CN101205478A - Adsorbent for solvent oil desulfurization and deodorization and preparation method thereof - Google Patents

Abstract

The invention relates to an adsorbent for desulfurization and deodorization of solvent oil and a preparation method thereof. The adsorbent is composed of active metals of Group VIII, Group IB and Group IIB in a reduced state and active metal oxides containing zinc oxide. The adsorbent is prepared by kneading, impregnating, sedimentation, co-precipitation and other methods. The adsorbent can absorb all the mercaptans and sulfides with foul smell in the oil, so as to achieve the purpose of deodorization, and at the same time, it can also remove solvent oil Thiophene, benzothiophene, dibenzothiophene and other thiophene organic sulfides in the oil can significantly reduce the sulfur content of the oil and obtain ultra-low sulfur solvent oil. This adsorbent not only has good desulfurization and deodorization effects on light solvent oils such as 110 ^# , 130 ^# and 150 ^# , but also has a good effect on heavy solvent oils such as 200 ^# and 260 ^# , and is especially suitable for conventional methods Heavy solvent oil that is difficult to desulfurize and deodorize. The adsorbent also has the characteristics of simple preparation method, large sulfur capacity and convenient regeneration.

Description

Adsorbent for solvent oil desulfurization and deodorization and preparation method thereof

technical field

The invention relates to an adsorbent for desulfurization and deodorization of solvent oil and a preparation method thereof.

Background technique

The deodorization of light oil is an essential process in petrochemical industry. Its purpose is to remove or convert the foul-smelling organic sulfur compounds into odorless substances in oil products to meet production needs and environmental protection requirements. With the exploitation of oil, the oil reserves on the earth are getting less and less. In recent years, with the heavy and inferior quality of crude oil and the improvement of crude oil processing depth, the content of mercaptans and sulfides in light oil products in refineries is relatively high, and the molecular structure is more complex, which makes the deodorization of oil products more difficult. difficulty. For this reason, refineries at home and abroad are actively exploring new technologies to improve the deodorization effect.

At present, the deodorization technology commonly used in industry is non-alkali deodorization technology. Its characteristic is that the raw material oil and the activator solution are fully mixed by the mixer, and react to remove mercaptans when they pass through the catalyst bed together with air. The domestic patent No. CN1248609A describes the preparation method of the impregnation solution for fixed-bed catalysts, which is to dissolve cobalt phthalocyanine compounds in 0.5-2% aqueous solution of alkali metal oxides. Since the solution is strongly alkaline, the cobalt phthalocyanine compound will be transformed into an inactive component, so that the active cobalt phthalocyanine compound concentration in the impregnating solution is reduced. The preparation method of the impregnation solution disclosed in U.S. Patent No. 4,913,802 is to add cobalt phthalocyanine compounds in 2% ammonia water and 1% quaternary ammonium alkali mixed solution, although the conversion of cobalt phthalocyanine compounds to inactive components can be slowed down, However, the bed catalyst prepared with this impregnation solution is easy to lose during the deodorization process, resulting in a short service life of the bed. The above-mentioned methods can only remove low-molecular-weight mercaptans and thioethers (with carbon numbers less than 6) contained in light solvent oils, but cannot remove high-molecular-weight mercaptans, thioethers, and thiophenes that are relatively high in heavy solvent oils. , benzothiophene, dibenzothiophene and other thiophene organic sulfides.

Contents of the invention

The object of the present invention is to provide an adsorbent for desulfurization and deodorization of solvent oil and a preparation method thereof.

The invention also provides a method for producing low-sulfur deodorized solvent oil (sulfur content < 1ppm).

The invention provides an adsorbent for desulfurization and deodorization of solvent oil, which is characterized in that: the adsorbent is composed of active metals selected from Group VIII, Group IB, and Group IIB and mixed metal oxides containing active zinc oxide. The loading amount of metal is 1-50wt%;

The active metal oxide containing zinc oxide refers to a mixed oxide formed of zinc oxide and silicon oxide, aluminum oxide, titanium oxide, or zirconium oxide, and the content of zinc oxide in the mixed metal oxide is 10-90%.

In the adsorbent used for solvent oil desulfurization and deodorization according to the present invention, the active metal is preferably selected from one or more of iron, cobalt, nickel, copper, and silver, and is preferably selected from one or both of cobalt and nickel .

