CN104383923B - A kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof - Google Patents
A kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof Download PDFInfo
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Abstract
The present invention provides a kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof.This gasoline, diesel hydrogenation ferrum-based catalyst is using ferrum as activity component metal, using the combination of one or both in zinc, copper and silver as the catalyst of aided metal；Wherein, the mol ratio of described activity component metal and described aided metal is 1-20:1；Being hydrogenated with the gross weight of ferrum-based catalyst for benchmark with described gasoline, diesel, the activity component metal of oxide form and the total amount of aided metal are 10-80%.The application of this gasoline, diesel hydrogenation ferrum-based catalyst includes its application in the hydrotreatment of direct steaming gasoline, straight-run diesel oil, coker gasoline, coker gas oil, catalytically cracked gasoline and catalytic cracking diesel oil.The ferrum-based catalyst of the present invention has the advantages such as cheaper starting materials is easy to get, processing technology is simple, while can being substantially reduced the production cost of hydrogenation catalyst, also has higher gasoline, diesel oil hydrogenation activity.
Description
Technical field
The present invention relates to a kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof, belong to the metal catalyst technology field in field of petroleum exploitation.
Background technology
Since nineteen twenty-six first set in the world had been referred to as the technology of " classic hydrogenation " later since German Industrial, hydrogenation technique has been passed by the course in a nearly century.Particularly over nearly 50 years, it is hydrogenated with a kind of important means as fecund gasoline, diesel oil and other high-quality intermediate oils, obtains very big attention and development.Many new hydrogenation catalysts and preparation method thereof are in succession emerged therebetween.
US3779903 is by being impregnated on the special carrier that the alumina sol of super-dry, roasting is prepared by nickel salt, tungsten salt, and further dry, roasting, prepares with tungsten oxide for main active, and nickel oxide is for helping active component, and fluorine is the hydrogenation catalyst of auxiliary agent.The preparation method that US4330395 discloses the hydrogenation catalyst on a kind of carrier being impregnated into by nickel salt and preparing with aluminium compound and tungsten compound for raw material, the catalyst obtained can activate with sulphur compound and fluorine compounds before use, obtains good intermediate oil hydrotreatment effect.CN101439289A discloses a kind of with carbamide or ammonia for reaction promoter, the method of reaction in-situ in carrier hole is adopted to make metal active constituent generate nickel molybdate (cobalt) or nickel tungstate (cobalt) compounds, such that it is able to avoid the reaction of metal and carrier, active component is more easy to cure, improves the activity of hydrogenation catalyst.
Do not have activity or activity not high owing to including the carrier in the traditional supported catalysts of the hydrogenation catalyst of above-mentioned prior art, and carrier proportion is very big, thus causing that the catalysis activity of loaded catalyst is difficult to meet the requirement producing ultra-low-sulphur diesel.So, in recent years, occur in that requisite carrier in abandoning tradition hydrogenation catalyst, and directly using itself containing the nickel of pore structure, cobalt, tungsten, the oxide of molybdenum or sulfide as non-loading type (Bulk) catalyst mainly comprised.US6582590 discloses the method adopting direct precipitation method to prepare non-supported hydrogenation catalyst, the method is to mix with alkali liquor after soluble molybdenum hydrochlorate and tungstates are dissolved in water, soluble nickel salt is dissolved in water again and keeps at 90 DEG C, then add the aqueous slkali of molybdenum, tungstates with certain speed, eventually pass through filtration, dry prepared non-supported hydrogenation desulphurization catalyst.The preparation method that US6712955, US6156695, US6783663 also disclose that similar non-supported hydrogenation catalyst, these technology all use in the molybdenum of the cobalt of VIII, nickel and Group VIA, tungsten one or both combination as activity component metal.CN101255356A also discloses a kind of preparation method reacted by urea melting and prepare nickel (cobalt)-tungsten (molybdenum) unsupported catalyst self with nano pore and high specific surface area, uses the catalyst that the method prepares to have good hydroprocessing activity.
As can be seen here, although for many years, researcheres have done a large amount of research work in non-loading type carrier and additive modification and the preparation of breakthrough unsupported catalyst that in recent years occurs, but using nickel, cobalt etc. as auxiliary agent, molybdenum, tungsten are not broken as the basic combination of main active component metal.Further, the common drawback of the preparation method of above-mentioned all prior aries is relatively costly, and its basic reason is in that exist as the nickel of active metal, cobalt, molybdenum and tungsten are not a large amount of in the earth's crust, and their price is much more expensive.
