CN109304210A - A kind of catalytic cracking catalyst preparation method of cracking wax tailings high-yield diesel oil - Google Patents
A kind of catalytic cracking catalyst preparation method of cracking wax tailings high-yield diesel oil Download PDFInfo
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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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- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The present invention provides a kind of catalytic cracking catalyst preparation method of cracking wax tailings high-yield diesel oil.The preparation method includes the following steps: (1) rare earth, phosphorus, the preparation of magnesium-modified Y type molecular sieve: NaY molecular sieve is exchanged through ammonium salt, rare-earth salts, then successively carries out phosphorus, magnesium-modified, it is characterised in that P Modification is magnesium-modified rear preceding；(2) shaping of catalyst: water, molecular sieve, clay, boehmite and binder are mixed, mashing, spray drying, roasting；(3) modified: water, magnesium salts being uniformly mixed with catalyst granules, adjust pH value, filtration drying.Catalyst of the present invention shows good heavy oil conversion performance and diesel oil selectivity during cracking wax tailings.
Description
Technical field
The present invention relates to a kind of preparation methods of catalytic cracking catalyst, specifically, being that a kind of cracking wax tailings are more
Produce the preparation method of diesel catalytic converter.
Background technique
Delayed coking is the residua upgrading technique important when former.As crude quality in poor quality and price are sluggish, prolong
Slow coking becomes more favourable in current oil refining scheme due to the flexibility to process raw material.Delayed coking working ability exists
China increases severely, and has been up to 110,000,000 tons within 2010.Wax tailings (CGO) are the major products of delayed coking, account for coking production
The 20-30 weight % of product, the utilization rate of wax tailings directly affect the economic benefit of refinery.
At abroad, wax tailings are used as catalytically cracked material through hydrogenated processing.For example, being split in the U.S. more than 50% catalysis
Change raw material through hydrogenated processing, and the fcc raw material in Europe 10% carries out hydrotreating.In China, due to lacking for hydrocracking unit
Weary and high operation cost mixes refining wax tailings using catalytic cracking unit and is more of practical significance.But with straight-run gas oil phase
Than arene content, the nitrogen content especially basic n content of wax tailings are higher, and arene content is generally 30% or so, and nitrogen contains
Amount is 0.35% or so.The acid centre that basic nitrogen compound is adsorbed on catalyst causes activated centre quantity to reduce, and reduces catalysis
Cracking conversion rate and product yield；Rather than basic nitrogen compound and aromatic hydrocarbons are deposited on catalyst surface and form coke, prevent other hydrocarbon
Contact of the substance with acid centre, influences the conversion ratio of catalytic cracking.It the characteristics of for wax tailings, has been proposed at present
Conversion method (DNCC) technique [Zhang, R.C. are adsorbed in some process modification methods, such as catalytic cracking；Shi,
W.Y.Denitrified Catalytic Cracking(DNCC)Technology for Coker Gas Oil
Processing.Pet.Process.Petrochem.1998,29,22-27], two-stage riser fluid catalytic cracking technique (TSR)
[Yuan,Q.M.；Wang,Y.L.；Li,C.Y.；Yang,C.H.；Shan,H.H.Study on conversion of coker
gas oil by two-stage riser fluid catalytic cracking.J.China Univ.Pet.
(Ed.Nat.Sci.) 2007,31 (1), 122-126], regional catalytic cracking (DFCC) technique [Li, Z.K.；Wang,G.；Liu,
Y.D.；Wang,H.；Liang,Y.M.；Xu,C.M.；Gao,J.S.Catalytic cracking constraints
analysis and divisional fluid catalytic cracking process for coker gas
Oil.Energy Fuels2012,26 (4), 2281-2291] and two sections of collaboration (TSS) catalytic cracking process [Zhang, J.H.；
Shan,H.H.；Liu,W.J.；Chen,X.B.；Li,C.Y.；Yang,C.H.Synergistic Process for Coker
Gas Oil Catalytic Cracking and Gasoline Reformation.Energy Fuels2013,27(2),
654-665] etc..Above-mentioned technique needs to be transformed existing apparatus in practical applications, increases refinery's investment and risk is big.Cause
This, the catalyst for developing the high diesel oil selectivity of efficient cracking wax tailings is undoubtedly processing coked waxy oil, improves diesel yield
Effective way.
103084206 A of CN discloses a kind of catalytic cracking catalyst and preparation method thereof of alkali resistant nitrogen high-yield diesel oil, institute
Stating catalyst includes cracking activity constituent element, mesoporous silica-alumina materials, binder and clay, wherein the cracking activity constituent element packet
The first Y type molecular sieve and the second Y type molecular sieve are included, with or without third Y type molecular sieve, wherein in first molecular sieve
Content of rare earth is calculated as 8-23 weight % with rare earth oxide, and iron content is with Fe2O3It is calculated as 0.1-3.0 weight %, copper content is in terms of CuO
For 0-3.0 weight %, phosphorus content is with P2O5It is calculated as 0-2.0 weight %, sodium oxide content is 0.1-2.5 weight %；Described second
Y type molecular sieve is the super-stable Y molecular sieves containing magnesium, and the third Y type molecular sieve is the DASY molecular sieve containing rare earth.It is described to urge
The preparation method of agent, including cracking activity constituent element, mesoporous silica-alumina materials, clay and binder are beaten, spray drying is washed
It washs, the step for filtering and drying.The catalyst be used for higher basic nitrogen hydrocarbon oil catalytic cracking, conversion ratio with higher and
Diesel yield.
