CN112221519A - Ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst, and preparation method and application thereof - Google Patents

Ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst, and preparation method and application thereof Download PDF

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CN112221519A
CN112221519A CN202011138367.1A CN202011138367A CN112221519A CN 112221519 A CN112221519 A CN 112221519A CN 202011138367 A CN202011138367 A CN 202011138367A CN 112221519 A CN112221519 A CN 112221519A
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pressure liquid
catalyst
ethylene cracking
cracking tar
phase hydrogenation
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CN112221519B (en
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王冬娥
田志坚
马怀军
曲炜
徐刚
张亚胜
潘多峰
崔军
杨亚奇
宋营来
史小松
米川
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Karamay Xianneng Kechuang Heavy Oil Development Co ltd
Dalian Institute of Chemical Physics of CAS
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Karamay Xianneng Kechuang Heavy Oil Development Co ltd
Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/06—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of high-pressure liquid-phase hydrogenation catalysts, in particular to a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar, a preparation method and application thereof, wherein the high-pressure liquid-phase hydrogenation catalyst for the ethylene cracking tar is obtained by the following method: dissolving a molybdenum source, a cobalt source or a nickel source and a sulfur source in a solvent with the boiling point higher than 190 ℃ to obtain a transparent solution; and after the crystallization of the transparent solution is finished, separating and washing the product, and then dispersing the product into an oily solvent to obtain the product. The ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is a high-dispersion nano cobalt or nickel modified molybdenum sulfide hydrogenation catalyst, and has high dispersibility and simultaneously exposes rich hydrogenation active sites; when the catalyst is used for high-pressure liquid-phase hydrogenation of ethylene cracking tar, the catalyst can be highly dispersed in a high-pressure hydrogenation system, and the rapid hydrogenation conversion of all components, especially heavy-component asphaltene in the ethylene cracking tar is realized, so that the coking inactivation of the catalyst is avoided, and no coking phenomenon occurs.

Description

Ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst, and preparation method and application thereof
Technical Field
The invention relates to the technical field of high-pressure liquid-phase hydrogenation catalysts, in particular to an ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst and a preparation method thereof, and further comprises an application of the ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst in the hydrogenation conversion of ethylene cracking tar.
Background
The ethylene tar is a high-temperature condensation product of a raw material and a product of an ethylene cracking raw material in a steam cracking process, the main component of the ethylene tar is an aromatic hydrocarbon compound, the main component is a mixture of polycyclic aromatic hydrocarbons with more than 90 percent of aromatic hydrocarbon, the side chain is short, the carbon-hydrogen ratio is high, the asphaltene content is high, the ash content is low, the heavy metal content is low, the composition of the ethylene tar is different along with different cracking raw materials and cracking conditions, and the yield is 15 to 20 percent of the ethylene yield. The ethylene tar is used for producing carbon black in China, most of the ethylene tar is mainly used as fuel oil to be burnt, however, the ethylene tar is not easy to burn, has low heat value, is easy to generate black smoke and coking during burning, has low utilization degree, causes resource waste and pollutes the environment.
From the present situation, the comprehensive utilization of ethylene tar in China just starts, and a small part of ethylene tar is used for extracting naphthalene and methylnaphthalene or preparing asphalt, needle coke and the like. The high-efficiency processing of ethylene cracking tar has the disadvantages of high overall utilization difficulty, low utilization rate and low economic benefit. Patent document No. 200610119517.8 discloses an integrated process for processing ethylene tar to extract industrial naphthalene (refined naphthalene), α -methylnaphthalene, and β -methylnaphthalene from a fraction of the ethylene tar at a temperature of 300 ℃ or lower. Therefore, how to fully and reasonably utilize the part of resources to generate the best economic benefit is an important subject to be solved urgently in the ethylene post-processing industry at home and abroad at present.
The gasoline and diesel oil is produced by using ethylene cracking tar as a raw material and adopting a hydrogenation light process, so that obvious economic and social benefits can be generated, and the current situation of energy shortage in China can be effectively relieved. The research on the hydrogenation technology of ethylene cracking tar is less, and the method mainly comprises a hydrogenation catalyst and a hydrogenation process. The document "hydrogenation of heavy components of ethylene cracking tar to produce diesel blending components" (Lizhong, Qilu petrochemical 2015, 43 (4): 253-255) reports a process for producing diesel blending components by hydrofining the heavy components of ethylene cracking tar (230-350 ℃) by using an alumina-supported CoMo hydrogenation catalyst.
