Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the residual oil hydrotreating catalyst, the preparation method and the recycling thereof, the residual oil hydrotreating catalyst prepared by the method has excellent demetallization performance, the residual oil hydrotreating catalyst prepared by the method can efficiently recycle catalyst carriers and active metal components, and meanwhile, the performance of the recycled regenerated catalyst is excellent, and the method also has the characteristics of simple process, low treatment cost and the like.
The first aspect of the invention provides a method for preparing a residuum hydrotreating catalyst, comprising:
(1) Drying biomass raw materials, crushing the biomass raw materials into wood chips, mixing and kneading the wood chips with an adhesive and an activating agent, and forming;
(2) Performing heat treatment on the molded product obtained in the step (1);
(3) Carbonizing the material obtained in the step (2) under protective gas, and then performing steam treatment;
(4) Repeating the step (3) for 1-5 times to obtain an intermediate, and then washing and drying to obtain the carbon carrier;
(5) Impregnating the carbon carrier obtained in the step (4) with an impregnating solution containing an active metal component, and drying and roasting to obtain the residual oil hydrotreating catalyst.
In the step (1), the biomass raw material may be one or more of wood, fruit shell and bamboo.
In the step (1), the drying conditions are as follows: and drying at 100-250 ℃ for 4-8 hours. The particle size of the wood chips is 150-400 meshes, preferably 200-300 meshes.
In the step (1), the adhesive is: one or more of starch, sesbania powder, polyvinyl alcohol, methyl cellulose and the like, wherein the activating agent is as follows: potassium carbonate and/or potassium hydroxide.
In the step (1), the mass ratio of the wood dust, the adhesive and the activator is as follows: 5-7: 3-5: 0.05 to 0.1
In step (1), the molding is performed by conventional means in the art.
In the step (2), the heat treatment conditions are as follows: treating at 250-500 ℃ for 1.0-3.0 h.
In the step (3), the condition of the carbonization treatment is as follows: the temperature is 400-1300 ℃, preferably 800-1200 ℃ and the time is 1-4 h. The shielding gas may be an inert gas and/or nitrogen.
In the step (3), the conditions of the steam treatment are as follows: the temperature is 80-200 ℃ and the time is 0.1-1.5 h.
In the step (4), the water washing is performed by adopting a conventional means in the field, and the drying conditions are as follows: and drying at 100-200 ℃ for 3-8 hours.
In step (5), the impregnating solution is preferably aqueous ammonia or other ammonia solution.
In the step (5), the impregnation may be performed by a conventional impregnation method such as saturated impregnation, supersaturation impregnation, etc., and may be performed in one step or may be performed in steps.
In the step (5), the drying adopts microwave drying, and the drying conditions are as follows: drying for 1-4 hours at 100-200 ℃, wherein the microwave power is 2-8 kW. The roasting conditions are as follows: roasting for 2-5 h at 300-600 ℃ in an inert atmosphere.
In the step (5), the residual oil hydrotreating catalyst comprises 3-20% of active metal components calculated by oxide and 80-97% of carbon carrier by weight of the catalyst.
In step (5), the active metal component is a metal containing nickel and/or vanadium, preferably nickel and vanadium.
Preferably, the residual oil hydrotreating catalyst has a vanadium mass content of 15% or less in terms of oxide and a nickel mass content of 5% or less in terms of oxide, based on the weight of the catalyst.
In a second aspect, the present invention provides a residuum hydrotreating catalyst prepared by the above process.
The pore distribution of the residuum hydrotreating catalyst is as follows: pore diameter<The ratio of the pore volume of 100nm pores to the total pore volume is 40% -70%, the ratio of the pore volume of 100-1000nm pores to the total pore volume is 20% -50%, and the pore diameter is>The pore volume of the 1000nm pores accounts for 10% -30% of the total pore volume. The residuum hydrogenation positionThe specific surface area of the catalyst is 100-450 m 2 The pore volume per gram is 0.45-2.0 mL/g.
The third aspect of the invention provides a recovery and utilization of the residuum hydrotreating catalyst.
The recycling method comprises the following steps:
(I) Extracting, drying and roasting a waste catalyst obtained after the residual oil hydrotreating catalyst is subjected to residual oil hydrotreating;
(II) adding the material obtained in the step (I) into an alkaline solution containing sodium for treatment, and then washing and filtering to obtain a sodium vanadate solution and a nickel-containing catalyst;
(III) adding the nickel-containing catalyst obtained in the step (II) into an acidic solution for treatment to obtain a nickel-containing solution and an acidic carbon carrier;
(IV) washing and drying the acid carbon carrier obtained in the step (III) to obtain a regenerated catalyst carrier;
(V) impregnating the carbon carrier obtained in the step (IV) with an impregnation liquid containing an active metal component, and drying and roasting to obtain the regenerated residual oil hydrotreating catalyst.