Above-mentioned patent is all to be introduced iron/copper/phosphorus using the rare earth modified activity stability for improving molecular sieve and adjusted acidity
Center intensity and density；There is d unoccupied orbital using iron and/or the distribution of copper ion electron outside nucleus, with the nitrogen-atoms containing lone pair electrons
Complex compound and selective absorption basic nitrogen compound are formed, toxic action of the alkali nitrogen to catalyst acid center is mitigated.Due to alkalization
Adduct molecule size is larger, and the catalyst and basic nitrogen compound of above-mentioned patented method preparation inevitably prevent other when acting on
The contact of hydrocarbon molecules and acidity of catalyst center, and above-mentioned patent does not consider aromatic hydrocarbons and non-alkali nitrification in wax tailings
Influence of the object to catalytic cracking.
Summary of the invention
The object of the present invention is to provide a kind of catalytic cracking catalyst preparation methods of cracking wax tailings high-yield diesel oil, should
Catalyst can reduce the adsorption capacity of nitride and aromatic hydrocarbons and acidity of catalyst center in wax tailings, reduce wax tailings to urging
Change the negative effect of cracking reaction, improves heavy oil conversion performance and diesel yield.
The present invention provides a kind of catalytic cracking catalyst preparation method of cracking wax tailings high-yield diesel oil, the party
Method includes the following steps: (1) rare earth, phosphorus, magnesium-modified Y type molecular sieve preparation: (a) carrying out NaY molecular sieve and ammonium salt solution
Ion exchange is filtered, washed, and is washed rear filter cake and is mixed with rare-earth salts, then roasts 1 under 400-700 DEG C, 1~50% water vapour
~3 hours, obtain rare earth modified Y type molecular sieve；(b) by rare earth modified Y type molecular sieve obtained in step (a) and phosphorous chemical combination
The mixed solution of object or phosphorus-containing compound and ammonium salt carry out ion exchange, be then filtered, washed, 300~600 DEG C, l~
It is roasted 0.5-3 hours under 100% water vapour, obtains rare earth and the composite modified Y type molecular sieve of phosphorus.(c) it will be obtained in step (a)
Rare earth and the composite modified Y type molecular sieve of phosphorus and magnesium salt solution carry out ion exchange, are then filtered, washed, obtain rare earth, phosphorus and
The composite modified Y type molecular sieve of magnesium.(2) shaping of catalyst: water, molecular sieve, clay, boehmite and binder are mixed,
Mashing, spray drying, roasting, obtain preformed catalyst solid particle；(3) modified: according to weight ratio catalyst solid particle: going
Ionized water: magnesium salts (in terms of magnesium)=1:2-10:0.001-0.05, preferably 1:3-7:0.005-0.03, by water, magnesium salts and catalyst
Particle is uniformly mixed, and acid is added and adjusts slurry pH value in 2.5-5.5, preferably 3.0-4.0, stirs 0.5h-3h, then crosses and be filtered dry
It is dry.
In method provided by the invention, the ion exchange of step (a) described in step (1) is according to ammonium salt: NaY molecule
Sieve: deionized water=0.15-1:l:1-50, the preferably weight ratio of 0.2-0.5:1:2-30 are by ammonium salt, NaY molecular sieve and deionization
It is that 2.0-6.0, preferably 2.0-5.0 are handed at preferably 60-90 DEG C at 40-130 DEG C that water, which is mixed with beating and uniformly adjusts the pH value of slurries,
It changes 0.5-4 hours, preferably 1-3 hours.
In method provided by the invention, the rear filter cake of washing of step (a) described in step (1) is mixed with rare-earth salts according to rare earth
Salt is (with RE2O3Meter): NaY molecular sieve=0.001-0.2:l, preferably 0.02-0.2:1.
In method provided by the invention, the ion exchange of step (b) described in step (1) is according to phosphorus-containing compound (with P
Meter): ammonium salt: NaY molecular sieve: deionized water=0.001-0.1:0-0.3:1:1-50, preferably 0.005-0.04:0-0.2:1:2-
Phosphorus-containing compound, ammonium salt, NaY molecular sieve and deionized water are mixed with beating by 30 weight ratio uniformly to be adjusted the pH value of slurries and is
2.0-6.0, preferably 2.0-5.0 are exchanged 0.5-3 hours, preferably 0.5-2 hours at preferably 60-90 DEG C at 40-130 DEG C.
In method provided by the invention, the ion exchange of step (c) described in step (1) is according to magnesium salts (in terms of Mg):
NaY molecular sieve: deionized water=0.001-0.05:1:1-50, the preferably weight ratio of 0.003-0.03:1:2-20 are by magnesium salts, NaY
It is 2.0-6.0, preferably 2.0-5.0 that molecular sieve and deionized water, which are mixed with beating and uniformly adjust the pH value of slurries, at 60-150 DEG C,
It is preferred that being exchanged 0.5-3 hours, preferably 0.5-2 hours at 70-100 DEG C.
In method provided by the invention, the ammonium salt is selected from ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, carbonic acid
It is one or several kinds of in ammonium, ammonium hydrogen carbonate, ammonium oxalate and ammonium phosphate.
In method provided by the invention, the rare-earth salts be it is a kind of in the chloride of rare earth, nitrate and sulfate or
It is several, preferred chloride.Wherein the rare earth is preferably lanthanum and/or cerium.
In method provided by the invention, the phosphorus compound be selected from orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate,
It is one or several kinds of in diammonium hydrogen phosphate, aluminum phosphate and pyrophosphoric acid.
In method provided by the invention, the magnesium salts is one in magnesium chloride, magnesium nitrate, hydroxy chloride magnesium and magnesium sulfate
Kind is several, preferably magnesium chloride.