The present invention also provides the above-mentioned preparation method for solvent oil desulfurization and deodorization adsorbent, which is characterized in that the preparation steps are as follows:

- Weigh zinc nitrate and VIII, IB, IIB metal salts into water, adjust the pH value to 1-2 with concentrated nitric acid to obtain a mixed solution of metal salts;

——Add the precipitating agent into the mixed solution of the above metal salts, raise the temperature to 80°C-100°C, and stir for 1-72 hours;

- After the obtained precipitate is suction filtered, washed and dried, it is calcined at 150°C-800°C for 1-24 hours.

In the above preparation method, the metal salts refer to soluble nitrates, chlorides, sulfates or/and combinations thereof; the precipitating agent can be selected from urea, ammonia, ammonium carbonate, sodium carbonate, sodium hydroxide or/and combinations thereof material; preferably urea, ammonia water; the stirring time is preferably 12-48 hours; the roasting temperature is preferably 300°C-550°C.

The term "solvent oil" used in the present invention means common solvent oil products, mainly including 110 ^# , 130 ^# , 150 ^# , 200 ^# , 260 ^# solvent oil, etc.

The term "sulfur" used in the present invention means those organic sulfides such as mercaptan, thioether, thiophene, benzothiophene, alkylthiophene, alkylbenzothiophene, dibenzothiophene and alkyl Substituted dibenzothiophenes.

Specifically, compared with the prior art, the preparation method of the adsorbent provided by the invention and the adsorption deodorization and desulfurization method have the following advantages:

1. The solvent oil adsorption deodorization desulfurization method provided by the present invention can not only remove low-molecular-weight mercaptans and thioethers (carbon number less than 6) contained in light solvent oils, but also remove higher-content thiols in heavy solvent oils. High molecular weight mercaptans and thioethers and organic sulfides such as thiophene, benzothiophene, and dibenzothiophene can be used to obtain low-sulfur solvent oil.

2. The raw materials of the adsorbent of the present invention are easy to obtain, the preparation method is greatly simplified, and the production cost is significantly reduced.

3. The adsorbent provided by the present invention has a large adsorption capacity for organic sulfur-containing compounds (including various mercaptans and thioethers as well as thiophene, benzothiophene, dibenzothiophene and their derivatives).

4. The use and regeneration of the adsorbent is convenient, and the good desulfurization effect can still be maintained after regeneration, and the service life of the adsorbent is long.

Description of drawings

Figure 1260 ^#The GC-FPD spectrogram of solvent oil.

Fig. 2 GC-FPD spectrogram of deodorized solvent oil product.

Detailed ways

In order to further illustrate the present invention, the following implementation examples are cited, but it does not limit the scope of the invention defined by the appended claims.

The preparation of embodiment 1 adsorbent.

As an illustrative example, the reduced metal solid adsorbent is produced as follows: Weigh 3.20 g of nickel nitrate hexahydrate, 7.35 g of zinc nitrate hexahydrate and 1.2 g of aluminum nitrate hexahydrate in 200 ml of distilled water, adjust the pH value to 1-2 with concentrated nitric acid , add 8.10g of urea and stir at 90°C for 24 hours to completely hydrolyze the precipitating agent, filter, wash with deionized water, and dry in vacuum to obtain a green solid, which is roasted at 500°C for 4 hours, the sample number is A.

Example 2

Same as embodiment 1, except that the amount of nickel nitrate added in embodiment 2 is 1.60g, and the sample number is B.

Example 3

Same as Example 1, except that the amount of nickel nitrate added in Example 3 is 4.80g, and the sample number is C.

Example 4

Same as Example 1, except that in Example 4, it was stirred at 90° C. for 12 hours, and the sample number was D.

Example 5

Same as Example 1, except that in Example 5, it was stirred at 90° C. for 6 hours, and the sample number was E.

Example 6

Same as Example 1, except that the calcination temperature in Example 6 is 400° C., and the sample number is F.

Example 7

Same as Example 1, except that the calcination temperature in Example 7 is 600° C., and the sample number is G.

Example 8

Same as Example 1, except that the firing time in Example 8 is 24 hours, and the sample number is H.

Example 9

With embodiment 1, just roasting time is 12 hours in embodiment 9, and sample number is 1.

Example 10

Same as Example 1, except that the firing time in Example 10 is 8 hours, and the sample number is J.

Example 11

Same as Example 1, except that the active metal in Example 11 is cobalt, and the sample number is K.

Example 12

Same as Example 1, except that the active metal is palladium in Example 12, and the sample number is L.

Example 13

Same as Example 1, except that the active metal is copper in Example 13, and the sample number is M.

