WO2023232021A1 - 一种拟薄水铝石及其制备方法、以及一种含该拟薄水铝石的催化裂化催化剂及其制备和应用 - Google Patents

一种拟薄水铝石及其制备方法、以及一种含该拟薄水铝石的催化裂化催化剂及其制备和应用 Download PDF

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WO2023232021A1
WO2023232021A1 PCT/CN2023/097087 CN2023097087W WO2023232021A1 WO 2023232021 A1 WO2023232021 A1 WO 2023232021A1 CN 2023097087 W CN2023097087 W CN 2023097087W WO 2023232021 A1 WO2023232021 A1 WO 2023232021A1
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pseudo
boehmite
aging
catalytic cracking
slurry
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PCT/CN2023/097087
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English (en)
French (fr)
Inventor
袁帅
林伟
于善青
刘博�
刘雨晴
严加松
宋海涛
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中国石油化工股份有限公司
中石化石油化工科学研究院有限公司
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Priority claimed from CN202210598594.5A external-priority patent/CN117181290A/zh
Priority claimed from CN202210598742.3A external-priority patent/CN117185327A/zh
Application filed by 中国石油化工股份有限公司, 中石化石油化工科学研究院有限公司 filed Critical 中国石油化工股份有限公司
Publication of WO2023232021A1 publication Critical patent/WO2023232021A1/zh

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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
    • C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide

Definitions

  • the invention relates to pseudo-boehmite and its preparation method.
  • the invention also relates to a heavy oil catalytic cracking catalyst containing the pseudo-boehmite and its preparation method and application.
  • Catalytic cracking is a heavy oil processing method.
  • Catalytic cracking catalysts usually include molecular sieves and matrix materials.
  • Alumina matrix has been widely used due to its good heavy oil cracking ability.
  • a commonly used alumina matrix material is pseudoboehmite.
  • Pseudo-boehmite is widely used in petroleum refining and petrochemical catalysts. It is often used as a binder for catalytic cracking catalysts and a precursor for hydrogenation catalyst carriers ( ⁇ -Al 2 O 3 ).
  • Pseudo-boehmite has good bonding properties after acidification and can be used as a binder for catalytic cracking catalysts. It can also form a certain mesoporous structure after the catalyst is prepared and formed.
  • pseudo-boehmite is AlOOH ⁇ nH 2 O (0 ⁇ n ⁇ 1, especially 0.08-0.62). It is an alumina compound with a greater water content than boehmite and a smaller grain size than boehmite. It is a crystal phase that is easily generated during the synthesis of aluminum hydroxide. The crystallization is incomplete and its typical crystal form is very thin wrinkled lamellae.
  • pseudo-boehmite There are many methods for preparing pseudo-boehmite, mainly including aluminum alkoxide hydrolysis and precipitation.
  • the precipitation method is divided into two categories: acid method and alkali method.
  • the aluminum alkoxide hydrolysis method uses metal aluminum and higher alcohols (n-amyl alcohol, n-hexanol, isopropanol) as raw materials, and forms aluminum alkoxide by reacting metal aluminum with alcohol in the presence of a catalyst, and then hydrolyzes it to obtain pseudo-boehmite.
  • metal aluminum and higher alcohols n-amyl alcohol, n-hexanol, isopropanol
  • the alkali precipitation method refers to the method of preparing pseudo-boehmite by neutralizing and precipitating acidic aluminum salts with alkali.
  • Aluminum salts include Al 2 (SO 4 ) 3 , Al (NO 3 ) 3 , AlCl 3 , etc., and alkali precipitants are commonly used. There are NaOH, NH 3 ⁇ H 2 O, NaAlO 2 , Na 2 CO 3 , etc.
  • the acid precipitation method refers to the method of preparing pseudo-boehmite by neutralizing and precipitating alkaline aluminates with acid.
  • the alkaline aluminates are generally sodium aluminate, and the acids used can be strong acids (HNO 3 , H 2 SO 4 , etc. ), it can also be a weak acid (NH 4 HCO 3 , NaHCO 3, etc.) and CO 2 , etc.
  • the NaAlO 2 -CO 2 method is also called the carbonization method.
  • the carbonization method to prepare pseudo-boehmite can rely on the sintering method to produce alumina, using the intermediate product NaAlO 2 solution and aluminum plant waste gas CO 2 as the As a reaction raw material, the process is simple, and by-products and waste liquids during the production process can be returned to the alumina production process for reuse. It is currently the lowest-cost method for industrial production of pseudo-boehmite.
  • the pseudo-boehmite prepared by the conventional carbonization method has low crystallinity and a pore diameter of only 3.8nm. When prepared into a catalytic cracking catalyst, it can only provide a mesoporous structure of 3.8nm. After the existing pseudo-boehmite is acidified, the catalytic cracking catalyst prepared has a pore diameter of no more than 4.5 nm, and it is difficult to form a pore structure with a larger pore diameter.
  • the molecular size of the catalytic cracking raw material is large, and its diffusion in the 3.8nm or 4.5nm pores is obviously hindered. This hindrance restricts the efficient diffusion and transformation of heavy oil raw material molecules, which is not conducive to reducing coke yield and improving product distribution.
  • CN110304644A discloses a method for producing high-purity, high-viscosity pseudo-boehmite by carbonization. It pre-decomposes and purifies sodium aluminate solution to obtain high-purity sodium aluminate solution, and then reacts with carbon dioxide gas to obtain high-purity pseudo-boehmite.
  • the pseudo-boehmite has a small pore size and cannot provide larger pore sizes when used in the preparation process of catalytic cracking catalysts.
  • the existing catalytic cracking catalyst coke prepared from pseudo-boehmite has poor selectivity.
  • pseudo-boehmite prepared by carbonization method can provide a larger possible pore size distribution after being acidified and peptized and used in catalytic cracking catalysts.
  • the first technical problem to be solved by the present invention is to provide a pseudo-boehmite that can produce a larger mesoporous structure after acidification.
  • the second technical problem to be solved by the present invention is to provide a method for preparing the pseudo-boehmite.
  • the third technical problem to be solved by the present invention is to provide a catalytic cracking catalyst that contains pseudo-boehmite with specific crystal characteristics and is used for catalytic cracking reaction with low coke yield.
  • the fourth technical problem to be solved by the present invention is to provide a preparation and application method of the catalytic cracking catalyst.
  • the present invention provides the following three groups of technical solutions A, B and C:
  • the pseudo-boehmite according to technical solution A1 characterized in that the possible pore diameter of the pseudo-boehmite is greater than 4.5nm and not more than 12nm, such as 4.8nm-11nm; the pseudo-boehmite
  • the possible pore diameter of the stone is preferably 5nm-10nm.
  • a method for preparing pseudo-boehmite including the following steps:
  • step (1) The concentration of the sodium aluminate solution is 5-60g/L calculated as Al 2 O 3 ; the sodium aluminate solution and CO 2.
  • the pH value of the reaction end point is 8.5-10.5.
  • step (1) The method according to technical scheme A5 or A6, characterized in that in step (1), the conditions for the reaction of the sodium aluminate solution with CO2 include a reaction starting temperature of 10-35°C, Gas containing CO 2 with a CO 2 concentration of 20% to 100% by volume is introduced into the solution to carry out the reaction, and the reaction end temperature is preferably 15 to 55°C.
  • step (2) The method according to technical scheme A5, A6 or A7, characterized in that in step (2), the aging temperature of the slurry is 120-180°C, the aging pressure is 0.2-1Mpa, and the aging time is 2-10h.
  • step (2) The method according to technical solution A5 or A8, characterized in that in step (2), the static aging time is 1-4h, such as 2-3h, and the aging time under stirring is 1-6h.
  • the catalytic cracking catalyst according to technical solution B1 characterized in that the pore volume of the pseudo-boehmite with specific crystal characteristics is 0.3cm 3 /g-0.58cm 3 /g, and the pore diameter may be greater than 4.5 nm-12nm, peptization index 90%-100%.
  • the possible pore diameter of the pseudo-boehmite is 5nm-10nm, and the crystallinity is 85%-110%.
  • the pseudo-boehmite has specific crystal characteristics.
  • the D (130) / D (020) of diaspore is preferably 1.1-1.3; the other molecular sieves are preferably one or more of MFI structure zeolite, Beta zeolite, and non-zeolite molecular sieves.
  • the catalytic cracking catalyst according to technical solution B1 characterized in that the Y-type molecular sieve is one or more of REY, REHY, DASY, SOY, PSRY, HSY, HRY; the other molecular sieves are One or more of HZSM-5, ZRP, ZSP.
  • a method for preparing a catalytic cracking catalyst which includes preparing pseudo-boehmite with specific crystal characteristics, and forming pseudo-boehmite and Y-type separation including the specific crystal characteristics. Slurry of subsieves, optional other molecular sieves, binder, clay and water, spray drying step.
  • step (1) The method according to technical solution B7, characterized in that in step (1), the Al 2 O 3 concentration of the sodium aluminate solution is 5-60g/L; the sodium aluminate solution reacts with CO 2 The endpoint pH is 8.5-10.5.
  • step (1) the conditions for the reaction of the sodium aluminate solution and CO2 include a reaction starting temperature of 10-35°C, Gas containing CO 2 with a CO 2 concentration of 20% by volume to 100% by volume is introduced into the solution to carry out the reaction.
  • the reaction end temperature is preferably 15-55°C.
  • the method according to technical solution B10 characterized in that the aging temperature is 135-180°C, the aging is preferably constant temperature aging, and the stirring speed of the stirring aging is preferably 50-400 r/min.
  • washing conditions in step (3) are: washing with deionized water at 70-100°C until the pH value of the wet filter cake is 7-7.5; step (3) The drying temperature is 70-98°C.
  • a catalytic cracking method including the step of contacting and reacting heavy oil with a catalytic cracking catalyst under FCC conditions, characterized in that the catalytic cracking catalyst is the catalytic cracking catalyst described in any one of technical solutions B1-B5 Or the step of contact reaction of the catalytic cracking catalyst obtained in any one of technical solutions B6-B13; the FCC conditions are such as: reaction temperature is 480-530°C, reaction time is 1-10 seconds, and the agent-oil ratio is 3-20:1 weight ratio.
  • the pseudo-boehmite according to any one of the aforementioned C series technical solutions, characterized in that the possible pore diameter of the pseudo-boehmite is greater than 4.5nm and not more than 12nm, such as 4.8nm-11nm, or 5nm. -10nm.
  • the pseudo-boehmite according to any one of the aforementioned C series technical solutions, characterized in that the crystallinity of the pseudo-boehmite is 85%-110%, such as 88%-108%.
  • the pseudo-boehmite according to any one of the aforementioned C series technical solutions, characterized in that the peptization index of the pseudo-boehmite is 90%-100%, such as 93%-99%.
  • the pseudo-boehmite according to any one of the aforementioned C series technical solutions, characterized in that the pore volume of the pseudo-boehmite is 0.3cm3/g-0.58cm3/g, for example, 0.31cm3/g- 0.52cm3/g.
  • a method for preparing pseudo-boehmite comprising the following steps:
  • step (1) The method for preparing pseudo-boehmite according to any one of the aforementioned C series technical solutions, characterized in that in step (1), the concentration of the sodium aluminate solution is 5-60g calculated as Al 2 O 3 /L; the end-point pH value of the reaction between the sodium aluminate solution and CO2 is 8.5-10.5.
  • step (1) the conditions for the reaction of the sodium aluminate solution and CO 2 include the reaction starting temperature 10-35°C, pass CO2- containing gas with a CO2 concentration of 20%-100% by volume (the balance is inert gas such as nitrogen) into the sodium aluminate solution to react, and the reaction end temperature is preferably 15-55°C.
  • step (2) The method for preparing pseudo-boehmite according to any one of the aforementioned C series technical solutions, characterized in that in step (2), the slurry aging temperature is 120-180°C, the aging pressure is 0.2-1MPa, and the aging time is 2-12h, for example, 2-10h.