In method provided by the invention, the molecular sieve includes 20-100 weight % rare earth, phosphorus, magnesium-modified Y type point
Son sieve and 0-80 weight % routine Y type molecular sieve；Content of rare earth is in rare earth, phosphorus, magnesium-modified Y type molecular sieve described in wherein with oxygen
Change rare earth and be calculated as 2-20wt%, phosphorus content is calculated as 0.1-10wt% with phosphorus, and content of magnesium is calculated as 0.1-5wt% with magnesium, and sodium oxide molybdena contains
Amount is calculated as 0.05-1.0wt% with sodium.Wherein the conventional Y type molecular sieve is HY, NH4Y, REY, USY, REUSY, Qi Tayuan
One kind of plain modified Y zeolite or their mixture.
In method provided by the invention, the clay is that kaolin, sepiolite, galapectite, montmorillonite or its acid are modified
Clay；Or mixtures thereof modified galapectite of preferred acid modified kaolin, acid.The modified clay process of the acid are as follows: pass through clay
600-1000 DEG C of calcining 1-5h, then press clay: water: concentrated hydrochloric acid or concentrated nitric acid mass ratio are 1:3-10:0.05-2, in 60-90
DEG C constant temperature under processing 1-6h modified clay is made.
In method provided by the invention, the boehmite can be boehmite, three boehmites, bayerite
One of or a combination thereof, preferred boehmite.
In method provided by the invention, the binder be one of Aluminum sol, aluminium chloride, silica solution or its
Mixture.
Conventional method implementation, specific implementation can be used in drying described in the method disclosed in the present, roasting, filtering
Method discloses the process in patent CN98117896.0, CN02103907.0, CN200610112685.4.
In method provided by the invention, the magnesium salts is one in magnesium chloride, magnesium nitrate, hydroxy chloride magnesium and magnesium sulfate
Kind is several, preferably magnesium chloride.
In method provided by the invention, the acid be selected from hydrochloric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, sulfuric acid, citric acid,
The one or more of boric acid, preferably oxalic acid and citric acid.
The molecular sieve that catalyst provided by the invention contains includes with rare earth, phosphorus, magnesium-modified Y type molecular sieve, the molecule
Sieve first introduces rare earth element, improves the activity stability of molecular sieve, then introduces P elements and adjusts the acidity of molecular sieve surface by force
Degree is finally introducing magnesium elements and adjusts acid intensity in microporous molecular sieve duct, reduces basic nitrogen compound, polycyclic in wax tailings
The adsorption capacity of aromatic hydrocarbons and acidity of catalyst center reduces basic nitrogen compound and polycyclic aromatic hydrocarbon in the stop of catalyst surface
Between, inhibit the two in the green coke condensation reaction of catalyst surface, reduces coke plug-hole phenomenon, improve the benefit at catalyst cracking center
With rate, catalyst heavy oil conversion performance is improved.In method for preparing catalyst provided by the invention, after shaping of catalyst, pass through
The unformed aluminium in acid medium removing duct is added, reduces the plug-hole effect of unformed aluminium.Meanwhile unformed aluminium itself is L
Acid site, the nitrogen compound and aromatic hydrocarbons being easy in absorption wax tailings, which are formed, adsorbs burnt blocking catalyst duct, passes through cleaning hole
Unformed aluminium in road can also reduce duct green coke plug-hole probability.Therefore, acid is added in catalyst detergent preparation process to be situated between
Matter can increase the smoothness in catalyst duct, improve the diffusion of diesel oil molecules, reduce the secondary cracking of diesel oil molecules, increase
Add catalytic cracking wax tailings diesel oil selective.
Specific embodiment
Following example is to features of the present invention further instruction, but protection scope of the present invention is not by these examples
Limitation.
(1) evaluation method used in example
Catalytic cracking reaction selective evaluation: catalyst cracking reaction is carried out in small fixed flowing bed (FFB) device
Selective evaluation.Catalyst first passes through 800 DEG C in advance, handles 10h under the conditions of 100% water vapour.Reaction raw materials oil is Urumchi
Effect of Catalysis In Petrochemistry raw material specifically comprises decompression residuum 40%, straight-run gas oil 30% and wax tailings 30%, and property is as shown in table 1,
500-535 DEG C of reaction temperature, air speed 12-15h-1, oil ratio 5.
1 raw material oil nature of table
(2) places of origin of raw materials used in example and specification
Kaolin: China Kaolin Co., Ltd, kaolinite 86 are % heavy.
Angstrom trachelospermum jasminoide: China Kaolin Co., Ltd, angstrom trachelospermum jasminoide 80 are % heavy.
USY zeolite, REY zeolite, ZSM-5 are Catalyst Factory of Lanzhou Petrochemical Company production.
Aluminum sol, hydrochloric acid, sulfuric acid, rare earth chloride, phosphoric acid, waterglass, alkaline silica sol: industrial goods come from Lanzhou Petrochemical
Company's catalyst plant.
Boehmite: alumina content is 75.4 heavy %, the production of Shandong Alumina factory.
NaY molecular sieve, Aluminum sol: industrial goods come from Catalyst Factory of Lanzhou Petrochemical Company.
Ammonium sulfate, diammonium hydrogen phosphate, magnesium chloride, ammonium chloride, cerous nitrate, lanthanum nitrate, ammonium phosphate, lanthanum chloride, magnesium nitrate, carbon
Sour ammonium, phosphoric acid, magnesium sulfate, ammonium nitrate, ammonium hydrogen sulfate, ferric nitrate, copper chloride: analysis is pure, Beijing Chemical Plant's production.
