CN1027739C - Hydrocarbon cracking catalyst composition containing vanadium-fixing agent - Google Patents

Abstract

The present invention relates to a hydrocarbon cracking catalyst composition containing vanadium-fixing agent particles, which consists of 95-60% by weight, preferably 90-70% by weight of semi-synthetic or fully synthetic cracking catalyst particles and 5-40% by weight, It is preferably composed of 10 to 30 weight percent vanadium-fixing agent particles, wherein the vanadium-fixing agent consists of 0.1-20 weight percent, preferably 1-10 weight percent (based on the weight of the vanadium-fixing agent) of alkaline earth metal elements and/or Composed of rare earth metal elements and the balance of alumina. The catalyst composition has good vanadium pollution resistance.

Description

The invention relates to a hydrocarbon cracking catalyst composition containing vanadium-fixing agent particles.

In the process of catalytic cracking of hydrocarbons, the organic vanadium compounds and organic nickel compounds in the raw oil will be deposited on the catalyst. When these catalysts are transported to the regeneration section for regeneration, under high temperature and the presence of water vapor, the organic vanadium compounds will be converted into Vanadic acid migrates into the zeolite structure of the catalyst, destroying its skeleton structure, resulting in a decrease in catalyst activity. In order to solve the above problems, it has been reported to add a tin-containing liquid passivator in the raw oil to prevent the organic vanadium compounds in the raw oil from depositing on the catalyst (Oil&Gas J., 1984, 82 (29), 127); USP 4228036 And USP 4222896 is to use Al ₂ O ₃ -AlPO ₄ -SiO ₂ or MgO-Al ₂ O ₃ -AlPO ₄ as the substrate of the catalyst to improve the anti-vanadium ability of the catalyst; Mix with zeolite and carrier to prepare catalyst; USP 4707461 uses kaolin and dolomite as carrier; EP 350280 uses alumina and rare earth oxide as carrier; adopt the above method to passivate the pollution of vanadium to catalyst, but when the catalyst is on When a large amount of vanadium is deposited, its inhibitory effect is limited. In USP 4650564, a method for cracking high metal content raw material oil is proposed, wherein a catalyst composition containing a cracking catalyst and an alumina diluent (the ratio of the two is 50:50 to 90:10) is used. The method can be based on the raw material Compared with the previous methods, diluents for different vanadium content in oil are more flexible in use.

On the basis of the prior art, the purpose of the present invention is to provide a cracking catalyst composition with good performance of suppressing vanadium pollution.

The cracking catalyst composition provided by the present invention consists of 95-60 wt%, preferably 90-70 wt% of semi-synthetic or fully synthetic cracking catalyst particles and 5-40 wt%, preferably 10-30 wt% of solid vanadium The vanadium-fixing agent consists of 0.1-20% by weight, preferably 1-10% by weight (based on the weight of the vanadium-fixing agent) of alkaline earth metal elements and/or rare earth metal elements and the balance of alumina.

Described semi-synthetic or fully synthetic cracking catalyst is existing semi-synthetic or fully synthetic cracking catalyst; Semi-synthetic cracking catalyst can contain zeolite active component, one or more are selected from silicon oxide, aluminum oxide, magnesium oxide, Inorganic oxides in silica-alumina, aluminum phosphate and aluminum silicate, and one or more clays selected from kaolin, halloysite, montmorillonite and sepiolite and/or cross-linked layered Clay: The fully synthetic cracking catalyst may contain zeolite active components, one or more inorganic oxides selected from silica, alumina, magnesia, silica-alumina, aluminum phosphate and aluminum silicate.

Said zeolite is X-type zeolite, Y-type zeolite, L-type zeolite, ZSM zeolite, mordenite, aluminum phosphate zeolite, silicoaluminophosphate zeolite, preferably Y-type zeolite, or the above-mentioned zeolite after physical or chemical treatment , or a mixture of more than one zeolite mentioned above, preferably one or more ion-exchanged zeolites selected from hydrogen, ammonium and/or rare earth ions.

The cracking catalyst composition provided by the present invention can be obtained by the following method: first prepare semi-synthetic or fully synthetic cracking catalyst particles according to the conventional preparation method of semi-synthetic or fully synthetic cracking catalysts, and then according to the conventional impregnation method, load 0.1 ～20% by weight, preferably 1～10% by weight (based on the weight of the vanadium-fixing agent) of alkaline earth metal elements and/or rare earth metal elements, dried at 80～200°C for 2～24 hours, roasted at 300～800°C for 1～ After 10 hours, the vanadium-fixing agent particles are obtained; according to the ratio (weight ratio) of 95-60:5-40, preferably 90-70:10-30, the catalyst particles and the vanadium-fixing agent particles are evenly mixed.

