CN116212937A - Preparation method of catalytic cracking catalyst for producing diesel oil in large quantity - Google Patents
Preparation method of catalytic cracking catalyst for producing diesel oil in large quantity Download PDFInfo
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- CN116212937A CN116212937A CN202310203360.0A CN202310203360A CN116212937A CN 116212937 A CN116212937 A CN 116212937A CN 202310203360 A CN202310203360 A CN 202310203360A CN 116212937 A CN116212937 A CN 116212937A
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- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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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
- 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
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a catalytic cracking catalyst for producing diesel oil in a plurality of modes, which respectively adopts different modes to treat pseudo-boehmite to form materials with different structures and performances, and the catalyst can be obtained by adding spray granulation after mixing, wherein the proportion of the pseudo-boehmite and the raw oil to be treated is related to the property of the raw oil to be treated to a certain extent. The catalyst can be used for obtaining higher diesel oil yield.
Description
Technical field: the invention relates to a preparation method of a catalytic cracking catalyst for producing more diesel oil, belonging to the field of catalyst preparation
The background technology is as follows:
catalytic cracking is an important means for crude oil processing, and more than 70% of gasoline and more than 30% of diesel oil in China are derived from catalytic cracking. The increasing worldwide demand for clean oil products has led to a diesel trend in the fuels of internal combustion engines. Compared with gasoline engines, diesel engines have the advantages of high power, high fuel oil heat efficiency, long service life, good starting performance, low carbon monoxide and hydrocarbon emissions, low oil consumption and the like, so that how to generate more diesel oil in the catalytic cracking process is a technical problem which needs to be solved urgently, and increasing the yield of diesel oil is an advantageous measure for the refinery to maximize the benefit.
In order to achieve the purpose of increasing the yield of diesel oil, the production process can be realized through the aspects of raw material configuration, product segmentation, device technology, process transformation and the like. The catalyst can also be used as a special catalyst, and the multi-diesel catalyst in China at present is mainly a series of catalysts for multi-diesel oil production such as MLC-500, DMC-2, CC-20D and the like which are developed by Dan Ke institute, and has better application effect. The agent can be used as a catalyst alone or as an auxiliary agent, and has a certain effect in increasing the yield of light oil. The catalyst has the defects that the acid and alkali modification is carried out on different components, the specific surface area is adjusted, the pore structure and the size distribution are adjusted, and the like, but basically, the diesel oil yield is difficult to be greatly improved, the preparation process is complex, and the like.
CN201110332284 discloses a catalytic cracking catalyst for producing diesel oil with high yield of alkali nitrogen, which can exhibit higher catalytic cracking activity in the process of catalytic cracking heavy oil, and can obtain higher conversion rate and higher diesel oil yield. The catalyst comprises cracking active components, mesoporous silica-alumina material, a binder and clay.
CN103506148A no more than 30 wt% ultrastable Y molecular sieve containing magnesium on a dry basis, 10 wt% to 70 wt% clay on a dry basis, and 10 wt% to 40 wt% inorganic oxide binder on an oxide basis; the unit cell constant of the modified Y-type molecular sieve is 2.420-2.440 nm, the weight percentage of P is 0.05-6%, the weight percentage of RE2O3 is 0.03-10%, the alumina is less than 22%, and the specific hydroxyl nest concentration is less than 0.35mmol/g. The catalytic cracking catalyst provided by the invention can reduce raw coke, improve the utilization rate of heavy oil and improve the yield of diesel oil.
Cn201410082884.X discloses a heavy oil catalytic cracking catalyst for producing more diesel oil and a preparation method thereof. The method comprises the steps of pulping and uniformly mixing a molecular sieve, pseudo-boehmite, clay, inorganic acid and deionized water, adding or not adding aluminum sol at the same time to prepare catalyst slurry, spray-drying, roasting, exchanging and washing with an ammonium sulfate and ammonium dihydrogen phosphate solution, and finally drying to obtain the catalyst. The method can effectively control the peptization degree of the pseudo-boehmite so as to avoid the influence of the fluctuation of the pore volume of the catalyst by the pseudo-boehmite acid. Compared with the prior art, the method provided by the invention can increase the pore volume of the catalyst and improve the heavy oil cracking capacity and the diesel oil yield of the catalyst.
CN200510084253.2 discloses a catalytic cracking promoter for producing more diesel oil and its preparation method, which is prepared by roasting spray microsphere containing kaolin, pseudo-boehmite and water glass at high temperature above 900 deg.c, extracting pore canal with strong alkali such as sodium hydroxide, and finally loading promoter prepared from phosphorus and rare earth, wherein the promoter does not contain any kind of zeolite component, sodium oxide is less than 0.6%, and at the same time, contains 1-3.5% phosphorus and 1-5% rare earth oxide by mass percent. By adding a certain amount of the cocatalyst, the diesel oil yield of the FCC catalytic device can be improved, the product distribution can be improved, and the utilization rate of the existing catalyst variety can be improved under the condition that the catalyst originally adopted by the oil refining device is not changed. In addition, the cocatalyst has the characteristics of simple preparation process, low cost and the like.
