CN104383923A - Gasoline and diesel hydrogenation iron-based catalyst and application thereof - Google Patents
Gasoline and diesel hydrogenation iron-based catalyst and application thereof Download PDFInfo
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Abstract
The invention provides a gasoline and diesel hydrogenation iron-based catalyst and its application. The gasoline and diesel hydrogenation iron-based catalyst is a catalyst prepared by using iron as an active component metal and using one of zinc, copper and silver or a combination of two of the metals as a co-metal catalyst, wherein molar ratio of the active component metal to the co-metal is 1-20:1. With the total weight of the gasoline and diesel hydrogenation iron-based catalyst as the reference, the total weight of oxides of the active component metal and the co-metal is 10-80%. The gasoline and diesel hydrogenation iron-based catalyst is applied in hydrotreatment of straight-run gasoline, straight-run diesel, coker gasoline, coker diesel, catalytically cracked gasoline and catalytically cracked diesel. The iron-based catalyst provided by the invention has advantages as follows: raw materials are cheap and easily available; and preparation technology is simple. Production cost of the hydrogenation catalyst can be reduced greatly. Meanwhile, the catalyst has high gasoline and diesel 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 in the world first set be called as the technology of " classic hydrogenation " afterwards since German Industrial, hydrogenation technique has been passed by the course in a nearly century.Particularly nearly ISUZU company comes, and hydrogenation, as a kind of important means of voluminous gasoline, diesel oil and other high-quality intermediate oils, obtains very large 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 obtained by nickel salt, tungsten salt, dry, roasting further again, obtained is main active with tungsten oxide, and nickel oxide is for helping active component, and fluorine is the hydrogenation catalyst of auxiliary agent.US4330395 discloses a kind of preparation method of the hydrogenation catalyst be impregnated into by nickel salt on the carrier that obtains for raw material with aluminium compound and tungsten compound, the catalyst obtained can activate with sulphur compound and fluorine compounds before use, obtains good intermediate oil hydrotreatment effect.CN101439289A disclose a kind of with urea or ammoniacal liquor 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, thus the reaction of metal and carrier can be avoided, active component is more easily cured, improves the activity of hydrogenation catalyst.
Because the carrier comprised in the traditional supported catalysts of the hydrogenation catalyst of above-mentioned prior art does not have activity or activity not high, and carrier proportion is very large, thus the catalytic activity of loaded catalyst is caused to be difficult to meet the requirement of producing ultra-low-sulphur diesel.So, in recent years, there is requisite carrier in abandoning tradition hydrogenation catalyst, and direct using the oxide of the nickel itself containing pore structure, cobalt, tungsten, molybdenum or sulfide as non-loading type (Bulk) catalyst of main composition.US6582590 discloses the method adopting direct precipitation method to prepare non-supported hydrogenation catalyst, the method be by soluble molybdenum hydrochlorate and tungstates water-soluble after mix with alkali lye, again that soluble nickel salt is water-soluble and at 90 DEG C keep, then add the aqueous slkali of molybdenum, tungstates with certain speed, eventually pass through filtration, dry obtained non-supported hydrogenation desulphurization catalyst.US6712955, US6156695, US6783663 also disclose the preparation method of similar non-supported hydrogenation catalyst, and these technology all to use in the cobalt of VIII, the molybdenum of nickel and VIA race, tungsten one or both combination as activity component metal.CN101255356A also discloses a kind of preparation method self by urea melting reaction preparation with nickel (cobalt)-tungsten (molybdenum) unsupported catalyst of nano pore and high specific surface area, uses the obtained catalyst of the method to have good hydroprocessing activity.
As can be seen here, although for many years, researchers 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 that cost is higher, and its basic reason is to 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 very 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 the problems of the technologies described above, the object of the present invention is to provide a kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof.Gasoline, diesel hydrogenation ferrum-based catalyst of the present invention, using iron as activity component metal, prepares as aided metal using the combination of one or both in zinc, copper and silver, has cost of manufacture cheap, the simple advantage of manufacture craft.
