CN112973786A

CN112973786A - Reactivation method of high-vanadium low-rare earth catalytic cracking balancing agent

Info

Publication number: CN112973786A
Application number: CN202110171571.1A
Authority: CN
Inventors: 施宗波; 卓润生; 刘新生; 张青; 钟嘉兴; 胡泽松
Original assignee: Runhe Catalytic Materials Zhejiang Co Ltd
Current assignee: Runhe Catalytic Materials Zhejiang Co Ltd
Priority date: 2021-02-08
Filing date: 2021-02-08
Publication date: 2021-06-18

Abstract

The invention discloses a reactivation method of a high-vanadium low-rare earth catalytic cracking balancing agent, which can improve the catalytic activity of the balancing agent, reduce the yield of low-added-value products (coke, dry gas and slurry oil) in a cracked product, improve the yield of high-added-value products (gasoline, diesel oil and liquefied gas) in the cracked product and obviously improve the total liquid yield after the balancing agent to be reactivated is respectively dipped in a rare earth metal precursor solution and a IIA metal hydroxide solution or emulsion for treatment; the waste catalyst can be recycled after being compounded, so that the waste is changed into valuable, the waste catalyst emission is reduced, the economic benefit of the catalyst is improved, and the method is worthy of popularization.

Description

Reactivation method of high-vanadium low-rare earth catalytic cracking balancing agent

Technical Field

The invention belongs to the technical field of catalytic cracking, and particularly relates to a reactivation method of a high-vanadium low-rare earth catalytic cracking balancing agent.

Background

In catalytic cracking processes, it is often necessary to incorporate some of the balancing agents in the new catalyst in order to prevent the new catalyst from being too active, balancing the reactivity.

The balancing agent is actually a spent catalyst used in catalytic cracking, and with the heavy and inferior crude oil used in domestic refineries, the vanadium and nickel contents in the balancing agent are high, which directly results in that the vanadium and nickel contents in the balancing agent are also very high, so that the balancing agent needs to be changed continuously in the using process.

A large amount of balancing agent waste materials are generated in domestic refineries every year, and the balancing agent is mainly treated by burying the balancing agent on the ground or separating heavy metals in the balancing agent through strong acid and ultrahigh temperature, and taking a silicon-rich component obtained after separation as a raw material to prepare other materials. No matter which way is adopted, more waste agents are discharged, and environmental pollution is caused.

In order to better process the balancing agent and increase the utilization value of the balancing agent as much as possible, patent CN106622398A discloses a modification method of catalytic cracking balancing agent, which achieves the purpose of improving the activity of the catalyst by acid treatment and IB, IB and rare earth treatment of the balancing agent. Although the method can improve the activity of the catalyst, the coke selectivity of the catalyst is not improved.

In addition, when the content of heavy metals such as vanadium and nickel in the balancing agent is higher, the improvement effect of the existing reviving method is more limited, and the activity is not obviously improved. Therefore, the prior method for reactivating and modifying the balancing agent needs to be further researched and improved.

Disclosure of Invention

The invention mainly solves the technical problem of providing a reactivation method of a high-vanadium low-rare earth catalytic cracking balancing agent, and the reactivated balancing agent can reduce coke generation and improve total liquid yield.

The invention provides a reactivation method of a catalytic cracking balancing agent, which comprises the step of respectively dipping a balancing agent to be reactivated into a rare earth metal precursor solution and a IIA metal hydroxide solution or emulsion.

According to the method, the Y-type molecular sieve in the catalytic cracking balancing agent is modified by using rare earth, so that the Na content in the catalyst is reduced, the rare earth content in the molecular sieve is increased, and the catalytic active sites of the molecular sieve are improved; the treated balancing agent is modified by using the IIA metal hydroxide, the IIA metal hydroxide has a passivation effect on V and Ni in the catalyst, and the dehydrogenation and deep cracking activity of the catalyst is reduced; the two modes are utilized to modify the balancing agent, and the balancing agent can play a synergistic role, so that the total liquid yield can be obviously improved, and the yield of coke, dry gas and oil slurry can be reduced.