CN201810355600.8 discloses a catalytic cracking catalyst for producing more diesel oil and a preparation method thereof, and the preparation method comprises the following steps: (1) Mixing and pulping raw materials and deionized water to prepare slurry; (2) spray-drying the slurry, followed by calcination and washing; wherein the raw materials comprise boron-containing substances other than boron phosphates, molecular sieves, clay minerals, and a fourth component comprising binding action. The catalyst of the invention has high diesel oil yield, heavy metal pollution resistance and simple preparation process.
In addition, to obtain higher diesel yields, heavier feed oils are required, which generally contain higher heavy metals, basic nitrogen and sulfides, and the catalyst is susceptible to poisoning and deactivation, and the sulfides in the flue gas are susceptible to exceeding standards, so that the influence of these adverse factors should be considered in designing the catalyst.
The invention comprises the following steps:
in order to solve the defects of the technology, the invention provides a preparation method of a high-yield diesel catalytic cracking catalyst, which comprises the following specific synthesis steps:
(1) Pulping pseudo-boehmite with water, acidifying, adding alkali liquor with a certain proportion, reacting for a period of time, adding magnesium chloride solution with a certain proportion, stirring uniformly, standing for aging, filtering and washing after the reaction is finished, and marking a filter cake as A;
(2) Pulping pseudo-boehmite with water, acidifying, adding a certain proportion of alkali liquor, reacting for a period of time, adding a certain proportion of aluminum sulfate solution, uniformly stirring, standing for aging, adding a certain proportion of water glass solution after the reaction is finished, filtering, washing, and marking a filter cake as B;
(3) Mixing A and B according to a certain proportion, pulping, adding USY, acidifying and spraying;
(4) And (5) collecting particles after spraying, roasting, exchanging and drying to obtain the target.
Wherein the pseudo-boehmite, the alkali solution and the magnesium chloride solution in the step (1) are added in the proportion of Al based on the weight of oxide 2 0 3 :Na 2 O:MgO＝1:(0.3-0.7):(0.07-0.1)。
The hydrochloric acid ratio used for acidification in step (1) was 3 Xwt MgO ％-wt Na2O ％。
In the step (2), pseudo-boehmite, alkali liquor, aluminum sulfate and water glass solution are added in proportion of Al based on the weight of oxide 2 0 3 :Na 2 O:Al 2 0 3 :SiO 2 ＝1:(0.9-1.3):(0.5-0.8):(0.1-0.2)。
The hydrochloric acid ratio used for acidification in step (2) is 2 Xwt Na2O ％-wt SiO2 ％。
The ratio of A and B in step (3) (1000 Xwt vanadium+0.1 wt sulfur)/wt MgO ％:(500×wt Nitrogen and nitrogen )/wt Al203 Percent of the total weight of the composition. Wherein, the weight vanadium, the weight sulfur and the weight nitrogen are the contents of vanadium, sulfur and nitrogen in the raw oil respectively in ppm.
The USY molecular sieve in step (3) is added in a proportion of 10-18wt% based on the dry basis of the title.
Ammonium chloride and lanthanum chloride are used in the exchange in the step (4), and the addition amount of the ammonium chloride is ensured to ensure the title compound Na 2 O is less than or equal to 0.5wt percent, and lanthanum chloride accounts for 3.5 to 8wt percent of the dry basis of the title compound in terms of oxide.
The invention has the advantages that:
(1) The acidification degree of the pseudo-boehmite in the A is controlled by the addition amount of hydrochloric acid, a part of the acidified pseudo-boehmite, liquid alkali and magnesium chloride form a layered structure after aging, the interlayer spacing is 0.5-0.85nm, interlayer ions can be exchanged, and the cracking depth of heavy oil macromolecules can be regulated and controlled.
(2) The acidification degree of the pseudo-boehmite in the step B is controlled by the addition amount of hydrochloric acid, a part of the acidified pseudo-boehmite and aluminum sulfate are aged to form mesoporous alumina, after water glass is added, the silicon oxide is embedded, so that the original pore structure can be still maintained during the acidification in the step 3, the distribution position of the aluminum oxide can be regulated and controlled according to the proportion of the silicon oxide, the proper acidity is realized, the cracking depth is controlled, and the small molecular products are not excessively produced.
(3) The metal content and the sulfur nitrogen content of the raw oil used by different refineries are different, and the catalyst formula is correspondingly adjusted.
