CN111420696A - Preparation of catalytic cracking catalyst - Google Patents
Preparation of catalytic cracking catalyst Download PDFInfo
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- CN111420696A CN111420696A CN202010356836.0A CN202010356836A CN111420696A CN 111420696 A CN111420696 A CN 111420696A CN 202010356836 A CN202010356836 A CN 202010356836A CN 111420696 A CN111420696 A CN 111420696A
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- catalyst
- catalytic cracking
- carboxylic acid
- acid polymer
- cracking catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title description 10
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000004927 clay Substances 0.000 claims abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000570 polyether Polymers 0.000 claims abstract description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 11
- 239000002002 slurry Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 22
- 238000005303 weighing Methods 0.000 description 21
- 239000000295 fuel oil Substances 0.000 description 17
- 239000003921 oil Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000005336 cracking Methods 0.000 description 11
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000009718 spray deposition Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052570 clay Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004231 fluid catalytic cracking Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 101710186154 S-adenosylmethionine synthase 1 Proteins 0.000 description 1
- 101710167538 S-adenosylmethionine synthase isoform type-1 Proteins 0.000 description 1
- 102100026115 S-adenosylmethionine synthase isoform type-1 Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- B01J29/084—Y-type faujasite
-
- B01J35/647—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
Abstract
A catalytic cracking catalyst comprises 20-40 wt% of Y-type molecular sieve based on dry basis, 30-50 wt% of clay based on dry basis, 10-30 wt% of binder based on alumina and 0.1-10 wt% of carboxylic acid polymer based on dry basis; the carboxylic acid polymer takes acrylic acid, methacrylic acid and/or maleic anhydride as a main chain, polyether with different side chain lengths is grafted, and mesopores with the size of 15nm-40nm are formed in a catalyst after roasting treatment, wherein the mesopore volume accounts for 5-40% of the total pore volume. After the carboxylic acid polymer is added into the catalytic cracking catalyst, the catalyst not only has good wear resistance, but also is suitable for the catalytic cracking process of heavy residual oil feed or raw oil, and can obviously improve the conversion rate and the product distribution.
Description
Technical Field
The present invention relates to the preparation of a catalytic cracking catalyst containing a carboxylic acid polymer.
Background
Fluid Catalytic Cracking (FCC) is an important crude oil secondary processing technology. In recent years, crude oil tends to be heavy and inferior, and the raw material processed by a catalytic cracking unit is also becoming heavy and inferior. In addition to the gradual deterioration of crude oil properties, the market demand for oil lightening is increased, and the production requirements for clean oil products (gasoline and diesel oil) are more and more strict, oil refining enterprises are newly added with measures such as crude oil hydrogenation, residual oil hydrogenation, hydrocracking, gasoline and diesel oil hydrogenation, and meanwhile, some new catalytic cracking processes, such as MIP, CGP, FDFCC, RHCC and the like, are generated. However, no matter crude oil hydrogenation, residual oil hydrogenation or a new catalytic cracking process is adopted, the catalytic cracking catalyst is required to have strong heavy oil macromolecule pre-cracking capability, the heavy oil conversion rate is improved, and the coke and dry gas selectivity is good, so that measures need to be taken to improve the pre-cracking capability of the catalytic cracking catalyst so as to adapt to the change of objective factors.
Because the heavy oil molecules are far larger than the aperture diameter of the Y-type molecular sieve and cannot enter the molecular sieve pore canal to be cracked by the molecular sieve, the cracking of the heavy oil molecules is generally carried out on the surface of a matrix, and the heavy oil catalytic cracking catalyst needs to have a large surface area of the matrix.
CN101745373A reports a catalytic cracking aid characterized by containing two aluminas with a stepped pore distribution, one being macroporous alumina and one being small pore alumina, having relatively concentrated pore distributions around 9nm and 60nm in addition to the pore distribution at 4nm, and having a high specific surface area and pore volume, facilitating the conversion of heavy oil macromolecules into valuable products.
