CN100377782C

CN100377782C - Hydrocarbon cracking catalyst and its use

Info

Publication number: CN100377782C
Application number: CNB200410074415XA
Authority: CN
Inventors: 田辉平; 陈振宇; 龙军; 达志坚; 张万虹; 唐立文; 许明德; 徐志成
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2004-09-15
Filing date: 2004-09-15
Publication date: 2008-04-02
Anticipated expiration: 2024-09-15
Also published as: CN1749364A

Abstract

The present invention discloses a cracking catalyst for hydrocarbons and an application thereof. The catalyst is prepared from 10 to 60 wt% of molecular sieve, 0 to 75 wt% of clay, 5 to 40 wt% of silicon bonding agent measured by SiO2, 0.1 to 10 wt% of aluminum oxide and 0 to 10 wt% of modified component measured by an oxide. The catalyst is obtained by maintaining serous fluid in a sol state before catalyst shaping in the method of the combination of a sol phase and a gel phase, controlling the temperature of spray-drying tail gas between 50 and 150DEG C to generate microspheric gel, and ageing and treating the microspheric gel through hole expansion. The catalyst having high substrate cracking activity, which is applied to a cracking reaction, is favorable to the cracking of heavy oil or the cracking of residual oil.

Description

A kind of preparation method of hydrocarbon cracking catalyzer

Technical field

The invention relates to a kind of catalyst and cracking of hydrocarbon and application thereof, more specifically say so about a kind of be the semi-synthetic hydrocarbon cracking catalyzer and the application thereof of binding agent with the Ludox.

Background technology

In recent years, because the heaviness of raw material and poor qualityization, the content of molecular sieve constantly increases in the catalyst, with boehmite and aluminium colloidal sol is the catalyst carrier of binding agent, can not tolerate the further increase of molecular sieve amount, cause the catalyst wear resistence poor, in addition, the price of boehmite and aluminium colloidal sol is higher, causes the catalyst cost higher.Therefore, must improve the caking property of catalyst carrier, guarantee that catalyst in use has good antiwear property.

U.S. Pat P3,867,308 disclosed employings contain the catalyst that the sodium Ludox is the semi-synthesizing technology preparation of binding agent, though the carrier cohesive force is strong, bulk density is big, be unfavorable for fluidisation, be not suitable for most of FCC apparatus uses of present stage, and surface area is low, pore volume is little, the matrix activity is low, is unfavorable for the catalytic cracking of residual oil.

U.S. Pat P3,957,689 disclosed employing aluminum sulfate cushioning liquid, preparation contains the catalyst that the sodium Ludox is the semi-synthesizing technology preparation of binding agent, and the content of aluminium oxide is the heavy % of 1-10 in the Ludox.The control range of pH when the method has been improved and has been the adhesive preparation catalyst with single Ludox.Problems such as but exist bulk density big equally, surface area is low, and pore volume is little, and the matrix activity is on the low side are not suitable for most of FCC apparatus uses of present stage.

U.S. Pat P3,972,835 disclose the catalyst that a kind of sodium-free silica sol is the semi-synthesizing technology preparation of binding agent, and wherein sodium-free silica sol makes waterglass by ion exchange resin.Though this catalyst strength is good, antiwear property is strong, and bulk density is big, is unfavorable for fluidisation, and surface area is low, and pore volume is little, is unfavorable for the catalytic cracking of residual oil, and the ion-exchange of the preparation of sodium-free silica sol need, the preparation process complexity, and cost is higher.

U.S. Pat P4,022,714 and USP4,107,088 disclose and have a kind ofly contained the Catalysts and its preparation method of sodium Ludox preparation with titanium, zirconium, iron, cerium, boron modification, carry out modification by these metal pair Ludox, can improve the specific area and the cracking activity of fresh catalyst, but exist bulk density big equally, problem such as pore volume is little is not suitable for present stage most of FCC apparatus and uses.

U.S. Pat P4,198,320 disclose a kind of preparation method who improves preventing from heavy metal pollution ability Cracking catalyst, and the Ludox, aluminium colloidal sol or the silicon-aluminum sol that disperse by the deposition colloid can improve the preventing from heavy metal ability of catalyst in the catalyst gel or on the catalyst of moulding.But unfavorable factors such as the silica sol binder catalyst of employing the method modification exists bulk density big equally, and surface area is low, and pore volume is little.

U.S. Pat P4,631,261 disclose a kind of preparation method of catalyst and cracking of hydrocarbon, are in the molecular sieve catalyst preparation process of binding agent at Ludox, add the gibbsite of handling through expansion drying.The silica-alumina gel molecular sieve catalyst of glue method preparation is compared together, has higher cracking activity, better gasoline and coke selectivity, and preventing from heavy metal ability.But unfavorable factors such as the catalyst that adopts this method to prepare exists bulk density big equally, and surface area is low, and pore volume is little.

U.S. Pat P5,961,817 and USP6,022,471 discloses a kind of contain gibbsite mesopore FCC catalyst and application, uses Ludox as binding agent in its preparation method, and has added gibbsite, and the catalyst of acquisition has more mesopore.But unfavorable factors such as the catalyst that adopts this method to prepare exists bulk density bigger than normal equally, and surface area is low, and pore volume is little; And, used two kinds of Ludox in its preparation method, a kind of is low sodium Ludox through ion-exchange, another kind is the Ludox of sulfur acid aluminium cushioning liquid, so preparation technology's relative complex.

By forefathers' work as can be seen, it is that the semi-synthetic catalytic cracking catalyst of adhesive preparation has good wear strength that employing contains the sodium Ludox, and preparation technology is simple, and the price of Ludox is also cheap than boehmite and aluminium colloidal sol, but exist bulk density big, unfavorable factors such as surface area is low, and pore volume is little, and the matrix activity is low.Though, can make catalyst have more mesopore by introducing aluminium oxide, or improve the cracking activity and the preventing from heavy metal ability of catalyst, catalyst buildup density is big, and surface area is low, and pore volume is little etc., and problem still exists.

Summary of the invention

The purpose of this invention is to provide a kind of usefulness and contain the microballoon synthetic zeolite catalysts cracking catalyst that the sodium Ludox is made binding agent; Another object of the present invention provides the cracking hydrocarbon method of using this catalyst.

Hydrocarbon cracking catalyzer provided by the invention is characterized in that this catalyst is by the clay of the molecular sieve of 10～60 heavy %, 0～75 heavy %, with SiO ₂The modified component in oxide of the silicon bonding of meter 5～40 heavy %, the aluminium oxide of 0.1～10 heavy % and 0～10 heavy % is formed, and obtains through following step:

(1) preparation of silicon bonding: with modulus is that 2.8～3.3 sodium silicate water is mixed with SiO ₂Meter, concentration are the solution of 3～20 heavy %, mix with inorganic acid, and the control temperature is 0～30 ℃, obtain endpoint pH and be 0.5～3.5, ultimate density is the Ludox of 3～12 heavy %;

(2) be chosen in colloidal sol and generate before, generate in or generate the back and add clay siccative or slurries, form Ludox-clay slurry;

(3) preparation molecular sieve pulp, and adjusting slurry pH value is 3.0～5.0;

(4) (a) and (b) optional one: (a) molecular sieve pulp, alumina powder, modified component slurries are evenly mixed with Ludox-clay slurry, and the pH value that makes final slurries is 2.5～3.2, the exhaust temperature of control spray shaping is 50～150 ℃, obtain the microspheroidal gel, its water content is 30～60 heavy %, with the microspheroidal gel at 60～90 ℃, the pH value is in 4.0～6.0 the deionized water aging 0.5～1 hour, microspheroidal gel after aging is washed in deionized water or ammonium sulfate solution, filter, get finished product after the drying; (b) molecular sieve pulp, modified component slurries are evenly mixed with Ludox-clay slurry, and the pH value that makes final slurries is 2.5～3.2, the exhaust temperature of control spray shaping is 50～150 ℃, obtain the microspheroidal gel, its water content is 30～60 heavy %, with the microspheroidal gel at 60～90 ℃, the pH value is aging more than 0.5 hour in 4.0～6.0 the deionized water, after microspheroidal gel after aging washed in deionized water or ammonium sulfate solution, in containing aluminum water solution, stir, and control pH value is 4.0～9.0, filters, must finished product after the drying.