Therefore, develop the gasoline, diesel hydrogenation catalyst that a kind of cost of manufacture is cheap, be still one of this area problem demanding prompt solution.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof.The gasoline, diesel hydrogenation ferrum-based catalyst of the present invention, using ferrum as activity component metal, prepares as aided metal using one or both the combination in zinc, copper and silver, has cost of manufacture cheap, the simple advantage of processing technology.
For reaching above-mentioned purpose, the present invention provides a kind of gasoline, diesel hydrogenation ferrum-based catalyst, and it is using ferrum as activity component metal, using the combination of one or both in zinc, copper and silver as the catalyst of aided metal；Wherein, the mol ratio of described activity component metal and described aided metal is 1-20:1；Being hydrogenated with the gross weight of ferrum-based catalyst for benchmark with described gasoline, diesel, the activity component metal of oxide form and the total amount of aided metal are 10-80%.
According to the specific embodiment of the present invention, it is preferable that above-mentioned gasoline, diesel hydrogenation ferrum-based catalyst is prepared by infusion process or coprecipitation.
According to the specific embodiment of the present invention, it is preferable that described infusion process comprises the following steps:
Activity component metal salt, aided metal salt are dissolved in deionized water, are made into impregnation liquid；
Described impregnation liquid is joined in carrier, obtains catalyst semi-finished product；
Described catalyst semi-finished product are stood 2-24 hour in atmosphere, then dries, then at air atmosphere, roasting 2-8h at 200-800 DEG C, obtain described gasoline, diesel hydrogenation ferrum-based catalyst.
In above-mentioned infusion process, the affiliated activity component metal in activity component metal salt and the mol ratio of the aided metal in aided metal salt are 1-20:1.
In above-mentioned infusion process, it is preferable that the volume of described impregnation liquid is identical with the saturated water adsorptive value of carrier.
In above-mentioned infusion process, it is preferable that the half-finished drying of described catalyst is to carry out in the baking oven of 120 DEG C.
In above-mentioned infusion process, it is preferable that described catalyst semi-finished product are heat up with the speed of 5 DEG C/min when carrying out roasting.
In above-mentioned infusion process, it is preferable that described carrier includes the combination of one or more in aluminium oxide, silicon dioxide, amorphous silica-alumina and zeolite molecular sieve etc..
According to the specific embodiment of the present invention, it is preferable that described coprecipitation comprises the following steps:
By uniform for the aqueous solution of the aqueous solution of activity component metal salt and aided metal salt and precipitant；
Then react 1-24h 40-95 DEG C of stirred in water bath, then in 40-95 DEG C of water-bath, stand aging 2-48h, be precipitated thing；
After being filtered by described precipitate, washing, dry, obtain catalyst precursor；
By described catalyst precursor at air atmosphere, roasting 2-8h at 200-800 DEG C, obtain metal-oxide；
Described metal-oxide is mixed with binding agent and carries out forming processes, obtain described gasoline, diesel hydrogenation ferrum-based catalyst.
In above-mentioned coprecipitation, the affiliated activity component metal in activity component metal salt and the mol ratio of the aided metal in aided metal salt are 1-20:1.
In above-mentioned coprecipitation, it is preferable that described forming processes can be extruded moulding or kneading and compacting.In the process of forming processes, it is possible to adopting conventional use of sesbania powder etc. as thickening agent, citric acid, acetic acid, nitric acid etc., as peptizer, carry out the forming operation such as extrusion or kneading with metal-oxide and binding agent after mixing.
According to the specific embodiment of the present invention, it is preferable that described coprecipitation is further comprising the steps of: the gasoline, diesel obtained after forming processes is hydrogenated with ferrum-based catalyst and carries out further roasting；It is highly preferred that the condition of this roasting is: with the heating rate of 5 DEG C/min, at air atmosphere, roasting 2-8h at 200-800 DEG C.
