CN1730614A

CN1730614A - Catalytic cracking catalyst and its preparation method

Info

Publication number: CN1730614A
Application number: CN 200510017836
Authority: CN
Inventors: 闫鸿飞; 刘金龙; 王文柯; 孟凡东; 陈曼桥; 李玖云; 胡滨
Original assignee: Sinopec Luoyang Petrochemical Engineering Corp; China Petrochemical Corp
Current assignee: Sinopec Luoyang Guangzhou Engineering Co Ltd
Priority date: 2005-08-01
Filing date: 2005-08-01
Publication date: 2006-02-08
Anticipated expiration: 2025-08-01
Also published as: CN1309472C

Abstract

The invention discloses a catalytic cracking catalyst and its preparation method, wherein the catalyst comprises 60-87 wt% of porcelain clay, 10-30 wt% of metal modified type Y molecular sieve, and 3-10 wt% of binding agent, the modifying metal includes one or more of Cu, Fe, Zn, Co, Ti, Ni, Sb, V, Mn and Mo, the content of the modifying metal in the type Y molecular sieve is 4-30%.

Description

A kind of catalytic cracking catalyst and preparation method thereof

Technical field

The invention belongs to the hydrocarbon oil refining field, relate to a kind of catalytic cracking catalyst and preparation method thereof.

Background technology

Enhancing along with environmental consciousness, national environmental protection department is to the increasingly stringent that requires of gasoline product sulphur content, and catalytic gasoline accounts for more than 80% in China's gasoline product, the change that processes raw material along with oil refining enterprise heavily becomes bad, cause the catalytic gasoline sulphur content of its production generally higher, thereby make the problem up to standard of content of sulfur in gasoline face severe situation.

At present, catalytic cracking unit adopts sulfur-lowing catalyst or auxiliary agent to reduce the existing a large amount of patent documentation reports of catalytic gasoline sulphur content.Introduce a kind of catalytic cracking catalyst as CN92108785A, this activity of such catalysts component is the mixture of Y zeolite and ZSM-5 molecular sieve, wherein Y zeolite accounts for 1.0～50.0% (weight) of catalyzer total amount, the ZSM-5 molecular sieve accounts for 0.1～20.0% (weight) of catalyzer total amount, Y zeolite is REY, the REHY of rare earth exchanged, and the USY that handles with physics or chemical process or the USY molecular sieve of rare earth exchanged.The ZSM-5 molecular sieve is HZSM-5 or with other element modified ZSM-5 molecular sieve, for example uses the ZSM-5 molecular sieve of modifications such as P, B, Ca, Mg, Ti, La.This catalyzer can improve gasoline octane rating and liquefied gas yield, but can not reduce content of sulfur in gasoline and olefin(e) centent.In the prior art, also have some technology can reduce content of olefin in gasoline, but cause gasoline octane rating to reduce.Other has some technology is to add the FCC system with the form of solid or liquid adjuvants, reach the purpose that removes sulphur content, its method is by using sulfur-lowing catalyst or auxiliary agent to strengthen hydrogen transfer reactions, making the saturated and then cracking of thiophene-type sulfide in the gasoline is that hydrogen sulfide removes, adopt this method easy flexibly, but it is often limited to fall the sulphur amplitude, and desulfurization degree is usually between 15%～30%.

Grace Davison company adopts ZnO/Al ₂O ₃Be main active component, successively produced GSR-1 and GSR-2 two generations sulfur prodegradant, add 10% GSR-2 auxiliary agent, can make the sulphur content of catalytically cracked gasoline reduce by 20%～30%; Engelhard company has released a kind of NaphthaMax-LSG sulfur-lowing catalyst, and its design concept is: improve catalyst activity, increase gasoline yield and transformation efficiency; Improve catalyzer hydrogen transfer reactions ability, promote that sulfide in petrol transforms to sulphur.Content of sulfur in gasoline reduction amplitude reaches 30% (" oil Refining Technologies and engineering " 2004 the 6th phase 1～4 page).

Summary of the invention

The present invention be directed in the prior art sulfur content of catalytic cracking gasoline and olefin(e) centent, to reduce amplitude lower, and a kind of catalytic cracking catalyst is provided.Use this catalyzer can obviously reduce the sulphur content and the olefin(e) centent of catalytically cracked gasoline.

The present invention also provides described Preparation of catalysts method in addition.

