阅读说明：本技术 废催化裂化催化剂的复活方法 (Method for reactivating waste catalytic cracking catalyst ) 是由 陈妍 凤孟龙 林伟 宋海涛 郭瑶庆 于 2020-06-17 设计创作，主要内容包括：本发明提供一种废催化裂化催化剂的复活方法,包括：将含污染金属的废催化裂化催化剂进行焙烧；焙烧后的产物置于含有结构保护剂的碱液中进行碱浸；碱浸后的产物依次进行水洗和酸洗,得到复活的催化裂化催化剂；其中,结构保护剂选自水玻璃、硅溶胶、偏铝酸钠和分子筛母液中的一种或多种,所述污染金属包括钒。经本发明的方法复活后的催化裂化催化剂结晶度可提高1％～10％,钒脱除率可达50％～80％,且相比于废催化剂裂化平衡剂的微反活性提高10～15,所得催化剂经多次循环再生后仍具有良好的活性稳定性。(The invention provides a method for reactivating a waste catalytic cracking catalyst, which comprises the following steps: roasting the waste catalytic cracking catalyst containing the pollution metals; placing the roasted product in an alkali liquor containing a structure protective agent for alkali leaching; sequentially washing and pickling the alkaline leached product to obtain a reactivated catalytic cracking catalyst; wherein the structure protective agent is selected from one or more of water glass, silica sol, sodium metaaluminate and molecular sieve mother liquor, and the pollution metal comprises vanadium. The crystallinity of the catalytic cracking catalyst reactivated by the method can be improved by 1-10%, the vanadium removal rate can reach 50-80%, the micro-reaction activity of the catalytic cracking catalyst is improved by 10-15 compared with that of a waste catalyst cracking balancing agent, and the obtained catalyst still has good activity stability after being recycled for multiple times.)

1. A method for reactivating a spent catalytic cracking catalyst, comprising:

roasting the waste catalytic cracking catalyst containing the pollution metals;

placing the roasted product in an alkali liquor containing a structure protective agent for alkali leaching; and

sequentially washing and pickling the alkaline leached product to obtain a reactivated catalytic cracking catalyst;

wherein the structure protective agent is selected from one or more of water glass, silica sol, sodium metaaluminate and molecular sieve mother liquor, and the pollution metal comprises vanadium.

2. The rejuvenation method according to claim 1, wherein the spent catalytic cracking catalyst contains silica 30 to 75%, alumina 20 to 65%, and vanadium 0.5 to 2%, based on the total weight of the spent catalytic cracking catalyst.

3. The rejuvenation method according to claim 2 wherein said spent catalytic cracking catalyst further comprises rare earth metals in an amount of from 0.1% to 5.5% based on the total weight of said spent catalytic cracking catalyst.

4. The rejuvenation process according to claim 1 wherein said contaminating metals further include a tramp metal selected from one or more of iron, nickel, calcium and sodium, said tramp metal being present in an amount of no more than 1.5% by weight based on the total weight of said spent catalytic cracking catalyst.

5. The revival method of claim 1, wherein the roasting temperature is 450-850 ℃, and the roasting time is 0.5-6 h.

6. The rejuvenation method according to claim 1 wherein the mass ratio of the structure-protecting agent to the spent catalytic cracking catalyst is (0.01 to 5): 100.

7. The revival method of claim 1, wherein the pH value of the alkali solution is 10-14.

8. The revival method according to claim 1, characterized in that the temperature of the alkaline leaching is 60 ℃ to 130 ℃ and the time of the alkaline leaching is 0.1h to 12 h.

9. Rejuvenation method according to claim 1, characterised in that the alkali in the lye is selected from one or more of the group consisting of sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide.

10. The reviving method of claim 9, wherein when the alkali in the alkali liquor is sodium hydroxide and/or potassium hydroxide, the alkali concentration is 3-15 g/L; when the alkali in the alkali liquor is sodium carbonate and/or potassium carbonate, the concentration of the alkali is 20-80 g/L.

11. The revival method according to claim 1, wherein the number of times of the water washing is 1-6, wherein in each time of the water washing process: the mass ratio of the product after alkaline leaching to water is 1: (2-10), the water temperature is 40-95 ℃, and the washing time is 0.1-3 h.

12. The rejuvenation method as defined in claim 1, wherein the acidic substance used in the acid washing is one or more selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium sulfate, ammonium chloride, ammonium phosphate and ammonium hydrogen phosphate.