The literature, "experimental research on gasoline preparation by hydrogenation of ethylene tar" (Liujian, modern chemical engineering, 2019,39 (2), 189-191) utilizes MoO as an active component3NiO or CoO and P2O5The carrier is a hydrogenation catalyst composed of active alumina, modified clay and zeolite, and the ethylene tar is hydrorefined by heating with a three-section heating furnace on a fixed bed device to obtain high-quality gasoline and diesel fuel. At present, the catalyst adopted by the ethylene cracking tar hydrogenation technology is mainly a supported catalyst.
Patent documents with application numbers 201710895230.2, 201710895330.5, 201710895344.7, 201710895356.X, 201810529518.2, 201810529547.9 and 201810529550.0 disclose a series of catalysts for producing fuel oil by hydrogenating tar, wherein the series of catalysts comprise an active component, an auxiliary agent and a carrier. The active component is selected from any one of Ni, Rh, Co, Mo and W, the auxiliary agent is one of alkali metal, alkaline earth metal, Fe, Zn, Sb, Bi and Cu, and the carrier is alumina or mordenite. The preparation process of the catalyst comprises the operations of active component impregnation, drying, roasting, auxiliary agent impregnation, drying, roasting and the like, and the preparation process of the catalyst needs high-temperature roasting and has various operation steps.
The literature, "study of ethylene tar whole-fraction hydrotreating process" (guangzhou chemical, 2017, 45 (21), 43-45) performs one-time shallow hydrofining on ethylene tar whole-fraction to obtain a product which can be used as a petroleum sulfonate raw material, and high-quality gasoline and diesel cannot be obtained due to insufficient hydrogenation depth.
Patent application No. 200810228387.00 discloses a process for producing gasoline and diesel oil fractions by passing the light fraction of ethylene tar through a hydrogenation protection reaction zone, a hydrorefining reaction zone and a hydrocracking reaction zone in this order, while the heavy fraction is used only as a general-purpose carbon fiber asphalt feedstock.
Patent document No. 201711325715.4 discloses a start-up method of an ethylene tar ebullated bed-fixed bed combined process, in which a fixed bed hydrogenation device is vulcanized, and then the material obtained in the reaction process of the fixed bed hydrogenation device is used as vulcanized oil in the start-up process of the ebullated bed hydrogenation device. The hydrogenation process of the ethylene tar mostly adopts a formed supported catalyst and a fixed bed reaction process, and most ethylene tar raw materials adopted in the research are hydrofining reaction of components with the temperature below 350 ℃ cut by once rectification.
In conclusion, in the prior art, only light components in the ethylene cracking tar can be hydrogenated, and the raw materials such as the ethylene cracking tar and the like have high contents of heavy components such as asphaltene and the like. Therefore, hydrofinishing of asphaltene components above 350 ℃ in fixed bed hydrogenation processes has been reported to be prone to plugging of the reaction bed and to deactivation of the catalyst. Therefore, the prior art is not suitable for efficiently realizing the production of high-quality gasoline and diesel oil by hydrogenating and lightening the whole fraction of the ethylene tar in one step.
Disclosure of Invention
The invention provides an ethylene cracking tar high-pressure liquid phase hydrogenation catalyst, a preparation method and application, overcomes the defects of the prior art, and can effectively solve the problems of low utilization rate of ethylene tar raw materials, catalyst inactivation and reactor blockage caused by high content of asphaltene components in the raw materials in the ethylene cracking tar hydrogenation technology.
One of the technical schemes of the invention is realized by the following measures: a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar is obtained by the following steps:
(1) dissolving a molybdenum source, a cobalt source or a nickel source and a sulfur source in a solvent with the boiling point higher than 190 ℃ to obtain a transparent solution; forming a transparent solution in which the atomic ratio of Co to Mo is 0.001 to 0.5, or the atomic ratio of Ni to Mo is 0.001 to 0.5;
(2) carrying out crystallization reaction on the transparent solution obtained in the step (1) at the temperature of 120-190 ℃ for 3-72 hours;
(3) after the crystallization reaction is finished, separating and washing the product, and then dispersing the product into an oily solvent (benzene or toluene and the like) to obtain the cobalt or nickel modified nano MoS2Catalyst slurry, namely a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the molybdenum source is one or a mixture of more than two of ammonium heptamolybdate, sodium molybdate, molybdic acid, molybdenum oxide and phosphomolybdic acid; the sulfur source is one or more of thiourea, thioacetamide, cysteine and glutathione with reducibility.