Catalytic cracking catalyst among the present invention is made up of the kaolin of 60～87 weight %, the metal-modified Y zeolite of 10～30 weight % and the binding agent of 3～10 weight %, all in total catalyst weight.Wherein kaolin is commercial kaolin; Metal-modified Y zeolite is to be formed through metal-modified by Y zeolite, wherein Y zeolite is a kind of in rare earth Y type molecular sieve (ReY), rare earth hydrogen Y zeolite (ReHY) and the rare earth superstable Y-type molecular sieve (ReUSY), described modified metal is one or more in copper, iron, zinc, cobalt, titanium, nickel, antimony, vanadium, manganese and the molybdenum, modified metal content is 4～30% in the Y zeolite, in shared weight percentage in the Y zeolite of modified metal-oxide after modification.Binding agent is various binding agents commonly used, for example silicon sol or a silicon-aluminum sol etc. in this area.

The preparation method of catalytic cracking catalyst of the present invention may further comprise the steps:

1) Y zeolite modification: nitrate, vitriol, acetate or the carbonate of modified metal are dissolved in the deionized water, utilize this solution impregnation on molecular sieve, under 80～280 ℃, dry, drying time is 30 minutes～240 minutes, carrying out roasting under 200～800 ℃ of conditions decomposes the modified metal salt, roasting time is 90 minutes～240 minutes, finally obtains metal modified molecular screen;

2) preparation catalyzer: kaolin, metal-modified Y zeolite and binding agent are mixed, make the microspheric catalytic cracking catalyst through adding steps such as water making beating, spraying drying, roasting.

Catalyzer of the present invention is used for the double lift pipe catalytic cracking device, and at the gasoline rising pipe reactor bottom bed reactor is set, making the gasoline rising pipe reactor is 300～600 ℃ in temperature of reaction, is preferably 400～550 ℃; Agent-oil ratio (weight ratio of catalyzer and stock oil) is 2～17, is preferably 4～12; The absolute pressure of reaction is 0.15～0.4Mpa, is preferably 0.2～0.35Mpa; Reaction times is 0.7～4.8 second, is preferably under 1.5～3.5 seconds the reaction conditions, and catalytically cracked gasoline is carried out upgrading, can make its sulphur content reduce by 50～70 weight %; And the reactions such as cracking, hydrogen transference, isomerization and aromizing by gasoline olefin in the gasoline rising pipe reactor, can make content of olefin in gasoline reduce by 20～40 volume percentage points, gasoline octane rating (RON) improves 0.3～2.0 unit, and the full device product distributes good.

Embodiment

Below describe the present invention in detail with embodiment, but embodiment does not limit the scope of application of the present invention.

Embodiment 1

117 gram zinc nitrates and 118 gram cupric nitrates are dissolved in the deionized water, then this solution evenly be impregnated on 600 grams rare earth superstable Y-type molecular sieves (productions of Chang Ling catalyst plant) and stir, toasted 2 hours down at 200 ℃ after putting into baking oven, put into the muffle furnace roasting after the taking-up, 600 ℃ of following roastings 3 hours, make the molecular sieve of metal oxide modified, gross weight is 700 grams, and wherein modified metal-oxide content is 14.3%.

Will 4200 add water after gram kaolin (productions of Suzhou China Kaolin Co., Ltd), 200 gram self-control silica sols (concentration is 25w%) and the mixing of above-mentioned made 700 mol sieve and pull an oar, conventional catalytic cracking catalyst step of preparation process such as spray-dried, roasting are made the good microspheric catalytic cracking catalyst of physical properties.This catalyzer physical properties sees Table 1.

The Main physical character of the catalytic cracking catalyst among table 1 embodiment 1

User mode		Regenerated catalyst
User mode		Regenerated catalyst	Apparent property	Carbon content/weight %	0.02
Micro-activity	63			Carbon content/weight %	0.02
Micro-activity	63	Physical properties		Specific surface area/m ²·g ^-1	124.36
Pore volume/mlg ^-1	0.19			Specific surface area/m ²·g ^-1	124.36
Pore volume/mlg ^-1	0.19		Abrasion index	1.35
Tap density/g (ml) ^-1	0.84		Abrasion index	1.35
Tap density/g (ml) ^-1	0.84		Size composition/weight %	＜20μm	2.85
20～40μm	8.88			＜20μm	2.85
20～40μm	8.88	40～80μm		52.36
80～110μm	22.71	40～80μm		52.36
80～110μm	22.71	＞110μm		13.20

Embodiment 2

Press embodiment 1, different is that metal-modified used molecular sieve is a rare earth Y type molecular sieve.