  • step (2) The method for preparing pseudo-boehmite according to any one of the aforementioned C series technical solutions, characterized in that the standing aging time in step (2) is 1-8h, such as 2.5-7h, or 1-4h, For example, 2-3h, aging time under stirring is 1-6h.
  • the conditions for static aging include: temperature is 120-180°C, preferably 135-180°C, pressure is 0.2-1MPa, time is 1-8h, such as 2.5-7h, and stirring speed is 100-450r/min;
  • Aging conditions under stirring include: temperature is 120-180°C, preferably 135-180°C, pressure is 0.2-1MPa, and time is 1-6h, such as 1-5h;
  • the ratio of the time of standing aging to the time of aging under stirring is 1-5:1, preferably 1.25-3:1.
  • step (3) washing with deionized water at 70-100°C until the filter cake is wet
  • the pH value is 7-7.5
  • drying is described in step (3), and the drying temperature is 70-98°C.
  • Pseudo-boehmite according to any one of the aforementioned C series technical solutions is used as a catalyst, carrier, and binder in the petroleum industry; in the automobile industry, it is used as a carrier coating for automobile exhaust gas treatment catalysts; in the field of fire protection Used as an additive for flame retardant materials; used in the paper industry as an ink-absorbing coating in high-end inkjet printing paper; used in the environmental protection industry as a gas purification adsorbent, drinking water fluoride remover, industrial wastewater color and odor eliminator ; Used as a coating additive in the construction industry; Used as a reinforcing agent in ceramic composites.
  • the other molecular sieves are one or more of MFI structure zeolite, Beta zeolite, and non-zeolite molecular sieves. More preferably, the other molecular sieves are one or more of HZSM-5, ZRP, and ZSP. ;and / or,
  • the Y-type molecular sieve is one or more of REY, REHY, DASY, SOY, PSRY, HSY, and HRY.
  • a catalytic cracking catalyst for preparing any one of the aforementioned C series technical solutions includes the following steps:
  • Form a slurry including the pseudo-boehmite, Y-type molecular sieve, optional other molecular sieves, binder, clay and water, and
  • the pseudo-boehmite slurry according to any one of the aforementioned C series technical solutions is beaten with water to form a pseudo-boehmite slurry, the solid content of which is preferably 5-25% by weight,
  • hydrochloric acid the mass ratio of HCl to the pseudo-boehmite calculated as alumina is 0.037-0.104, and the concentration of hydrochloric acid can be 10-37% by weight,
  • a colloidal slurry containing Y-type molecular sieve, optional other molecular sieves, binder, clay and water to obtain a colloidal slurry.
  • the solid content of the slurry is preferably 20-40% by weight.
  • a catalytic cracking method including the step of contacting and reacting heavy oil with a catalytic cracking catalyst under FCC conditions, characterized in that the catalytic cracking catalyst is a catalytic cracking catalyst according to any one of the aforementioned C series technical solutions.
  • sodium aluminate and sodium metaaluminate are synonymous, and both refer to: NaAlO 2 .
  • the wavelength of the spectral line, ⁇ is the half-peak width of the specific diffraction peak of pseudo-boehmite (unit: radians), ⁇ is the Bragg diffraction angle of the diffraction peak (unit: degrees), that is, D (130) means that the sample is perpendicular to (130)
  • the possible pore diameter of the pseudo-boehmite is greater than 4.5nm and not more than 12nm, such as 4.5nm-9nm, or 4.8nm-11nm, or 5-10nm, or 5nm-9nm. , or 6-8.5nm, or 7-9nm, or 7.4-8.5nm, or 7.8-8.5nm.
  • the pore size refers to the diameter.
  • the pseudo-boehmite provided by the present invention has a crystallinity of 85%-110%, such as 88%-108%, or 90%-105%, or 99%-105%.
  • the peptization index of the pseudo-boehmite is 90%-100%, for example, 93%-99%.
  • the pseudo-boehmite provided by the present invention has a pore volume of 0.3cm 3 /g-0.58cm 3 /g, such as 0.31cm 3 /g-0.52cm 3 /g, or 0.33-0.5 cm 3 /g.
  • the invention also provides a method for preparing the pseudo-boehmite, which method includes the following steps:
  • the second slurry Aging the first slurry under certain conditions to obtain an aged slurry (called the second slurry); preferably, the aging under certain conditions: first let it stand for aging, and then age under stirring, The aging temperature is above 100°C and not more than 185°C;
  • the concentration of the sodium aluminate solution is preferably 5-60g/L in terms of Al 2 O 3 .
  • the sodium aluminate solution can be Commercially available or prepared according to existing methods.
  • the preparation method of the sodium aluminate solution includes: reacting aluminum hydroxide and alkali solution at a temperature of 90-120°C for 1-4 hours, and diluting to an Al 2 O 3 concentration of 5-60 g/L.
  • the alkali solution is, for example, sodium hydroxide solution.
  • the causticity ratio of the sodium aluminate solution is, for example, 1.0-3.2.
  • step (1) the sodium aluminate solution and CO 2 are contacted and reacted, and a gas containing CO 2 can be passed into the sodium aluminate solution to carry out the reaction, so
  • the volume concentration of CO2 in the CO2- containing gas is 20-100%, for example, 40-100% by volume (the balance is an inert gas such as nitrogen).
  • step (1) the pH value of the reaction end point of the sodium aluminate solution and CO2 is 8.5-10.5.
  • the reaction starting temperature is preferably 10-35°C, and the temperature at the end of the reaction is preferably 15-55°C.
  • step (1) the sodium aluminate solution and CO 2 are contacted and reacted.
  • the reaction time of the reaction between the sodium aluminate solution and CO 2 is preferably 20-70 minutes.
  • the conditions for the reaction of sodium aluminate solution and CO2 include: reaction starting temperature 10-35°C, reaction time 20-70 minutes, reaction End temperature 15-55°C.
  • the end-point pH value of the reaction between sodium aluminate solution and CO2 is 8.5-10.5.
  • the sodium aluminate solution reacts with CO2 , and the sodium aluminate solution is contacted with a CO2 -containing gas.
  • the volume concentration of CO2 in the CO2 - containing gas is 20%-100% (the balance is an inert gas such as nitrogen).
  • the first slurry is aged under certain conditions.
  • the aging temperature is 100-185°C, such as 120-180°C, preferably 135-180°C.
  • the first slurry can be heated to 100-185°C, preferably 120-180°C, or 135-180°C, and then aged at this temperature.
  • the time for the first slurry to rise from the reaction end temperature to the aging temperature does not exceed 60 minutes.
  • the temperature from the beginning of aging to the end of aging is carried out at a constant temperature.
  • the constant temperature aging refers to controlling the temperature of static aging and stirring aging to be basically unchanged.
  • the difference between the temperature of static aging and stirring aging is preferably not more than 2 °C.
  • the aging pressure is preferably 0.2-1MPa.
  • step (2) the stirring speed is controlled at 50-400 r/min.
  • the stirring can adopt existing stirring methods. Through stirring, the aging slurry rotates in the aging kettle driven by the stirring paddle.
  • the aging time is 2-12h, for example, 2-10h.
  • step (2) it is first left to stand and aged at a certain temperature and then aged under stirring.
  • stirring is not performed during aging, so that the slurry is in a static state, for example, the slurry is allowed to stand for a period of time.
  • the first slurry is aged at the aging temperature for 1-8 hours, such as 2.5-7 hours, for 1-4 hours, such as 2-3 hours, and then aged with stirring at the aging temperature for 1-6 hours.
  • the stirring speed is 50-450r/min, such as 50-400r/min, or 60-400r/min, or 100-400r/min.
  • step (2) the first slurry is aged under certain conditions, the aging temperature is 100-185°C, such as 120-180°C, and the pressure is 0.2-1MPa Aging is carried out by constant temperature reaction for 2-10 hours; among which, the first slurry is left to stand for aging for 1-4 hours, such as 2-3 hours, and then the aging temperature and pressure are maintained, stirring is applied, and the stirring speed is controlled to 50-400r/min, such as 60-400r/ min, stirring aging time 1-6h.
  • the aging temperature is 100-185°C, such as 120-180°C
  • the pressure is 0.2-1MPa Aging is carried out by constant temperature reaction for 2-10 hours; among which, the first slurry is left to stand for aging for 1-4 hours, such as 2-3 hours, and then the aging temperature and pressure are maintained, stirring is applied, and the stirring speed is controlled to 50-400r/min, such as 60-400r/ min, stirring aging time 1-6h.
  • the conditions for static aging include: temperature is 120-180°C, preferably 135-180°C, pressure is 0.2-1MPa, and time is 1 -8h, such as 2.5-7h, stirring speed is 100-450r/min;
  • Aging conditions under stirring include: temperature is 120-180°C, preferably 135-180°C, pressure is 0.2-1MPa, and time is 1-6h, such as 1-5h;
  • the ratio of the time of standing aging to the time of aging under stirring is 1-5:1, preferably 1.25-3:1.
  • the aging temperature is 135-180°C.
  • the catalyst obtained in this way can have a better effect of increasing the total yield of liquefied gas and gasoline. .
  • step (3) the aged slurry is filtered, washed and dried to obtain pseudo-boehmite with specific crystal characteristics and variable pore size distribution.
  • the washing condition is to wash with deionized water at 70-100°C until the pH of the wet filter cake is 7-7.5.
  • the drying temperature is preferably 60-98°C, such as 70-98°C, preferably 70-95°C, and the drying time is, for example, 2-4 hours.
  • the pseudo-boehmite provided by the present invention has specific crystal characteristics, such as high crystallinity, large grain size, large pore size, and good peptization (after peptization, it can have large pore size and good durability). Grinding performance), it still has a larger pore size after acidification treatment.
  • the preparation method of pseudo-boehmite provided by the present invention is green, environmentally friendly, low-cost and easy to implement. It can obtain pseudo-boehmite with specific crystal characteristics and variable pore size distribution.
  • the pseudo-boehmite has high crystallinity, Large grain size, large pore size, good peptization (after peptization, it can have a larger pore size and good wear resistance), and after acidification treatment, it can have a larger pore size and good adhesion. .
  • the pseudo-boehmite provided by the present invention can be used for catalyst preparation. Its specific grain morphology makes it easier to accumulate to form a stable mesoporous structure when preparing catalysts, and can obtain larger resiliency than the existing technology. Pore size, the pseudo-boehmite can be directly acidified without pore expansion treatment to obtain a catalyst with larger or several pore sizes, and the catalyst has good strength. For example, when used in the preparation of catalytic cracking catalysts, it can produce an obvious mesopore distribution, and a catalytic cracking catalyst with several pore sizes larger than 5 nm can be obtained, and the catalyst strength can be maintained while significantly improving the catalyst pore structure.
  • the prepared catalytic cracking catalyst can promote the efficient diffusion of heavy oil macromolecules, reaction intermediates and product molecules in the catalyst, reduce coke yield and optimize product distribution.
  • the invention also provides a catalytic cracking catalyst, which contains 10%-50% by weight of Y-type molecular sieve on a dry basis, 0-40% by weight of other molecular sieves on a dry basis, and 10%-50% by weight of alumina on a dry basis.
  • the catalytic cracking catalyst prepared with the pseudo-boehmite according to the present invention has higher liquefied gas and gasoline yields.
  • the catalytic cracking catalyst provided by the invention contains Y-type molecular sieve.
  • the Y-type molecular sieve is, for example, one or more of REY, REHY, DASY, SOY, PSRY, HSY, and HRY.
  • the catalytic cracking catalyst provided by the present invention may optionally contain other molecular sieves other than Y-type molecular sieves. Based on the weight of the catalytic cracking catalyst, on a dry basis, the content of the other molecular sieves is, for example, 0-40% by weight, or 0-30% % by weight, or 1-20% by weight.
  • the other molecular sieves include, for example, one or more of MFI structure zeolite, Beta zeolite, and non-zeolite molecular sieves.
