CN103785483B - A kind of method of hydrogenation catalyst and preparation method and lightweight oil hydrofining - Google Patents
A kind of method of hydrogenation catalyst and preparation method and lightweight oil hydrofining Download PDFInfo
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- CN103785483B CN103785483B CN201210420963.8A CN201210420963A CN103785483B CN 103785483 B CN103785483 B CN 103785483B CN 201210420963 A CN201210420963 A CN 201210420963A CN 103785483 B CN103785483 B CN 103785483B
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Abstract
The present invention discloses a kind of hydrogenation catalyst, this hydrogenation catalyst comprises group vib metal component on described tooth spherical alumina support of tooth spherical alumina support and load and group VIII metal component, wherein, the Kong Rongwei 0.6-0.8mL/g of described tooth spherical alumina support, specific surface area is 340-400m2/ g. Present invention also offers the preparation method of this hydrogenation catalyst, and a kind of method of lightweight oil hydrofining. Hydrogenation catalyst provided by the invention is used for kerosene hydrogenation refining plant, it is possible to give full play to the hydrogenation performance of catalyzer, and the pressure drop effectively maintaining hydrogenation unit system is stablized, and extends the running period of hydrogenation unit.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and a kind of method of its preparation method and lightweight oil hydrofining.
Background technology
Along with the fast development of civil aviation cause, has there is the situation that supply falls short of demand in aviation kerosene. The main method producing boat coal at present is straight run kerosene fraction hydrofining. Kerosene(oil)fraction hydrofining under low pressure operates, and hydrogenation depth is shallow, can only mercaptan removal, can not obviously improve the other products quality of kerosene, as indexs such as aromaticity content, smoke point, nitrogen content, acid contents without positive effect. In addition, industrially carry out in unifining process to kerosene, there is pressure drop rise speed problem faster to some extent in hydrogenation unit in operation process.
CN101376826A discloses a kind of hydrogenation technological process for long distillate coking kerosene. The operational condition of adjustment delayed coking unit fractionating system, takes the cut point being suitable for, and cuts out long distillate coking kerosene and enters hydrogenation unit and carry out hydrofining, produces aviation kerosene. Raw material and technique are selected by the method, but do not relate to the improvement of Hydrobon catalyst. Due to the sulphur of coking distillate, nitrogen, alkene, diene content height, the requirement of catalyst hydrogenation performance is higher.
CN101497044A discloses a kind of teeth spherical heavy oil hydrotreating catalyst and its preparation method. This catalyzer includes active ingredient, auxiliary agent and tooth spherical alumina support. Active ingredient comprises the compound of cobalt and nickel, also comprises aluminium or/and the compound of tungsten; Auxiliary agent comprises the compound of phosphorus, silicon, boron or halogen or aforementioned compound two or more arbitrarily; Each component is taking teeth spherical heavy oil hydrotreating catalyst gross weight as benchmark: cobalt compound 2-6%, nickel compound 3-10%, aluminum compound 0-26%, tungsten compound 0-8%, auxiliary agent 0.5-2%; The shape of alumina supporter is that tooth is spherical. The method is mainly used in the Catalysts and its preparation method etc. of the mink cell focus hydrotreatments such as long residuum, vacuum residuum, wax tailings. Owing to the molecular weight ratio lightweight oil of mink cell focus is big, and the foreign matter content contained in mink cell focus is also many than lightweight oil, so being applicable to the catalyzer of mink cell focus, can not be equally applicable to lightweight oil hydrofining.
Summary of the invention
The present inventor is by a large amount of experiments, hydrogenation unit system bed pressure drop raises too fast major cause, and to be summarized as three: one relevant with the shape of catalyzer, the bed porosity of bar shaped catalyst filling is less, and uneven, and long-time running easily causes apparatus system pressure drop rise; Two is relevant with the intensity of catalyzer, and when catalyst strength is poor, the easy cracked formation dust of catalyzer, fills bed hole, cause bed porosity less further, cause apparatus system pressure drop rise; Three is relevant with product composition, and when in product, olefin(e) centent is higher, owing to olefin saturation thermal discharge is big so that bed medial temperature height, easy coking, causes bed pressure drop to raise too fast.
Raising too fast problem to overcome hydrogenation unit system bed pressure drop, the present invention provides a kind of hydrogenation catalyst, and this catalyzer has suitable hole to be held and bigger specific surface area, it is possible to effectively overcomes hydrogenation unit system bed pressure drop and raises too fast problem.
2nd object of the present invention is to provide the preparation method of hydrogenation catalyst according to the present invention.
3rd object of the present invention is to provide the hydrogenation catalyst that the preparation method of hydrogenation catalyst according to the present invention prepares.
4th object of the present invention is to provide the method for the lightweight oil hydrofining of hydrogenation catalyst according to the present invention.
