, the catalyst is heated to 600 ℃ from normal temperature in a reactor under the atmosphere of hydrogen and nitrogen mixed gas with the hydrogen mass content of 5-75%, the temperature is kept for 4-12 hours, then the temperature is reduced to 25-35 ℃, the catalyst is pre-wetted by naphtha which does not contain aromatic hydrocarbon and unsaturated hydrocarbon, 0.5-15% of carbon disulfide or dimethyl disulfide is added into the naphtha after the catalyst is pre-wetted, and the circulation is carried out for 4-8 hours.

Preferably, the reaction temperature of the first-stage hydrogenation reaction is 35-150 ℃, the pressure is 2.0-6.0MPa, and the hydrogen-oil ratio is 600-800;

the reaction temperature of the two-stage pre-hydrogenation reaction is 120-210 ℃, the pressure is 2.0-6.0MPa, and the hydrogen-oil ratio is 600-800-;

the reaction temperature of the hydrofining reaction is 270-380 ℃, the pressure is 2.0-6.0MPa, and the hydrogen-oil ratio is 600-800-.

Compared with the prior art, the beneficial effect of this application includes:

the device for producing the solvent oil by hydrogenating the carbon nine through the inferior cracking forms a stable reaction system capable of long-period operation by arranging the degumming tower, the first-stage hydrogenation reactor, the first-stage oil-gas separator, the second-stage pre-hydrogenation reactor, the second-stage main hydrogenation reactor, the second-stage oil-gas separator and the fractionating tower, does not need to be stopped frequently to replace a catalyst, and is low in production cost and good in economic benefit.

The application provides a method for producing solvent oil by poor cracking carbon nine hydrogenation, the device for producing solvent oil by poor cracking carbon nine hydrogenation is used, and proper catalysts are matched in each reactor through filtering, degumming, one-stage hydrogenation reaction, first oil-gas separation, two-stage pre-hydrogenation reaction, hydrofining reaction, second oil-gas separation and fractionation.

Drawings

To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.

FIG. 1 is a schematic diagram of an apparatus for producing solvent oil by hydrogenating nine cracked carbon with poor quality provided in example 1;

FIG. 2 is a schematic diagram of the bottom structure of a section of a hydrogenation reactor provided in example 1;

FIG. 3 is a schematic structural view of a gas distributor provided in example 1;

fig. 4 is a schematic diagram of the top structure of a section of a hydrogenation reactor provided in example 1.

Reference numerals:

1-a degumming tower; 2-a first-stage hydrogenation reactor; 3-a second-stage pre-hydrogenation reactor; 4-a two-stage main hydrogenation reactor; 5-first-stage oil-gas separator; 6-a heater; 7-two-stage oil-gas separator; 8-a stabilizer column; 9-a fractionation column; 10-a first stage recycle hydrogen compressor; 11-two-stage recycle hydrogen compressor; 12-a gas distributor; 13-material outlet; 14-conical baffle.

Detailed Description

Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

Example 1

As shown in fig. 1, the present embodiment provides an apparatus for producing solvent oil by hydrogenating carbon nine through poor cracking, which includes a degumming tower 1, a first-stage hydrogenation reactor 2, a second-stage pre-hydrogenation reactor 3, a second-stage main hydrogenation reactor 4, a first-stage oil-gas separator 5, a heater 6, a second-stage oil-gas separator 7, a stabilizing tower 8, a fractionating tower 9, a first-stage recycle hydrogen compressor 10, and a second-stage recycle hydrogen compressor 11.

The lower part of the degumming tower 1 is provided with 3 feed inlets with different heights, each feed inlet has a difference of 2 tower plates, and the top outlet of the degumming tower 1 is communicated with the bottom raw material inlet of the first hydrogenation reactor 2. The first hydrogenation reactor 2 is a hot wall bubbling bed reactor, and a reduction catalyst is arranged in the first hydrogenation reactor. The bottom of the first hydrogenation reactor 2 is provided with a gas inlet and a bottom raw material inlet (as shown in fig. 2), the bottom raw material inlet is arranged in the middle, the gas inlet is arranged at a position deviated from the center and is communicated with a gas distributor 12, and the gas distributor 12 is in a multi-ring shape and is provided with vent holes inclined at 45 degrees (as shown in fig. 3).