CN1255530 and US5164073 adopt natural materials with larger pore volume, such as attapulgite, palygorskite, diatomite and the like as catalyst matrix materials to improve the heavy oil conversion capacity of the catalyst; EP0550271a1, US5051385, US5997729 improve the performance of cracking catalysts by adding a siliceous material, such as water glass, during the preparation of the aluminium-based catalysts to produce amorphous, large pore aluminium silicates.
CN1209442C discloses a cracking catalyst and a preparation method thereof, wherein the catalyst contains 5-60 wt% of medium-large pore alumina, 5-60 wt% of zeolite, 5-40 wt% of binder and 5-85 wt% of clay, and the average pore diameter of the medium-large pore alumina is not less than 3 nm. The macroporous alumina can be a dehydration product of boehmite or/and pseudo-boehmite at the temperature of below 900 ℃.
CN1978593B reportA catalytic cracking catalyst is characterized by that said catalyst contains a mesoporous material with pseudo-boehmite structure, said mesoporous material contains alumina, silica and metal oxide, such as magnesium oxide or rare earth oxide, etc. CN1964785A reports an FCC process using a mesoporous catalyst that is free of
Having central pores concentrated in
Patent CN1210031A discloses a method for modifying catalytic cracking carrier, which comprises roasting a mixture of kaolin and ammonium sulfate at high temperature, washing with water to obtain modified kaolin, but the catalyst carrier prepared by the method has small pore volume, low macroporous distribution ratio, low activity of the catalyst prepared from the carrier, and high slurry yield.
Patent CN1098130A discloses a preparation method of a cracking catalyst and a carrier, which comprises mixing clay and water, pulping, acidifying with hydrochloric acid, adding pseudo-boehmite, pulping, adding alumina sol after aging, stirring uniformly, adding a ground molecular sieve, continuing pulping, spray drying, washing with water, and drying. The method adopts the composite aluminum-based binder of the aluminum sol and the pseudo-boehmite, but the pore volume of the catalyst and the carrier prepared by the method is smaller, the distribution ratio of medium and large pores is lower, and the method is not suitable for heavy oil catalytic cracking.
Patent CN104549541A discloses a method for preparing a heavy oil catalytic cracking catalyst carrier, which comprises adding at least two silicon sources during the preparation process of the catalyst carrier, mixing clay, alumina and silica according to a certain proportion, and performing a certain process to obtain the catalyst carrier, wherein the carrier has a large micropore distribution proportion, weak acidity, and weak pre-cracking capability for heavy oil macromolecules, so that the catalyst prepared from the carrier has low micro-reverse activity.
Patents CN1388213A and CN1690170A disclose a preparation method of a silica-alumina-based petroleum hydrocarbon cracking catalyst, which does not need to prepare amorphous silica-alumina separately and shortens the preparation process, mainly by introducing water glass or silica sol during the preparation process of the catalyst. However, the activity of the catalyst carrier prepared by the method is not high, and the pore structure is not obviously improved.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalytic cracking catalyst containing carboxylic acid polymer, and the excellent pore size distribution of the catalyst can improve the cracking capability of heavy oil and the yield of light oil.
The invention provides a catalytic cracking catalyst, which comprises 20-40 wt% of Y-type molecular sieve based on dry basis, 30-50 wt% of clay based on dry basis, 10-30 wt% of binder based on alumina and 0.1-10 wt% of carboxylic acid polymer based on dry basis; the carboxylic acid polymer takes acrylic acid, methacrylic acid and/or maleic anhydride as a main chain, polyether with different side chain lengths is grafted, and mesopores with the size of 15nm-40nm are formed in a catalyst after roasting treatment, wherein the mesopore volume accounts for 5-40% of the total pore volume.
In the catalytic cracking catalyst provided by the invention, the molecular weight of the carboxylic acid polymer is between 1 million and 10 million, and accounts for 0.5 wt% -3 wt% of the total weight of the catalyst.
In the catalytic cracking catalyst provided by the invention, the percentage of the volume of a mesopore with the aperture of 15nm-40nm in the total pore volume is 10% -35%.
