CN107344103B - Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof - Google Patents

Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof Download PDF

Info

Publication number
CN107344103B
CN107344103B CN201610288624.7A CN201610288624A CN107344103B CN 107344103 B CN107344103 B CN 107344103B CN 201610288624 A CN201610288624 A CN 201610288624A CN 107344103 B CN107344103 B CN 107344103B
Authority
CN
China
Prior art keywords
molecular sieve
catalyst
pore volume
modified
hydrocracking catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610288624.7A
Other languages
Chinese (zh)
Other versions
CN107344103A (en
Inventor
高杭
杜艳泽
柳伟
秦波
王凤来
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201610288624.7A priority Critical patent/CN107344103B/en
Publication of CN107344103A publication Critical patent/CN107344103A/en
Application granted granted Critical
Publication of CN107344103B publication Critical patent/CN107344103B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B01J35/617—
    • B01J35/635—
    • B01J35/638—
    • 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
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Abstract

The invention discloses a hydrocracking catalyst for producing high-quality ethylene raw materials to the maximum extent, and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: uniformly mixing the macroporous alumina powder, the modified USY molecular sieve and the active metal component, then adding an acid solution, fully rolling and forming, then drying and roasting to obtain the hydrocracking catalyst. The modified USY molecular sieve has the following properties after being roasted: the total pore volume is 0.76-1.25 ml/g; wherein the mesoporous volume is 0.55-1.05 ml/g; the mesoporous volume accounts for 65-90% of the total pore volume; the molar ratio of the silicon oxide to the aluminum oxide is 10-35; the specific surface area is 680-1050 m2(ii) in terms of/g. The hydrocracking catalyst prepared by the method has the characteristics of high hydrocracking property, good selectivity of target products and the like, and can be used for producing high-quality ethylene cracking raw materials to the maximum extent.