A material outlet 13 is formed in the side wall of the upper part of the first section of hydrogenation reactor 2 and is communicated with an inlet of the first section of oil-gas separator 5, a conical partition plate 14 is arranged near the material outlet 13, and inert ceramic balls are filled around the conical partition plate 14; the upper part of one hydrogenation reactor 2 is provided with a counterweight section (as shown in fig. 4) composed of inert ceramic balls.

The bottom material outlet of the first-stage oil-gas separator 5 is provided with two branch pipelines, one of which is communicated with the top inlet of the second-stage pre-hydrogenation reactor 3, and the other is communicated with the bottom raw material inlet of the first-stage hydrogenation reactor 2, and is used for returning part of the separated materials into the first-stage hydrogenation reactor 2 for circular reaction; and a top gas outlet of the first-stage oil-gas separator 5 is communicated with a first-stage recycle hydrogen compressor 10 for compressing and recycling hydrogen.

The second-stage pre-hydrogenation reactor 3 and the second-stage main hydrogenation reactor 4 are both fixed bed hydrogenation reactors. A heater 6 is arranged between the second-stage pre-hydrogenation reactor 3 and the second-stage main hydrogenation reactor 4 and is used for ensuring that the material entering the second-stage main hydrogenation reactor 4 meets the requirement of reaction temperature. An outlet of the heater 6 is communicated with a top inlet of the second-stage main hydrogenation reactor 4, a bottom outlet of the second-stage main hydrogenation reactor 4 is communicated with a second-stage oil-gas separator 7, a bottom outlet of the second-stage oil-gas separator 7 is communicated with an inlet of the stabilizing tower 8, a top outlet of the second-stage oil-gas separator 7 is communicated with a second-stage recycle hydrogen compressor 11, and an outlet of the second-stage recycle hydrogen compressor 11 is communicated with a top inlet of the second-stage pre-hydrogenation reactor 3.

The bottom outlet of the stabilizer 8 is communicated with the inlet of the fractionating tower 9, the top outlet of the stabilizer 8 outputs dry gas, the top outlet of the fractionating tower 8 outputs mixed dimethylbenzene, the middle outlet outputs mixed trimethylbenzene, and the bottom outlet outputs mixed tetramethylbenzene.

Example 2

First, the components of the poor cracking carbon nine used in the embodiments of the present application are described, which are specifically shown in table 1 below:

TABLE 1 compositions of poor cracking carbon nine

Cyclopentadiene, methylcyclopentadiene, dicyclopentadiene, methyldicyclopentadiene and dimethylcyclopentadiene in Table 1 are components which easily self-polymerize and are components which easily generate a gum.

The embodiment provides a method for producing solvent oil by poor-quality cracking carbon nine hydrogenation, which is performed by using the device for producing solvent oil by poor-quality cracking carbon nine hydrogenation provided in embodiment 1, and comprises the following steps:

feeding the filtered poor-quality cracking carbon nine raw material (the colloid content is 1500mg/100ml) into a degumming tower 1 to remove the colloid, then feeding the filtered poor-quality cracking carbon nine raw material and hydrogen into a first-stage hydrogenation reactor 2, and carrying out first-stage hydrogenation reaction in the first-stage hydrogenation reactor 2 by using a reduction state catalyst;

inputting a first-stage hydrogenation reaction product from a first-stage hydrogenation reactor 2 into a first-stage oil-gas separator 5 for first oil-gas separation, inputting a liquid product into a second-stage pre-hydrogenation reactor 3 for second-stage pre-hydrogenation reaction, inputting gas into a first-stage circulating hydrogen compressor 10 for compression, and returning the gas to the first-stage hydrogenation reactor 2 or inputting the gas into the second-stage pre-hydrogenation reactor 3;

the first-stage liquid product is subjected to a second-stage pre-hydrogenation reaction in a second-stage pre-hydrogenation reactor 3 by using a vulcanized catalyst, the second-stage pre-hydrogenation reaction liquid product is heated by a heater 6 and then is input into a second-stage main hydrogenation reactor 4, and a hydrofining reaction is carried out under the action of a hydrofining catalyst;

inputting the product of the hydrofining reaction into a two-section oil-gas separator 7 for second oil-gas separation, inputting the liquid product into a stabilizing tower 8, and then inputting the liquid product into a fractionating tower 9 for fractionation to obtain solvent oil including mixed xylene, mixed trimethylbenzene and mixed tetramethylbenzene; the gas is input into a second-stage recycle hydrogen compressor 11 to be compressed and then returns to a second-stage pre-hydrogenation reactor 3.

