CN108355711B - A kind of catalytic cracking catalyst and its preparation method and application - Google Patents

Abstract

The invention discloses a catalytic cracking catalyst and a preparation method and application thereof. The catalyst uses kaolin or montmorillonite as a carrier, and uses molybdenum naphthenate and/or iron naphthenate as active components. Then, a dilute acid impregnation solution of iron naphthenate and/or molybdenum naphthenate is added for impregnation, and the reacted material is dried to prepare a catalytic cracking catalyst. The catalytic cracking catalyst can be applied to the process of treating cellulose and waste plastics, which not only improves the overall conversion rate of cellulose and waste plastics, but also promotes the target reaction to improve the liquid yield.

Description

A kind of catalytic cracking catalyst and its preparation method and application

technical field

The invention belongs to the technical field of solid waste treatment, and particularly relates to a catalytic cracking catalyst and a preparation method and application thereof.

Background technique

The waste generated by the use of a large number of plastic products not only seriously pollutes the environment, but also causes waste of resources. At present, the consumption of plastic products is huge, and a large amount of waste plastic is generated every year. However, the recycling collection and classification efficiency of waste plastics are generally low, and it is difficult to continuously supply various types of waste plastics. Large-scale continuous production. Although the output of cellulose is relatively large, many of them are directly incinerated, causing a lot of air pollution and waste of resources. At present, there have been some studies on the liquefaction technology of plastics and the optimal utilization of cellulose. If waste plastics are added to cellulose and co-pyrolyzed together, the advantages of pyrolysis of the two can be used, and the output of valuable products of the two can be higher. . However, the research on the direct liquefaction of plastics and cellulose has found that the reaction conditions and catalysts required by the two are quite different. Directly liquefying waste plastics and cellulose together has a great impact on the types of reactants, reaction conditions, catalysts, etc. etc. have higher requirements, which poses certain challenges to the co-processing of waste plastics and cellulose.

SUMMARY OF THE INVENTION

Aiming at the deficiencies in the prior art, the present invention provides a catalytic cracking catalyst and a preparation method and application thereof. The catalytic cracking catalyst can improve the conversion rate of the catalytic cracking reaction, and promote the progress of the target reaction, thereby increasing the liquid yield. The application of the catalytic cracking catalyst in the waste plastic and fiber treatment process can improve the economic and environmental benefits of the entire process.

A first aspect of the present invention provides a catalytic cracking catalyst, the catalytic cracking catalyst uses kaolin or montmorillonite as a carrier, and uses molybdenum naphthenate and/or iron naphthenate as active components, based on the weight of the catalytic cracking catalyst , kaolin or montmorillonite accounts for 37.5%-87.5%, molybdenum naphthenate and/or iron naphthenate accounts for 12.5%-62.5%, preferably kaolin or montmorillonite accounts for 50%-70%, molybdenum naphthenate and / or iron naphthenate 30%-50%.

A second aspect of the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising the following steps:

1) The kaolin or montmorillonite is calcined at 400-550°C for 2-10h, preferably the heating rate to the calcination temperature is 5-10°C/min;

2) adding the kaolin or montmorillonite obtained after step 1) roasting into the reactor, then adding the dilute acid dipping solution of iron naphthenate and/or molybdenum naphthenate in the reactor to impregnate, preferably while impregnating Stir, stirring speed 100-150r/min, stirring time 0.5-2.5h;

3) drying the reacted material in step 2) at 100-150° C. for 2-6 hours to prepare a catalytic cracking catalyst.

In the preparation method of the catalytic cracking catalyst, the dilute acid described in step 2) is at least one of hydrochloric acid, nitric acid and acetic acid, and the mass concentration of the dilute acid impregnation solution is 5%-20%.

The immersion solution can be an organic solution, preferably an ethanol solution. Said impregnation adopts conventional impregnation method, such as saturated impregnation method or supersaturated impregnation method.

The catalytic cracking catalyst of the present invention can be formed by conventional methods, such as tablet forming, etc. During the forming process, forming aids can be added as required. In the present invention, the material obtained after drying in step (3) can be shaped to obtain a shaped catalytic cracking catalyst. After the tablet is formed, it is sieved as required to obtain a particle size of 30 to 70 mesh, preferably 40 to 60 mesh.