In the step (I), the drying conditions are: drying at 100-200 ℃ for 2-5 h. The roasting condition is that roasting is carried out for 2-10 hours at 300-500 ℃.
Wherein in the step (I), the total mass content of nickel and vanadium of the roasted waste catalyst is more than 15%, preferably more than 30%, and the pore volume of the roasted waste catalyst is less than 0.2mL/g.
In the step (II), the alkaline solution containing sodium is one or more of sodium hydroxide, sodium carbonate or sodium bicarbonate. The treatment condition is that ultrasonic oscillation treatment is carried out for 2-5 hours at 150-300 ℃.
In the step (II), the obtained sodium vanadate solution is recycled. The ammonium salt can be added into the sodium vanadate solution for precipitation, so that ammonium metavanadate solid is obtained.
In the step (III), the acidic solution is one or more of nitric acid, hydrochloric acid, sulfuric acid or citric acid. The treatment condition is that the treatment is carried out for 1-5 hours at the temperature of 10-100 ℃.
In step (IV), the washing is a conventional technical means in the art, and the drying conditions are: the temperature is 150-300 ℃ and the time is 3-5 h.
The impregnating solution in the step (V) can be prepared from vanadium salt and/or nickel salt which are purchased in the market, and can also be prepared from recovered nickel and vanadium metal.
Compared with the prior art, the invention has the following advantages:
the residuum hydrotreating catalyst obtained by the method has excellent performance, and after the residuum hydrotreating catalyst obtained by the method is converted into a waste catalyst through long-period operation, the catalyst carbon carrier and the active metal nickel vanadium can be efficiently recovered, and the recovered and reused regenerated catalyst still has excellent performance.
Detailed Description
The technical scheme and technical effects of the present invention will be further described with reference to the following examples, but are not limited thereto.
Example 1
Preparation of a hydrotreating catalyst:
drying 5000 g of bamboo scraps, crushing the bamboo scraps to 200 meshes, mixing and kneading the bamboo scraps with 5000 g of starch and 500g of potassium hydroxide, and forming; carrying out heat treatment on the molded product at 300 ℃ for 2 hours; carbonizing in an inert protective gas atmosphere at 900 ℃ for 3 hours; then carrying out steam treatment at 150 ℃ for 2 hours, then continuing carbonization, and repeating the steam treatment for 3 times in total; the obtained carrier was washed with water and dried at 130℃for 5 hours to obtain a carbon carrier. Preparing nickel-vanadium solution, wherein the solution solvent is dilute ammonia water; the carbon carrier is soaked in nickel and vanadium active metal solution, then is dried for 3 hours at 140 ℃ by microwave with the microwave power of 4kW, and finally is roasted for 3 hours at 400 ℃ in inert gas atmosphere, thus obtaining the catalyst A-1.
(II) recycling the hydrotreating catalyst:
catalyst A-1 was run on a 200mL unit (space velocity: 0.4, temperature: 420 ℃, relevant properties of the catalyst are shown in Table 1) and removed after deactivation of the catalyst; extracting the deactivated catalyst, drying at 180 ℃ for 3 hours, and roasting at 400 ℃ for 3 hours, wherein the total mass content of nickel and vanadium in the roasted waste catalyst is 55wt%, and the pore volume of the roasted waste catalyst is 0.12mL/g; immersing 100g of waste catalyst into a sodium carbonate solution, carrying out ultrasonic oscillation treatment for 2 hours at 180 ℃, washing with hot water, and filtering to obtain a sodium vanadate solution and a nickel-containing catalyst; precipitating the sodium vanadate solution by adopting ammonium salt, and recovering to obtain 90g of ammonium metavanadate solid; immersing a nickel-containing catalyst into nitric acid, and treating for 5 hours at 50 ℃ to obtain a nickel nitrate solution and an acidic carbon carrier; washing the acidic carbon carrier, and drying at 150 ℃ for 3 hours to obtain 35.8g of regenerated catalyst carrier A; then the same method as in the first step is adopted to impregnate the active metal nickel vanadium, and finally the regenerated catalyst A-2 is obtained. The regenerated catalyst was subjected to residuum hydrotreatment again, and the evaluation conditions were the same as those of the catalyst A-1, and the results are shown in Table 1.
Example 2
The same as in example 1, except that (a) the raw material was changed to Arundo donax, catalyst B-1 was produced; and (2) the total mass content of nickel and vanadium in the deactivated and roasted waste catalyst is 60wt%, 95g of ammonium metavanadate and 34.9g of regenerated catalyst carrier B are recovered, and finally the regenerated catalyst B-2 is obtained.
