CN110180585B

CN110180585B - Gasoline hydrofining catalyst and preparation method thereof

Info

Publication number: CN110180585B
Application number: CN201910424850.7A
Authority: CN
Inventors: 席鸿飞; 宋兆伟; 杨大奎
Original assignee: Beijing Gaoxin Lihua Technology Co ltd
Current assignee: Beijing Gaoxin Lihua Technology Co ltd
Priority date: 2019-05-21
Filing date: 2019-05-21
Publication date: 2022-01-14
Anticipated expiration: 2039-05-21
Also published as: CN110180585A

Abstract

The invention discloses a gasoline hydrofining catalyst and a preparation method thereof. The catalyst comprises alumina, a modified TS-1 molecular sieve and active metal components, wherein the active metal components are molybdenum oxide and cobalt oxide. The hydrofining catalyst is suitable for hydrofining of FCC gasoline, has the characteristics of high activity, high selectivity and long service life, not only has higher liquid product yield, but also can enable the product to meet the requirements of sulfur content, olefin content and aromatic hydrocarbon content in national six standards of gasoline, and can reduce the loss of octane number.

Description

Gasoline hydrofining catalyst and preparation method thereof

Technical Field

The invention relates to a gasoline hydrofining catalyst and a preparation method thereof, belonging to the technical field of petroleum product hydrogenation catalysts.

Background

Along with the rapid development of social economy and the great improvement of living standard of people, the number of automobiles on roads is rapidly increased, the problem of solving or reducing air pollution is urgent, and the following national and international environmental protection regulations are stricter and the emission standard of fuel oil is higher and higher. Beijing and some other cities have begun to implement the national six emission standard which is more stringent than the European five/national five standard, and China will all implement the national six standard by 2020, which is a new challenge that domestic oil refinery manufacturers must face. Although many oil refinery enterprises can provide gasoline which completely meets the national six standards, the more severe operating conditions or the more expensive catalyst are required to produce gasoline which meets the national six standards, thereby increasing the production cost and reducing the profit of the enterprises.

In long-term scientific research and production practice, various gasoline hydrofining catalysts are developed to meet the requirements of gasoline product indexes and environmental protection. At present, the conventional gasoline hydrofining catalyst mainly uses alumina as a carrier, and uses metal elements of group VIII and/or group VIB as active components, and may further contain an auxiliary component to further improve the performance of the catalyst.

CN102872891A discloses a poor gasoline hydrotreating catalyst and its preparation and application. The catalyst takes silicon-aluminum oxide as a carrier, takes oxides of W, Mo, Ni and P as active components, and is supplemented with a small amount of Li oxide and La oxide. However, although the catalyst can be used for hydrofining the catalytic gasoline and coker gasoline mixed oil with the sulfur content of 2854 mu g/g, the nitrogen content of 760 mu g/g and the mixing ratio of 3:1, the sulfur content and the nitrogen content after hydrofining are both more than 20 mu g/g and are far higher than the sulfur and nitrogen contents required by the national six standards, so the catalyst cannot be used for producing the national six standards gasoline.

CN102335612A discloses a selective hydrodesulfurization catalyst and a preparation method thereof. The catalyst takes Co-Mo as active component metal and SiO₂-Al₂O₃As carrier, alkali metal oxide, alkaline earth metal oxide and phosphorus oxide as assistant. The catalyst has good hydrodesulfurization selectivity on full-fraction FCC gasoline, the olefin saturation rate is about 10 percent, the octane number loss is not more than 0.8 unit, and the catalyst can be used for treating high-sulfur and high-olefin FCC gasoline, but the sulfur content of the obtained hydrogenation product is over 45 mu g/g, and the sulfur content of the hydrogenation product can not meet the standard requirement of the sulfur content of national six-gasoline.