Catalyst provided by the invention be preferably by the clay of the molecular sieve of 10～40 heavy %, 10～50 heavy %, with SiO ₂The silicon bonding of meter 10～30 heavy %, the aluminium oxide of 0.1～5 heavy % and 0～5 heavy % form in the modified component of oxide.

In the catalyst provided by the invention, said molecular screening is from the molecular sieve of faujasite, β zeolite, MFI structure and in the modenite one or more.

Said faujasite is selected from one of HY, REY, REHY, USY, REUSY, DASY, REDASY or two or more mixture wherein, and the content of rare earth of wherein said REY, REHY, REHX, REUSY and REDASY is with RE ₂O ₃Count 0.5～20 heavy %.Said faujasite can also be in being selected from the periodic table of elements one or more element modified obtaining in IIA, IVA, VA, IIB, IVB, the VIIIB family, wherein preferred one or more element modified faujasites that obtain in Mg, Ca, Sr, Ba, Sn, P, Sb, Zn, Ti, Zr and Fe.

In the catalyst provided by the invention, said clay is selected from a kind of in kaolin, halloysite, galapectite, imvite and the bentonite or two or more mixture wherein.

In the catalyst provided by the invention, in the preparation of said step (1) silicon bonding, inorganic acid is selected from and contains or one or more in the sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid of sulfur acid aluminium cushioning liquid not, and said Ludox endpoint pH is 0.8～3.0.

In the catalyst provided by the invention, step (4) (a) in said alumina powder be in boehmite, boehmite, boehmite and the gibbsite powder one or more; (b) the said aluminum water solution that contains is one or more the aqueous solution that contains in aluminium colloidal sol, polymeric aluminum chloride, alchlor and the aluminum sulfate in, and wherein alumina content is 0.1～2 heavy %.

In the catalyst provided by the invention, the exhaust temperature of the described spray shaping of step (4) is preferably 80～120 ℃, and its water content is 40～50 heavy %.

In the catalyst provided by the invention, said modified component is selected from periodic table of elements middle rare earth element (RE), IIA, IVA, VA, IIB, IVB, VIB, one of compound of VIIIB family element or two or more mixture wherein, said rare earth element can be single rare earth, as La, Ce, Pr, rare earth that Nd etc. are single or mishmetal, the preferred Mg of said IIA family's element, Ca, Sr or Ba, the preferred Sn of said IYA element, preferred P of said VA element or Sb, the preferred Zn of said IIB element, preferred Ti of said IVB element or Zr, preferred Cr of said VIB element or Mo, the preferred Fe of said VIIIB family's element, preferred element is RE and/or P in the wherein said modified component.

The present invention also provides a kind of hydrocarbon oil catalytic cracking method of using this catalyst, is 450～700 ℃ of temperature, preferred 460～680 ℃, weight (hourly) space velocity (WHSV) 0.2～20 hour ^-1, preferred 1～10 hour ^-, the agent weight of oil is than being under 2～12, preferred 3～10 the condition cracking reaction to take place.

In the cracking method provided by the invention, said hydrocarbon ils is selected from decompressed wax oil, reduced crude, hydrogenation tail oil, decompressed wax oil and mixes refining decompression residuum, decompressed wax oil and mix refining reduced crude, decompressed wax oil and mix coking wax oil, decompressed wax oil and mix refining hydrogenation tail oil, decompressed wax oil and mix in the refining deasphalted oil one or more.

Catalyst provided by the invention has characteristics such as medium bulk density, wear-resistant, macropore volume, cracking activity height.Compared with prior art, catalyst provided by the invention has bigger pore volume, has improved the accessibility of catalyst active center, more helps big molecule hydrocarbon and diffuses into catalyst, has strengthened the cracking to macromolecule hydrocarbon.Catalyst provided by the invention has higher matrix cracking activity, helps the cracking of heavy oil or residual oil.Catalyst provided by the invention has good wear strength, can tolerate higher molecular sieve consumption.Catalyst buildup density provided by the invention is moderate, is fit to most of FCC apparatus uses of present stage.

In the catalyst provided by the invention, said preparation method and existing method for preparing catalyst have bigger improvement, and technology is simple, is easy to realize industrialization.Prior art adopts colloidal sol to become glue, the catalyst of preparation has good wear strength, unfavorable factors such as but exist bulk density big, pore volume is little, and the matrix activity is low, though adopt gel process can make catalyst obtain higher specific surface area and pore volume, but catalyst buildup density is less, and the carrier cohesive force is poor, and the molecular sieve dosis tolerata is low, and the hydrogel filtration difficulty causes preparation technology comparatively complicated; Catalyst provided by the invention, adopt the method for colloidal sol and gel phase combination, keep slurries to be in dissolved colloidal state before shaping of catalyst, pulping process is simple, by the cold nebulization moulding, generate the microspheroidal gel, avoided the problem of hydrogel filtration difficulty, the reaming of wearing out is again handled, and has improved the physical and chemical performance of catalyst effectively, and in catalyst preparation process, introduce aluminium oxide, improved the cracking activity of matrix.What deserves to be mentioned is that vapo(u)rizing temperature reduces significantly, reduced energy consumption, and can improve the treating capacity of device.

The specific embodiment

The present invention is further illustrated by the following examples, but content not thereby limiting the invention.

Embodiment 1

Get 2.1L hydrochloric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 36-38), add 10.0Kg decationized Y sieve water and dilute.Get the 9.6Kg sodium silicate (commercially available, contain SiO ₂Concentration 26.0 heavy %, modulus is 3.2), add 11.6Kg decationized Y sieve water and dilute, stir the sodium silicate that will dilute down and slowly add in the above-mentioned hydrochloric acid weak solution, obtain SiO ₂Concentration 7.5 heavy %, the Ludox of pH value 2.3.

In above-mentioned Ludox, add 4.7Kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %), stirred 1 hour, kaolin is fully disperseed.

Adding 3.8KgDASY molecular sieve (the Shandong catalyst plant is produced, and solid content is 92.0 heavy %) in 6.8Kg decationized Y sieve water, after homogenizer fully disperses, is 3.5 with the watery hydrochloric acid adjust pH; (Shandong Aluminum Plant produces, and contains Al with 0.53kg gibbsite fine powder ₂O ₃The heavy % of concentration 95.3) and molecular sieve pulp join respectively in above-mentioned Ludox-clay slurry, continue stirring 0.5 hour, obtaining solid content is that 20.4 heavy %, pH value are 3.2 dissolved colloidal state catalyst slurry.