Description

Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof
Technical Field
The invention relates to a hydrocracking catalyst for producing high-quality ethylene raw materials, a preparation method and application thereof.
Background
According to statistics, the market demand of basic chemical raw materials suitable for producing chemical raw materials in China reaches 8700 × t by 2020, but the whole oil refining industry can only provide 6080 × t basic raw materials, the gap of the basic chemical raw materials reaches 2600 39104 t, and the basic chemical raw materials become the development bottleneck of the chemical industry in China.
The distribution and properties of the hydrocracked products are mainly determined by the hydrocracking catalyst. Wherein the cracking center in the hydrocracking catalyst is mainly provided by the molecular sieve, so that the performance of the catalyst is improved by improving the performance of the molecular sieve. Kouming et al (MCM-22 molecular sieve modification research progress [ J)]Contemporary chemical industry, 2015, 44 (11): 2629-2634) through the structural change of the molecular sieve after the alkali treatment and the hydrothermal treatment of the MCM-22 molecular sieve, the molecular sieve after the alkali treatment maintains the original microporous structure and has more mesoporous structures and macroporous structures. Engineering and time of year (influence of modification of Y molecular sieve on its structure and acidity [ J)]Petrochemical technology and applications, 2011, 29 (5): 401-405), which shows that a large number of secondary pores can be formed on the Y molecular sieve after modification such as hydrothermal treatment, hydrothermal-oxalic acid treatment and the like, and this shows that the water vapor treatment can play a role in expanding pores, the mesoporous pore volume can be further increased after non-framework aluminum is removed by oxalic acid, the acid type and acid amount of the Y molecular sieve can be adjusted in a large range, the total acid amount is reduced after modification, the strong L acid amount is increased after hydrothermal treatment, and the strong B acid amount can be increased by hydrothermal-oxalic acid combined dealumination. Qin Zhen et al (physicochemical properties of small-grain Y molecular sieves with different Si/Al ratios and hydrocracking performance [ J ]]Petrochemical, 2013, 42 (10): 1080-1085) shows that the framework stability of the small-grain Y molecular sieve is increased along with the increase of the silicon-aluminum ratio; the acid amount is reduced along with the increase of the silicon-aluminum ratio, and small crystal grain Y molecular sieves with different silicon-aluminum ratios have different acid center distributions; the pore structure of the small-grain Y molecular sieve is not obviously changed along with the silicon-aluminum ratio, and compared with the industrial Y molecular sieveThe small-grain Y molecular sieve has a larger specific surface area, which is beneficial to heavy oil conversion. The small crystal grain Y molecular sieve with the silicon-aluminum ratio of 5.2 has moderate acidity, developed pore passages and better framework stability, and the hydrocracking catalyst taking the small crystal grain Y molecular sieve as the carrier has high activity, high light oil selectivity and high chemical raw material yield, thereby being the active component of the preferable light oil type hydrocracking catalyst. Wangyangmajun et al (research progress on modification of ultrastable Y molecular sieves [ J)]Silicate report, 2015, 34 (11): 3243-3250) introduces methods of dealumination modification, supported acid modification, supported cation or oxide modification, molecular sieve compound modification and the like of the ultrastable Y molecular sieve, and shows that the ultrastable Y molecular sieve has good crystallinity, higher silicon-aluminum ratio, larger pore size and pore volume, high specific surface area and hydrothermal stability, and proper acid amount and acid strength after modification, so that the ultrastable Y molecular sieve can be used as a carrier or an acid component to prepare a catalyst and shows good catalytic performance. Meanwhile, the modification research of the ultrastable Y molecular sieve is considered to be continued, on one hand, the research on the aspect of acid center, namely the USY molecular sieve has B acid and L acid centers, and how to prepare the catalyst with specific acid centers to achieve the optimal catalytic activity is a problem to be overcome; on the other hand, the recycling frequency of the catalyst prepared by the ultrastable Y molecular sieve (or the modified ultrastable Y molecular sieve) is required to be improved, the production cost is reduced, and the production efficiency is improved. Penghua et al (influence of modified Y molecular sieves on middle distillate selective hydrocracking catalysts [ J)]Petro-chemical (petroleum processing), 2006 (supplement): 171-173) shows that the modified Y molecular sieve has lower total acid content and higher L acid ratio, which is beneficial to improving the middle distillate selectivity of the catalyst and keeping better activity; in the product (A)<370 ℃ distillate) conversion of 60%, the middle distillate (150 ℃ distillate and 370 ℃) selectivity of the pilot-sized catalyst HC-670 is 68.3%, while the middle distillate selectivity of the same industrial catalyst is only 61.8%. Li Ming Xiao et al (influence of hydrothermal and nitric acid treatments on the Performance of modified Y molecular sieves [ J)]Petrochemical, 2012, 43 (4): 412-419) shows that the dealumination amount of the Y molecular sieve is increased, the specific surface area is reduced and the total acid amount is reduced along with the increase of the hydrothermal treatment temperature; removing non-framework aluminum in the Y molecular sieve along with the increase of the concentration of nitric acidIn addition, the relative crystallinity, specific surface area and silicon to aluminum ratio increase. The activity and selectivity of the hydrocracking catalyst prepared by the modified Y molecular sieve are improved, wherein the hydrocracking catalyst prepared by the Y molecular sieve after being subjected to hydro-thermal treatment at 680 ℃ and nitric acid treatment at 0.6mol/L