  • the MFI structure zeolite is, for example, one or more of HZSM-5, ZRP, and ZSP
  • the beta zeolite is, for example, H ⁇
  • the non-zeolite molecular sieve is, for example, aluminum phosphate molecular sieve (AlPO molecular sieve), silicoaluminophosphorus molecular sieve (SAPO molecular sieve). one or more.
  • AlPO molecular sieve aluminum phosphate molecular sieve
  • SAPO molecular sieve silicoaluminophosphorus molecular sieve
  • the catalytic cracking catalyst provided by the present invention contains clay.
  • the clay is selected from one or more clays used as cracking catalyst components, such as kaolin, halloysite (halloysite), montmorillonite, diatomaceous earth, saponite, retort clay, seafoam One or more of stone, attapulgite, hydrotalcite and bentonite. These clays are well known to those of ordinary skill in the art.
  • the content of the clay in the catalytic cracking catalyst provided by the present invention is 10-80% by weight on a dry basis, such as 20-55% by weight, or 30-50% by weight.
  • the catalytic cracking catalyst provided by the invention contains a binder.
  • the binder is an alumina binder.
  • the content of the alumina binder is 3-20% by weight, for example, 5-15% by weight. .
  • the alumina binder is preferably aluminum sol, and the catalytic cracking catalyst contains 3-20 wt%, such as 4-10 wt% or 5-15 wt% aluminum sol based on alumina.
  • the catalytic cracking catalyst provided by the present invention has a pore distribution between 3-4nm, such as 3.5-4nm, and also has obvious pore distribution between 4.5-10nm, such as 5-9.5nm or 6.5-9nm, preferably 7.7-8.6nm. pore size distribution.
  • the catalytic cracking catalyst has a dual pore size distribution.
  • the pores with smaller pores may have a pore diameter of 3.5-4nm, and the pores with larger pores may have a pore diameter of 4.5-10nm, such as 5-9.5nm or 6.5nm. -9nm is preferably 7.7-8.6nm.
  • the invention also provides a preparation method of the catalyst of the invention, which preparation method generally includes forming a slurry including pseudo-boehmite according to the invention, Y-type molecular sieve, optional other molecular sieves, binder, clay and water. , spray drying, optional washing and drying steps. Spray drying, washing and drying are existing technologies, and the present invention has no special requirements.
  • the catalytic cracking catalyst can be prepared according to existing methods, for example, according to the methods disclosed in patents CN1098130A and CN1362472A.
  • the preparation method of the catalytic cracking catalyst includes It includes: beating the pseudo-boehmite according to the present invention with water to form a pseudo-boehmite slurry, the solid content of the pseudo-boehmite slurry is preferably 5-25% by weight, and then adding hydrochloric acid, HCl and
  • the mass ratio of pseudo-boehmite according to the present invention based on alumina is preferably 0.037-0.104, and the concentration of hydrochloric acid can be 10-37% by weight, and then mixed with Y-type molecular sieves, optional other molecular sieves, and binders.
  • clay and water slurries are mixed to obtain a colloidal slurry, the solid content of the slurry is preferably 20-40% by weight, spray-dried, optionally washed and dried.
  • the preparation method of the catalytic cracking catalyst provided by the present invention may also include preparing the pseudo-boehmite according to the present invention, and forming the pseudo-boehmite according to the present invention, Y-type molecular sieve, alumina binder, clay and water. slurry, spray drying step.
  • the present invention also provides a catalytic cracking method, which includes the step of contacting and reacting heavy oil with the catalytic cracking catalyst provided by the present invention under heavy oil FCC conditions.
  • the heavy oil is one or more of vacuum wax oil, atmospheric pressure residual oil, vacuum residual oil, and heavy deasphalted oil
  • the FCC conditions are reaction conditions for fluidized catalytic cracking of heavy oil, Normally, the reaction temperature of this reaction is 480-530°C, the reaction time is 1-10 seconds, and the agent-to-oil ratio is 3-20:1 by weight.
  • the catalytic cracking catalyst provided by the present invention contains the pseudo-boehmite according to the present invention, has significantly larger mesopores, for example, can have obvious mesopores with a pore diameter of 5-10 nm, and has better resistance to heavy oil molecules. Diffusion properties, high accessibility of active centers, and lower coke selectivity.
  • the catalytic cracking catalyst provided by the present invention is used for catalytic cracking of heavy oil. Compared with the existing catalytic cracking catalyst containing conventional pseudo-boehmite, it has lower coke selectivity and can have higher gasoline yield and liquefied gas yield under preferred circumstances. Rate.
  • the catalytic cracking catalyst preparation method provided by the invention does not need to increase the usage of other binders, and can produce significantly larger mesopores under the condition that the catalyst strength is qualified.
  • the catalyst can have more mesopores larger than 5 nm, significantly improving
  • the pore structure of the catalyst is conducive to promoting the efficient diffusion of heavy oil macromolecules, reaction intermediates and product molecules in the catalyst. Under optimal circumstances, it can increase the yield of gasoline and liquefied gas.
  • the crystallinity and grain size D of the sample were measured by X-ray powder diffraction (XRD), using the RIPP139-90 and RIPP140-90 standard methods (see “Petrochemical “Industrial Analytical Method” (RIPP test method) edited by Yang Cuiding et al., Science Press, published in 1990).
  • the standard sample number is S87-16b, which was prepared by the Petrochemical Science Research Institute and is commercially available. After calibration, its pseudo-boehmite crystallinity is 98.0%. Calculate the crystallinity of the sample according to the following formula:
  • Crystallinity net integrated intensity of the sample/net integrated intensity of the standard sample ⁇ 98.0
  • the pore distribution and pore volume of the sample were determined by the low-temperature nitrogen static capacity adsorption method, the specific surface area and pore volume were calculated using the two-parameter BET formula, and the pore size distribution was calculated using the BJH formula.
  • the highest point of the pore size distribution curve corresponds to The pore size is the possible pore size of the sample.
  • the American Micromeritics ASAP 2405N V1.01 automatic adsorption instrument was used. The sample was vacuumed and degassed at 1.33 ⁇ 10 -2 Pa and 300°C for 4 hours. N2 was used as the adsorption medium, and the adsorption-desorption isotherm of the sample was measured at 77.4K. .
  • the sodium aluminate used in the examples was produced by Shanghai McLean Biochemical Technology Co., Ltd., with a causticity ratio of 1 and analytical purity.
  • a sodium aluminate solution with a concentration of 20gAl 2 O 3 /L is reacted with a carbon dioxide gas with a volume fraction of 40% (the volume fraction of carbon dioxide is 40% and the remainder is nitrogen) to form a gel, and the endpoint pH value is controlled to 9.5.
  • the obtained slurry is transferred to the aging kettle, it is left to be aged for 3 hours at 135°C and 0.35 MPa. While maintaining this temperature and pressure, start stirring, maintain the stirring rate at 150 r/min, and continue aging for 1 hour.
  • SC1 catalyst contained 30% by weight of molecular sieve, 42% by weight of kaolin, 25% by weight of SP1 pseudoboehmite, and 3% by weight of aluminum sol.
  • a sodium aluminate solution with a concentration of 45gAl 2 O 3 /L is contacted with carbon dioxide gas with a volume fraction of 60% (CO 2 volume fraction is 60%, the remainder is nitrogen), and the end point pH value is controlled to 10.3.
  • carbon dioxide gas with a volume fraction of 60% CO 2 volume fraction is 60%, the remainder is nitrogen
  • the end point pH value is controlled to 10.3.
  • HSY-12 molecular sieve, ZSP-3 molecular sieve, kaolin, water, SP2 pseudo-boehmite binder and aluminum sol were formed into a slurry according to the conventional preparation method of catalytic cracking catalyst, and then spray-dried to prepare into microsphere catalyst, and the prepared catalytic cracking catalyst is designated as SC2.
  • SC2 catalyst contained 30% by weight of molecular sieves (HSY-12 molecular sieve and ZSP-3 molecular sieve), 42% by weight of kaolin, 25% by weight of SP2 pseudoboehmite, and 3% by weight of aluminum sol.
  • a sodium aluminate solution with a concentration of 8gAl 2 O 3 /L is contacted with carbon dioxide gas with a volume fraction of 35% (CO 2 volume fraction is 35%, the rest is nitrogen), and the end point pH value is controlled to 9.3.
  • CO 2 volume fraction is 35%, the rest is nitrogen
  • the end point pH value is controlled to 9.3.
  • the obtained slurry is separated from solid and liquid, and continuously washed with 75°C deionized water for half an hour until the pH value of the wet filter cake is 7.1, to obtain a pseudo-boehmite wet filter cake with impurities removed.
  • the wet filter cake was dried at 75°C for 4 hours and crushed to obtain pseudo-boehmite powder SP3. Its physical and chemical properties are shown in Table 1.
  • a sodium aluminate solution with a concentration of 15gAl 2 O 3 /L is contacted with carbon dioxide gas with a volume fraction of 50% (CO 2 volume fraction is 50%, the remainder is nitrogen), and the endpoint pH value is controlled to 9.7.
  • CO 2 volume fraction is 50%, the remainder is nitrogen
  • the endpoint pH value is controlled to 9.7.
  • the obtained slurry is separated from solid and liquid, and continuously washed with 80°C deionized water for half an hour until the pH value of the wet filter cake is 7.3, to obtain a pseudo-boehmite wet filter cake with impurities removed.
  • the wet filter cake was dried at 85°C for 4 hours and crushed to obtain pseudo-boehmite powder SP4. Its physical and chemical properties are shown in Table 1.
  • the obtained slurry is separated from solid and liquid, and continuously washed with 90°C deionized water for half an hour until the pH value of the wet filter cake is 7.4, to obtain a pseudo-boehmite wet filter cake with impurities removed.
  • the wet filter cake was dried at 95°C for 4 hours and crushed to obtain pseudo-boehmite powder SP5. Its physical and chemical properties are shown in Table 1.
  • a sodium aluminate solution with a concentration of 20gAl 2 O 3 /L is reacted with carbon dioxide gas gelation with a volume fraction of 40%, and the endpoint pH value is controlled to 9.5.
  • the obtained slurry is transferred to the aging kettle, it is left to stand for aging at 90°C for 3 hours.
  • the solid and liquid of the obtained slurry are separated and washed continuously with deionized water at 78°C for half an hour to obtain the product filter cake with the impurities removed. Dry for 3 hours and crush to obtain pseudo-boehmite powder DP1. Its physical and chemical properties are shown in Table 1.
  • Molecular sieve (same as the molecular sieve used in Example 1), kaolin, water, DP1 pseudo-boehmite binder and aluminum sol are formed into a slurry according to the conventional preparation method of catalytic cracking catalyst, and spray-dried to prepare a microsphere catalyst.
  • the prepared The catalytic cracking catalyst is marked as DC1 (refer to the preparation method of Example 1).
  • the obtained DC1 catalyst contained 30% by weight of molecular sieve, 42% by weight of kaolin, 25% by weight of DP1 pseudoboehmite, and 3% by weight of aluminum sol.
  • a sodium aluminate solution with a concentration of 20gAl 2 O 3 /L is reacted with carbon dioxide gas gelation with a volume fraction of 40%, and the endpoint pH value is controlled to 9.5.
  • the obtained slurry was transferred to the aging kettle, it was left to be aged for 3.5 hours at 135°C and 0.35MPa.
  • the obtained slurry was separated from solid and liquid, and washed continuously with deionized water at 80°C for half an hour to obtain a pseudo-boehmite wet filter cake with impurities removed.
  • the wet filter cake was dried at 80°C for 3 hours and crushed to obtain pseudo-boehmite powder DP2. Its physical and chemical properties are shown in Table 1.
  • Molecular sieve, kaolin, water, DP2 pseudo-boehmite binder and aluminum sol are formed into a slurry according to the conventional catalytic cracking catalyst preparation method, and spray-dried to prepare a microsphere catalyst.