For reaching above-mentioned purpose, the invention provides a kind of gasoline, diesel hydrogenation ferrum-based catalyst, it is using iron 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; With the gross weight of described gasoline, diesel hydrogenation ferrum-based catalyst for benchmark, 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, preferably, above-mentioned gasoline, diesel hydrogenation ferrum-based catalyst is prepared by infusion process or coprecipitation.
According to the specific embodiment of the present invention, preferably, described infusion process comprises the following steps:
Activity component metal salt, aided metal salt are dissolved in deionized water, are made into maceration extract;
Described maceration extract is joined in carrier, obtains catalyst semi-finished product;
Described catalyst semi-finished product are left standstill 2-24 hour in atmosphere, then dry, then at air atmosphere, 200-800 DEG C roasting 2-8h, obtain described gasoline, diesel hydrogenation ferrum-based catalyst.
In above-mentioned infusion process, the mol ratio of the activity component metal in the activity component metal salt added and the aided metal in aided metal salt is 1-20:1.
In above-mentioned infusion process, preferably, the volume of described maceration extract is identical with the saturated water adsorptive value of carrier.
In above-mentioned infusion process, preferably, the half-finished oven dry of described catalyst carries out in the baking oven of 120 DEG C.
In above-mentioned infusion process, preferably, 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, preferably, described carrier comprises the combination of one or more in aluminium oxide, silica, amorphous aluminum silicide and zeolite molecular sieve etc.
According to the specific embodiment of the present invention, preferably, described coprecipitation comprises the following steps:
By activity component metal salt and the aqueous solution of aided metal salt and the aqueous solution of precipitating reagent even;
Then at 40-95 DEG C of stirred in water bath reaction 1-24h, then leave standstill aging 2-48h in 40-95 DEG C of water-bath, be precipitated thing;
After being carried out by described sediment filtering, wash, drying, obtain catalyst precursor;
By described catalyst precursor roasting 2-8h at air atmosphere, 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 mol ratio of the activity component metal in the activity component metal salt added and the aided metal in aided metal salt is 1-20:1.
In above-mentioned coprecipitation, preferably, described forming processes can be extruded moulding or kneading and compacting.In the process of forming processes, the sesbania powder that routine can be adopted to use etc. are as thickener, and citric acid, acetic acid, nitric acid etc., as peptizing agent, carry out the forming operation such as extrusion or kneading after mixing with metal oxide and binding agent.
According to the specific embodiment of the present invention, preferably, described coprecipitation is further comprising the steps of: the gasoline, diesel hydrogenation ferrum-based catalyst obtained after forming processes is carried out further roasting; More preferably, the condition of this roasting is: with the heating rate of 5 DEG C/min, roasting 2-8h at air atmosphere, 200-800 DEG C.
In above-mentioned coprecipitation, preferably, described binding agent comprises the combination of one or more in aluminium oxide, Ludox, Alumina gel, waterglass etc., and 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 sediment being carried out filter, wash, drying, optionally can also pulverize, then the catalyst precursor obtained be carried out roasting.
In above-mentioned coprecipitation, preferably, described sedimentary oven dry carries out in the baking oven of 120 DEG C.
In above-mentioned coprecipitation, preferably, described catalyst precursor is heat up with the speed of 5 DEG C/min when carrying out roasting.
In above-mentioned coprecipitation, preferably, described precipitating reagent comprises NaOH, KOH, Na
2cO
3, K
2cO
3, Na
2s, (NH
4)
2the combination of one or more in S, urea and ammoniacal liquor etc., the mol ratio of total metal of described precipitating reagent and described activity component metal and described aided metal is 1-6:1.When adopting ammoniacal liquor as precipitating reagent, can directly use, without the need to preparing the aqueous solution of precipitating reagent.