has good medium oil (C) on the premise of keeping higher n-dodecane conversion rate4~8Hydrocarbon) selectivity, yield of medium oil 51.07%. Kingwenlan (hydrocracking performance of combined modified Y-type molecular sieve [ J)]Journal of fuel chemistry, 2009, 37 (4): 454-458) shows that the addition of CTAB can keep the Y-type molecular sieve at a high relative crystallinity and improve the SiO performance during the dealumination of oxalic acid in the Y-type molecular sieve2/Al2O3In contrast, the unit cell constant is reduced. The acid content of the Y-type molecular sieve with CTAB participating in modification is obviously reduced, and the reason is determined by the improvement of the silicon-aluminum ratio and the amine poisoning of partial acid sites. The hydrocracking catalyst prepared by CTAB participating in the modified Y-shaped molecular sieve has higher activity and yield of middle distillate oil, and has the VGO conversion rate 2.42 percent higher and the yield of the middle distillate oil 4.20 percent higher than that of the middle distillate oil type hydrocracking catalyst which is industrially applied at present. The reason is that the Y-type molecular sieve with CTAB participating in modification has richer mesopores, so that macromolecules in VGO can be more close to the acid sites of the catalyst, and simultaneously, a cracked product can quickly leave the active sites of the catalyst to avoid secondary cracking, so that the catalyst has higher activity and the yield of middle distillate oil. Patent 200610001864.0 describes a method for modifying a Y-type molecular sieve, which comprises adding a surfactant during the acid dealumination process to obtain a Y-type molecular sieve with a high silica-alumina ratio (the molar silica-alumina ratio of silica to alumina is 9-15), and maintaining a high crystallinity, wherein the secondary pores of the modified Y-type molecular sieve are greatly increased, and the acid structure is further improved. Patent 200810104303.2 describes a modification method of an HY type molecular sieve, which comprises the steps of impregnating an HY type molecular sieve with a certain amount of 5-10% silica sol, drying at 120 ℃, roasting at 450 ℃, and finally dealuminizing with an ammonium fluoride aqueous solution with a certain concentration to obtain a micro-mesoporous modified molecular sieve.
Patent 200810105644.1 describes a method for modifying NaY type molecular sieve, which uses a screen to separate the ion exchange resin from the molecular sieve slurry, and uses the concentration difference to realize the exchange between hydrogen ions and sodium ions without contacting the two, thereby alleviating the problem of subsequent wastewater treatment. The sodium oxide content of the obtained modified molecular sieve can be reduced to below 1wt%, and the crystallinity is kept above 80%. Patent 201110331019.0 discloses a method for modifying NaY molecular sieve, which comprises adding mixed acid into a mixture of NaY molecular sieve, buffer solution and water, pulping uniformly, adjusting the pH value to 4.0-6.5, carrying out exchange reaction at 70-95 ℃, washing, and drying. The method realizes no ammonium discharge and alleviates the problem of subsequent wastewater treatment. The sodium oxide content of the obtained modified molecular sieve can be reduced to below 0.5wt%, and the crystallinity is kept above 85%. Patent 201310114414.2 discloses a modification method of a USY molecular sieve, which comprises the steps of modifying 0.10-0.35 mol/L citric acid at 50-120 ℃, adding 0.1-3.5 ml/min ammonium fluosilicate solution after the temperature is raised to 60-90 ℃, reacting for 1-6 hours after the ammonium fluosilicate solution is added, washing, and drying to obtain the modified USY molecular sieve. The specific surface, the secondary pore volume and the proportion of the medium and strong acid of the molecular sieve are obviously improved. Patents 201310240740.8 and 201410131823.8 describe a combined modification method of a mesoporous-rich ultrastable Y molecular sieve, which comprises the steps of mixing a solution of an organic acid and an inorganic salt solution, heating the mixed solution in a closed container under the condition of stirring, carrying out a reaction for a set time, washing the reaction, carrying out suction filtration to neutrality, and drying to obtain the modified molecular sieve. The modified molecular sieve has obviously raised secondary pore content, increased Si/Al ratio and reduced unit cell constant. Patent 201410131458.0 discloses a method for modifying USY molecular sieve, which comprises modifying ammonium fluorosilicate and citric acid mixed solution at 50-120 deg.C to obtain modified USY molecular sieve rich in secondary pore structure, high crystallinity and rich medium and strong acid. Patent 201510131458.0 discloses a modified Y-type molecular sieve and its modification method, which comprises treating Y-type molecular sieve with alkaline solution, and removing aluminum and supplementing silicon to obtain Y-type molecular sieve with high Si/Al ratio. The modified molecular sieve has the characteristics of large proportion of strong acid, especially large proportion of strong B acid.
The existing research results show that the physicochemical properties of the molecular sieve can be changed by adopting different modification methods, so that the catalytic performance of the molecular sieve is effectively improved. The improvement of the molecular sieve performance can greatly improve the reaction activity of the catalyst and the selectivity of a target product.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrocracking catalyst for producing high-quality ethylene raw materials to the maximum extent and a preparation method thereof. The hydrocracking catalyst has the characteristics of high hydrocracking property, good target product selectivity and the like, and can be used for producing high-quality ethylene cracking raw materials to the maximum extent.
The preparation method of the catalyst comprises the following steps:
uniformly mixing the macroporous alumina powder, the modified USY molecular sieve and the active metal component, then adding an acid solution, fully rolling and forming, then drying and roasting to obtain the hydrocracking catalyst.