  • the prepared catalytic cracking catalyst is recorded as DC2 (reference Preparation method of Example 1).
  • the obtained DC2 catalyst contained 30 weights of molecular sieves. % by weight, 42% by weight of kaolin, 25% by weight of DP2 pseudoboehmite, and 3% by weight of aluminum sol.
  • a high-purity sodium aluminate solution with an Al 2 O 3 content of 45 g/L is used as the raw material, and CO 2 with a concentration of 40% is introduced to perform the gelation reaction.
  • the flow rate per hour is controlled at 3.0m3/h, and the reaction time is controlled at 40 minutes. , control the residual Al 2 O 3 to 5g/l, and control the final temperature to 35°C.
  • the slurry was separated and washed, and the filter cake was washed with high-purity water at 85°C until the pH value of the filter cake was 7.0. Add the filter cake prepared above to high-purity water and stir, then add urea with a concentration of 8g/L.
  • Molecular sieve, kaolin, water, DP3 pseudo-boehmite binder and aluminum sol are formed into a slurry according to the conventional catalytic cracking catalyst preparation method, and spray-dried to prepare a microsphere catalyst.
  • the prepared catalytic cracking catalyst is recorded as DC3 (reference Preparation method of Example 1).
  • the obtained DC3 catalyst contained 30% by weight of molecular sieve, 42% by weight of kaolin, 25% by weight of DP3 pseudoboehmite, and 3% by weight of aluminum sol.
  • a sodium aluminate solution with a concentration of 45gAl 2 O 3 /L is contacted with carbon dioxide gas with a volume fraction of 60% (CO 2 volume fraction is 60%, the remainder is nitrogen), and the end point pH value is controlled to 10.3.
  • carbon dioxide gas with a volume fraction of 60% CO 2 volume fraction is 60%, the remainder is nitrogen
  • the end point pH value is controlled to 10.3.
  • the obtained slurry was transferred to the aging kettle, it was aged for 3.5 hours at a stirring rate of 450 r/min at 180°C and 1.0 MPa.
  • the obtained slurry is separated from solid and liquid, and continuously washed with 95°C deionized water for half an hour until the pH value of the wet filter cake is 7.3, to obtain a pseudo-boehmite wet filter cake with impurities removed.
  • the wet filter cake was dried at 90°C for 4 hours and crushed to obtain pseudo-boehmite powder DP4. Its physical and chemical properties are shown in Table 1.
  • the acid-aluminum ratio (concentration 36% by weight HCl:Al 2 O 3 mass ratio) is 0.2, the solid content of the acidification mixture is 10% by weight; the roasting temperature is 550°C, and the roasting time is 2 hours.
  • the pseudo-boehmite provided by the present invention has higher crystallinity, larger grain size and larger D (130) / D (020) , larger pore diameter, and better peptizing properties. And some pores of the roasted sample after peptization are still larger. It can be seen that compared with the existing pseudo-boehmite, the pseudo-boehmite provided by the present invention is used for the preparation of catalytic cracking catalysts, has a higher possible pore size, and can provide more mesoporous structures.
  • Examples 6-10 illustrate the catalytic cracking reaction performance of the pseudo-boehmite provided by the present invention.
  • Comparative Examples 5-8 illustrate the reaction performance of the catalytic cracking catalyst prepared from pseudo-boehmite in Comparative Examples 1-3.
  • the pseudo-boehmite provided by the present invention has larger grain size and larger D (130) /D (020) , larger pore diameter, higher crystallinity, and better peptizing properties. Moreover, the possible pore diameter of the calcined sample after peptization is still relatively large. As can be seen from Table 2, the catalytic cracking catalyst provided by the present invention has a larger mesopore distribution. In addition to the pore distribution at 3.8 nm, there is a certain mesopore distribution everywhere with higher pore diameters. Catalysts prepared from conventional pseudoboehmite only have mesopore distribution at 3.8 nm.
  • the catalytic cracking catalyst provided by the present invention has significantly lower coke selectivity, higher gasoline yield and liquefied gas yield.
  • the D (130) of the pseudo-boehmite of the specific characteristics is 7.8-8.2 and the D (130) /D (020) is higher than 1.2, it is possible to have significantly higher gasoline and liquefaction Gas production rate.

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Abstract

本发明提供了一种拟薄水铝石，其晶粒大小D(130)和D(020)的比值为D(130)/D(020)＝1.0-1.5，优选地，1.1-1.3。本发明还提供了该拟薄水铝石的制备方法、含该拟薄水铝石的催化裂化催化剂及该催化裂化催化剂的制备方法和应用。该拟薄水铝石应用于催化裂化催化剂中，能够在催化剂强度合格的情况下产生明显的中孔分布，显著改善催化剂的孔结构，对促进重油大分子、反应中间物和产物分子在催化剂中的高效扩散、降低焦炭产率、优化产物分布具有重要的意义。所述拟薄水铝石制备方法绿色环保，成本低廉，易于实施。

Description

一种拟薄水铝石及其制备方法、以及一种含该拟薄水铝石的催化裂化催化剂及其制备和应用 技术领域
本发明涉及一种拟薄水铝石及其制备方法。本发明还涉及一种含该拟薄水铝石的重油催化裂化催化剂及其制备方法和应用。
背景技术
催化裂化是重油加工的重油手段，目前使用的催化裂化催化剂通常包括分子筛和基质材料，氧化铝基质由于具有良好的重油裂化能力，得到了广泛应用。一种常用的氧化铝基质材料是拟薄水铝石。拟薄水铝石在石油炼制和石油化工催化剂中应用广泛，常用作催化裂化催化剂的粘结剂以及加氢催化剂载体(γ-Al2O3)的前驱物。拟薄水铝石酸化后具有良好的粘结性能，可以作为催化裂化催化剂的粘结剂，在催化剂制备成形后还能够形成一定的中孔结构。
拟薄水铝石的化学式为AlOOH·nH2O(0<n<1，特别地0.08-0.62)，是含水量大于薄水铝石而晶粒粒径小于薄水铝石的铝氧化合物。它是合成氢氧化铝过程中易生成的一种晶相，结晶不完整，其典型晶型是很薄的皱折片晶。