13. The rejuvenation method as defined in claim 1 wherein said acid wash has a pH of 2 to 5.

14. The reviving method of claim 1, wherein the washing temperature of the acid washing is 60-120 ℃, the acid washing time is 0.1-3 h, and the mass ratio of liquid to solid in the acid washing is (2-10): 1.

15. a revival method according to claim 1, further comprising: and putting the product after acid washing into one or more of a group IVB metal salt solution, a group IIIB metal salt solution and an organic antimony salt solution for passivation treatment.

Technical Field

The invention relates to the technical field of catalysts, in particular to a reactivation method of a waste catalytic cracking catalyst.

Background

The catalytic cracking catalyst is the catalyst with the largest application amount in the oil refining process, the application amount of the catalytic cracking catalyst in China is nearly 20 ten thousand tons at present, about half of the catalytic cracking catalyst cannot be recovered along with the removal of flue gas or catalytic slurry oil, and about 10 ten thousand tons of waste catalytic cracking catalyst can be generated every year. The prior FCC spent catalyst has mainly used a landfill method. The new edition ' national hazardous waste record ' of ' 8.1 of 2016 adds 117 kinds of hazardous waste, and the catalytic cracking waste catalyst is classified as hazardous waste HW50, and the emission is strictly prohibited.

The treatment method of the catalytic cracking catalyst (FCC) waste agent comprises demetallization, building material preparation and the like, wherein the most valuable is the demetallization reactivation as the catalyst for reuse. The pollution metals of the waste catalytic cracking catalyst mainly comprise vanadium, iron and nickel, wherein the vanadium metal has the greatest destructiveness to the catalytic cracking catalyst structure and has larger influence on the activity. And the vanadium oxide has stronger mobility to generate vanadic acid or sodium vanadate and the like, so that the demetallization of vanadium has higher industrial significance, and the metal vanadium on the waste agent can be effectively prevented from transferring to the fresh agent.

Vanadium is a pollution metal which causes permanent damage to the activity of a catalyst, a demetallization reactivation method of an FCC waste agent is a Demet method which is commonly adopted by foreign industries, the Demet process comprises a series of steps of oxidation, chlorination, vulcanization and the like, although the demetallization is complete, the process is complex, the energy consumption is high, and each step has great danger. For the vanadium-containing waste catalyst, CN201110422634A adopts a mixed roasting method of a waste agent and sodium carbonate, sodium vanadate generated at high temperature is washed and removed, but the vanadium removal effect is limited, and the activity is temporarily increased in weak acid washing, so that the activity cannot be permanently improved. CN105251525B adopts organic acid and inorganic acid to remove vanadium, the silicon-aluminum oxide base is partially removed, the pore canal is enlarged, although the temporary activity is improved, the mechanical strength is poor, the inactivation is easier, and the acid liquor is difficult to process by adopting the organic acid method.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The invention aims to overcome at least one defect in the prior art and provides a method for reactivating a waste catalytic cracking catalyst, so as to solve the problems that the activity of the vanadium-containing FCC waste agent cannot be improved for a long time after being reactivated, the mechanical property is poor and the like, so that the effective recycling is difficult to realize.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a method for reactivating a waste catalytic cracking catalyst, which comprises the following steps: roasting the waste catalytic cracking catalyst containing the pollution metals; placing the roasted product in an alkali liquor containing a structure protective agent for alkali leaching; and sequentially washing and pickling the alkaline leached product to obtain a reactivated catalytic cracking catalyst; wherein the structure protective agent is selected from one or more of water glass, sodium metaaluminate and molecular sieve mother liquor, and the pollution metal comprises vanadium.

According to one embodiment of the present invention, the content of silica in the waste catalytic cracking catalyst is 30% to 75%, the content of alumina is 20% to 65%, and the content of vanadium is 0.5% to 2%, based on the total weight of the waste catalytic cracking catalyst.

According to an embodiment of the present invention, the spent catalytic cracking catalyst further comprises rare earth metals, and the content of the rare earth metals is 0.1% to 5.5% based on the total weight of the spent catalytic cracking catalyst.

According to one embodiment of the present invention, the contaminant metals further comprise a hetero metal selected from one or more of iron, nickel, calcium and sodium, the hetero metal content not exceeding 1.5% based on the total weight of the spent catalytic cracking catalyst.