In the method, the modified USY molecular sieve has the following properties after being roasted: the total pore volume is 0.76-1.25 ml/g, preferably 0.80-1.10 ml/g; wherein the mesoporous pore volume is 0.55-1.05 ml/g, preferably 0.60-0.95 ml/g, and more preferably 0.68-0.90 ml/g; the mesoporous volume accounts for 65-90%, preferably 70-85% of the total pore volume; the molar ratio of the silicon oxide to the aluminum oxide is 10-35, preferably 12-30; the specific surface area is 680-1050 m2Per g, preferably 800 to 950m2/g。
In the method, the modified USY molecular sieve is prepared by the following steps:
adding a Y-type molecular sieve into a pressure-resistant container filled with one or more organic alkali solutions of tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide with the concentration of 0.05-0.35 mol/L under the condition of stirring, sealing the system, introducing compressed air, nitrogen or inert gas and the like into the pressure-resistant container to increase the pressure to 0.2-1.0 MPa, heating to 50-90 ℃, carrying out constant-temperature treatment for 0.5-3 hours, releasing the pressure, carrying out suction filtration until the pH value is less than 9, drying for 6-24 hours at 80-120 ℃, and then stripping at 450-650 DEG CRoasting for 2-8 hours under the condition to obtain the modified USY type molecular sieve. The Y-type molecular sieve added into the organic alkali solution is in a hydrogen type, and the molar ratio of silicon oxide to aluminum oxide is 10-55, preferably 18-45; the specific surface area is 650 to 950m2Per g, preferably 750 to 900m2(ii)/g; the mass ratio of the addition amount of the Y-type molecular sieve to water in the organic alkali solution is 1: 5-20, preferably 1: 7.5-1: 15.
in the method, the hydrocracking catalyst comprises the following components in percentage by weight: the modified USY molecular sieve is generally 20-70%, preferably 30-50%; the content of the aluminum oxide is generally 30-70%, preferably 40-60%; the group VIB metal (calculated by oxide) is generally 6-15%, preferably 8-12%; the amount of the group VIII metal (calculated as oxide) is generally 2% to 8%, preferably 3% to 6%.
When the catalyst is used for treating VGO, the reaction conditions are all in the presence of hydrogen, the reaction pressure is 10-20 MPa, the reaction temperature is 350-430 ℃, the volume ratio of hydrogen to oil is 500-1800, and the liquid hourly volume space velocity is 0.5-5.0 h-1。
Compared with the prior art, the method has the following advantages: the catalyst adopts the modified USY molecular sieve obtained by high-pressure organic alkali treatment in the preparation process, the molecular sieve has larger pore volume and specific surface area, and better accessibility and diffusion performance of active sites, and the accessibility of the reactive active sites of the catalyst and the diffusion performance of the molecular sieve are improved. The organic alkali treated molecular sieve can modify the molecular sieve without introducing alkali metal ions (such as sodium, potassium and the like), so that the process of ion exchange after the molecular sieve is modified is avoided, the operation steps are reduced, the energy consumption and the discharge of waste water are reduced, and the cost of the molecular sieve is effectively reduced. The pressurizing process can improve the treatment depth of the molecular sieve under the condition of keeping the crystallinity of the molecular sieve, so that the molecular sieve has a more developed secondary structure, and the active site accessibility and the diffusion performance of the molecular sieve are improved. The catalyst is beneficial to improving the hydrogenation ring-opening reaction of cyclic hydrocarbon in the raw material and reducing the occurrence of excessive cracking reaction of small molecular hydrocarbon in the hydrocracking process, so that the yield of C2-C4 light hydrocarbon components, light naphtha and hydrocracking tail oil in the finally obtained hydrocracking product is greatly improved, the cycloparaffin content of the hydrocracking tail oil is greatly reduced, and the yield of triene in the steam cracking process can be improved.
Detailed Description
The following examples further illustrate the preparation of the present invention, but are not to be construed as limiting the process of the present invention.
Example 1
Uniformly mixing macroporous alumina powder, a modified USY molecular sieve and an active metal component, adding an acid solution, fully rolling and forming, drying for 8 hours at 110 ℃, and finally roasting for 4 hours at 500 ℃ to obtain the hydrocracking catalyst. The catalyst properties are given in table 1.
The preparation steps of the modified USY molecular sieve are as follows: preparing 0.25mol/L tetrapropylammonium bromide solution, adding silica/alumina molar ratio of 35 and specific surface area of 780m into the solution2The mass ratio of the addition amount of the USY molecular sieve to water in the solution is 1:8, the system is sealed, compressed air, nitrogen or inert gas and the like are introduced into a pressure-resistant container to be pressurized to 0.30MPa, then the pressure is increased to 1.5 hours at 70 ℃, the pressure is relieved, and the USY molecular sieve is washed until the pH value is less than 10, so that the modified USY molecular sieve is obtained. The modified USY molecular sieve has the following properties after roasting: the pore volume with the pore diameter of 3-6 nm accounts for 28% of the total pore volume of the USY molecular sieve; the pore volume with the pore diameter of 7-11 nm accounts for 32% of the total pore volume of the USY molecular sieve; the mole ratio of silicon oxide to aluminum oxide in the molecular sieve is 18, the specific surface area is 896m2The pore volume was 0.96 ml/g.
Example 2
Uniformly mixing the macroporous alumina powder, the modified USY molecular sieve and the active metal component, adding an acid solution, fully rolling and forming, drying at 110 ℃ for 6 hours, and finally roasting at 490 ℃ for 4 hours to obtain the hydrocracking catalyst. The catalyst properties are given in table 1.