In above-mentioned coprecipitation, it is preferable that described binding agent includes the combination of one or more in aluminium oxide, Ludox, Alumina gel, waterglass etc., the consumption of described binding agent is the 20%-80% of described gasoline, diesel hydrogenation ferrum-based catalyst gross weight.
In above-mentioned coprecipitation, after described precipitate is filtered, washing, dry, it is also possible to optionally pulverize, then the catalyst precursor obtained is carried out roasting.
In above-mentioned coprecipitation, it is preferable that described sedimentary drying is to carry out in the baking oven of 120 DEG C.
In above-mentioned coprecipitation, it is preferable that described catalyst precursor is heat up with the speed of 5 DEG C/min when carrying out roasting.
In above-mentioned coprecipitation, it is preferable that described precipitant includes NaOH, KOH, Na2CO3、K2CO3、Na2S、(NH4)2The mol ratio of total metal of the combination of one or more in S, carbamide and ammonia etc., described precipitant and described activity component metal and described aided metal is 1-6:1.When adopting ammonia as precipitant, it is possible to directly use, it is not necessary to the aqueous solution of preparation precipitant.
In above-mentioned coprecipitation, the concentration of the aqueous solution of described activity component metal salt and aided metal salt and the aqueous solution of precipitant can be carried out the regulation and control of routine by those skilled in the art, as long as disclosure satisfy that above-mentioned proportionate relationship and reaction can being made to be smoothed out.And, the aqueous solution of described activity component metal salt and aided metal salt can be dissolved in, for activity component metal salt and aided metal salt, the aqueous solution remixed in deionized water respectively, it is also possible to be dissolved in, for activity component metal salt and aided metal salt, the aqueous solution formed in deionized water simultaneously.Can be the aqueous solution of precipitant is joined in the aqueous solution of activity component metal salt and aided metal salt and stir by uniform for the aqueous solution of the aqueous solution of activity component metal salt and aided metal salt and precipitant concrete operations.
In above-mentioned infusion process and coprecipitation, it is preferable that described activity component metal salt includes the combination of one or more in ferric nitrate, iron sulfate, iron chloride and iron phosphate etc..
In above-mentioned infusion process and coprecipitation, it is preferable that described aided metal salt includes the combination of one or more in nitrate, sulfate, chlorate and phosphate etc..Wherein, described nitrate includes zinc nitrate, copper nitrate and silver nitrate；Described sulfate includes zinc sulfate, copper sulfate and silver sulfate；Described chlorate includes zinc chloride and copper chloride；Described phosphate includes zinc phosphate, cupric phosphate and silver phosphate.
The gasoline, diesel hydrogenation ferrum-based catalyst of the present invention is after preparing by above-mentioned infusion process or coprecipitation, it is possible to directly uses, and processes without presulfurization.But, according to the specific embodiment of the present invention, it is preferable that described gasoline, diesel hydrogenation ferrum-based catalyst is the gasoline, diesel hydrogenation ferrum-based catalyst processed through presulfurization, and presulfurization activation can make catalyst obtain and better be hydrogenated with effect.Described presulfurization processes the pre-curing technology of the hydrogenation catalyst that this area can be adopted conventional and carries out, and the presulfurization oil adopted or presulfurization agent etc. can also be presulfurization oil commonly used in the art or presulfurization agent etc..The temperature that described presulfurization processes is 200-450 DEG C, and pressure is 1-10MPa, and the time that presulfurization processes is 4-48 hour, and liquid hourly space velocity (LHSV) is 0.5-10h-1, hydrogen to oil volume ratio is 100-800；Preferably, the temperature that described presulfurization processes is 280-380 DEG C, and pressure is 2-6MPa, and the time that presulfurization processes is 6-24 hour, and liquid hourly space velocity (LHSV) is 1-4h-1, hydrogen to oil volume ratio is 200-500.
The present invention also provides for above-mentioned gasoline, diesel hydrogenation ferrum-based catalyst application in the hydrotreatment of direct steaming gasoline, straight-run diesel oil, coker gasoline, coker gas oil, catalytically cracked gasoline and catalytic cracking diesel oil.It is saturated etc. that described hydrotreatment can include the hydrogenation of hydrodesulfurization, hydrodenitrogeneration and aromatic hydrocarbons.