The reduction catalyst is a nickel-based hydrogenation catalyst and comprises an active component, an auxiliary agent and a carrier, wherein the active component is Ni, the auxiliary agent is Mg, Mo, Zn and Li, and the carrier is made of macroporous Al₂O₃Mixing with metal salt solution of an auxiliary agent, molding, and roasting at 900 ℃; in the reduction catalyst, the content of nickel oxide is 32 percent; the sulfidized catalyst takes alumina as a carrier, takes Mo and Ni in an oxidation state as active metals and vanadium as an auxiliary metal, wherein the active metals account for 11 percent of the total mass of the sulfidized catalyst, and the content of the auxiliary metal accounts for 2 percent of the total mass of the sulfidized catalyst; the hydrofining catalyst takes alumina as a carrier, Mo and Ni in an oxidation state as active metals and vanadium as an auxiliary metal, wherein the active metals account for 28 percent of the total mass of the hydrofining catalyst, and the content of the auxiliary metal accounts for 0.2 percent of the total mass of the hydrofining catalyst.

The preparation method of the reduced catalyst comprises the following steps: loading a saturated salt solution of nickel into a catalyst carrier under a vacuum state by the carrier, and then discharging moisture in the nickel salt through reduced pressure evaporation to obtain a semi-finished product of the catalyst containing high-concentration nickel salt; controlling the furnace temperature of the semi-finished product in a roasting furnace to be 450 ℃ so that the nickel salt is completely converted into nickel oxide; and then heating the catalyst in a reactor under the atmosphere of hydrogen and nitrogen mixed gas with the hydrogen mass content of 25%, heating from the normal temperature to 600 ℃, keeping the temperature constant for 6 hours, then cooling to 25-35 ℃, pre-wetting the catalyst by using naphtha without containing aromatic hydrocarbon and unsaturated hydrocarbon, adding 11% of carbon disulfide or dimethyl disulfide into the naphtha after the pre-wetting of the catalyst is finished, and circulating for 4-8 hours.

The reaction temperature of the first-stage hydrogenation reaction is 40 ℃, the pressure is 3.5MPa, and the hydrogen-oil ratio is 600;

the reaction temperature of the two-stage pre-hydrogenation reaction is 150 ℃, the pressure is 3.5MPa, and the hydrogen-oil ratio is 600;

the reaction temperature of the hydrofining reaction is 300 ℃, the pressure is 3.5MPa, and the hydrogen-oil ratio is 600.

Example 3

The embodiment provides a method for producing solvent oil by poor-quality cracking and carbon nine hydrogenation, which is performed by using the device for producing solvent oil by poor-quality cracking and carbon nine hydrogenation provided by the embodiment 1, and comprises the following steps:

feeding the filtered poor-quality cracking carbon nine raw material into a degumming tower 1 to remove colloid, then feeding the poor-quality cracking carbon nine raw material and hydrogen into a first-stage hydrogenation reactor 2, and carrying out a first-stage hydrogenation reaction in the first-stage hydrogenation reactor 2 by using a reduction state catalyst;

inputting a first-stage hydrogenation reaction product from the first-stage hydrogenation reactor 2 into a first-stage oil-gas separator 5 for first oil-gas separation, inputting a liquid product into the second-stage pre-hydrogenation reactor 3 for second-stage pre-hydrogenation reaction, inputting gas into a first-stage circulating hydrogen compressor 10 for compression, and then returning the gas to the first-stage hydrogenation reactor 2 or inputting the gas into the second-stage pre-hydrogenation reactor 3;