The test data of the invention show that the method for reactivating the balancing agent has obvious improvement effect on the activity and selectivity of the balancing agent with higher heavy metal content, and overcomes the defect that the improvement effect of the balancing agent with high heavy metal content in the prior art is not obvious.

The 'respectively' only means that the balancing agent to be reactivated needs to be respectively impregnated by two systems of rare earth metal precursor solution and IIA metal hydroxide solution or emulsion, and the sequence and the times of impregnation are not limited. Namely, the balancing agent to be reactivated can be obtained by firstly dipping a rare earth metal precursor solution and then dipping a IIA metal hydroxide solution or emulsion; or dipping IIA metal hydroxide solution or emulsion firstly and then dipping rare earth metal precursor solution; or dipping IIA metal hydroxide solution or emulsion, then dipping rare earth metal precursor solution, and then dipping rare earth metal precursor solution once, and the like.

According to the common general knowledge and the common technical knowledge in the field, it should be understood that the method of the present invention is not limited to only the impregnation step, and for the method of the present invention, a person skilled in the art can perform post-treatment on the impregnated sample by using post-treatment methods (such as drying, roasting, etc.) conventional in the art to obtain the balancing agent product which can be put into production use, but it is within the protection scope of the present invention as long as the balancing agent (waste catalyst) to be reactivated is treated by impregnation with the rare earth metal precursor solution and the IIA metal hydroxide solution or emulsion.

The term "impregnation" refers to a treatment of soaking a solid powder or a shaped solid (carrier or bulk-containing catalyst) of a certain shape and size in a solution of a soluble compound containing an active component, including equal-volume impregnation and non-equal-volume impregnation:

the equal-volume impregnation refers to an impregnation mode that the solution is used for just filling all pores of the impregnated object; as known to those skilled in the art, when the method of equal volume impregnation is used, since the components in the solution are not lost, the impregnation can be directly followed by post-treatment operations such as drying.

The non-isometric impregnation refers to an impregnation mode except for the isometric impregnation; in some embodiments of the present invention, when the amount of the solution used is large (the volume of the solution is significantly larger than the volume of the balancing agent to be reactivated), the impregnation mode is non-isovolumetric impregnation, and when the impregnation is performed by this method, it is necessary to perform impregnation for a period of time to allow ions in the solution to undergo ion exchange with the balancing agent, and after filtration, the post-treatment operations such as drying are performed.

By "rejuvenation" is meant an increase in the catalytic activity of the less active balancing agent (catalyst), as opposed to "deactivation" of the catalyst.

The rare earth metal precursor refers to a substance capable of ionizing rare earth metal cations in a solution.

In the present invention, the solvent is water unless otherwise specified, either the "solution" or the "emulsion".

The "IIA metal hydroxide solution or emulsion" is due to the fact that IIA metal hydroxides such as magnesium hydroxide and calcium hydroxide have low solubility in water, when the amount of IIA metal hydroxide added to water is small, the IIA metal hydroxide solution is formed, and when the amount of IIA metal hydroxide added to water exceeds the solubility, the IIA metal hydroxide emulsion is formed.

Further, the rare earth metal precursor is selected from rare earth metal soluble salt and/or rare earth metal hydroxide.

In a particular embodiment of the invention, the rare earth precursor is a rare earth chloride and/or a rare earth hydroxide.

In one embodiment of the present invention, the rare earth metal precursor is a rare earth metal hydroxide.

Further, the rare earth oxide contained in the rare earth precursor solution is: the mass ratio of the balancing agent to be reactivated is 0.3-2.0: 100, preferably 0.5 to 1.5: 100, preferably 0.6-1.2: 100, more preferably 1.2: 100.

further, the concentration of the rare earth metal precursor solution: the amount of the rare earth oxide is 0.1g to 5g, preferably 0.12g to 2.4g, more preferably 0.24g to 2.4g, and still more preferably 0.24g to 100g of the rare earth oxide per 100g of the solution, in terms of the rare earth oxide per 100g of the solution to 100g of the solution.