Embodiment 1
The preparation of rare earth, phosphorus, magnesium-modified Y type molecular sieve:
1000 grams of NaY molecular sieves (butt) are taken, after being beaten with 10 kilograms of deionized waters, 300 grams of ammonium sulfate are added, adjust pH value
It is 3.5, is exchanged 1 hour in 90 DEG C, filter and be washed with water, it is then that filter cake and 100 grams of lanthanum chlorides (in terms of rare earth oxide) is mixed
It closes, is roasted 2 hours under 650 DEG C and 30% vapor, obtain rare-earth modified molecular-sieve；By roasting sample obtained above, with 5
The mashing of kilogram deionized water, is added 50 grams of diammonium hydrogen phosphates (in terms of phosphorus), and adjusting pH value is 4.0, exchanges 1 hour in 80 DEG C, filtering
Washing, then filter cake roasts 1 hour at 600 DEG C, obtains phosphorus rare-earth modified molecular-sieve；By above-mentioned phosphorus rare-earth modified molecular-sieve with
8 kilograms of deionized waters, 20 grams of magnesium chlorides (in terms of magnesium) are mixed with beating, and adjusting pH value is 3.8, react 1 hour at 95 DEG C, mistake
Filter, washing obtain rare earth, phosphorus and the composite modified molecular sieve Y1 of magnesium.
The preparation of the modified clay of acid:
500 grams of kaolin of 600 DEG C of roastings 5 hours are taken, after being beaten with 5000 kilograms of deionized waters, 1000 grams of dense salt is added
Acid reacts 6 hours at 60 DEG C, obtains the modified clay N1 of acid.
Catalyst preparation:
(1) it forms: 2000 grams of deionized waters, 80 grams of earth solution butt, Aluminum sol butt 200 being added in a kettle
Gram, 400 grams of boehmite butt, 600 grams of the modified clay N1 butt of above-mentioned acid and above-mentioned rare earth, phosphorus, magnesium-modified molecular sieve
650 grams and 70 grams of USY butt of Y1 butt, mashing stirs evenly after sixty minutes, is spray-dried, roasts obtained catalyst granules.
(2) modified: 2000 grams of deionized waters to be added in a kettle, 60 grams of magnesium chloride hexahydrates and 400 grams step (1) are urged
Catalyst particles, mashing are 3.5 with careless acid for adjusting pH value after twenty minutes, and after reaction 1 hour, filtering drying is up to the method for the present invention
The FCC catalyst of preparation, is denoted as C1.
Embodiment 2
The preparation of rare earth, phosphorus, magnesium-modified Y type molecular sieve:
1000 grams of NaY molecular sieves (butt) are taken, after being beaten with 50 kilograms of deionized waters, 150 grams of ammonium chlorides are added, adjust pH value
Be 2.1, in 45 DEG C exchange 4 hours, filter and be washed with water, then by filter cake with 100 grams of lanthanum nitrates and 200 grams of cerous nitrates (with dilute
Native oxide meter) mixing, it is roasted 3 hours at 400 DEG C, obtains rare-earth modified molecular-sieve；By roasting sample obtained above, use
50 kilograms of deionized water mashing, are added 100 grams of ammonium phosphate (in terms of phosphorus), and adjusting pH value is 2.0, exchange 0.5 hour in 130 DEG C, mistake
Drainage is washed, and then filter cake lower roasting 0.5 hour under 600 DEG C and 100% vapor, obtains phosphorus rare-earth modified molecular-sieve；It will be upper
Phosphorus rare-earth modified molecular-sieve is stated to be mixed with beating with 50 kilograms of deionized waters, 50 grams of magnesium nitrates (in terms of magnesium), adjusting pH value is 2.0,
It reacts 0.5 hour, is filtered, washed at 150 DEG C, obtain rare earth, phosphorus and the composite modified molecular sieve Y2 of magnesium.
The preparation of the modified clay of acid:
500 grams of galapectite of 1000 DEG C of roastings 1 hour are taken, after being beaten with 1500 grams of deionized waters, 50 grams of concentrated nitric acid is added,
It is reacted 1 hour at 90 DEG C, obtains the modified clay N2 of acid.
Catalyst preparation:
(1) it forms: 2000 grams of deionized waters, 160 grams of earth solution butt, Aluminum sol butt 60 being added in a kettle
Gram, 600 grams of boehmite butt, 150 grams of the modified clay N2 butt of above-mentioned acid and above-mentioned rare earth, phosphorus, magnesium-modified molecular sieve
1030 grams of Y2 butt, mashing stirs evenly after sixty minutes, is spray-dried, roasts obtained catalyst granules.
(2) modified: 800 grams of deionized waters to be added in a kettle, 160 grams of magnesium chloride hexahydrates and 400 grams step (1) are urged
Catalyst particles, mashing are 5.4 with lemon acid for adjusting pH value after forty minutes, and after reaction 3 hours, filtering drying is up to present invention side
The FCC catalyst of method preparation, is denoted as C2.
Embodiment 3
The preparation of rare earth, phosphorus, magnesium-modified Y type molecular sieve:
1000 grams of NaY molecular sieves (butt) are taken, after being beaten with 1 kilogram of deionized water, 1000 grams of ammonium carbonates are added, adjust pH value
Be 5.8, exchanged 0.5 hour in 130 DEG C, filter and be washed with water, then by filter cake and 10 grams of cerous nitrates (in terms of rare earth oxide)
Mixing, roasts 1 hour under 700 DEG C and 50% vapor, obtains rare-earth modified molecular-sieve；By roasting sample obtained above,
It is beaten with 2 kilograms of deionized waters, 10 grams of phosphoric acid (in terms of phosphorus) is added, adjusting pH value is 5.9, is exchanged 3 hours in 40 DEG C, and drainage is crossed
It washes, then filter cake roasts 3 hours under 300 DEG C and 50% vapor, obtains phosphorus rare-earth modified molecular-sieve；Above-mentioned phosphorus rare earth is changed
Property molecular sieve be mixed with beating with 2 kilograms of deionized waters, 2 grams of magnesium sulfate (in terms of magnesium), adjust pH value be 5.7, react 3 at 60 DEG C
Hour, it is filtered, washed, obtains rare earth, phosphorus and the composite modified molecular sieve Y3 of magnesium.