The cobalt source is one or a mixture of more than two of cobalt chloride, cobalt nitrate and cobalt acetate; or the nickel source is one or a mixture of more than two of nickel chloride, nickel nitrate and nickel acetate.
In the above transparent solution, the atomic ratio of Co to Mo is preferably 0.1 to 0.3, or the atomic ratio of Ni to Mo is preferably 0.1 to 0.3.
In the step (1), the solvent with the boiling point higher than 190 ℃ is one or a mixture of more than two of glycol, diethylene glycol and glycerol.
The crystallization reaction temperature is preferably 140 ℃ to 180 ℃; the crystallization reaction time is preferably 24 hours to 48 hours.
The crystallization mode can adopt the common crystallization modes such as oven of a closed system, electric furnace and the like for heating crystallization, microwave heating crystallization, open system heating crystallization and the like.
The second technical scheme of the invention is realized by the following measures: a preparation method of a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar comprises the following steps:
(1) dissolving a molybdenum source, a cobalt source or a nickel source and a sulfur source in a solvent with the boiling point higher than 190 ℃ to obtain a transparent solution; forming a transparent solution in which the atomic ratio of Co to Mo is 0.001 to 0.5, or the atomic ratio of Ni to Mo is 0.001 to 0.5;
(2) carrying out crystallization reaction on the transparent solution obtained in the step (1) at the temperature of 120-190 ℃ for 3-72 hours;
(3) after the crystallization reaction is finished, separating and washing the product, and then dispersing the product into an oily solvent (benzene or toluene and the like) to obtain the cobalt or nickel modified nano MoS2Catalyst slurry, namely a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar.
The following is further optimization or/and improvement of the second technical scheme of the invention:
the molybdenum source is one or a mixture of more than two of ammonium heptamolybdate, sodium molybdate, molybdic acid, molybdenum oxide and phosphomolybdic acid; the sulfur source is one or more of thiourea, thioacetamide, cysteine and glutathione with reducibility.
The cobalt source is one or a mixture of more than two of cobalt chloride, cobalt nitrate and cobalt acetate; or the nickel source is one or a mixture of more than two of nickel chloride, nickel nitrate and nickel acetate.
In the above transparent solution, the atomic ratio of Co to Mo is preferably 0.1 to 0.3, or the atomic ratio of Ni to Mo is preferably 0.1 to 0.3.
In the step (1), the solvent with the boiling point higher than 190 ℃ is one or a mixture of more than two of glycol, diethylene glycol and glycerol.
The crystallization reaction temperature is preferably 140 ℃ to 180 ℃; the crystallization reaction time is preferably 24 hours to 48 hours.
The third technical scheme of the invention is realized by the following measures: an application of a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar in the hydrogenation conversion of the ethylene cracking tar.
The third technical scheme of the invention is further optimized or/and improved as follows:
the ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst is used for three ethylene cracking tar high-pressure liquid-phase hydrogenation reactions, namely a kettle reaction, a suspension bed reaction and a gas lift reaction.
The ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is a high-dispersion nano cobalt or nickel modified molybdenum sulfide hydrogenation catalyst, and has high dispersibility and simultaneously exposes rich hydrogenation active sites; when the catalyst is used for high-pressure liquid-phase hydrogenation of ethylene cracking tar, the catalyst can be highly dispersed in a high-pressure hydrogenation system, and the rapid hydrogenation conversion of all components, especially heavy-component asphaltene in the ethylene cracking tar is realized, so that the coking inactivation of the catalyst is avoided, no coking phenomenon occurs, and the hydrogenation activity of the high-pressure liquid-phase hydrogenation catalyst of the ethylene cracking tar is better.
Drawings
FIG. 1 is an XRD spectrum of a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar, commercial product MoS, in example 9 of the present invention2As a control.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar according to example 9 of the present invention, and a commercial MoS2As a control.
FIG. 3 is a transmission electron microscope (HRTEM) photograph of the catalyst for high-pressure liquid-phase hydrogenation of ethylene cracking tar in example 9 of the present invention, commercial product MoS2As a control.
In FIG. 1 of the drawingsWherein A represents the ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst in the embodiment 9 of the invention, and B represents the commercial product MoS2A catalyst.
In FIG. 2, the left image represents the product MoS2Catalyst, the right figure represents the high pressure liquid phase hydrogenation catalyst for ethylene cracking tar according to the invention in example 9.