In the art, the rare earth metal elements include: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc).

In the invention, the rare earth metal is selected from one or more of yttrium, lanthanum and cerium.

In a particular embodiment of the invention, the rare earth metal is selected from lanthanum and/or yttrium.

In one embodiment of the invention, the rare earth metal is lanthanum.

Further, the ratio of IIA metal oxide contained in the IIA metal hydroxide solution or emulsion, calculated as IIA metal oxide: the mass ratio of the balancing agent to be reactivated is 0.5-5.0: 100, preferably 0.5-2: 100, preferably 0.8-1.2: 100, more preferably 1.0: 100.

further, the concentration of the IIA metal hydroxide solution or emulsion: calculated by IIA metal oxide, the content of the metal oxide is 0.1g of IIA metal oxide/100 g of solution to 1g of IIA metal oxide/100 g of solution or emulsion, preferably 0.1g of IIA metal oxide/100 g of solution or emulsion to 0.5g of IIA metal oxide/100 g of solution or emulsion, and more preferably 0.2g of IIA metal oxide/100 g of solution or emulsion.

In a particular embodiment of the invention, the IIA metal is selected from magnesium and/or calcium.

In one embodiment of the invention, the IIA metal is magnesium.

Further, drying the balancing agent after each impregnation; further, the temperature of the drying treatment is 100 to 200 ℃, preferably 100 to 150 ℃, and more preferably 120 ℃.

It is to be understood that each drying treatment is independently selected from the process conditions described above.

Further, when the impregnation is non-equal volume impregnation, the time for each impregnation is independently selected from 1h or more, preferably 1h to 10h, preferably 1h to 5h, and more preferably 2 h.

In order to further increase the catalytic activity of the balancing agent, the latter should be subjected to a calcination treatment at least after any one impregnation.

Further, the balancing agent is subjected to a roasting treatment at least after the last impregnation.

For optimum results, the balancing agent may be calcined after each impregnation.

The equilibrium agent can be roasted after each impregnation, the total liquid yield of the cracked product can be further improved, and the roasting process can promote and stabilize the beneficial modification of the rare earth or IIA metal hydroxide on the equilibrium agent.

Further, the roasting treatment temperature is 600-900 ℃, preferably 650-800 ℃.

In a specific embodiment of the present invention, the baking treatment temperature is 700 ℃.

Further, the roasting treatment time is 1-5 hours, and preferably 1.5-3 hours.

In a specific embodiment of the present invention, the calcination treatment time is 2 hours.

When the number of firing times is greater than 1, it is understood that each firing treatment is independently selected from the process conditions described above.

The invention has the beneficial effects that:

(1) the method of the invention uses rare earth and IIA metal hydroxide to modify the balancing agent, can reactivate the balancing agent, reduce Na content in the catalyst, passivate V and Ni in the catalyst to improve the activity of the catalyst, reduce the yield of low value-added products (coke, dry gas and slurry oil) in the cracked products, improve the yield of high value-added products (gasoline, diesel oil and liquefied gas) in the cracked products, and obviously improve the total liquid yield.

(2) The method can recycle the waste catalyst after compounding, changes waste into valuable, reduces the emission of the waste catalyst, improves the economic benefit of the catalyst, and is worthy of popularization.

Detailed Description

The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the specific implementation mode of the invention, the BET low-temperature nitrogen adsorption method is used for measuring the specific surface area of a sample, the X-ray fluorescence spectrometer is used for measuring the element composition of the sample, and the wear index analyzer is used for measuring the wear index of the sample.

Physicochemical information of the balancing agent to be reactivated used in the specific embodiment of the present invention is shown in table 1.

TABLE 1 physical and chemical information of Rebate

Comparative example 1

The FCC balancer was reactivated without any treatment and the cracking performance was as shown in Table 3.