Embodiment 3

366 gram Xiao Suangus are dissolved in the deionized water, then this solution evenly be impregnated on 700 grams rare earth superstable Y-type molecular sieves (productions of Chang Ling catalyst plant) and stir, toasted 3 hours down at 180 ℃ after putting into baking oven, put into the muffle furnace roasting after the taking-up, 620 ℃ of following roastings 3 hours, make the molecular sieve of cobalt oxide modification, gross weight is 850 grams, and cobalt oxide content is 17.6%. in the molecular sieve

With adding the water making beating after 3900 gram kaolin (production of Suzhou China Kaolin Co., Ltd), 250 gram self-control silica sols and the mixing of above-mentioned made 850 mol sieve, in spray-dryer, be spray dried to the good microspheric catalytic cracking catalyst of physical properties.Conventional catalytic cracking catalyst step of preparation process such as spray-dried, roasting are made the good microspheric catalytic cracking catalyst of physical properties.

Embodiment 4

Press embodiment 3, different is that metal-modified used molecular sieve is a rare earth HY type molecular sieve.

Embodiment 5

113 gram iron nitrates and 292 gram zinc nitrates are dissolved in the deionized water, then this solution evenly be impregnated on 800 grams rare earth Y type molecular sieves (productions of Chang Ling catalyst plant) and stir, toasted 2.5 hours down at 220 ℃ after putting into baking oven, put into the muffle furnace roasting after the taking-up, 650 ℃ of following roastings 3 hours, make the molecular sieve of metal oxide modified, gross weight is 1000 grams, and metal oxide content is 20.0% in the molecular sieve.

With adding the water making beating after 3750 gram kaolin (production of Suzhou China Kaolin Co., Ltd), 250 gram self-control alumina sols and the mixing of above-mentioned made 1000 mol sieve, in spray-dryer, be spray dried to the good microspheric catalytic cracking catalyst of physical properties.Conventional catalytic cracking catalyst step of preparation process such as spray-dried, roasting are made the good microspheric catalytic cracking catalyst of physical properties.

Embodiment 6

Press embodiment 5, different is that metal-modified used molecular sieve is a rare earth superstable Y-type molecular sieve.

Embodiment 7

On the double lift pipe catalytic cracking testing apparatus, test defeated heavy oil (sulphur content is 0.78 weight %), treatment capacity 30 kg/day of mixing of heavy oil riser tube processing tube; The gasoline rising pipe charging oil that oil riser steams (sulphur content is 0.097 weight %) of attaching most importance to, treatment capacity 15 kg/day, the bottom of gasoline rising pipe reactor is provided with a bed reactor.Catalyst system therefor is embodiment 1 catalyzer, and the main character of operational condition and gasoline is listed in table 2.

Wherein the comparative example processes the quality of gasoline situation of the defeated raw material of same pipe for conventional catalytic cracking unit.This device is provided with a heavy oil riser reactor, and treatment capacity is 30kg/d.The CC-20D industry poiser that catalyzer is produced for the Chang Ling catalyst plant.

Embodiment 8

Press embodiment 7, different is that catalyzer is embodiment 2 catalyzer, and operational condition and gasoline main character are listed in table 2.

Embodiment 9

Press embodiment 7, different is that catalyzer is embodiment 3 catalyzer, and operational condition and gasoline main character are listed in table 2.

Embodiment 10

Press embodiment 7, different is that catalyzer is embodiment 4 catalyzer, and operational condition and gasoline main character are listed in table 2.

Embodiment 11

Press embodiment 7, different is that catalyzer is embodiment 5 catalyzer, and operational condition and gasoline main character are listed in table 2.

Embodiment 12

Press embodiment 7, different is that catalyzer is embodiment 6 catalyzer, and operational condition and gasoline main character are listed in table 2.