A third aspect of the present invention provides an application of the above-mentioned catalytic cracking catalyst, which can be applied to a process for treating cellulose and waste plastics, comprising the following steps:

(1) waste plastics are added in catalytic reactor A, under the effect of catalyst 1, catalytic cracking reaction is carried out, and the cracked product of gained obtains liquid product I, gas I and insoluble matter I through separation;

(2) the liquid product I of step (1) gained is passed into tetrahydrofuran, cyclohexane solvent successively after cooling and extracts, respectively obtains the tetrahydrofuran solution containing liquid product II, the cyclohexane solution containing liquid product III and the remaining liquid product IV;

(3) the tetrahydrofuran solution containing liquid product II obtained in step (2) and the cyclohexane solution containing liquid product III are respectively subjected to distillation treatment to remove solvent, respectively obtained liquid product II and liquid product III;

(4) adding cellulose and the liquid product II of step (3) gained in catalytic reactor B, carry out catalytic reaction under the effect of catalyst 2, obtain liquid product i, gas i and insoluble matter i through separation;

(5) the liquid product i obtained in step (4) is cooled and successively passed into tetrahydrofuran and cyclohexane solvent for extraction to obtain respectively the tetrahydrofuran solution containing liquid product ii, the cyclohexane solution containing liquid product iii and the remaining liquid product iv, which is treated by distillation to remove the solvent to obtain liquid product ii and liquid product iii;

(6) the remaining liquid product IV obtained in step (2) and step (5), the remaining liquid product iv and the insoluble matter I and insoluble matter i obtained in step (1) and step (4), respectively, are added to the catalyst In the reactor C, a deep catalytic cracking reaction is carried out under the action of the catalyst 3, and the resulting cracked product is separated to obtain a liquid product V, a gas V and an insoluble matter V;

(7) the liquid product V of step (6) gained is passed into tetrahydrofuran, cyclohexane solvent successively after cooling and extracts, respectively obtains the tetrahydrofuran solution containing liquid product VI, the cyclohexane solution containing liquid product VII and the remaining Liquid product VIII, treated by distillation to remove solvent, to obtain liquid product VI and liquid product VII;

Wherein, the catalyst 2 adopts the catalytic cracking catalyst described in the first aspect and the second aspect.

In the present invention, the catalytic reactors A, B and C are all slurry-bed catalytic cracking reactors.

In the present invention, the waste plastics in step (1) mainly include one or more mixtures of polyethylene plastics (PE), polypropylene plastics (PP) and polystyrene (PS). Not less than 80% of the total mass of added waste plastics.

In the present invention, the catalyst 1 described in step (1) is a HY molecular sieve catalyst. The usage amount of the catalyst 1 is 5%-20% of the total mass of the added waste plastic, preferably 10%-15%.

In the present invention, the reaction conditions of the catalytic cracking reaction described in step (1) are as follows: the reaction temperature is 350-550°C, preferably 400-480°C; the reaction time is 30-150 minutes, preferably 45-120 minutes; the reaction Under stirring, the stirring rate is 350-600 rev/min, preferably 400-500 rev/min; hydrogen needs to be introduced into the reaction, and the hydrogen partial pressure is 2-4 MPa, preferably 2.5-3.5 MPa.

In the present invention, the cooling described in step (2), step (5) and step (7) preferably cools liquid product I, liquid product cooling i and liquid product V to room temperature.

In the present invention, the distillation treatment described in step (3), step (5) and step (7) is a conventional distillation method in the art to remove tetrahydrofuran or cyclohexane solvent.

In the present invention, the cellulose described in step (4) is one or more of plant fibrous substances such as straw, bark, and straw.

In the present invention, before the cellulose described in step (4) is added to the catalytic reactor B, it is preferably subjected to pretreatment, such as at least one of pulverization and dehydration treatment. In the pulverization mentioned therein, the length of the powder obtained by pulverization is preferably not more than 20 mm. The dehydration treatment is carried out under anaerobic conditions, the treatment temperature is 100-200° C., and the treatment time is 60-120 minutes.

In the present invention, the liquid product II obtained in step (3) is added in step (4), and the mass ratio of cellulose to liquid product II is 0.8-1.2:1.

In the present invention, the usage amount of the catalyst 2 described in step (4) accounts for 2.5%-15% of the mass of the added cellulose. When step (4) adds catalyst 2, add the sulfur source that mass content is 4000-8000ppm in terms of sulfur as vulcanizing agent, and the mass ratio of sulfur content and iron and molybdenum total content is 5-7: 1, wherein the selected sulfur source It is one or more of sulfur, hydrogen sulfide, carbon disulfide, etc.

In the present invention, the reaction conditions of the catalytic reaction described in step (4) are as follows: the reaction temperature is 400-600° C., preferably 450-550° C.; the reaction time is 30-100 minutes, preferably 60-100 minutes; Under stirring, the stirring rate is 350-600 rev/min, preferably 400-500 rev/min; hydrogen needs to be introduced into the reaction, and the hydrogen partial pressure is 4-8 MPa, preferably 5-6.5 MPa. Further, the preferred reaction conditions are as follows: the reaction temperature of the catalytic reaction in step (4) is at least 50°C higher than the reaction temperature of the catalytic reaction in step (1), and the hydrogen partial pressure ratio of the catalytic reaction in step (4) is higher than that in step (4). The hydrogen partial pressure of the catalytic reaction in step (1) is at least 2MPa higher.