Comparative example 2

50 g of lanthanum chloride solution (1.2 g of La) were added by an equal volume impregnation method₂O₃Per 100g of solution) to 100Drying the gram of spent regenerant in the equilibrium agent at 120 ℃, and roasting the product for 2 hours at 700 ℃ to obtain the comparative reactivated FCC equilibrium agent Tr-FCC-2.

The cracking performance of Tr-FCC-2 is shown in Table 3. Na of Tr-FCC-2₂The O content was 0.37 wt%.

Comparative example 3

50 g of lanthanum chloride solution (2.4 g of La) were added by an equal volume impregnation method₂O₃Solution/100 g) was dipped into 100g of the equilibrium agent to be reactivated, dried at 120 c and calcined at 700 c for 2 hours to obtain the comparative reactivated FCC equilibrium agent Tr-FCC-3.

The cracking performance of Tr-FCC-3 is shown in Table 3. Na of Tr-FCC-3₂The O content was 0.36 wt%.

Comparative example 4

500 g of lanthanum chloride solution (0.24 g of La) was added₂O₃Solution/100 g) and 100g of the balance agent to be reactivated are mixed, exchanged for 2 hours at room temperature, filtered, washed, dried at 120 ℃, roasted for 2 hours at 700 ℃ to obtain the comparative reactivated FCC balance agent Tr-FCC-4.

The cracking performance of Tr-FCC-4 is shown in Table 3. Na of Tr-FCC-4₂The O content was 0.23 wt%.

Comparative example 5

500 g of magnesium hydroxide emulsion (0.2 g of MgO/100 g of emulsion) and 100g of balance agent to be reactivated are mixed, exchanged for 2 hours at room temperature, filtered, washed, dried at 120 ℃, and calcined for 2 hours at 700 ℃ to obtain the comparative reactivated FCC balance agent Tr-FCC-5.

The cracking performance of Tr-FCC-5 is shown in Table 3. Na of Tr-FCC-5₂The O content was 0.22 wt%.

Example 1

50 g of lanthanum chloride solution (2.4 g of La) were added by an equal volume impregnation method₂O₃/100g solution) into 100g of a to-be-reactivated equilibration agent, dried at 120 ℃ and calcined at 700 ℃ for 2 hours to give sample a.

500 grams of magnesium hydroxide emulsion (0.2 grams of MgO per 100 grams of emulsion) was mixed with 100 grams of sample A, exchanged at room temperature for 2 hours, filtered, washed, dried at 120 ℃ and calcined at 700 ℃ for 2 hours to yield the comparative reactivated FCC balancer Rec-FCC-1.

The cracking performance of Rec-FCC-1 is shown in Table 3. Na of Rec-FCC-1₂The O content was 0.21 wt%.

Example 2

50 g of lanthanum chloride solution (2.4 g of La) were added by an equal volume impregnation method₂O₃/100 grams of solution) into 100 grams of the equilibration agent to be reactivated and dried at 120 c to provide sample B.

500 grams of magnesium hydroxide emulsion (0.2 grams of MgO per 100 grams of emulsion) was mixed with 100 grams of sample B, exchanged at room temperature for 2 hours, filtered, washed, dried at 120 ℃ and calcined at 700 ℃ for 2 hours to yield the comparative reactivated FCC balancer Rec-FCC-2.

The cracking performance of Rec-FCC-2 is shown in Table 3. Na of Rec-FCC-2₂The O content was 0.20 wt%.

Example 3

500 g of magnesium hydroxide emulsion (0.2 g of MgO per 100g of emulsion) was mixed with 100g of a spent equilibrating agent, exchanged at room temperature for 2 hours, filtered, washed, dried at 120 ℃ and calcined at 700 ℃ for 2 hours to obtain sample C.

50 g of lanthanum chloride solution (2.4 g of La) were added by an equal volume impregnation method₂O₃/100g solution) was dipped into 100g of sample C, dried at 120℃ and calcined at 700℃ for 2 hours to give the comparative reactivated FCC equilibria Rec-FCC-3.

The cracking performance of Rec-FCC-3 is shown in Table 3. Na of Rec-FCC-3₂The O content was 0.21 wt%.