The reduction catalyst is a nickel-based hydrogenation catalyst and comprises an active component, an auxiliary agent and a carrier, wherein the active component is Ni, the auxiliary agent is Mg, Mo, Zn and Li, and the carrier is made of macroporous Al₂O₃Mixing with metal salt solution of an auxiliary agent, molding, and roasting at 750 ℃; in the reduction catalyst, the content of nickel oxide is 26 percent; the sulfidized catalyst takes alumina as a carrier, takes Mo and Ni in an oxidation state as active metals and vanadium as an auxiliary metal, wherein the active metals account for 12 percent of the total mass of the sulfidized catalyst, and the content of the auxiliary metal accounts for 0.5 percent of the total mass of the sulfidized catalyst; the hydrofining catalyst takes alumina as a carrier, Mo and Ni in an oxidation state as active metals and vanadium as an auxiliary metal, wherein the active metals account for 24 percent of the total mass of the hydrofining catalyst, and the content of the auxiliary metal accounts for 0.2 percent of the total mass of the hydrofining catalyst.

The preparation method of the reduced catalyst comprises the following steps: loading a saturated salt solution of nickel into a catalyst carrier under a vacuum state by the carrier, and then discharging moisture in the nickel salt through reduced pressure evaporation to obtain a semi-finished product of the catalyst containing high-concentration nickel salt; controlling the furnace temperature of the semi-finished product in a roasting furnace to 400 ℃ to completely convert nickel salt into nickel oxide; and then heating the catalyst in a reactor under the atmosphere of hydrogen and nitrogen mixed gas with the hydrogen mass content of 25%, raising the temperature to 600 ℃ from normal temperature, keeping the temperature constant for 4 hours, then cooling to 25-35 ℃, pre-wetting the catalyst by using naphtha which does not contain aromatic hydrocarbon and unsaturated hydrocarbon, adding 12% of carbon disulfide or dimethyl disulfide into the naphtha after the catalyst is pre-wetted, and circulating for 4-8 hours.

The reaction temperature of the first-stage hydrogenation reaction is 40 ℃, the pressure is 3.5MPa, and the hydrogen-oil ratio is 800;

the reaction temperature of the two-stage pre-hydrogenation reaction is 120 ℃, the pressure is 3.5MPa, and the hydrogen-oil ratio is 800;

the reaction temperature of the hydrofining reaction is 380 ℃, the pressure is 3.5MPa, and the hydrogen-oil ratio is 800.

Example 4

The reduction catalyst is a nickel-based hydrogenation catalyst and comprises an active component, an auxiliary agent and a carrier, wherein the active component is Ni, the auxiliary agent is Mg, Mo, Zn and Li, and the carrier is made of macroporous Al₂O₃Mixing with metal salt solution of an auxiliary agent, molding, and roasting at 900 ℃; in the reduction catalyst, the content of nickel oxide is 32%; the sulfidized catalyst takes alumina as a carrier, takes Mo and Ni in oxidation state as active metals and zirconium as an auxiliary metal, wherein the active metals account for 10 percent of the total mass of the sulfidized catalyst, and the content of the auxiliary metal accounts for the sulfidized catalyst0.3% of the total mass of the agent; the hydrofining catalyst takes alumina as a carrier, and takes Mo and Co active metals in an oxidation state and zirconium as auxiliary metal, wherein the active metal accounts for 28 percent of the total mass of the hydrofining catalyst, and the content of the auxiliary metal accounts for 0.2 percent of the total mass of the hydrofining catalyst.

The preparation method of the reduced catalyst comprises the following steps: loading a saturated salt solution of nickel into a catalyst carrier under a vacuum state by the carrier, and then discharging moisture in the nickel salt through reduced pressure evaporation to obtain a semi-finished product of the catalyst containing high-concentration nickel salt; controlling the temperature of the semi-finished product in a roasting furnace to 380 ℃ to completely convert nickel salt into nickel oxide; and then heating the catalyst in a reactor under the atmosphere of hydrogen and nitrogen mixed gas with the hydrogen mass content of 50%, heating from the normal temperature to 600 ℃, keeping the temperature constant for 8 hours, then cooling to 25-35 ℃, pre-wetting the catalyst by using naphtha without containing aromatic hydrocarbon and unsaturated hydrocarbon, adding 12% of carbon disulfide or dimethyl disulfide into the naphtha after the pre-wetting of the catalyst is finished, and circulating for 6 hours.