In addition, in the process of hydrorefining catalytic gasoline, although some conventional hydrodesulfurization catalysts have good desulfurization effect, the octane number of the gasoline is seriously reduced due to the large saturation of olefin, so that the service performance of the gasoline is greatly reduced. Therefore, the development of a gasoline hydrorefining catalyst with high hydrodesulfurization selectivity and reduced octane number loss is an urgent research task for gasoline hydrogenation catalyst scientists.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a gasoline hydrofining catalyst with high activity, high selectivity and long service life and a preparation method thereof. The catalyst of the invention is used for hydrofining gasoline raw materials, not only has higher yield of liquid products, but also can enable the products to meet the requirements of sulfur content, olefin content and aromatic hydrocarbon content in national six standards of gasoline, and can reduce the loss of octane number.

The invention provides a gasoline hydrofining catalyst, which comprises alumina, a modified TS-1 molecular sieve and active metal components, wherein the active metal components are molybdenum oxide and cobalt oxide.

Further, the modified TS-1 molecular sieve is a boron modified molecular sieve B-TS-1, wherein the content of boron accounts for 0.1-3.0% of the mass of the boron modified molecular sieve B-TS-1, and is preferably 0.5-2.0%.

The gasoline hydrofining catalyst takes the mass of the catalyst as a reference, the contents of molybdenum oxide and cobalt oxide are 15-30%, and the contents of alumina and a modified TS-1 molecular sieve are 70-85%.

Further, in the gasoline hydrofining catalyst, the mass ratio of alumina to the modified TS-1 molecular sieve is (50-83): (17-50), preferably (58-78): (22-42).

Further, in the gasoline hydrofining catalyst, the mass ratio of molybdenum oxide to cobalt oxide is 100: (20-45), preferably, the mass ratio of the molybdenum oxide to the cobalt oxide is 100: (25-37).

Further, the alumina is preferably γ -Al₂O₃。

Furthermore, the aluminum oxide is gallium modified aluminum oxide, and the content of gallium in terms of gallium oxide accounts for less than 10% of the mass of the aluminum oxide, and is preferably 3% -9%.

The second aspect of the present invention provides a preparation method of a gasoline hydrorefining catalyst, comprising: mixing water and a peptizing agent to prepare a peptizing agent water solution; adding pseudo-boehmite and a modified TS-1 molecular sieve into the peptizing agent aqueous solution respectively, and kneading and curing to form slurry; and then mixing the molybdenum oxide and cobalt oxide precursors with the slurry, kneading, molding, drying and roasting to obtain the gasoline hydrofining catalyst.

Further, the modified TS-1 molecular sieve is a boron modified molecular sieve B-TS-1, and the TS-1 molecular sieve is prepared by adopting a conventional method in the field, wherein the molar ratio of titanium to silicon of the molecular sieve is 1 (30-50); boron is preferably introduced in the preparation process of the TS-1 molecular sieve, for example, a boron source (such as boric acid) is introduced in a synthesis system of the TS-1 molecular sieve, so that the boron-modified molecular sieve B-TS-1 is obtained.

Further, the molybdenum oxide precursor may be selected from ammonium heptamolybdate, and the cobalt oxide precursor may be selected from basic cobalt carbonate.

Further, the peptizing agent is one or more of nitric acid, oxalic acid and citric acid.

Further, the pseudo-boehmite is gallium modified pseudo-boehmite, wherein the method for introducing gallium into the pseudo-boehmite can adopt a coprecipitation method, for example, a gallium precursor and an alumina precursor are precipitated together, and the gallium precursor can be selected from at least one of gallium nitrate, gallium acetate, gallium carbonate, gallium oxalate and the like.

Further, the mass ratio of the peptizing agent to the water is 1: (9-11), wherein the mass ratio of the sum of the pseudo-boehmite and the molecular sieve to the peptizer aqueous solution is 100: (85-91).

Further, the shape of the catalyst can be selected according to requirements, and can be a tooth ball type. The drying conditions were as follows: the drying temperature is 100-120 ℃, and the drying time is 7-14 hours; the roasting conditions were as follows: the roasting temperature is 500-600 ℃, and the roasting time is 10-24 hours.

