CN1025865C - Reforming catalyst containing beta zeolite - Google Patents

Abstract

The present invention relates to a reforming catalyst containing beta zeolite, which contains 0.04-2.0 wt% of a VIII group noble metal or 0.04-2.0 wt% of a VIII group noble metal and 0.04-2.7 wt% of a VIIB group metal or 0.04-1.8 wt% of an IVA group metal and the balance carrier, wherein the carrier contains potassium and phosphorus-containing beta zeolite with a silicon-aluminum ratio greater than 40 and alumina. The catalyst has higher activity and aromatization selectivity than industrial platinum-rhenium and platinum-tin catalysts, and has better resistance to sulfur poisoning.

Description

The invention relates to a reforming catalyst supported by modified beta zeolite and alumina.

Catalytic reforming is an important process in oil refining and petrochemical industries. It can not only provide high-octane gasoline, produce aromatics and other chemical raw materials, but also produce hydrogen by-product. In recent years, the requirements for environmental protection at home and abroad have become increasingly stringent, and motor gasoline is gradually developing towards unleaded. In addition, with the development of the chemical industry and chemical fiber industry, it is extremely urgent to increase the production of aromatics. Therefore, it is necessary to continuously improve the existing reforming catalysts or develop new catalysts to meet the requirements for increasing the production of aromatics and producing high-octane gasoline components. .

At present, the catalysts widely used in the catalytic reforming process are platinum-rhenium series and platinum-tin series catalysts, and their supports are all ν-Al ₂ O ₃ . The metal components in the catalyst provide the function of hydrodehydrogenation, and the support provides the acidic function. The common weakness of bifunctional catalysts is poor aromatization activity for low-carbon paraffins, especially for the conversion of C ₆ paraffins.

In order to further improve the activity and selectivity of reforming catalysts, research on reforming catalysts containing molecular sieves has been carried out both at home and abroad. Chevron has developed a reforming catalyst loaded with platinum L-type molecular sieves (GB Z114150A, USP4448841). It has good activity and selectivity for aromatization of low-carbon paraffins, but poor sulfur resistance and unsatisfactory stability.

Aiming at the problems existing in the prior art, the object of the present invention is to provide a reforming catalyst with high aromatization activity and good sulfur resistance.

The reforming catalyst provided by the invention contains 0.04 to 2.0 wt%, preferably 0.3 to 0.8 wt% of a Group VIII noble metal and 0.04 to 2.7 wt%, preferably 0.1 to 1.4 wt% of a Group VIIB metal or 0.04 to 1.8 wt% %, preferably 0.1 to 0.8 wt% of a Group IVA metal, and the balance carrier; the carrier contains (based on the weight of the carrier) 20 to 80 wt%, preferably 30 to 70 wt% modified beta zeolite and 80 to 20 wt% % by weight, preferably 70 to 30% by weight of alumina; modified zeolite beta is silicon containing 0.5 to 2.5% by weight, preferably 1.0 to 2.0% by weight of potassium and 0.01 to 0.5% by weight, preferably 0.03 to 0.3% by weight of phosphorus Beta zeolite with aluminum ratio greater than 40, preferably 50-100.

The catalyst provided by the present invention can also be composed of 0.04 to 2.0 wt%, preferably 0.3 to 0.8 wt% of a Group VIII noble metal and the rest of the carrier, and the carrier contains (based on the weight of the carrier) 45 to 20 wt% of modified beta zeolite and 55 to 80% by weight of alumina, the modified zeolite beta contains (based on the weight of the zeolite) 0.5 to 2.5% by weight, preferably 1.0 to 2.0% by weight of potassium and 0.01 to 0.5% by weight, preferably 0.03 to 0.3% by weight Beta zeolite with silicon-aluminum ratio of % phosphorus greater than 40, preferably 50-100.

Said noble metal of group VIII is preferably platinum, metal of group VIIB is preferably rhenium, metal of group IVA is preferably tin, aluminum oxide can be η-Al ₂ O ₃ or ν-Al ₂ O ₃ , preferably ν- Al ₂ O ₃ , the catalyst can also contain 0.1-2.0 wt% of halogen, the halogen can be chlorine or fluorine, preferably chlorine, when the catalyst contains rhenium, the catalyst can also contain 0.01-0.5 wt%, preferably 0.02-0.24 wt% sulfur.

Catalyst provided by the invention can be made by following method:

Method I:

1, according to the method among CN1043450A, prepare potassium-containing 0.5～2.5 weight % by Naβ zeolite, preferably 1.0～2.0 weight % and phosphorus 0.01～0.5 weight %, preferably 0.03～0.3 weight %, the silicon-alumina ratio greater than 40 beta zeolite, It is only necessary that the silicon-aluminum ratio of the Hβ zeolite obtained after dealumination in this method is greater than 40.