Example 3
The procedure of example 1 was repeated except that the carrier was subjected to steam treatment for 1.5 hours and then carbonization was continued, and the steam treatment and carbonization were repeated 4 times to prepare catalyst C-1; and (2) the total mass content of nickel and vanadium in the waste catalyst after the deactivation roasting in the step (II) is 58. 58 wt percent, 92.9g of ammonium metavanadate and 34.5g of regenerated catalyst carrier C are recovered, and finally the regenerated catalyst C-2 is obtained.
Example 4
The procedure of example 1 was repeated except that the carrier was subjected to steam treatment for 2.5 hours and then further carbonized, and the steam treatment and carbonization were repeated 4 times to prepare catalyst D-1; and (2) immersing 100g of the catalyst into a sodium carbonate solution, carrying out ultrasonic vibration treatment for 2.5h at 180 ℃ to obtain 92.5g of ammonium metavanadate and 34.3g of regenerated catalyst carrier D, and finally obtaining the regenerated catalyst D-2.
Example 5
In the same manner as in example 1 except that in (II), 100g of the spent catalyst was immersed in a sodium carbonate solution, and subjected to ultrasonic vibration at 200℃for 3 hours, 90.4g of ammonium metavanadate and 35.6g of regenerated catalyst carrier E were recovered, and finally regenerated catalyst E-2 was obtained.
Comparative example 1
The industrial deactivated demetallization catalyst of residuum hydrogenating apparatus in some refinery is mainly molybdenum, nickel, vanadium and aluminum. Extracting the waste catalyst, drying at 180 ℃ for 3 hours, roasting at 400 ℃ for 3 hours, wherein the nickel vanadium molybdenum content in the roasted catalyst is 48wt%, immersing 100g of the catalyst in a sodium carbonate solution, treating at 180 ℃ for 3 hours, washing with hot water, filtering to obtain sodium vanadate, sodium molybdate and sodium aluminate solution and nickel slag solid, regulating the pH value to precipitate aluminum hydroxide, then dropwise adding ammonia water, regulating the pH value, and separating 6.1g of ammonium molybdate and 86.3g of ammonium vanadate; and immersing the nickel slag solid into nitric acid to obtain nickel nitrate solution.
Comparative example 2
In the same manner as in example 1 except that the preparation method of the hydrotreating catalyst (one), the carbonization treatment and the steam treatment were performed only once, to obtain a catalyst F-1; and the regenerated catalyst carrier F and the regenerated catalyst F-2 are obtained by the same method.
TABLE 1 Properties of the catalysts obtained in examples and comparative examples and test evaluation results
Numbering device
|
A-1
|
A-2
|
B-1
|
C-1
|
D-1
|
E-1
|
F-1
|
Specific surface area, m 2 /g
|
187
|
186
|
203
|
174
|
169
|
171
|
218
|
Pore volume, mL/g
|
1.34
|
1.29
|
1.23
|
1.38
|
1.40
|
1.32
|
1.18
|
Pore distribution, percent
|
|
|
|
|
|
|
|
<100nm
|
53
|
48
|
63
|
50
|
48
|
51
|
70
|
100-1000nm
|
26
|
25
|
21
|
26
|
24
|
23
|
18
|
>1000nm
|
21
|
27
|
26
|
24
|
28
|
26
|
12
|
Reactive metal
|
|
|
|
|
|
|
|
V 2 O 5 ,wt%
|
14.5
|
14.5
|
14.5
|
14.5
|
14.5
|
14.5
|
14.5
|
NiO,wt%
|
3
|
3
|
3
|
3
|
3
|
3
|
3
|
Demetallization rate%
|
97.6
|
97.5
|
97.4
|
98.0
|
97.3
|
97.6
|
93.2 |
TABLE 2 recovery and Metal recovery and content of the support
|
Example 1
|
Example 2
|
Example 3
|
Example 4
|
Example 5
|
Comparative example 1
|
Comparative example 2
|
Recovery rate of vanadium, percent
|
98.1
|
97.6
|
98.2
|
97.6
|
98.7
|
86.8
|
89.2
|
Ammonium metavanadate content%
|
99.6
|
99.7
|
99.8
|
99.4
|
99.5
|
90.2
|
99.2
|
Nickel nitrate content, percent
|
95.6
|
95.4
|
95.2
|
95.7
|
95.1
|
89.5
|
94.5
|
Carrier recovery%
|
96.1
|
95.8
|
96.5
|
95.8
|
94.6
|
0
|
86.8 |
As can be seen from Table 2, the catalyst prepared by the technical scheme of the invention has a higher demetallization rate than that of the comparative example, the recovery rate of vanadium and the carrier is far higher than that of comparative example 1 and comparative example 2 when the catalyst is recycled, and the contents of ammonium metavanadate and nickel nitrate are also higher than those of the comparative example.