In 110 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 55.0 heavy % with these slurries.

With the micro-spherical catalyst gel at 90 ℃, the pH value is in the deionized water of 4.0-6.0 aging 1 hour, filter, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, washed 10 minutes with 60～70 ℃ deionized water again, and to regulate the pH value with ammoniacal liquor be 8.0～9.0, after filtration, 120 ℃ of dryings 2 hours, 650 ℃ of roastings 2 hours, the gained catalyst is numbered A.

Catalyst A consist of 35 heavy % kaolin, 35 heavy %DASY molecular sieves, 25 heavy %SiO ₂Binding agent and 5 heavy %Al ₂O ₃

Comparative Examples 1

This Comparative Examples explanation is a binding agent with the Ludox that contains the sodium silicate preparation, handles through sol-gel process, but does not introduce the conventional catalytic cracking catalyst of aluminium oxide.

In above-mentioned Ludox, add 5.4Kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.

Adding 3.8KgDASY molecular sieve (the Shandong catalyst plant is produced, and solid content is 92.0 heavy %) in 6.8Kg decationized Y sieve water, after homogenizer fully disperses, is 3.5 with the watery hydrochloric acid adjust pH.Molecular sieve pulp is joined in above-mentioned Ludox-clay slurry, continue to stir 0.5h, obtaining solid content is that 20.5 heavy %, pH value are 3.0 dissolved colloidal state catalyst slurry.

In 110 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 55.2 heavy % with these slurries.

With the micro-spherical catalyst gel at 90 ℃, the pH value is aging 1h in the deionized water of 4.0-6.0, filter, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, again with 60-70 ℃ deionized water washing 10 minutes, and to regulate the pH value with ammoniacal liquor be 8.0-9.0, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.The gained comparative catalyst numbers DB-1.

Comparative catalyst DB-1 consists of 40 heavy % kaolin, 35 heavy %DASY molecular sieves, 25 heavy %SiO ₂Binding agent.

Comparative Examples 2

This Comparative Examples explanation is a binding agent with the Ludox that contains the sodium silicate preparation, does not introduce aluminium oxide, and the conventional catalytic cracking catalyst of handling without sol-gel process.

According to Comparative Examples 1 described method, preparing solid content is that 20.5 heavy %, pH value are 3.0 dissolved colloidal state catalyst slurry.

These slurries according to a conventional method in 250 ℃ of following spray drying formings of exhaust temperature, are obtained the micro-spherical catalyst particle.

The catalyst of drying and moulding was washed 10 minutes in 60-70 ℃ deionized water, filter, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, use 60-70 ℃ deionized water to wash again 10 minutes, and to regulate the pH value with ammoniacal liquor be 8.0-9.0, after filtration, 120 ℃ of dry 2h, and 650 ℃ of roasting 2h.The gained comparative catalyst numbers DB-2.

Comparative catalyst DB-2 consists of 40 heavy % kaolin, 35 heavy %DASY molecular sieves, 25 heavy %SiO ₂Binding agent.

The BET specific surface that catalyst A, contrast medium DB-1 and DB-2 record with cryogenic nitrogen absorption, the pore volume that the water droplet method records, intensity (abrasion index) that the fluidisation abrasion method records and pile than all listing in the table 1.

Table 1

Numbering	Catalyst	Specific area m ²/g	Pore volume mL/g	Abrasion index %h ^-1	Heap compares g/mL
Numbering	Catalyst	Specific area m ²/g	Pore volume mL/g	Abrasion index %h ^-1	Heap compares g/mL	Embodiment 1	A	306	0.38	1.2	0.66
Comparative Examples 1	DB-1	304	0.38	0.6	0.68	Embodiment 1	A	306	0.38	1.2	0.66
Comparative Examples 1	DB-1	304	0.38	0.6	0.68	Comparative Examples 2	DB-2	311	0.32	0.2	0.74

By the data of table 1 as can be seen, catalyst A provided by the invention is compared with the catalyst DB-1 that does not introduce aluminium oxide, introduce aluminium oxide after, the physico-chemical property of catalyst not have variation substantially; Compare with comparative catalyst DB-2, have bigger pore volume and moderate bulk density with the conventional method preparation.

Embodiment 2

Get 0.63L sulfuric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 95-98), add 8.0kg decationized Y sieve water and dilute, cooling.Get the 7.7Kg sodium silicate (commercially available, contain SiO ₂Concentration 26.0 heavy %, modulus is 3.2), add 8.0Kg decationized Y sieve water and dilute, stir the sodium silicate that will dilute down and slowly add in the above-mentioned sulfuric acid weak solution, obtain SiO ₂Concentration 8.2 heavy %, the Ludox of pH value 2.5.

In above-mentioned Ludox, add 4.1Kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.(Shandong Aluminum Plant produces, and contains Al to add 0.86Kg boehmite fine powder again ₂O ₃Concentration 93.6 heavy %), stir 0.5h.

(the Shandong catalyst plant is produced, and solid content is 93.0 heavy %, RE to add the 2.7KgMOY molecular sieve in 7.0Kg decationized Y sieve water ₂O ₃Content 5.6 heavy %, P ₂O ₅Content 1.8 heavy %), the 1.1KgREHY molecular sieve (produce, and solid content is 95.0 heavy %, RE by the Shandong catalyst plant ₂O ₃The heavy % of content 3.4), 0.5KgREY divides that (the Shandong catalyst plant is produced, and solid content is 94.0 heavy %, RE in sieve ₂O ₃Content 16.5 heavy %), after homogenizer fully disperses, be 3.5 with the watery hydrochloric acid adjust pH.Molecular sieve pulp is joined in above-mentioned Ludox-clay slurry, stirs 0.5h, add again the 0.6Kg re chloride (Baotou rare earth factory in the Inner Mongol produces, based on lanthanum, RE ₂O ₃Content 10.6 heavy %, wherein La ₂O ₃53.2 heavy %, CeO ₂13.0 heavy %, Pr ₆O ₁₁13.0 heavy %, Nd ₂O ₃20.8 weigh %) and 0.22Kg phosphoric acid (Beijing Chemical Plant produces, chemical pure, concentration 85 heavy %), continue to stir 0.5h, obtaining solid content is that 24.1 heavy %, pH value are 3.4 dissolved colloidal state catalyst slurry.

In 100 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 60.2 heavy % with these slurries.

With the micro-spherical catalyst gel at 80 ℃, the pH value is aging 1h in the deionized water of 4.0-6.0, filter, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, again with 60-70 ℃ deionized water washing 10 minutes, and to regulate the pH value with ammoniacal liquor be 8.0-9.0, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.The gained catalyst is numbered B.

Catalyst B consists of 30 heavy % kaolin, 40 heavy % molecular sieves (MOY molecular sieve 25 heavy %, REHY molecular sieve 10 heavy %, REY molecular sieve 5 heavy %), 20 heavy %SiO ₂Binding agent, 8 heavy %Al ₂O ₃Modified component (RE with 2 heavy % ₂O ₃Be 0.65 heavy %, P ₂O ₅Be 1.35 heavy %).

Comparative Examples 3

This Comparative Examples explanation is a binding agent with the Ludox that contains the sodium silicate preparation, handles through sol-gel process, but does not introduce the olefine lowering catalyst of aluminium oxide.

In above-mentioned Ludox, add 5.1Kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.