Said impregnation method is preferably a saturated impregnation method. The size and distribution of the alumina particles are matched to the cracking catalyst particles.

The cracking catalyst composition of the invention has good anti-vanadium ability, can maintain high conversion rate and gasoline yield when the vanadium content on the catalyst is high, and the preparation method is simple and the raw materials are easy to obtain. In the presence of high temperature and water vapor, the vanadium-fixing agent in the catalyst composition of the present invention can form a solid metal salt with vanadium, fix vanadium, and reduce its damage to the zeolite structure, so the catalyst composition of the present invention allows High vanadium capacity, suitable for catalytic cracking process of high vanadium feedstock oil, residual oil and heavy oil.

The present invention will be further described below by way of examples.

Example 1

Take 100 grams of γ-Al ₂ O ₃ (prepared from pseudo-boehmite* by roasting at 550°C for 2 hours) and calcium chloride solution (10.64 grams of CaCl ₂ 2H ₂ O dissolved in 45 ml of water) and mix evenly. Dry at 120°C for 4 hours, and bake at 600°C for 1 hour to obtain a vanadium-fixing agent containing 2.07% by weight of calcium and the balance of γ-Al ₂ O ₃ .

According to the ratio (weight ratio) of 80:20, ZCM-7 cracking catalyst (containing rare earth ultra-stable Y-type zeolite, produced by Qilu Petrochemical Company Catalyst Factory) and the above-mentioned vanadium-fixing agent are uniformly mixed to obtain the cracking catalyst combination provided by the present invention object, denoted as A.

＊Produced by Shandong Aluminum Plant.

Example 2-3

Take 100 grams of γ-Al ₂ O ₃ and 16 ml of rare earth chloride solution (Inner Mongolia Baotou Chemical Plant) with a concentration of 275 g/L, mix evenly, dry at 100°C for 6 hours, and roast at 600°C for 1 hour to obtain rare earth-containing 1.24% by weight and balance γ-Al ₂ O ₃ vanadium fixation agent.

According to the ratio (weight ratio) of 80:20, ZCM-7 cracking catalyst and CRC-1 catalyst (semi-synthetic cracking catalyst with rare earth Y-type zeolite as active component, produced by Qilu Petrochemical Company Catalyst Factory) and the above-mentioned solid vanadium Agents are mixed uniformly to obtain the cracking catalyst composition provided by the present invention, respectively marked as B and C.

Example 4-5

Mix 18 grams of rare earth chloride solution (concentration of 275 g/L) and 21 grams of calcium chloride solution (concentration of 33% by weight) evenly, add 50 grams of γ-Al ₂ O ₃ , stir well, and dry at 110°C After 4 hours, roasting at 600°C for 1 hour, the vanadium-fixing agent containing 0.62% by weight of rare earth, 4.86% by weight of calcium and the balance of alumina was obtained.

According to the ratio (weight ratio) of 90:10 and 80:20, ZCM-7 cracking catalyst and the above-mentioned vanadium-fixing agent are uniformly mixed to obtain the cracking catalyst composition provided by the present invention, respectively marked as D and E.

Example 6

Take 2.75 grams of γ-Al ₂ O ₃ and 10 milliliters of magnesium chloride solution with a concentration of 46.0 grams per liter, mix evenly, dry at 120°C for 5 hours, and roast at 550°C for 4 hours to obtain 4.12% by weight of magnesium and the balance of alumina vanadium fixative.

According to the ratio (weight ratio) of 85:15, ZCM-7 cracking catalyst and the above-mentioned vanadium-fixing agent are uniformly mixed to obtain the cracking catalyst composition provided by the present invention, which is marked as F.

Example 7

Take 50 grams of γ-Al ₂ O ₃ and add 32.8 grams of calcium chloride solution with a concentration of 33% by weight, mix evenly, dry at 100°C for 4 hours, and roast at 600°C for 1 hour to obtain 7.84% by weight of calcium and the remaining oxidized Aluminum vanadium fixation agent.

According to the ratio (weight ratio) of 90:10, ZCM-7 cracking catalyst and the above-mentioned vanadium-fixing agent are uniformly mixed to obtain the cracking catalyst composition provided by the present invention, marked as G.