In above-mentioned coprecipitation, the concentration of described activity component metal salt and the aqueous solution of aided metal salt and the aqueous solution of precipitating reagent can carry out conventional regulation and control by those skilled in the art, as long as can meet above-mentioned proportionate relationship and reaction can be made to carry out smoothly.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 mixed again in deionized water respectively, also can be dissolved in for activity component metal salt and aided metal salt the aqueous solution formed in deionized water simultaneously.Can for the aqueous solution of precipitating reagent to be joined in the aqueous solution of activity component metal salt and aided metal salt and to stir by activity component metal salt and the aqueous solution of aided metal salt and the uniform concrete operations of the aqueous solution of precipitating reagent.
In above-mentioned infusion process and coprecipitation, preferably, described activity component metal salt comprises the combination of one or more in ferric nitrate, ferric sulfate, iron chloride and ferric phosphate etc.
In above-mentioned infusion process and coprecipitation, preferably, described aided metal salt comprises the combination of one or more in nitrate, sulfate, chlorate and phosphate etc.Wherein, described nitrate comprises zinc nitrate, copper nitrate and silver nitrate; Described sulfate comprises zinc sulfate, copper sulphate and silver sulfate; Described chlorate comprises zinc chloride and copper chloride; Described phosphate comprises trbasic zinc phosphate, cupric phosphate and silver orthophosphate.
Gasoline, diesel hydrogenation ferrum-based catalyst of the present invention, after being prepared by above-mentioned infusion process or coprecipitation, can directly be used, and without presulfurization process.But according to the specific embodiment of the present invention, preferably, described gasoline, diesel hydrogenation ferrum-based catalyst is the gasoline, diesel hydrogenation ferrum-based catalyst through presulfurization process, presulfurization activation can make catalyst obtain better hydrogenation effect.Described presulfurization process can adopt the pre-curing technology of the hydrogenation catalyst of this area routine to carry out, the presulfurization oil that the presulfurization oil adopted or presulfurization agent etc. also can use for this area routine or presulfurization agent etc.The temperature of described presulfurization process is 200-450 DEG C, and pressure is 1-10MPa, and the time of presulfurization process 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 of described presulfurization process is 280-380 DEG C, and pressure is 2-6MPa, and the time of presulfurization process 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 the above-mentioned application of gasoline, diesel hydrogenation ferrum-based catalyst 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 hydrotreatment can comprise the hydrotreated lube base oil etc. of hydrodesulfurization, hydrodenitrogeneration and aromatic hydrocarbons.
In the applications described above, preferably, 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; More preferably, 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.
In the applications described above, the apparatus and method of described hydrotreatment and technological process can be the gasoline of this area routine, the apparatus and method of diesel oil hydrogenation and technological process.This hydrotreatment can be carried out in a reactor, also can carry out in multiple parallel connection or tandem reactor, and that is, catalyst of the present invention can be seated in a reactor in a set of flow process or multiple reactor and carry out hydrotreatment.When not changing existing gasoline, diesel oil hydrogenation technological process, catalyst of the present invention has good hydrogenation effect.
The present invention adopts iron 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 VIA race, 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, ferrum-based catalyst of the present invention has the advantages such as cheaper starting materials is easy to get, manufacture craft is simple, while can greatly reducing the production cost of hydrogenation catalyst, also there is higher gasoline, diesel oil hydrogenation is active.Hydrogenation ferrum-based catalyst of the present invention breaches the restriction that traditional 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 of the present invention and technique effect are described in further detail, but can not be interpreted as 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 maceration extract;
The diameter this maceration extract dropwise being joined 10g extruded moulding is in the oxidation aluminum strip of 1.5mm, obtains catalyst semi-finished product;
Described catalyst semi-finished product are left standstill 2-24 hour in atmosphere, then to dry 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.The total amount recording iron zinc-copper oxide in this catalyst FZC be 31%(with the gross weight of this catalyst FZC 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 NaOH is dissolved in 80mL deionized water, obtains sodium hydroxide solution; While stirring sodium hydroxide solution is slowly joined 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 leave standstill aging 24 hours, be precipitated thing;
This sediment is filtered while hot, then spends deionized water and approximate 7 to pH value, then dry in the baking oven of 120 DEG C, then with the ramp of 5 DEG C/min, 500 DEG C, roasting 2 hours under air atmosphere, obtain iron zinc oxide;
By this iron 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 peptizing agent; This peptizing agent added this mixed-powder and fully mediate, 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.The total amount recording iron zinc oxide in this catalyst FZ be 31%(with the gross weight of this catalyst FZ 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 maceration extract;
The diameter this maceration extract dropwise being joined 10g extruded moulding is in the oxidation aluminum strip of 1.5mm, obtains catalyst semi-finished product;
Described catalyst semi-finished product are left standstill 2-24 hour in atmosphere, then to dry 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.The content recording tungsten oxide in this comparative catalyst is 27%, the content of nickel oxide be 4%(all with the gross weight of this comparative catalyst for benchmark).