(the Shandong catalyst plant is produced, and solid content is 93.0 heavy %, RE to add the 2.7KgMOY molecular sieve in 7.0Kg decationized Y sieve water ₂O ₃Content 5.6 heavy %, P ₂O ₅Content 1.8 heavy %), the 1.1KgREHY molecular sieve (produce, and solid content is 95.0 heavy %, RE by the Shandong catalyst plant ₂O ₃Content 3.4 heavy %), the 0.5KgREY molecular sieve (produce, and solid content is 94.0 heavy %, RE by the Shandong catalyst plant ₂O ₃Content 16.5 heavy %), after homogenizer fully disperses, be 3.5 with the watery hydrochloric acid adjust pH.Molecular sieve pulp is joined in above-mentioned Ludox-clay slurry, stirs 0.5h, add again the 0.6Kg re chloride (Baotou rare earth factory in the Inner Mongol produces, based on lanthanum, RE ₂O ₃Content 10.6 heavy %, wherein La ₂O ₃53.2 heavy %, CeO ₂13.0 heavy %, Pr ₆O ₁₁13.0 heavy %, Nd ₂O ₃20.8 weigh %) and 0.22Kg phosphoric acid (Beijing Chemical Plant produces, chemical pure, concentration 85 heavy %), continue to stir 0.5h, obtaining solid content is that 23.9 heavy %, pH value are 3.2 dissolved colloidal state catalyst slurry.

In 100 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 59.7 heavy % with these slurries.

With the micro-spherical catalyst gel at 80 ℃, the pH value is aging 1h in the deionized water of 4.0-6.0, filter, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, again with 60-70 ℃ deionized water washing 10 minutes, and to regulate the pH value with ammoniacal liquor be 8.0-9.0, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.The gained comparative catalyst is numbered DB-3.

Comparative catalyst DB-3 consists of 38 heavy % kaolin, 40 heavy % molecular sieves (MOY molecular sieve 25 heavy %, REHY molecular sieve 10 heavy %, REY molecular sieve 5 heavy %), 20 heavy %SiO ₂Modified component (the RE of binding agent and 2 heavy % ₂O ₃Be 0.65 heavy %, P ₂O ₅Be 1.35 heavy %).

Comparative Examples 4

This Comparative Examples explanation is a binding agent with the Ludox that contains the sodium silicate preparation, does not introduce aluminium oxide, and the olefine lowering catalyst of handling without sol-gel process.

According to Comparative Examples 3 described methods, preparing solid content is that 23.9 heavy %, pH value are 3.2 dissolved colloidal state catalyst slurry.

With these slurries according to a conventional method in 280 ℃ of following spray drying formings of exhaust temperature, the micro-spherical catalyst particle that obtains.

The catalyst of drying and moulding was washed 10 minutes in 60-70 ℃ deionized water, filter, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, use 60-70 ℃ deionized water to wash again 10 minutes, and to regulate the pH value with ammoniacal liquor be 8.0-9.0, after filtration, 120 ℃ of dry 2h, and 650 ℃ of roasting 2h.Obtain the comparative catalyst, be numbered DB-4.

Comparative catalyst DB-4 consists of 38 heavy % kaolin, 40 heavy % molecular sieves (MOY molecular sieve 25 heavy %, REHY molecular sieve 10 heavy %, REY molecular sieve 5 heavy %), 20 heavy %SiO ₂Modified component (the RE of binding agent and 2 heavy % ₂O ₃Be 0.65 heavy %, P ₂O ₅Be 1.35 heavy %).

The BET specific surface that catalyst B, contrast medium DB-3 and DB-4 record with cryogenic nitrogen absorption, the pore volume that the water droplet method records, intensity (abrasion index) that the fluidisation abrasion method records and heap compare all lists in table 2.

Table 2

Example number	Catalyst	Specific area m ²/g	Pore volume mL/g	Abrasion index %h ^-1	Heap compares g/mL
Example number	Catalyst	Specific area m ²/g	Pore volume mL/g	Abrasion index %h ^-1	Heap compares g/mL	Embodiment 2	B	316	0.40	1.5	0.64
Comparative Examples 3	DB-3	308	0.40	1.3	0.63	Embodiment 2	B	316	0.40	1.5	0.64
Comparative Examples 3	DB-3	308	0.40	1.3	0.63	Comparative Examples 4	DB-4	335	0.35	0.8	0.69

By the data of table 2 as can be seen, catalyst B provided by the invention is compared with the comparative catalyst DB-3 that does not introduce aluminium oxide, introduce aluminium oxide in the catalyst after, the physico-chemical property of catalyst not have variation substantially; Compare with comparative catalyst DB-4, have bigger pore volume and moderate bulk density with the conventional method preparation.

Embodiment 3

Get 0.47L sulfuric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 95-98), add 8.0Kg decationized Y sieve water and dilute, the cooling back adds the 1.3Kg aluminum sulfate solution, and (Shandong Aluminum Plant produces, and contains Al ₂O ₃Concentration 7.4 heavy %).Get the 5.8Kg sodium silicate (commercially available, contain SiO ₂Concentration 26.0 heavy %, modulus is 3.2), add 8.0Kg decationized Y sieve water and dilute, stir the sodium silicate that will dilute down and slowly add in above-mentioned sulfuric acid-aluminum sulfate weak solution, obtain SiO ₂Concentration 6.4 heavy %, the Ludox of pH value 2.8.

In above-mentioned Ludox, add 6.6Kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.

Add 2.2KgDASY molecular sieve (the Shandong catalyst plant is produced, and solid content is 92.0 heavy %) in 6.8kg decationized Y sieve water, the 1.8KgZRP-1 molecular sieve (produce, and solid content is 85.0 heavy %, RE by the Shandong catalyst plant ₂O ₃Content 1.7 heavy %, P ₂O ₅Content 4.8 heavy %), after homogenizer fully disperses, be 4.0 with the watery hydrochloric acid adjust pH.Molecular sieve pulp is joined in above-mentioned Ludox-clay slurry, stirs 0.5h, add again the 0.5Kg re chloride (Baotou rare earth factory in the Inner Mongol produces, based on lanthanum, RE ₂O ₃Content 10.6 heavy %, wherein La ₂O ₃53.2 heavy %, CeO ₂13.0 heavy %, Pr ₆O ₁₁13.0 heavy %, Nd ₂O ₃20.8 heavy %), continue to stir 0.5h, obtaining solid content is that 24.1 heavy %, pH value are 3.5 dissolved colloidal state catalyst slurry.

In 120 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 60.4 heavy % with these slurries.

At 90 ℃, the pH value is aging 1h in the deionized water of 4.0-6.0, filters with the micro-spherical catalyst gel, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, use 60-70 ℃ deionized water to wash again 10 minutes, and to regulate pH value with ammoniacal liquor be 8.0-9.0, filtration.

Catalyst gel after the washing is joined 5 times in the deionized water of catalyst butt amount, and (the Shandong catalyst plant is produced, and contains Al to add 0.23Kg aluminium colloidal sol ₂O ₃The heavy % of concentration 22.1), control pH value is 6.0-8.0, kept 10 minutes, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.Gained catalyst numbering C.

Catalyst C consists of 49 heavy % kaolin, 35 heavy % molecular sieves (DASY molecular sieve 20 heavy %, ZRP-1 molecular sieve 15 heavy %), 15 heavy %SiO ₂Binding agent, 0.5 heavy %Al ₂O ₃With with RE ₂O ₃The modified component of meter 0.5 heavy %.