The present invention provides a kind of hydrogenation catalyst, this hydrogenation catalyst comprises group vib metal component on described tooth spherical alumina support of tooth spherical alumina support and load and group VIII metal component, wherein, the Kong Rongwei 0.6-0.8mL/g of described tooth spherical alumina support, specific surface area is 340-400m2/g��
Present invention also offers the preparation method of a kind of hydrogenation catalyst, wherein, the method comprises the following steps, (1) aluminium source is mixed with the part by weight of 1:0.01-0.05:0.01-0.04:0.01-0.06 with peptizing agent, expanding agent, shaping assistant, it is that tooth is spherical by the mixture forming obtained, and dry and roasting, obtain tooth spherical alumina support; (2) tooth spherical alumina support obtained with step (1) with the soluble salt solution of group VIII metal component for group vib metal component is contacted, and health successively, drying and roasting.
Present invention also offers the hydrogenation catalyst prepared by aforesaid method.
Present invention also offers a kind of method of hydrofining, when the method is included in hydrofining, hydrogenation catalyst is contacted with lightweight oil, wherein, described hydrogenation catalyst is described hydrogenation catalyst provided by the invention.
Hydrogenation catalyst provided by the invention, has suitable Kong Rong owing to adopting, and the tooth ball-aluminium oxide of bigger specific surface area is as carrier, it is to increase the speed of external diffusion mass transfer, and the reactive behavior of catalyzer improved; Support of the catalyst adopts tooth spherical in addition, further increases the porosity of beds, and tooth spherical form makes catalyst loading easy and even; In addition, hydrogenation catalyst provided by the invention also has high compressive strength, not easily efflorescence during filling, avoid, owing to loading uneven, catalyzer is used the detrimentally affect caused, the problem that beds easily subsides can not be produced, avoid catalyst bridging and produce channel and local superheating, reduce catalyzer coking, extending catalyst work-ing life. In addition, hydrogenation catalyst provided by the invention can effectively reduce the olefin(e) centent generated in oil, alleviates bed coking, is conducive to maintaining system pressure drop and stablizes. In sum, hydrogenation catalyst provided by the invention is used for kerosene hydrogenation refining plant, it is possible to give full play to the hydrogenation performance of catalyzer, and the pressure drop effectively maintaining hydrogenation unit system is stablized, and extends the running period of hydrogenation unit.
Under preferable case of the present invention, by the kind of the active ingredient of selecting catalyst and content, improve the reactive behavior of catalyzer further, it is to increase the processing load of catalyzer, thus reduce catalyzer coking, be more conducive to the pressure drop maintaining hydrogenation unit system to stablize.
The preparation method of hydrogenation catalyst provided by the invention, is mixed in proportion by control aluminium source and peptizing agent, expanding agent and shaping assistant, it is possible to obtaining Kong Rongwei 0.6-0.8mL/g, specific surface area is 340-400m2The tooth spherical alumina support of/g. In addition, when preparing the lightweight oil hydrogenation catalyst of the present invention, shaping assistant is added, it is possible to increase the toughness of extruded material when making to prepare carrier, be conducive to shaping. In addition, with peptizing agent with the use of so that the alumina supporter of preparation takes into account higher physical strength.
By adding auxiliary agent in optimal way, it is possible to improve the catalytic activity of hydrogenation catalyst further.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
The picture of the hydrogenation catalyst that Fig. 1 provides for the embodiment of the present invention 1.
Embodiment
Hereinafter the specific embodiment of the present invention is described in detail. Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The present invention provides a kind of hydrogenation catalyst, this hydrogenation catalyst comprises group vib metal component on described tooth spherical alumina support of tooth spherical alumina support and load and group VIII metal component, wherein, the Kong Rongwei 0.6-0.8mL/g of described tooth spherical alumina support, specific surface area is 340-400m2/g��
According to described hydrogenation catalyst provided by the invention, if the described alumina supporter spherical object that can be conducive to realizing the present invention that is tooth well known by persons skilled in the art, under preferable case, the particle diameter of tooth spherical alumina support provided by the invention is 1.5-4mm, described in each, tooth spherical alumina support has 4-8 tooth, and above-mentioned multiple tooth is uniformly distributed. The tooth spherical alumina support of above-mentioned shape is similar to the shape stayed after the degree of depth that spherical watermelon radially evenly cuts several lobe and excision is less than the radius of watermelon. Under further preferable case, the ratio of the spherical girth of the maximum width of groove formed between tooth and tooth and the spherical place of tooth is 1:4-8, the ratio of the spherical radius of the full depth of groove formed between tooth and tooth and the spherical place of tooth is 1:1.25-5, and in described tooth spherical alumina support, the distribution of tooth is Scroll-type. Select above-mentioned tooth spherical alumina support, be more conducive to realizing the object of the present invention.
In the present invention, described tooth is the protuberance on alumina supporter, and when the maximum width of the groove formed between tooth and tooth refers to groove genesis analysis, the middle width of groove is also the corresponding width in transversal perimeter. The full depth of the groove formed between tooth and tooth refers to the outer end of tooth and the ultimate range of groove.