According to one embodiment of the invention, the temperature of calcination is 550 ℃ to 850 ℃, preferably 600 ℃ to 750 ℃; the roasting time is 0.5-6 h, preferably 1-5 h.

According to one embodiment of the invention, the dry-basis mass ratio of the structure protective agent to the waste catalytic cracking catalyst is (0.01-5): 100.

According to one embodiment of the invention, the pH value of the alkaline solution is 10 to 14, preferably 10 to 13.

According to one embodiment of the invention, the temperature of alkaline leaching is between 40 ℃ and 130 ℃, preferably between 70 ℃ and 120 ℃; the alkaline leaching time is 0.1-12 h, preferably 2-8 h.

According to one embodiment of the invention, the base in the lye is selected from one or more of the group consisting of sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide.

According to one embodiment of the invention, when the alkali in the alkali liquor is sodium hydroxide and/or potassium hydroxide, the alkali concentration is 3-15 g/L; when the alkali in the alkali liquor is sodium carbonate and/or potassium carbonate, the concentration of the alkali is 20-80 g/L. According to one embodiment of the invention, the number of washing times is 1-6, wherein in each washing process: the mass ratio of the product after alkaline leaching to water is 1: (2-10), wherein the water temperature is 40-95 ℃, and preferably 75-95 ℃; the washing time is 0.1 to 3 hours, preferably 0.5 to 2 hours.

According to an embodiment of the present invention, the acidic substance used in the acid washing is selected from one or more of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, ammonium sulfate, ammonium chloride, ammonium phosphate, and ammonium hydrogen phosphate, and is not limited thereto.

According to one embodiment of the present invention, the pH of the acid wash is 2 to 5, preferably 3 to 5.

According to one embodiment of the invention, the washing temperature of the acid washing is 70 ℃ to 120 ℃, preferably 70 ℃ to 90 ℃; the pickling time is 0.1-3 h, and the liquid-solid mass ratio in pickling is (2-10): 1.

according to an embodiment of the present invention, further comprising: and putting the product after acid washing into one or more of IVB group metal salt solution, IIIB group metal salt solution and organic antimony salt solution for passivation treatment, wherein the passivation treatment temperature is 25-100 ℃, and the passivation treatment can be carried out by adopting an equal-volume internal impregnation method, a rinsing method or an over-volume impregnation method.

The invention has the beneficial effects that:

the method for reactivating the waste catalytic cracking catalyst provided by the invention can avoid the damage of the molecular sieve structure of the catalyst, effectively remove the pollution metal and improve the crystallinity of the catalyst, thereby improving the overall activity of the catalyst. The crystallinity of the reactivated catalytic cracking catalyst can be improved by 1-10%, the vanadium removal rate can reach 50-80%, and compared with the micro-reaction activity of the waste catalyst before reactivation, the micro-reaction activity of the catalyst is improved by 10-15%, and the catalyst still has good activity stability after being recycled for multiple times.

Detailed Description

The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.

The invention provides a method for reactivating a waste catalytic cracking catalyst, which comprises the following steps: roasting the waste catalytic cracking catalyst containing the pollution metals; placing the roasted product in an alkali liquor containing a structure protective agent for alkali leaching; and sequentially washing and pickling the alkaline leached product to obtain a reactivated catalytic cracking catalyst; wherein the structure protective agent is selected from one or more of water glass, silica sol, sodium metaaluminate and molecular sieve mother liquor, and the pollution metal comprises vanadium (V).

The inventor researches and discovers that the activity loss of the waste catalytic cracking catalyst mainly has three reasons, namely that partial molecular sieve crystal frameworks on the catalyst collapse to cause the loss of an activity center position, and secondly, in the using process of the catalyst, some metals with stronger alkalinity cover the acid position on the surface of the catalyst to cause the reduction of the activity of the catalyst; furthermore, part of the active sites of the catalyst are covered by carbon deposits, so that the activity is lost.