The preparation of the modified clay of acid:
Take 850 DEG C roasting 3 hours 300 grams and 580 DEG C of galapectite roast 2 hours 200 grams of kaolin, with 1500 grams of deionizations
After water mashing, 50 grams of concentrated nitric acid is added, is reacted 1 hour at 90 DEG C, obtains the modified clay N3 of acid.
Catalyst preparation:
(1) it forms: 2000 grams of deionized waters, 120 grams of Aluminum sol butt, boehmite butt being added in a kettle
160 grams, 1200 grams of the modified clay N3 butt of above-mentioned acid and above-mentioned rare earth, phosphorus, magnesium-modified 104 grams of molecular sieve Y3 butt and REY
416 grams of butt, mashing stirs evenly after sixty minutes, is spray-dried, roasts obtained catalyst granules.
(2) modified: 4000 grams of deionized waters to be added in a kettle, 7 grams of magnesium chloride hexahydrates and 400 grams step (1) are urged
Catalyst particles, after sixty minutes, adjusting pH value with hydrochloric acid is 2.5, and after reaction 0.5 hour, filtering drying is up to present invention side for mashing
The FCC catalyst of method preparation, is denoted as C3.
Embodiment 4
The preparation of rare earth, phosphorus, magnesium-modified Y type molecular sieve:
1000 grams of NaY molecular sieves (butt) are taken, after being beaten with 20 kilograms of deionized waters, 110 grams of ammonium nitrate and 40 grams are added
Ammonium hydrogen sulfate, adjusting pH value is 5.8, exchanges 0.5 hour in 130 DEG C, filters and be washed with water, then by filter cake and 50 grams of lanthanum nitrates
(in terms of rare earth oxide) mixing, roasts 1.5 hours at 550 DEG C, obtains rare-earth modified molecular-sieve；By roasting obtained above
Sample is beaten with 5 kilograms of deionized waters, and 8 grams of diammonium hydrogen phosphates (in terms of phosphorus) are added, and adjusting pH value is 4.2, exchanges 1.5 in 80 DEG C
Hour, filtering washing, then filter cake roasts 2 hours at 500 DEG C, obtains phosphorus rare-earth modified molecular-sieve；Above-mentioned phosphorus rare earth is changed
Property molecular sieve be mixed with beating with 3 kilograms of deionized waters, 2 grams of magnesium nitrates and 2 grams of magnesium sulfate (in terms of magnesium), adjust pH value be 4.2, in
It reacts 1 hour, is filtered, washed at 90 DEG C, obtain rare earth, phosphorus and the composite modified molecular sieve Y4 of magnesium.
Catalyst preparation:
(1) it forms: 2000 grams of deionized waters of addition, 80 grams of Aluminum sol butt and 320 grams of silica solution butt in a kettle,
500 grams of boehmite butt, 600 grams of kaolin butt, 100 grams of galapectite butt and above-mentioned rare earth, phosphorus, magnesium-modified molecule
240 grams and 60 grams of ZSM-5 butt of Y4 butt are sieved, mashing stirs evenly after sixty minutes, is spray-dried, roasts obtained catalyst particles
Grain.
(2) modified: the catalyst of 1700 grams of deionized waters, 36 grams of magnesium nitrates and 387 grams of steps (1) being added in a kettle
Particle, after mashing 35 minutes, adjusting pH value with hydrochloric acid and oxalic acid mixed liquor is 4.0, and after reaction 2 hours, filtering drying is up to this
The FCC catalyst of inventive method preparation, is denoted as C4.
Comparative example 1
It is prepared according to 103084206 A providing method of patent CN: 5000 grams of NaY molecules in terms of butt being added in reaction kettle
Sieve and 4000 grams of deionized waters are slowly added to 150 grams of lanthanum chloride (in terms of rare earth) under high degree of agitation, with 4 weight % dilute hydrochloric acid tune
PH=3.5 is saved, is warming up at 90 DEG C and stirs 1.5 hours, is filtered, is washed, it is dry；Then in 650 DEG C, 100% steam atmosphere
" one hands over one times " rare earth sodium Y molecular sieve is made in lower roasting 2 hours.
It takes 2000 grams of rare earth sodium Y molecular sieve butt obtained above to be put into reaction kettle, 1600 grams of deionized waters is added, swash
30 grams of lanthanum chlorides, 32 grams of ferric nitrates, 0.3 gram of copper chloride and 50 grams of ammonium dihydrogen phosphates are slowly added under strong stirring, with 4% weight
Dilute hydrochloric acid regulation system PH=3.5 is measured, 90 DEG C of stirrings is warming up to and filters for 1 hour, wash, it is dry, rare earth, iron, copper, phosphorus is made and changes
Property molecular sieve DY-1.
The preparation of catalytic cracking catalyst:
2000 grams of deionized waters and 400 grams of boehmite butt are added in a kettle, and add into obtained slurries
Enter 80 grams of peptizations of hydrochloric acid that concentration is 36 weight %, is warming up to 65 DEG C and is acidified 1 hour, be separately added into 600 grams of kaolin and aluminium is molten
It 200 grams of glue butt, stirs 20 minutes, adds 650 grams of the molecular sieve DY-1 butt and USY of above-mentioned rare earth, iron, copper, P Modification
70 grams of butt, mashing stirs evenly after sixty minutes, and microspherical catalyst is made in spray drying.By the microspherical catalyst at 500 DEG C
Roasting 1 hour, then washed to sodium oxide content with ammonium sulfate less than 0.25 weight % at 60 DEG C, finally with 10 times of deionized waters
Elution dries to get comparison FCC catalyst at 110 DEG C after filtering, is denoted as D1.