In the applications described above, it is preferable that the temperature of described hydrotreatment is 200-500 DEG C, pressure is 1-10MPa, and liquid hourly space velocity (LHSV) is 0.1-10h-1, hydrogen to oil volume ratio is 100-2000；It is highly preferred that the temperature of described hydrotreatment is 250-400 DEG C, pressure is 2-8MPa, and liquid hourly space velocity (LHSV) is 0.5-8h-1, hydrogen to oil volume ratio is 200-1000.
In the applications described above, the apparatus and method of described hydrotreatment and technological process can be the conventional gasoline in this area, the apparatus and method of diesel oil hydrogenation and technological process.This hydrotreatment can carry out in a reactor, it is also possible to carries out in multiple reactors in parallel or series, say, that the catalyst of the present invention can be seated in a reactor in a set of flow process or carry out hydrotreatment in multiple reactor.When not changing existing gasoline, diesel oil hydrogenation technological process, the catalyst of the present invention has and is hydrogenated with effect preferably.
The present invention adopts ferrum as activity component metal, and one or both the combination in zinc, copper and silver, as aided metal, adopts ripe and simple preparation method, prepared ferrum-based catalyst；And adopt this ferrum-based catalyst as the hydrogenation catalyst of gasoline, diesel oil first, instead of using the molybdenum of Group VIA, tungsten as activity component metal, using the cobalt of VIII, nickel as the traditional hydrogenation catalyst for gasoline, diesel oil hydrogenation of aided metal.Compared to traditional gasoline, diesel oil hydrogenation catalyst, the ferrum-based catalyst of the present invention has the advantages such as cheaper starting materials is easy to get, processing technology is simple, while can being substantially reduced the production cost of hydrogenation catalyst, also has higher gasoline, diesel oil hydrogenation activity.The hydrogenation ferrum-based catalyst of the present invention breaches the restriction that tradition hydrogenation catalyst continues to use the activity component metal of many decades, therefore has long-range industrial application value.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme and technique effect are described in further detail, but it is not intended that can the restriction of practical range to the present invention.
Embodiment 1
The present embodiment provides a kind of gasoline, diesel hydrogenation ferrum-based catalyst, and it prepares for adopting infusion process.
This preparation method comprises the following steps:
15.18g ferric nitrate, 3.65g zinc nitrate and 1.52g copper nitrate are dissolved in 10mL deionized water, are made into impregnation liquid；
This impregnation liquid is added dropwise in the oxidation aluminum strip that diameter is 1.5mm of 10g extruded moulding, obtains catalyst semi-finished product；
Described catalyst semi-finished product are stood 2-24 hour in atmosphere, dries in the baking oven of 120 DEG C, then with the ramp of 5 DEG C/min, 500 DEG C, roasting 4 hours under air atmosphere, obtain described gasoline, diesel hydrogenation ferrum-based catalyst FZC.Recording the total amount of ferrum zinc-copper oxide in this catalyst FZC is that the 31%(gross weight with this catalyst FZC is for benchmark).In catalyst, the mensuration of the oxide total content of activity component metal and aided metal and computational methods are mensuration well known in the art and computational methods.
Embodiment 2
The present embodiment provides a kind of gasoline, diesel hydrogenation ferrum-based catalyst, and it prepares for adopting coprecipitation.
This preparation method comprises the following steps:
32.44g iron chloride and 6.82g zinc chloride are dissolved in 250mL deionized water, obtain the aqueous solution of iron chloride and zinc chloride；8g sodium hydroxide is dissolved in 80mL deionized water, obtains sodium hydroxide solution；While stirring sodium hydroxide solution is slowly added in the aqueous solution of iron chloride and zinc chloride；
Then react 4 hours the stirred in water bath of 80 DEG C, be then cooled to 60 DEG C and stand aging 24 hours, be precipitated thing；
By this precipitate filtered while hot, then approximate 7 with deionized water wash to pH value, then dry in the baking oven of 120 DEG C, then the ramp with 5 DEG C/min, 500 DEG C, roasting 2 hours under air atmosphere, obtain ferrum zinc oxide；
By this ferrum zinc oxide of 4.5g, 10g boehmite (binding agent), 0.4g sesbania powder is mixed into uniform powder, obtains mixed-powder；0.3g citric acid and 0.3g nitric acid are dissolved in 10mL deionized water, form peptizer；This peptizer is added this mixed-powder and fully mediates, banded extruder is extruded into the bar of diameter 1.5mm, this bar is dried in the baking oven of 120 DEG C, then 500 DEG C, roasting 4 hours under air atmosphere, obtains described gasoline, diesel hydrogenation ferrum-based catalyst FZ.Recording the total amount of ferrum zinc oxide in this catalyst FZ is that the 31%(gross weight with this catalyst FZ is for benchmark).