The preparation steps of the modified USY molecular sieve are as follows: tetraethyl ammonium bromide solution with the concentration of 0.30mol/L is prepared, and silica/alumina molar ratio of 25 and specific surface area of 785m are added into the solution2Hydrogen USY molecular sieve,/g, UThe mass ratio of the addition amount of the SY molecular sieve to water in the solution is 1:11, the system is sealed, compressed air, nitrogen or inert gas and the like are introduced into a pressure-resistant container to be pressurized to 0.7MPa, then the pressure is increased to 1.0 hour at 80 ℃, the pressure is relieved, and the USY molecular sieve is washed until the pH value is less than 10, so that the modified USY molecular sieve is obtained. The modified USY molecular sieve has the following properties after roasting: the pore volume with the pore diameter of 3-6 nm accounts for 28% of the total pore volume of the USY molecular sieve; the pore volume with the pore diameter of 7-11 nm accounts for 40% of the total pore volume of the USY molecular sieve; the mole ratio of silicon oxide to aluminum oxide in the molecular sieve is 15, and the specific surface area is 904m2The pore volume is 0.86 ml/g.
Example 3
Uniformly mixing the macroporous alumina powder, the modified USY molecular sieve and the active metal component, then adding an acid solution, fully rolling and forming, then drying for 8 hours at the temperature of 110 ℃, and finally roasting for 3 hours at the temperature of 520 ℃ to obtain the hydrocracking catalyst. The catalyst properties are given in table 1.
The preparation steps of the modified USY molecular sieve are as follows: preparing tetrabutylammonium bromide solution with the concentration of 0.20mol/L, adding silica/alumina molar ratio of 32 and specific surface area of 740m into the solution2The mass ratio of the addition amount of the USY molecular sieve to water in the solution is 1:18, the system is sealed, compressed air, nitrogen or inert gas and the like are introduced into a pressure-resistant container to be pressurized to 0.55MPa, then the pressure is increased to 1.5 hours at 75 ℃, the pressure is relieved, and the USY molecular sieve is washed until the pH value is less than 10, so that the modified USY molecular sieve is obtained. The modified USY molecular sieve has the following properties after roasting: the pore volume with the pore diameter of 3-6 nm accounts for 25% of the total pore volume of the USY molecular sieve; the pore volume with the pore diameter of 7-11 nm accounts for 38% of the total pore volume of the USY molecular sieve; the mole ratio of silicon oxide to aluminum oxide in the molecular sieve is 13, the specific surface area is 875m2The pore volume is 0.90 ml/g.
Example 4
Uniformly mixing macroporous alumina powder, a modified USY molecular sieve and an active metal component, adding an acid solution, fully rolling and forming, drying for 8 hours at 100 ℃, and finally roasting for 6 hours at 480 ℃ to obtain the hydrocracking catalyst. The catalyst properties are given in table 1.
The preparation steps of the modified USY molecular sieve are as follows: preparing 0.15mol/L tetrapropylammonium bromide solution, adding 29 parts of silica/alumina molar ratio into the solution, and obtaining 716m specific surface area2The mass ratio of the addition amount of the USY molecular sieve to water in the solution is 1:12, the system is sealed, compressed air, nitrogen or inert gas and the like are introduced into a pressure-resistant container to be pressurized to 0.45MPa, then the pressure is increased to 1.0 hour at 70 ℃, the pressure is relieved, and the USY molecular sieve is washed until the pH value is less than 10, so that the modified USY molecular sieve is obtained. The modified USY molecular sieve has the following properties after roasting: the pore volume with the pore diameter of 3-6 nm accounts for 31% of the total pore volume of the USY molecular sieve; the pore volume with the pore diameter of 7-11 nm accounts for 32% of the total pore volume of the USY molecular sieve; the molecular sieve has a mole ratio of 15 to 864m of silica/alumina2The pore volume is 0.95 ml/g.
Example 5
Uniformly mixing the macroporous alumina powder, the modified USY molecular sieve and the active metal component, then adding an acid solution, fully rolling and forming, then drying for 8 hours at 120 ℃, and finally roasting for 4 hours at 500 ℃ to obtain the hydrocracking catalyst. The catalyst properties are given in table 1.
The preparation steps of the modified USY molecular sieve are as follows: preparing 0.32mol/L tetrapropylammonium bromide solution, adding silica/alumina molar ratio of 31 and specific surface area of 765m2The mass ratio of the addition amount of the USY molecular sieve to water in the solution is 1:16, the system is sealed, compressed air, nitrogen or inert gas and the like are introduced into a pressure-resistant container to be pressurized to 0.55MPa, then the pressure is increased to 1.5 hours at 70 ℃, the pressure is relieved, and the USY molecular sieve is washed until the pH value is less than 10, so that the modified USY molecular sieve is obtained. The modified USY molecular sieve has the following properties after roasting: the pore volume with the pore diameter of 3-6 nm accounts for 28% of the total pore volume of the USY molecular sieve; the pore volume with the pore diameter of 7-11 nm accounts for 32% of the total pore volume of the USY molecular sieve; the molecular sieve has a silica/alumina molar ratio of 19 and a specific surface area of 886m2The pore volume is 1.06 ml/g.
Example 6
Uniformly mixing the macroporous alumina powder, the modified USY molecular sieve and the active metal component, adding an acid solution, fully rolling and forming, drying for 6 hours at 100 ℃, and finally roasting for 4 hours at 490 ℃ to obtain the hydrocracking catalyst. The catalyst properties are given in table 1.
The preparation steps of the modified USY molecular sieve are as follows: preparing 0.28mol/L tetraethylammonium bromide solution, adding 25 mole ratio of silicon oxide to aluminum oxide and 775m specific surface area2The mass ratio of the addition amount of the USY molecular sieve to water in the solution is 1:16, the system is sealed, compressed air, nitrogen or inert gas and the like are introduced into a pressure-resistant container to be pressurized to 0.65MPa, then the pressure is increased to 2.0 hours at 70 ℃, the pressure is relieved, and the USY molecular sieve is washed until the pH value is less than 10, so that the modified USY molecular sieve is obtained. The modified USY molecular sieve has the following properties after roasting: the pore volume with the pore diameter of 3-6 nm accounts for 28% of the total pore volume of the USY molecular sieve; the pore volume with the pore diameter of 7-11 nm accounts for 40% of the total pore volume of the USY molecular sieve; the mole ratio of silicon oxide to aluminum oxide in the molecular sieve is 12, the specific surface area is 924m2The pore volume is 0.95 ml/g.