2. According to the conventional preparation method of the reforming catalyst, the product of step I is loaded with 0.2 to 1.5% by weight, preferably 0.2 to 1.4% by weight of a Group VIIB metal or 0.2 to 1.0% by weight, preferably 0.2 to 0.8% by weight A Group IVA metal.

3. The solution of the resultant in the first step and a diacid-based tetraammine compound of Group VIII noble metal at an appropriate concentration shall be in a liquid-solid ratio of 20-2:1, preferably 5-3:1 (weight ratio) Mix evenly, react at 15-80°C for 1-72 hours, the concentration of the noble metal compound solution is such that the loading of the noble metal on the zeolite is 0.2-2.0% by weight, preferably 0.3-0.8% by weight, then dry, 200-500 °C, preferably at 260-400 °C for 2-5 hours and then reduced.

4. The product obtained in the second step is reacted with the solution of the Group VIII noble metal compound according to the method of the third step, dried, roasted and reduced.

5. According to the conventional preparation method of the reforming catalyst, prepare and support 0.2 to 2.0 wt. % of a Group VIII noble metal, preferably 0.2 to 0.8 wt. % and 0.2 to 3.0 wt. % of a VIIB Group metal, preferably 0.2 to 1.4 wt. % or 0.2-2.0% by weight of a Group IVA metal, preferably 0.2-0.8% by weight, or 0.2-3.0% by weight of a Group VIIB metal, preferably 0.2-1.4% by weight or 0.2-2.0% by weight of a Group IVA metal , preferably 0.2 to 0.8% by weight of alumina.

6. Combine the product from step 3 with the product from step 5, or the product from step 4 containing Group VIIB metals, in a ratio of 2 to 8:8 to 2, preferably 3 to 7:7 to 3 (weight ratio) The resultant of Step 5 containing Group VIIB metal or alumina, or the product of Step 4 containing Group IVA metal and the result of Step 5 containing Group IVA metal or alumina, or by 4.5-2 : The ratio of 5.5 to 8 (weight ratio) mixes the product obtained in step 3 with alumina evenly, and shapes it.

Method II:

1, according to the method among CN1043450A, prepare potassium-containing 0.5～2.5 weight % by Naβ zeolite, preferably 1.0～2.0 weight % and phosphorus 0.01～0.5 weight %, preferably 0.03～0.3 weight %, the silicon-alumina ratio greater than 40 beta zeolite, It is only necessary that the silicon-aluminum ratio of the Hβ zeolite obtained after dealumination in this method is greater than 40.

2. Carry 0.2 to 1.5% by weight, preferably 0.2 to 1.4% by weight, of a Group VIIB metal or 0.2 to 1.0% by weight, preferably 0.2 to 0.8% by weight, of the beta zeolite obtained in step 1 according to the conventional preparation method for reforming catalysts % A Group IVA metal.

3. According to the conventional preparation method for reforming catalysts, prepare 0.2-3.0% by weight of a Group VIIB metal, preferably 0.2-1.4% by weight or 0.2-2.0% by weight of a Group IVA metal, preferably 0.2-0.8% by weight Alumina precursor.

4. Mix the product from step 1 with the product from step 3 in a ratio of 2 to 8:8 to 2, preferably 3 to 7:7 to 3 (weight ratio), or mix the product from step 2 containing Group VIIB metals admixing the result with a Group VIIB-containing step 3 result or an alumina precursor, or admixing a Group IVA metal-containing step 2 result with a Group IVA metal-containing step 3 result or an alumina precursor; or According to the ratio of 4.5～2:5.5～8 (weight ratio), the product obtained in the first step is mixed with the alumina precursor. The solution of the tetraammine compound is mixed evenly at a liquid-solid ratio of 15～1:1, preferably 4～2:1 (weight ratio), and reacted for 1～72 hours at 15～80°C. The concentration of the noble metal compound solution is in the range of Make the noble metal content on the obtained catalyst be 0.04-2.0% by weight, preferably 0.3-0.8% by weight, then dry, calcinate at 200-500°C, preferably 260-400°C for 2-5 hours, and reduce.

In the 2nd and 5th steps of said method I and the 2nd and 3rd steps of method II, when beta zeolite or alumina is loaded with rhenium, sulfuration treatment should be carried out according to the conventional preparation method of rhenium-containing reforming catalysts , the sulfur content of the product obtained in this step depends on the content of its rhenium metal, which can be 0.01 to 0.5% by weight, preferably 0.02 to 0.24% by weight. The said alumina and alumina precursors can be commonly used in reforming catalysts Prepared alumina and alumina precursors, alumina can be η- or ν-Al ₂ O ₃ , the alumina precursor can be aluminum hydroxide, and the reduction step is carried out according to the conventional reduction method in the preparation of reforming catalysts of. Said molding step is carried out according to the conventional molding method in the preparation of reforming catalyst, which can be extrusion molding, tablet molding and drop ball molding and so on. The calcining process after shaping in the 4th step of the method II is carried out according to the conventional method in the preparation of reforming catalysts.