Comparative Examples 5

This Comparative Examples explanation is a binding agent with the Ludox that contains the sodium silicate preparation, handles through sol-gel process, but does not introduce the low-carbon olefines high-output catalyst of aluminium oxide.

In above-mentioned Ludox, add 6.7Kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.

Add 2.2KgDASY molecular sieve (the Shandong catalyst plant is produced, and solid content is 92.0 heavy %) in 6.8Kg decationized Y sieve water, the 1.8KgZRP-1 molecular sieve (produce, and solid content is 85.0 heavy %, RE by the Shandong catalyst plant ₂O ₃Content 1.7 heavy %, P ₂O ₅Content 4.8 heavy %), after homogenizer fully disperses, be 4.0 with the watery hydrochloric acid adjust pH.Molecular sieve pulp is joined in above-mentioned Ludox-clay slurry, stirs 0.5h, add again the 0.5kg re chloride (Baotou rare earth factory in the Inner Mongol produces, based on lanthanum, RE ₂O ₃Content 10.6 heavy %, wherein La ₂O ₃53.2 heavy %, CeO ₂13.0 heavy %, Pr ₆O ₁₁13.0 heavy %, Nd ₂O ₃20.8 heavy %), continue to stir 0.5h, obtaining solid content is that 24.0 heavy %, pH value are 3.5 dissolved colloidal state catalyst slurry.

In 120 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 60.3 heavy % with these slurries.

With the micro-spherical catalyst gel at 90 ℃, the pH value is aging 1h in the deionized water of 4.0-6.0, filter, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, again with 60-70 ℃ deionized water washing 10 minutes, and to regulate the pH value with ammoniacal liquor be 8.0-9.0, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.Obtain comparative catalyst DB-5.

Comparative catalyst DB-5 consists of 49.5 heavy % kaolin, 35 heavy % molecular sieves (DASY molecular sieve 20 heavy %, ZRP-1 molecular sieve 15 heavy %), 15 heavy %SiO2 binding agents and with RE ₂O ₃The modified component of meter 0.5 heavy %.

Comparative Examples 6

This Comparative Examples explanation is a binding agent with the Ludox that contains the sodium silicate preparation, does not introduce aluminium oxide, and the low-carbon olefines high-output catalyst of handling without sol-gel process.

According to Comparative Examples 5 described methods, preparing solid content is that 24.0 heavy %, pH value are 3.5 dissolved colloidal state catalyst slurry.

These slurries according to a conventional method in 300 ℃ of following spray drying formings of exhaust temperature, are obtained the micro-spherical catalyst particle.

The catalyst of drying and moulding was washed 10 minutes in 60-70 ℃ deionized water, filter, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, use 60-70 ℃ deionized water to wash again 10 minutes, and to regulate the pH value with ammoniacal liquor be 8.0-9.0, after filtration, 120 ℃ of dry 2h, and 650 ℃ of roasting 2h.Obtain comparative catalyst DB-6.

Comparative catalyst DB-6 consists of 49.5 heavy % kaolin, 35 heavy % molecular sieves (DASY molecular sieve 20 heavy %, ZRP-1 molecular sieve 15 heavy %), 15 heavy %SiO ₂Binding agent and with RE ₂O ₃The modified component of meter 0.5 heavy %.

The BET specific surface that catalyst C, contrast medium DB-5 and DB-6 record with cryogenic nitrogen absorption, the pore volume that the water droplet method records, intensity (abrasion index) that the fluidisation abrasion method records and heap compare all lists in table 3.

Table 3

Example number	Catalyst	Specific area m ²/g	Pore volume mL/g	Abrasion index %h ^-1	Heap compares g/mL
Example number	Catalyst	Specific area m ²/g	Pore volume mL/g	Abrasion index %h ^-1	Heap compares g/mL	Embodiment 3	C	270	0.41	1.8	0.65
Comparative Examples 5	DB-5	275	0.41	1.8	0.65	Embodiment 3	C	270	0.41	1.8	0.65
Comparative Examples 5	DB-5	275	0.41	1.8	0.65	Comparative Examples 6	DB-6	281	0.37	1.2	0.70

By the data of table 3 as can be seen, catalyst C provided by the invention compares with the comparative catalyst DB-5 that does not introduce aluminium oxide, introduce aluminium oxide in the catalyst after, the physico-chemical property of catalyst not have variation substantially; Compare with comparative catalyst DB-6, have bigger pore volume and moderate bulk density with the conventional method preparation.

Embodiment 4

With 96.8gFeCl ₃6H ₂O is dissolved in the 2.6Kg decationized Y sieve water, adds 2.2KgDASY molecular sieve (the Shandong catalyst plant is produced, and solid content is 92.0 heavy %) and floods, and oven dry is after 550 ℃ of roasting 2h, and obtaining containing the Fe amount is the Fe modification DASY molecular sieve of 1.0 heavy %.

Get 1.4L sulfuric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 95-98), add 8.0Kg decationized Y sieve water and dilute, cooling.Get the 15.4Kg sodium silicate (commercially available, contain SiO ₂Concentration 26.0 heavy %, modulus is 3.2), add 8.5Kg decationized Y sieve water and dilute, stir the sodium silicate that will dilute down and slowly add in the above-mentioned sulfuric acid weak solution, obtain SiO ₂Concentration 11.9 heavy %, the Ludox of pH value 1.5.

In above-mentioned Ludox, add 5.3kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.

In 4.0Kg decationized Y sieve water, add the DASY molecular sieve of above-mentioned Fe modification, after homogenizer fully disperses, join in above-mentioned Ludox-clay slurry, stir 0.5h.Obtaining solid content is that 22.2 heavy %, pH value are 2.8 dissolved colloidal state catalyst slurry.

In 150 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 62.8 heavy % with these slurries.

At 60 ℃, the pH value is aging 1h in 4.0～6.0 the deionized water, filters with the micro-spherical catalyst gel, with 60～70 ℃ ammonium sulfate solution washings 10 minutes, filter, use 60-70 ℃ deionized water to wash again 10 minutes, and to regulate pH value with ammoniacal liquor be 8.0～9.0, filtration.

Catalyst gel after the washing is joined 4 times in the deionized water of catalyst butt amount, add 0.47 kilogram of AlCl ₃6H ₂O dissolving, control pH value is 6.0-8.0, kept 10 minutes, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.The gained catalyst is numbered D.

Catalyst D consists of DASY molecular sieve, the 40 heavy %SiO of 39 heavy % kaolin, 20 heavy %Fe modifications ₂Binding agent and 1 heavy %Al ₂O ₃

Embodiment 5

With 10.4gZnCl ₂And 83.7gMgCl ₂6H ₂O is dissolved in the 1.3kg decationized Y sieve water, (the Shandong catalyst plant is produced to add the 1.1KgDASY molecular sieve, solid content is 92.0 heavy %) to flood, oven dry is after 550 ℃ of roasting 2h, and to obtain containing the Zn amount be 0.5 heavy %, contain the Mg amount is Zn, the Mg modification DASY molecular sieve of 1.0 heavy %.