拟薄水铝石的制备方法很多，主要包括醇铝水解法和沉淀法等，沉淀法又分为酸法和碱法两大类。
醇铝水解法以金属铝和高级醇(正戊醇、正己醇、异丙醇)为原料，通过在催化剂存在下金属铝与醇反应形成醇铝，再水解得到拟薄水铝石。但该方法生产成本高，生产工艺复杂。
碱沉淀法是指利用碱中和沉淀酸性铝盐制备拟薄水铝石的方法，常用的铝盐有Al2(SO4)3，Al(NO3)3，AlCl3等，常用碱沉淀剂有NaOH，NH3·H2O，NaAlO2，Na2CO3等。
酸沉淀法是指采用酸中和沉淀碱性铝酸盐制备拟薄水铝石的方法，碱性铝酸盐一般为铝酸钠，所用的酸可以是强酸(HNO3、H2SO4等)，也可为弱酸(NH4HCO3、NaHCO3等)及CO2等。其中NaAlO2-CO2法又称碳化法，碳化法制备拟薄水铝石可以依托烧结法生产氧化铝工艺，利用中间产物NaAlO2溶液和铝厂废气CO2作 为反应原料，工艺简单，且生产过程中的副产物、废液等都可以返回氧化铝的生产流程再利用，是目前工业生产拟薄水铝石成本最低的方法。
常规碳化法制备的拟薄水铝石结晶度低，可几孔径仅为3.8nm，制备成催化裂化催化剂时仅能提供3.8nm的中孔结构。现有拟薄水铝石经过酸化处理后，所制备的催化裂化催化剂，可几孔径不超过4.5nm，难以形成可几孔径更大的孔道结构。催化裂化原料分子尺寸较大，在3.8nm或4.5nm的孔道内扩散受到明显的阻碍作用。这种阻碍作用限制了重油原料分子的高效扩散和转化，不利于降低焦炭产率和提升产物分布。
CN110304644A公开了一种碳化法生产高纯高黏拟薄水铝石的方法。其通过预分解提纯铝酸钠溶液得到高纯铝酸钠溶液后和二氧化碳气反应，得到了高纯拟薄水铝石。但该拟薄水铝石可几孔径不高，用于催化裂化催化剂制备过程中无法提供更大的孔径。
现有拟薄水铝石制备的催化裂化催化剂焦炭选择性不佳。目前尚未见文献报道通过碳化法制备的拟薄水铝石酸化胶溶后应用于催化裂化催化剂中能够提供更大的可几孔径分布。
发明内容
本发明要解决的第一个技术问题是提供一种酸化后能够产生更大中孔结构的拟薄水铝石。
本发明要解决的第二个技术问题是提供一种该拟薄水铝石的制备方法。
本发明要解决的第三个技术问题是提供一种催化裂化催化剂，该催化剂含有特定晶体特征的拟薄水铝石，用于催化裂化反应焦炭产率较低。
本发明要解决的第四个技术问题是提供所述催化裂化催化剂的制备和应用方法。
具体来说，本发明提供了下述三组技术方案A、B和C：
A1.一种拟薄水铝石，其特征在于，所述拟薄水铝石的晶粒大小D(130)＝4nm-10nm，D(130)/D(020)为1.0-1.5。
A2.按照技术方案A1所述的拟薄水铝石，其特征在于，所述拟薄水铝石的可几孔径大于4.5nm且不超过12nm例如为4.8nm-11nm；所述拟薄水铝石的可几孔径优选为5nm-10nm。
A3.按照技术方案A1或A2所述的拟薄水铝石，其特征在于，该拟薄水铝石的D(130)/D(020)为1.1-1.3。
A4.按照技术方案A1、A2或A3所述的拟薄水铝石，其特征在于，所述拟薄水铝石的胶溶指数为90％-100％,所述胶溶指数例如为93％-99％；所述拟薄水铝石的结晶度为85％-110％,所述拟薄水铝石的结晶度例如为88％-108％；所述拟薄水铝石的孔容为0.3cm3/g-0.58cm3/g例如为0.31cm3/g-0.52cm3/g。
A5.一种拟薄水铝石的制备方法，包括以下步骤：
(1)使铝酸钠溶液与CO2反应，形成第一浆液；
(2)使所述第一浆液在一定条件下老化，得到老化之后的浆料；所述一定条件下老化：先静止老化，然后在搅拌下老化，老化温度为100℃以上且不超过185℃；
(3)老化之后的浆料过滤、洗涤、干燥。
A6.按照技术方案A5所述的方法，其特征在于，步骤(1)中，所述铝酸钠溶液的浓度以Al2O3计为5-60g/L；所述铝酸钠溶液与CO2反应终点pH值为8.5-10.5。
A7.按照技术方案A5或A6所述的方法，其特征在于，步骤(1)中，所述铝酸钠溶液与CO2反应的条件包括，反应起始温度10-35℃，在铝酸钠溶液中通入CO2浓度为20％-100体积％的含CO2气体进行反应，反应终点温度优选15-55℃。
A8.按照技术方案A5、A6或A7所述的方法，其特征在于，步骤(2)中浆料老化温度为120-180℃，老化压力为0.2-1Mpa，老化时间为2-10h。
A9.按照技术方案A5或A8所述的方法，其特征在于，步骤(2)中静止老化时间为1-4h例如2-3h，搅拌下老化时间为1-6h。
A10.按照技术方案A5、A6或A7或A8或A9所述的方法，其特征在于，所述老化温度为135-180℃，所述老化优选为恒温老化。
A11.按照技术方案A5、A6或A7或A8所述的方法，其特征在于，所述搅拌老化的搅拌速度为50-400r/min。
A12.技术方案A1-A4任一项所述的拟薄水铝石在催化剂制备中的应用。
B1.一种催化裂化催化剂，含有以干基计10重量％-50重量％的Y型分子筛、以干基计0-40重量％的其它分子筛、以氧化铝计10重量-40重量％的具有特定晶体特征的拟薄水铝石、以氧化物计3重量-20重量％的粘结剂和以干基计10重量-80重量％的粘土；所述的具有特定晶体特征的拟薄水铝石，D(130)/D(020)＝1-1.5，D(130)＝4nm-10nm，其中D(130)表示拟薄水铝石晶粒的XRD谱图中(130)峰所代表的晶面的晶粒尺寸，D(020)表示拟薄水铝石晶粒的XRD谱图中(020)峰所代表的晶面的晶粒尺寸。
B2.按照技术方案B1所述的催化裂化催化剂，其特征在于，所述具有特定晶体特征的拟薄水铝石的孔容为0.3cm3/g-0.58cm3/g，可几孔径大于4.5nm-12nm，胶溶指数90％-100％，优选的，所述拟薄水铝石的可几孔径为5nm-10nm，结晶度为85％-110％，所述具有特定晶体特征的拟薄水铝石的D(130)/D(020)优选为1.1-1.3；所述的其它分子筛优选为MFI结构沸石、Beta沸石、非沸石分子筛的一种或几种。
B3.按照技术方案B1所述的催化裂化催化剂，其特征在于，所述Y型分子筛为REY、REHY，DASY、SOY、PSRY、HSY、HRY中的一种或多种；所述的其它分子筛为HZSM-5、ZRP、ZSP中的一种或多种。
B4.按照技术方案B1-B3任一项所述的催化裂化催化剂，其特征在于，所述的具有特定晶体特征的拟薄水铝石，D(130)为6.5-8.2nm例如7.8-8.2nm，D(130)/D(020)为1.22-1.29，可几孔径优选为7.4-8.5nm例如7.8-8.5nm。
B5.按照技术方案B1-B4任一项所述的催化裂化催化剂，其特征在于，所述催化裂化催化剂的可几孔径为3.5-4nm和4.5-10nm。
B6.一种催化裂化催化剂的制备方法，包括制备特定晶体特征的拟薄水铝石，形成包括所述特定晶体特征的拟薄水铝石、Y型分 子筛、任选的其它分子筛、粘结剂、粘土和水的浆液，喷雾干燥的步骤。
B7.按照技术方案B6所述的方法，其特征在于，其中，所述特定晶体特征的拟薄水铝石的制备方法包括以下步骤：
(1)将铝酸钠溶液与CO2反应，生成第一浆液；
(2)将上述第一浆液在一定条件下老化，形成第二浆液；所述一定条件下老化：先静止老化，然后在搅拌下老化，老化温度为100℃以上且不超过185℃；
(3)第二浆液过滤、洗涤、干燥得到具有特定晶体特征的拟薄水铝石。
B8.按照技术方案B7所述的方法，其特征在于，步骤(1)中，所述铝酸钠溶液的Al2O3浓度为5-60g/L；所述铝酸钠溶液与CO2反应终点pH值为8.5-10.5。
B9.按照技术方案B7或B8所述的方法，其特征在于，步骤(1)中，所述铝酸钠溶液与CO2反应的条件包括，反应起始温度10-35℃，在铝酸钠溶液中通入CO2浓度为20体积％-100体积％的含CO2气体进行反应，反应终点温度优选15-55℃。
B10.按照技术方案B7、B8或B9所述的方法，其特征在于，老化压力为0.2-1Mpa，老化时间为2-10h；优选的，步骤(2)中静止老化时间为1-4h例如2-3h后，搅拌下老化时间为1-6h。
B11.按照技术方案B10所述的方法，其特征在于，所述老化温度为135-180℃，所述老化优选为恒温老化，所述搅拌老化的搅拌速度优选为50-400r/min。
B12.根据技术方案B7所述的方法，其特征在于，步骤(3)所述洗涤条件为：用70-100℃的去离子水洗涤至湿滤饼pH值为7-7.5；步骤(3)所述干燥，干燥温度为70-98℃。
B13.按照技术方案B6所述的方法，其特征在于，所述催化裂化催化剂的制备方法为包括：将具有特定晶体特征的拟薄水铝石与水打浆，形成拟薄水铝石浆液，其固含量优选为5-25重量％，加入盐酸，HCl与以氧化铝计的具有特定晶体特征的拟薄水铝石的质量比为0.037-0.104，盐酸的浓度可以为10-37重量％，然后与含Y型 分子筛、任选的其它分子筛、粘结剂、粘土和水的浆液混合得到胶体浆液，浆液的固含量优选为20-40重量％，喷雾干燥，任选洗涤和干燥。
B14.一种催化裂化方法，包括在FCC条件下，将重油与催化裂化催化剂接触反应的步骤，其特征在于，所述的催化裂化催化剂为技术方案B1-B5任意一项所述的催化裂化催化剂或技术方案B6-B13任一项得到的催化裂化催化剂接触反应的步骤；所述的FCC条件例如：反应温度为480-530℃，反应时间1-10秒，剂油比为3-20：1重量比。
C1.一种拟薄水铝石，其特征在于，所述拟薄水铝石的晶粒大小D(130)和D(020)的比值为D(130)/D(020)＝1.0-1.5，优选地，1.1-1.3。
C2.根据前述C系列技术方案中任一项的拟薄水铝石，其特征在于，晶粒大小D由X射线粉末衍射法(XRD)测量，根据Scherrer公式计算晶粒大小D，其中K＝1.075，λ为阳极辐射Kα1谱线的波长，β为拟薄水铝石特定衍射峰的半峰宽(单位为弧度)，θ为衍射峰的Bragg衍射角(单位为度)，即，D(130)表示样品在垂直于(130)晶面的晶粒大小，β130为样品(130)衍射峰(对应2θ＝38.3°)的半峰宽；D(020)表示样品在垂直于(020)晶面的晶粒大小，β020为样品(020)衍射峰(对应2θ＝14.1°)的半峰宽。
C3.根据前述C系列技术方案中任一项的拟薄水铝石，其特征在于，拟薄水铝石的分子式为AlOOH·nH2O，n＝0.08-0.62，其晶粒大小D(130)不大于10nm。
C4.根据前述C系列技术方案中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的晶粒大小D(130)＝4nm-10nm，优选地，6.5-8.2nm，或者7.8-8.2nm。
C5.根据前述C系列技术方案中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的可几孔径大于4.5nm且不超过12nm，例如4.8nm-11nm，或者5nm-10nm。
C6.根据前述C系列技术方案中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的结晶度为85％-110％，例如88％-108％。
C7.根据前述C系列技术方案中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的胶溶指数为90％-100％，例如93％-99％。
C8.根据前述C系列技术方案中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的孔容为0.3cm3/g-0.58cm3/g，例如0.31cm3/g-0.52cm3/g。
C9.一种制备拟薄水铝石的方法，包括以下步骤：
(1)使铝酸钠溶液与CO2反应，形成第一浆液；
(2)使所述第一浆液在一定条件下老化，得到老化之后的浆料；所述一定条件下老化：先静置老化，然后在搅拌下老化，老化温度为100℃以上且不超过185℃；
(3)老化之后的浆料过滤、洗涤、干燥。
C10.按照前述C系列技术方案中任一项的制备拟薄水铝石的方法，其特征在于，步骤(1)中，所述铝酸钠溶液的浓度以Al2O3计为5-60g/L；所述铝酸钠溶液与CO2反应终点pH值为8.5-10.5。