Compared with the current industrial platinum-rhenium and platinum-tin catalysts, the catalyst provided by the invention has higher aromatization activity and better resistance to sulfur poisoning.

The present invention will be further described below by embodiment.

Example 1

1, prepare the modified beta zeolite containing potassium 1.8 weight % and phosphorus 0.08 weight % by the method of example 1 among CN1043450A, the Pt (NH ₃ ) that the modified beta zeolite and concentration are 2 mg/ml (in Pt) ₄ The Cl ₂ solution was mixed evenly at a liquid-solid ratio of 3:1, soaked at room temperature for 24 hours, dried, calcined at 300°C for 2 hours, and reduced with hydrogen at 500°C for 4 hours to obtain a modified β Zeolite, recorded as Ptβ-1.

2. Take CB-6 platinum-rhenium catalyst (containing 0.3% by weight of platinum, 0.3% by weight of rhenium, 1.1% by weight of chlorine and the balance ν-Al ₂ O ₃ , produced by Changling Oil Refinery) and reduce it with hydrogen at 500°C for 4 hours , and then sulfide with hydrogen sulfide until the sulfur content on the catalyst is 0.05% by weight.

3. Grind the product from step 1 and step 2 to below 100 mesh respectively, and mix them in a ratio of 1:1 (weight ratio). Uniform, tablet molding, promptly get the catalyst containing platinum 0.45 weight %, rhenium 0.15 weight % and balance carrier, carrier contains (based on carrier weight) 50 weight % potassium 1.8 weight % and phosphorus 0.08 weight % (based on Beta zeolite weight basis) modified zeolite beta and 50% by weight of ν-alumina, the catalyst is designated as A.

Example 2

1. Same as step 1 of Example 1.

2. Take 3861-I industrial platinum-tin catalyst (produced by No. 3 Petroleum Plant, containing 0.37% by weight of platinum, 0.3% by weight of tin, 1.1% by weight of chlorine and the balance of alumina) and reduce it with hydrogen at 500°C.

3. Grind the products obtained in step 1 and step 2 to below 100 mesh respectively, then mix them evenly in a ratio of 1:2 (weight ratio), and press them into tablets to obtain a 0.45% by weight platinum and 0.2% by weight tin Catalyst B, the carrier contains 33% by weight of modified zeolite beta and 67% by weight of alumina.

Example 3

1. Same as step 1 of Example 1.

2. Take SB aluminum hydroxide (imported from West Germany) and HReO ₄ solution with a concentration of 2.5 mg/ml (calculated as Re) and mix them at a liquid-solid ratio (weight ratio) of 2:1, soak at room temperature for 24 hours, and filter , washed, calcined at 500°C for 4 hours, reduced with hydrogen at 500°C for 4 hours, sulfurized with H ₂ S to a sulfur content of 0.08% by weight (based on the weight of Al ₂ O ₃ ), and 0.5% by weight of rhenium can be obtained. % (based on the weight of Al ₂ O ₃ ) of alumina.

3. Grind the resultant from step 1 and step 2 to less than 100 mesh, then mix it uniformly in a ratio of 3:1 (weight ratio), and press it into a tablet to obtain a catalyst containing 0.45% by weight of platinum and 0.13% by weight of rhenium C, the carrier contains 75% by weight of modified β zeolite and 25% by weight of alumina.

Example 4

1. Same as step 1 of Example 1.

2. Take aluminum hydroxide containing 0.5% by weight of Sn (based on the weight of alumina) (produced by Fushun Petroleum No. % of alumina.

3. Grind the products of step 1 and step 2 to below 100 mesh respectively, then mix them uniformly in a ratio of 3:1 (weight ratio), and press them into tablets to obtain a catalyst containing 0.45% by weight of platinum and 0.13% by weight of tin D, the carrier contains 75% by weight of modified zeolite beta and 25% by weight of alumina.

Example 5

1. Reflux Naβ (produced by Fushun Petroleum No. 3 Plant) with a silicon-aluminum ratio of 29 and 0.5N HCl (analytically pure) at 100°C for 1.5 hours, and the liquid-solid ratio is 4:1. After filtration, wash with deionized water until the pH of the filtrate 6 to 7, then dried at 110°C for 2 hours, and calcined at 500°C for 2 hours to obtain Hβ zeolite with a silicon-aluminum ratio of 66.