Example 7
Uniformly mixing the macroporous alumina powder, the modified USY molecular sieve and the active metal component, then adding an acid solution, fully rolling and forming, then drying for 8 hours at the temperature of 110 ℃, and finally roasting for 3 hours at the temperature of 520 ℃ to obtain the hydrocracking catalyst. The catalyst properties are given in table 1.
The preparation steps of the modified USY molecular sieve are as follows: preparing tetrabutylammonium bromide solution with the concentration of 0.33mol/L, adding silica/alumina molar ratio of 42 and specific surface area of 740m into the solution2The mass ratio of the addition amount of the USY molecular sieve to water in the solution is 1:12, the system is sealed, compressed air, nitrogen or inert gas and the like are introduced into a pressure-resistant container to be pressurized to 0.35MPa, then the pressure is increased to 1.5 hours at 85 ℃, the pressure is relieved, and the USY molecular sieve is washed until the pH value is less than 10, so that the modified USY molecular sieve is obtained. The modified USY molecular sieve has the following properties after roasting: the pore volume with the pore diameter of 3-6 nm accounts for 25% of the total pore volume of the USY molecular sieve; the pore volume with the pore diameter of 7-11 nm accounts for 38% of the total pore volume of the USY molecular sieve; the mole ratio of silica to alumina in the molecular sieve is 22The specific surface area is 855m2The pore volume is 0.90 ml/g.
Example 8
Uniformly mixing macroporous alumina powder, a modified USY molecular sieve and an active metal component, adding an acid solution, fully rolling and forming, drying for 8 hours at 100 ℃, and finally roasting for 6 hours at 480 ℃ to obtain the hydrocracking catalyst. The catalyst properties are given in table 1.
The preparation steps of the modified USY molecular sieve are as follows: preparing tetrapropylammonium bromide solution with concentration of 0.32mol/L, adding silica/alumina molar ratio of 29 and specific surface area of 756m into the solution2The mass ratio of the addition amount of the USY molecular sieve to water in the solution is 1:16, the system is sealed, compressed air, nitrogen or inert gas and the like are introduced into a pressure-resistant container to be pressurized to 0.80MPa, then the pressure is increased to 1.0 hour at 80 ℃, the pressure is relieved, and the USY molecular sieve is washed until the pH value is less than 10, so that the modified USY molecular sieve is obtained. The modified USY molecular sieve has the following properties after roasting: the pore volume with the pore diameter of 3-6 nm accounts for 31% of the total pore volume of the USY molecular sieve; the pore volume with the pore diameter of 7-11 nm accounts for 32% of the total pore volume of the USY molecular sieve; the mole ratio of silicon oxide to aluminum oxide in the molecular sieve is 18, the specific surface area is 894m2The pore volume is 0.95 ml/g.
Comparative example 1
The same as example 1 except that the USY molecular sieve was not modified, the hydrocracking catalyst properties are as shown in Table 1.
Comparative example 2
The difference from example 1 is that the USY molecular sieve modification treatment is carried out under atmospheric conditions, and the hydrocracking catalyst properties are as shown in table 1.
And (5) evaluating the catalytic performance.
The evaluation apparatus was a 200m1 compact hydrogenation apparatus, and the catalyst was presulfided before the activity evaluation. The properties of the raw oil and the reaction process conditions used for evaluating the catalyst activity are shown in tables 2 and 3, and the results of comparing the catalyst reaction performance are shown in table 4. When the catalyst is evaluated, raw oil firstly passes through a hydrofining catalyst bed layer and then directly enters a hydrocracking catalyst bed layer, and the organic nitrogen content in the raw oil is controlled to be lower than 10ppm when the raw oil passes through the hydrofining catalyst bed layer.
TABLE 1 composition of the catalyst
Serial number Modified USY molecular sieve (wt%) USY molecular sieve (wt%) Nickel oxide (wt%) Cobalt oxide (wt%) Tungsten oxide (wt%) Molybdenum oxide (wt%)
Example 1 55 3.8 --- 12.5 ---
Example 3 60 3.5 --- 12.6 ---
Example 5 48 --- 3.6 --- 12.3
Example 7 42 --- 4.2 --- 12.6
Comparative example 1 --- 55 4.0 --- 11.9 ---
Comparative example 2 --- 55 4.1 --- 11.7 ---
TABLE 2 Process conditions
pressure/MPa 15.7
Space velocity (R1/R2)/h-1 1.0/1.5
Volume ratio of hydrogen to oil 1300
TABLE 3 Properties of the raw materials
Density (20 ℃ C.), g/cm3 0.9145
Distillation range/. degree.C
IBP/10% 358/376
30%/50% 400/430
70%/90% 455/489
95%/FBP 514/535
Freezing point/. degree.C 32
Carbon residue in wt% 0.30
S，wt% 1.62
N，wt% 0.13
TABLE 4 catalyst reactivity
Catalyst and process for preparing same Example 1 Example 3 Example 5 Example 7 Comparative example 1 Comparative example 2
Reaction temperature of 362 363 362 362 366 364
BMCI value 9.9 9.9 9.6 9.6 9.8 9.8
Yield and wt% of C2-C4 light hydrocarbon components 1.53 1.68 1.73 1.82 1.98 1.92
Yield of light naphtha, wt.% 3.8 4.0 4.3 4.3 3.4 3.6
Yield of tail oil, wt.% 40.6 40.3 39.9 38.6 36.5 37.5
(C2-C4 + lightNaphtha + tail oil) yield, wt.% 45.9 45.9 45.9 44.7 41.8 43.2
The hydrocracking reaction result shows that compared with the comparative catalyst, when the same tail oil BMCI value is maintained, the reaction temperature of the catalyst is 3-4 ℃ lower, and the total yield of C2-C4, light naphtha and tail oil is improved by 2.84-4.10 wt% compared with the comparative catalyst. The catalyst prepared by the method has the characteristics of high hydrogenation activity, good hydrogenation ring-opening performance and high selectivity of target products.