C11.按照前述C系列技术方案中任一项的制备拟薄水铝石的方法，其特征在于，步骤(1)中，所述铝酸钠溶液与CO2反应的条件包括，反应起始温度10-35℃，在铝酸钠溶液中通入CO2浓度为20％-100体积％的含CO2气体(余量为惰性气体如氮气)进行反应，反应终点温度优选15-55℃。
C12.按照前述C系列技术方案中任一项的制备拟薄水铝石的方法，其特征在于，步骤(2)中浆料老化温度为120-180℃，老化压力为0.2-1MPa，老化时间为2-12h，例如，2-10h。
C13.按照前述C系列技术方案中任一项的制备拟薄水铝石的方法，其特征在于，步骤(2)中静置老化时间为1-8h，例如2.5-7h，或1-4h，例如2-3h，搅拌下老化时间为1-6h。
C14.按照前述C系列技术方案中任一项的制备拟薄水铝石的方法，其特征在于，所述老化温度为135-180℃，所述老化优选为恒温老化。
C15.按照前述C系列技术方案中任一项的制备拟薄水铝石 的方法，其特征在于，所述搅拌老化的搅拌速度为50-450r/min，100-400r/min。
C16.按照前述C系列技术方案中任一项的制备拟薄水铝石的方法，其特征在于，步骤(2)中，
静置老化的条件包括：温度为120-180℃，优选135-180℃，压力为0.2-1MPa，时间为1-8h，例如2.5-7h，搅拌速度为100-450r/min；
搅拌下老化的条件包括：温度为120-180℃，优选135-180℃，压力为0.2-1MPa，时间为1-6h，例如1-5h；
优选地，静置老化的时间与搅拌下老化的时间的比值为1-5:1，优选1.25-3:1。
C17.按照前述C系列技术方案中任一项的制备拟薄水铝石的方法，其特征在于，步骤(3)所述洗涤条件为：用70-100℃的去离子水洗涤至湿滤饼pH值为7-7.5；步骤(3)所述干燥，干燥温度为70-98℃。
C18.按照前述C系列技术方案中任一项的拟薄水铝石在石油工业中用作催化剂、载体、粘结剂；在汽车工业中用作汽车尾气处理催化剂的载体涂层；在消防领域用作阻燃材料的添加剂；在造纸行业中用作高档喷墨打印纸中的吸墨涂层；在环保行业中用作气体净化吸附剂、饮用水除氟剂、工业污水颜色和气味消除剂；在建筑行业用作涂料添加剂；陶瓷复合材料中的增强剂中的用途。
C19.一种催化裂化催化剂，含有以干基计10重量％-50重量％的Y型分子筛、以干基计0-40重量％的其它分子筛、以氧化铝计10重量-40重量％的按照前述C系列技术方案中任一项的拟薄水铝石、以氧化物计3重量-20重量％的粘结剂和以干基计10重量-80重量％的粘土；
优选地，所述的其它分子筛为MFI结构沸石、Beta沸石、非沸石分子筛的一种或几种，更优选地，所述的其它分子筛为HZSM-5、ZRP、ZSP中的一种或多种；和/或，
优选地，所述Y型分子筛为REY、REHY，DASY、SOY、PSRY、HSY、HRY中的一种或多种。
C20.一种制备前述C系列技术方案中任一项的催化裂化催 化剂的方法，包括以下的步骤：
制备按照前述C系列技术方案中任一项的拟薄水铝石，
形成包括所述的拟薄水铝石、Y型分子筛、任选的其它分子筛、粘结剂、粘土和水的浆液，和
喷雾干燥。
C21.按照前述C系列技术方案中任一项的制备催化裂化催化剂的方法，其特征在于，所述方法为包括：
将按照前述C系列技术方案中任一项的拟薄水铝石与水打浆，形成拟薄水铝石浆液，其固含量优选为5-25重量％，
加入盐酸，HCl与以氧化铝计的所述的拟薄水铝石的质量比为0.037-0.104，盐酸的浓度可以为10-37重量％，
然后与含Y型分子筛、任选的其它分子筛、粘结剂、粘土和水的浆液混合得到胶体浆液，浆液的固含量优选为20-40重量％，
喷雾干燥，和
任选地，洗涤和干燥。
C22.一种催化裂化方法，包括在FCC条件下，将重油与催化裂化催化剂接触反应的步骤，其特征在于，所述的催化裂化催化剂为按照前述C系列技术方案中任一项的催化裂化催化剂或按照前述C系列技术方案中任一项的制备催化裂化催化剂的方法得到的催化裂化催化剂；例如，所述的FCC条件包括：反应温度为480-530℃，反应时间1-10秒，剂油比为3-20:1重量比。
具体实施方式
本文中，压强为表压，除非明确指出。
本文中，含量是基于重量百分比的值，除非明确指出。
本文中，铝酸钠和偏铝酸钠是同义的，均是指：NaAlO2。
本发明提供一种的拟薄水铝石，所述拟薄水铝石的晶粒大小D(130)和D(020)的比值为D(130)/D(020)＝1.0-1.5，优选地，1.1-1.4，或者1.1-1.3，或者1.2-1.35，或者1.22-1.29。
晶粒大小D由X射线粉末衍射法(XRD)测量，根据Scherrer公式计算晶粒大小D，其中K＝1.075，λ为阳极辐射Kα1 谱线的波长，β为拟薄水铝石特定衍射峰的半峰宽(单位为弧度)，θ为衍射峰的Bragg衍射角(单位为度)，即，D(130)表示样品在垂直于(130)晶面的晶粒大小，β130为样品(130)衍射峰(对应2θ＝38.3°)的半峰宽；D(020)表示样品在垂直于(020)晶面的晶粒大小，β020为样品(020)衍射峰(对应2θ＝14.1°)的半峰宽。
本发明提供的拟薄水铝石，所述拟薄水铝石的分子式为AlOOH·nH2O，n＝0.08-0.62，其晶粒大小D(130)不大于10nm。
本发明提供的拟薄水铝石，所述拟薄水铝石的晶粒大小D(130)＝4nm-10nm，优选地，5nm-8.5nm，或者5.1-8.5nm，或者5.5-8.5nm，或者6-8.2nm，或者6.5-8.2nm，或者7.8-8.2nm。
本发明提供的拟薄水铝石，所述拟薄水铝石的可几孔径大于4.5nm且不超过12nm，例如4.5nm-9nm，或者4.8nm-11nm，或者5-10nm，或者5nm-9nm，或者6-8.5nm，或者7-9nm，或者7.4-8.5nm，或者7.8-8.5nm。所述孔径指直径。
本发明提供的拟薄水铝石，所述拟薄水铝石的结晶度为85％-110％，例如88％-108％，或者90％-105％，或者99％-105％。
本发明提供的拟薄水铝石，所述拟薄水铝石的胶溶指数为90％-100％，例如93％-99％。
本发明提供的拟薄水铝石，所述拟薄水铝石的孔容为0.3cm3/g-0.58cm3/g，例如0.31cm3/g-0.52cm3/g，或者0.33-0.5cm3/g。
本发明还提供一种所述拟薄水铝石的制备方法，该方法包括以下步骤：
(1)使铝酸钠(或称偏铝酸钠)溶液与CO2反应，形成第一浆液；
(2)使所述第一浆液在一定条件下老化，得到老化之后的浆料(称为第二浆液)；优选地，所述一定条件下老化：先静置老化，然后在搅拌下老化，老化温度为100℃以上且不超过185℃；
(3)老化之后的浆料过滤、洗涤、干燥。
根据本发明所述拟薄水铝石的制备方法，在步骤(1)中，所述铝酸钠溶液的浓度以Al2O3计优选为5-60g/L。所述铝酸钠溶液可以 商购或按照现有方法制备。例如，所述铝酸钠溶液的制备方法包括：将氢氧化铝和碱液在温度90-120℃下反应1-4h，稀释到Al2O3浓度为5-60g/L。所述碱液例如为氢氧化钠溶液。所述铝酸钠溶液的苛性比例如为1.0-3.2。
根据本发明所述拟薄水铝石的制备方法，在步骤(1)中，使铝酸钠溶液与CO2接触反应，可以在铝酸钠溶液中通入含CO2的气体进行反应，所述含CO2气体中CO2的体积浓度为20-100％，例如为40-100体积％(余量为惰性气体如氮气)。
根据本发明所述拟薄水铝石的制备方法，在步骤(1)中，铝酸钠溶液与CO2反应终点的pH值为8.5-10.5。
根据本发明所述拟薄水铝石的制备方法，在步骤(1)中，反应起始温度优选为10-35℃，反应终点时的温度优选为15-55℃。
根据本发明所述拟薄水铝石的制备方法，在步骤(1)中，使铝酸钠溶液与CO2接触反应，铝酸钠溶液与CO2反应的反应时间优选为20-70分钟。
根据本发明所述拟薄水铝石的制备方法，在步骤(1)中，铝酸钠溶液与CO2反应的条件包括，反应起始温度10-35℃，反应时间20-70分钟，反应终点温度15-55℃。铝酸钠溶液与CO2反应终点pH值为8.5-10.5。优选的，所述铝酸钠溶液与CO2反应，将铝酸钠溶液与含CO2的气体接触反应，所述含CO2的气体中CO2的体积浓度为20％-100％(余量为惰性气体如氮气)。
根据本发明所述拟薄水铝石的制备方法，在步骤(2)中，使所述第一浆液在一定条件下老化。在一种实施方式中，老化温度为100-185℃，例如120-180℃，优选135-180℃。可以将第一浆液加热到100-185℃，优选120-180℃，或135-180℃，然后在该温度下老化。优选的，第一浆液从反应终点温度升高到老化温度的时间不超过60分钟。优选的，从老化开始到老化结束的温度在恒温下进行，所述恒温老化是指控制静置老化和搅拌老化的温度基本不变，例如静置老化和搅拌老化温度的相差最好不超过2℃。
根据本发明所述拟薄水铝石的制备方法，在步骤(2)中，老化压力优选为0.2-1MPa。
根据本发明所述拟薄水铝石的制备方法，在步骤(2)中，搅拌速度控制50-400r/min。所述搅拌可以采用现有搅拌方法，通过搅拌，老化浆液在搅拌桨的带动下在老化釜中旋转。
根据本发明所述拟薄水铝石的制备方法，在步骤(2)中，所述老化的老化时间为2-12h，例如，2-10h。
根据本发明所述拟薄水铝石的制备方法，在步骤(2)中，先在一定温度下静置老化然后在搅拌下老化。所述静置老化，老化时不进行搅拌，使浆液处于静止状态例如将浆液静置一段时间。优选的，先将第一浆液在老化温度下静置老化1-8h，例如2.5-7h，1-4小时例如2-3h，然后在老化温度下搅拌老化1-6小时。搅拌速度50-450r/min，例如50-400r/min，或者60-400r/min，或者100-400r/min。
根据本发明所述拟薄水铝石的制备方法，在步骤(2)中，使第一浆液在一定条件下老化，老化温度为100-185℃，例如120-180℃，压力为0.2-1MPa恒温反应2-10h进行老化；其中，先将第一浆液静置老化1-4小时例如2-3h，然后保持老化温度和压力，施加搅拌，搅拌速度控制50-400r/min例如60-400r/min，搅拌老化时间1-6h。
根据本发明所述拟薄水铝石的制备方法，在步骤(2)中，静置老化的条件包括：温度为120-180℃，优选135-180℃，压力为0.2-1MPa，时间为1-8h，例如2.5-7h，搅拌速度为100-450r/min；
搅拌下老化的条件包括：温度为120-180℃，优选135-180℃，压力为0.2-1MPa，时间为1-6h，例如1-5h；
优选地，静置老化的时间与搅拌下老化的时间的比值为1-5:1，优选1.25-3:1。
根据本发明所述拟薄水铝石的制备方法，在步骤(2)中，所述老化的温度为135-180℃，这样获得的催化剂可以具有更好的增加液化气和汽油总产率效果。
根据本发明所述拟薄水铝石的制备方法，在步骤(3)中，老化之后的浆料经过过滤、洗涤、干燥，得到具有特定晶体特征和可几孔径分布的拟薄水铝石。例如，所述洗涤条件为用70-100℃的去离子水洗涤至湿滤饼的pH为7-7.5。所述干燥温度优选为60-98℃例如70-98℃，优选70-95℃，干燥时间例如2-4h。
本发明提供的拟薄水铝石具有特定晶体特征，结晶度高、晶粒尺寸大、具有较大可几孔径、胶溶性好(胶溶后可以具有较大的可几孔径并具有良好的耐磨性能)，酸化处理后仍具有较大的可几孔径。
本发明提供的拟薄水铝石的制备方法，绿色环保，成本低廉，易于实施，可以得到具有特定晶体特征和可几孔径分布的拟薄水铝石，该拟薄水铝石结晶度高、晶粒尺寸大、可几孔径大、胶溶性好(胶溶后可以具有较大的可几孔径并具有良好的耐磨性能)，酸化处理后具有较大的可几孔径和良好的粘结性。
本发明提供的拟薄水铝石，可以用于催化剂制备，其特定的晶粒形貌，在制备催化剂的时候更容易堆积形成稳定的中孔结构，能够获得比现有技术更大的可几孔径，所述拟薄水铝石可以不经扩孔处理直接酸化得到较大可几孔径的催化剂并使催化剂具有良好的强度。例如用于催化裂化催化剂制备能够产生明显的中孔分布，可以获得具有大于5nm可几孔径的催化裂化催化剂，在显著改善催化剂孔结构的情况下保持催化剂强度合格。所制备的催化裂化催化剂，能促进重油大分子、反应中间物和产物分子在催化剂中的高效扩散，降低焦炭产率，优化产物分布。