Embodiment 4
The present embodiment provides the catalyst of embodiment 1-3 to carry out the application of hydrotreatment to coker gas oil.
The catalyst of embodiment 1-3 has all carried out presulfurization process before application, makes catalyst have better hydrogenation effect.Described presulfurization adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out, and it is the presulfurization of wet method original position, namely adopt wet method presulfurization, and presulfurization rear catalyst does not draw off, and directly proceeds hydrogenation reaction in the reactor.Presulfurization oil is for containing 5wt%CS
2n-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 oil
4 20) be 0.8196, sulfur content is 1256ppm, and total nitrogen content is 745ppm.Raw material adopts plunger displacement pump to pump into, reacted oil sample after the cooling of high separator, 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 to carry out the application of hydrotreatment to catalytic cracking diesel oil.
The catalyst of embodiment 1-3 has all carried out presulfurization process before application, makes catalyst have better hydrogenation effect.Described presulfurization adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out, and it is the presulfurization of wet method original position, namely adopt wet method presulfurization, and presulfurization rear catalyst does not draw off, and directly proceeds hydrogenation reaction in the reactor.Presulfurization oil is for containing 5wt%CS
2n-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 oil
4 20) be 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, reacted oil sample after the cooling of high separator, 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-fragrant 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 to carry out the application of hydrotreatment to full cut FCC gasoline.
The catalyst of embodiment 1-3 has all carried out presulfurization process before application, makes catalyst have better hydrogenation effect.Described presulfurization adopts 10mL high-temperature and high-pressure hydrogenation micro-reactor to carry out, and it is the presulfurization of wet method original position, namely adopt wet method presulfurization, and presulfurization rear catalyst does not draw off, and directly proceeds hydrogenation reaction in the reactor.Presulfurization oil is for containing 5wt%CS
2n-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 cut FCC gasoline, its proportion (d
4 20) be 0.7296, sulfur content is 470ppm, and research octane number (RON) (RON) is 92.0.Raw material adopts plunger displacement pump to pump into, reacted oil sample after the cooling of high separator, 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-fragrant 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 hydrogenation ferrum-based catalyst of the present invention possesses higher hydrodesulfurization, denitrogenation and de-virtue activity.And, when hydrogenation ferrum-based catalyst of the present invention is used for gasoline hydrogenation process, the loss of octane number of gasoline can be made very low.Although the desulfurization of hydrogenation ferrum-based catalyst of the present invention, denitrogenation and de-fragrant rate are a little less than conventional load type Ni-W catalyst (comparative catalyst), the active constituent metal that ferrum-based catalyst of the present invention adopts and nickel salt, cobalt salt, tungsten salt and molybdenum salt etc. that the price of aided metal adopts well below traditional hydrogenation catalyst.Further, hydrogenation ferrum-based catalyst of the present invention breaches the restriction that traditional hydrogenation catalyst continues to use the activity component metal of many decades, therefore has long-range industrial application value.
Claims (10)
1. a gasoline, diesel hydrogenation ferrum-based catalyst, it is using iron 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; With the gross weight of described gasoline, diesel hydrogenation ferrum-based catalyst for benchmark, the activity component metal of oxide form and the total amount of aided metal are 10-80%.