For the waste catalytic cracking catalyst, the pollution metals mainly comprise vanadium, iron and nickel, wherein the vanadium metal is easy to migrate, can continuously destroy the crystal structure of the molecular sieve of the catalytic cracking catalyst for many times, and has larger influence on the activity. The effective removal of the pollution metals such as vanadium and the like has important significance for the reactivation and reutilization of the FCC spent catalyst. However, after the vanadium-containing FCC waste agent is reactivated by the existing method, the activity of the obtained catalyst cannot be improved for a long time, and the mechanical property is deteriorated, so that the effective recycling is difficult to realize. The inventor of the invention finds that vanadium oxide is fully oxidized and converted into high-valence vanadium oxide which can be fully dissolved in alkali by roasting the waste catalytic cracking catalyst containing the polluted metal at high temperature, and then the roasted product is subjected to mild alkali leaching in alkali liquor containing a structure protective agent, so that on one hand, vanadium oxide in the catalyst is converted into vanadate and enters into alkali solution to obtain the waste catalyst after vanadium removal, and on the other hand, the structure protective agent in the alkali liquor can prevent a molecular sieve in the catalyst from being damaged and can improve the crystallinity to a certain extent, and further improve the activity stability of the catalyst after reactivation (the activity stability can be ensured after repeated cycle regeneration). Compared with the waste catalyst cracking balancing agent, the reactivated catalytic cracking catalyst obtained by the method has obviously improved micro-reaction activity stability and good application prospect.

In some embodiments, the spent catalytic cracking catalyst has a silica content of 30% to 75%, e.g., 30%, 34%, 40%, 42%, 50%, 55%, 60%, 66%, 70%, etc., an alumina content of 20% to 65%, e.g., 20%, 25%, 27%, 30%, 32%, 35%, 49%, 50%, 62%, etc., and a vanadium content of 0.5% to 2%, e.g., 0.5%, 0.7%, 0.9%, 1%, 1.2%, 1.5%, 2%, etc., based on the total weight of the spent catalytic cracking catalyst. The conventional catalytic cracking catalyst also contains rare earth metals, and the content of the rare earth metals (RE) is generally 0.1-5.5%, but the method has no special limitation on the specific composition of the waste catalytic cracking catalyst, can be a common waste catalytic cracking balancing agent, and aims at the vanadium removal and reactivation treatment of the waste catalyst with the vanadium content of 0.5-2.0%. It will be appreciated by those skilled in the art that a lower vanadium content is not necessary for vanadium removal.

According to the present invention, the aforementioned contaminating metals also include miscellaneous metals including, but not limited to, iron (Fe), nickel (Ni), calcium (Ca), sodium (Na), etc., which are not more than 1.5% by weight, i.e., other contaminating metals except vanadium, based on the total weight of the spent catalytic cracking catalyst. Vanadium can be removed when the content of other polluted metals is too high, but the activity of other polluted metals is greatly influenced, so that the revival effect of the invention cannot be achieved.

The foregoing method for reactivating the spent catalytic cracking catalyst will be described in detail.

First, the spent catalytic cracking catalyst containing the contaminant metals is calcined, in some embodiments at a temperature of 450 ℃ to 850 ℃, preferably 600 ℃ to 750 ℃, such as 600 ℃, 620 ℃, 670 ℃, 700 ℃, 710 ℃, 730 ℃, and the like. The time for calcination is 0.5h to 6h, preferably 1h to 5h, such as 1h, 2h, 3h, 4h, 4.5h, etc. The vanadium oxide of the waste catalytic cracking catalyst is fully oxidized into high-valence vanadium oxide, namely vanadium pentoxide after the high-temperature roasting. The roasting temperature and time can influence the oxidation degree of vanadium, the vanadium pentoxide can be fully dissolved in alkali, but the molecular sieve structure of the catalyst is easily damaged due to the overhigh temperature, so that the selection of the proper roasting temperature and time is important.

Then, the roasted product is put into alkali liquor containing a structure protective agent for alkali leaching.

According to the invention, the pH value of the alkali liquor is 10-14, preferably 10-13, such as 10, 11, 12, etc., so as to promote the improvement of the crystallinity of the molecular sieve under the condition of ensuring that the structure of the molecular sieve is not damaged. In the alkaline leaching process, the vanadium oxide obtained after roasting is converted into vanadate and enters an alkaline solution, so that vanadium is removed. The alkali in the alkali liquor is selected from sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide and the like, and the type and concentration of the alkali can be adjusted according to actual needs to ensure that the pH value of the alkali liquor is in a proper range. For example, when sodium hydroxide is selected, the concentration of the sodium hydroxide solution is 3-15 g/L; when the basic carbonate is selected, such as sodium carbonate and potassium carbonate, the concentration of the basic carbonate solution is 20-80 g/L.