Example 14

Same as Example 1, except that the active metal is rhodium in Example 13, and the sample number is N.

Example 15

Same as Example 1, except that the active metal is platinum in Example 15, and the sample number is O.

Example 16

With embodiment 1, just change the aluminum nitrate among the embodiment 1 into the sodium silicate of equal quality, sample number is P.

Example 17

Same as Example 1, just change the aluminum nitrate in Example 1 into titanium oxide of equal quality, and the sample number is Q.

Example 18

Same as Example 1, except that the aluminum nitrate in Example 1 is changed to equal-quality zirconia, and the sample number is R.

Example 19

Same as Example 1, except that the aluminum nitrate in Example 1 is changed to equal-quality zirconia and equal-quality aluminum nitrate, and the sample number is S.

Example 20

Same as Example 1, except that the aluminum nitrate in Example 1 is changed to equal mass of zirconia and equal mass of titanium nitrate, and the sample number is T.

Example 21

For the deodorization of 110 ^# solvent oil (70 ~ 110 ℃ cut) provided by Baling Petrochemical Group Company, the deodorization and desulfurization ability of the solid adsorbent prepared in the test embodiment 1-20: the adsorbent of the following amount is loaded into In a steel tubular adsorber. This solid adsorbent is placed on the frit of the reactor, reduced with hydrogen, and pumped down through the reactor with mineral spirits containing about 10 mg/l sulfur at a flow rate of 1 ml/min. Solid adsorbents and deodorized solvent oil products.

Adsorbents A-T are all effective in completely deodorizing mineral spirits under the conditions shown in Table 1 and completely removing organic sulfides under the deodorizing conditions shown. The experimental results are shown in Table 1. The adsorbent has a strong adsorption capacity for sulfur in the sulfur-containing molecules in 110# solvent oil, and each gram of the adsorbent can remove almost 100% of the sulfur-containing molecules in 12000ml of oil. The breakthrough sulfur capacity of the solvent oil treated with adsorbents A-T is more than 0.12 g sulfur/g adsorbent, and the saturated sulfur capacity can exceed 0.24 g sulfur/g adsorbent. Several regeneration experiments have been carried out on the adsorbent A. The regeneration conditions are as follows. The sulfurized adsorbent A is treated for 2-4 hours under the regeneration conditions of a temperature of 470°C, a pressure of 0.1Mpa, and an oxygen partial pressure of 0.001-0.1Mpa to generate regeneration. The adsorbent is then treated at 450° C., under the activation conditions of total pressure 0.1Mpa and hydrogen partial pressure 0.01-0.1Mpa for 2-4 hours to generate an activated adsorbent. The resulting activated sorbent was then used in the next cycle to equally effectively deodorize mineral spirits completely and significantly reduce the sulfur content under the deodorizing conditions shown. The experimental results are shown in Table 2. It can be seen from Table 2 that the adsorption performance of the adsorbent is basically maintained through simple regeneration.

Table 1 Adsorption properties of various adsorbents

Note: The sulfur content of raw solvent oil (110 ^# ) is 10mg/l, H ₂ /oil=300Nl/l, LHSV=120h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Table 1 (continued) Adsorption properties of various adsorbents

Note: The sulfur content of raw solvent oil (110 ^# ) is 10mg/l, H ₂ /oil=300Nl/l, LHSV=120h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Table 2 Adsorption performance of regenerated adsorbent

Note: The adsorbent is A, the sulfur content of raw solvent oil (110 ^# ) is 10mg/l, H ₂ /oil=300Nl/l, LHSV=120h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Example 22

For the deodorization of 170 ^# solvent oil (90～170 ℃ cut) provided by Baling Petrochemical Group Company, the deodorization and desulfurization ability of the solid adsorbent prepared in the test embodiment 1-20: the adsorbent of the following amount is loaded into In a steel tubular adsorber. This solid adsorbent is placed on the frit of the reactor, reduced with hydrogen and pumped down through the reactor with mineral spirits containing about 50 mg/l sulfur at a flow rate of 0.1 ml/min. Sulfurized solid adsorbents and deodorized mineral spirits products.