Embodiment 3
The present embodiment provides a kind of gasoline, diesel hydrogenation catalyst, catalyst as a comparison.
The preparation method of this comparative catalyst comprises the following steps:
4.74g ammonium metatungstate and 2.26g nickel nitrate are dissolved in 10mL deionized water, are made into impregnation liquid；
This impregnation liquid is added dropwise in the oxidation aluminum strip that diameter is 1.5mm of 10g extruded moulding, obtains catalyst semi-finished product；
Described catalyst semi-finished product are stood 2-24 hour in atmosphere, dries in the baking oven of 120 DEG C, then with the ramp of 5 DEG C/min, 500 DEG C, roasting 4 hours under air atmosphere, obtain described comparative catalyst.Recording the content of tungsten oxide in this comparative catalyst is 27%, and the content of nickel oxide is that 4%(is all with the gross weight of this comparative catalyst for benchmark).
Embodiment 4
The present embodiment provides the catalyst of embodiment 1-3 that coker gas oil carries out the application of hydrotreatment.
The catalyst of embodiment 1-3 has all carried out presulfurization process before application, makes catalyst have and is better hydrogenated with effect.Described presulfurization adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out, and it is wet method original position presulfurization, namely adopts wet method presulfurization, and presulfurization rear catalyst does not draw off, and directly proceeds hydrogenation reaction in the reactor.Presulfurization oil is containing 5wt%CS2N-decane solution, the temperature of presulfurization is 300 DEG C, and pressure is 4MPa, and liquid hourly space velocity (LHSV) is 1.5h-1, hydrogen to oil volume ratio is 300.
The hydrotreatment of the present embodiment adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out.Evaluate raw material and adopt grand celebration coker gas oil, the proportion (d of this coker gas oil4 20) it is 0.8196, sulfur content is 1256ppm, and total nitrogen content is 745ppm.Raw material adopts plunger displacement pump to pump into, and reacted oil sample is after high separator cools down, at low separator collection analysis.The temperature of hydrotreatment is 360 DEG C, and pressure is 6MPa, and liquid hourly space velocity (LHSV) is 1.0h-1, hydrogen to oil volume ratio is 800.Evaluating catalyst result after hydrotreatment is as shown in table 1.
Table 1
| Catalyst | Desulfurization degree, % | Denitrification percent, % |
| FZC | 83 | 69 |
| FZ | 81 | 71 |
| Comparative catalyst | 97 | 83 |
Embodiment 5
The present embodiment provides the catalyst of embodiment 1-3 that catalytic cracking diesel oil carries out the application of hydrotreatment.
The catalyst of embodiment 1-3 has all carried out presulfurization process before application, makes catalyst have and is better hydrogenated with effect.Described presulfurization adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out, and it is wet method original position presulfurization, namely adopts wet method presulfurization, and presulfurization rear catalyst does not draw off, and directly proceeds hydrogenation reaction in the reactor.Presulfurization oil is containing 5wt%CS2N-decane solution, the temperature of presulfurization is 300 DEG C, and pressure is 4MPa, and liquid hourly space velocity (LHSV) is 1.5h-1, hydrogen to oil volume ratio is 300.
The hydrotreatment of the present embodiment adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out.Evaluate raw material and adopt grand celebration catalytic cracking diesel oil, the proportion (d of this catalytic cracking diesel oil4 20) it is 0.8796, sulfur content is 890ppm, and total nitrogen content is 920ppm, and total arene content is 55.2v%.Raw material adopts plunger displacement pump to pump into, and reacted oil sample is after high separator cools down, at low separator collection analysis.The temperature of hydrotreatment is 360 DEG C, and pressure is 6MPa, and liquid hourly space velocity (LHSV) is 1.0h-1, hydrogen to oil volume ratio is 800.Evaluating catalyst result after hydrotreatment is as shown in table 2.
