CN113117763B

CN113117763B - Passivation method of vulcanization type hydrogenation catalyst

Info

Publication number: CN113117763B
Application number: CN201911423704.9A
Authority: CN
Inventors: 徐黎明; 高玉兰; 佟佳; 杨涛; 杨占林
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2019-12-31
Filing date: 2019-12-31
Publication date: 2023-01-10
Anticipated expiration: 2039-12-31
Also published as: CN113117763A

Abstract

The invention discloses a passivation method of a vulcanized hydrogenation catalyst, which comprises the steps of firstly placing the vulcanized hydrogenation catalyst in a closed container, vacuumizing the container, reducing the temperature, and introducing nitrogen or carbon dioxide for treatment; then the obtained material is heated up and finally passivated by passivation gas. According to the method, the catalyst is passivated by adopting ozone at low temperature, so that a compact oxide layer is formed on the surface of the catalyst, oxygen in the air is prevented from further acting with metal sulfides in the pore channel of the catalyst, the self-heating reaction of the catalyst is avoided, and the safety of catalyst storage, transportation and filling is improved.

Description

Passivation method of vulcanization type hydrogenation catalyst

Technical Field

The invention belongs to the technical field of petrochemical industry, and particularly relates to a treatment method of a vulcanized hydrogenation catalyst.

Background

In recent years, the tendency of crude oil deterioration is increasingly obvious, and the requirement of each country for clean fuel is increasing, the hydrogenation process is one of the most effective means for producing clean fuel, wherein an efficient hydrogenation catalyst is the key of the process. The conventional hydrogenation catalyst is in an oxidation state, while substances which really have an active function in actual use are in a vulcanization state, so the substances are required to be vulcanized in a reactor before use. The most common at present are in-situ prevulcanisation and ex-situ prevulcanisation techniques. The ex-situ presulfurization technology can be divided into two types according to the existence state of metal on the catalyst: one is the ex-situ presulfurization technology, in which the active metal on the catalyst and sulfurizing agent form complex or oxysulfide. The other is to carry out complete sulfidation of the catalyst outside the reactor to generate high-activity metal sulfide, and then carry out passivation for safe storage, transportation and loading, namely complete ex-reactor presulfiding technology.

The outside presulfurization of the hydrogenator changes the oxidation state of the catalyst metal to the sulfidation state. The activity and stability of the sulfided catalyst are higher than those of the oxidic catalyst. Contact of the metal sulphides with oxygen may give rise to concentrated exotherms and even autoignitions which necessitate isolation of the catalyst from air and hence deactivation of the catalyst after presulfiding to protect the metal sulphides within the catalyst pores from oxidation.

Passivation techniques are generally divided into gas passivation, liquid passivation and solid passivation. Gas passivation is mainly by O ₂ Oxidizing the surface of the reduced catalyst by the oxidizing gas under a certain temperature condition to form a compact oxide film so as to protect the interior of the catalyst from being oxidized by air. The liquid passivation mainly uses organic hydrocarbon to form a protective layer on the surface of the catalyst by methods such as spraying, dipping, stirring and the like. The solid passivation is mainly realized by fusing a passivating agent on the surface of the catalyst to achieve the purpose of protection.

109675643A discloses a hydrogenation catalyst which is sulfurized and passivated by distillate oil or oxygen-containing substances. The protective film formed by the liquid phase passivator can be removed during the reaction, but the recovery of the removed liquid can bring trouble to a refinery, and the quality of the product can be influenced by mixing the raw oil after the raw oil is introduced.

Disclosure of Invention

In view of the problems in the prior art, the invention aims to provide a passivation method of a vulcanization type hydrogenation catalyst. According to the method, the catalyst is passivated by adopting ozone at low temperature, so that a compact oxide layer is formed on the surface of the catalyst, oxygen in the air is prevented from further acting with metal sulfides in a catalyst pore channel, the self-heating reaction of the catalyst is avoided, and the safety of catalyst storage, transportation and filling is improved.