Example 4

500 grams of magnesium hydroxide emulsion (0.2 grams of MgO per 100 grams of emulsion) was mixed with 100 grams of the rebalance agent to be reactivated, exchanged at room temperature for 2 hours, filtered, washed and dried at 120 ℃ to give sample D.

50 g of lanthanum chloride solution (2.4 g of La) were added by an equal volume impregnation method₂O₃/100g solution) was dipped into 100g of sample D, dried at 120 c and calcined at 700 c for 2 hours to obtain the comparative reactivated FCC equilibria Rec-FCC-4.

The cracking performance of Rec-FCC-4 is shown in Table 3. Na of Rec-FCC-4₂The O content was 0.20 wt%.

Example 5

500 g of lanthanum hydroxide solution (0.24 g of La) was added₂O₃/100g solution) with 100g of the equilibration agent to be reactivated, exchanged at room temperature for 2 hours, filtered, washed, dried at 120 ℃ and calcined at 700 ℃ for 2 hours to obtain sample E.

500 grams of magnesium hydroxide emulsion (0.2 grams of MgO per 100 grams of emulsion) was mixed with 100 grams of sample E, exchanged at room temperature for 2 hours, filtered, washed, dried at 120 ℃ and calcined at 700 ℃ for 2 hours to yield the comparative reactivated FCC balancer Rec-FCC-5.

The cracking performance of Rec-FCC-5 is shown in Table 3. Na of Rec-FCC-5₂The O content was 0.21 wt%.

Example 6

500 g of calcium hydroxide emulsion (0.2 g CaO/100 g of emulsion) was mixed with 100g of a rebalance agent to be reactivated, exchanged at room temperature for 2 hours, filtered, washed, dried at 120 ℃ and calcined at 700 ℃ for 2 hours to obtain sample F.

50 g of lanthanum chloride solution (2.4 g of La) were added by an equal volume impregnation method₂O₃/100 grams solution) was dipped into 100 grams of sample F, dried at 120 c and calcined at 700 c for 2 hours to yield the comparative reactivated FCC equilibria Rec-FCC-6.

The cracking performance of Rec-FCC-6 is shown in Table 3. Na of Rec-FCC-6₂The O content was 0.20 wt%.

Example 7

500G of magnesium hydroxide emulsion (0.2G of MgO per 100G of emulsion) was mixed with 100G of a spent equilibrating agent, exchanged at room temperature for 2 hours, filtered, washed, dried at 120 ℃ and calcined at 700 ℃ for 2 hours to obtain sample G.

50 g of yttrium chloride solution (2.4 g of Y) were added by an equal volume impregnation method₂O₃/100G solution) was dipped into 100G of sample G, dried at 120 c and calcined at 700 c for 2 hours to give the comparative reactivated FCC equilibria Rec-FCC-7.

The cracking performance of Rec-FCC-7 is shown in Table 3. Na of Rec-FCC-7₂The O content was 0.19 wt%.

Test example 1

The catalytic cracking reactions of the samples of the examples and comparative examples were evaluated on a micro fluidized bed reactor (ACE) and a matched gas chromatograph, and the Research Octane Number (RON) was analyzed using a gas chromatograph 7980A from Agilent corporation. The properties of the test stock oils are shown in Table 2. The catalytic cracking performance of the samples of examples and comparative examples after calcination at 700 ℃ for 2 hours is shown in Table 3.

Other tests are described in (national Standard of test methods for Petroleum and Petroleum products, published in 1989 by the Chinese Standard Press).

TABLE 2 Properties of the feed oils

TABLE 3 catalytic cracking performance of rejuvenation of the Balancing agent

The raw material residual oil is tested, the reaction temperature is 530 ℃, and the agent-oil ratio is 7.5

Total liquid recovery is gasoline, diesel oil and liquefied gas

As can be seen from Table 3, the rare earth modifies the balancing agent, the conversion rate is improved, the coke yield is reduced, but the dry gas yield is also obviously increased, and the total liquid yield is not obviously improved. The IIA metal modifies the balancing agent, the conversion rate is slightly reduced, the coke and dry gas yield is reduced, and the total liquid yield is improved by nearly 1%.