Table 2
| Catalyst | Desulfurization degree, % | Denitrification percent, % | De-virtue rate, % |
| FZC | 81 | 61 | 45 |
| FZ | 78 | 59 | 43 |
| Comparative catalyst | 91 | 70 | 56 |
Embodiment 6
The present embodiment provides the catalyst of embodiment 1-3 that full fraction FCC gasoline carries out the application of hydrotreatment.
The catalyst of embodiment 1-3 has all carried out presulfurization process before application, makes catalyst have and is better hydrogenated with effect.Described presulfurization adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out, and it is wet method original position presulfurization, namely adopts wet method presulfurization, and presulfurization rear catalyst does not draw off, and directly proceeds hydrogenation reaction in the reactor.Presulfurization oil is containing 5wt%CS2N-decane solution, the temperature of presulfurization is 300 DEG C, and pressure is 2MPa, and liquid hourly space velocity (LHSV) is 1.5h-1, hydrogen to oil volume ratio is 300.
The hydrotreatment of the present embodiment adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out.Evaluate raw material and adopt full fraction FCC gasoline, its proportion (d4 20) it is 0.7296, sulfur content is 470ppm, and research octane number (RON) (RON) is 92.0.Raw material adopts plunger displacement pump to pump into, and reacted oil sample is after high separator cools down, at low separator collection analysis.The temperature of hydrotreatment is 320 DEG C, and pressure is 4MPa, and liquid hourly space velocity (LHSV) is 1.0h-1, hydrogen to oil volume ratio is 300.Evaluating catalyst result after hydrotreatment is as shown in table 3.
Table 3
| Catalyst | Desulfurization degree, % | RON | Yield of gasoline, % |
| FZC | 80 | 91 | 99.8 |
| FZ | 77 | 91 | 99.9 |
| Comparative catalyst | 94 | 90 | 99.9 |
In the above-described embodiments, the desulfurization degree of catalyst, denitrification percent, de-virtue rate, the RON of oil product and the mensuration of yield of gasoline and computational methods are mensuration well known in the art and computational methods.
The result of table 1, table 2 and table 3 illustrates that the hydrogenation ferrum-based catalyst of the present invention possesses higher hydrodesulfurization, denitrogenation and takes off virtue activity.And, when the hydrogenation ferrum-based catalyst of the present invention processes for gasoline hydrogenation, it is possible to the loss of octane number making gasoline is very low.Although the hydrogenation desulfurization of ferrum-based catalyst of the present invention, denitrogenation and de-virtue rate are slightly below conventional load type Ni-W catalyst (comparative catalyst), but nickel salt, cobalt salt, tungsten salt and molybdenum salt etc. that the price of the active constituent metal that adopts of the ferrum-based catalyst of the present invention and aided metal adopts well below tradition hydrogenation catalyst.Further, the hydrogenation ferrum-based catalyst of the present invention breaches the restriction that tradition hydrogenation catalyst continues to use the activity component metal of many decades, therefore has long-range industrial application value.
Claims (11)
1. a gasoline, diesel hydrogenation ferrum-based catalyst, it is using ferrum as activity component metal, using the combination of one or both in zinc, copper and silver as the catalyst of aided metal；Wherein, the mol ratio of described activity component metal and described aided metal is 1-20:1；Being hydrogenated with the gross weight of ferrum-based catalyst for benchmark with described gasoline, diesel, the activity component metal of oxide form and the total amount of aided metal are 10-80%；
And described gasoline, diesel hydrogenation ferrum-based catalyst is the gasoline, diesel hydrogenation ferrum-based catalyst processed through presulfurization after being prepared by infusion process or coprecipitation, the temperature that described presulfurization processes is 200-450 DEG C, pressure is 1-10MPa, the time that presulfurization processes is 4-48 hour, and liquid hourly space velocity (LHSV) is 0.5-10h-1, hydrogen to oil volume ratio is 100-800.
2. gasoline, diesel according to claim 1 hydrogenation ferrum-based catalyst, wherein, described infusion process comprises the following steps:
Activity component metal salt, aided metal salt are dissolved in deionized water, are made into impregnation liquid；
Described impregnation liquid is joined in carrier, obtains catalyst semi-finished product；
Described catalyst semi-finished product are stood 2-24 hour in atmosphere, then dries, then at air atmosphere, roasting 2-8h at 200-800 DEG C, obtain described gasoline, diesel hydrogenation ferrum-based catalyst.