According to described hydrogenation catalyst provided by the invention, the Kong Rong of described tooth spherical alumina support and specific surface area can realize the object of the present invention in above-mentioned scope, but under preferable case, the 0.65-0.75mL/g of described tooth spherical alumina support, specific surface area is 345-395m2/g
According to described hydrogenation catalyst provided by the invention, there is no particular limitation for the content of described group vib metal component and group VIII metal component, it is possible to suitably selects in the content range of the hydrogenation catalyst of routine. Under preferable case, for making described hydrogenation catalyst have better high active of hydrogenation catalysis, relative to the described hydrogenation catalyst of 100 weight parts, with the oxide basis of the oxide compound of group vib metal and group VIII metal, the content of described group vib metal component is 1-30 weight part, more preferably 6-25 weight part; The content of described group VIII metal component is 1-10 weight part, more preferably 3-8 weight part.
According to described hydrogenation catalyst provided by the invention, described group vib metal component and group VIII metal component can be selected according to prior art, and under preferable case of the present invention, described group vib metal is molybdenum, and described group VIII metal is nickel.
According to described hydrogenation catalyst provided by the invention, it is preferable that in situation, described hydrogenation catalyst is also containing auxiliary agent, and described auxiliary agent is one or more in the compound of boron, phosphorus and fluorine, such as, in boric acid, Vanadium Pentoxide in FLAKES and Neutral ammonium fluoride one or more; Relative to the described hydrogenation catalyst of 100 weight parts, in boron, phosphorus and fluorine element, the content of described auxiliary agent is 0.5-5 weight part, it is preferable to 1-3.5 weight part. Described hydrogenation catalyst adds a certain amount of above-mentioned auxiliary agent, it is possible to effectively improve the catalytic activity of catalyzer, reduce catalyzer coking, extending catalyst work-ing life.
Present invention also offers the preparation method of a kind of hydrogenation catalyst, the method comprises the following steps: aluminium source is mixed with the part by weight of 1:0.01-0.05:0.01-0.04:0.01-0.06 by (1) with peptizing agent, expanding agent, shaping assistant, it is that tooth is spherical by the mixture forming obtained, and dry and roasting, obtain tooth spherical alumina support; (2) tooth spherical alumina support obtained with step (1) with the soluble salt solution of group VIII metal component for group vib metal component is contacted, and health successively, drying and roasting.
According to preparation method provided by the invention, by aluminium source is mixed with above-mentioned part by weight with peptizing agent, expanding agent and shaping assistant, preferably mix with the part by weight of 1:0.01-0.035:0.02-0.03:0.01-0.04, make the alumina supporter obtained have suitable Kong Rong and specific surface area, and there is higher intensity. Aluminium source and peptizing agent, expanding agent, the mixed uniformly method of shaping assistant can be adopted common method well known by persons skilled in the art, in order to make the alumina supporter pore size distribution obtained evenly and there is higher intensity, under preferable case of the present invention, peptizing agent can once add, can also add in batches, such as aluminium source is mixed with expanding agent, shaping assistant and part peptizing agent, carry out mixed grind 30-180 minute; Being mixed by the mixture of part peptizing agent with above-mentioned mixed grind, carry out mixed grind 30-180 minute, what make that raw material mixes is more even so that obtained alumina supporter pore size distribution evenly and there is higher intensity.
According to preparation method provided by the invention, after raw material is mixed, it is that tooth is spherical by the mixture forming obtained, and dry and roasting, obtain tooth spherical alumina support. Wherein, it is spherical that shaping method can adopt any one known method that alumina supporter is shaped to tooth, such as, in CN101497044A embodiment 1 preparation method of scheme 1. Tooth of the present invention is spherical can be that any one tooth well known by persons skilled in the art is spherical. Under preferable case, the particle diameter of tooth spherical alumina support provided by the invention is 1.5-4mm, and described in each, tooth spherical alumina support has 4-8 tooth, and above-mentioned multiple tooth is uniformly distributed. The tooth spherical alumina support of above-mentioned shape is similar to the shape stayed after the degree of depth that spherical watermelon radially evenly cuts several lobe and excision is less than the radius of watermelon.
A preferred embodiment of the invention, the ratio of the spherical girth of the maximum width of groove formed between tooth and tooth and the spherical place of tooth is 1:4-8, the ratio of the spherical radius of the full depth of groove formed between tooth and tooth and the spherical place of tooth is 1:1.25-5, and in described tooth spherical alumina support, the distribution of tooth is Scroll-type. Specifically as shown in Figure 1.
According to preparation method provided by the invention, after the mixture forming of step (1), to be also dried and roasting, condition that is dry and roasting can be selected in relative broad range, under preferable case, dry condition comprises: temperature 80-120 DEG C, 1-4 hour time; The condition of roasting comprises: temperature 400-600 DEG C, 3-6 hour time. Before drying and roasting, also comprising the step of health, the condition of health comprises: temperature 15-25 DEG C, and the time is 10-120 minute.