The first aspect of the invention provides a passivation method of a vulcanization type hydrogenation catalyst, which comprises the following steps:

(1) Putting the sulfuration state hydrogenation catalyst into a closed container, vacuumizing the container, cooling to-200-0 ℃, introducing nitrogen or carbon dioxide, and treating for 0.1-20 hours, wherein the pressure of the nitrogen or carbon dioxide is 0.5-15 MPa;

(2) And (2) heating the material obtained in the step (1), and then further introducing passivation gas for passivation.

In the passivation method of the vulcanized hydrogenation catalyst, the reaction conditions in the step (1) are as follows: the vacuum degree is-0.05 to-0.1 MPa, and preferably-0.08 to-0.1 MPa; the temperature is-180 to-40 ℃; the flow rate of nitrogen or carbon dioxide is 5-1500 mL/min.

In the passivation method of the sulfided hydrogenation catalyst, the sulfided hydrogenation catalyst in the step (1) can be prepared by a conventional method, and the sulfided hydrogenation catalyst can be prepared by first preparing the oxidation-state hydrogenation catalyst and then performing sulfiding, or can be directly prepared in the preparation process of the hydrogenation catalyst. Generally, the hydrogenation catalyst uses inorganic refractory oxide as a carrier, and uses group VIII and VIB metals as active metal components, wherein the group VIII metal is selected from Ni and/or cobalt, and the group VIB metal is selected from Mo and/or W. The inorganic refractory oxide is generally one or more of alumina, silica and molecular sieve. Based on the weight of the hydrogenation catalyst in a sulfurized state, the content of VIII group metal calculated by elements is 0.5-12, and the content of VIB group metal calculated by elements is 5-35. The hydrogenation catalyst may also contain an auxiliary component, which is generally one or more of phosphorus, fluorine, titanium, zirconium, boron and the like, and the content of the auxiliary component in the catalyst is generally below 30 wt%.

In the passivation method of the sulfuration type hydrogenation catalyst, the temperature in the step (2) is raised to-100-80 ℃, and the treatment is preferably carried out for 1-500 min at the temperature of-50 ℃.

In the passivation method of the vulcanized hydrogenation catalyst, the passivation treatment temperature in the step (2) is-100 to 80 ℃, preferably-50 to 50 ℃; the flow rate of the passivating gas is 100-50000 mL/h, preferably 360-20000 mL/h, more preferably 600-10000 mL/h, and the pressure is 0-20 MPa, preferably 0.1-10 MPa.

In the passivation method of the sulfuration type hydrogenation catalyst, in the step (2), the passivation gas is an ozone-containing gas, the ozone-containing gas is a mixed gas of ozone and a carrier gas, wherein the carrier gas is a gas which does not interact with both the hydrogenation catalyst and the ozone, and can be an inert gas and/or nitrogen, and is preferably nitrogen or carbon dioxide gas.

In the passivation method of the vulcanized hydrogenation catalyst, the passivation process in the step (2) is divided into two sections, wherein the passivation temperature of the first section is-100-0 ℃, preferably-50-0 ℃, further preferably-30-5 ℃, and the volume content of ozone in the passivation gas is 0.5-50%, preferably 1-20%; the contact time of the passivation gas and the catalyst is 1-200 min, the second-stage passivation temperature is 0-80 ℃, preferably-10-30 ℃, and further preferably-5-20 ℃; the volume content of the ozone in the passivation gas is 0.1-50%, preferably 0.2-30%, and the contact time of the passivation gas and the catalyst is 1-100 min.

In the passivation method of the vulcanized hydrogenation catalyst, the passivation gas can pass through the passivation treatment process in the step (2) at one time or can be kept still.

In a second aspect, the invention provides a passivated sulphided hydrogenation catalyst obtained after treatment with the above-described passivation method.