(4) The invention uses USY molecular sieve as active component, and adopts lower adding proportion, so that it can be fully dispersed in A and B, raise accessibility and utilization efficiency, reduce hydrogen transfer activity, prevent excessive cracking, and is more favorable for producing more diesel oil and reducing coke.
(5) The spray particles are exchanged by lanthanum chloride, a part of rare earth ions enter the interlayer of A, a magnesia-alumina spinel structure is formed in the regenerator, the effect of trapping metal can be achieved, and when the trapped metal vanadium enters, the effect of a sulfur transfer agent can be achieved, so that two problems are solved at one time. Part of rare earth ions enter B and are embedded into a silicon-aluminum space structure, and the acidity and the acid quantity of B are regulated and controlled. In addition, a part of rare earth ions enter the USY molecular sieve pore canal, so that the hydrothermal stability and the vanadium resistance of the USY are improved, and the service life and the selectivity of the USY are improved.
(6) In the steps 1 and 2, the non-acidified or partially-acidified pseudo-boehmite exists and can be used as a cracking place of heavy oil macromolecules, and in the step 3, the pseudo-boehmite can partially play a role in bonding. The granularity of A and B is small, and the molecular sieve has certain adhesive property, and the proportion of the added molecular sieve is low, so that no additional adhesive is needed, and the abrasion property can also meet the use requirement of the device.
The specific embodiment is as follows:
the present invention will be further illustrated by the following examples, but the present invention is not limited to these examples.
The raw materials used in the examples were as follows:
the following materials were all taken from the manufacturing plant of Qingdao Huicheng environmental protection technology group Co., ltd.
Pseudo-boehmite: burning off 36.5%;
alkali liquor: 350/L, na 2 An O meter;
magnesium chloride solution: 4.5wt%, calculated as MgO;
aluminum sulfate solution: 90/L, with Al 2 0 3 Counting;
water glass solution: 180g/L in SiO 2 Counting;
hydrochloric acid: 13wt%;
lanthanum chloride: 20.3% by RE 2 0 3 Counting;
USY molecular sieve: 25% burn and unit cell parameter 24.52.
Catalyst evaluation:
using an ACE evaluation unit, the catalyst was subjected to pretreatment at 800 ℃ for 17 hours with 100% steam aging, 9g of the catalyst was added, the reaction temperature was 505 ℃ and the catalyst to oil ratio was 9.
The data for evaluating the raw oil are as follows:
table 1 evaluation of raw oil data used
Example 1:
(1) 1000g of pseudo-boehmite is added with 3175g of water for pulping, hydrochloric acid is added for acidification, 544mL of alkali liquor is added for reaction for a period of time, 987g of magnesium chloride solution is added for standing and aging, filtering and washing are carried out, and A1 is marked;
(2) 1000g of pseudo-boehmite is added with 3175g of water for pulping, hydrochloric acid is added for acidification, 1632mL of alkali liquor is added for reaction for a period of time, 3527mL of aluminum sulfate solution is added for standing and aging, 353mL of water glass solution is added for filtration and washing, and B1 is marked.
(3) The ratio of A1 to B1 is 0.239:0.761, 395g of USY molecular sieve was added, and the spray was acidified.
(4) Roasting the catalyst particles, pulping, adding ammonium chloride for washing, then adding 591g of lanthanum chloride solution, and carrying out air flow drying to obtain the catalyst ZC-1.
Example 2:
(1) 1000g of pseudo-boehmite is added with 3175g of water for pulping, hydrochloric acid is added for acidification, 816mL of alkali liquor is added, 1129g of magnesium chloride solution is added after a period of reaction, standing and aging are carried out, filtering and washing are carried out, and A2 is marked;
(2) 1000g of pseudo-boehmite is added with 3175g of water for pulping, hydrochloric acid is added for acidification, 1814mL of alkali liquor is added for reaction for a period of time, 4233mL of aluminum sulfate solution is added for standing and aging, 494mL of water glass solution is added for filtration and washing, and B2 is marked.
(3) The ratio of A2 to B2 is 0.202:0.798, 353g of USY molecular sieve was added and the spray acidified.
(4) Roasting the catalyst particles, pulping, adding ammonium chloride for washing, then adding 788g of lanthanum chloride solution, and carrying out air flow drying to obtain the catalyst ZC-2.
Example 3:
(1) 1000g of pseudo-boehmite is added with 3175g of water for pulping, hydrochloric acid is added for acidification, 1088mL of alkali liquor is added, 1270g of magnesium chloride solution is added after a period of reaction, standing and aging are carried out, filtering and washing are carried out, and A3 is marked;
(2) 1000g of pseudo-boehmite is added with 3175g of water for pulping, hydrochloric acid is added for acidification, 2177mL of alkali liquor is added for reaction for a period of time, 4938mL of aluminum sulfate solution is added for standing and aging, 599mL of sodium silicate solution is added for filtration and washing, and B3 is marked.