Comparative example 2
The preparation of Modified Zeolite Y:
Rare-earth modified molecular-sieve in embodiment 1 is roasted 1000 grams of sample, is beaten with 5 kilograms of deionized waters, is added 50
Gram diammonium hydrogen phosphate (in terms of phosphorus) and 20 grams of magnesium chlorides (in terms of magnesium), adjusting pH value is 4.0, is exchanged 1 hour in 80 DEG C, crosses drainage
It washes, then filter cake roasts 1 hour at 600 DEG C, obtains modified molecular screen；By above-mentioned modified molecular screen and 8 kilograms of deionized waters
It is mixed with beating, adjusting pH value is 3.8, is reacted 1 hour at 95 DEG C, is filtered, washed to obtain sieve sample to be DY-2.
Catalyst preparation:
(1) it forms: 2000 grams of deionized waters, 80 grams of earth solution butt, Aluminum sol butt 200 being added in a kettle
Gram, 400 grams of boehmite butt, 600 grams of the modified clay N1 butt of above-mentioned acid and 650 grams of modified molecular screen DY-2 butt above-mentioned
With 70 grams of USY butt, mashing stirs evenly after sixty minutes, is spray-dried, roast obtained catalyst granules.
(2) modifying process is denoted as D2 with the modifying process in embodiment 1, the FCC catalyst of preparation.
Comparative example 3
The preparation of Modified Zeolite Y:
Rare-earth modified molecular-sieve in embodiment 1 is roasted 1000 grams of sample, is beaten with 8 kilograms of deionized waters, is added 20
Gram magnesium chloride (in terms of magnesium), adjusting pH value is 3.8, reacts 1 hour, is filtered, washed at 95 DEG C；By rare earth obtained above and
Magnesium-modified molecular sieve filter cake is beaten with 5 kilograms of deionized waters, and 50 grams of diammonium hydrogen phosphates (in terms of phosphorus) are added, and adjusting pH value is 4.0,
It is exchanged 1 hour in 80 DEG C, filtering washing, then filter cake roasts 1 hour at 600 DEG C, and obtaining sieve sample is DY-3.
Catalyst preparation:
(1) it forms: 2000 grams of deionized waters, 80 grams of earth solution butt, Aluminum sol butt 200 being added in a kettle
Gram, 400 grams of boehmite butt, 600 grams of the modified clay N1 butt of above-mentioned acid and 650 grams of modified molecular screen DY-3 butt above-mentioned
With 70 grams of USY butt, mashing stirs evenly after sixty minutes, is spray-dried, roast obtained catalyst granules.
Modifying process is denoted as D3 with the modifying process in embodiment 1, the FCC catalyst of preparation.
The catalyst reaction performance evaluation result of embodiment 1-4 and comparative example 1-3 preparation is listed in Table 2 below.
The catalyst fixed bed evaluation result of table 2
| Catalyst | C1 | C2 | C3 | C4 | D1 | D2 | D3 |
| Dry gas | 3.02 | 2.87 | 3.04 | 2.93 | 3.38 | 2.96 | 2.88 |
| Liquefied gas | 13.17 | 13.09 | 12.98 | 14.45 | 13.06 | 12.68 | 12.11 |
| Gasoline | 36.78 | 36.88 | 35.48 | 34.02 | 37.41 | 38.96 | 37.36 |
| Diesel oil | 34.85 | 35.11 | 36.19 | 36.21 | 32.56 | 26.02 | 26.6 |
| Heavy oil | 5.07 | 4.92 | 5.36 | 5.62 | 6.12 | 12.57 | 14.57 |
| Coke | 7.11 | 7.13 | 6.95 | 6.77 | 7.47 | 6.81 | 6.48 |
| Conversion ratio | 60.08 | 59.97 | 58.45 | 58.17 | 61.32 | 61.41 | 58.83 |
| Total liquid yield | 84.8 | 85.08 | 84.65 | 84.68 | 83.03 | 77.66 | 76.07 |
From fixed bed evaluation result it is found that in the case where mixing 30% wax tailings of refining, using the method for the present invention preparation
Catalyst has lower heavy oil yield and higher diesel yield, and it is good to illustrate that the catalyst of the method for the present invention preparation has
Wax tailings conversion capability and diesel oil selectivity.Compared with 2 catalyst of comparative example (D2) and 3 catalyst of comparative example (D3), this hair
The catalyst heavy oil yield of bright method preparation declines to a great extent, and illustrates the modification order of phosphorus, magnesium elements during molecular sieve modified
There is important influence to the performance of catalyst.Phosphorus and magnesium elements are introduced simultaneously during molecular sieve modified or first introduce magnesium
P elements are introduced after element cannot all realize heavy oil conversion performance height and the good double goal of gasoline selective simultaneously.With comparative example
1 catalyst (D1) is compared, and in the case where conversion ratio improves and heavy oil declines, the catalyst of the method for the present invention preparation has more
Excellent diesel oil selectivity and coke selectivity.In wax tailings catalytic cracking process, due to nitrogen compound and aromatic hydrocarbon molecule
It is readily adsorbed in acidity of catalyst and is centrally formed coke blocking catalyst duct, cause the acid centre in duct can not cracking weight
Oil molecule influences the heavy oil conversion rate and diesel yield of catalytic cracking.The invention patent is strong using phosphorus modulation molecular sieve surface
Strong acid center in acid site and magnesium modulation molecular sieve pore passage improves the coke selectivity of acid centre in duct, reduces cracking
Green coke plug-hole during wax tailings；Meanwhile it is modified using acid after shaping of catalyst, the unformed aluminium in duct is cleared up, is mentioned
The diffusion of high diesel oil molecules inhibits secondary cracking of the diesel oil molecules in duct, to improve catalytic cracking wax tailings