Get 1.2L sulfuric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 95-98), add 8.0Kg decationized Y sieve water and dilute, cooling.Get the 11.5Kg sodium silicate (commercially available, contain SiO ₂Concentration 26.0 heavy %, modulus is 3.2), add 8.0kg decationized Y sieve water and dilute, stir the sodium silicate that will dilute down and slowly add in the above-mentioned sulfuric acid weak solution, obtain SiO ₂Concentration 10.3 heavy %, the Ludox of pH value 0.8.

In above-mentioned Ludox, add 7.5Kg imvite (southization Red Hill bentonite Co., Ltd produces, and solid content is 78.6 heavy %), stir 1h, kaolin is fully disperseed.

In 2.0Kg decationized Y sieve water, add the DASY molecular sieve of above-mentioned Zn, Mg modification, after homogenizer fully disperses, join in above-mentioned Ludox-clay slurry, stir 0.5h.Obtaining solid content is that 25.2 heavy %, pH value are 2.5 dissolved colloidal state catalyst slurry.

In 80 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 53.6 heavy % with these slurries.

At 70 ℃, the pH value is aging 1h in 4.0～6.0 the deionized water, filters with the micro-spherical catalyst gel, with 60～70 ℃ ammonium sulfate solution washings 10 minutes, filter, use 60-70 ℃ deionized water to wash again 10 minutes, and to regulate pH value with ammoniacal liquor be 8.0～9.0, filtration.

Catalyst gel after the washing is joined 5 times in the deionized water of catalyst butt amount, and (Shandong Aluminum Plant produces, and contains Al to add the 1.35kg aluminum sulfate solution ₂O ₃The heavy % of concentration 7.4), control pH value is 6.0-8.0, kept 10 minutes, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.The gained catalyst is numbered E.

Catalyst E consists of DASY molecular sieve, the 30 heavy %SiO of 59 heavy % imvites, 10 heavy %Zn and Mg modification ₂Binding agent and 1 heavy %Al ₂O ₃

Embodiment 6

(the Shandong catalyst plant is produced to add the 4.3KgDASY molecular sieve in 9.0Kg decationized Y sieve water, solid content is 92.0 heavy %), after homogenizer fully disperses, join in the above-mentioned Ludox, and adding 1.63Kg phosphoric acid (Beijing Chemical Plant produces, chemical pure, concentration 85 heavy %), (Shandong Aluminum Plant produces, and contains Al with 1.1kg boehmite fine powder ₂O ₃Concentration 93.6 heavy %), stir 0.5h.Obtaining solid content is that 20.1 heavy %, pH value are 3.2 dissolved colloidal state catalyst slurry.

In 120 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 54.0 heavy % with these slurries.

With the micro-spherical catalyst gel at 80 ℃, the pH value is aging 1h in 4.0～6.0 the deionized water, filter, with 60～70 ℃ ammonium sulfate solution washings 10 minutes, filter, again with 60-70 ℃ deionized water washing 10 minutes, and to regulate the pH value with ammoniacal liquor be 8.0～9.0, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.The gained catalyst is numbered F.

Catalyst F consists of 40 heavy %DASY molecular sieves, 40 heavy %SiO ₂Binding agent, 10 heavy %Al ₂O ₃With with P ₂O ₅The modified component of meter 10 heavy %.

Embodiment 7

Get 0.31L sulfuric acid (Beijing Chemical Plant produces, chemical pure, the heavy % of concentration 95-98), add 8.0Kg decationized Y sieve water and dilute, cooling.Get the 3.9Kg sodium silicate (commercially available, contain SiO ₂Concentration 26.0 heavy %, modulus is 3.2), add 8.0Kg decationized Y sieve water and dilute, stir the sodium silicate that will dilute down and slowly add in the above-mentioned sulfuric acid weak solution, obtain SiO ₂Concentration 4.9 heavy %, the Ludox of pH value 2.8.

With 1.44Kg Zr (SO ₄) ₂6H ₂O is dissolved in the 8.0Kg decationized Y sieve water, joins in the above-mentioned Ludox, adds 7.2Kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %) again, stirs 1h, and kaolin is fully disperseed.

Adding 3.3KgDASY molecular sieve (the Shandong catalyst plant is produced, and solid content is 92.0 heavy %) in 6.0Kg decationized Y sieve water, after homogenizer fully disperses, is 4.0 with the watery hydrochloric acid adjust pH.Molecular sieve pulp is joined in above-mentioned Ludox-clay slurry, stir 0.5h.Obtaining solid content is that 21.5 heavy %, pH value are 3.2 dissolved colloidal state catalyst slurry.

In 120 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 57.4 heavy % with these slurries.

At 60 ℃, the pH value is aging 1h in the deionized water of 4.0-6.0, filters with the micro-spherical catalyst gel, with 60-70 ℃ ammonium sulfate solution washing 10 minutes, filter, use 60-70 ℃ deionized water to wash again 10 minutes, and to regulate pH value with ammoniacal liquor be 8.0-9.0, filtration.

Catalyst gel after the washing is joined 5 times in the deionized water of catalyst butt amount, and (the Shandong catalyst plant is produced, and contains Al to add 1.1Kg aluminium colloidal sol ₂O ₃The heavy % of concentration 22.1), control pH value is 6.0-8.0, keeps 10 minutes, and after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h obtain catalyst, are numbered G.

Catalyst G consists of 53 heavy % kaolin, 30 heavy %DASY molecular sieves, 10 heavy %SiO ₂Binding agent, 2 heavy %Al ₂O ₃With modified component in ZrO 5 heavy %.

Embodiment 8

With 114.1g SnCl ₂2H ₂O is dissolved in the 3.9kg decationized Y sieve water, adds 3.3KgDASY molecular sieve (the Shandong catalyst plant is produced, and solid content is 92.0 heavy %) and floods, and oven dry is after 550 ℃ of roasting 2h, and obtaining containing the Sn amount is the Sn modification DASY molecular sieve of 2.0 heavy %.

In above-mentioned Ludox, add 6.1Kg halloysite (kaolin company in Suzhou produces, and solid content is 74.0 heavy %), stir 1h, kaolin is fully disperseed.

In 8.0Kg decationized Y sieve water, add the DASY molecular sieve of above-mentioned Sn modification, after homogenizer fully disperses, join in above-mentioned Ludox-clay slurry, stir 0.5h.Obtaining solid content is that 23.6 heavy %, pH value are 3.3 dissolved colloidal state catalyst slurry.

In 100 ℃ of following spray shapings of exhaust temperature, obtaining solid content is the micro-spherical catalyst gel of 58.5 heavy % with these slurries.

At 80 ℃, the pH value is aging 1h in 4.0～6.0 the deionized water, filters with the micro-spherical catalyst gel, with 60～70 ℃ ammonium sulfate solution washings 10 minutes, filter, use 60-70 ℃ deionized water to wash again 10 minutes, and to regulate pH value with ammoniacal liquor be 8.0～9.0, filtration.

Catalyst gel after the washing is joined 3 times in the deionized water of catalyst butt amount, and (the Shandong catalyst plant is produced, and contains Al to add 2.7Kg aluminium colloidal sol ₂O ₃The heavy % of concentration 22.1), control pH value is 6.0-8.0, kept 10 minutes, after filtration, 120 ℃ of dry 2h, 650 ℃ of roasting 2h.The gained catalyst is numbered H.

Catalyst H consists of 45 heavy % kaolin, 30 heavy %Sn modification DASY molecular sieves, 20 heavy %SiO ₂Binding agent and 5 heavy %Al ₂O ₃

Following examples illustrate the application of catalyst provided by the invention in cracking hydrocarbon oil.