The reaction temperature of the first-stage hydrogenation reaction is 40 ℃, the pressure is 5.5MPa, and the hydrogen-oil ratio is 700;

the reaction temperature of the two-stage pre-hydrogenation reaction is 200 ℃, the pressure is 5.5MPa, and the hydrogen-oil ratio is 700;

the reaction temperature of the hydrofining reaction is 350 ℃, the pressure is 5.5MPa, and the hydrogen-oil ratio is 700.

Comparative example 1

And feeding by using a conventional degumming tower.

The feed inlet of the conventional degumming tower is arranged in the middle of the tower, and only a single raw material is designed, and only one feed inlet is reserved. The feed inlet is arranged in the middle of the tower, the carbon nine has less reflux space in the tower, and the effluent can carry a certain amount of colloid; one feed inlet only degumps raw materials with relatively stable properties, once the raw materials are well matched with the original designed raw materials, some useful components are discharged along with materials at the bottom of the tower, and the yield is reduced; the raw material difference is higher than the effluent colloid in the raw material design process, and if the colloid is qualified, the effluent quantity at the bottom of the tower needs to be increased.

In the application, the material inlet is arranged at the lower part of the tower, so that the reflux height of the material in the tower is increased, and the colloid content of the effluent is ensured to be very low; three material flow inlets are arranged to meet the requirements of raw materials with different qualities;

after degumming, the raw gum content obtained in example 2 was reduced to 10mg/100ml, whereas the gum content of comparative example 1 was 400mg/100 ml.

After degumming in the manner of comparative example 1, the feedstock did not meet the hydrotreating requirements and could not be used.

Comparative example 2

Unlike example 2, the hydrogen to oil ratio was 200.

The inlet temperature of the first hydrogenation reactor 2 is controlled to be 40 ℃, and the temperature rise distribution of the reactor, the product quality and the coking condition of the device are monitored at any time. The results are shown in table 2 below:

TABLE 2 comparison of results

Comparative example 3

In contrast to example 2, hydrogen and the feedstock were mixed and fed into the first hydrogenation reactor 2 through one inlet.

Comparative example 4

Unlike example 2, the gas inlet of the first hydrogenation reactor section 2 is not connected to the gas distributor 12.

Comparative example 5

Unlike the embodiment 2, the gas inlet of the first hydrogenation reactor 2 is not connected to the gas distributor 12, but is connected to a straight pipe with a plurality of holes on the upper part for gas distribution.

The temperature difference and the colloid of comparative example 2, comparative example 3, comparative example 4 and comparative example 5 were compared, and the results are shown in table 3 below:

TABLE 3 temperature differential and gum comparison results

Comparative example 6

Different from the embodiment 2, the upper part of one hydrogenation reactor 2 is not provided with a counterweight section consisting of inert ceramic balls.

Because no matter is arranged on the upper part of the reactor to press the catalyst, the catalyst flows out from the material outlet and enters the gas-liquid separation tank, and finally, catalyst particles move to the circulating pump along with the material, so that the circulating pump is worn out.

Because the amount is too small, (the filling height of the top porcelain ball and the diameter of the reactor are 1:1, the upward force of the material is blocked by the cone because the internal structure of the reactor is in the cone shape) the catalyst does not flow out of the reactor in a large amount, but the catalyst moves up and down in the reactor, the particles rub with each other, the particles of the catalyst are pulverized, and the particles enter the second-stage hydrogenation reactor along with oil products, so that a plugging device at the top of the second-stage hydrogenation reactor is forced to stop working.

Comparative example 7

Unlike example 2, no secondary prehydrogenation reactor 3 is provided.

Example 2 and comparative example 7 reaction conditions the comparative example is shown in table 4 below:

TABLE 4 comparison of the reaction conditions

The yields of the products of examples 2, 3 and 4 and other index data are shown in table 5 below:

TABLE 5 product index

As can be seen from Table 5 above, the product obtained by the present application has excellent properties and high yield. Since the comparative examples have various problems, the products obtained by the comparative examples have no comparative value and are not listed in the application.

Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.

Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims

1. The utility model provides a device of nine hydrogenation production solvent oil of cracking carbon of inferior quality which characterized in that includes:

the degumming tower is used for pretreating inferior cracked carbon nine;

the fractionating tower is used for fractionating to obtain a target product;

2. The device for producing the solvent oil by hydrogenating the carbon nine through the poor-quality cracking is characterized in that the lower part of the degumming tower is provided with 3 feed inlets with different heights, and each feed inlet is different by 2 tower plates.

3. The apparatus for producing solvent oil by hydrogenation of carbon nine through poor cracking according to claim 1, wherein the first-stage hydrogenation reactor is a hot-wall bubbling bed reactor;

4. The device for producing the solvent oil by hydrogenating the carbon nine through the poor-quality cracking according to claim 3, wherein an outlet of the first section of the hydrogenation reactor is arranged on the side wall of the upper part, a conical partition plate is arranged at the outlet of the first section of the hydrogenation reactor, and inert ceramic balls are filled around the conical partition plate;

the upper part of the first segment of the hydrogenation reactor is provided with a counterweight segment consisting of inert ceramic balls.

5. The apparatus for producing solvent oil by hydrogenation of carbon nine through poor cracking according to claim 1, wherein the two-stage pre-hydrogenation reactor and the two-stage main hydrogenation reactor are both fixed bed hydrogenation reactors.

6. The device for producing the solvent oil by hydrogenating the carbon nine through poor cracking according to any one of claims 1 to 5, wherein a heater is arranged between the secondary pre-hydrogenation reactor and the secondary main hydrogenation reactor;

7. A method for producing solvent oil by hydrogenating poor-quality cracked carbon nine, which is characterized by being carried out by using the device for producing solvent oil by hydrogenating poor-quality cracked carbon nine disclosed by any one of claims 1-6, and comprising the following steps of:

8. The method for producing the solvent oil by hydrogenating the carbon nine through poor cracking according to claim 7, wherein the reduced catalyst is a nickel-based hydrogenation catalyst and comprises an active componentThe active component is Ni, the auxiliary agent is one or more of Mg, Mo, Zn and Li, and the carrier is made of macroporous Al₂O₃Mixing with metal salt solution of assistant, molding, and roasting at 600-1200 deg.C; in the reduction catalyst, the content of nickel oxide is 25-65%; the sulfidation catalyst takes alumina as a carrier, one or more of W, Mo and Ni in an oxidation state as an active metal, and one or more of vanadium, zirconium or lanthanide series metal as an auxiliary metal, wherein the active metal accounts for 5-15% of the total mass of the sulfidation catalyst, and the content of the auxiliary metal accounts for 0.5-5% of the total mass of the sulfidation catalyst; the hydrofining catalyst takes alumina as a carrier, one or more of W, Mo and Co in an oxidation state as active metal, and one or more of vanadium, zirconium or lanthanide series metal as auxiliary metal, wherein the active metal accounts for 15-45% of the total mass of the hydrofining catalyst, and the content of the auxiliary metal accounts for 0.1-0.5% of the total mass of the hydrofining catalyst.

9. The method for producing the solvent oil by hydrogenating the carbon nine through poor cracking according to claim 7, wherein the preparation method of the reduced catalyst comprises the following steps:

then, the catalyst is heated to 600 ℃ from normal temperature for 4-12 hours under the atmosphere of hydrogen and nitrogen mixed gas with the hydrogen mass content of 5-75% in a reactor, then the temperature is reduced to 25-35 ℃, then the catalyst is pre-moistened by naphtha without aromatic hydrocarbon and unsaturated hydrocarbon, 0.5-15% of carbon disulfide or dimethyl disulfide is added into the naphtha after the catalyst is pre-moistened, and the circulation is carried out for 4-8 hours.

10. The method for producing solvent oil by hydrogenating carbon nine through poor quality cracking according to any one of claims 7 to 9, wherein the reaction temperature of the first-stage hydrogenation reaction is 35 to 150 ℃, the pressure is 2.0 to 6.0MPa, and the hydrogen-oil ratio is 600-;

the reaction temperature of the hydrofining reaction is 270-380 ℃, the pressure is 2.0-6.0MPa, and the hydrogen-oil ratio is 600-800.