Claims (11)

1. A preparation method of a hydrocracking catalyst for producing high-quality ethylene raw materials to the maximum extent is characterized by comprising the following steps: the method comprises the following steps: uniformly mixing macroporous alumina powder, a modified USY molecular sieve and an active metal component, adding an acid solution, fully rolling, forming, drying and roasting to obtain a hydrocracking catalyst; the active metal components are VIB group metals and VIII group metals;
the modified USY molecular sieve has the following properties after being roasted: the total pore volume is 0.76-1.25 mL/g; wherein the mesoporous volume is 0.55-1.05 mL/g; the mesoporous volume accounts for 65-90% of the total pore volume; the molar ratio of the silicon oxide to the aluminum oxide is 10-35; the specific surface area is 680-1050 m2/g；
The hydrocracking catalyst comprises the following components in percentage by weight: the modified USY molecular sieve is 20% -60%; 30% -70% of macroporous alumina; the VIB group metal accounts for 6-15% of oxides; the VIII group metal accounts for 2-8% in terms of oxide, and the sum of the contents of all components is 100%.
2. The method of claim 1, wherein the method is performed in a batch modeCharacterized in that: the total pore volume is 0.80-1.10 mL/g; wherein the mesoporous volume is 0.60-0.95 mL/g; the mesoporous volume accounts for 70-85% of the total pore volume; the molar ratio of the silicon oxide to the aluminum oxide is 12-30; the specific surface area is 800-950 m2/g。
3. The method of claim 1, wherein: the preparation steps of the modified USY molecular sieve are as follows: adding the Y-type molecular sieve into a pressure-resistant container filled with one or more organic alkali solutions of tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide with the concentration of 0.05-0.35 mol/L under the condition of stirring, sealing the system, introducing compressed air, nitrogen or inert gas into the pressure-resistant container to increase the pressure to 0.2-1.0 MPa, then heating to 50-90 ℃, carrying out constant-temperature treatment for 0.5-3 hours, releasing the pressure, carrying out suction filtration until the pH value is less than 9, drying at 80-120 ℃ for 6-24 hours, and then roasting at 450-650 ℃ for 2-8 hours to obtain the modified USY-type molecular sieve.
4. The method of claim 3, wherein: the Y-type molecular sieve added into the organic alkali solution is in a hydrogen form.
5. The method of claim 4, wherein: adding the Y-type molecular sieve into the organic alkali solution, wherein the molar ratio of silicon oxide to aluminum oxide is 10-55; the specific surface area is 650 to 950m2/g。
6. The method of claim 5, wherein: adding the Y-type molecular sieve into the organic alkali solution, wherein the molar ratio of silicon oxide to aluminum oxide is 18-45; the specific surface area is 750-900 m2/g。
7. The method of claim 3, wherein: the mass ratio of the addition amount of the Y-type molecular sieve to water in the organic alkali solution is 1: 5-20.
8. The method of claim 7, wherein: the mass ratio of the addition amount of the Y-type molecular sieve to the water in the organic alkali solution is 1: 7.5-1: 15.
9. a hydrocracking catalyst for producing high-quality ethylene raw material to the maximum extent is characterized in that: prepared by the process of any one of claims 1 to 8.
10. The catalyst of claim 9, wherein: the catalyst comprises the following components in percentage by weight: 30% -50% of modified USY molecular sieve; 40% -60% of macroporous alumina; the VIB group metal accounts for 8% -12% of oxides; the VIII group metal accounts for 3% -6% of oxides; and the sum of the contents of all the components is 100 percent.
11. The catalyst of claim 9 or 10 for treating VGO, characterized in that: the reaction conditions are all under the existence of hydrogen, the reaction pressure is 10-20 MPa, the reaction temperature is 350-430 ℃, the volume ratio of hydrogen to oil is 500-1800, and the liquid hourly space velocity is 0.5-5.0 h-1。
CN201610288624.7A 2016-05-05 2016-05-05 Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof Active CN107344103B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610288624.7A CN107344103B (en) 2016-05-05 2016-05-05 Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610288624.7A CN107344103B (en) 2016-05-05 2016-05-05 Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107344103A CN107344103A (en) 2017-11-14
CN107344103B true CN107344103B (en) 2020-07-07