In FIG. 3, the upper diagram represents the product MoS2Catalyst, the lower diagram represents the high pressure liquid phase hydrogenation catalyst for ethylene cracking tar according to the invention, described in example 9.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is prepared by the following preparation method:
(1) dissolving a molybdenum source, a cobalt source or a nickel source and a sulfur source in a solvent with the boiling point higher than 190 ℃ to obtain a transparent solution; forming a transparent solution in which the atomic ratio of Co to Mo is 0.001 to 0.5, or the atomic ratio of Ni to Mo is 0.001 to 0.5;
(2) carrying out crystallization reaction on the transparent solution obtained in the step (1) at the temperature of 120-190 ℃ for 3-72 hours;
(3) after the crystallization reaction is finished, separating and washing the product, and then dispersing the product into an oily solvent to obtain the cobalt or nickel modified nano MoS2Catalyst slurry, namely a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar.
The high-pressure liquid-phase hydrogenation reaction is one of ideal methods for realizing the hydrogenation saturation and lightening of asphaltene, the full fraction of ethylene cracking tar can be subjected to hydrogenation conversion through one-step reaction, the process generally comprises the steps of uniformly mixing a dispersion type catalyst and raw oil to form slurry, then feeding the slurry and high-pressure hydrogen into a reactor together to perform catalytic hydrocracking reaction under the hydrogen condition, and finally obtaining the high-quality light gasoline and diesel oil.
The high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar provided by the invention can realize the technology for producing high-quality gasoline and diesel oil by full-component hydrogenation of ethylene cracking tar in one step, and can avoid the inactivation of the catalyst and the blockage of a bed layer in the reaction process.
Example 2: the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is prepared by the following preparation method:
(1) dissolving a molybdenum source, a cobalt source or a nickel source and a sulfur source in a solvent with the boiling point higher than 190 ℃ to obtain a transparent solution; forming a transparent solution in which the atomic ratio of Co to Mo is 0.001 or 0.5, or the atomic ratio of Ni to Mo is 0.001 or 0.5;
(2) carrying out crystallization reaction on the transparent solution obtained in the step (1) at the temperature of 120 ℃ or 190 ℃ for 3 hours or 72 hours;
(3) after the crystallization reaction is finished, separating and washing the product, and then dispersing the product into an oily solvent to obtain the cobalt or nickel modified nano MoS2Catalyst slurry, namely a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar.
Example 3: as optimization of the above embodiment, the molybdenum source is one or a mixture of more than two of ammonium heptamolybdate, sodium molybdate, molybdic acid, molybdenum oxide and phosphomolybdic acid; the sulfur source is one or more of thiourea, thioacetamide, cysteine and glutathione with reducibility.
Example 4: as optimization of the embodiment, the cobalt source is one or a mixture of more than two of cobalt chloride, cobalt nitrate and cobalt acetate; or the nickel source is one or a mixture of more than two of nickel chloride, nickel nitrate and nickel acetate.
Example 5: as optimization of the above embodiment, in the transparent solution, the atomic ratio of Co to Mo is preferably 0.1 to 0.3, or the atomic ratio of Ni to Mo is preferably 0.1 to 0.3.
Example 6: as optimization of the above embodiment, in the step (1), the solvent with the boiling point higher than 190 ℃ is one or a mixture of more than two of glycol, diethylene glycol and glycerol.
Example 7: as optimization of the above embodiment, the crystallization reaction temperature is preferably 140 ℃ to 180 ℃; the crystallization reaction time is preferably 24 hours to 48 hours.
In the preparation method of the invention;
in the step (2), the crystallization mode can adopt common crystallization modes such as an oven of a closed system, an electric furnace and the like for heating crystallization, microwave heating crystallization, open system heating crystallization and the like.
In the step (3), the product separation can adopt the existing known product separation methods such as polar solvent settling separation, reduced pressure suction filtration separation, centrifugal separation and the like, the product washing adopts deionized water and ethanol for washing, then benzene, toluene and other oily solvents are used for washing, the oil solubility of the catalyst is maintained, the washed catalyst is directly dispersed into the oily solvent without drying, and the cobalt or nickel modified nano MoS is obtained2A catalyst slurry.
In the step (3), benzene or toluene is adopted as the oily solvent.
Example 8: the application of the high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar in the above embodiment in the hydrogenation conversion of ethylene cracking tar can be performed according to the following method:
mixing an ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst with ethylene cracking tar to perform high-pressure liquid-phase hydrogenation reaction, wherein the mixing mode can be pre-mixed and then added into a reactor or added into the reactor and then mixed; the mass percentage of the catalyst (the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst) is 0.01-5.0%, preferably 1.0-2.0%; the reaction temperature is 300 ℃ to 480 ℃, preferably 420 ℃ to 450 ℃; the reaction pressure is from 10MPa to 25MPa, preferably from 14MPa to 18 MPa.