Compared with the prior art, the passivation method of the vulcanization type hydrogenation catalyst has the following advantages:

1. in the passivation method of the vulcanized hydrogenation catalyst, the passivated hydrogenation catalyst can be stably stored in the air, does not generate self-heating/spontaneous combustion reaction, can be stored, transported and filled under natural conditions, and is the same as an oxidation state catalyst.

2. The passivation method of the vulcanized hydrogenation catalyst comprises the steps of firstly, contacting the vulcanized hydrogenation catalyst with nitrogen or carbon dioxide under the vacuum condition for pretreatment, adsorbing the nitrogen or carbon dioxide in catalyst holes at low temperature to be adsorbed on active sites of a carrier, filling liquid nitrogen or liquid carbon dioxide in the catalyst holes when the temperature is continuously reduced to the liquefaction temperature, then heating the gas adsorbed on the surface of the carrier for desorption, exposing the surface active sites, slowly gasifying the gas in the holes, and keeping the gas in the holes continuously adsorbed on the active sites. And then passivation treatment is carried out. The passivation treatment is only carried out on the surface of the catalyst, a compact protective film is formed on the surface of the catalyst, the metal sulfide in the pore canal of the catalyst is not influenced, and the high activity state of the active metal component of the catalyst is maintained. When the catalyst contacts with oxygen in the air, the dense oxide film on the surface isolates the oxygen from the metal sulfide, and the spontaneous reaction of the catalyst is avoided. On the other hand, oxidation of oxygen at low temperature is slow, and a dense oxide film cannot be formed, so that the metal in the catalyst is easily oxidized to lose the hydrogenation activity of the catalyst.

3. In the passivation method of the vulcanization type hydrogenation catalyst, the used nitrogen and/or carbon dioxide are inert gases, do not react with the catalyst, are easy to remove and have no influence on the environment.

4. In the passivation method of the vulcanized hydrogenation catalyst, the vulcanized hydrogenation catalyst obtained after passivation treatment is directly heated to the reaction temperature in the startup of the hydrogenation device, so that the catalyst vulcanization and activation processes in the conventional startup process are omitted, the startup time is greatly saved, the heat release phenomenon does not occur in the heating process, and the method is simple to operate and environment-friendly.

Detailed Description

The technical features of the present invention will be further described below by way of examples, which are not intended to limit the present invention.

Example 1

Taking an industrially produced catalyst FH-40C, pre-vulcanizing to prepare a vulcanized catalyst, placing the catalyst in a closed container, vacuumizing to the vacuum degree of-0.05 MPa, then cooling to-180 ℃, introducing nitrogen at the nitrogen pressure of 3MPa and the flow rate of 100mL/h, keeping for 1h, raising the temperature to-100 ℃ after closing the nitrogen, introducing nitrogen containing 15 percent of ozone, introducing nitrogen at the gas pressure of 3.5MPa and the flow rate of 1000mL/h, keeping for 0.5h to obtain a finished product catalyst A, replacing with nitrogen, and taking out the catalyst for later use.

Example 2

Taking an industrially produced catalyst FH-40C, pre-vulcanizing to prepare a vulcanized catalyst, placing the catalyst in a closed container, vacuumizing to the vacuum degree of-0.1 MPa, then cooling to-50 ℃, introducing carbon dioxide, introducing the carbon dioxide at the pressure of 1MPa and the flow rate of 200mL/h, keeping for 2h, closing the carbon dioxide, raising the temperature to-10 ℃, introducing carbon dioxide gas containing 10% of ozone, keeping for 0.2h at the gas pressure of 4.0MPa and the flow rate of 1200mL/h, then raising the temperature to 20 ℃, keeping for 0.1h at the flow rate of 1500mL/h, thus obtaining a finished product catalyst B, replacing with nitrogen, and then taking out the catalyst for later use.

