CN103131468A - Hydrofining and/or hydroisomerizing cracking system and process for low-temperature Fischer-Tropsch synthetic oil - Google Patents
Hydrofining and/or hydroisomerizing cracking system and process for low-temperature Fischer-Tropsch synthetic oil Download PDFInfo
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Abstract
The invention relates to a hydrofining and/or hydroisomerizing cracking system and a process thereof for low-temperature Fischer-Tropsch synthetic oil, wherein a hydrofining unit adopts a liquid-phase hydrogenation and lower feeding mode, so that the hydrogen concentration is more reasonable in axial distribution along a reactor. In addition, because hydrogen consumed in the liquid-phase hydrofining reaction process comes from liquid-phase saturated dissolved hydrogen, a recycle hydrogen compressor can be omitted when the hydrofining unit is operated independently, and thus the investment and operation cost of the device are reduced.
Description
Technical field
The present invention relates to a kind of system of processing and technique of low temperature Fischer-Tropsch synthesis oil, more specifically, relate to a kind of low temperature hydrogenation of Fischer-Tropsch synthesis oil and make with extra care and/or hydroisomerizing cracking system and technique.
Background technology
Tradition low temperature hydrogenation of Fischer-Tropsch synthesis oil treating process all adopts fixed-bed reactor, and feeding manner is upper feeding, and bed temperature gradient and pressure drop are all larger, the easy coking in reactor top.In addition, hydrogen needs circulation, needs the configuration cycles hydrogen compressor, and plant investment and running cost are higher.
C-C cleavage reaction in tradition hydroisomerizing cracking unit, easily cause the bed reaction temperature rising, easily cause on the one hand a large amount of secondary cracking reactions, consume a large amount of hydrogen, cause simultaneously liquid product yield to descend, the risk of initiation " temperature runaway " accident is also arranged on the other hand.
CN1594507A discloses a kind of technique for Fischer-Tropsch synthesis of heavy hydrocarbon and/or kettle bottom wax hydrocracking, and it comprises the fixed bed hydrogenation process for refining that uses efficient disperse type catalyzer floating bed hydrocracking technique and use Supported Nickel Catalyst.In the document, for the method that product separation has adopted stage trapping to combine, sepn process is complicated.In addition, can be found out by process flow sheet (accompanying drawing 1), fixed bed hydrogenation refining reaction device 8 is the feeding manners that use upper feeding, therefore, be difficult to avoid aforementioned bed temperature gradient and pressure drop all larger, the easy coking in reactor top, hydrogen needs circulation, need the configuration cycles hydrogen compressor, the problem that plant investment and running cost are higher.
The present invention is devoted to solve the above-mentioned problems in the prior art.
Summary of the invention
An object of the present invention is to provide a kind of low temperature hydrogenation of Fischer-Tropsch synthesis oil refining system, comprising:
Fixed-bed reactor are used for the low temperature hydrogenation of Fischer-Tropsch synthesis oil refining, contain Hydrobon catalyst in described fixed bed; With
Separation column is used for fractionation by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil,
Wherein, the pan feeding entrance of described fixed-bed reactor is positioned at bottom or the bottom of described fixed-bed reactor; And the refining reacting product outlet of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is positioned at top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
Another object of the present invention is to provide a kind of low temperature hydrogenation of Fischer-Tropsch synthesis oil and makes with extra care and hydroisomerizing cracking system, comprising:
Fixed-bed reactor are used for the low temperature hydrogenation of Fischer-Tropsch synthesis oil refining, contain Hydrobon catalyst in described fixed bed;
Slurry attitude bed or ebullated bed reactor are used for the heavy component hydroisomerizing cracking by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil, and described slurry attitude bed or ebullated bed reactor contain the hydroisomerizing cracking catalyst; With
Separation column is used for fractionation by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil and the product that obtained by the heavy component hydroisomerizing cracking of the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil;
Wherein, the pan feeding entrance of described fixed-bed reactor is positioned at bottom or the bottom of described fixed-bed reactor; And the refining reacting product outlet of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is positioned at top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