Example 9: the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is prepared by the following preparation method:
1mmol of ammonium heptamolybdate, 21 mmol of L-cysteine and 0.14mmol of cobalt chloride are dissolvedThe Co/Mo atomic ratio in 60 ml of ethylene glycol was 0.02. Heating in water bath at 60 deg.C, stirring for 1 hr to obtain red transparent solution, transferring to 100ml PTFE liner, placing into stainless steel hydrothermal kettle, and sealing. And (4) transferring the hydrothermal kettle into an oven for crystallization reaction at 120 ℃ for 72 hours, and naturally cooling to room temperature. Suction filtration, washing with deionized water and absolute ethyl alcohol three times respectively. Finally, after washing three times with toluene, the resulting Co-modified MoS was washed2The sample is dispersed in toluene solution to form 0.1g/ml catalyst slurry (i.e. the high pressure liquid phase hydrogenation catalyst for ethylene cracking tar according to the present invention, the same as in the subsequent examples), and stored for later use.
For comparison, commercial MoS was selected2And (6) performing characterization. XRD, SEM and HRTEM characterization of the two samples found that both products exhibited predominantly MoS2Crystal phase structure, but different from commercial MoS2Bulk multilayer stacked structure of (1), MoS prepared in example 9 of the invention2With enlarged interlamination (see fig. 1), nanoparticle size (see fig. 2), fewer number of stacked layers, and smaller lamella size (see fig. 3), as follows:
XRD (X-ray powder diffraction) is used for characterization of crystalline phase structure and interlayer spacing, and the result shows that the catalyst prepared in example 9 (black powder is MoS)2) The degree of crystallization is good, the calculated interlayer spacing is 0.98 nm, compared to the standard MoS2A significant increase in the interlayer spacing of 0.62 nm (see FIG. 1);
the particle size and morphology were characterized by SEM (scanning electron microscope) showing the MoS prepared in example 92The catalyst is spherical particles with a particle size of 30nm to 50nm (see fig. 2).
The layer spacing, the number of stacked layers, and the size of the lamella were characterized by HRTEM (high resolution transmission electron microscope), and the HRTEM photograph shows the MoS prepared in example 92Nanosheets with the length of the lamella dimension of 5nm to 10 nm, 3 to 5 stacked layers and the interlayer spacing expanded to 0.98 nm (see figure 3); the content of Co or Ni is characterized by ICP, and the result shows that the Co or Ni element is equivalent to the added amount.
The catalyst slurry prepared in example 9 of the present invention was cracked with ethyleneTar mixing, catalyst (Co modified MoS)2Sample, same as in subsequent examples) was added at 0.5 wt.%. In the suspension bed hydrogenation reaction, the reaction temperature is 300 ℃, the reaction pressure is 10MPa, the reaction lasts for 4 hours, and the hydrogenation activity is far higher than that of the commercial MoS2(see Table 1).
Example 10: the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is prepared by the following preparation method:
0.58 mmol of phosphomolybdic acid, 21 mmol of glutathione and 1.4mmol of cobalt nitrate were dissolved in 60 ml of diethylene glycol, the Co/Mo atomic ratio being 0.2. Ultrasonic dissolving for 0.5 hr to obtain red transparent solution, transferring to 100ml PTFE liner, placing in microwave reactor, sealing, performing thermal crystallization reaction with 160 deg.C microwave solvent for 36 hr, and naturally cooling to room temperature. Suction filtration, washing with deionized water and absolute ethyl alcohol three times respectively. Finally, after washing with toluene three times, Co-modified MoS will be obtained2The sample, dispersed in toluene solution to form 0.1g/ml catalyst slurry, and stored for use.
The catalyst slurry prepared in example 10 of the present invention was mixed with ethylene cracking tar in an amount of 1.0 wt.%. In the kettle type hydrogenation reaction, the reaction temperature is 350 ℃, the reaction pressure is 14MPa, the reaction is carried out for 4 hours, and the hydrogenation activity is far higher than that of the commercial MoS2(see Table 1).