According to the method of Example 1 in CN1043450A, the above-mentioned Hβ zeolite is modified to obtain the modified β zeolite containing 1.8% by weight of potassium and 0.08% by weight of phosphorus.

Mix the modified β zeolite with the Pt(NH ₃ ) ₄ Cl ₂ solution with a concentration of 2 mg/ml (calculated as Pt) according to the liquid-solid ratio of 3:1, soak at room temperature for 24 hours, dry, and roast at 300°C After 3 hours, it was reduced with hydrogen at 500°C for 4 hours to obtain a modified zeolite beta containing 0.6% by weight of platinum.

2. The ν-Al ₂ O ₃ containing Sn0.5 weight % (identical to the 2nd step gain of Example 4) and the 1st step gained product are by Ptβ: tin-containing Al ₂ O ₃ weight ratio is the ratio of 3:7 Mix evenly, grind, and press into tablets to obtain catalyst E. The catalyst contains 0.2% by weight of Pt, 0.35% by weight of tin and the rest of the carrier, and the carrier contains 30% by weight of modified β zeolite and 70% by weight of ν-Al ₂ O ₃ %.

Example 6

1, the modified beta zeolite (same as example 5) and tin-containing aluminum hydroxide (same as example 4) are mixed uniformly in a ratio of 7:3 (weight ratio), and 0.4 milliliters of acetic acid (chemically pure) is added per 10 grams of material , Beijing Chemical Plant) and 6 ml of deionized water were added with acetic acid and deionized water, kneaded and extruded, dried at 120°C for 5 hours, and roasted at 550°C for 3 hours.

2. Mix the product obtained in step 1 with a Pt(NH ₃ ) ₄ Cl ₂ solution with a concentration of 2.5 mg/ml (calculated as Pt) in a ratio of 4:1 (weight ratio), soak at room temperature for 28 hours, and dry Calcined at 320°C for 3 hours and reduced with hydrogen at 500°C for 4 hours to obtain catalyst F containing 0.15% by weight of tin and 1.0% by weight of platinum.

Mix the product obtained in step 1 with a Pt(NH ₃ ) ₄ Cl ₂ solution with a concentration of 2.5 mg/ml (calculated as Pt) in a ratio of 2:1 (weight ratio), react at 40°C for 18 hours, and dry. Calcined at 400°C for 3 hours and reduced with hydrogen at 540°C for 4 hours to obtain catalyst G containing 0.15% by weight of tin and 0.5% by weight of platinum.

Example 7

1. Same as step 1 of Example 5.

2. Mix the product obtained in step 1 with SB alumina (imported from West Germany) at a ratio of 3:7 (weight ratio), grind, and press into tablets to obtain catalyst H containing 0.18% by weight of platinum.

3. Mix the product obtained in step 1 with SB alumina in a ratio of 4:6 (weight ratio), grind, and press into tablets to obtain Catalyst I with platinum 0.24 wt%.

4. Mix the product obtained in step 1 with SB alumina in a ratio of 1:1 (weight ratio), grind, and press into tablets to obtain a comparative catalyst containing 0.3% by weight of platinum, which is designated as comparative-1.

Example 8

1, get the Hβ zeolite obtained in the 1st step of example 5, by the method for example 3 among CN1043450A, make the modified β zeolite that the silicon-aluminum ratio of potassium 1.5 weight % and phosphorus 0.12 weight % is 66, the modified β zeolite Mix well with Pt(NH ₃ ) ₄ Cl ₂ solution with a concentration of 2 mg/ml (calculated as Pt) at a ratio of 6:1 (weight ratio), react at 60°C for 10 hours, and slowly evaporate to dryness at 100°C while stirring solution, roasted at 250°C for 5 hours, and reduced at 500°C for 4 hours to obtain zeolite beta containing 1.2 wt% platinum.

2. Prepare the aluminum oxide containing rhenium 1.5% by weight according to the second step of example 3, except that the concentration of _HReO solution is 3.75 mg/ml (calculated as Re), and the liquid-solid ratio is 4:1 (weight ratio).

3. Mix the products obtained in step 1 and step 2 uniformly in a ratio of 4:6 (weight ratio), grind them, and press them into tablets to obtain a catalyst J containing 0.48% by weight of platinum and 0.9% by weight of rhenium.

Example 9

1. Prepare the modified zeolite beta containing potassium 1.8 weight and phosphorus 0.08 weight by the method in the first step of example 5 (only the silicon-aluminum ratio of H beta zeolite is 60), and then the beta zeolite and concentration are 1.5 mg/ml The Pt(NH ₃ ) ₄ Cl ₂ solution (calculated as Pt) was uniformly mixed at a liquid-solid ratio of 2:1 (weight ratio), reacted at room temperature for 30 hours, then evaporated to dryness at 100°C, and calcined at 320°C for 3 hours. Reduction at 500°C yields zeolite beta containing 0.3% by weight of platinum, which is called Ptbeta-2 zeolite.