Embodiment 9

Under 800 ℃ temperature and 100% water vapour atmosphere, to the aging 4h of catalyst A.On heavy oil microreactor, be that 227-475 ℃ decompressed wax oil (its character is as shown in table 4) carries out catalytic cracking with the catalyst A after aging to boiling range, reaction condition is that reaction temperature is 482 ℃, weight (hourly) space velocity (WHSV) is 16h ^-1, agent weight of oil ratio is 5.The results are shown in Table 5.

In the table 5, conversion ratio=100-diesel yield-heavy oil productive rate.Heavy oil refers to that boiling point is the cut more than 330 ℃, and the boiling range of gasoline is C ₅-204 ℃, the boiling range of diesel oil is 204-330 ℃.

Comparative Examples 7～8

The cracking method of comparative catalyst DB-1 and DB-2 is used in following Comparative Examples explanation.

Press aging comparative catalyst DB-1 of method and the DB-2 of embodiment 9, and same feedstock oil is carried out catalytic cracking with the catalyst after aging.The results are shown in Table 5.

Table 4

Feedstock oil	Decompressed wax oil
Feedstock oil	Decompressed wax oil	Density (20 ℃), gcm ^-3	0.8652
Viscosity, mm ²·S ^-1	14.58	Density (20 ℃), gcm ^-3	0.8652
Viscosity, mm ²·S ^-1	14.58	Asphalitine, heavy %	0.686
Conradson carbon residue, heavy %	0.04	Asphalitine, heavy %	0.686
Conradson carbon residue, heavy %	0.04	Boiling range, ℃ IBP 10% 50% 90% 95% FBP	227 289 389 446 458 475

Table 5

The embodiment numbering	Catalyst	The heavy % of conversion ratio	Product yield, heavy %
			Product yield, heavy %					Gas	Coke	Gasoline	Diesel oil	Heavy oil
			Embodiment 9	A	73.4	13.1	1.3	Gas	Coke	Gasoline	Diesel oil	Heavy oil	59.0	17.0	9.6
Comparative Examples 7	DB-1	71.5	Embodiment 9	A	73.4	13.1	1.3	12.3	1.1	58.1	17.6	10.9	59.0	17.0	9.6
Comparative Examples 7	DB-1	71.5	Comparative Examples 8	DB-2	68.5	10.9	1.1	12.3	1.1	58.1	17.6	10.9	56.5	18.3	13.2

By the data of table 5 as can be seen, compare with the cracking method for hydrocarbon oil that uses the comparative catalyst, cracking method provided by the invention has higher conversion ratio, higher yield of gasoline and stronger heavy oil cracking ability.

Embodiment 10

Under 800 ℃ temperature and 100% water vapour atmosphere, to the aging 4h of catalyst B.On the small fixed flowing bed device, the feedstock oil of decompressed wax oil being mixed 34 heavy % reduced crudes with the catalyst B after aging carries out catalytic cracking (its character is as shown in table 6), the catalyst loading amount is 90g, and appreciation condition is that reaction temperature is 500 ℃, and weight (hourly) space velocity (WHSV) is 20h ^-1, agent weight of oil ratio is 4.The results are shown in Table 7.

Comparative Examples 9～10

Press aging comparative catalyst DB-3 of method and the DB-4 of embodiment 10, and same feedstock oil is carried out catalytic cracking with the catalyst after aging.The results are shown in Table 7.

Table 6

Feedstock oil	Decompressed wax oil is mixed 34 heavy % reduced crudes
Feedstock oil	Decompressed wax oil is mixed 34 heavy % reduced crudes	Density (20 ℃), gcm ^-3	0.9066
Carbon residue, heavy %	3.20	Density (20 ℃), gcm ^-3	0.9066
Carbon residue, heavy %	3.20	Condensation point, ℃	40
Viscosity, mm ²·S ^-1		Condensation point, ℃	40
Viscosity, mm ²·S ^-1		100℃	11.0
80℃	18.83	100℃	11.0
80℃	18.83	Element is formed, heavy %
C	85.7	Element is formed, heavy %
C	85.7	H	12.8
S	0.77	H	12.8
S	0.77	N	0.38
Hydrocarbon system forms, heavy %		N	0.38
Hydrocarbon system forms, heavy %		Saturated hydrocarbons	57.5
Aromatic hydrocarbons	24.5	Saturated hydrocarbons	57.5
Aromatic hydrocarbons	24.5	Colloid	16.9
Asphalitine	1.1	Colloid	16.9
Asphalitine	1.1	Tenor, ppm
Fe	5.3	Tenor, ppm
Fe	5.3	Ni	5.0
Cu	0.04	Ni	5.0
Cu	0.04	V	0.8
Na	1.2	V	0.8
Na	1.2	Vacuum distillation range, ℃
Initial boiling point	-	Vacuum distillation range, ℃
Initial boiling point	-	5％	217
10％	276	5％	217
10％	276	30％	362
50％	414	30％	362
50％	414	70％	456
90％	537	70％	456
90％	537	Characterization factor	12.0

Table 7

Example number	Embodiment 10	Comparative Examples 9	Comparative Examples 10
Example number	Embodiment 10	Comparative Examples 9	Comparative Examples 10	Catalyst	B	DB-3	DB-4
Conversion ratio, heavy %	66.2	64.8	61.5	Catalyst	B	DB-3	DB-4
Conversion ratio, heavy %	66.2	64.8	61.5	Product yield, heavy % casing head gasoling diesel oil heavy oil coke	14.8 48.6 21.3 12.5 2.8	14.4 47.8 21.2 14.0 2.6	13.2 46.1 21.6 16.9 2.2
Olefin(e) centent in the gasoline, %	26.7	28.2	29.5		14.8 48.6 21.3 12.5 2.8	14.4 47.8 21.2 14.0 2.6	13.2 46.1 21.6 16.9 2.2

By the data of table 7 as can be seen, compare with the method for using the comparative catalyst, cracking method provided by the invention has higher conversion ratio and yield of gasoline, olefin(e) centent in stronger heavy oil cracking ability and the lower gasoline fraction.

Embodiment 11

Under 800 ℃ temperature and 100% water vapour atmosphere, to the aging 4h of catalyst C.On heavy oil microreactor, be that 227-475 ℃ decompressed wax oil (its character is as shown in table 4) carries out catalytic cracking with the catalyst C after aging to boiling range, reaction condition is that reaction temperature is 520 ℃, weight (hourly) space velocity (WHSV) is 16h ^-1, agent weight of oil ratio is 4.The results are shown in Table 8.

Comparative Examples 11～12

Press aging comparative catalyst DB-5 of method and the DB-6 of embodiment 11, and same feedstock oil is carried out catalytic cracking with the catalyst after aging.The results are shown in Table 8.