Example 11: the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is prepared by the following preparation method:
7mmol of molybdic acid, 21 mmol of thioacetamide and 3.15mmol of cobalt acetate were dissolved in 60 ml of glycerol, the Co/Mo atomic ratio being 0.45. Stirring for 3 hours to form a red transparent solution, transferring the red transparent solution into a 100ml round-bottom flask, connecting the round-bottom flask with a condenser tube, heating the round-bottom flask in oil bath at 190 ℃ for crystallization reaction for 3 hours, and naturally cooling the round-bottom flask to room temperature. Suction filtration, washing with deionized water and absolute ethyl alcohol three times respectively. Finally, after washing with toluene three times, Co-modified MoS will be obtained2The sample, dispersed in toluene solution to form 0.1g/ml catalyst slurry, and stored for use.
The catalyst slurry prepared in example 11 of the present invention was mixed with ethylene cracking tar in an amount of catalyst added2.0 wt.%. In the gas-lift hydrogenation reaction, the reaction temperature is 400 ℃, the reaction pressure is 18MPa, the reaction is carried out for 4 hours, and the hydrogenation activity is far higher than that of the commercial MoS2(see Table 1).
Example 12: the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is prepared by the following preparation method:
7mmol of molybdenum oxide, 21 mmol of thiourea and 0.14mmol of nickel chloride were dissolved in 60 ml of ethylene glycol, the Ni/Mo atomic ratio being 0.02. Heating in 75 deg.C water bath, stirring for 1 hr to obtain red transparent solution, transferring to 100ml PTFE liner, placing into stainless steel hydrothermal kettle, and sealing. And (4) transferring the hydrothermal kettle into an oven for crystallization reaction at 140 ℃ for 48 hours, and naturally cooling to room temperature. Suction filtration, washing with deionized water and absolute ethyl alcohol three times respectively. Finally, after washing with toluene three times, Ni-modified MoS will be obtained2The sample, dispersed in toluene solution to form 0.1g/ml catalyst slurry, and stored for use.
The catalyst slurry prepared in example 12 of the present invention was mixed with ethylene cracking tar in an amount of 3.0 wt.%. In the gas-lift hydrogenation reaction, the reaction temperature is 430 ℃, the reaction pressure is 20 MPa, the reaction is carried out for 4 hours, and the hydrogenation activity is far higher than that of the commercial MoS2(see Table 1).
Example 13: the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is prepared by the following preparation method:
7mmol of sodium molybdate, 21 mmol of L-cysteine and 1.4mmol of nickel nitrate were dissolved in 60 ml of diethylene glycol, the Ni/Mo atomic ratio being 0.2. The solution was dissolved by ultrasonic for 1 hour to form a red transparent solution, which was transferred to a 100ml teflon liner, charged into a microwave synthesizer, and sealed. Heating the mixture by microwave at 180 ℃ for crystallization reaction for 12 hours, and naturally cooling the mixture to room temperature. Suction filtration, washing with deionized water and absolute ethyl alcohol three times respectively. Finally, after washing with toluene three times, Ni-modified MoS will be obtained2The sample, dispersed in toluene solution to form 0.1g/ml catalyst slurry, and stored for use.
The catalyst slurry prepared in example 13 of the present invention was mixed with ethylene cracking tar in an amount of 4.0 wt.%. In the kettle type hydrogenation reaction, the reaction temperature is 450 ℃, and the reaction pressure is 22 MPaThe hydrogenation activity is much higher than that of commercial MoS after reaction for 4 hours2(see Table 1).
Example 14: the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst is prepared by the following preparation method:
1mmol of ammonium molybdate, 21 mmol of glutathione and 3.15mmol of nickel acetate are dissolved in 60 ml of glycerol, and the Ni/Mo atomic ratio is 0.45. Stirring for 4 hours to form a red transparent solution, transferring the red transparent solution into a 100ml round-bottom flask, connecting with a condenser tube, carrying out circulating reflux crystallization reaction for 6 hours in an oil bath at 190 ℃, and naturally cooling to room temperature. And (5) carrying out suction filtration, and washing with deionized water and absolute ethyl alcohol respectively. Finally, after washing with toluene three times, Ni-modified MoS will be obtained2The sample, dispersed in toluene solution to form 0.1g/ml catalyst slurry, and stored for use.
The catalyst slurry prepared in inventive example 14 was mixed with ethylene cracking tar in an amount of 5.0 wt.%. In the suspension bed hydrogenation reaction, the reaction temperature is 480 ℃, the reaction pressure is 25MPa, the reaction is carried out for 4 hours, and the hydrogenation activity is far higher than that of the commercial MoS2(see Table 1).