Adsorbents A-T are all effective in completely deodorizing mineral spirits under the conditions shown in Table 3 and completely removing organic sulfides under the deodorizing conditions shown. The experimental results are shown in Table 3. The adsorbent has a strong adsorption capacity for sulfur in the sulfur-containing molecules in 110# solvent oil, and every gram of the adsorbent can remove almost 100% of the sulfur-containing molecules in 2400ml of oil. The breakthrough sulfur capacity of the solvent oil treated with adsorbents A-T is more than 0.12 g sulfur/g adsorbent, and the saturated sulfur capacity can exceed 0.24 g sulfur/g adsorbent. Several regeneration experiments have been carried out on the adsorbent A. The regeneration conditions are as follows. The sulfurized adsorbent A is treated for 2-4 hours under the regeneration conditions of a temperature of 470°C, a pressure of 0.1Mpa, and an oxygen partial pressure of 0.01-0.1Mpa, resulting in regeneration The adsorbent is then treated at 450° C., under the activation conditions of total pressure 0.1Mpa and hydrogen partial pressure 0.01-0.1Mpa for 2-4 hours to generate an activated adsorbent. The resulting activated sorbent was then used in the next cycle to equally effectively deodorize mineral spirits completely and significantly reduce the sulfur content under the deodorizing conditions shown. The experimental results are shown in Table 4. It can be seen from Table 4 that the adsorption performance of the adsorbent is basically maintained through simple regeneration.

Table 3 Adsorption properties of various adsorbents

Note: The sulfur content of raw solvent oil (170 ^# ) is 50mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Table 3 (continued) Adsorption properties of various adsorbents

Note: The sulfur content of raw solvent oil (170 ^# ) is 50mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Adsorption performance of table 4 regenerated adsorbent

Note: The adsorbent is A, the sulfur content of raw solvent oil (170 ^# ) is 50mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Example 23

For the deodorization of 200 ^# solvent oil (110～200°C fraction) provided by Baling Petrochemical Group Company, test the deodorization and desulfurization ability of the solid adsorbent prepared in Examples 1-20: put the following amount of adsorbent into In a steel tubular adsorber. This solid adsorbent is placed on the frit of the reactor, reduced with hydrogen, and pumped down through the reactor with mineral spirits containing about 100 mg/l sulfur at a flow rate of 0.1 ml/min. Sulfurized solid adsorbents and deodorized mineral spirits products.

Adsorbents A-T are all effective in completely deodorizing solvent oil under the conditions shown in Table 5 and completely removing organic sulfides under the deodorizing conditions shown. The experimental results are shown in Table 5. The adsorbent has a strong adsorption capacity for sulfur in the sulfur-containing molecules in 200# solvent oil, and each gram of the adsorbent can remove almost 100% of the sulfur-containing molecules in 1200ml of oil. The breakthrough sulfur capacity of the solvent oil treated with adsorbents A-T is more than 0.12 g sulfur/g adsorbent, and the saturated sulfur capacity can exceed 0.24 g sulfur/g adsorbent. Several regeneration experiments have been carried out on the adsorbent A. The regeneration conditions are as follows. The sulfurized adsorbent A is treated for 2-4 hours under the regeneration conditions of a temperature of 470°C, a pressure of 0.1Mpa, and an oxygen partial pressure of 0.01-0.1Mpa to generate regeneration. The adsorbent is then treated at 450° C., under the activation conditions of total pressure 0.1Mpa and hydrogen partial pressure 0.01-0.1Mpa for 2-4 hours to generate an activated adsorbent. The resulting activated sorbent was then used in the next cycle to equally effectively deodorize mineral spirits completely and significantly reduce the sulfur content under the deodorizing conditions shown. The experimental results are shown in Table 6. It can be seen from Table 6 that the adsorption performance of the adsorbent is basically maintained through simple regeneration.

Adsorption properties of various adsorbents in table 5

Note: The sulfur content of raw solvent oil (200 ^# ) is 100mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Table 5 (continued) Adsorption properties of various adsorbents

Note: The sulfur content of raw solvent oil (200 ^# ) is 100mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Adsorption performance of table 6 regenerated adsorbent

Note: The adsorbent is A, the sulfur content of raw solvent oil (200 ^# ) is 100mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Example 24

For the deodorization of 260 ^# solvent oil (140～260 ℃ cut) provided by Baling Petrochemical Group Company, the deodorization and desulfurization ability of the solid adsorbent prepared in the test embodiment 1-20: the adsorbent of the following amount is loaded into In a steel tubular adsorber. This solid sorbent is placed on the frit of the reactor, reduced with hydrogen and pumped down through the reactor with mineral spirits containing about 145 mg/l sulfur at a flow rate of 0.1 ml/min. Sulfurized solid adsorbents and deodorized mineral spirits products.