According to preparation method provided by the invention, the condition of health in step (2), drying and roasting can also be selected in relative broad range, it is preferable that in situation, the condition of health comprises: temperature 15-25 DEG C, and the time is 10-60 minute; Dry condition comprises: temperature 80-120 DEG C, 1-4 hour time; The condition of roasting comprises: temperature 400-600 DEG C, 2-8 hour time.
According to preparation method provided by the invention, the consumption of group vib metal component and group VIII metal component can be selected in relative broad range, under preferable case, the consumption of described group vib metal component and group VIII metal component makes in the hydrogenation catalyst obtained, relative to the described hydrogenation catalyst of 100 weight parts, with the oxide basis of the oxide compound of group vib metal and group VIII metal, the content of described group vib metal component is 1-30 weight part, more preferably 6-25 weight part; The content of described group VIII metal component is 1-10 weight part, more preferably 3-8 weight part.
According to preparation method provided by the invention, described group vib metal component and group VIII metal component can be selected according to prior art, and under preferable case of the present invention, described group vib metal is molybdenum, and described group VIII metal is nickel.
According to preparation method provided by the invention, it is preferable that in situation, also comprising interpolation auxiliary agent in the method preparation process, described auxiliary agent is one or more in the compound containing boron, phosphorus and fluorine, such as, in boric acid, Vanadium Pentoxide in FLAKES and Neutral ammonium fluoride one or more; The consumption of described auxiliary agent makes in the hydrogenation catalyst obtained, and relative to the described hydrogenation catalyst of 100 weight parts, in boron, phosphorus and fluorine element, the content of described auxiliary agent is 0.5-5 weight part, it is preferable to 1-3.5 weight part.
In the present invention, the interpolation time of auxiliary agent does not limit, it is possible to first add in aluminium source before preparing carrier, it is also possible to preparing interpolation in carrier process, it is also possible to add when supported V IB race's metal component and group VIII metal component. Aluminium source, preferably before being mixed with peptizing agent, expanding agent, shaping assistant in aluminium source, is first mixed by the present invention with auxiliary agent, be conducive to that auxiliary agent mixes with carrier evenly.
According to preparation method provided by the invention, described aluminium source is the aluminium source that can be used in preparing hydrogenation catalyst alumina supporter well known by persons skilled in the art, aluminum hydroxide solid elastomer HC06 prepared by such as Shandong great continuous heavy rain petrochemical complex science and technology limited-liability company.
The kind of described peptizing agent does not have concrete restriction, such as, can be mineral acid and/or organic acid. Under preferable case of the present invention, described peptizing agent can be nitric acid, sulfuric acid, hydrochloric acid, citric acid and acetic acid one or more. The addition manner of described peptizing agent is also not particularly limited, and when selecting above-mentioned two or more acid as peptizing agent, two or more acid can separately be added, it is also possible to add after mixing in batches.
The soluble compound of described molybdenum can be the molybdenum compound of any one solubility well known by persons skilled in the art, it is preferable to ammonium molybdate.
The soluble compound of described nickel can be the nickel compound of any one solubility well known by persons skilled in the art, it is preferable to one or more in nickelous nitrate, nickel acetate and basic nickel carbonate.
Solubility described in the present invention refers to the dissolving properties of material in water, diluted acid or ammoniacal liquor.
Present invention also offers a kind of hydrogenation catalyst prepared by above-mentioned preparation method.
Present invention also offers a kind of method of lightweight oil hydrofining, when the method is included in hydrofining, hydrogenation catalyst is contacted with lightweight oil, wherein, described hydrogenation catalyst is hydrogenation catalyst as above.
Method according to lightweight oil hydrofining of the present invention, described hydrofining condition preferably includes: hydrogen dividing potential drop is 0.5-5MPa, and temperature of reaction is 180-360 DEG C, and lightweight oil volume space velocity is 2-10h-1, hydrogen to oil volume ratio is 30-300.
Method according to lightweight oil hydrofining of the present invention, during for kerosene hydrogenation refining reaction, there is the activity of good hydrogenating desulfurization, hydrodenitrification, and in product, olefin(e) centent is lower, showing excellent hydrogenation performance and activity stability, device long-term operation is stablized.
In the present invention, hydrogenation catalyst needed to carry out prevulcanized before reacting, and to improve the activity of catalyzer, the condition of prevulcanized can adopt various method well known by persons skilled in the art.
The present invention is further detailed explanation by the following examples.
In following examples, the compositional analysis of stock oil and generation oil adopts the AgilentHP-6890 type chromatographic product composition being furnished with HPPlot-Q capillary column and fid detector
The Kong Rong of carrier and specific surface area adopt the full-automatic materialization absorption instrument of MICROMERITICS company of U.S. ASAP2020-M+C to measure.
The heap of catalyzer is than measuring by holding catalyzer in the graduated cylinder of 250mL, then constantly container is tamped 30 minutes, until 250ml graduated cylinder again can not be contained any more catalyzer, the then weight of weighing container inner catalyst, divided by the volume of container, draw the heap ratio of this catalyzer.