Example 3

Taking an industrially produced catalyst 1, preparing a sulfurized catalyst by pre-sulfurization, placing the catalyst in a closed container, vacuumizing to a vacuum degree of-0.08 MPa, then cooling to-160 ℃, introducing nitrogen at a pressure of 5MPa and a flow rate of 200mL/h, keeping for 2h, closing the nitrogen, raising the temperature to-80 ℃, introducing nitrogen containing 10% of ozone at a gas pressure of 6.0MPa and a flow rate of 2000mL/h, keeping for 0.5h, then raising the temperature to-50 ℃, increasing the flow rate to 3000mL/h, keeping for 0.1h, obtaining a finished product catalyst C, replacing with nitrogen, and taking out the catalyst for later use.

Example 4

Taking an industrially produced catalyst FH-40C, pre-vulcanizing to prepare a vulcanized catalyst, placing the catalyst in a closed container, vacuumizing to the vacuum degree of-0.08 MPa, then cooling to-120 ℃, introducing carbon dioxide, introducing the carbon dioxide at the pressure of 2MPa and the flow rate of 300mL/h, keeping for 2h, closing the carbon dioxide, raising the temperature to-10 ℃, introducing carbon dioxide containing 8% of ozone, keeping for 0.5h at the gas pressure of 3.0MPa and the flow rate of 2000mL/h, raising the temperature to 30 ℃, keeping for 0.15h at the flow rate of 5000mL/h, obtaining a finished product catalyst D, replacing with nitrogen, and taking out the catalyst for later use.

Comparative example 1

The same as example 2, except that the ozone-containing carbon dioxide gas was changed to 2% oxygen-containing carbon dioxide, catalyst E was obtained.

Comparative example 2

Taking an industrially produced catalyst FH-40C, preparing a vulcanized catalyst through prevulcanization, replacing with nitrogen, heating to 80 ℃, replacing with nitrogen containing 0.5% of oxygen, keeping the temperature for 2 hours, cooling, replacing with nitrogen, and taking out at room temperature to obtain a finished product catalyst F.

Evaluation of catalyst Activity

The catalysts obtained in examples 1 to 4 and comparative examples 1 to 2 were evaluated for activity stability, and the evaluation test was conducted on a 200mL fixed bed hydrotreater. After the device is airtight, introducing hydrogen, directly heating to 150 ℃ at the speed of 20 ℃/h, introducing raw oil, and continuously heatingKeeping the temperature to 350 ℃ for 8h, and then sampling and analyzing. The raw oil for evaluation was a normal-three-line raw oil (distillation range 170-350 ℃ C., density (20 ℃ C.) 0.8661 g/cm) ³ The S content is 11452 mu g/g, the N content is 109.7 mu g/g), and the process conditions are as follows: the reaction pressure is 6.0MPa, and the volume space velocity is 1.5h ^-1 The reaction temperature is 350 ℃, and the hydrogen-oil ratio is 1200. The evaluation results are shown in Table 1.

Test for evaluation of exothermic Property

The catalysts obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to an exothermic test in air, and 25g of the catalyst was taken out and put into an autothermal tester, and the temperature was raised to 150 ℃ and maintained at the temperature for 3 hours, to examine the exothermic state of the catalyst in air, and the results are shown in Table 2. The autothermal tester is a device that measures the exothermic heat of oxidation of a material. The measurement chamber is kept adiabatic and the exothermic heat of oxidation of the measurement object can be monitored by a thermocouple inserted therein. The more the temperature is raised, the greater the exotherm.