Example 8

Take 50 grams of γ-Al ₂ O ₃ and 23 milliliters of rare earth chloride solution with a concentration of 275 grams per liter, mix evenly, dry at 100°C for 6 hours, and roast at 600°C for 1 hour to obtain 3.59% by weight of rare earth and the balance Vanadium fixation agent for alumina.

According to the ratio (weight ratio) of 90:10, ZCM-7 cracking catalyst and the above-mentioned vanadium fixation agent are uniformly mixed to obtain the cracking catalyst composition provided by the present invention, denoted as H.

Comparative example 1

Using γ-Al ₂ O ₃ as vanadium-fixing agent, ZCM-7 cracking catalyst and vanadium-fixing agent were uniformly mixed at a ratio (weight ratio) of 80:20 to obtain a comparative cracking catalyst composition, which was recorded as Comparison-1.

Example 9

1. Refer to the Mitchell method (Ind.Eng.Chem., Prod.Res.Dev., 19, 209, 1980) to contaminate the catalyst with vanadium: roast the catalyst at 600°C for 1 hour, and use an appropriate amount of vanadium naphthenate solution The catalyst was impregnated, dried at 100°C for 24 hours, and calcined at 600°C for 6 hours to remove all organic matter on the catalyst.

2. Contaminate catalysts A, B and comparison-1 according to the above method, so that the vanadium content is 0.3% by weight (based on the weight of the catalyst); at 800°C and 100% water vapor, the catalyst is aged for 4 hours , The reaction performance of the catalyst was evaluated on a micro-reactor device. The reaction raw material oil was 923 wax oil (specific gravity 0.8652, carbon residue 0.04% by weight, distillation range 227-475°C), and the reaction conditions were: temperature 500°C, solvent-to-oil ratio 5, The weight space velocity is 16 hours ^-1 , and the catalyst is 4 grams. The reaction results are shown in Table 1.

Table 1

Catalyst Contrast-1 A B

Conversion rate, weight % 64.67 68.52 68.95

Material Gas 19.21 18.33 16.88

material

Coke 2.99 2.63 2.62

flat

C ₅ ～204℃ 42.47 47.56 49.46

Balance,

204～303℃ 18.16 17.96 17.50

Heavy

% ＞330℃ 17.17 13.52 13.56

As can be seen from Table 1, under the same vanadium pollution amount, compared with the comparison catalyst, the conversion rate of catalysts A and B is about 4 units higher, the gas yield is slightly lower, and the gasoline yield is higher by 5 to 7 units; The catalyst composition provided by the invention has good anti-vanadium ability.

Example 10

Contaminate and aging catalyst C, D, CRC-1 and ZCM-7 by the method for example 9, evaluate catalyst reaction performance on microreactor device, reaction feed oil is 641 light diesel oil (distillation range is 235～337 ℃), reaction condition The formula is: temperature 460°C, catalyst-oil ratio 3.2, weight space velocity 16 hours ^-1 , reaction time 70 seconds, catalyst loading 5.0 grams. The reaction result is that the micro-reaction activity of catalyst C is 5 units higher than that of the CRC-1 catalyst, and the micro-reaction activity of catalyst D is 7 units higher than that of the ZCM-7 catalyst. It can be seen that the catalyst composition provided by the invention has good anti-vanadium ability.

Example 11

Contaminate catalyst E, F and ZCM-7 by the method for example 9, under 760 ℃, under 100% water vapor condition, catalyst is carried out aging treatment after 4 hours, evaluate catalyst reaction performance on the micro-reactor device, reaction stock oil is 923 Wax oil, the reaction conditions are: temperature 500°C, solvent-to-oil ratio 6, weight space velocity 16 hours ⁻¹ , catalyst 5 grams. The reaction results are shown in Table 2.

Table 2

Catalyst E F ZCM-7

Vanadium content, wt% 0.5 0.5 0.5

Conversion rate, weight % 72.14 72.90 66.24

Gasoline yield, wt% 48.09 49.45 44.49

Hydrogen/Methane 0.38 0.40 0.45

Coke/Conversion 0.048 0.046 0.048

As can be seen from table 2, under the same situation of vanadium pollution amount, compared with the catalyzer not containing vanadium-fixing agent, the conversion ratio and the gasoline yield of catalyst E and F are higher, illustrate that the catalyst composition provided by the invention has good Resistance to vanadium.