A further object of the present invention is to provide a kind ofly carries out hydrorefined technique to the low temperature Fischer-Tropsch synthesis oil, wherein adopts aforementioned low temperature hydrogenation of Fischer-Tropsch synthesis oil refining system, and described technique comprises the following steps successively:
The raw material that comprises the low temperature Fischer-Tropsch synthesis oil of heating or preheating is sent in described fixed-bed reactor, and under described Hydrobon catalyst effect, made described raw material carry out hydrofining reaction; With
The very wet of described hydrofining reaction product is partly sent into is mutually carried out fractionation in described separation column, thereby obtain various fraction products,
Wherein, the raw material that comprises the low temperature Fischer-Tropsch synthesis oil is entered in described fixed-bed reactor by bottom or the bottom of described fixed-bed reactor, and the refining reaction product of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is discharged by top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
A further object of the present invention is to provide a kind of technique of the low temperature Fischer-Tropsch synthesis oil being carried out hydrofining and hydroisomerizing cracking, wherein adopts aforementioned low temperature hydrogenation of Fischer-Tropsch synthesis oil to make with extra care and hydroisomerizing cracking system, and described technique comprises the following steps successively:
The raw material that comprises the low temperature Fischer-Tropsch synthesis oil of heating or preheating is sent in described fixed-bed reactor, and under described Hydrobon catalyst effect, made described raw material carry out hydrofining reaction;
Heavy component in the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil is sent in described slurry attitude bed or ebullated bed reactor after heating or preheating, and under the effect of described hydroisomerizing cracking catalyst, make described heavy component carry out the hydroisomerizing cracking reaction; With
With the very wet of described hydrofining reaction product mutually part and hydroisomerizing cracked reaction product send into and carry out fractionation in described separation column, thereby obtain various fraction products,
Wherein, the raw material that comprises the low temperature Fischer-Tropsch synthesis oil is entered in described fixed-bed reactor by bottom or the bottom of described fixed-bed reactor, and the refining reaction product of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is discharged by top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
Hydrofining system of the present invention and technique are descended the mode of charging by employing, guaranteed that whole temperature of reactor gradient is minimum, thereby made hydrogen concentration more reasonable along the reactor axial distribution.In addition, easy and simple to handle, the cycle of operation is long, has overcome fixed bed hydrogenation catalyst for refining bed top " knot lid " problem that pressure drop is large.Because the required hydrogen of reaction process comes from the saturated dissolved hydrogen of liquid phase, thereby save circulating hydrogen compressor, reduced plant investment and running cost.
Hydrofining of the present invention and hydroisomerizing cracking system and technique have advantages of above-mentioned hydrofining system and technique, simultaneously in slurry attitude bed/boiling bed hydrogenation isocracking unit by to the point of the cut after hydrofining the heavy distillate of the 370 ℃ isocracking that circulates, can guarantee the positive structure of purpose product/isomery ratio, thereby make diesel product have lower condensation point and cold filter clogging temperature.Due to the full back-mixing that can realize gas, liquid, solid three phase materials in reactor, the high pressure drop that can avoid fixed bed top coking to produce, the while can also guarantee the homogeneity of inside reactor temperature of reaction.In addition, save the links such as injection of cold hydrogen, also helped the running period of extending catalyst.
In addition, in low temperature hydrogenation of Fischer-Tropsch synthesis oil of the present invention refining and/or hydroisomerizing cracking system and technique, liquid-phase hydrogenatin refined unit and slurry attitude bed/boiling bed hydrogenation isocracking can realize flexibly independently production decision between the unit, can according to the market requirement, singly open partial devices and produce the products such as petroleum naphtha, diesel oil and Fischer-Tropsch wax.
Description of drawings
Fig. 1 is the process flow sheet of documents CN1594507A.