The structure protective agent is selected from water glass, silica sol, sodium metaaluminate, molecular sieve mother liquor and the like, or other silicon/aluminum components with the same function. For the invention, the structure protective agent can prevent the molecular sieve in the catalyst from being damaged under the alkaline leaching condition, and can improve the crystallinity to a certain extent, thereby improving the activity stability of the reactivated catalyst. In the prior art, acid leaching is generally adopted for post-treatment, the acid activation of acid on the surface active site of the catalyst can cause transient improvement of the activity of the catalyst, the acid leaching does not contribute to the improvement of the crystallinity, the molecular sieve structure can be damaged due to too low pH, so that high activity is difficult to keep after repeated regeneration, namely good activity stability is difficult to ensure, and therefore, the excellent catalytic activity stability of the catalyst after reactivation is realized by adding a structure protective agent with specific content. Generally, the mass ratio of the structure protective agent to the waste catalytic cracking catalyst is (0.01-5): 100, for example, 0.01:100, 0.05:100, 1:100, 2:100, 3:100, 4.5:100, 5.5:100, etc., the selection and proportion of the structure protective agent are determined according to the type and pH of the alkaline leaching solution, and the mass ratio refers to the mass ratio of a dry basis, for example, when the structure protective agent is a molecular sieve mother liquor, etc., the mass ratio refers to the mass ratio of the dry basis in the molecular sieve mother liquor to the waste catalytic cracking catalyst. The structure protective agent is added into the alkali liquor, so that the molecular sieve in the catalyst is prevented from being damaged in the alkali leaching process, the crystallinity can be partially improved by 1-10%, and the activity stability of the catalyst after reactivation is further improved.

In some embodiments, the temperature of alkaline leaching is from 40 ℃ to 130 ℃, preferably from 60 ℃ to 130 ℃, more preferably from 70 ℃ to 120 ℃, e.g., 70 ℃, 75 ℃, 80 ℃, 87 ℃, 90 ℃, 95 ℃, 100 ℃, etc. The alkaline leaching time is 0.1 to 12 hours, preferably 0.5 to 12 hours, more preferably 2 to 10 hours, such as 2 hours, 3 hours, 4.6 hours, 5 hours, 6 hours, 7 hours, 9 hours and the like. The better effect of improving the crystallinity of the catalyst cannot be obtained when the alkaline leaching temperature is too low or the time is too short, and the crystallinity is damaged when the temperature is too high.

Further, the product after alkaline leaching is sequentially subjected to water washing and acid washing. Wherein the washing with water can adopt a leaching method or an immersion method. The number of washing times is 1-6. Wherein the mass ratio of the product after alkaline leaching to water in each water washing process is 1 (2-10), such as: 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:9, etc.; the water temperature is 40 ℃ to 95 ℃, preferably 75 ℃ to 95 ℃, for example 75 ℃, 80 ℃, 82 ℃, 85 ℃, 90 ℃, 95 ℃ and the like, and the washing time is 0.1h to 3h, preferably 0.5h to 2h, for example 0.5h, 0.8h, 1h, 1.5h and the like. In some embodiments, the water wash process may also be facilitated by agitation.

The product after washing with water is washed with acid, typically with weak acid. The acidic substances in the acid solution adopted in the acid washing process include but are not limited to one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium sulfate, ammonium chloride, ammonium phosphate and ammonium hydrogen phosphate, and the pH value of the acid washing is 2-5, preferably 2.5-4. In some embodiments, the washing temperature of the acid wash is 70 ℃ to 120 ℃, preferably 70 ℃ to 110 ℃, more preferably 70 ℃ to 90 ℃, such as 70 ℃, 80 ℃, 85 ℃, 89 ℃, etc.; the pickling time is 0.1-3 h, and the liquid-solid ratio in pickling, namely the mass ratio of acid to the product after washing is (2-10): 1, preferably (3-6): 1, e.g., 3:1, 4:1, 5:1, 6:1, etc. On one hand, the method can partially remove nickel, iron and other pollution metals and alkali metal ions in the alkaline leaching process by weak acid washing; another aspect can be to acid activate the catalyst to provide acidic sites on the interior surface, thereby restoring and increasing the activity of the spent catalyst.