Example 12

Contaminate and age catalyst G by the method for example 9, H and ZCM-7, make its vanadium content be 0.24 weight %, evaluate catalyst reactivity on the micro-reactor device, evaluation condition is identical with example 9. The reaction results are shown in Table 3.

table 3

Catalyst G H ZCM-7

Agent to oil ratio 6 6 6

Conversion rate, weight % 75.60 65.80 63.40

Material Gas 20.55 17.40 16.91

material

Coke 2.16 2.24 1.93

flat

C ₅ ～204℃ 52.89 46.16 44.57

Balance,

204～303℃ 15.23 19.80 19.09

Heavy

% ＞330℃ 9.18 14.40 17.50

As can be seen from table 3, under the same situation of vanadium pollution amount, compare with the catalyzer that does not contain vanadium-fixing agent, the conversion rate and the gasoline yield of catalyst G and H are higher, illustrate that the catalyst composition provided by the invention has good Resistance to vanadium.

Example 13

Contaminate catalyst H by the method of example 9, at 760 ℃, normal pressure, aging 4 hours under 100% water vapor, evaluate catalyst reaction performance on the micro-reactor device, evaluation condition is identical with example 9, and reaction result is shown in Table 4.

Table 4

Vanadium content, wt% 0 0.24 0.46 0.78

Agent to oil ratio 3 6 6 6

Conversion rate, weight % 76.28 77.34 73.92 51.24

Material Gas 17.03 21.08 18.14 13.43

material

Coke 2.29 3.60 3.99 3.71

flat

C ₅ ~204°C 56.97 52.65 51.79 34.10

Balance,

204～330℃ 14.10 14.83 16.09 21.85

Heavy

% ＞330℃ 9.62 7.83 9.98 26.91

As can be seen from Table 4, when the vanadium pollution amount is 0.46% by weight, the conversion rate of catalyst H is 73.92% by weight, and the gasoline yield can reach more than 50%. 51.24% by weight, indicating that the catalyst composition provided by the present invention has good anti-vanadium ability.

Claims (6)

1. The hydrocarbon cracking catalyst composition is characterized in that it consists of 95-60% by weight of semi-synthetic or fully synthetic cracking catalyst particles and 5-40% by weight of vanadium-fixing agent particles, wherein the vanadium-fixing agent consists of 0.1-20% by weight (Based on the weight of the vanadium-fixing agent) consisting of alkaline earth metal elements or rare earth metal elements and the balance of alumina, the semi-synthetic cracking catalyst contains zeolite active components, one or more than one selected from silica, alumina , magnesium oxide, silica-alumina, inorganic oxides in aluminum phosphate and aluminum silicate, and one or more clays selected from kaolin, halloysite, montmorillonite and sepiolite and/or Cross-linked layered clay, the fully synthetic cracking catalyst contains zeolite active components, one or more than one selected from silica, alumina, magnesia, silica-alumina, aluminum phosphate or aluminum silicate inorganic oxides, The cracking catalyst composition can be prepared by the following method: first prepare semi-synthetic or fully synthetic cracking catalyst particles according to the conventional preparation method of semi-synthetic or fully synthetic cracking catalysts, and then carry 0.1- 20% by weight (based on the weight of the vanadium-fixing agent) of alkaline-earth metal elements or rare-earth metal elements, dried at 80-200°C for 2-24 hours, and roasted at 300-800°C for 1-10 hours to obtain the vanadium-fixing agent particles; - The ratio (weight ratio) of 60:5-40, the catalyst particles and the vanadium-fixing agent particles are evenly mixed. 2. The composition according to claim 1, characterized in that the content of the cracking catalyst particles is 90-70% by weight, and the content of the vanadium-fixing agent is 10-30% by weight. 3. The composition according to claim 1, characterized in that the vanadium-fixing agent contains 1-10% by weight (based on the weight of the vanadium-fixing agent) of alkaline earth metal elements or rare earth metal elements and the balance of alumina Vanadium-fixing agent particles. 4. The composition according to claim 1, characterized in that said zeolite is X-type zeolite, Y-type zeolite, L-type zeolite, ZSM zeolite, mordenite, aluminum phosphate zeolite, silicoaluminophosphate zeolite. 5. The composition of claim 1, wherein said alkaline earth metal element is calcium or magnesium. 6. The composition of claim 4 wherein said zeolite is a Y zeolite.