In a third aspect, the present invention provides a method for hydrofining FCC gasoline, comprising: in the presence of hydrogen, the FCC gasoline raw material contacts the gasoline hydrofining catalyst to carry out hydrofining reaction, and a hydrofining gasoline product is obtained.

The hydrofining conditions were as follows: the reaction pressure is 2.5-5.0 MPa, the volume ratio of hydrogen to oil is (300-600): 1, the reaction temperature is 220-300 ℃, and the liquid hourly space velocity is 2-6 h^-1。

Compared with the prior art, the gasoline hydrofining catalyst and the preparation method thereof have the following advantages:

1. the gasoline hydrofining catalyst of the invention can effectively remove sulfur in FCC gasoline, especially remove sulfur-containing organic matters which are difficult to remove, such as 4,6-DMDBT and the like, simultaneously can crack naphthenes after hydrodesulfurization into olefin or cut off side chains to form olefin and naphthenes without side chains, and can also carry out hydroisomerization and aromatization, thereby reducing the octane number loss of gasoline hydrofining products, and even keeping the octane number unchanged or slightly increasing the octane number.

2. The boron modified molecular sieve B-TS-1 is introduced into the gasoline hydrofining catalyst, the boron modified molecular sieve B-TS-1 not only has an MFI molecular sieve structure, and titanium species such as four-coordinated framework titanium, non-coordinated framework titanium and the like provide Lewis acid centers, but also adjusts the structure and the acid property of the molecular sieve, is more favorable for the diffusion of benzothiophene organic sulfur compounds in molecular sieve pores, and enhances the adsorption and the hydrogenation decomposition of the benzothiophene organic sulfur compounds, thereby improving the activity and the selectivity of the catalyst.

3. The gallium modified alumina is preferably adopted in the catalyst of the invention and is matched with the boron modified molecular sieve B-TS-1, so that the selective desulfurization capability of the catalyst is further enhanced, the occurrence of side reactions is reduced, and the liquid yield is improved.

4. The preparation method of the catalyst provided by the invention adopts a preparation method of mixing and kneading the carrier and the active component, so that the catalyst still has a good pore structure under the condition of properly increasing the content of the hydrogenation metal, the coordination effect between the active metal and the carrier component is improved, the hydrodesulfurization activity and selectivity of the catalyst are improved, and the octane number loss is favorably reduced.

5. Compared with the prior art, the FCC gasoline hydrofining method has the advantages of long service life of the catalyst, high reaction airspeed and remarkable beneficial effect. The process method can produce the gasoline product which meets the national six standard of gasoline, particularly the sulfur content of the gasoline product reaches or is less than 10 mu g/g of the national six standard, the octane number loss is little or not lost or slightly increased, and the index requirements of the olefin content being less than 18 percent by volume, the aromatic hydrocarbon content being less than 35 percent by volume, the benzene content being less than 0.8 percent by volume and the like are met.

Detailed Description

The invention will be further illustrated by the following specific examples, without restricting its scope to these examples. Other variations and modifications within the spirit and scope of the invention may occur to those skilled in the art without departing from the spirit and scope of the invention. In the following examples, all proportions or percentages are by mass unless otherwise specified.

Example 1

Mixing nitric acid, citric acid and deionized water to prepare a colloidal solvent aqueous solution, wherein the ratio of the nitric acid to the citric acid is 1:1, and the ratio of the sum of the nitric acid and the citric acid to the deionized water is 1: mixing pseudo-boehmite and a boron modified molecular sieve B-TS-1 (the content of boron accounts for 1% of the mass of the boron modified molecular sieve B-TS-1, and the molar ratio of titanium to silicon is 1:33) with a peptizing agent aqueous solution to prepare a carrier slurry, grinding ammonium heptamolybdate and basic cobalt carbonate for 10-15 minutes to form mixed powder, mixing and kneading the slurry and the mixed powder of the active components to form a blank, molding the blank to obtain a tooth spherical catalyst blank, drying the tooth spherical catalyst blank at 110 ℃ for 12 hours, and finally roasting at 550 ℃ for 24 hours to obtain a catalyst finished product Cat1, wherein the specific composition and the physical properties are shown in Table 1.