Diesel oil selectivity.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (27)
1. a kind of catalytic cracking catalyst preparation method of cracking wax tailings high-yield diesel oil, which is characterized in that the method packet
It includes following steps: (1) NaY molecular sieve and ammonium salt solution (a) rare earth, phosphorus, magnesium-modified Y type molecular sieve preparation: being subjected to ion
Exchange, is filtered, washed, washes rear filter cake and mix with rare-earth salts, and it is small that 1-3 is then roasted under 400-700 DEG C, 1%-50% water vapour
When, obtain rare earth modified Y type molecular sieve；(b) by rare earth modified Y type molecular sieve obtained in step (a) and phosphorus-containing compound or
The mixed solution of phosphorus-containing compound and ammonium salt carries out ion exchange, is then filtered, washed, in 300-600 DEG C, l%-100% water
Roasted 0.5-3 hours under steam, obtain rare earth and the composite modified Y type molecular sieve of phosphorus, will (c) be obtained in step (b) rare earth and
The composite modified Y type molecular sieve of phosphorus and magnesium salts carry out ion exchange, are then filtered, washed, it is composite modified to obtain rare earth, phosphorus and magnesium
Y type molecular sieve；(2) shaping of catalyst: water, molecular sieve, clay, boehmite and binder are mixed, mashing, done by spraying
Dry, roasting, obtains preformed catalyst solid particle；(3) modified: according to weight ratio, step (2) catalyst solid particle: go from
Sub- water: deionized water, magnesium salts are uniformly mixed by magnesium salts=1:2-10:0.001-0.05 with catalyst solid particle, and acid is added and adjusts
Slurry pH value is saved in 2.5-5.5, stirs 0.5h-3h, then filtration drying, wherein the magnesium salts is in terms of magnesium.
2. method for preparing catalyst according to claim 1, which is characterized in that the ion of step (a) described in step (1)
Be exchanged for according to ammonium salt: NaY molecular sieve: deionized water=0.15-1:l:1-50 weight ratio is by ammonium salt, NaY molecular sieve and goes
It is 2.0-6.0 that ionized water, which is mixed with beating and uniformly adjusts the pH value of slurries, is exchanged 0.5-4 hours at 40-130 DEG C.
3. method for preparing catalyst according to claim 1 or 2, which is characterized in that step (a) described in step (1)
Ion exchange is according to ammonium salt: NaY molecular sieve: deionized water=0.2-0.5:1:2-30 weight ratio is by ammonium salt, NaY molecular sieve
Being mixed with beating with deionized water and uniformly adjusting the pH value of slurries is 2.0-5.0, is exchanged 1-3 hours at 60-90 DEG C.
4. method for preparing catalyst according to claim 1, which is characterized in that after the washing of step (a) described in step (1)
Filter cake is mixed with rare-earth salts according to weight ratio rare-earth salts: NaY molecular sieve=0.001-0.2:l, the rare-earth salts is with RE2O3Meter.
5. method for preparing catalyst according to claim 1 or 2, which is characterized in that step (a) described in step (1)
Wash rear filter cake to be mixed with rare-earth salts according to weight ratio rare-earth salts: NaY molecular sieve=0.02-0.2:1, the rare-earth salts is with RE2O3
Meter.
6. method for preparing catalyst according to claim 1, which is characterized in that the ion of step (b) described in step (1)
It is exchanged for according to phosphorus-containing compound: ammonium salt: NaY molecular sieve: deionized water=0.001-0.1:0-0.3:1:1-50 weight ratio
It is 2.0-6.0 that phosphorus-containing compound, ammonium salt, NaY molecular sieve and deionized water, which are mixed with beating, and uniformly adjust the pH value of slurries,
It is exchanged 0.5-3 hours at 40-130 DEG C, the phosphorus-containing compound is in terms of P.
7. method for preparing catalyst according to claim 1 or 6, which is characterized in that step (b) described in step (1)
Ion exchange is according to phosphorus-containing compound: ammonium salt: NaY molecular sieve: deionized water=0.005-0.04:0-0.2:1:2-30 weight
It is 2.0- that phosphorus-containing compound, ammonium salt, NaY molecular sieve and deionized water are mixed with beating and uniformly adjust the pH value of slurries by amount ratio
5.0, it is exchanged 0.5-2 hours at 60-90 DEG C, the phosphorus-containing compound is in terms of P.
8. method for preparing catalyst according to claim 1, which is characterized in that the ion of step (c) described in step (1)
Be exchanged for according to magnesium salts: NaY molecular sieve: deionized water=0.001-0.05:1:1-50 weight ratio is by magnesium salts, NaY molecular sieve
Being mixed with beating with deionized water and uniformly adjusting the pH value of slurries is 2.0-6.0, is exchanged 0.5-3 hours at 60-150 DEG C, described
Magnesium salts is in terms of Mg.
9. method for preparing catalyst according to claim 1 or 8, which is characterized in that step (c) described in step (1)
Ion exchange is according to magnesium salts: NaY molecular sieve: deionized water=0.003-0.03:1:2-20 weight ratio divides magnesium salts, NaY
It is 2.0-5.0 that son sieve and deionized water, which are mixed with beating and uniformly adjust the pH value of slurries, is exchanged 0.5-2 hours at 70-100 DEG C,
The magnesium salts is in terms of Mg.