TABLE 1 evaluation results of catalysts

Catalyst numbering	S，μg/g	N，μg/g
			Catalyst A	15.2	<1.0
Catalyst B	18.4	<1.0
			Catalyst C	13.6	<1.0
Catalyst D	16.1	<1.0
			Catalyst E	43.2	<1.0
Catalyst F	57.9	0.3

TABLE 2 exothermic results for the catalysts

Item	Catalyst 1	Catalyst A	Catalyst B	Catalyst C	Catalyst D	Catalyst E	Catalyst F
								Elevated temperature	0.5	—	—	—	—	0.1	0.15

Claims

1. A process for the passivation of a sulfided hydrogenation catalyst, said process comprising the steps of:

(1) Putting the hydrogenation catalyst in a vulcanization state into a closed container, vacuumizing the container, cooling to-200-0 ℃, introducing nitrogen or carbon dioxide, and treating for 0.1-20 hours, wherein the pressure of the nitrogen or carbon dioxide is 0.5-15 MPa;

(2) And (2) heating the material obtained in the step (1), and then further introducing passivating gas for passivating, wherein the passivating gas is an ozone-containing gas.

2. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 1, wherein: the reaction conditions in the step (1) are as follows: the vacuum degree is-0.05 to-0.1 MPa, and the temperature is-180 to-40 ℃.

3. A process for the passivation of a sulfided hydrogenation catalyst as recited in claim 1, wherein: the reaction conditions in the step (1) are as follows: the vacuum degree is-0.08 to-0.1 MPa.

4. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 1, wherein: the flow rate of the nitrogen or the carbon dioxide in the step (1) is 5-1500 mL/min.

5. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 1, wherein: and (3) heating to-100-80 ℃ in the step (2) for treatment.

6. A process for the passivation of a sulfided hydrogenation catalyst as recited in claim 1, wherein: and (3) heating to-50 ℃ in the step (2) for treatment.

7. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 1, wherein: the passivation treatment temperature in the step (2) is-100-80 ℃, the flow rate of the passivation gas is 100-50000 mL/h, and the pressure is 0-20 MPa.

8. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 7, wherein: the passivation treatment temperature in the step (2) is-50 ℃.

9. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 7, wherein: the flow rate of the passivating gas in the step (2) is 360-20000 mL/h.

10. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 7, wherein: the flow rate of the passivating gas in the step (2) is 600-10000 mL/h.

11. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 7, wherein: the pressure of the passivation gas in the step (2) is 0.1-10 MPa.

12. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 1, wherein: the ozone-containing gas in the step (2) is a mixed gas of ozone and a carrier gas, wherein the carrier gas is a gas which has no interaction with both the hydrogenation catalyst and the ozone and is nitrogen or carbon dioxide.

13. A process for the passivation of a sulfided hydrogenation catalyst as claimed in claim 1, wherein: the passivation process in the step (2) is divided into two sections, wherein the passivation temperature of the first section is-100-0 ℃, the volume content of ozone in the passivation gas is 0.5-50%, and the contact time of the passivation gas and the catalyst is 1-200 min; the second-stage passivation temperature is-10-50 ℃, the volume content of ozone in the passivation gas is 0.1-50%, and the contact time of the passivation gas and the catalyst is 1-100 min.

14. A process for the passivation of a sulfided hydrogenation catalyst as recited in claim 13, wherein: the first-stage passivation temperature in the passivation process in the step (2) is-50-0 ℃.

15. A process for the passivation of a sulfided hydrogenation catalyst as recited in claim 13, wherein: the first-stage passivation temperature in the passivation process in the step (2) is-30 to-5 ℃.

16. A process for the passivation of a sulfided hydrogenation catalyst as recited in claim 13, wherein: the volume content of ozone in the first section of passivation gas in the passivation process in the step (2) is 1-20%.

17. A process for the passivation of a sulfided hydrogenation catalyst as recited in claim 13, wherein: the second passivation temperature in the passivation process in the step (2) is-10 to 30 ℃.

18. A process for the passivation of a sulfided hydrogenation catalyst as recited in claim 13, wherein: the second passivation temperature in the passivation process in the step (2) is-5 to 20 ℃.

19. A process for the passivation of a sulfided hydrogenation catalyst as recited in claim 13, wherein: the volume content of ozone in the second section of passivation gas in the passivation process in the step (2) is 0.2-30%.

20. A passivated sulphided hydrogenation catalyst obtained after treatment with a passivation process according to any one of claims 1 to 19.