In the present invention, the catalyst 3 described in step (6) is a HZSM-5 and HY composite molecular sieve catalyst, and the mass ratio of HZSM-5 and HY is 0.5-2:1, preferably HZSM-5 and HY modified with phosphorus and tungsten. The HY composite molecular sieve catalyst, wherein the mass content of phosphorus is 1.5%-7.0%, and the mass content of tungsten is 0.3%-2.0%. The usage amount of the catalyst 3 is 5%-18%, preferably 8%-13%, of the total mass of all the reaction materials added to the catalytic reactor C in step (6).

In the present invention, the preparation method of the catalyst 3 is preferably as follows: mixing HZSM-5 and HY to obtain a composite molecular sieve, impregnating the composite molecular sieve with a phosphoric acid solution with a mass concentration of 10%-20%, drying at 80-110 ° C for 1-3 hour; impregnate the composite molecular sieve again with an aqueous solution of sodium tungstate with a mass concentration of 1%-2%, dry it at 80-110°C for 5-10 hours, and finally roast it at 330-380°C for 4-7 hours, and obtain the catalyst after molding 3.

In the present invention, the catalyst 3 can be formed by conventional methods, such as tablet forming, etc., and a forming aid can be added as required during the forming process. After the tablet is formed, it is screened as required, and the solid particles with a particle size of 30 to 70 mesh, preferably 40 to 60 mesh, are taken as the catalyst 3 . The possible existence form of phosphorus in the described phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve catalyst is one or more of phosphotungstic acid, phosphorus oxide, phosphotungstic acid salt, phosphoric acid, phosphate, etc., The possible existing forms of tungsten are one or more of phosphotungstic acid, tungsten oxide, phosphotungstic acid salt, etc., preferably the catalyst prepared by the above method.

In the present invention, the reaction conditions for the deep catalytic cracking reaction in step (6) are: the reaction temperature is 400-700°C, preferably 500-600°C; the reaction time is 60-150 minutes; the reaction is carried out under stirring, and the stirring rate is It is 350-600 rev/min; it is necessary to feed hydrogen in the reaction, and the hydrogen partial pressure is 5-10MPa. Further, the preferred reaction conditions are as follows: the reaction temperature of the catalytic reaction in step (6) is at least 50°C higher than the reaction temperature of the catalytic reaction in step (4), and the hydrogen partial pressure ratio of the catalytic reaction in step (6) is higher than that in step (6). The hydrogen partial pressure of the catalytic reaction in step (4) is at least 1 MPa higher.

Compared with the prior art, the present invention has the following advantages:

The catalytic cracking catalyst provided by the present invention uses kaolin or montmorillonite as a carrier, and uses molybdenum naphthenate and/or iron naphthenate as active components. The catalytic cracking catalyst is more conducive to the catalytic cracking of cellulose, and is suitable for In the process of co-processing waste plastic and cellulose, it is beneficial to the formation of the target product, and at the same time, it is also conducive to the separation of the catalyst from the raw material, so as to reduce the further pollution of the catalyst to the raw material.

Cellulose and waste plastics are two kinds of solid wastes that are difficult to handle. The present invention combines the treatment of cellulose with the catalytic cracking of waste plastics, and at the same time turns wastes into treasures. Compared with the conventional co-processing of waste plastics and cellulose, the invention not only improves the overall conversion rate, but also promotes the target reaction to improve the cyclohexane The yield of solubles and tetrahydrofuran solubles reduces the amount of insolubles. In particular, the liquid product obtained by the extraction of tetrahydrofuran after the catalytic cracking of waste plastic is co-pyrolyzed with cellulose, and under the action of the catalytic cracking catalyst provided by the present invention, it is more helpful to improve the polar product in the cellulose catalytic reaction process. Solubilization increases the conversion rate of cellulose. In addition, the present invention collects and mixes the insoluble matter after the catalytic reaction of waste plastics and cellulose, and adds the remaining liquid products that are not extracted by tetrahydrofuran and cyclohexane after the catalytic reaction of waste plastics and cellulose, and under the action of the catalyst, carry out The deep catalytic cracking reaction reduces the generation of a large amount of waste residue. For the waste residue which is difficult to treat, especially the HZSM-5 and HY composite molecular sieve catalyst modified by phosphorus and tungsten of the present invention, the cracking temperature is relatively mild, and the cracking rate is high.

In addition, the invention has the advantages of simple process flow, mild reaction conditions, simplicity and practicability, and low cost, solves the problems of difficult disposal and low recycling value of a large number of waste plastics and cellulose, and not only alleviates the environmental pollution caused by a large number of waste plastics and cellulose Pressure, and turning waste into treasure, significantly improve the added value of waste plastics and cellulose.