The ZQJ-II type Intelligent testing machine for particle that the intensity of catalyzer adopts big connection intelligent trier factory to manufacture measures;
The compositional analysis of catalyzer adopts Hitachi's U-3900 ultra-violet and visible spectrophotometer to measure;
Reagent is commercially available product, and wherein aluminum hydroxide solid elastomer is purchased from the great continuous heavy rain petrochemical complex in Shandong science and technology limited-liability company, product grade: HC06; Sodium polyacrylate is purchased from Shandong Wan Hua Chemical Industry Science Co., Ltd.
Embodiment 1
(1) carrier preparation
Aluminum hydroxide solid elastomer 100g is mixed with the phosphoric acid 22g of 35 weight %, add sesbania powder 3g, sodium polyacrylate 3g mixed grind 30min, then the dust technology 55g of 2 weight % is added, mixed grind 40min is continued with mixing pan, add in the hopper of forcing machine, extruded by the spherical orifice plate of tooth, then obtain shaping carrier through pellet processing machine pelletizing. Then, at 25 DEG C, leave standstill 1 hour, in air atmosphere at 100 DEG C dry 2 hours, then at 500 DEG C roasting 4 hours, obtained particle diameter is the alumina supporter that the tooth of 2.5mm is spherical. The outward appearance of described tooth spherical alumina support is as shown in Figure 1, tooth spherical alumina support described in each has equally distributed 5 teeth, the ratio of the spherical girth of the maximum width of groove formed between tooth and tooth and the spherical place of tooth is 1:5, the ratio of the spherical radius of the full depth of groove formed between tooth and tooth and the spherical place of tooth is 1:2, and in described tooth spherical alumina support, the distribution of tooth is Scroll-type. Kong Rong and the specific surface area of described tooth spherical alumina support are as shown in table 1.
(2) catalyst preparing
Deionized water 60g, Ammonium Heptamolybdate 122g, nickelous nitrate 84g are mixed, then supplement deionized water and it is mixed with uniform 300mL solution, above-mentioned solution is sprayed onto above 476g alumina supporter that step (1) repeatedly prepared, obtain wet sphere catalyst, after leaving standstill 30 minutes at 25 DEG C, put into baking oven drying 2 hours at 110 DEG C, then 450 DEG C of roastings 4 hours, after cooling, namely obtain lightweight oil hydrogenation catalyst. The shape of this catalyzer is as shown in Figure 1. The heap of this catalyzer is more as shown in table 1 than with intensity. Relative to the hydrogenation catalyst of 100 weight parts, in this catalyzer, the composition of group vib metal component, group VIII metal component and auxiliary agent is as shown in table 2.
Embodiment 2
(1) carrier preparation
Aluminum hydroxide solid elastomer 100g is mixed with the phosphatase 11 7g of 35 weight %, add sesbania powder 1g, sodium polyacrylate 3g mixed grind 60min, then the dust technology 55g of 6 weight % is added, mixed grind 60min is continued with mixing pan, add in the hopper of forcing machine, extruded by the spherical orifice plate of tooth, then obtain shaping carrier through pellet processing machine pelletizing. Then, at 20 DEG C, leave standstill 1 hour, in air atmosphere at 80 DEG C dry 4 hours, then at 600 DEG C roasting 3 hours, the alumina supporter that obtained identical with shape in embodiment 1 step (1) tooth is spherical. Kong Rong and the specific surface area of described tooth spherical alumina support are as shown in table 1.
(2) catalyst preparing
Deionized water 60g, Ammonium Heptamolybdate 55g, nickelous nitrate 168g are mixed, then supplement deionized water and it is mixed with uniform 300mL solution, above-mentioned solution is sprayed onto above 476g alumina supporter that step (1) repeatedly prepared, obtain wet sphere catalyst, after leaving standstill 40 minutes at 20 DEG C, put into baking oven drying 1 hour at 120 DEG C, then 500 DEG C of roastings 4 hours, after cooling, namely obtain hydrogenation catalyst. The shape of this catalyzer is identical with Fig. 1. The heap of this catalyzer is more as shown in table 1 than with intensity. Relative to the hydrogenation catalyst of 100 weight parts, in this catalyzer, the composition of group vib metal component, group VIII metal component and auxiliary agent is as shown in table 2.
Embodiment 3
(1) carrier preparation
Aluminum hydroxide solid elastomer 100g is mixed with the phosphoric acid 6g of 35 weight %, add sesbania powder 3g, sodium polyacrylate 2g mixed grind 120min, then the dust technology 55g of 4% is added, mixed grind 120min is continued with mixing pan, add in the hopper of forcing machine, extruded by the spherical orifice plate of tooth, then obtain shaping carrier through pellet processing machine pelletizing. Then, at 15 DEG C, leave standstill 1 hour, in air atmosphere at 120 DEG C dry 1 hour, then at 400 DEG C roasting 6 hours, the alumina supporter that obtained identical with shape in embodiment 1 step (1) tooth is spherical. Kong Rong and the specific surface area of described tooth spherical alumina support are as shown in table 1.