3. gasoline, diesel according to claim 2 hydrogenation ferrum-based catalyst, wherein, described carrier includes the combination of one or more in aluminium oxide, silicon dioxide, amorphous silica-alumina and zeolite molecular sieve.
4. gasoline, diesel according to claim 1 hydrogenation ferrum-based catalyst, wherein, described coprecipitation comprises the following steps:
By uniform for the aqueous solution of the aqueous solution of activity component metal salt and aided metal salt and precipitant；
Then react 1-24h 40-95 DEG C of stirred in water bath, then in 40-95 DEG C of water-bath, stand aging 2-48h, be precipitated thing；
After being filtered by described precipitate, washing, dry, obtain catalyst precursor；
By described catalyst precursor at air atmosphere, roasting 2-8h at 200-800 DEG C, obtain metal-oxide；
Described metal-oxide is mixed with binding agent and carries out forming processes, obtain described gasoline, diesel hydrogenation ferrum-based catalyst.
5. gasoline, diesel according to claim 4 hydrogenation ferrum-based catalyst, wherein, described binding agent includes the combination of one or more in aluminium oxide, Ludox, Alumina gel and waterglass, and the consumption of described binding agent is the 20%-80% of described gasoline, diesel hydrogenation ferrum-based catalyst gross weight.
6. gasoline, diesel according to claim 4 hydrogenation ferrum-based catalyst, wherein, described precipitant includes NaOH, KOH, Na2CO3、K2CO3、Na2S、(NH4)2The mol ratio of total metal of the combination of one or more in S, carbamide and ammonia, described precipitant and described activity component metal and described aided metal is 1-6:1.
7. the gasoline, diesel hydrogenation ferrum-based catalyst according to claim 2 or 4, wherein, described activity component metal salt includes the combination of one or more in ferric nitrate, iron sulfate, iron chloride and iron phosphate；Described aided metal salt includes the combination of one or more in nitrate, sulfate, chlorate and phosphate.
8. gasoline, diesel according to claim 1 hydrogenation ferrum-based catalyst, wherein, the temperature that described presulfurization processes is 280-380 DEG C, and pressure is 2-6MPa, and the time that presulfurization processes is 6-24 hour, and liquid hourly space velocity (LHSV) is 1-4h-1, hydrogen to oil volume ratio is 200-500.
9. the gasoline, diesel hydrogenation ferrum-based catalyst application in the hydrotreatment of direct steaming gasoline, straight-run diesel oil, coker gasoline, coker gas oil, catalytically cracked gasoline and catalytic cracking diesel oil described in any one of claim 1-8.
10. application according to claim 9, wherein, the temperature of described hydrotreatment is 200-500 DEG C, and pressure is 1-10MPa, and liquid hourly space velocity (LHSV) is 0.1-10h-1, hydrogen to oil volume ratio is 100-2000.
11. application according to claim 10, wherein, the temperature of described hydrotreatment is 250-400 DEG C, and pressure is 2-8MPa, and liquid hourly space velocity (LHSV) is 0.5-8h-1, hydrogen to oil volume ratio is 200-1000.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310303258.4A CN104383923B (en) | 2013-07-18 | 2013-07-18 | A kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof |
| EP14826159.7A EP3023147B1 (en) | 2013-07-18 | 2014-07-18 | Iron-based hydrogenation catalyst and applications thereof |
| CN201480000780.8A CN104918698B (en) | 2013-07-18 | 2014-07-18 | A kind of iron-based hydrogenation catalyst and application thereof |
| PCT/CN2014/082463 WO2015007230A1 (en) | 2013-07-18 | 2014-07-18 | Iron-based hydrogenation catalyst and applications thereof |
| CA2917361A CA2917361C (en) | 2013-07-18 | 2014-07-18 | Iron-based hydrogenation catalyst and use thereof |
| US14/905,719 US10335773B2 (en) | 2013-07-18 | 2014-07-18 | Fe-based hydrogenation catalyst and use thereof |
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| CN106928004B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of selective hydrogenation method of C 3 fractions |
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