Description of drawings

Fig. 1 is the process flow schematic diagram of the present invention;

The reference numerals are explained as follows: 1. Catalytic reactor A; 2. Gas-liquid-solid separator a; 3. An extraction device a using tetrahydrofuran and cyclohexane as solvents is arranged in sequence; 4. Catalytic reactor B; 5. Gas-liquid Liquid-solid separation device b; 6, successively provided with extraction device b with tetrahydrofuran and cyclohexane as solvents; 7, catalytic reactor C; 8, gas-solid separation device c; 9, successively provided with tetrahydrofuran and cyclohexane Extraction device c for solvent; 21, liquid product I; 22, gas I; 23 insoluble matter I; 31, liquid product II, 32, liquid product III; 33, remaining liquid product IV; 51, liquid product i; 52 , gas i; 53, insoluble matter i; 61, liquid product ii; 62, liquid product iii; 63, remaining liquid product iv; 81, liquid product V; 82, gas V; 83, insoluble matter V; 91, liquid Product VI; 92, liquid product VII; 93, remaining liquid product VIII.

Detailed ways

The application of the catalytic cracking catalyst of the present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not therefore limited to the scope of the following examples. In the present invention, wt% represents mass fraction.

As shown in Figure 1, the application of the catalytic cracking catalyst provided by the present invention comprises the following steps:

(1) waste plastics are added in catalytic reactor A1, under the effect of catalyst 1, catalytic cracking reaction is carried out, and the resulting cracked product obtains liquid product I21, gas I22 and insoluble matter I2 through gas-liquid-solid separator a2 twenty three;

(2) the liquid product I 21 of step (1) gained is successively passed into the extraction device a 3 with tetrahydrofuran and cyclohexane as solvents after cooling, and extracts, respectively obtains the tetrahydrofuran solution containing liquid product II, the liquid product containing The cyclohexane solution of III and the remaining liquid product IV 33;

(3) the tetrahydrofuran solution containing liquid product II obtained in step (2) and the cyclohexane solution containing liquid product III are respectively subjected to distillation treatment to remove solvent, respectively obtained liquid product II 31 and liquid product III 32;

(4) cellulose is first added to catalytic reactor B 4 for dehydration treatment, and then the liquid product II 31 obtained in step (3) is added, and catalytic reaction is carried out under the action of catalyst 2, and is passed through gas-liquid-solid separator b 5 separate and obtain liquid product i 51, gas i 52 and insoluble matter i 53;

(5) liquid product i 51 obtained in step (4) is successively passed into the extraction device b 6 with tetrahydrofuran and cyclohexane as solvents after cooling, and extraction is carried out to obtain respectively the tetrahydrofuran solution containing liquid product ii, the liquid containing A cyclohexane solution of product iii and the remaining liquid product iv 63, treated by distillation to remove the solvent, yielding liquid product ii 61 and liquid product iii 62;

(6) the remaining liquid product IV 33 obtained in step (2) and step (5), the remaining liquid product IV 63 and the insoluble matter I 23 and insoluble matter I 53 obtained in step (1) and step (4) respectively Join in catalytic reactor C7, carry out deep catalytic cracking reaction under the effect of catalyst 3, the obtained cracked product is separated through gas-liquid-solid separation device c8 to obtain liquid product V81, gas V82 and insoluble matter V83;

(7) the liquid product V81 of step (6) gained is passed into the extraction device c 9 that is provided with tetrahydrofuran and cyclohexane as a solvent successively after cooling, and extracts, respectively obtains the tetrahydrofuran solution containing liquid product VI, the liquid product containing The cyclohexane solution of VII and the remaining liquid product VIII 93 were worked up by distillation to remove the solvent to give liquid product VI 91 and liquid product VII 92.

Wherein, the insoluble matter V 83 is the waste residue that no longer participates in the reaction, and the remaining liquid product VIII 93 can be recycled to the catalytic reactor C 7 for further catalytic cracking reaction.

Wherein, the product in table 1 is gas, cyclohexane soluble matter, tetrahydrofuran soluble matter, waste residue, wherein, gas is gas I 22, gas i 52 and gas V 82, and cyclohexane soluble matter is liquid product III 32, Liquid product iii 62 and liquid product VII 92, tetrahydrofuran solubles are liquid product ii 61 and liquid product VI 91, residues are insolubles V 83 and remaining liquid product VIII 93. The conversion rate refers to the percentage of the total mass of gas, cyclohexane soluble matter and tetrahydrofuran soluble matter in the product to the mass of the four products. In the present invention, the gas is mainly lower olefins with carbon 4 or less such as ethylene and propylene.