2. Mix the Ptβ zeolite obtained in the first step with the CB-6 catalyst in a ratio of 1:1 (weight ratio), grind, and press into tablets to obtain a catalyst K containing 0.3% by weight of platinum and 0.15% by weight of rhenium.

Example 10

The dehydrocyclization activity and selectivity of the catalyst were evaluated on a pressurized continuous micro-reactor device. The reaction conditions were: the reaction raw material was n-hexane, the reaction temperature was 480°C, the reaction pressure was 9.81×10 ⁵ Pa, and the weight space velocity was 13.6 Hour ⁻¹ , the reaction results are shown in Table 1.

It can be seen from Table 1 that the aromatization activity of the catalyst provided by the present invention is higher than that of industrial platinum-rhenium and platinum-tin catalysts, and its selectivity is also greatly improved.

Example 11

The anti-sulfur poisoning performance of catalysts A and B was evaluated on an atmospheric pulse microreactor, and compared with industrial platinum-rhenium catalyst CB-6, platinum-tin catalyst 3861-I and platinum-loaded L zeolite. Reaction conditions: thiophene (Beijing Chemical plant, chemically pure) is a poison, the reaction raw material is n-hexane, the reaction temperature is 490 °C, the hydrogen flow rate is 60 ml/min, the catalyst loading is 0.1 g, and 2 microliters of thiophene is injected on the catalyst to poison the metal center , and then purged with hydrogen to remove the reversibly adsorbed sulfur. The reaction results are shown in Table 2, which lists the activity and selectivity of the catalyst before sulfur injection, after sulfur injection and after purging with hydrogen for 70 minutes.

The platinum-loaded L zeolite catalyst was prepared according to the literature (Acta Petroleum Sinica, 4(4), 15, 1988), and contained 0.6 wt% platinum, which was recorded as PtL catalyst.

It can be seen from Table 2 that after sulfur injection, the activity and aromatics yield of catalysts A and B decreased slightly, and their activity and aromatics selectivity recovered well after hydrogen purging, while the sulfur poisoning resistance of PtL catalyst was poor .

Example 12

The dehydrogenation isomerization activity and selectivity of the catalyst were evaluated on the normal pressure pulse micro-reactor device. The reaction conditions were: the raw material was methylcyclopentane, the temperature was 490° C., the catalyst device was 0.1 g, and the hydrogen flow rate was 60 ml/min. The feed volume was 2 microliters. At the same time, the anti-sulfur ability of the catalyst was also evaluated, the poison was thiophene, and the injection volume was 2 microliters. The reaction results are shown in Table 3.

It can be seen from the table that the dehydrogenation isomerization activity of the catalyst provided by the invention is higher than that of industrial platinum-rhenium and platinum-tin catalysts, and the aromatization activity tends to increase after sulfur poisoning.

Example 13

Evaluate catalyst dehydrocyclization activity and selectivity under the same condition as example 10, the results are shown in Table 4, as can be seen from the table, the dehydrocyclization activity of catalyst of the present invention is all higher than platinum-loaded beta zeolite; Its selectivity And stability has also been improved.

Example 14

The sulfur resistance of the catalyst was evaluated under the same conditions as in Example 11. The reaction results are shown in Table 5. It can be seen from Table 5 that the catalyst has better sulfur resistance, and its activity and selectivity are higher than those of industrial platinum-rhenium and platinum-tin catalysts.

Example 15

The dehydroisomerization activity of the catalyst was evaluated under the same conditions as in Example 12. The reaction results are shown in Table 6. It can be seen from Table 6 that the activity of the catalyst provided by the present invention is higher than that of industrial platinum-plutonium and platinum-tin catalysts, and the selectivity of aromatics tends to increase after sulfur poisoning.

Example 16

Evaluate the dehydrocyclization activity and selectivity of catalyst E, F, G, H and I under the same raw material and pressure condition as example 10, and compare with CB-6 and 3861-I catalyst, its result is shown in Table 7 .

It can be seen from the table that the catalyst provided by the present invention has higher aromatics yield, conversion rate and aromatics selectivity than the platinum-rhenium and platinum-tin catalysts. The aromatics selectivity of Catalysts H and I was comparable to that of Comparative-1 catalyst, although the content of Ptβ in Comparative-1 catalyst was higher than that of Catalysts H and I.