Further, the method of the present invention further comprises: and (3) placing the product after acid washing in one or more of water-soluble metal salt solutions such as IIIB group metal salt solution, IVB group metal salt solution, antimony salt solution and the like, and performing mixed exchange at room temperature to 100 ℃, such as equal-volume impregnation, rinsing or volume impregnation, so as to passivate metallic nickel. Since the remaining metallic nickel may have an adverse effect on the catalytic cracking reaction (e.g., increased dry gas), the metallic nickel may be passivated by adding metal ions during the acid washing. In some embodiments, the temperature of the passivation process is from 25 ℃ to 100 ℃.

And finally, washing and neutralizing the product obtained in the previous step to be neutral, and drying to obtain the reactivated catalytic cracking catalyst.

According to the invention, the waste catalytic cracking catalyst containing the polluted metal is firstly roasted at high temperature, the oxidation is converted into high-valence vanadium oxide which can be fully dissolved in alkali, and then the roasted product is subjected to mild alkali leaching in alkali liquor containing a structure protective agent, so that the polluted metal is effectively removed and the crystallinity of the catalyst is improved on the premise of ensuring that the molecular sieve structure of the catalyst is not damaged, and further the overall activity of the catalyst is improved. The crystallinity of the reactivated catalytic cracking catalyst obtained by the method can be improved by 1-10%, the vanadium removal rate can reach 50-80%, and the micro-reaction activity of the reactivated catalytic cracking catalyst is improved by 10-15 compared with that of a waste catalyst cracking balancing agent, so that the reactivated catalytic cracking catalyst has a good application prospect.

The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.

The spent catalytic cracking catalyst used in this example was two equilibria C1 and C2 from medium petrochemical refineries, the basic chemical composition of which is shown in table 1.

Chemical composition was determined by X-ray fluorescence (XRF). The method is characterized by referring to ASTM D7085-04(2010) standard guide for chemical element determination-X-ray fluorescence spectrometry determination guide in the fluid catalytic cracking catalyst.

The catalyst micro-inverse activity was determined using NB/SH/T0952-2017.

The crystallinity of the catalyst was tested by X-ray diffraction.

TABLE 1

Example 1

1) Weighing 10 g of waste catalytic cracking catalyst C1, and roasting at 660 ℃ for 5h to obtain a roasted product;

2) the product obtained in step 1) was homogeneously mixed with 50g of a 25g/L sodium carbonate solution (pH about 11.8) to which water glass was simultaneously added at a dry concentration of 1 g/L. Stirring at 110 deg.C at 500r/min for 5h to perform alkaline leaching treatment (sealing saturated vapor pressure);

3) washing the sample obtained after the alkaline leaching treatment in the step 2) twice in 50g of 70 ℃ distilled water for 30min each time, filtering to obtain 10.8 g of sample (calculated by dry basis), namely the catalyst after the water washing treatment, adding the catalyst after the water washing treatment into 50g of hydrochloric acid solution with the pH value of 3.5, and stirring at 95 ℃ for 60min at 400r/min for weak acid washing treatment.

And then soaking and washing the product subjected to weak acid washing twice by using 80g of deionized water, collecting a solid product, drying to obtain 98g of the treated catalyst, measuring that the content of the metal vanadium is reduced to 0.24 wt%, the crystallinity is 16.5%, and measuring that the micro-reaction activity is 72%.

4) The catalyst after the reaction was fully coked at 750 ℃ to regenerate and then subjected to cracking reaction as a catalyst, and after this regeneration cycle was repeated three times, the microreflective activity was measured again to be 67.

Example 2

The spent catalytic cracking catalyst was replaced with C2 and treated according to the method of example 1, and since the nickel content was high, 4g of 0.4% antimony oxalate solution was added after weak acid washing for isovolumetric impregnation, resulting in a treated catalyst with a vanadium content of 0.28%, a crystallinity of 15.8% and a microreaction of 68. The catalyst after the reaction was fully coked and regenerated at 700 ℃ and then subjected to cracking reaction as a catalyst, and after three cycles of such regeneration, the micro-reaction activity was measured again to be 64.