The preparation method of the catalyst 2-A used in the embodiment of the present invention is as follows: 1) calcining the raw kaolin powder at 430° C. for 6 h, wherein the heating rate to the calcination temperature is 7° C./min; 2) after calcining step 1) The obtained kaolin is added to the reactor, and then the immersion solution of dilute hydrochloric acid of iron naphthenate and molybdenum naphthenate is added to the reactor to carry out supersaturated immersion. The ethanol solution, in which the mass fraction of hydrochloric acid is 12%, is stirred during immersion, the stirring rate is 125r/min, and the stirring time is 1.5h; 3) The reacted material in step 2) is dried at 130 ° C for 4 hours, and then pressed into tablets Shape, sieve, and take the solid particles with a particle size of 40 mesh to 60 mesh as catalyst 2-A, and the added materials satisfy: based on the weight of the catalytic cracking catalyst, kaolin accounts for 60%, iron naphthenate accounts for 15%, and cyclic Molybdenum alkanoate accounts for 25%.

The preparation method of the catalyst 2-B used in the embodiment of the present invention is specifically as follows: the dilute hydrochloric acid in the preparation method of the catalyst 2-A is changed to acetic acid, and the added material satisfies: based on the weight of the catalytic cracking catalyst, the kaolin clay accounts for 62% %, iron naphthenate accounts for 18%, molybdenum naphthenate accounts for 20%, and others are the same as the preparation method of catalyst 2-A.

The preparation method of the catalyst 2-C used in the embodiment of the present invention is specifically as follows: the kaolin in the preparation method of the catalyst 2-A is replaced by montmorillonite, and the added material satisfies: by the weight of the catalyst, the montmorillonite accounts for 55%, iron naphthenate accounting for 23%, molybdenum naphthenate accounting for 22%, and others are the same as the preparation method of catalyst 2-A.

The HZSM-5 and HY composite molecular sieve catalyst CAT-A modified by phosphorus and tungsten used in the embodiment of the present invention is as follows: the mass ratio of HZSM-5 and HY composite molecular sieve is 1:1, the mass content of phosphorus is 3%, and the mass ratio of tungsten is 3%. Its mass content is 1.2%, and its preparation method is as follows: mix HZSM-5 with HY molecular sieve, impregnate the composite molecular sieve with a phosphoric acid solution with a mass concentration of 15%, and dry it at 100 ° C for 2 hours; use tungsten with a mass concentration of 1.5%. The composite molecular sieve was impregnated with sodium aqueous solution, dried at 100°C for 8 hours, and finally calcined at 350°C for 6 hours. After tableting and sieving, solid particles with a particle size of 40 mesh to 60 mesh were taken as phosphorus and tungsten modified particles. HZSM-5 and HY composite molecular sieve catalyst CAT-A.

The HZSM-5 and HY composite molecular sieve catalyst CAT-B used in the embodiment of the present invention is as follows: the mass ratio of HZSM-5 and HY composite molecular sieve is 1:1, and the preparation method is as follows: HZSM-5 and HY composite molecular sieve are mixed, It was dried at 100 °C for 8 hours, and finally calcined at 350 °C for 6 hours. After tableting and sieving, solid particles with a particle size of 40 mesh to 60 mesh were taken as HZSM-5 and HY composite molecular sieve catalyst CAT-B.

Example 1

A total of 2 g of a mixture of three plastics, 50wt% HDPE, 30wt% PET, and 20wt% PS, was selected as the raw material for the waste plastic reaction, and was added to the slurry bed catalytic cracking reactor A, under the catalysis of HY molecular sieve catalyst. In the catalytic cracking reaction, the amount of HY molecular sieve added is 12% of the total mass of the waste plastic. The reaction conditions of the catalytic cracking reaction are as follows: the reaction temperature is 445 ° C, the reaction time is 60 minutes, and the stirring rate is 440 rpm. In the catalytic reactor A, hydrogen gas was introduced, and the hydrogen partial pressure was 2.6 MPa, and the reacted product was separated to obtain liquid product I, gas I and insoluble matter I; the liquid product I was cooled to room temperature and then passed into tetrahydrofuran, The cyclohexane solvent is extracted to obtain respectively the tetrahydrofuran solution containing liquid product II, the cyclohexane solution containing liquid product III and the remaining liquid product IV; the obtained tetrahydrofuran solution containing liquid product II and the cyclic product containing liquid product III are obtained. The hexane solution was subjected to distillation treatment to remove the solvent to obtain liquid product II and liquid product III; 2 g of straw was pulverized to a powder with a length of about 10 mm, and then dehydrated under anaerobic conditions, the treatment temperature was 130 ° C, and the treatment time For 70 minutes, the pretreated straw was added to the slurry-bed catalytic cracking reactor B, and then the catalyst 2-A was added to the slurry-bed catalytic cracking reactor B, and the usage amount of the catalyst 2-A accounted for the added cellulose. At the same time, add the sulfur with a mass content of 6000ppm in terms of sulfur as a vulcanizing agent, so that the mass ratio of the sulfur content in the catalytic cracking reactor B to the total content of iron and molybdenum is 6:1, and the liquid product II is passed into the slurry state bed catalytic cracking reactor B, and then react under the following reaction conditions: the reaction temperature is 500 ° C, the reaction time is 70 minutes, the stirring rate is 430 rev/min, and the reaction needs to be added to the slurry state bed catalytic cracking reactor B. Pass hydrogen into the middle, the hydrogen partial pressure is 5.3MPa, and the product after the reaction is separated to obtain liquid product i, gas i and insoluble matter i; after cooling the obtained liquid product i to room temperature, pass into tetrahydrofuran and cyclohexane successively The solvent is extracted to obtain the tetrahydrofuran solution containing liquid product ii, the cyclohexane solution containing liquid product iii and the remaining liquid product iv, and the tetrahydrofuran solution containing liquid product ii and the cyclohexane solution containing liquid product iii are distilled. Work-up to remove solvent yields liquid product ii and liquid product iii.