Adsorbents A-T are all effective in completely deodorizing solvent oil under the conditions shown in Table 7 and completely removing organic sulfides under the deodorizing conditions shown. The experimental results are shown in Table 7. The adsorbent has a strong adsorption capacity for sulfur in the sulfur-containing molecules in 260# solvent oil, and each gram of the adsorbent can remove almost 100% of the sulfur-containing molecules in 1200ml of oil. The maximum sulfur capacity of the solvent oil treated with adsorbents A-T exceeds 0.17 g sulfur/g adsorbent, and the saturated sulfur capacity can exceed 0.24 g sulfur/g adsorbent. Figure 1 and Figure 2 show the GC-FPD detection results of solvent oil and deodorized solvent oil products respectively. It can be clearly seen that the organic sulfide molecules in solvent oil can be completely removed, and the adsorbent A has been tested many times. Regeneration experiment, the regeneration conditions are as follows, the sulfurized adsorbent A is treated for 2-4 hours under the regeneration conditions of temperature 470 ° C, pressure 0.1Mpa, and oxygen partial pressure 0.01-0.1Mpa to produce a regenerated adsorbent, and then make the adsorbent The sorbent is treated for 2-4 hours under the activation conditions of 450°C, total pressure 0.1Mpa and hydrogen partial pressure 0.01-0.1Mpa to produce activated adsorbent. The resulting activated sorbent was then used in the next cycle to equally effectively deodorize mineral spirits completely and significantly reduce the sulfur content under the deodorizing conditions shown. The experimental results are shown in Table 8. It can be seen from Table 8 that the adsorption performance of the adsorbent is basically maintained through simple regeneration.

Adsorption properties of various adsorbents in table 7

Note: The sulfur content of raw solvent oil (260 ^# ) is 145mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Table 7 (continued) Adsorption properties of various adsorbents

Note: The sulfur content of raw solvent oil (260 ^# ) is 145mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Adsorption performance of table 8 regenerated adsorbent

Note: The adsorbent is A, the sulfur content of raw solvent oil (260 ^# ) is 145mg/l, H ₂ /oil=300Nl/l, LHSV=12h ^-1 . Regeneration conditions: temperature 470°C, _O2 partial pressure 0.001MPa, treatment time 2 hours.

Claims (10)

1. An adsorbent for solvent oil desulfurization and deodorization, characterized in that: the adsorbent is composed of active metals selected from group VIII, IB, and IIB and mixed metal oxides containing active zinc oxide, the active metal The loading amount is 1-50wt%; The active metal oxide containing zinc oxide refers to a mixed oxide formed of zinc oxide and silicon oxide, aluminum oxide, titanium oxide, or zirconium oxide, and the content of zinc oxide in the mixed metal oxide is 10-90%. 2. The adsorbent for solvent oil desulfurization and deodorization according to claim 1, wherein the active metal is selected from one or more of iron, cobalt, nickel, copper, and silver. 3. The adsorbent for solvent oil desulfurization and deodorization according to claim 1, wherein the active metal is selected from one or both of cobalt and nickel. 4. a preparation method for solvent oil desulfurization and deodorization sorbent as claimed in claim 1, characterized in that the preparation steps are as follows: - Weigh zinc nitrate and VIII, IB, IIB metal salts into water, adjust the pH value to 1-2 with concentrated nitric acid to obtain a mixed solution of metal salts; ——Add the precipitating agent into the mixed solution of the above metal salts, raise the temperature to 80°C-100°C, and stir for 1-72 hours; - After the obtained precipitate is suction filtered, washed and dried, it is calcined at 150°C-800°C for 1-24 hours. 5. According to the preparation method for solvent oil desulfurization and deodorization adsorbent according to claim 4, it is characterized in that metal salts refer to soluble nitrates, chlorides, sulfates or/and combinations thereof. 6. According to the preparation method for solvent oil desulfurization and deodorization adsorbent according to claim 5, it is characterized in that the precipitating agent is selected from urea, ammonia, ammonium carbonate, sodium carbonate, sodium hydroxide or/and its composition. 7. According to the preparation method for solvent oil desulfurization and deodorization adsorbent according to claim 6, it is characterized in that: the selected precipitant is urea and ammonia water. 8. According to the preparation method for solvent oil desulfurization and deodorization adsorbent according to claim 4, it is characterized in that: the stirring time is preferably 12-48 hours. 9. The method for preparing an adsorbent for solvent oil desulfurization and deodorization according to claim 4, characterized in that the calcination temperature is 300°C-550°C. 10. The adsorbent of claim 1 is used for solvent oil desulfurization and deodorization.

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