Example 17

The activity of Catalyst K was evaluated under the same conditions as in Example 10 and compared with CB-6 and Ptβ-2. The results are shown in Table 8.

It can be seen from Table 8 that the catalyst provided by the present invention has higher aromatics yield, aromatics selectivity and total conversion than CB-6 and Ptβ-2 catalysts, and its activity stability is also better.

Table 1

Reaction time

Reminder Hour 0.5 1 3 5 7

chemical reaction performance

agent

Aromatics yield, weight % 11.64 11.71 11.85 11.38 11.87

A Total conversion rate, weight % 85.38 85.37 84.06 83.97 83.86

Aromatics selectivity, % 13.6 13.7 14.1 13.6 14.2

Aromatics yield, wt% 3.13 2.73 2.84 2.86

CB-6 total conversion rate, weight % 54.83 55.23 56.63 57.03

Aromatics selectivity, % 5.7 4.9 5.0 5.0

Aromatics yield, wt% 8.90 9.22 9.75 9.14 8.97

B Total conversion rate, weight % 83.4 83.13 82.53 82.33 81.45

Aromatics selectivity, % 10.7 11.1 11.8 11.1 11.0

Aromatics yield, weight % 0,53 0.61 0.72 0.62

3861-1 Total conversion rate, weight % 31.49 36.61 38.27 37.53

Aromatics selectivity, % 1.7 1.7 1.9 1.7

Table 2

Aromatics yield Total conversion Aromatics selection Purging after selection

Catalyst Selective recovery

Weight% Weight% Property% Rate%

Before sulfur injection 32.46 98.26 33.0

A After sulfur injection 15.03 81.83 18.4

After purge 29.06 89.14 32.6 98.8

Before sulfur injection 16.21 66.61 24.3

CB-6 After sulfur injection 7.42 50.82 14.6

After purge 15.51 69.33 22.4 92.2

Before sulfur injection 31.05 90.25 34.4

B After sulfur injection 11.66 80.14 14.5

After purge 29.69 87.60 33.9 98.5

Before sulfur injection 16.70 70.30 23.8

3861-Ⅰ After sulfur injection 4.56 44.08 10.3

After purge 12.27 61.79 19.9 83.6

Before sulfur injection 62.5 99.1

63.1

After sulfur injection 7.5 30.7

24.4

PtL* After purge 17.2 52.0 52.4

** 33.1

*Note: The reaction temperature is 500°C, and the injection volume of thiophene is 1 microliter.

** Note: Catalyst activity and selectivity after purging for 80 minutes.

table 3

Aromatics yield Total conversion Aromatics selectivity

catalyst

Weight% Weight% %

Before sulfur injection 71.48 99.11 72.1

A

After sulfur injection 76.05 98.21 77.4

Before sulfur injection 48.99 71.51 68.5

CB-6

After sulfur injection 50.19 65.05 77.2

Before sulfur injection 74.91 99.19 75.5

B

After sulfur injection 78.46 98.26 79.8

Before sulfur injection 47.53 74.65 63.7

3861-Ⅰ

After sulfur injection 49.08 67.02 73.2

Table 4

Reaction time,

Reminder Hour 0.5 1 3 5 7

chemical reaction performance

agent

Aromatics yield, wt% 10.14 9.52 9.51 8.71 8.14

P+β-1 total conversion rate, weight % 84.63 83.60 82.30 80.38 80.31

Aromatics selectivity, % 12.0 11.4 11.6 10.8 10.1

Aromatics yield, wt% 14.41 13.94 13.78 13.32 12.51

C Total conversion rate, weight % 85.72 85.71 84.93 84.28 83.60

Aromatics selectivity, % 16.8 16.3 16.2 15.8 14.9

Aromatics yield, wt% 10.68 10.69 10.18 9.91 10.47

D Total conversion rate, weight % 83.79 84.47 83.33 83.30 83.59

Aromatics selectivity, % 12.7 12.7 12.2 11.8 12.5

table 5

Aromatics yield Total conversion Aromatics selectivity

catalyst

Weight% Weight% %

Before sulfur injection 33.59 94.93 35.4

C After sulfur injection 13.74 77.68 17.7

After purge 26.21 85.15 30.8

Before sulfur injection 16.21 66.61 24.3

CB-6 After sulfur injection 7.42 50.82 14.6

After purge 15.51 69.33 22.4

Before sulfur injection 33.77 91.88 36.8

D After sulfur flow 10.63 74.07 14.4

After purge 24.56 85.78 28.6

Before sulfur injection 16.70 70.30 23.8

3861-Ⅰ After sulfur injection 4.56 44.08 10.3

After purge 12.27 61.79 19.9

Table 6

Aromatics yield Total conversion Aromatics selectivity

catalyst

Weight% Weight% %

Before sulfur injection 52.02 97.07 53.6

C

After sulfur injection 75.16 97.48 77.1

Before sulfur injection 48.99 71.51 68.5

CB-6

After sulfur injection 50.19 65.05 77.2

Before sulfur injection 66.85 99.22 67.4

D.