Table 8

Example number	Embodiment 11	Comparative Examples 11	Comparative Examples 12
Example number	Embodiment 11	Comparative Examples 11	Comparative Examples 12	Catalyst	C	DB-5	DB-6
Conversion ratio, heavy %	80.3	78.0	76.4	Catalyst	C	DB-5	DB-6
Conversion ratio, heavy %	80.3	78.0	76.4	Product yield, heavy % casing head gasoling diesel oil heavy oil coke	32.3 46.6 13.8 5.9 1.4	31.6 45.2 14.7 7.3 1.2	30.8 44.4 15.5 8.1 1.2
Olefins yield, % C ₃ ^＝ C ₄ ^＝ C ₅ ^＝ ∑C ₃ ^＝～C ₅ ^＝	10.9 13.8 10.5 35.2	10.9 13.7 10.3 34.9	10.7 13.5 10.2 34.4		32.3 46.6 13.8 5.9 1.4	31.6 45.2 14.7 7.3 1.2	30.8 44.4 15.5 8.1 1.2

By the data of table 8 as can be seen, compare with the method for using the comparative catalyst, cracking method provided by the invention has higher conversion ratio, higher gas and yield of gasoline, good productivity of low carbon olefin hydrocarbon, stronger heavy oil cracking ability.

Embodiment 12～16

Under 800 ℃ temperature and 100% water vapour atmosphere, catalyst D, E, F, G, H were worn out 4 hours.On heavy oil microreactor, be that 227-475 ℃ decompressed wax oil (its character is as shown in table 4) carries out catalytic cracking with catalyst D, E after aging, F, G, H to boiling range respectively, reaction condition is that reaction temperature is 482 ℃, weight (hourly) space velocity (WHSV) is 16h ^-1, agent weight of oil ratio is 5.The results are shown in Table 9.

Table 9

Example number	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16
Example number	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16	Catalyst	D	E	F	G	H
Conversion ratio, heavy %	67.1	63.7	78.8	69.9	71.4	Catalyst	D	E	F	G	H
Conversion ratio, heavy %	67.1	63.7	78.8	69.9	71.4	Product yield, heavy % casing head gasoling diesel oil heavy oil coke	10.2 55.4 17.6 15.3 1.5	9.6 52.8 17.8 18.5 1.3	12.8 64.5 14.7 6.5 1.5	11.0 57.3 16.8 13.3 1.6	11.5 58.5 16.3 12.3 1.4

Claims

1. the preparation method of a hydrocarbon cracking catalyzer is characterized in that this method preparation is by the clay of the molecular sieve of 10～60 heavy %, 0～75 heavy %, with SiO ₂The catalyst that the modified component in oxide of the silicon bonding of meter 5～40 heavy %, the aluminium oxide of 0.1～10 heavy % and 0～10 heavy % is formed comprises the steps:

(1) preparation of silicon bonding: with modulus is that 2.8～3.3 sodium silicate water is mixed with SiO ₂Meter, concentration are the solution of 8.5～20 heavy %, mix with inorganic acid, and the control temperature is 0～30 ℃, obtain endpoint pH and be 0.5～3.5, ultimate density is the Ludox of 3～12 heavy %;

(4) (a) and (b) optional one: (a) molecular sieve pulp, alumina powder, modified component slurries are evenly mixed with Ludox-clay slurry, and the pH value that makes final slurries is 2.5～3.2, the exhaust temperature of control spray shaping is 50～150 ℃, obtain the microspheroidal gel, its water content is 30～60 heavy %, with the microspheroidal gel at 60～90 ℃, the pH value is in 4.0～6.0 the deionized water aging 0.5～1 hour, microspheroidal gel after aging is washed in deionized water or ammonium sulfate solution, filter, get finished product after the drying; (b) molecular sieve pulp, modified component slurries are evenly mixed with Ludox-clay slurry, and the pH value that makes final slurries is 2.5～3.2, the exhaust temperature of control spray shaping is 50～150 ℃, obtain the microspheroidal gel, its water content is 30～60 heavy %, with the microspheroidal gel at 60～90 ℃, the pH value is in 4.0～6.0 the deionized water aging 0.5～1 hour, after microspheroidal gel after aging washed in deionized water or ammonium sulfate solution, in containing aluminum water solution, stir, and control pH value is 4.0～9.0, filters, must finished product after the drying.

2. according to the preparation method of claim 1, it is characterized in that said catalyst is by the clay of the molecular sieve of 10～40 heavy %, 10～50 heavy %, with SiO ₂The aluminium oxide of silicon bonding, 0.1～5 heavy % of meter 10～30 heavy % and form in the modified component of oxide 0～5 heavy %.

3. according to the preparation method of claim 1, said molecular screening is from the molecular sieve of faujasite, β zeolite, MFI structure and in the modenite one or more.

4. according to the preparation method of claim 3, said faujasite is selected from a kind of among HY, REY, REHY, USY, REUSY, DASY and the REDASY or two or more mixture wherein, and the content of rare earth of wherein said REY, REHY, REUSY and REDASY is with RE ₂O ₃Count 0.5～20 heavy %.

5. according to the preparation method of claim 4, said faujasite one or more in being selected from Mg, Ca, Sr, Ba, Sn, P, Sb, Zn, Ti, Zr and Fe are element modified.

6. according to the preparation method of claim 1, said clay is selected from a kind of in kaolin, halloysite, galapectite, imvite and the bentonite or two or more mixture wherein.

7. according to the preparation method of claim 1, in the preparation of said step (1) silicon bonding, inorganic acid is selected from and contains or one or more in sulfuric acid, hydrochloric acid, nitric acid and the phosphoric acid of sulfur acid aluminium cushioning liquid not, and said Ludox endpoint pH is 0.8～3.0.

8. according to the preparation method of claim 1, step (4) (a) in said alumina powder be one or more mixture in boehmite, boehmite, boehmite and the gibbsite powder.

9. according to the preparation method of claim 1, step (4) in (b) the said aluminum water solution that contains be one or more the aqueous solution that contains in aluminium colloidal sol, polymeric aluminum chloride, alchlor and the aluminum sulfate, wherein alumina content is 0.1～2 heavy %.

10. according to the preparation method of claim 1, wherein the exhaust temperature of spray shaping is 80～120 ℃ described in the step (4), and microspheroidal gel water content is 40～50 heavy %.

11. according to the preparation method of claim 1, said modified component is selected from one of periodic table of elements middle rare earth element, IIA, IVA, VA, IIB, IVB, VIB and VIIIB family element or the compound of two or more element wherein.

12. according to the preparation method of claim 11, said rare earth element is selected from one of La, Ce, Pr and Nd or their mixture.

13. preparation method according to claim 11, said II A family element is selected from Mg, Ca, Sr or Ba, said IVA element is Sn, said VA element is selected from P or Sb, said IIB element is Zn, said IVB element is selected from Ti or Zr, and said VIB element is selected from Cr or Mo, and said VIIIB family element is Fe.

14., it is characterized in that said element is RE and/or P according to the preparation method of claim 11.

15. preparation method's gained Cracking catalyst of claim 1 is 450～700 ℃ in temperature, weight (hourly) space velocity (WHSV) is 0.2～20 hour ^-1, the agent weight of oil is than being application under 2～12 cracking reaction conditions.

16. according to the application of claim 15, the feedstock oil of said cracking reaction is selected from decompressed wax oil, reduced crude, hydrogenation tail oil, decompressed wax oil and mixes refining decompression residuum, decompressed wax oil and mix refining reduced crude, decompressed wax oil and mix coking wax oil, decompressed wax oil and mix refining hydrogenation tail oil and decompressed wax oil and mix in the refining deasphalted oil one or more.

17. according to the application of claim 15, it is characterized in that in temperature be 460～680 ℃, weight (hourly) space velocity (WHSV) is 1～10 hour ^-1, agent weight of oil ratio is under 3～10 conditions cracking reaction to take place.