The remaining liquid product IV, the remaining liquid product iv and the insolubles I and the insolubles i are added to the slurry bed catalytic cracking reactor C to carry out a deep catalytic cracking reaction, and the phosphorus and tungsten modified HZSM- 5 and HY composite molecular sieve as catalyst CAT-A, the usage amount of this catalyst is 10% of the total mass of all reaction materials added to the slurry bed catalytic cracking reactor C, and the deep catalytic cracking reaction is carried out under the following reaction conditions: reaction temperature is 560 ° C, the reaction time is 100 minutes, the stirring speed is 440 rev/min, and hydrogen is introduced into the slurry-bed catalytic cracking reactor C as needed in the reaction, and its hydrogen partial pressure is 7.0 MPa, and the obtained cracked product is obtained by separation Liquid product V, gas V and insoluble matter V; The liquid product V of gained is passed into tetrahydrofuran, cyclohexane solvent successively after cooling to carry out extraction, obtain respectively the tetrahydrofuran solution containing liquid product VI, the cyclohexane containing liquid product VII The solution and the remaining liquid product VIII were treated by distillation to remove the solvent to give liquid product VI and liquid product VII.

Example 2

Just change the reaction conditions of the catalytic cracking reaction carried out in the catalyzing bed catalytic cracking reactor A in the embodiment 1 to: the reaction temperature is 440 ° C, the reaction time is 140 minutes, and the stirring speed is 480 rev/min. Introduce hydrogen into the slurry catalytic cracking reactor A, the hydrogen partial pressure is 3.4MPa, and the conditions for the deep catalytic cracking reaction in the slurry catalytic cracking reactor C are changed to: the reaction temperature is 580 ℃, and the reaction time is 70 minutes , the stirring speed is 500 rev/min, and hydrogen is introduced into the slurry-bed catalytic cracking reactor C as needed in the reaction, and the hydrogen partial pressure is 7.1 MPa.

Example 3

Only the catalyst 2-A in Example 1 was replaced with a catalyst 2-B, and the usage amount of the catalyst 2-B accounted for 8% of the added cellulose, and the others were the same as those in Example 1.

Example 4

Only the catalyst 2-A in Example 1 was replaced with a catalyst 2-C, and the usage amount of the catalyst 2-C accounted for 4% of the added cellulose, and the others were the same as those in Example 1.

Example 5

The catalyst CAT-A in Example 1 was replaced with CAT-B, and the others were the same as those in Example 1.

Comparative Example 1

Take a total of 2g of a mixture of three plastics of 50wt% HDPE, 30wt% PET and 20wt% PS, pulverize 2g of straw to a powder with a length of about 10mm, and add them to the slurry bed catalytic cracking reactor. Catalytic cracking reaction is carried out under the catalysis of HY molecular sieve, the addition amount of HY molecular sieve is 12% of the total mass of waste plastic and cellulose, and the reaction conditions of catalytic cracking reaction are as follows: the reaction temperature is 520 ℃, the reaction time is 70 minutes, and the stirring rate is 430 r/min, in the reaction, hydrogen needs to be introduced into the slurry bed catalytic cracking reactor, and the hydrogen partial pressure is 5.6 MPa, and the product after the reaction is separated to obtain a liquid product 1, a gas and a waste residue; the liquid product 1 is cooled. After reaching room temperature, successively feed tetrahydrofuran and cyclohexane solvent for extraction, respectively obtain the tetrahydrofuran solution containing liquid product 2, the cyclohexane solution containing liquid product 3 and the remaining liquid product IV, and the tetrahydrofuran solution containing liquid product 2 is obtained respectively. , the cyclohexane solution containing the liquid product 3 is distilled to remove the solvent, and the liquid product 2 and the liquid product 3 are obtained.