After sulfur injection 75.02 96.98 77.4

Before sulfur injection 47.53 74.65 63.7

3861-I

After sulfur injection 49.08 67.02 73.2

Table 7

Catalyst Reaction Weight Space Velocity Aromatics Yield Total Conversion Aromatics

Catalyst Platinum Content Temperature Selectivity

Weight % ℃ Hour Weight % Weight %

E 0.2 480 5.3 11.13 87.22 12.8

F 1.0 480 13.6 8.75 82.11 10.7

500 13.6 13.86 84.87 16.3

G 0.5 480 13.6 4.28 72.1 5.9

500 13.6 5.87 75.92 7.7

520 13.6 8.11 78.81 10.3

H 0.18 480 5.3 16.52 93.0 17.7

I 0.24 480 7.0 15.47 88.6 17.5

CB-6 0.30 480 6.6 4.39 70.82 6.2

480 13.2 2.82 57.59 4.92

3861-I 0.37 480 13.6 0.61 36.61 1.7

Contrast-1 0.3 480 8.8 14.3 84.1 17.0

Table 8

Reaction time,

Reminder Hour 0.5 1 3 5 7 9

chemical reaction performance

agent

Aromatics yield, wt% 12.91 9.89 12.21 10.19 10.77 11.13

K Total conversion rate, weight % 83.05 83.2 83.27 83.13 83.01 82.7

Aromatics selectivity, % 15.5 11.9 14.7 12.3 13.0 13.5

Aromatics yield, wt% 7.25 7.52 7.81 7.65 7.45 7.73

Ptβ-2 total conversion, weight % 83.7 80.34 79.23 79.06 78.42 77.84

Aromatics selectivity, % 8.7 9.4 9.9 9.7 9.5 9.9

Aromatics yield, wt% 3.13 2.73 2.84 2.86

CB-6 total conversion rate, weight % 54.83 55.23 56.63 57.03

Aromatics selectivity, % 5.7 4.9 5.0 5.0

Claims (10)