Comparative example:
the commodity MoS2The sample, dispersed in toluene solution to form 0.1g/ml catalyst slurry, and stored for use.
Commercial catalyst slurry was mixed with ethylene cracking tar with 2.0 wt.% catalyst addition. In the suspension bed hydrogenation reaction, the reaction temperature is 430 ℃, the reaction pressure is 18MPa, the reaction time is 4h, and the hydrogenation activity is shown in Table 1.
As can be seen from Table 1, compared with the comparative example, the high-pressure liquid-phase hydrogenation catalyst for ethylene pyrolysis tar of examples 9 to 14 of the present invention can improve the conversion rate of asphaltenes in the ethylene pyrolysis tar, increase the yield of gasoline and diesel, and has no coking.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention adopts a high boiling point solvent to realize the one-step solution chemical synthesis method to prepare the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst. The high boiling point solvent adopted in the preparation process has small autogenous pressure in the crystallization process, ensures the low-pressure uniform crystallization in the solution synthesis process, and is beneficial to producing high-dispersion nano-scale catalytic materials. In addition, the hydrogenation catalyst prepared by the method is a completely sulfurized cobalt or nickel modified molybdenum sulfide hydrogenation catalyst (namely the ethylene cracking tar high-pressure liquid phase hydrogenation catalyst), and the catalyst does not need to be sulfurized when used in the high-pressure liquid phase hydrogenation reaction at the later stage;
(2) the catalyst does not need to be dried in the preparation process, and the influence of particle agglomeration and growth of the catalyst on the dispersibility and the exposure of an active site of the catalyst caused by the drying process is avoided. After the catalyst is washed and separated, the catalyst is directly washed by an oily solvent such as benzene or toluene, so that the lipophilicity and high dispersibility of the catalyst are ensured. Dispersing the separated hydrogenation catalyst in an oily solvent to form catalyst slurry, adding the catalyst slurry into ethylene cracking tar to perform high-pressure liquid-phase hydrogenation reaction, and ensuring that the catalyst is fully and uniformly dispersed in the ethylene cracking tar in the reaction process;
(3) the catalyst characterization results of the present invention show that commercial hydrogenation catalyst (MoS) is comparable to the control sample2) The intrinsic nanometer structure of the molybdenum sulfide material is still maintained after the cobalt or nickel is modified, and the independent cobalt or nickel sulfide crystal phase is not generated. The hydrogenation catalyst prepared by the method has the nanometer characteristics of small particle size, no obvious agglomeration, large interlayer spacing, short lamella, few stacking layers and the like, so that more catalytic hydrogenation active sites are exposed, and the hydrogenation catalyst has good dispersibility and lipophilicity;
(4) the prepared molybdenum sulfide hydrogenation catalyst modified by high-dispersion nano cobalt or nickel has high dispersibility and exposes abundant hydrogenation active sites. When the catalyst is used for high-pressure liquid-phase hydrogenation of ethylene cracking tar, the catalyst can be highly dispersed in a high-pressure hydrogenation system, and the rapid hydrogenation conversion of all components, especially heavy-component asphaltene in the ethylene cracking tar is realized, so that the coking and inactivation of the catalyst are avoided. The reaction results are detailed in Table 1, the conversion rate of the asphaltenes in the hydrogenation reaction of the ethylene cracking tar can reach 99.5 percent, the yield of the light gasoline and diesel oil can reach 59.6 percent, and the conversion rate is far higher than that of a control sample product MoS2Ethylene cracking tar addition of catalystHydrogen activity and no coking phenomenon.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Figure DEST_PATH_IMAGE002

Claims (10)

1. A preparation method of a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar is characterized by comprising the following steps:
(1) dissolving a molybdenum source, a cobalt source or a nickel source and a sulfur source in a solvent with the boiling point higher than 190 ℃ to obtain a transparent solution; forming a transparent solution in which the atomic ratio of Co to Mo is 0.001 to 0.5, or the atomic ratio of Ni to Mo is 0.001 to 0.5;
(2) carrying out crystallization reaction on the transparent solution obtained in the step (1) at the temperature of 120-190 ℃ for 3-72 hours;
(3) after the crystallization reaction is finished, separating and washing the product, and then dispersing the product into an oily solvent to obtain the cobalt or nickel modified nano MoS2Catalyst slurry, namely a high-pressure liquid-phase hydrogenation catalyst for ethylene cracking tar.