(2) catalyst preparing
Deionized water 60g, Ammonium Heptamolybdate 224g, nickelous nitrate 178g are mixed, then supplement deionized water and it is mixed with uniform 300mL solution, above-mentioned solution is sprayed onto above 476g alumina supporter that step (1) repeatedly prepared, obtain wet sphere catalyst, after leaving standstill 30 minutes at 15 DEG C, put into baking oven drying 4 hours at 90 DEG C, then 600 DEG C of roastings 4 hours, after cooling, namely obtain hydrogenation catalyst. The shape of this catalyzer is identical with Fig. 1. The heap of this catalyzer is more as shown in table 1 than with intensity. Relative to the hydrogenation catalyst of 100 weight parts, in this catalyzer, the composition of group vib metal component, group VIII metal component and auxiliary agent is as shown in table 2.
Embodiment 4
(1) carrier preparation
Aluminum hydroxide solid elastomer 100g is mixed with the phosphoric acid 27g of 35 weight %, add sesbania powder 5g, citric acid 3g, sodium polyacrylate 4g mixed grind 30min, then the dust technology 55g of 2 weight % is added, mixed grind 30min is continued with mixing pan, add in the hopper of forcing machine, extruded by the spherical orifice plate of tooth, then obtain shaping carrier through pellet processing machine pelletizing. Then, at 20 DEG C, leave standstill 1 hour, in air atmosphere at 110 DEG C dry 2 hours, then at 600 DEG C roasting 3 hours, the alumina supporter that obtained identical with shape in embodiment 1 step (1) tooth is spherical. Kong Rong and the specific surface area of described tooth spherical alumina support are as shown in table 1.
(2) catalyst preparing
Deionized water 60g, Ammonium Heptamolybdate 40g and nickelous nitrate 201g are mixed, then supplement deionized water and it is mixed with uniform 300mL solution, above-mentioned solution is sprayed onto above 476g alumina supporter that step (1) repeatedly prepared, obtain wet sphere catalyst, after leaving standstill 30 minutes at 15 DEG C, put into baking oven drying 3 hours at 110 DEG C, then 450 DEG C of roastings 4 hours, after cooling, namely obtain hydrogenation catalyst. The shape of this catalyzer is identical with Fig. 1. The heap of this catalyzer is more as shown in table 1 than with intensity. Relative to the hydrogenation catalyst of 100 weight parts, in this catalyzer, the composition of group vib metal component, group VIII metal component and auxiliary agent is as shown in table 2.
Embodiment 5
Adopt the preparation method of the hydrogenation catalyst of embodiment 4, the difference is that, do not add auxiliary agent, obtained hydrogenation catalyst.
Comparative example 1
Adopt the preparation method of the hydrogenation catalyst of embodiment 1, the difference is that, carrier adopts Kong Rongwei 0.6mL/g, and specific surface area is 350m2The cylindrical shaped alumina carrier (petrochemical industry catalyzer Fushun branch company system of China is standby) of/g.
Comparative example 2
(1) carrier preparation
Aluminum hydroxide solid elastomer 100g is mixed with the phosphatase 24 .3g of 35 weight %, add sesbania powder 7g, sodium polyacrylate 5g mixed grind 30min, then the dust technology 55g of 1% is added, mixed grind 30min is continued with mixing pan, add in the hopper of forcing machine, extruded by the spherical orifice plate of tooth, then obtain shaping carrier through pellet processing machine pelletizing. Then, at 25 DEG C, leave standstill 1 hour, in air atmosphere at 100 DEG C dry 2 hours, then at 500 DEG C roasting 4 hours, the alumina supporter that obtained tooth is spherical. Kong Rong and the specific surface area of described tooth spherical alumina support are as shown in table 1.
(2) catalyst preparing
The preparation of catalyzer adopts the preparation method of embodiment 1.
Table 1
Table 2
| Embodiment sequence number | Molybdenum oxide (weight part) | Nickel oxide (weight part) | Auxiliary agent (weight part) |
| Embodiment 1 | 15.8 | 3.4 | 3.2 |
| Embodiment 2 | 7.4 | 7.3 | 2.5 |
| Embodiment 3 | 23.5 | 5.8 | 0.82 |
| Embodiment 4 | 5.1 | 8.7 | 4.1 |
The application of the lightweight oil hydrogenation catalyst that embodiment 6-11 is prepared for illustration of embodiment 1-5 in kerosene hydrogenation refining reaction.
Embodiment 6
The catalyzer 100mL being respectively charged into embodiment 1 in hydrogenation unit reactor, is warming up to 320 DEG C, then under a hydrogen atmosphere, with the kerosene prevulcanized 8 hours of the dimethyl disulphide containing 2 weight %.
Then the laboratory catalytic hydrogenation reaction of kerosene is carried out, reaction conditions: hydrogen dividing potential drop 3.0MPa, temperature of reaction 320 DEG C, volume space velocity 2.0h-1, hydrogen to oil volume ratio 100. React after 24 hours, as shown in table 3 as the composition of the kerosene of stock oil and the generation oil of reaction generation.