Family

ID=60252909

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610288624.7A Active CN107344103B (en) 2016-05-05 2016-05-05 Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107344103B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069427A (en) * 1991-08-16 1993-03-03 国际壳版研究有限公司 The carbon monoxide-olefin polymeric that contains modified zeolite of Y-type
CN103100417A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069427A (en) * 1991-08-16 1993-03-03 国际壳版研究有限公司 The carbon monoxide-olefin polymeric that contains modified zeolite of Y-type
CN103100417A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Y型分子筛碱处理改性的研究;梁筱敏等;《中国化学会第29届学术年会摘要集——第27分会：多孔功能材料》;20141231;全文 *

Also Published As

Publication number Publication date
CN107344103A (en) 2017-11-14

Similar Documents

Publication Publication Date Title
CN107344110B (en) Catalyst for producing hydrocracking tail oil with low straight-chain alkane content and preparation method and application thereof
CN107344111B (en) Hydrocracking catalyst for maximum production of low-freezing diesel oil and preparation method and application thereof
CN109775716B (en) Hierarchical pore Y-type molecular sieve rich in L acid and preparation method thereof
CN104556124B (en) A kind of ammonium fluoroborate Modified Zeolite Y and preparation method thereof
CN102019196B (en) Method for improving pore structure of kaolin microsphere in-situ crystallization product
CN103551186B (en) Composite molecular sieve-containing medium oil type hydrocracking catalyst, preparation method and application thereof
CN107344113B (en) Hydrocracking catalyst for producing high aromatic hydrocarbon latent naphtha and preparation method and application thereof
CN109775718A (en) A kind of modified Y-Y isomorphous molecular sieve and its preparation method and application
CN107344115B (en) Modified Y-Beta composite molecular sieve and preparation method and application thereof
CN104588076B (en) Hydrocracking catalyst and preparation method thereof
CN106140287A (en) The preparation method of hydrocracking catalyst
CN107344719B (en) Y-Y type isomorphous composite molecular sieve and preparation method thereof
CN105712373A (en) Modified Y type molecular sieve and preparation method thereof
CN105709820A (en) Hydrocracking catalyst, and preparation method thereof
CN104588078B (en) Hydrocracking catalyst and preparation method thereof
CN107344103B (en) Hydrocracking catalyst for maximum production of high-quality ethylene raw material and preparation method and application thereof
CN107344112B (en) Hydrocracking catalyst for producing high-quality catalytic reforming raw material and preparation method and application thereof
CN107344108A (en) A kind of catalyst for improving hydrocracking tail oil viscosity index (VI) and preparation method thereof
CN107344114B (en) Modified Y/ZSM-48 composite molecular sieve and preparation method and application thereof
CN107344104B (en) Hydrocracking catalyst for producing high-quality ethylene raw material and preparation method and application thereof
CN107344109B (en) Produce the hydrocracking catalyst and preparation method thereof of high-quality hydrocracking tail oil
CN114471742A (en) Modified Y-type molecular sieve and preparation method and application thereof
CN104826653B (en) A kind of method for preparing hydrocracking catalyst
CN106140281A (en) A kind of preparation method of middle oil type hydrocracking catalyst
CN106140319A (en) A kind of preparation method of middle oil type hydrocracking catalyst carrier

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant