CN113559860A

CN113559860A - Catalyst carrier and preparation method and application thereof

Info

Publication number: CN113559860A
Application number: CN202010348554.6A
Authority: CN
Inventors: 王振; 胡大为; 杨清河; 孙淑玲; 韩伟; 户安鹏; 邓中活
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-04-28
Filing date: 2020-04-28
Publication date: 2021-10-29

Abstract

The invention provides a catalyst carrier and a preparation method thereof, wherein the catalyst carrier comprises inorganic heat-resistant oxide, nickel oxide and a compound thereof, wherein the absorbances of the catalyst carrier at 630nm and 500nm are respectively F when the catalyst carrier is measured by diffuse reflection ultraviolet visible spectrum₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3 to 3.0. The catalyst carrier can be used for preparing hydrogenation catalyst, and the obtained catalyst can greatly improve the activity on the premise of meeting the basic activity requirementThe service life of the catalyst is prolonged, the production efficiency is improved, and the catalyst has a good application prospect.

Description

Catalyst carrier and preparation method and application thereof

Technical Field

The invention relates to the field of catalysts, in particular to a catalyst carrier and a preparation method and application thereof.

Background

The heavy oil processing, especially the deep processing of the residual oil, is not only beneficial to improving the utilization rate of the crude oil and relieving the tension trend of energy supply, but also can reduce the environmental pollution and realize the high-efficiency clean utilization of energy.

For heavy raw oil, after being pretreated by a hydrogenation process, secondary processing is carried out, so that the yield of light oil can be improved, and the content of pollutants such as sulfur, nitrogen and the like in the oil can be reduced, therefore, the demand of the market on the light oil is continuously increased, and the environmental protection regulations tend to be strict today, and the heavy raw oil is generally favored by oil refining manufacturers. Compared with light oil products, heavy oil contains a large amount of impurities such as sulfur, nitrogen, metal and the like, and contains easily coking species such as asphaltene and the like, so that the heavy oil has higher requirements on the activity and the stability of the catalyst. The deactivation of the heavy oil hydrogenation catalyst is caused by two factors, namely, the deposition of metal to destroy the original active phase structure of the catalyst, and carbon deposits on the surface of the active phase to cover the active center, so that the reaction performance of the catalyst is reduced. Therefore, how to improve the stability of the active phase structure of the catalyst and reduce the damage, aggregation and poisoning of the active phase structure of the catalyst in the reaction process is a key technology for improving the activity stability of the catalyst.

CN107583659A discloses a gasoline selective hydrodesulfurization catalyst, wherein a composite alumina carrier containing zinc aluminate spinel is prepared by a non-constant pH alternative titration method, and the catalyst prepared by loading cobalt and molybdenum has good selectivity and reaction stability in the gasoline hydrodesulfurization process.

Compared with distillate oil, the heavy oil hydrogenation catalyst needs higher reaction activity and has higher requirement on activity stability, and the prior art which is not disclosed can well meet the requirements of both the activity and the stability of the catalyst, thereby seriously influencing the actual industrial application effect of the catalyst.

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

Disclosure of Invention

A primary object of the present invention is to overcome at least one of the above-mentioned drawbacks of the prior art, and to provide a catalyst carrier and a preparation method thereof, so as to apply the catalyst carrier to the preparation of a catalyst, and solve the problem that the activity and stability of the catalyst are difficult to be considered in the conventional heavy oil hydrogenation catalyst.

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

the invention provides a catalyst carrier, which comprises inorganic heat-resistant oxide, nickel oxide and a compound thereof, wherein the absorbances of the catalyst carrier at 630nm and 500nm are respectively F when the catalyst carrier is measured by diffuse reflection ultraviolet visible spectrum₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3 to 3.0.

According to one embodiment of the invention, the inorganic refractory oxide is alumina and the composite is a nickel aluminate spinel.

According to one embodiment of the invention, the nickel content is 1% to 10% calculated as oxide and based on the total weight of the catalyst support.

According to one embodiment of the invention, the catalyst support further comprises a promoter selected from metallic promoters and/or non-metallic promoters.

According to one embodiment of the invention, the promoter is a metal promoter, and the content of the metal promoter is 0.1-4% calculated on element and based on the weight of the catalyst carrier.

According to one embodiment of the invention, the auxiliary agent is a non-metal auxiliary agent, and the content of the non-metal auxiliary agent is 0.5-20% calculated by elements and based on the weight of the catalyst carrier.

The invention also provides a preparation method of the catalyst carrier, which comprises the following steps: mixing an inorganic heat-resistant oxide precursor, a nickel source and a forming auxiliary agent to obtain a mixture, and forming; and roasting the formed product at 600-800 ℃ for 1-10 h to obtain the catalyst carrier.

According to one embodiment of the invention, the temperature of the calcination is 650 ℃ to 730 ℃.

According to one embodiment of the present invention, the temperature rise rate of the firing is 50 ℃/hr to 600 ℃/hr.

According to one embodiment of the present invention, the inorganic refractory oxide precursor is pseudo-boehmite, and the nickel source is selected from one or more of nickel nitrate, nickel sulfate and basic nickel carbonate.

According to an embodiment of the present invention, the forming process further comprises adding an auxiliary precursor to the mixture, so that the catalyst carrier contains an auxiliary selected from a metal auxiliary and/or a non-metal auxiliary.

According to one embodiment of the present invention, the forming aid comprises a peptizing agent selected from one or more of aqueous nitric acid, aqueous hydrochloric acid and aqueous citric acid, and a lubricant selected from one or more of sesbania powder, citric acid, starch and carboxymethyl cellulose.

According to one embodiment of the invention, the forming process comprises: kneading the mixture to obtain a plastic body; and drying the plastic body after molding to obtain a molded product.

According to one embodiment of the invention, the method of shaping is selected from one or more of extrusion, rolling, tabletting and granulation.

According to one embodiment of the invention, the drying temperature is 100-250 ℃ and the drying time is 1-6 h.

The invention also provides the application of the catalyst carrier in the preparation of hydrogenation catalysts.

According to the technical scheme, the invention has the beneficial effects that:

the catalyst carrier containing the spinel structure is prepared by adopting a specific process, can be used for preparing a hydrogenation catalyst, and when the catalyst carrier is applied to hydrogenation reaction, the service life of the catalyst can be greatly prolonged, the production efficiency can be improved on the premise of meeting the basic activity requirement, and the catalyst carrier has a good application prospect.

Detailed Description

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

In the field of catalysis, it is generally accepted that the formation of spinel structures generally affects the initial activity of the catalyst. However, the inventors of the present invention have found that, although the formation of the spinel structure affects the initial activity of the catalyst, the formation of the spinel structure in a proper amount does not have a great influence on the overall activity of the catalyst, and the spinel structure formed gradually releases the reactivity as the catalyst participates in the extension of the reaction process. Furthermore, if the catalyst carrier contains the spinel structure, the catalyst carrier can be used as a functional carrier, the flexibility of subsequent loading of active components is further improved, the application range of the catalyst is expanded, and the activity of other components is not influenced in the process of forming the spinel structure.

Experiments show that when the ratio Q representing the content of the spinel structure in the carrier is 1.3-3.0, the catalyst prepared by the catalyst carrier can obtain better initial activity and better activity stability, and the ratio Q is preferably 1.4-2.8. When the Q value is less than 1.3, the improvement of the activity stability is not obvious; when the Q value is more than 3.0, the initial activity is too low, which affects the normal use of the catalyst.

In some embodiments, the inorganic refractory oxide is preferably alumina and the composite is a nickel aluminate spinel. That is, the catalyst support contains alumina, nickel and a nickel aluminate spinel structure.

In some embodiments, the nickel content is 1% to 10%, such as 2%, 3%, 4%, 5%, 6%, 7%, 10%, etc., on an oxide basis and based on the total weight of the catalyst support. By controlling the content of nickel, the amount of the formed nickel aluminate spinel can be controlled, thereby ensuring that the initial catalytic activity is not too low while the stability of the catalytic activity is improved.

The catalyst carrier of the invention can further comprise an auxiliary agent, wherein the auxiliary agent can be a metal auxiliary agent and/or a non-metal auxiliary agent, the metal auxiliary agent is selected from one or more of alkali metal, alkaline earth metal and rare earth metal, such as potassium, sodium, magnesium, lanthanum and the like, and the non-metal auxiliary agent is selected from one or more of boron and silicon.

When the metal auxiliary agent is added, the content of the metal auxiliary agent is 0.1-4% by element and based on the weight of the catalyst carrier. For example, when magnesium is contained in the catalyst support, the content of magnesium is 0.4% to 4%, and the content of magnesium is adjusted to adjust the acidity or basicity of the catalyst support, thereby reducing the amount of coke deposited. When the catalyst carrier contains lanthanum, the lanthanum content is 0.1-2.0%. By adding a proper amount of lanthanum on the catalyst carrier, the growth of carrier grains can be inhibited during high-temperature roasting, the dispersion degree of active components is improved, and the catalytic activity is further improved.

When the non-metal additive is added, the content of the non-metal additive is 0.5 to 20 percent calculated by elements and based on the weight of the catalyst carrier. For example, when the catalyst carrier contains boron, the content of boron is 0.5% -6%, and the pore structure of the catalyst carrier can be improved by adding boron, so that the diffusion performance of the catalyst carrier is improved. When the catalyst carrier contains silicon, the content of the silicon is 3% -20%, the property of the carrier can be adjusted by controlling the content of the silicon in the catalyst carrier, and the stability of the catalytic activity is improved.

The catalyst support of the present invention may also contain sulfur. Experiments show that when the carrier contains sulfur element, the activity and activity stability of the catalyst can be obviously improved. Generally, the sulfur content is 0.6% to 4% by element based on the catalyst support content.

The above-mentioned auxiliary agents to be added to the catalyst carrier may be added in one kind or in plural kinds simultaneously, but the total amount of the added auxiliary agents does not generally exceed the total content range of the above-mentioned metal auxiliary agents or non-metal auxiliary agents.

The present invention also provides a method for preparing the catalyst carrier, comprising: mixing an inorganic heat-resistant oxide precursor and a nickel source, adding a forming auxiliary agent, and carrying out forming treatment; and roasting the formed product at 600-800 ℃ for 1-10 h to obtain the catalyst carrier.

Experiments show that the catalyst carrier with the spinel structure can be formed only by roasting at the temperature of 600-800 ℃ for 1-10 hours in the preparation method of the invention. The roasting temperature is too low or the roasting time is too short, the content of spinel in the obtained catalyst carrier is too low, and the activity stability improvement effect is not obvious; if the roasting temperature is too high or the roasting time is too long, the spinel content in the obtained catalyst carrier is too high, and the initial activity of the catalyst is influenced.

According to the present invention, the temperature of the calcination is preferably 610 to 780 ℃, more preferably 630 to 750 ℃, and most preferably 650 to 730 ℃, for example 650 ℃, 660 ℃, 680 ℃, 700 ℃, 710 ℃, 720 ℃ or the like. One skilled in the art should be able to select the appropriate firing time according to the firing temperature.

In the present invention, the above-mentioned roasting is a roasting that is conventional in the art, and can be raised from the ambient temperature to the roasting temperature, and the temperature raising rate during roasting can be 50 ℃/hr to 600 ℃/hr, preferably 100 ℃/hr to 550 ℃/hr, for example, 110 ℃/hr, 130 ℃/hr, 150 ℃/hr, 200 ℃/hr, 230 ℃/hr, 350 ℃/hr, 400 ℃/hr, 500 ℃/hr, 520 ℃/hr, and the like.

In some embodiments, the inorganic refractory oxide precursor is pseudo-boehmite and the nickel source is selected from one or more of nickel nitrate, nickel sulfate, and nickel hydroxycarbonate.

In addition, the present invention also includes the addition of an auxiliary precursor prior to the shaping process to introduce the desired auxiliary. For example, when magnesium is introduced, the magnesium source may be one or more of magnesium oxide, magnesium salt; when boron is introduced, the boron source is one or more of boron trioxide, boric acid and borate; when lanthanum is introduced, the lanthanum source is one or more of lanthanum nitrate and lanthanum salt; when silicon is introduced, the silicon source is one or more of silicon dioxide, silicic acid and silicate; when sulfur is introduced, the sulfur source may be one or more of sulfuric acid, metal sulfates. Of course, one skilled in the art can select other water-soluble salts of these metals or non-metals according to specific circumstances, and the present invention is not particularly limited thereto.

After the raw materials are mixed, a forming aid is added, and the obtained mixture is further subjected to forming treatment. The forming aid generally includes a peptizer and a lubricant, and may also include other substances, and the invention is not limited thereto. Peptizing agents include, but are not limited to, one or more of aqueous nitric acid, aqueous hydrochloric acid, and aqueous citric acid, and lubricants include, but are not limited to, one or more of sesbania powder, citric acid, starch, and carboxymethyl cellulose.

Further, the forming treatment comprises mixing the inorganic heat-resistant oxide precursor, a nickel source, a forming aid and optionally an aid for kneading treatment to obtain a plastic body; and drying the plastic body after molding to obtain a molded product.

Specifically, the method of forming is selected from one or more of extruding, rolling, tabletting and granulating. The catalyst carrier may be formed into various shapes which are easy to handle, such as spheres, honeycombs, bird nests, tablets or strips (such as clover, butterfly, cylinder, etc.), according to different requirements. The addition amount of each raw material meets the content range of each element of the catalyst carrier by taking the total weight of the catalyst as a reference; the dosage of the water and the dosage of each forming auxiliary agent are that the materials formed by mixing the nickel source, the pseudo-boehmite, each auxiliary agent and the like are enough to meet the requirement of subsequent forming. Sufficient for subsequent forming is to mean that the water/powder ratio in the mixed material is suitable, as is well known to those skilled in the art.

In some embodiments, the plastic body is dried at 100-250 ℃ after molding, such as 100 ℃, 120 ℃, 135 ℃, 170 ℃, 210 ℃, 230 ℃ and the like, and the drying time is 1-6 h, such as 1h, 2h, 4h, 5h, 6h and the like.

In conclusion, the catalyst carrier with the spinel structure is obtained through a specific process, and when the catalyst carrier is used for preparing a hydrogenation catalyst, the service life of the catalyst is greatly prolonged, the production efficiency is improved on the premise that the obtained catalyst meets the basic activity requirement, and the catalyst carrier has a good application prospect.

The following examples further illustrate the invention but should not be construed as limiting it. The reagents used in these examples, except where specifically indicated, were chemically pure reagents and were commercially available.

In the following examples and comparative examples, the composition of the catalyst was determined by X-ray fluorescence spectroscopy (XRF), as specified in petrochemical analysis method RIPP 133-90.

In the following examples and comparative examples, the formation of nickel aluminate spinel structure in the catalyst was determined by ultraviolet visible light spectroscopy (DRUVS). The instrument adopts a Cary300 ultraviolet visible light analyzer of Agilent company, and the wavelength ranges are as follows: 190 nm-1100 nm, wavelength precision: ± 0.1nm, wavelength reproducibility: ± 0.1nm, baseline stability: 0.0003/h, stray light: 0.02% or less, photometric accuracy: + -0.003.

The activity of the catalyst is characterized by desulfurization rate, denitrification rate, carbon residue removal rate and demetalization rate, and the activity stability of the catalyst is characterized by the change of the desulfurization rate, the denitrification rate, the carbon residue removal rate and the demetalization rate after the catalyst works for 100 hours and 1000 hours.

Example 1

This example serves to illustrate the preparation of the catalyst support of the present invention.

Mixing uniformly the dry powder RPB100 of pseudo-boehmite produced by 1 kg of Changling catalyst factory and 30 g of sesbania powder, mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder to form plastic bodies, extruding the plastic bodies into butterfly-shaped strips with the diameter of 1.1 mm, drying the wet strips at 120 ℃ for 3 hours, heating the wet strips to 630 ℃ at 200 ℃/hour, and keeping the temperature at 630 ℃ for 4 hours to obtain the nickel-containing catalyst carrier.

Based on the total weight of the catalyst carrier, a carbon-sulfur analyzer is adopted to determine the sulfur content in the catalyst carrier, and an ultraviolet-visible light spectrum method is adopted to determine the nickel aluminate spinel NiAl on the catalyst carrier₂O₄The content of nickel oxide in the catalyst carrier was measured by an X-ray fluorescence spectrometer, and the measurement results are shown in table 1.

Example 2

This example illustrates the preparation of the catalyst support of the present invention

Mixing uniformly the dry powder RPB100 of pseudo-boehmite produced by 1 kg of Changling catalyst factory and 30 g of sesbania powder, mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid at room temperature, extruding into butterfly-shaped strips with the diameter of 1.1 mm after kneading into plastic bodies on a double-screw extruder, drying the wet strips at 120 ℃ for 3 hours, heating to 650 ℃ at 200 ℃/hour, and keeping the temperature at 650 ℃ for 4 hours to obtain the nickel-containing catalyst carrier.

Example 3

Mixing uniformly the dry powder RPB100 of pseudo-boehmite produced by 1 kg of Changling catalyst factory and 30 g of sesbania powder, mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder to form plastic bodies, extruding the plastic bodies into butterfly-shaped strips with the diameter of 1.1 mm, drying the wet strips at 120 ℃ for 3 hours, heating the wet strips to 780 ℃ at 200 ℃/hour, and keeping the temperature at 780 ℃ for 4 hours to obtain the nickel-containing catalyst carrier.

Example 4

Mixing uniformly the dry powder RPB100 of pseudo-boehmite produced by 1 kg of Changling catalyst factory and 30 g of sesbania powder, mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of nitric acid, extruding the mixture into a butterfly-shaped strip with the diameter of 1.1 mm after kneading the mixture on a double-screw extruder, drying the wet strip at 120 ℃ for 3 hours, heating to 630 ℃ at 200 ℃/hour, and keeping the temperature at 630 ℃ for 4 hours to obtain the nickel-containing catalyst carrier.

Comparative example 1

Mixing uniformly the dry powder RPB100 of pseudo-boehmite produced by 1 kg of Changling catalyst factory and 30 g of sesbania powder, mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid at room temperature, extruding into butterfly-shaped strips with the diameter of 1.1 mm after kneading into plastic bodies on a double-screw extruder, drying the wet strips at 120 ℃ for 3 hours, heating to 400 ℃ at 200 ℃/hour, and keeping the temperature at 400 ℃ for 4 hours to obtain the nickel-containing catalyst carrier.

Comparative example 2

The preparation method comprises the steps of uniformly mixing 1 kg of pseudo-boehmite dry glue powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2 l of mixed aqueous solution containing 26 g/l of NiO and 39 g/l of sulfuric acid at room temperature, extruding into butterfly-shaped strips with the diameter of 1.1 mm after kneading into plastic bodies on a double-screw extruder, drying wet strips at 120 ℃ for 3 hours, heating to 900 ℃ at 200 ℃/hour, and keeping the temperature at 900 ℃ for 4 hours to obtain the nickel-containing catalyst carrier.

The total weight of the catalyst carrier is used as a reference, and a carbon-sulfur analyzer is adopted to determine the catalystMeasuring sulfur content in catalyst carrier by ultraviolet visible light spectrum method₂O₄The content of nickel oxide in the catalyst carrier was measured by an X-ray fluorescence spectrometer, and the measurement results are shown in table 1.

TABLE 1

Test examples 1 to 4

100 g of the catalyst carriers of examples 1 to 4 and comparative examples 1 and 2 were weighed, respectively, and 120 ml of the carrier containing MoO was used₃The mixed solution of molybdenum oxide and phosphoric acid of 148 g/l was immersed for 1 hour, dried at 110 ℃ for 3 hours, and then activated at 400 ℃ for 3 hours to prepare the corresponding catalysts of test examples 1 to 4.

Comparative test examples 1 to 2

100 g of the catalyst supports of comparative examples 1 and 2 were weighed out separately and 120 ml of MoO-containing catalyst support was used₃148 g/L of a mixed solution of molybdenum oxide and phosphoric acid was immersed for 1 hour, dried at 110 ℃ for 3 hours, and then activated at 400 ℃ for 3 hours to prepare the corresponding catalyst of test examples 1-2.

Comparative test example 3

The preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder by a conventional method, uniformly mixing the mixture with 1.2L of sulfuric acid aqueous solution containing 39 g/L of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder into a plastic body, extruding the plastic body into butterfly-shaped strips with phi of 1.1 mm, drying wet strips at 120 ℃ for 3 hours, heating to 800 ℃ at 200 ℃/hour, and keeping the temperature at 800 ℃ for 4 hours to obtain the carrier.

Weighing 100 g of the carrier, and using 120 ml of MoO-containing carrier₃154 g/L and NiO 37 g/L of mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid are soaked for 1 hour, dried for 3 hours at 120 ℃, and activated for 3 hours at 400 ℃ to prepare the catalyst.

Comparative test example 4

The preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.2L of sulfuric acid aqueous solution containing 39 g/L of sulfuric acid at room temperature, kneading the mixture on a double-screw extruder into a plastic body, extruding the plastic body into butterfly-shaped strips with the diameter of 1.1 mm, drying wet strips at 120 ℃ for 3 hours, and roasting the wet strips at 800 ℃ for 3 hours to obtain the carrier.

Weighing 100 g of the carrier, and using 120 ml of MoO-containing carrier₃154 g/L and 37 g/L NiO of the mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid are soaked for 1 hour, the mixed solution is dried for 2 hours at the temperature of 120 ℃, the dried catalyst is heated to 650 ℃ at the temperature of 300 ℃/hour, and the temperature is kept constant for 3 hours at 650 ℃ to prepare the catalyst.

The catalysts in each of the test examples 1 to 4 and comparative test examples 1 to 4 obtained above were crushed into particles having a diameter of 0.8 to 1.2 mm, and the catalyst loading was 100 ml. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14 MPa, and the liquid hourly space velocity is 0.6 h^-1And the volume ratio of hydrogen to oil is 1000, samples are taken after the reaction is carried out for 100 hours and 1000 hours respectively, and the content of nickel and vanadium in the treated oil is measured by adopting an inductively coupled plasma emission spectrometer (ICP-AES). (the apparatus is PE-5300 plasma photometer of PE company, USA, see petrochemical analysis method RIPP124-90)

The sulfur content was measured by an electric method (see petrochemical analysis method RIPP 62-90).

The nitrogen content was determined by an electrometric method (see petrochemical analysis method RIPP 63-90).

The carbon residue content is determined by a micro-method (the specific method is shown in petrochemical analysis method RIPP 148-90).

The removal rates of sulfur, carbon residue, nitrogen and metals were calculated according to the following formulas:

the results of removing impurities of the catalysts of test examples 1 to 4 and comparative test examples 1 to 4 are shown in Table 2.

TABLE 2

As can be seen from the results in table 2, the catalyst prepared by using the catalyst carrier of the present invention has significantly improved overall impurity removal activity stability compared with the prior art, the initial reaction activity of the catalyst (i.e. the removal performance of each impurity when the catalyst is operated for 100 hours) is close to the prior art, but the reaction stability of the catalyst (i.e. the reduction of the removal performance of each impurity after the catalyst is operated for 1000 hours) is greatly improved, so that the overall performance of the catalyst is significantly improved. Therefore, after the catalyst carrier disclosed by the invention is adopted, the service life of the catalyst is greatly prolonged, the production efficiency is improved and the catalyst carrier has a good application prospect on the premise of meeting the basic activity requirement.

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

Claims

1. A catalyst carrier is characterized by comprising inorganic heat-resistant oxide, nickel oxide and a compound thereof, wherein the absorbances of the catalyst carrier at 630nm and 500nm are respectively F when the catalyst carrier is measured by diffuse reflection ultraviolet visible spectrum₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3 to 3.0.

2. The catalyst carrier according to claim 1, wherein the inorganic refractory oxide is alumina and the composite is a nickel aluminate spinel.

3. The catalyst support according to claim 1, wherein the nickel content is 1% to 10% calculated as oxide and based on the total weight of the catalyst support.

4. The catalyst carrier according to claim 1, further comprising a promoter selected from a metallic promoter and/or a non-metallic promoter.

5. The catalyst carrier of claim 4, wherein the promoter is a metal promoter, and the content of the metal promoter is 0.1-4% by element and based on the total weight of the catalyst carrier.

6. The catalyst carrier of claim 4, wherein the promoter is a non-metallic promoter, and the content of the non-metallic promoter is 0.5 to 20% by element and based on the total weight of the catalyst carrier.

7. A preparation method of a catalyst carrier is characterized by comprising the following steps:

mixing an inorganic heat-resistant oxide precursor, a nickel source and a forming auxiliary agent to obtain a mixture, and forming; and

and roasting the formed product at the temperature of 600-800 ℃ for 1-10 h to obtain the catalyst carrier.

8. The method of claim 7, wherein the temperature of the calcination is 650 ℃ to 730 ℃.

9. The method according to claim 7, wherein the temperature increase rate of the calcination is 50 ℃/hr to 600 ℃/hr.

10. The preparation method according to claim 7, wherein the inorganic refractory oxide precursor is pseudo-boehmite, and the nickel source is one or more selected from nickel nitrate, nickel sulfate and basic nickel carbonate.

11. The method according to claim 7, further comprising adding an auxiliary precursor to the mixture before the forming process, so that the catalyst support contains an auxiliary selected from a metal auxiliary and/or a non-metal auxiliary.

12. The method according to claim 7, wherein the forming aid comprises a peptizing agent selected from one or more of an aqueous nitric acid solution, an aqueous hydrochloric acid solution and an aqueous citric acid solution, and a lubricant selected from one or more of sesbania powder, citric acid, starch and carboxymethyl cellulose.

13. The production method according to claim 7, wherein the molding process includes:

kneading the mixture to obtain a plastic body;

drying the plastic body after molding to obtain a molded product;

wherein the shaping method is selected from one or more of extruding, rolling ball, tabletting and granulating.

14. The method according to claim 13, wherein the drying temperature is 100 ℃ to 250 ℃ and the drying time is 1h to 6 h.

15. Use of a catalyst support according to any one of claims 1 to 6 in the preparation of a hydrogenation catalyst.