The distribution and conversion ratio of the products obtained in Table 1 Examples 1-5 and Comparative Example 1 are compared

Numbering Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Product distribution, wt% gas 8.9 8.2 9.0 9.5 10.2 13.5 cyclohexane solubles 30.6 34.8 32.6 33.5 29.3 19.8 Tetrahydrofuran solubles 50.7 46.9 49.6 45.7 39.1 24.2 The residue 9.8 10.1 8.8 11.3 21.4 42.5 Conversion rate, wt% 90.2 89.9 91.2 88.7 78.6 57.5

Claims (20)

1. the application of a catalytic cracking catalyst in processing cellulose and waste plastics technology, comprises the following steps: (1) waste plastics are added in catalytic reactor A, carry out catalytic cracking reaction under the effect of catalyst 1, and the cracked product of gained obtains liquid product I, gas I and insoluble matter I through separation; (2) the liquid product I of step (1) gained is passed into tetrahydrofuran, cyclohexane solvent successively after cooling and extracts, respectively obtains the tetrahydrofuran solution containing liquid product II, the cyclohexane solution containing liquid product III and the remaining liquid product IV; (3) the tetrahydrofuran solution containing liquid product II obtained in step (2) and the cyclohexane solution containing liquid product III are respectively subjected to distillation treatment to remove solvent, respectively obtained liquid product II and liquid product III; (4) adding cellulose and the liquid product II of step (3) gained in catalytic reactor B, carry out catalytic reaction under the effect of catalyst 2, obtain liquid product i, gas i and insoluble matter i through separation; (5) the liquid product i obtained in step (4) is cooled and successively passed into tetrahydrofuran and cyclohexane solvent for extraction to obtain respectively the tetrahydrofuran solution containing liquid product ii, the cyclohexane solution containing liquid product iii and the remaining liquid product iv, which is treated by distillation to remove the solvent to obtain liquid product ii and liquid product iii; (6) the remaining liquid product IV obtained in step (2) and step (5), the remaining liquid product iv and the insoluble matter I and insoluble matter i obtained in step (1) and step (4), respectively, are added to the catalyst In the reactor C, a deep catalytic cracking reaction is carried out under the action of the catalyst 3, and the resulting cracked product is separated to obtain a liquid product V, a gas V and an insoluble matter V; (7) the liquid product V of step (6) gained is passed into tetrahydrofuran, cyclohexane solvent successively after cooling and extracts, respectively obtains the tetrahydrofuran solution containing liquid product VI, the cyclohexane solution containing liquid product VII and the remaining Liquid product VIII, treated by distillation to remove solvent, to obtain liquid product VI and liquid product VII; Wherein, the catalyst 1 is a HY molecular sieve catalyst, the catalyst 3 is a HZSM-5 and HY composite molecular sieve catalyst, and the catalyst 2 is a catalytic cracking catalyst. Molybdenum alkanoate and/or iron naphthenate are the active components, based on the weight of the catalytic cracking catalyst, kaolin or montmorillonite accounts for 37.5%-87.5%, molybdenum naphthenate and/or iron naphthenate accounts for 12.5%- 62.5%. 2. according to the application described in claim 1, it is characterized in that in the described catalytic cracking catalyst, in the weight of catalytic cracking catalyst, kaolin or montmorillonite account for 50%-70%, molybdenum naphthenate and/or naphthenic acid Ferric acid accounts for 30%-50%. 3. according to the described application of claim 1, it is characterized in that the preparation method of described catalytic cracking catalyst comprises the following steps: 1) calcining kaolin or montmorillonite raw powder at 400-550℃ for 2-10h; 2) adding the kaolin or montmorillonite obtained after step 1) roasting into the reactor, then adding the dilute acid dipping solution of iron naphthenate and/or platinum naphthenate in the reactor to impregnate; 3) drying the reacted material in step 2) at 100-150° C. for 2-6 hours to prepare a catalytic cracking catalyst. 4. according to the described application of claim 3, it is characterized in that step 1) adopts the heating rate of 5-10 ℃/min to heat kaolin or montmorillonite former powder to roasting temperature. 5. The application according to claim 3, characterized in that in step 2) stirring is performed while dipping, the stirring rate is 100-150r/min, and the stirring time is 0.5-2.5h. 6. according to the application described in claim 3, it is characterized in that the dilute acid described in step 2) is at least one in hydrochloric acid, nitric acid and acetic acid; In dilute acid dipping solution, the mass fraction of dilute acid is 5%-20% %; the impregnation in step 2) adopts a supersaturated impregnation method or a saturated impregnation method. 