In the catalytic cracking catalyst provided by the invention, the binder is one or more than one of aluminum sol, silica sol, silicon-aluminum gel, acid-soluble pseudo-boehmite and phosphor-aluminum gel, and accounts for 10-20 wt% of the total weight of the catalyst.
Compared with the prior heavy oil catalytic cracking catalyst technology, the catalytic cracking catalyst of the invention has the following advantages:
1. the addition of the carboxylic acid polymer optimizes the pore size distribution of the catalyst, increases the pre-cracking places of heavy oil macromolecules and improves the conversion rate of heavy oil;
2. the carboxylic acid polymer is added, so that the catalyst has better wear resistance on the premise of not increasing or even reducing the using amount of the binder;
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
(1) 955g of alumina sol is weighed, 1000g of water is added, and the mixture is stirred evenly;
(2) weighing 1210g of kaolin, adding into the slurry obtained in the step (1), and fully and uniformly stirring;
(3) weighing 2333g of EUSY molecular sieve slurry, and adding the slurry into the slurry in the step (2);
(4) weighing 10g of carboxylic acid polymer, adding into the slurry in the step (3), uniformly stirring, weighing 431g of pseudo-boehmite, adding into 500g of water, uniformly stirring, adding hydrochloric acid for acidification, and stirring for 1 h;
(5) spray-forming with L X-15 centrifugal spray tower, calcining, washing, and drying to obtain catalytic cracking catalyst A.
Example 2
(1) 909g of alumina sol is weighed, 900g of water is added, and the mixture is stirred uniformly;
(2) weighing 1210g of kaolin, adding into the slurry obtained in the step (1), and fully and uniformly stirring;
(3) weighing 2333g of EUSY molecular sieve slurry, and adding the slurry into the slurry in the step (2);
(4) weighing 20g of carboxylic acid polymer, adding into the slurry in the step (3), uniformly stirring, weighing 431g of pseudo-boehmite, adding into 400g of water, uniformly stirring, adding hydrochloric acid for acidification, and stirring for 1 h;
(5) spray-forming with L X-15 centrifugal spray tower, calcining, washing, and drying to obtain catalytic cracking catalyst B.
Example 3
(1) 727g of alumina sol is weighed, 800g of water is added, and the mixture is stirred uniformly;
(2) weighing 1210g of kaolin, adding into the slurry obtained in the step (1), and fully and uniformly stirring;
(3) weighing 2333g of EUSY molecular sieve slurry, and adding the slurry into the slurry in the step (2);
(4) weighing 60g of carboxylic acid polymer, adding the carboxylic acid polymer into the slurry in the step (3), uniformly stirring, weighing 431g of pseudo-boehmite, adding 350g of water, uniformly stirring, adding hydrochloric acid for acidification, and stirring for 1 h;
(5) spray-forming with L X-15 centrifugal spray tower, calcining, washing, and drying to obtain catalytic cracking catalyst, denoted as C.
Example 4
(1) Weighing 545g of alumina sol, adding 650g of water, and uniformly stirring;
(2) weighing 1210g of kaolin, adding into the slurry obtained in the step (1), and fully and uniformly stirring;
(3) weighing 2333g of EUSY molecular sieve slurry, and adding the slurry into the slurry in the step (2);
(4) weighing 100g of carboxylic acid polymer, adding into the slurry in the step (3), uniformly stirring, weighing 431g of pseudo-boehmite, adding into 300g of water, uniformly stirring, adding hydrochloric acid for acidification, and stirring for 1 h;
(5) spray-forming with L X-15 centrifugal spray tower, calcining, washing, and drying to obtain catalytic cracking catalyst D.