(3) The ratio of A3 to B3 is 0.227:0.773, 272g of USY molecular sieve was added and the spray was acidified.
(4) Roasting the catalyst particles, pulping, adding ammonium chloride for washing, then adding 542g of lanthanum chloride solution, and carrying out air flow drying to obtain the catalyst ZC-3.
Example 4:
(1) 1000g of pseudo-boehmite is added with 3175g of water for pulping, hydrochloric acid is added for acidification, 1270mL of alkali liquor is added, 1411g of magnesium chloride solution is added after a period of reaction, standing and aging are carried out, filtering and washing are carried out, and A4 is marked;
(2) 1000g of pseudo-boehmite is added with 3175g of water for pulping, hydrochloric acid is added for acidification, 2358mL of alkali liquor is added for reaction for a period of time, 5644mL of aluminum sulfate solution is added, standing and aging are carried out, 706mL of sodium silicate solution is added, filtering and washing are carried out, and B4 is marked.
(3) The ratio of A4 to B4 was 0.283:0.717, 439g of USY molecular sieve was added and the spray was acidified.
(4) Roasting the catalyst particles, pulping, adding ammonium chloride for washing, then adding 443g of lanthanum chloride solution, and carrying out air flow drying to obtain the catalyst ZC-4.
The four catalyst samples were aged with 2 stimulation diesel catalysts available on the market, and compared with ACE for evaluation, with the following data:
table 2ACE evaluation of product distribution
As can be seen from the above table, the samples obtained in the examples all significantly improved the diesel yield compared to the comparative samples.
Claims (8)
1. The preparation process of the catalyst for catalytic cracking of diesel oil includes the following steps:
(1) Pulping pseudo-boehmite with water, acidifying, adding alkali liquor with a certain proportion, reacting for a period of time, adding magnesium chloride solution with a certain proportion, stirring uniformly, standing for aging, filtering and washing after the reaction is finished, and marking a filter cake as A;
(2) Pulping pseudo-boehmite with water, acidifying, adding a certain proportion of alkali liquor, reacting for a period of time, adding a certain proportion of aluminum sulfate solution, uniformly stirring, standing for aging, adding a certain proportion of water glass solution after the reaction is finished, filtering, washing, and marking a filter cake as B;
(3) Mixing A and B according to a certain proportion, pulping, adding USY, acidifying and spraying;
(4) And (5) collecting particles after spraying, roasting, exchanging and drying to obtain the target.
2. The process according to claim 1, wherein the pseudo-boehmite, the alkali solution and the magnesium chloride solution in the step (1) are added in a proportion of Al in terms of the weight of the oxide 2 0 3 :Na 2 O:MgO=1:(0.3-0.7):(0.07-0.1)。
3. The process according to claim 1, wherein the hydrochloric acid used for the acidification in step (1) is present in a proportion of 3 ✕ wt MgO %-wt Na2O %。
4. The process according to claim 1, wherein the pseudo-boehmite, the alkali solution, the aluminum sulfate and the water glass solution in the step (2) are added in a proportion of Al by weight of oxide 2 0 3 :Na 2 O:Al 2 0 3 :SiO 2 =1:(0.9-1.3):(0.5-0.8):(0.1-0.2)。
5. The process according to claim 1, wherein the hydrochloric acid used for the acidification in step (2) is present in a proportion of 2 ✕ wt Na2O %-wt SiO2 %。
6. According to claimThe process according to book 1, characterized in that the ratio of A and B in step (3) (1000 ✕ wt vanadium+0.1 wt sulfur)/wt MgO %:(500✕wt Nitrogen and nitrogen )/wt Al203 Percent of the total weight of the composition. Wherein, the weight vanadium, the weight sulfur and the weight nitrogen are the contents of vanadium, sulfur and nitrogen in the raw oil respectively in ppm.
7. The process according to claim 1, wherein the USY molecular sieve is added in step (3) in a proportion of 10 to 18% by weight based on the dry weight of the title.
8. The process according to claim 1, wherein ammonium chloride and lanthanum chloride are used in the exchange in step (4), the ammonium chloride being added in an amount to ensure the title compound Na 2 O is less than or equal to 0.5wt percent, and lanthanum chloride accounts for 3.5 to 8wt percent of the dry basis of the title compound in terms of oxide.
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| CN115318275A (en) * | 2022-08-30 | 2022-11-11 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking flue gas treatment three-effect auxiliary agent |
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| CN115318275A (en) * | 2022-08-30 | 2022-11-11 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking flue gas treatment three-effect auxiliary agent |
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