Example 2

Mixing nitric acid, citric acid and deionized water to prepare a colloidal solvent aqueous solution, wherein the ratio of the nitric acid to the citric acid is 1:1, and the ratio of the sum of the nitric acid and the citric acid to the deionized water is 1: 10; gallium oxide and pseudo-boehmite (the mass content of alumina is 70 percent) are precipitated together, gallium modified pseudo-boehmite (the content of gallium oxide accounts for 7.1 percent of the mass of the pseudo-boehmite in terms of alumina) and gallium modified pseudo-boehmite and boron modified molecular sieve B-TS-1 (the content of boron accounts for 1 percent of the mass of the boron modified molecular sieve B-TS-1, and the molar ratio of titanium to silicon is 1:33) are mixed with a peptizing agent aqueous solution to prepare carrier slurry, wherein the ratio of the sum of the gallium modified pseudo-boehmite and the molecular sieve to the peptizing agent aqueous solution is 100:88, grinding ammonium heptamolybdate and basic cobaltous carbonate for 10-15 minutes to form mixed powder; and kneading the slurry and the active component mixture to form a catalyst blank, molding the blank to obtain a tooth-sphere-shaped catalyst blank, drying the tooth-sphere-shaped catalyst blank at 110 ℃ for 12 hours, and finally roasting at 550 ℃ for 24 hours to obtain a finished catalyst Cat2, wherein the specific composition and physical properties are shown in Table 1.

Example 3

The preparation method of the catalyst is the same as that of the example 2, but the content of boron accounts for 1.5 percent of the mass of the boron modified molecular sieve B-TS-1; the proportion of the gallium modified pseudo-boehmite to the boron modified molecular sieve B-TS-1 is adjusted to obtain a finished catalyst Cat3, and the specific composition and physical properties are shown in Table 1.

Example 4

The preparation method of the catalyst is the same as that of the example 2, only the content of boron in the boron modified molecular sieve B-TS-1 is changed to 0.5 percent; the weight ratio of the gallium modified pseudo-boehmite to the boron modified molecular sieve B-TS-1 is changed to obtain a finished catalyst Cat4, and the specific composition and physical properties are shown in Table 1.

Example 5

The preparation method of the catalyst is the same as that of the example 2, only the content of the gallium oxide is adjusted to account for 8.6 percent of the pseudo-boehmite by the weight of the alumina; and changing the mass ratio of ammonium molybdate to basic cobalt carbonate to obtain a finished catalyst Cat5, wherein the specific composition and physical properties are shown in Table 1.

Example 6

The preparation method of the catalyst is the same as that of the example 2, only the content of the gallium oxide is adjusted to account for 4.3 percent of the pseudoboehmite by the weight of the alumina; and changing the mass ratio of ammonium molybdate to basic cobalt carbonate to obtain a finished catalyst Cat6, wherein the specific composition and physical properties are shown in Table 1.

Comparative example 1

The preparation method of the catalyst is the same as that of example 1, except that boron modified molecular sieve B-TS-1 is not added, and the finished catalyst product DCat1 is obtained, wherein the specific composition and physical properties are shown in Table 1.

Comparative example 2

The catalyst was prepared as in example 1 except that the molecular sieve was only TS-1 and was not boron modified to give the finished catalyst Dcat2, the specific composition and physical properties of which are shown in Table 1.

TABLE 1 catalyst composition and physical Properties

Item	Cat1	Cat2	Cat3	Cat4	Cat5	Cat6	Dcat1	Dcat2
									Catalyst composition
Content of molybdenum oxide%	15.3	15.3	15.3	15.3	16.2	15.9	15.3	15.3
									Content of cobalt oxide%	5.3	5.3	5.3	5.3	4.5	4.8	5.5	5.5
Molecular sieve content,%	19.6	19.6	24.1	26.8	19.6	19.6	-	19.6
									Of aluminium oxideContent (a) of	Balance of	Balance of	Balance of	Balance of	Balance of	Balance of	Balance of	Balance of
Properties of the catalyst
									Bulk ratio, g/cm³	0.55	0.56	0.55	0.56	0.57	0.61	0.57	0.57
Specific surface area, m²/g	195	246	245	248	222	234	213	198
									Pore volume, mL/g	0.54	0.68	0.76	0.72	0.66	0.57	0.55	0.56
Crush strength, N/grain	30	31	35	33	32	32	27	30

Evaluation test of catalyst

The test product is used for the evaluation test of the FCC gasoline hydrodesulfurization catalyst, wherein the raw material properties of the FCC gasoline are shown in Table 2. The catalysts of examples 1-6 and comparative examples 1 and 2 were used for the hydrorefining reaction under the following reaction conditions: the temperature is 260 ℃, the pressure is 3MPa, and the liquid hourly space velocity is 3h^-1Hydrogen to oil ratio 400/1V/V, evaluationThe valence results are given in Table 3.

TABLE 2 FCC gasoline feedstock Properties

Item	Total sulfur,. mu.g/g	Mercaptan sulfur,. mu.g/g	Olefin, V%	Aromatic hydrocarbon, V%	Benzene content, V%	RON
							Detection value	1025	12	39.5	13.6	0.79	91.5

TABLE 3 FCC gasoline hydrodesulfurization Activity evaluation results

Item	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative example 1	Comparative example 2
									Catalyst numbering	Cat1	Cat2	Cat3	Cat4	Cat5	Cat6	DCat1	DCat2
Product Properties
									Sulfur content, μ g/g	10	8	7	8	7	6	20	15
Olefin content, V%	12	13	15	12	13	14	23	19
									Aromatic content, V%	27	29	29	28	28	29	25	25
RON	90.5	90.9	91.5	91.3	91.2	91.1	87.4	89.0

The catalysts prepared in example 1 and comparative example 1 were used for catalyst stability test under the following reaction conditions: the temperature is 260 ℃, the pressure is 3MPa, and the liquid hourly space velocity is 3h^-1The hydrogen-oil ratio is 400/1V/V, the catalyst is continuously used for 1000h, and the sulfur removal effect of the catalyst on the raw oil is tested and is calculated by the sulfur removal percentage of the raw oil; the compositions of the raw materials used therein are shown in Table 2, and the evaluation results are shown in Table 4.

TABLE 4 catalyst stability comparison

Time/h	100	300	500	700	1000
						Cat1	>99	>99	>99	>99	>99
Dcat1	98.2	97.7	97.2	96.8	96.6

As can be seen from the results in Table 3, the performance of the catalyst of the present invention is significantly better than that of the catalyst of the comparative example, and the catalysts of the examples of the present invention can be used for refining FCC gasoline, thereby obtaining gasoline meeting the national emission standard of six. The gasoline product obtained in this way can be directly used as vehicle fuel and can also be used as blending component of gasoline fuel to meet various environmental protection requirements.

As can be seen from table 4, the desulfurization activity of the catalyst in example 1 was not substantially changed over the experimental time span of 1000 hours, whereas the desulfurization activity of the catalyst in comparative example 1 was significantly reduced as the reaction time was prolonged. It follows from this that: compared with the catalysts in the comparative examples, the catalysts in the examples have quite good stability, and further the service life of the catalyst provided by the invention is long.

It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention, and are not to be construed as limiting the present invention, and any modifications, equivalent substitutions, improvements and the like made without departing from the spirit and principle defined by the claims and the equivalent forms thereof should be included in the protection scope of the present invention.

Claims

1. A gasoline hydrofining catalyst comprises alumina, a modified TS-1 molecular sieve and active metal components, wherein the active metal components are molybdenum oxide and cobalt oxide;

the modified TS-1 molecular sieve is a boron modified molecular sieve B-TS-1; the content of boron accounts for 0.1-3.0% of the mass of the boron modified molecular sieve B-TS-1; the boron modified molecular sieve B-TS-1 is obtained by introducing a boron source into a TS-1 molecular sieve synthesis system; the titanium-silicon molar ratio of the TS-1 molecular sieve is 1: (30-50);

based on the mass of the catalyst, the contents of molybdenum oxide and cobalt oxide are 15-30%, and the contents of alumina and a modified TS-1 molecular sieve are 70-85%;

the mass ratio of the alumina to the modified TS-1 molecular sieve is (50-83): (17-50).

2. The gasoline hydrofining catalyst of claim 1, wherein the content of boron is 0.5-2.0% of the mass of boron modified molecular sieve B-TS-1.

3. The gasoline hydrofining catalyst according to claim 1 or 2, wherein the mass ratio of the alumina to the modified TS-1 molecular sieve is (58-78): (22-42).

4. The gasoline hydrofinishing catalyst according to claim 1 or 2, characterized in that the mass ratio of molybdenum oxide to cobalt oxide is 100: (20-45).

5. The gasoline hydrofinishing catalyst according to claim 1 or 2, characterized in that the mass ratio of molybdenum oxide to cobalt oxide is 100: (25-37).

6. The gasoline hydrofining catalyst according to claim 1, wherein the alumina is gallium-modified alumina, and the content of gallium in terms of gallium oxide accounts for less than 10% of the mass of the alumina before modification.

7. The gasoline hydrofining catalyst according to claim 1, wherein the alumina is gallium modified alumina, and the content of gallium in terms of gallium oxide accounts for 3% -9% of the mass of the alumina before modification.

8. A method for preparing the gasoline hydrofinishing catalyst as claimed in any one of claims 1 to 7, comprising: mixing water and a peptizing agent to prepare a peptizing agent water solution; adding pseudo-boehmite modified by pseudo-boehmite or gallium and the modified TS-1 molecular sieve into the peptizing agent aqueous solution respectively, and kneading and curing to form slurry; and then mixing the molybdenum oxide precursor and the cobalt oxide precursor with the slurry, kneading, molding, drying and roasting to obtain the gasoline hydrofining catalyst.

9. The method of claim 8, wherein the molybdenum oxide precursor is selected from ammonium heptamolybdate, and the cobalt oxide precursor is selected from basic cobalt carbonate; the peptizing agent is one or more of nitric acid, oxalic acid and citric acid; the mass ratio of the peptizing agent to the water is 1: (9-11), wherein the mass ratio of the sum of the gallium modified pseudo-boehmite and the modified TS-1 molecular sieve to the peptizer aqueous solution is 100: (85-91).

10. The method for preparing a gasoline hydrofinishing catalyst according to claim 8, characterized in that the drying conditions are as follows: the drying temperature is 100-120 ℃, and the drying time is 7-14 hours; the roasting conditions were as follows: the roasting temperature is 500-600 ℃, and the roasting time is 10-24 hours.

11. A process for the hydrofinishing of FCC gasoline comprising: in the presence of hydrogen, an FCC gasoline raw material is contacted with the gasoline hydrofining catalyst of any one of claims 1 to 7 to carry out hydrofining reaction, and a hydrofined gasoline product is obtained.

12. The process of claim 11, wherein the hydrofinishing is carried out under the following operating conditions: the reaction pressure is 2.5-5.0 MPa, the volume ratio of hydrogen to oil is (300-600): 1, the reaction temperature is 220-300 ℃, and the liquid hourly space velocity is 2-6 h^-1。