Example 3

1) Weighing 10 g of waste catalytic cracking catalyst C1, and roasting at 550 ℃ for 6h to obtain a roasted product;

2) the product obtained in step 1) is mixed homogeneously with 50g of a sodium carbonate solution (pH of about 12) having a sodium carbonate concentration of 20g/L, sodium metaaluminate having a sodium metaaluminate concentration of 2g/L being added simultaneously to the sodium carbonate solution. Sealing at 130 deg.C, stirring at 300r/min for 1h, and performing alkaline leaching treatment;

3) washing the sample obtained after the alkaline leaching treatment in the step 2) in 60g of distilled water at 90 ℃ for three times, each time for 60min, so as to obtain 11.5 g (calculated on a dry basis) of the catalyst after the water washing treatment, adding the catalyst after the water washing treatment into 60g of phosphoric acid solution with the pH value of 3.5, and stirring at 110 ℃ for 60min at 400r/min for weak acid washing treatment.

And then, soaking and washing the product subjected to weak acid washing treatment once by using 60g of deionized water, collecting a solid product, drying to obtain 10.3g of the treated catalyst, and determining that the content of the metal vanadium is reduced to 0.35%, the crystallinity is 16.0%, and the micro-reaction activity is 70.

4) The catalyst after the reaction is fully burnt and regenerated at 720 ℃, and then used as the catalyst to carry out cracking reaction, and after the regeneration is circulated for three times, the micro-reaction activity is measured again to be 65.

Example 4

1) Weighing 10 g of waste catalytic cracking catalyst C1, and roasting at 450 ℃ for 6h to obtain a roasted product;

2) uniformly mixing the product obtained in the step 1) with 50g of sodium carbonate solution (pH is 12.2) with the concentration of 60g/L, wherein silica sol with the concentration of 5g/L is simultaneously added into the sodium carbonate solution. Stirring at 110 ℃ for 2h at 500r/min for alkaline leaching treatment;

3) washing the sample obtained after the alkaline leaching treatment in the step 2) in 40g of 60 ℃ distilled water for 4 times, wherein each time is 20min, obtaining 10.8 g of filter cake (calculated by dry basis), namely the catalyst after the water washing treatment, adding the catalyst after the water washing treatment into 50g of ammonium phosphate solution with the pH value of 4, and stirring at 95 ℃ and 400r/min for 60min for weak acid washing treatment.

And then, soaking and washing the product subjected to weak acid washing treatment with 70g of deionized water for three times, collecting a solid product, drying to obtain 9.8g of the treated catalyst, and determining that the content of the metal vanadium is reduced to 0.32%, the crystallinity is 13.7%, and the micro-reaction activity is 67.

4) The catalyst after the reaction was fully coked and regenerated at 700 ℃ and then used as a catalyst for a cracking reaction, and after three cycles of such regeneration, the micro-reactivity was measured again to be 62.

Example 5

1) Weighing 10 g of waste catalytic cracking catalyst C1, and roasting at 800 ℃ for 1h to obtain a roasted product;

2) uniformly mixing the product obtained in the step 1) with 50g of sodium hydroxide solution (pH is 13.1) with the concentration of 5g/L, and simultaneously adding water glass into the alkali solution to obtain the product with the dry-basis concentration of 1 g/L. Stirring at 90 ℃ for 3h at 400r/min for alkaline leaching treatment;

3) washing the sample obtained after the alkaline leaching treatment in the step 2) in 40g of 60 ℃ distilled water for 5 times, wherein each time is 25min, filtering and washing the obtained solution to obtain 10.6 g of filter cake (calculated by dry basis), namely the catalyst after the water washing treatment, adding the catalyst after the water washing treatment into 50g of mixed solution of ammonium chloride and hydrochloric acid with the pH value of 3.5, and stirring at 95 ℃ and 400r/min for 60min for weak acid washing treatment.

Then, the product after the weak acid washing treatment is soaked and washed for 2 times by 100g of deionized water, a solid product is collected and dried to obtain 10.2g of the treated catalyst, the content of the metal vanadium is measured to be reduced to 0.29%, the crystallinity is 14.2%, and the micro-reaction activity is 61.

4) The catalyst after the reaction is fully burnt and regenerated at 680 ℃, and then is used as the catalyst to carry out cracking reaction, and after the regeneration is circulated for three times, the micro-inverse activity is measured again to be 58.

Comparative example 1

1) After 10 g of the spent catalytic cracking catalyst was weighed and mixed uniformly with 50g of a 25g/L sodium carbonate solution (pH 11.8), sodium metaaluminate was added to the sodium carbonate solution at the same time at a concentration of 1 g/L.