2. The method for preparing the ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst according to claim 1, wherein the molybdenum source is one or a mixture of more than two of ammonium heptamolybdate, sodium molybdate, molybdic acid, molybdenum oxide and phosphomolybdic acid; or/and the sulfur source is one or a mixture of more than two of thiourea, thioacetamide, cysteine and glutathione with reducibility.
3. The method for preparing the catalyst for high-pressure liquid-phase hydrogenation of ethylene cracking tar according to claim 1 or 2, wherein the cobalt source is one or a mixture of more than two of cobalt chloride, cobalt nitrate and cobalt acetate; or the nickel source is one or a mixture of more than two of nickel chloride, nickel nitrate and nickel acetate.
4. The method for preparing the ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst according to claim 1 or 2, wherein the atomic ratio of Co to Mo in the transparent solution is preferably 0.1 to 0.3, or the atomic ratio of Ni to Mo is preferably 0.1 to 0.3.
5. The method for preparing the ethylene cracking tar high-pressure liquid-phase hydrogenation catalyst according to claim 3, wherein the atomic ratio of Co to Mo in the transparent solution is preferably 0.1 to 0.3, or the atomic ratio of Ni to Mo is preferably 0.1 to 0.3.
6. The method for preparing the catalyst for high-pressure liquid-phase hydrogenation of ethylene cracking tar according to claim 1, 2 or 5, wherein in the step (1), the solvent with the boiling point higher than 190 ℃ is one or a mixture of more than two of ethylene glycol, diethylene glycol and glycerol.
7. The method for preparing the catalyst for high-pressure liquid-phase hydrogenation of ethylene cracking tar according to claim 3 or 4, wherein in the step (1), the solvent with the boiling point higher than 190 ℃ is one or a mixture of more than two of ethylene glycol, diethylene glycol and glycerol.
8. The method for preparing the catalyst for high-pressure liquid-phase hydrogenation of ethylene cracking tar according to any one of claims 1 to 7, wherein the crystallization reaction temperature is preferably 140 ℃ to 180 ℃; or/and the crystallization reaction time is preferably 24 hours to 48 hours.
9. The high-pressure liquid-phase hydrogenation catalyst for the ethylene cracking tar prepared by the preparation method of any one of claims 1 to 8 is applied to the hydrogenation conversion of the ethylene cracking tar.
10. The use of claim 9, wherein the ethylene cracking tar high pressure liquid phase hydrogenation catalyst is used for three ethylene cracking tar high pressure liquid phase hydrogenation reactions, namely a tank reaction, a suspension bed reaction and a gas lift reaction.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113444539A (en) * 2021-06-10 2021-09-28 克拉玛依市先能科创重油开发有限公司 Preparation method of catalyst for heavy oil liquid phase suspension bed hydrogenation device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106611837A (en) * 2015-10-27 2017-05-03 上海交通大学 Cobalt-intercalated molybdenum sulfide secondary battery material and preparation method and application thereof
CN108067257A (en) * 2016-11-16 2018-05-25 中国科学院大连化学物理研究所 A kind of preparation method of the nano molybdenum disulfide hydrogenation catalyst of high activity position exposure
CN109569635A (en) * 2017-09-28 2019-04-05 中国石油化工股份有限公司 For Tar production fuel oil hydrogenation catalysts
CN110538676A (en) * 2018-05-29 2019-12-06 中国石油化工股份有限公司 Catalyst for hydrogenation refining of cracked tar
CN111229258A (en) * 2018-11-29 2020-06-05 中国科学院大连化学物理研究所 Preparation method of high-activity molybdenum sulfide hydrogenation catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106611837A (en) * 2015-10-27 2017-05-03 上海交通大学 Cobalt-intercalated molybdenum sulfide secondary battery material and preparation method and application thereof
CN108067257A (en) * 2016-11-16 2018-05-25 中国科学院大连化学物理研究所 A kind of preparation method of the nano molybdenum disulfide hydrogenation catalyst of high activity position exposure
CN109569635A (en) * 2017-09-28 2019-04-05 中国石油化工股份有限公司 For Tar production fuel oil hydrogenation catalysts
CN110538676A (en) * 2018-05-29 2019-12-06 中国石油化工股份有限公司 Catalyst for hydrogenation refining of cracked tar
CN111229258A (en) * 2018-11-29 2020-06-05 中国科学院大连化学物理研究所 Preparation method of high-activity molybdenum sulfide hydrogenation catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113444539A (en) * 2021-06-10 2021-09-28 克拉玛依市先能科创重油开发有限公司 Preparation method of catalyst for heavy oil liquid phase suspension bed hydrogenation device

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