2. gasoline, diesel hydrogenation ferrum-based catalyst according to claim 1, it is prepared by infusion process or coprecipitation.
3. gasoline, diesel hydrogenation ferrum-based catalyst according to claim 2, wherein, described infusion process comprises the following steps:
Activity component metal salt, aided metal salt are dissolved in deionized water, are made into maceration extract;
Described maceration extract is joined in carrier, obtains catalyst semi-finished product;
Described catalyst semi-finished product are left standstill 2-24 hour in atmosphere, then dry, then at air atmosphere, 200-800 DEG C roasting 2-8h, obtain described gasoline, diesel hydrogenation ferrum-based catalyst.
4. gasoline, diesel hydrogenation ferrum-based catalyst according to claim 3, wherein, described carrier comprises the combination of one or more in aluminium oxide, silica, amorphous aluminum silicide and zeolite molecular sieve.
5. gasoline, diesel hydrogenation ferrum-based catalyst according to claim 2, wherein, described coprecipitation comprises the following steps:
By activity component metal salt and the aqueous solution of aided metal salt and the aqueous solution of precipitating reagent even;
Then at 40-95 DEG C of stirred in water bath reaction 1-24h, then leave standstill aging 2-48h in 40-95 DEG C of water-bath, be precipitated thing;
After being carried out by described sediment filtering, wash, drying, obtain catalyst precursor;
By described catalyst precursor roasting 2-8h at air atmosphere, 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;
Wherein, preferably, described binding agent comprises 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 hydrogenation ferrum-based catalyst according to claim 5, wherein, described precipitating reagent comprises NaOH, KOH, Na
2cO
3, K
2cO
3, Na
2s, (NH
4)
2the combination of one or more in S, urea and ammoniacal liquor, the mol ratio of total metal of described precipitating reagent and described activity component metal and described aided metal is 1-6:1.
7. the gasoline, diesel hydrogenation ferrum-based catalyst according to any one of claim 3-6, wherein, described activity component metal salt comprises the combination of one or more in ferric nitrate, ferric sulfate, iron chloride and ferric phosphate; Described aided metal salt comprises the combination of one or more in nitrate, sulfate, chlorate and phosphate.
8. the gasoline, diesel hydrogenation ferrum-based catalyst according to any one of claim 3-7, wherein, described gasoline, diesel hydrogenation ferrum-based catalyst is the gasoline, diesel hydrogenation ferrum-based catalyst through presulfurization process, the temperature of described presulfurization process is 200-450 DEG C, pressure is 1-10MPa, the time of presulfurization process 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 of described presulfurization process is 280-380 DEG C, and pressure is 2-6MPa, and the time of presulfurization process is 6-24 hour, and liquid hourly space velocity (LHSV) is 1-4h
-1, hydrogen to oil volume ratio is 200-500.
9. the application of gasoline, diesel hydrogenation ferrum-based catalyst 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 3-8.
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; Preferably, 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.
Priority Applications (6)
| 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 |
| PCT/CN2014/082463 WO2015007230A1 (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 |
| EP14826159.7A EP3023147B1 (en) | 2013-07-18 | 2014-07-18 | Iron-based hydrogenation catalyst and applications thereof |
| US14/905,719 US10335773B2 (en) | 2013-07-18 | 2014-07-18 | Fe-based hydrogenation catalyst and use thereof |
| CA2917361A CA2917361C (en) | 2013-07-18 | 2014-07-18 | Iron-based hydrogenation catalyst and use thereof |
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| CN201310303258.4A CN104383923B (en) | 2013-07-18 | 2013-07-18 | A kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106190232B (en) * | 2016-07-02 | 2018-05-08 | 东营联合石化有限责任公司 | A kind of method of oil hydrofinishing production propylene cracking stock |
| CN108250013A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of method of acetylene hydrogenation in two back end hydrogenation technique of carbon |
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