Comparative example 3
Adopt the method for embodiment 6, the difference is that, the catalyzer of comparative example 1 is used for the laboratory catalytic hydrogenation reaction of kerosene. Reacting after 24 hours, the composition of the generation oil that reaction generates is as shown in table 3.
Table 3
| Catalyst sample | Comparative example 1 | Embodiment 1 | |
| Oil product title | Stock oil | Generate oil | Generate oil |
| Density (20 DEG C), g/cm3 | 0.807 | 0.801 | 0.796 |
| Boiling range scope, DEG C | 182-263 | 183-262 | 183-260 |
| Sulphur, �� g/g | 2435 | 55 | 10 |
| Mercaptan sulfur, �� g/g | 70 | 10 | 2 |
| Nitrogen, �� g/g | 82 | 5 | 2 |
| Alkene, v% | 31.6 | 1.6 | 0.5 |
| Aromatic hydrocarbons, v% | 16.1 | 10.6 | 6.8 |
| Smoke point, mm | 25 | 27 | 28 |
Embodiment 7
Adopting the method for embodiment 6 that catalyzer is carried out prevulcanized, the catalyzer of embodiment 1 is used for the laboratory catalytic hydrogenation reaction of kerosene, the composition of reaction conditions and reaction raw materials oil and reaction generation oil of generation after 24 hours is as shown in table 4.
Table 4
Embodiment 8-9
Adopt the method for embodiment 6, the difference is that, the catalyzer of embodiment 2 and 3 is used for the laboratory catalytic hydrogenation reaction of kerosene. Reacting after 24 hours, the sulphur of the generation oil that reaction generates, nitrogen content are as shown in table 5.
Embodiment 10
Adopt the method for embodiment 6, the difference is that, the catalyzer of embodiment 4 is used for the laboratory catalytic hydrogenation reaction of kerosene, reaction conditions: hydrogen dividing potential drop 4.2MPa, temperature of reaction 200 DEG C, volume space velocity 2.5h-1, hydrogen to oil volume ratio 200. Reacting after 24 hours, the sulphur of the generation oil that reaction generates, nitrogen content are as shown in table 5.
Embodiment 11
Adopt the method for embodiment 6, the difference is that, the catalyzer of embodiment 5 is used for the laboratory catalytic hydrogenation reaction of kerosene, reaction conditions: hydrogen dividing potential drop 2.2MPa, temperature of reaction 360 DEG C, volume space velocity 6h-1, hydrogen to oil volume ratio 60. Reacting after 24 hours, the sulphur of the generation oil that reaction generates, nitrogen content are as shown in table 5.
Comparative example 4
Adopt the method for embodiment 6, the difference is that, the catalyzer of comparative example 2 is used for the laboratory catalytic hydrogenation reaction of kerosene. Reacting after 24 hours, the sulphur of the generation oil that reaction generates, nitrogen content are as shown in table 5.
Table 5
Embodiment 12
According to the method for embodiment 6, the catalyzer of embodiment 1 being carried out sulfuration, then the catalyzer of embodiment 1 is used for the coker gasoline hydrogenation unit of domestic B refinery, condition and the result of operation are as shown in table 6.
Table 6
Embodiment 13-14 is that the work-ing life in order to catalyzer is described is longer, and the time that the pressure drop of maintenance hydrogenation unit is stable is longer.
Embodiment 13-14
Adopt the method for embodiment 6, the catalyzer of embodiment 1 and 5 is respectively used to the small-sized hydrogenation catalyst evaluating apparatus of kerosene. Reacting after 1000 hours, the pressure of system is 3.2MPa, and the sulphur of generation oil, nitrogen and olefin(e) centent that reaction generates are as shown in table 7.
Comparative example 5-6
Adopt the method for embodiment 6, the catalyzer of comparative example 1 and 2 is respectively used to the small-sized hydrogenation catalyst evaluating apparatus of kerosene. Reacting after 500 hours, the pressure of system is 3.2MPa, and the sulphur of generation oil, nitrogen and olefin(e) centent that reaction generates are as shown in table 7.
Table 7
Can be found out by table 1-7, tooth ball-aluminium oxide provided by the invention has bigger specific surface area and intensity, it is prepared into hydrogenation catalyst using this tooth ball-aluminium oxide as carrier in the catalytic hydrogenation reaction of kerosene, shows higher catalytic activity and reaction stability, and can effectively maintain the reaction pressure drop of device, when hydrogenation catalyst provided by the invention makes system pressure drop be elevated to 3.2MPa from 3.0MPa compared with prior art, device continous-stable extends 500 hours runtime, effectively extends the steady running cycle of device.
Below the preferred embodiment of the present invention is described in detail; but, the detail that the present invention is not limited in above-mentioned enforcement mode, within the scope of the technical conceive of the present invention; the technical scheme of the present invention can being carried out multiple simple variant, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technology feature described in above-mentioned embodiment, when not contradiction, it is possible to combined by any suitable mode, in order to avoid unnecessary repetition, various possible array mode is illustrated by the present invention no longer separately.