7. The application according to claim 1 is characterized in that the usage amount of the catalyst 1 described in the step (1) is 5%-20% of the total mass of the added waste plastic; the catalytic cracking reaction described in the step (1) The reaction conditions are as follows: the reaction temperature is 350-550 ℃; the reaction time is 30-150 minutes; the reaction is carried out under stirring, and the stirring rate is 350-600 rpm; 4MPa. 8. The application according to claim 7, characterized in that the usage amount of the catalyst 1 in step (1) is 10%-15% of the total mass of the added waste plastics. 9. according to the application described in claim 7, it is characterized in that the reaction condition of the described catalytic cracking reaction of step (1) is as follows: temperature of reaction is 400-480 ℃; reaction time is 45-120 minutes; reaction is carried out under stirring , the stirring speed is 400-500 rev/min; hydrogen needs to be introduced into the reaction, and the hydrogen partial pressure is 2.5-3.5MPa. 10. The application according to claim 1 is characterized in that the usage amount of the catalyst 2 described in step (4) accounts for 2.5%-15% of the cellulose mass; step (4) adds the catalyst 2 while adding the mass content to Sulfur is calculated as 4000-8000ppm of sulfur source as vulcanizing agent, the mass ratio of sulfur content to the total content of iron and molybdenum is 5-7:1, the selected sulfur source is: one or more of sulfur, hydrogen sulfide and carbon disulfide kind. 11. The application according to claim 1, wherein the reaction conditions of the catalytic reaction described in step (4) are as follows: the reaction temperature is 400-600 °C; the reaction time is 30-100 minutes; the reaction is carried out under stirring, The stirring speed is 350-600 rev/min; hydrogen needs to be introduced into the reaction, and the hydrogen partial pressure is 4-8MPa. 12. The application according to claim 11 is characterized in that the reaction conditions of the catalytic reaction described in step (4) are as follows: the reaction temperature is 450-550 ° C; the reaction time is 60-100 minutes; the reaction is carried out under stirring, The stirring speed is 400-500 rev/min; hydrogen needs to be introduced into the reaction, and the hydrogen partial pressure is 5-6.5MPa. 13. The application according to claim 11 or 12, wherein the reaction temperature of the catalytic reaction described in step (4) is at least 50°C higher than the reaction temperature of the catalytic reaction described in step (1), and the reaction temperature of the catalytic reaction described in step (4) is at least 50°C higher. The hydrogen partial pressure of the catalytic reaction is at least 2MPa higher than the hydrogen partial pressure of the catalytic cracking reaction described in step (1). 14. The application according to claim 1, wherein the catalyst 3 described in step (6) is a HZSM-5 and HY composite molecular sieve catalyst modified by phosphorus and tungsten, wherein the mass content of phosphorus is 1.5%-7.0% , the mass content of tungsten is 0.3%-2.0%. 15. The application according to claim 1 or 14, characterized in that the usage amount of catalyst 3 is 5%-18% of the total mass of all added reaction materials added to catalytic reactor C in step (6). 16. The application according to claim 15, characterized in that the usage amount of catalyst 3 is 8%-13% of the total mass of all added reaction materials added to catalytic reactor C in step (6). 17. according to the described application of claim 14, it is characterized in that the preparation method of the catalyst 3 described in step (6) is: HZSM-5 and HY are mixed with mass ratio 0.5-2:1 to obtain composite molecular sieve, with mass concentration Impregnate composite molecular sieve with 10%-20% phosphoric acid solution, the mass ratio of phosphoric acid solution and composite molecular sieve is 0.5-1:1, dry at 80-110 ℃ for 1-3 hours, and then use the mass concentration of 1%-2% The sodium tungstate solution is impregnated with composite molecular sieve, the mass ratio of sodium tungstate solution and composite molecular sieve is 0.5-1:1, dried at 80-110 °C for 5-10 hours, and then calcined at 330-380 °C for 4-7 hours , and the catalyst 3 was obtained after molding. 18. application according to claim 1 is characterized in that the reaction condition of the described deep catalytic cracking reaction of step (6) is: reaction temperature is 400-700 ℃; reaction time is 60-150 minutes; reaction is carried out under stirring , the stirring speed is 350-600 rev/min; hydrogen needs to be introduced into the reaction, and the hydrogen partial pressure is 5-10MPa. 19. The application according to claim 18, wherein the reaction temperature of the deep catalytic cracking reaction in step (6) is 500-600°C. 20. according to the described application of claim 18 or 19, it is characterized in that the reaction temperature of the described deep catalytic cracking reaction of step (6) is at least 50 ℃ higher than the reaction temperature of the described catalytic reaction of step (4), step (6) ) The hydrogen partial pressure of the deep catalytic cracking reaction is at least 1MPa higher than the hydrogen partial pressure of the catalytic reaction in step (4).