1. A reforming catalyst containing zeolite beta, characterized in that the catalyst contains 0.04 to 2.0% by weight, a Group VIII noble metal Pt and 0.04 to 2.7% by weight a Group VIII metal Re or 0.04 to 1.8% by weight, an IVA Group metal Sn and the rest of the carrier, the carrier contains (based on the weight of the carrier) 20 to 80% by weight of modified β zeolite and 80 to 20% by weight of alumina, and the modified β zeolite contains (based on the weight of the zeolite) 0.5 to 2.5% by weight of potassium and 0.01 to 0.5% by weight of phosphorus, beta zeolite with a silicon-aluminum ratio greater than 40. 2. A reforming catalyst containing zeolite beta, characterized in that the catalyst contains 0.04-2.0% by weight of a Group VIII noble metal Pt and the rest of the carrier, and the carrier contains (based on the weight of the carrier) 45-20% by weight of modified zeolite beta and 55-80% by weight of alumina, the modified zeolite beta is a zeolite beta containing (based on the weight of the zeolite) 0.5-2.5% by weight of potassium and 0.01-0.5% by weight of phosphorus and a silicon-aluminum ratio greater than 40. 3. Catalyst according to claim 1 or 2, characterized in that: (1) The preparation method of the catalyst is (method Ⅰ): a. Prepare zeolite beta containing 0.5-2.5% by weight of potassium and 0.01-0.5% by weight of phosphorus and having a silicon-aluminum ratio greater than 40. b. Loading the product obtained in step a with 0.2-1.5 wt% of a Group VIIB metal Re or 0.2-1.0 wt% of a Group IVA metal Sn. c. Mix the product obtained in step a with a solution of a diacid-based tetraammine compound of Group VIII noble metal Pt at an appropriate concentration at a liquid-solid ratio of 20 to 2:1 (weight ratio), and heat the mixture at 15 to 80°C. The reaction is carried out at 200-500° C. for 1 to 72 hours, and the concentration of the noble metal compound solution is preferably such that the noble metal content on the zeolite is 0.2 to 2.0% by weight, then dried, roasted at 200 to 500 ° C for 2 to 5 hours, and then reduced. d. react the product obtained in step b with the Pt solution of Group VIII noble metal according to the method of step c, dry, roast and reduce. e. Preparation of a Group VIII noble metal Pt0.2-2.0% by weight and a Group VIIB metal Re0.2-3.0% by weight or a Group IVA metal Sn0.2-2.0% by weight, or a Group VIIB metal loaded 0.2 to 3.0 wt% of Re or 0.2 to 2.0 wt% of a Group IVA metal, Sn, alumina. f. Mix the product of step c with the product of step e in a ratio of 2 to 8:8 to 2 (weight ratio), or combine the product of step d containing Group VIIB metal Re with the product of step D containing Group VIIIB metal Re Step e result or aluminum oxide, or the d step result containing IVA group metal Sn and the e step result containing IVA group metal Sn or alumina are mixed homogeneously, or by 4.5～2:5.5～8 (weight Ratio) Mix the result of step c with alumina evenly, and shape it; (2) The preparation method of the catalyst can also be (method Ⅱ): a. Prepare zeolite beta containing 0.5-2.5% by weight of potassium and 0.01-0.5% by weight of phosphorus and having a silicon-aluminum ratio greater than 40. b. loading 0.2 to 1.5% by weight of a Group VIIB metal Re or 0.2 to 1.0% by weight of a Group IVA metal Sn on the beta zeolite obtained in step a, c. preparing an alumina precursor loaded with 0.2-3.0 wt% of a Group VIIB metal Re or 0.2-2.0 wt% of a Group IVA metal Sn. d. Mix the product of step a with the product of step c in a ratio of 2 to 8:8 to 2 (weight ratio), or mix the product of step b containing VIIB group metal Re with VIIB group metal Re Mix the product of step c or the precursor of alumina, or mix the product of step b containing Group IVA metal Sn with the product of step c containing Group IVA metal Sn or the precursor of aluminum oxide, or press 4.5 to 2: The ratio of 5.5 to 8 (weight ratio) is mixed with the product obtained in step a and the alumina precursor. After mixing evenly, it is molded, dried, and roasted, and then combined with a diacid group tetraammine of a group VIII noble metal Pt at an appropriate concentration. The compound solution is mixed evenly at a liquid-solid ratio of 15-1:1 (weight ratio), and reacted at 15-80°C for 1-72 hours. The concentration of the precious metal compound solution is such that the precious metal content on the obtained catalyst is 0.04-2.0 wt. % is appropriate, then dry, bake at 200-500°C for 2-5 hours, and reduce. 4. The catalyst according to claim 1, characterized in that the catalyst contains 0.3-0.8% by weight of a Group VIII noble metal Pt, 0.1-1.4% by weight of a Group VIIB metal Re or 0.1-0.8% by weight of a Group IVA metal Metal Sn and the balance carrier, the carrier contains 30-70 wt% modified zeolite beta and 70-30 wt% alumina, the modified zeolite beta contains 1.0-2.0 wt% potassium and 0.03-0.3 wt% phosphorus, and its silicon-alumina The ratio is 50-100. 5. The catalyst according to claim 3, characterized in that the liquid-solid ratio in the c and d steps of said method I is 5 to 3:1, the calcination temperature is 260 to 400°C, and the resultant of this step contains 0.3 to 3:1 0.8% by weight of Pt, a Group VIII noble metal. 6. The catalyst according to claim 3, characterized in that in the step e of said method I, the alumina contains 0.2 to 0.8% by weight of a noble metal of Group VIII Pt and 0.2 to 1.4% by weight of a metal of Group VIIB Re or 0.2% by weight ~0.8 wt% Group IVA metal Sn, or contain 0.2~1.4 wt% Group VIIB metal Re or 0.2~0.8 wt% Group IVA metal Sn. 7. The catalyst according to claim 3, characterized in that the product of step c and the product of step e in step f of said method I, or the product of step d containing VIIB group metal Re and the product of step d containing VIIB The e-step product or aluminum oxide of group metal Re, or the d-step product containing IVA group Sn and the e-step product or aluminum oxide containing IVA group metal Sn are by 3～7:7～3 (weight than) mixed in proportions. 8. The catalyst according to claim 3, characterized in that the alumina precursor in said method II is aluminum hydroxide, and the alumina precursor in step c of said method II contains 0.2 to 1.4% by weight of a Group VIIB metal Re or 0.2 to 0.8% by weight of a Group IVA metal Sn. 9. The catalyst according to claim 3, characterized in that the product of step a and the product of step c in step d of said method II, or the product of step b containing VIIB group metal Re and the product of step b containing VIIB The c-step product or alumina precursor of group metal Re, or the b-step product containing IVA group metal Sn and the c-step product or aluminum oxide precursor containing IVA group metal Sn are according to 3～7: Mixed in a ratio (weight ratio) of 7 to 3. 10. The catalyst according to claim 3, characterized in that the liquid-solid ratio in step d of said method II is 4-2:1, and the calcination temperature is 260-400°C.