In addition, can also carrying out arbitrary combination between the various different enforcement mode of the present invention, as long as it does not run counter to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. a lightweight oil hydrogenation catalyst, this lightweight oil hydrogenation catalyst comprises group vib metal component on described tooth spherical alumina support of tooth spherical alumina support and load and group VIII metal component, it is characterized in that, the Kong Rongwei 0.6-0.8mL/g of described tooth spherical alumina support, specific surface area is 340-400m2/ g; Described group vib metal component is molybdenum, and described group VIII metal component is nickel; Relative to the described lightweight oil hydrogenation catalyst of 100 weight parts, with the oxide basis of the oxide compound of group vib metal and group VIII metal, the content of described group vib metal component is 1-30 weight part, and the content of described group VIII metal component is 1-10 weight part.
2. lightweight oil hydrogenation catalyst according to claim 1, wherein, the particle diameter of tooth spherical alumina support is 1.5-4mm, and described in each, tooth spherical alumina support has 4-8 tooth.
3. lightweight oil hydrogenation catalyst according to claim 1 and 2, wherein, the ratio of the spherical girth of the maximum width of groove formed between tooth and tooth and the spherical place of tooth is 1:4-8.
4. lightweight oil hydrogenation catalyst according to claim 3, wherein, the ratio of the spherical radius of the full depth of groove formed between tooth and tooth and the spherical place of tooth is 1:1.25-5.
5. lightweight oil hydrogenation catalyst according to claim 4, wherein, in described tooth spherical alumina support, the distribution of tooth is Scroll-type.
6. lightweight oil hydrogenation catalyst according to claim 1, wherein, the Kong Rongwei 0.65-0.75mL/g of described tooth spherical alumina support, specific surface area is 345-395m2/g��
7. lightweight oil hydrogenation catalyst according to claim 1, wherein, relative to the described lightweight oil hydrogenation catalyst of 100 weight parts, with the oxide basis of the oxide compound of group vib metal and group VIII metal, the content of described group vib metal component is 6-25 weight part, and the content of described group VIII metal component is 3-8 weight part.
8. lightweight oil hydrogenation catalyst according to claim 1, wherein, described lightweight oil hydrogenation catalyst is also containing auxiliary agent, and described auxiliary agent is one or more in the compound of boron, phosphorus and fluorine; Relative to the described lightweight oil hydrogenation catalyst of 100 weight parts, in boron, phosphorus and fluorine element, the content of described auxiliary agent is 0.5-5 weight part.
9. the preparation method of a lightweight oil hydrogenation catalyst, it is characterised in that, the method comprises the following steps:
(1) aluminium source is mixed with the part by weight of 1:0.01-0.05:0.01-0.04:0.01-0.06 with peptizing agent, expanding agent, shaping assistant, it is that tooth is spherical by the mixture forming obtained, and dry and roasting, obtain tooth spherical alumina support;
(2) tooth spherical alumina support obtained with step (1) with the soluble salt solution of group VIII metal component for group vib metal component is contacted, and health successively, drying and roasting;
Wherein, described group vib metal component is molybdenum, and described group VIII metal component is nickel; The consumption of described group vib metal component and group VIII metal component makes in the hydrogenation catalyst obtained, relative to the described hydrogenation catalyst of 100 weight parts, with the oxide basis of the oxide compound of group vib metal and group VIII metal, the content of described group vib metal component is 1-30 weight part, and the content of described group VIII metal component is 1-10 weight part.
10. preparation method according to claim 9, wherein, the method is also included in before being mixed with peptizing agent, expanding agent, shaping assistant in aluminium source, is first mixed with auxiliary agent in aluminium source, and described auxiliary agent is one or more in the compound of boron, phosphorus and fluorine; The consumption of described auxiliary agent makes in the lightweight oil hydrogenation catalyst obtained, and relative to the described lightweight oil hydrogenation catalyst of 100 weight parts, in boron, phosphorus and fluorine element, the content of described auxiliary agent is 0.5-5 weight part.
The lightweight oil hydrogenation catalyst that 11. are obtained by the preparation method described in claim 9 or 10.
The method of 12. 1 kinds of lightweight oil hydrofinings, when the method is included in hydrofining, lightweight oil hydrogenation catalyst is contacted with lightweight oil, it is characterised in that, described lightweight oil hydrogenation catalyst is lightweight oil hydrogenation catalyst described in any one in claim 1-8 and 11.
13. methods according to claim 12, wherein, described hydrofining condition comprises: hydrogen dividing potential drop is 0.5-5MPa, and temperature of reaction is 180-360 DEG C, and lightweight oil volume space velocity is 2-10h-1, hydrogen to oil volume ratio is 30-300.
14. methods according to claim 13, wherein, described lightweight oil is kerosene.
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| CN101497044A (en) * | 2009-03-10 | 2009-08-05 | 北京高新利华催化材料制造有限公司 | Teeth spherical heavy oil hydrotreating catalyst and preparation method thereof |
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