本发明还提供一种催化裂化催化剂，以干基重量为基准，含有以干基计10重量％-50重量％的Y型分子筛、0-40重量％的其它分子筛，以氧化铝计10重量-40重量％(例如15-35重量％，或者20-30重量％)的根据本发明的拟薄水铝石、以氧化物计3重量-20重量％的粘结剂和以干基计10重量-80重量％的粘土。
在相同条件下，用根据本发明的拟薄水铝石制备的催化裂化催化剂具有更高的液化气和汽油收率。
在本发明提供的催化裂化催化剂中，含有Y型分子筛。所述Y型分子筛例如REY、REHY，DASY、SOY、PSRY、HSY、HRY中的一种或多种。
在本发明提供的催化裂化催化剂中，任选地，还可含有Y型分子筛以外的其它分子筛。以所述催化裂化催化剂的重量为基准，以干基计，所述的其它分子筛的含量例如为0-40重量％，或者0-30 重量％，或者1-20重量％。所述其它分子筛例如具有MFI结构沸石、Beta沸石、非沸石分子筛的一种或几种。所述MFI结构沸石例如HZSM-5、ZRP、ZSP中的一种或多种，所述beta沸石例如Hβ，非沸石分子筛例如磷酸铝分子筛(AlPO分子筛)、硅铝磷分子筛(SAPO分子筛)中的一种或多种。优选为具有MFI结构的分子筛，可以进一步提高液化气收率。
在本发明提供的催化裂化催化剂中，含有粘土。所述粘土选自用作裂化催化剂组分的粘土中的一种或几种，例如高岭土、多水高岭土(埃洛石)、蒙脱土、硅藻土、皂石、累托土、海泡石、凹凸棒石、水滑石、膨润土中的一种或几种。这些粘土为本领域普通技术人员所公知。优选的，以干基计本发明提供的催化裂化催化剂中所述粘土的含量为10重量-80重量％，例如20-55重量％，或者30-50重量％。
本发明提供的催化裂化催化剂中，含有粘结剂，所述的粘结剂为氧化铝粘结剂，所述氧化铝粘结剂的含量为3-20重量％，例如为5-15重量％。
所述氧化铝粘结剂优选铝溶胶，所述催化裂化催化剂中含有以氧化铝计3-20重量％，例如4-10重量％或5-15重量％的铝溶胶。
本发明提供的所述催化裂化催化剂在孔径3-4nm例如3.5-4nm之间具有孔分布，和在孔径4.5-10nm，例如5-9.5nm或6.5-9nm优选7.7-8.6nm之间也具有明显的孔径分布。优选的，所述催化裂化催化剂具有双可几孔径分布，孔径较小孔的可几孔径为3.5-4nm，孔径较大孔的可几孔径在孔径为4.5-10nm，例如5-9.5nm或6.5-9nm优选7.7-8.6nm。
本发明还提供了本发明所述催化剂的制备方法，该制备方法通常包括形成包括根据本发明的拟薄水铝石、Y型分子筛、任选的其它分子筛、粘结剂、粘土和水的浆液，喷雾干燥，任选洗涤和干燥的步骤。喷雾干燥、洗涤、干燥为现有技术，本发明没有特殊要求。可以按照现有方法制备催化裂化催化剂，例如按照专利CN1098130A、CN1362472A所公开的方法制备。
根据一种优选的实施方式，所述催化裂化催化剂的制备方法包 括：将所述根据本发明的拟薄水铝石与水打浆，形成拟薄水铝石浆液，所述拟薄水铝石浆液其固含量优选5-25重量％，然后加入盐酸，HCl与以氧化铝计的根据本发明的拟薄水铝石的质量比优选为0.037-0.104，盐酸的浓度可以为10-37重量％，然后与含Y型分子筛、任选的其它分子筛、粘结剂、粘土和水的浆液混合得到胶体浆液，浆液的固含量优选为20-40重量％，喷雾干燥，任选洗涤和干燥。
本发明提供的催化裂化催化剂制备方法还可以包括制备根据本发明的拟薄水铝石，形成包括所述根据本发明的拟薄水铝石、Y型分子筛、氧化铝粘结剂、粘土和水的浆液，喷雾干燥的步骤。
本发明还提供了一种催化裂化方法，包括在重油FCC的条件下将重油与本发明提供的催化裂化催化剂接触反应的步骤。其中，所述的重油例如减压蜡油、常压渣油、减压渣油、重脱沥青油中的一种或多种，所述的FCC条件，为重油流化催化裂化的反应条件，通常情况下，该反应的反应温度为480-530℃，反应时间1-10秒，剂油比为3-20:1重量比。
本发明提供的催化裂化催化剂，含有所述的根据本发明的拟薄水铝石，具有明显更大的中孔，例如可以在孔径为5-10nm具有明显中孔，对重油分子具有更好的扩散性能，活性中心可接近性高，焦炭选择性更低。本发明提供的催化裂化催化剂用于重油催化裂化，较现有含常规拟薄水铝石的催化裂化催化剂具有更低的焦炭选择性，优选情况下可以具有更高的汽油收率和液化气收率。
本发明提供的催化裂化催化剂制备方法，无需增加其它粘结剂的使用量，能够在催化剂强度合格的情况下产生明显更大的中孔，例如催化剂可以具有更多大于5nm的中孔，显著改善催化剂的孔结构，有利于促进重油大分子、反应中间物和产物分子在催化剂中高效扩散，优选的情况下可以提高汽油和液化气的产率。
具体实施方式
下面的实施将对本发明进一步说明，但不能用于限制本发明。
本申请中，样品的结晶度和晶粒大小D由X射线粉末衍射法(XRD)测量，采用RIPP139-90、RIPP140-90标准方法(见《石油化 工分析方法》(RIPP试验方法)杨翠定等编，科学出版社，1990年出版)测定。
采用外标法，通过测量试样与标样S87-16b的2θ＝38.3°处(130晶面)的积分强度，计算出试样中拟薄水铝石的结晶度。标样编号为S87-16b，由石油化工科学研究院制备且市售可得。经标定，其拟薄水铝石结晶度为98.0％。按照下式计算试样的结晶度：
结晶度＝试样的净积分强度/标样的净积分强度×98.0
根据Scherrer公式计算晶粒大小，其中K＝1.075，λ为阳极辐射Kα1谱线的波长，β为拟薄水铝石特定衍射峰的半峰宽，θ为衍射峰的Bragg衍射角。D(130)表示样品在垂直于(130)晶面的晶粒大小，β130为样品(130)衍射峰的半峰宽。D(020)表示样品在垂直于(020)晶面的晶粒大小，β020为样品(020)衍射峰的半峰宽。
在本申请中，样品的可几孔分布和孔容由低温氮静态容量吸附法测定，利用两参数BET公式计算比表面积和孔容，利用BJH公式计算孔径分布，孔径分布曲线的最高点对应的孔径大小为样品的可几孔径。采用美国Micromeritics公司ASAP 2405N V1.01自动吸附仪，样品在1.33×10-2Pa、300℃下抽真空脱气4h，以N2为吸附介质，在77.4K下测定样品的吸附-脱附等温线。
在本申请中，胶溶指数的测定：称取拟薄水铝石10克，经600℃焙烧3小时，置于保干器中冷却，温度降至室温后，称重得W0克，得到干基a0＝W0/10，称取拟薄水铝石重量m1＝6/a0克，将称取m1克拟薄水铝石置于100mL的聚四氟乙烯杯中，加入去离子水至40克，使用磁力转子搅拌均匀后，再加入20mL 0.19N的稀硝酸溶液，磁力搅拌20分钟，将全部溶液倒入离心管中，放入离心机中，以1900转/min的转速，离心分离20分钟。倾倒出上部胶体溶液，放于称重过的坩埚中，于80℃烘干，600℃焙烧3小时，置于保干器中冷却，温度降至室温后，称重得m2克，胶溶指数DI＝(m2/6)*100％。
实施例所用的铝酸钠，上海麦克林生化科技有限公司生产，苛性比1，分析纯。
实施例1
将浓度为20gAl2O3/L的铝酸钠溶液与体积分数40％的二氧化碳气(其中，二氧化碳体积分数为40％，其余为氮气)成胶反应，控制终点PH值9.5。将所得浆料转移至老化釜后，于135℃、0.35MPa下静置老化3h，保持该温度和压力条件下，启动搅拌，保持搅拌速率150r/min，继续老化1h。老化结束后将所得浆液固液分离，85℃去离子水连续洗涤半小时至湿滤饼pH值7.1，得到脱除杂质的拟薄水铝石湿滤饼。湿滤饼于80℃干燥3h，粉碎得到拟薄水铝石粉体SP1，其物化性质见表1。
取714.5克氧化铝含量为21重量％的铝溶胶加入1565.5克脱阳离子水中，开启搅拌，加入2763克固含量为76重量％的高岭土分散60分钟，得到分散好的高岭土浆液。取2049克氧化铝含量为61重量％的SP1拟薄水铝石加入8146克脱阳离子水中，在搅拌状态下加入210ml质量浓度为36％的盐酸，酸化60分钟后加入分散好的高岭土浆液，然后加入磨细的分子筛(为HSY-12分子筛和ZSP-3分子筛，以干基计HSY-12分子筛：ZSP-3分子筛重量比为14：1；均为中国石化催化剂齐鲁分公司产品；其中HSY-12分子筛，Re2O3含量11.6重量％，结晶度50.3％，Na2O含量0.9重量％，Si/Al摩尔比为2.5，磨细粒度d(0.5)＝2.6，d(0.9)＝6.6)；ZSP-3分子筛：Fe2O3含量1.7重量％，P2O5含量3.9重量％，结晶度78％，Na2O含量0.05重量％，Si/Al摩尔比为25，磨细粒度d(0.5)＝3.9，d(0.9)＝7.8)各实施例、对比例用的分子筛相同)1500克(以干基计)，搅拌均匀后，进行喷雾干燥和洗涤处理，烘干得到催化剂，记为SC1。其中以干基计，所得到的SC1催化剂中含有分子筛30重量％，高岭土42重量％，SP1拟薄水铝石25重量％，铝溶胶3重量％。
实施例2
将浓度为45gAl2O3/L的铝酸钠溶液与体积分数60％的二氧化碳气(CO2体积分数60％，其余为氮气)接触反应，控制终点PH值10.3。将所得浆料转移至老化釜后，于180℃、1.0MPa下静置老化2.5h，然后保持温度和压力180℃、1.0MPa条件下，启动搅拌，保持搅拌速率450r/min，老化1h。老化结束后将所得浆液固液分离， 用95℃去离子水连续洗涤半小时至湿滤饼pH值7.3，得到脱除杂质的拟薄水铝石湿滤饼。湿滤饼于90℃干燥4h，粉碎得到拟薄水铝石粉体SP2，其物化性质见表1。
参考实施例1的制备方法，将HSY-12分子筛、ZSP-3分子筛、高岭土、水、SP2拟薄水铝石粘合剂以及铝溶胶按常规的催化裂化催化剂的制备方法形成浆液、喷雾干燥制备成微球催化剂，所制备的催化裂化催化剂记为SC2。其中以干基计，所得到的SC2催化剂中含有分子筛(HSY-12分子筛和ZSP-3分子筛)30重量％，高岭土42重量％，SP2拟薄水铝石25重量％，铝溶胶3重量％。
实施例3
将浓度为8gAl2O3/L的铝酸钠溶液与体积分数35％的二氧化碳气(CO2体积分数35％，其余为氮气)接触反应，控制终点PH值9.3。将所得浆料转移至老化釜后，于120℃、0.2MPa下静置老化4h，然后保持温度和压力120℃、0.2MPa条件下，启动搅拌，保持搅拌速率100r/min，老化2.5h。老化结束后将所得浆液固液分离，用75℃去离子水连续洗涤半小时至湿滤饼pH值7.1，得到脱除杂质的拟薄水铝石湿滤饼。湿滤饼于75℃干燥4h，粉碎得到拟薄水铝石粉体SP3，其物化性质见表1。
按照实施例1的方法，用SP3代替SP1制备催化剂，得到SC3。
实施例4
将浓度为15gAl2O3/L的铝酸钠溶液与体积分数50％的二氧化碳气(CO2体积分数50％，其余为氮气)接触反应，控制终点PH值9.7。将所得浆料转移至老化釜后，于150℃、0.48MPa下静置老化5h，然后保持温度和压力150℃、0.48MPa条件下，启动搅拌，保持搅拌速率250r/min，老化4h。老化结束后将所得浆液固液分离，用80℃去离子水连续洗涤半小时至湿滤饼pH值7.3，得到脱除杂质的拟薄水铝石湿滤饼。湿滤饼于85℃干燥4h，粉碎得到拟薄水铝石粉体SP4，其物化性质见表1。
按照实施例1的方法，用SP4代替SP1制备催化剂，得到SC4。
实施例5
将浓度为55gAl2O3/L的铝酸钠溶液与体积分数90％的二氧化 碳气(CO2体积分数90％，其余为氮气)接触反应，控制终点PH值10.0。将所得浆料转移至老化釜后，于160℃、0.62MPa下静置老化7h，然后保持温度和压力160℃、0.62MPa条件下，启动搅拌，保持搅拌速率350r/min，老化5h。老化结束后将所得浆液固液分离，用90℃去离子水连续洗涤半小时至湿滤饼pH值7.4，得到脱除杂质的拟薄水铝石湿滤饼。湿滤饼于95℃干燥4h，粉碎得到拟薄水铝石粉体SP5，其物化性质见表1。
按照实施例1的方法，用SP5代替SP1制备催化剂，得到SC5。
对比例1