Comparative example
(1) Weighing 1000g of alumina sol, adding 1000g of water, and uniformly stirring;
(2) weighing 1210g of kaolin, adding into the slurry obtained in the step (1), and fully and uniformly stirring;
(3) weighing 2333g of EUSY molecular sieve slurry, and adding the slurry into the slurry in the step (2);
(4) weighing 431g of pseudo-boehmite, adding the pseudo-boehmite, adding 500g of water, stirring uniformly, adding hydrochloric acid for acidification, and stirring for 1 h;
(5) spray-forming with L X-15 centrifugal spray tower, calcining, washing, and drying to obtain catalytic cracking catalyst, and recording as DB.
The physicochemical analysis data of the catalysts prepared in the examples and comparative examples are shown in Table 1.
TABLE 1 catalyst physicochemical analysis data
The catalysts of the examples and comparative examples were subjected to 100% steam aging at 800 ℃ for 17 hours.
The micro-reaction activity of light oil of the catalyst is measured by adopting an MAT-1 heavy oil micro-reaction device produced by Beijing Wilkend technology Limited, the reaction raw material is Hongkong straight-run light diesel oil (fraction 235-337 ℃), the reaction temperature is 460 ℃, the reaction time is 70s, the catalyst loading is 5g, the oil inlet amount is 1.50g, and the micro-reaction result of the light oil is shown in the following table.
TABLE 2 catalyst microreactivity results
The fixed fluidized bed evaluation of the catalyst, the raw oil used by an FCC device is selected as the raw oil for evaluation, the properties of the raw oil are shown in Table 3, the reaction temperature is 510 ℃, and the mass airspeed is 20h-1The oil-to-oil weight ratio was 6.0, and the evaluation results are shown in Table 4.
TABLE 3 basic Properties of the stock oils
TABLE 4 catalyst evaluation results
The data in table 1 show that the physical indexes of the catalytic cracking catalysts prepared in examples 1 to 4 are superior to those of the comparative example, the catalysts of the examples have lower abrasion indexes, and the numerical values of the specific surface area and the pore volume are obviously improved after the carboxylic acid polymer is added, so that the catalysts are far higher than the catalysts of the comparative example, the pore distribution of the catalysts is more reasonable due to the addition of the carboxylic acid polymer, and the catalysts are theoretically more favorable for the cracking reaction of heavy oil.
From the data in table 2, the microreaction of the catalyst to which the carboxylic acid polymer was added was significantly improved, and from the analysis of the fixed bed evaluation data in table 4, the heavy oil yield of the catalyst containing the carboxylic acid polymer was reduced, the conversion rate was improved, and the product distribution was relatively reasonable.
Claims (4)
1. A catalytic cracking catalyst comprises 20-40 wt% of Y-type molecular sieve based on dry basis, 30-50 wt% of clay based on dry basis, 10-30 wt% of binder based on alumina and 0.1-10 wt% of carboxylic acid polymer based on dry basis; the carboxylic acid polymer takes acrylic acid, methacrylic acid and/or maleic anhydride as a main chain, polyether with different side chain lengths is grafted, and mesopores with the size of 15nm-40nm are formed in a catalyst after roasting treatment, wherein the mesopore volume accounts for 5-40% of the total pore volume.
2. The catalytic cracking catalyst of claim 1, wherein the molecular weight of the carboxylic acid polymer is between 1 and 10 ten thousand, and is 0.5 to 3 wt% of the total weight of the catalyst.
3. The catalytic cracking catalyst of claim 1, wherein the catalyst has a mesopore volume of 15nm to 40nm in a percentage of 10% to 35% of the total pore volume.
4. The catalytic cracking catalyst of claim 1, wherein the binder is one or more of alumina sol, silica-alumina gel, acid-soluble pseudo-boehmite and phospho-alumina gel, and accounts for 10 wt% to 20 wt% of the total weight of the catalyst.
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2020
- 2020-04-29 CN CN202010356836.0A patent/CN111420696A/en active Pending
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| CN1831090A (en) * | 2005-03-11 | 2006-09-13 | 石油大学(北京) | Macropore catalytic cracking catalyst synthesized by granular formwork method |
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| Title |
|---|
| 侯祥麟主编: "《中国炼油技术 第2版》", 31 July 2001, 北京：中国石化出版社 * |
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