Meanwhile, rare earth and IIA metal are adopted to modify the balancing agent (examples 1, 3, 5, 6 and 7), the total liquid yield is improved by 2.6-3.5%, and the coke and dry gas yield is also reduced, so that the rare earth and IIA metal pair simultaneously plays a synergistic role in modifying the balancing agent, and the total liquid yield is obviously improved.

Comparing example 1 and example 2, and example 3 and example 4, the rare earth and IIA metal modified the balancing agent, and the total liquid yield of the cracked product was further improved by the calcination treatment between the two treatments, indicating that the calcination process can promote and stabilize the beneficial modification of the balancing agent by the rare earth or IIA metal hydroxide.

In addition, according to the data in Table 1, the catalyst V to be reactivated used in the examples of the present invention₂O₅The content is as high as 1.464 percent, which shows that the balancing agent with high heavy metal content can have good revival effect.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. A reactivation method of a catalytic cracking balancing agent is characterized in that the balancing agent to be reactivated is respectively dipped into a rare earth metal precursor solution, a IIA metal hydroxide solution or an emulsion.

2. The method according to claim 1, wherein the rare earth metal precursor is selected from the group consisting of rare earth metal soluble salts and/or rare earth metal hydroxides, preferably rare earth metal chlorides and/or rare earth metal hydroxides, more preferably rare earth metal hydroxides.

3. The method according to claim 1, wherein the rare earth oxide contained in the rare earth precursor solution is, in terms of rare earth oxide: the mass ratio of the balancing agent to be reactivated is 0.3-2.0: 100, preferably 0.5 to 1.5: 100, preferably 0.6-1.2: 100, more preferably 1.2: 100.

4. the method of claim 1, wherein the rare earth precursor solution has a concentration of: the amount of the rare earth oxide is 0.1g to 5g, preferably 0.12g to 2.4g, more preferably 0.24g to 2.4g, and still more preferably 0.24g to 100g of the rare earth oxide per 100g of the solution, in terms of the rare earth oxide per 100g of the solution to 100g of the solution.

5. A process according to any one of claims 1 to 4, wherein the rare earth metal is selected from one or more of yttrium, lanthanum and cerium, preferably lanthanum and/or yttrium, more preferably lanthanum.

6. The process of claim 1, wherein the IIA metal oxide contained in the IIA metal hydroxide solution or emulsion: the mass ratio of the balancing agent to be reactivated is 0.5-5.0: 100, preferably 0.5-2: 100, preferably 0.8-1.2: 100, more preferably 1.0: 100.

7. the method as claimed in claim 1, wherein the concentration of said IIA metal hydroxide solution or emulsion is: calculated by IIA metal oxide, the content of the metal oxide is 0.1g of IIA metal oxide/100 g of solution to 1g of IIA metal oxide/100 g of solution or emulsion, preferably 0.1g of IIA metal oxide/100 g of solution or emulsion to 0.5g of IIA metal oxide/100 g of solution or emulsion, and more preferably 0.2g of IIA metal oxide/100 g of solution or emulsion.

8. A process as claimed in any one of claims 1 to 7, wherein the IIA metal is selected from magnesium and/or calcium, preferably magnesium.

9. The method according to claim 1, characterized in that the balancing agent is dried after each impregnation; further, the temperature of the drying treatment is 100-200 ℃, preferably 100-150 ℃, and more preferably 120 ℃;

10. The method of claim 1, wherein the balancing agent is calcined at least after any one impregnation; further, roasting the balancing agent at least after the last impregnation; furthermore, roasting treatment is carried out after each impregnation;

further, the roasting treatment temperature is 600-900 ℃, preferably 650-800 ℃, and more preferably 700 ℃;

further, the roasting treatment time is 1-5 hours, preferably 1.5-3 hours, and more preferably 2 hours.