10. method for preparing catalyst according to claim 1, which is characterized in that modified described in step (3): according to weight
Amount is than catalyst solid particle: deionized water: magnesium salts=1:3-7:0.005-0.03 mixes water, magnesium salts with catalyst granules
Uniformly, acid is added and adjusts slurry pH value in 3.0-4.0, stirs 0.5h-3h, then filtration drying, the magnesium salts is in terms of Mg.
11. method for preparing catalyst according to claim 1, which is characterized in that the ammonium salt is selected from ammonium chloride, sulfuric acid
It is one or several kinds of in ammonium, ammonium hydrogen sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate and ammonium phosphate.
12. method for preparing catalyst according to claim 1 or 4, which is characterized in that the rare-earth salts is the chlorine of rare earth
It is one or more of in compound, nitrate and sulfate, wherein the rare earth is preferably lanthanum and/or cerium.
13. method for preparing catalyst according to claim 1 or 4, which is characterized in that the rare-earth salts is the chlorine of rare earth
Compound.
14. method for preparing catalyst according to claim 1, which is characterized in that the phosphorus compound be selected from orthophosphoric acid,
It is one or several kinds of in phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate and pyrophosphoric acid.
15. method for preparing catalyst according to claim 1, which is characterized in that the magnesium salts is selected from magnesium chloride, nitric acid
It is one or more of in magnesium, hydroxy chloride magnesium and magnesium sulfate.
16. according to claim 1 or method for preparing catalyst described in 15, which is characterized in that the magnesium salts is magnesium chloride.
17. method for preparing catalyst according to claim 1, which is characterized in that the molecular sieve includes 20-100 weight
Measure % rare earth, phosphorus and the composite modified Y type molecular sieve and 0-80 weight % routine Y type molecular sieve of magnesium.
18. according to claim 1 or method for preparing catalyst described in 17, which is characterized in that the rare earth, phosphorus and magnesium are compound
Content of rare earth is calculated as 2-20wt% with rare earth oxide in modified Y type molecular sieve, and phosphorus content is calculated as 0.1-10wt% with phosphorus, and magnesium contains
Amount is calculated as 0.1-5wt% with magnesium, and sodium oxide content is calculated as 0.05-1.0wt% with sodium.
19. method for preparing catalyst according to claim 17, which is characterized in that the conventional Y type molecular sieve be HY,
NH4Y, one kind of REY, USY, REUSY or their mixture.
20. method for preparing catalyst according to claim 1, which is characterized in that the clay is kaolin, Hai Pao
Stone, galapectite, montmorillonite or the modified clay of its acid.
21. method for preparing catalyst according to claim 1, which is characterized in that the clay be sour modified kaolin,
Or mixtures thereof modified galapectite of acid.
22. method for preparing catalyst according to claim 20, which is characterized in that the modified clay process of the acid are as follows:
By clay through 600-1000 DEG C of calcining 1-5h, then press clay: water: concentrated hydrochloric acid or concentrated nitric acid mass ratio are 1:3-10:0.05-2,
1-6h is handled under 60-90 DEG C of constant temperature, and the modified clay of acid is made.
23. method for preparing catalyst according to claim 1, which is characterized in that the boehmite can be one
One of boehmite, three boehmites, bayerite or a combination thereof.
24. method for preparing catalyst according to claim 1, which is characterized in that the boehmite can be one
Boehmite.
25. method for preparing catalyst according to claim 1, which is characterized in that the binder is Aluminum sol, alkali formula chlorine
Change or mixtures thereof one of aluminium, silica solution.
26. method for preparing catalyst according to claim 1, which is characterized in that the acid is selected from hydrochloric acid, nitric acid, phosphorus
The one or more of acid, acetic acid, oxalic acid, sulfuric acid, citric acid, boric acid.
27. according to claim 1 or method for preparing catalyst described in 26, which is characterized in that the acid is oxalic acid and lemon
Acid.
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| CN110479362A (en) * | 2019-09-03 | 2019-11-22 | 四川润和催化新材料股份有限公司 | A kind of high-yield diesel oil and the catalyst of low-carbon olefines high-output and the preparation method and application thereof |
| CN112237940A (en) * | 2020-07-01 | 2021-01-19 | 湖南聚力催化剂股份有限公司 | Preparation method of yield-increasing diesel oil catalytic cracking auxiliary agent |
| CN113976098A (en) * | 2021-11-09 | 2022-01-28 | 青岛惠城环保科技股份有限公司 | Preparation method of alkaline catalyst for thermal cracking of waste plastics |
| CN116265107A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst for producing diesel oil in large quantity |
| CN116273142A (en) * | 2023-03-06 | 2023-06-23 | 青岛惠城环保科技集团股份有限公司 | Preparation method of diesel catalytic cracking catalyst for increasing yield |
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| CN103157506A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst with high light oil yield and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110479362A (en) * | 2019-09-03 | 2019-11-22 | 四川润和催化新材料股份有限公司 | A kind of high-yield diesel oil and the catalyst of low-carbon olefines high-output and the preparation method and application thereof |
| CN112237940A (en) * | 2020-07-01 | 2021-01-19 | 湖南聚力催化剂股份有限公司 | Preparation method of yield-increasing diesel oil catalytic cracking auxiliary agent |
| CN113976098A (en) * | 2021-11-09 | 2022-01-28 | 青岛惠城环保科技股份有限公司 | Preparation method of alkaline catalyst for thermal cracking of waste plastics |
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| CN116265107A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst for producing diesel oil in large quantity |
| CN116273142A (en) * | 2023-03-06 | 2023-06-23 | 青岛惠城环保科技集团股份有限公司 | Preparation method of diesel catalytic cracking catalyst for increasing yield |
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