将浓度为20gAl2O3/L的铝酸钠溶液与体积分数40％的二氧化碳气成胶反应，控制终点PH值9.5。将所得浆料转移至老化釜后，于90℃静置老化3h，老化结束后将所得浆液固液分离，78℃去离子水连续洗涤半小时，得到脱除杂质的产物滤饼，于90℃干燥3h，粉碎得到拟薄水铝石粉体DP1，其物化性质见表1。
将分子筛(同实施例1所用分子筛)、高岭土、水、DP1拟薄水铝石粘合剂以及铝溶胶按常规的催化裂化催化剂的制备方法形成浆液、喷雾干燥制备成微球催化剂，所制备的催化裂化催化剂记为DC1(参考实施例1的制备方法)。其中以干基计，所得到的DC1催化剂中含有分子筛30重量％，高岭土42重量％，DP1拟薄水铝石25重量％，铝溶胶3重量％。
对比例2
将浓度为20gAl2O3/L的铝酸钠溶液与体积分数40％的二氧化碳气成胶反应，控制终点PH值9.5。将所得浆料转移至老化釜后，于135℃、0.35MPa下静置老化3.5h。老化结束后将所得浆液固液分离，80℃去离子水连续洗涤半小时，得到脱除杂质的拟薄水铝石湿滤饼。湿滤饼于80℃干燥3h，粉碎得到拟薄水铝石粉体DP2，其物化性质见表1。
将分子筛、高岭土、水、DP2拟薄水铝石粘合剂以及铝溶胶按常规的催化裂化催化剂的制备方法形成浆液、喷雾干燥制备成微球催化剂，所制备的催化裂化催化剂记为DC2(参考实施例1的制备方法)。其中以干基计，所得到的DC2催化剂中含有分子筛30重 量％，高岭土42重量％，DP2拟薄水铝石25重量％，铝溶胶3重量％。
对比例3
以Al2O3含量45g/L的高纯度铝酸钠溶液为原料，通入浓度为40％的CO2进行成胶反应，控制每小时的流量在3.0m3/h，反应时间控制在40分钟，控制Al2O3残留5g/l，终温控制35℃。反应后浆液进行分离洗涤，用85℃的高纯水洗涤滤饼，直至滤饼pH值7.0。将上述制得的滤饼加入高纯水搅拌，再加入浓度为8g/L的尿素，搅拌50min后，把料浆移入高压釜设备，控制釜温150℃，压力0.6MPa，静置老化3h。老化结束后用85℃去离子水连续洗涤半小时，过滤后在90℃下烘干。粉碎得到最终产品拟薄水铝石DP3，其物化性质见表1。
将分子筛、高岭土、水、DP3拟薄水铝石粘合剂以及铝溶胶按常规的催化裂化催化剂的制备方法形成浆液、喷雾干燥制备成微球催化剂，所制备的催化裂化催化剂记为DC3(参考实施例1的制备方法)。其中以干基计，所得到的DC3催化剂中含有分子筛30重量％，高岭土42重量％，DP3拟薄水铝石25重量％，铝溶胶3重量％。
对比例4
将浓度为45gAl2O3/L的铝酸钠溶液与体积分数60％的二氧化碳气(CO2体积分数60％，其余为氮气)接触反应，控制终点PH值10.3。将所得浆料转移至老化釜后，于180℃、1.0MPa下保持搅拌速率450r/min，老化3.5h。老化结束后将所得浆液固液分离，用95℃去离子水连续洗涤半小时至湿滤饼pH值7.3，得到脱除杂质的拟薄水铝石湿滤饼。湿滤饼于90℃干燥4h，粉碎得到拟薄水铝石粉体DP4，其物化性质见表1。
参考实施例1的方法用DP4制备代替SP1制备催化剂DC4。
表1拟薄水铝石性质
*酸化条件：酸铝比(浓度36重量％HCl:Al2O3质量比)为0.2，酸化混合物固含量10重量％；焙烧温度为550℃，焙烧时间2h。
由表1可见，本发明提供的拟薄水铝石，结晶度较高，晶粒尺寸较大且D(130)/D(020)较大，可几孔径较大，胶溶性能较好，且胶溶后焙烧样品的可几孔仍然较大。可知，与现有拟薄水铝石相比，本发明提供的拟薄水铝石用于催化裂化催化剂制备，具有更高的可几孔径，能够提供更多的中孔结构。
实施例6-10
实施例6-10说明本发明提供的拟薄水铝石的催化裂化反应性能。
将SC1-SC5催化剂经800℃，17小时100％水蒸气老化后，在小型固定流化床反应器(ACE)上评价其催化裂化反应性能，裂化气和产品油分别收集由气相色谱分析。催化剂装量为9g，反应温度500℃，重时空速为16h-1，ACE实验的原料油性质见表3，评价结果见表4。
对比例5-8
对比例5-8说明对比例1-3中拟薄水铝石制备的催化裂化催化剂的反应性能。
DC1-DC4催化剂经800℃，17小时100％水蒸气老化后，在小型固定流化床反应器(ACE)上评价其催化裂化反应性能，ACE实验的原料油性质见表3，评价结果列于表4中。
表2
由表1可知，本发明提供的拟薄水铝石，晶粒尺寸较大且D(130)/D(020)较大，可几孔径较大，结晶度较高，胶溶性能较好，且胶溶后焙烧样品的可几孔径仍然较大。由表2可见，本发明提供的催化裂化催化剂具有较大的中孔分布，除了在3.8nm处具有孔分布外，在更高孔径处处均有一定的中孔分布。常规拟薄水铝石制备的催化剂仅在3.8nm处具有中孔分布。
表3
表4
由表4可知，本发明提供的催化裂化催化剂，具有明显更低的焦炭选择性，具有更高的汽油收率和液化气产率。尤其是在所述特定特征的拟薄水铝石的D(130)为7.8-8.2的情况下和D(130)/D(020)高于1.2情况下，可以具有明显更高的汽油和液化气产率。

Claims (22)

  1. 一种拟薄水铝石，其特征在于，所述拟薄水铝石的晶粒大小D(130)和D(020)的比值为D(130)/D(020)＝1.0-1.5，优选地，1.1-1.3。
  2. 根据前述权利要求中任一项的拟薄水铝石，其特征在于，晶粒大小D由X射线粉末衍射法(XRD)测量，根据Scherrer公式计算晶粒大小D，其中K＝1.075，λ为阳极辐射Kα1谱线的波长，β为拟薄水铝石特定衍射峰的半峰宽(单位为弧度)，θ为衍射峰的Bragg衍射角(单位为度)，即，D(130)表示样品在垂直于(130)晶面的晶粒大小，β130为样品(130)衍射峰(对应2θ＝38.3°)的半峰宽；D(020)表示样品在垂直于(020)晶面的晶粒大小，β020为样品(020)衍射峰(对应2θ＝14.1°)的半峰宽。
  3. 根据前述权利要求中任一项的拟薄水铝石，其特征在于，拟薄水铝石的分子式为AlOOH·nH2O，n＝0.08-0.62，其晶粒大小D(130)不大于10nm。
  4. 根据前述权利要求中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的晶粒大小D(130)＝4nm-10nm，优选地，6.5-8.2nm，或者7.8-8.2nm。
  5. 根据前述权利要求中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的可几孔径大于4.5nm且不超过12nm，例如4.8nm-11nm，或者5nm-10nm。
  6. 根据前述权利要求中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的结晶度为85％-110％，例如88％-108％。
  7. 根据前述权利要求中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的胶溶指数为90％-100％，例如93％-99％。
  8. 根据前述权利要求中任一项的拟薄水铝石，其特征在于，所述拟薄水铝石的孔容为0.3cm3/g-0.58cm3/g，例如0.31cm3/g-0.52cm3/g。
  9. 一种制备拟薄水铝石的方法，包括以下步骤：
    (1)使铝酸钠溶液与CO2反应，形成第一浆液；
    (2)使所述第一浆液在一定条件下老化，得到老化之后的浆料；所述一定条件下老化：先静置老化，然后在搅拌下老化，老化温度为100℃以上且不超过185℃；
    (3)老化之后的浆料过滤、洗涤、干燥。
  10. 按照前述权利要求中任一项的制备拟薄水铝石的方法，其特征在于，步骤(1)中，所述铝酸钠溶液的浓度以Al2O3计为5-60g/L；所述铝酸钠溶液与CO2反应终点pH值为8.5-10.5。
  11. 按照前述权利要求中任一项的制备拟薄水铝石的方法，其特征在于，步骤(1)中，所述铝酸钠溶液与CO2反应的条件包括，反应起始温度10-35℃，在铝酸钠溶液中通入CO2浓度为20％-100体积％的含CO2气体(余量为惰性气体如氮气)进行反应，反应终点温度优选15-55℃。
  12. 按照前述权利要求中任一项的制备拟薄水铝石的方法，其特征在于，步骤(2)中浆料老化温度为120-180℃，老化压力为0.2-1MPa，老化时间为2-12h，例如，2-10h。
  13. 按照前述权利要求中任一项的制备拟薄水铝石的方法，其特征在于，步骤(2)中静置老化时间为1-8h，例如2.5-7h，或1-4h，例如2-3h，搅拌下老化时间为1-6h。
  14. 按照前述权利要求中任一项的制备拟薄水铝石的方法，其特征在于，所述老化温度为135-180℃，所述老化优选为恒温老化。
  15. 按照前述权利要求中任一项的制备拟薄水铝石的方法，其特征在于，所述搅拌老化的搅拌速度为50-450r/min，100-400r/min。
  16. 按照前述权利要求中任一项的制备拟薄水铝石的方法，其特征在于，步骤(2)中，
    静置老化的条件包括：温度为120-180℃，优选135-180℃，压力为0.2-1MPa，时间为1-8h，例如2.5-7h，搅拌速度为100-450r/min；
    搅拌下老化的条件包括：温度为120-180℃，优选135-180℃，压力为0.2-1MPa，时间为1-6h，例如1-5h；
    优选地，静置老化的时间与搅拌下老化的时间的比值为1-5:1，优选1.25-3:1。
  17. 按照前述权利要求中任一项的制备拟薄水铝石的方法，其特征在于，步骤(3)所述洗涤条件为：用70-100℃的去离子水洗涤至湿滤饼pH值为7-7.5；步骤(3)所述干燥，干燥温度为70-98℃。
  18. 按照前述权利要求中任一项的拟薄水铝石在石油工业中用作催化剂、载体、粘结剂；在汽车工业中用作汽车尾气处理催化剂的载体涂层；在消防领域用作阻燃材料的添加剂；在造纸行业中用作高档喷墨打印纸中的吸墨涂层；在环保行业中用作气体净化吸附剂、饮用水除氟剂、工业污水颜色和气味消除剂；在建筑行业用作涂料添加剂；陶瓷复合材料中的增强剂中的用途。
  19. 一种催化裂化催化剂，含有以干基计10重量％-50重量％的Y型分子筛、以干基计0-40重量％的其它分子筛、以氧化铝计10重量-40重量％的按照前述权利要求中任一项的拟薄水铝石、以氧化物计3重量-20重量％的粘结剂和以干基计10重量-80重量％的粘土；
    优选地，所述的其它分子筛为MFI结构沸石、Beta沸石、非沸石分子筛的一种或几种，更优选地，所述的其它分子筛为HZSM-5、ZRP、ZSP中的一种或多种；和/或，
    优选地，所述Y型分子筛为REY、REHY，DASY、SOY、PSRY、HSY、HRY中的一种或多种。
  20. 一种制备前述权利要求中任一项的催化裂化催化剂的方法，包括以下的步骤：
    制备按照前述权利要求中任一项的拟薄水铝石，
    形成包括所述的拟薄水铝石、Y型分子筛、任选的其它分子筛、粘结剂、粘土和水的浆液，和
    喷雾干燥。
  21. 按照前述权利要求中任一项的制备催化裂化催化剂的方法，其特征在于，所述方法为包括：
    将按照前述权利要求中任一项的拟薄水铝石与水打浆，形成拟薄水铝石浆液，其固含量优选为5-25重量％，
    加入盐酸，HCl与以氧化铝计的所述的拟薄水铝石的质量比为0.037-0.104，盐酸的浓度可以为10-37重量％，
    然后与含Y型分子筛、任选的其它分子筛、粘结剂、粘土和水的浆液混合得到胶体浆液，浆液的固含量优选为20-40重量％，
    喷雾干燥，和
    任选地，洗涤和干燥。
  22. 一种催化裂化方法，包括在FCC条件下，将重油与催化裂化催化剂接触反应的步骤，其特征在于，所述的催化裂化催化剂为按照前述权利要求中任一项的催化裂化催化剂或按照前述权利要求中任一项的制备催化裂化催化剂的方法得到的催化裂化催化剂；例如，所述的FCC条件包括：反应温度为480-530℃，反应时间1-10秒，剂油比为3-20:1重量比。
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