2) Stirring at 110 ℃ for 2h at 500r/min for alkaline leaching treatment (sealing), washing the filtered sample twice in 50g of 70 ℃ distilled water for 30min each time, filtering to obtain 10.8 g (calculated by dry basis) of the washed catalyst, adding the washed catalyst into 50g of hydrochloric acid solution with the pH value of 3.5, and stirring at 95 ℃ for 60min at 400r/min for weak acid washing treatment.

And then, soaking and washing the product subjected to weak acid washing treatment by using 40g of deionized water, collecting a solid product, drying to obtain 98g of the treated catalyst, and determining that the content of the metal vanadium is reduced to 0.65%, the crystallinity is 12.5%, and the micro-reaction activity is 59.

3) The catalyst after the reaction was fully coked and regenerated at 700 ℃ and then used as a catalyst for a cracking reaction, and after three cycles of such regeneration, the micro-reactivity was measured again to be 52.

Comparative example 2

10 g of the spent catalytic cracking catalyst C1 was weighed out and calcined at 550 ℃ for 4 hours, the calcined, water-washed catalyst was added to 50g of hydrochloric acid solution with pH 3.5, and the mixture was stirred at 400r/min at 95 ℃ for 60 minutes for weak acid washing. Then, the catalyst is soaked and washed twice by 80g of deionized water, a solid product is collected and dried to obtain 9.8g of the treated catalyst, and the content of the metal vanadium is measured to be reduced to 0.76%, the crystallinity is 12.2%, and the micro-reaction activity is 62. The catalyst after the reaction was fully coked at 720 ℃ to regenerate and then used as a catalyst to conduct a cracking reaction, and after this regeneration cycle was repeated three times, the microreaction activity was measured again to be 45.

Comparative example 3

1) Weighing 10 g of waste catalytic cracking catalyst C1, and roasting at 550 ℃ for 5h to obtain a roasted product;

2) mixing with 50g 25g/L sodium carbonate solution (pH of 11.8), and stirring at 110 deg.C for 2 hr at 500r/min for alkaline leaching treatment (sealed alkaline leaching);

3) washing the sample obtained after the alkaline leaching treatment in the step 2) twice in 50g of 80 ℃ distilled water for 30min each time, filtering to obtain 10.8 g of filter cake (calculated by dry basis), namely the catalyst after the water washing treatment, adding the catalyst after the water washing treatment into 50g of hydrochloric acid solution with the pH value of 3.5, and stirring at 95 ℃ for 60min at 400r/min for weak acid washing treatment.

And then, soaking and washing the product subjected to weak acid washing treatment with 80g of deionized water for three times, collecting a solid product, drying to obtain 9.8g of the treated catalyst, and determining that the content of the metal vanadium is reduced to 0.25%, the crystallinity is 10.4%, and the micro-reaction activity is 54.

4) The catalyst after the reaction was fully coked at 680 ℃ to regenerate, and then used as a catalyst to perform a cracking reaction, and after the regeneration cycle was repeated three times, the micro-reactivity was measured again to be 43.

Comparative example 4

Weighing 10 g of waste catalytic cracking catalyst, mixing with 1g of anhydrous sodium carbonate, roasting with a muffle furnace at 550 ℃ for 30 minutes, cooling, adding into 50g of 80 ℃ deionized water, stirring for 30 minutes, filtering, washing a filter cake obtained by filtering for multiple times, then leaching with 1g of ammonium dihydrogen phosphate aqueous solution with the concentration of 2.5% of ammonium dihydrogen phosphate, finally drying to obtain 10.5g of treated catalyst, determining that the content of metal vanadium is reduced to 0.20%, the crystallinity is 10.3%, the micro-reaction activity is 70, fully burning and regenerating the reacted catalyst at 700 ℃, and then performing cracking reaction as the catalyst, wherein the micro-reaction activity of the catalyst is 43 after the regeneration is cycled for three times.

In conclusion, the method for reactivating the waste catalytic cracking catalyst can improve the crystallinity of the catalyst on the basis of effectively reducing the vanadium content of the waste catalytic cracking catalyst by 50-80%, the vanadium removal can reach 80% under the optimal condition, the activity of the catalyst is improved by 10-15%, and the obtained catalyst still has good activity stability after being recycled for multiple times, thereby having very important practical significance for recycling the waste catalyst.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.