Defeated operational condition and the gasoline main character of mixing heavy oil of table 2 processing tube

Embodiment	Contrast	7	8	9	10	11	12
Embodiment	Contrast	7	8	9	10	11	12	Heavy oil riser reactor temperature of reaction/℃	510	510	510	510	510	510	510
Heavy oil riser reactor agent-oil ratio	6.8	6.8	6.8	6.8	6.8	6.8	6.8	Heavy oil riser reactor temperature of reaction/℃	510	510	510	510	510	510	510
Heavy oil riser reactor agent-oil ratio	6.8	6.8	6.8	6.8	6.8	6.8	6.8	Heavy oil riser reactor reaction times/s	2.9	2.9	2.9	2.9	2.9	2.9	2.9
Heavy oil riser reactor reaction pressure (absolute pressure)/MPa	0.28	0.28	0.28	0.28	0.28	0.28	0.28	Heavy oil riser reactor reaction times/s	2.9	2.9	2.9	2.9	2.9	2.9	2.9
	0.28	0.28	0.28	0.28	0.28	0.28	0.28	Catalyst regeneration temperature/℃	700	700	700	700	700	700	700
Gasoline rising pipe reactor reaction temperature/℃	-	450	450	450	450	450	450	Catalyst regeneration temperature/℃	700	700	700	700	700	700	700
Gasoline rising pipe reactor reaction temperature/℃	-	450	450	450	450	450	450	Gasoline rising pipe reactor agent-oil ratio	-	5.1	5.1	5.1	5.1	5.1	5.1
Gasoline rising pipe reactor reaction time/s	-	2.2	2.2	2.2	2.2	2.2	2.2	Gasoline rising pipe reactor agent-oil ratio	-	5.1	5.1	5.1	5.1	5.1	5.1
Gasoline rising pipe reactor reaction time/s	-	2.2	2.2	2.2	2.2	2.2	2.2	Gasoline rising pipe reactor reaction pressure (absolute pressure)/MPa	-	0.28	0.28	0.28	0.28	0.28	0.28
The gasoline main character									-	0.28	0.28	0.28	0.28	0.28	0.28
The gasoline main character								Sulphur content/μ g.g ^-1	985	385	368	362	355	340	350
Octane value (RON)	92.7	93.3	93.0	93.4	93.2	92.9	93.5	Sulphur content/μ g.g ^-1	985	385	368	362	355	340	350
Octane value (RON)	92.7	93.3	93.0	93.4	93.2	92.9	93.5	Olefin(e) centent/v%	45.6	17.5	16.6	17.3	17.0	17.0	18.0
Sulphur content reduction/w% ^{[annotating 1]}	-	60.9	62.6	63.2	64.0	65.5	64.5	Olefin(e) centent/v%	45.6	17.5	16.6	17.3	17.0	17.0	18.0
Sulphur content reduction/w% ^{[annotating 1]}	-	60.9	62.6	63.2	64.0	65.5	64.5	Octane value increases ^{[annotating 2]}	-	0.6	0.3	0.7	0.5	0.2	0.8
Olefin(e) centent reduces percentage point/v% ^{[annotating 3]}	-	28.1	29.0	28.3	28.5	28.5	27.6	Octane value increases ^{[annotating 2]}	-	0.6	0.3	0.7	0.5	0.2	0.8

Table 2[annotates 1]: with respect to the comparative example, reduce percentage ratio.

Table 2[annotates 2]: with respect to the comparative example, absolute increased value.

Table 2[annotates 3]: with respect to the comparative example, the volume percentage of reduction is counted.

Claims

1. catalytic cracking catalyst, it is characterized in that: this catalyzer is in total catalyst weight, kaolin by 60～87 weight %, the binding agent of the metal-modified Y zeolite of 10～30 weight % and 3～10 weight % is formed, described metal-modified Y zeolite is to be formed through metal-modified by Y zeolite, used modified metal is a copper, iron, zinc, cobalt, titanium, nickel, antimony, vanadium, in manganese and the molybdenum one or more, modified metal content is 4～30% in the Y zeolite, in shared weight percentage in the Y zeolite of modified metal-oxide after modification.

2. method for preparing the described catalyzer of claim 1 is characterized in that: may further comprise the steps:

1) Y zeolite modification: nitrate, vitriol, acetate or the carbonate of modified metal are dissolved in the deionized water, utilize this solution impregnation on molecular sieve, under 80～280 ℃, dry, drying time is 30 minutes～240 minutes, under 200～800 ℃ of conditions, carry out roasting then, roasting time is 90 minutes～240 minutes, obtains metal modified molecular screen;

2) preparation catalyzer: kaolin, the metal-modified Y zeolite of step 1) gained and binding agent are mixed by the described proportioning of claim 1, make catalytic cracking catalyst through adding water making beating, spraying drying, roasting.