Fig. 2 is the schema of one embodiment of the invention.
Embodiment
Low temperature hydrogenation of Fischer-Tropsch synthesis oil refining system of the present invention comprises:
Fixed-bed reactor are used for the low temperature hydrogenation of Fischer-Tropsch synthesis oil refining, contain Hydrobon catalyst in described fixed bed; With
Separation column is used for fractionation by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil,
Wherein, the pan feeding entrance of described fixed-bed reactor is positioned at bottom or the bottom of described fixed-bed reactor; And the refining reacting product outlet of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is positioned at top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
Refining and the hydroisomerizing cracking of low temperature hydrogenation of Fischer-Tropsch synthesis oil of the present invention system comprises:
Fixed-bed reactor are used for the low temperature hydrogenation of Fischer-Tropsch synthesis oil refining, contain Hydrobon catalyst in described fixed bed;
Slurry attitude bed or ebullated bed reactor are used for the heavy component hydroisomerizing cracking by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil, and described slurry attitude bed or ebullated bed reactor contain the hydroisomerizing cracking catalyst; With
Separation column is used for fractionation by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil and the product that obtained by the heavy component hydroisomerizing cracking of the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil;
Wherein, the pan feeding entrance of described fixed-bed reactor is positioned at bottom or the bottom of described fixed-bed reactor; And the refining reacting product outlet of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is positioned at top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
In each system of the present invention, be used for the mode that the refining fixed-bed reactor of low temperature hydrogenation of Fischer-Tropsch synthesis oil adopt lower charging, guaranteed that whole temperature of reactor gradient is minimum, thereby made hydrogen concentration more reasonable along the reactor axial distribution.In addition, easy and simple to handle, the cycle of operation is long, has overcome fixed bed hydrogenation catalyst for refining bed top " knot lid " problem that pressure drop is large.Because the required hydrogen of reaction process comes from the saturated dissolved hydrogen of liquid phase, thereby save circulating hydrogen compressor, reduced plant investment and running cost.Such fixed-bed reactor can be selected the fixed-bed reactor of feeding manner under known employing, and are except adopting lower feeding manner, without particular limitation to reactor.
In each system of the present invention, after hydrofining〉heavy distillate of the 370 ℃ slurry attitude bed of the isocracking/boiling bed hydrogenation isocracking reactor that circulates guaranteed the positive structure of purpose product/isomery ratio, thereby made diesel product have lower condensation point and cold filter clogging temperature.Due to the full back-mixing that can realize gas, liquid, solid three phase materials in reactor, the high pressure drop that can avoid fixed bed top coking to produce, the while can also guarantee the homogeneity of inside reactor temperature of reaction.In addition, save the links such as injection of cold hydrogen, also helped the running period of extending catalyst.Such slurry attitude bed/boiling bed hydrogenation isocracking reactor can be selected the known similar reactor that is used for similar system.
In each system of the present invention, separation column is used for fractionation by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil and the product that obtained by the heavy component hydroisomerizing cracking of the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil.This type of distillation tower is known for those of ordinary skills, can select known similar distillation tower.
In hydrofining of the present invention and/or hydroisomerizing cracking system, described system further comprises necessary utility appliance, for example fresh feed pump, process furnace, high pressure hot separator and circulating hydrogen compressor, and necessary pipeline etc.These equipment can adopt the similar devices for similar system, and their setting also can be definite by those of ordinary skill after having read this specification sheets, and therefore, therefore not to repeat here.
In a specific embodiments of hydrofining of the present invention and/or hydroisomerizing cracking system, described Hydrobon catalyst contains NiO, MoO
3, P
2O
5And Al
2O
3, and NiO:MoO
3: P
2O
5: Al
2O
3Weight ratio can be 0.02-0.06:0.12-0.16:0.01-0.02:1.Preferably, catalyzer also contains TiO
2, and NiO:MoO
3: P
2O
5: TiO
2: Al
2O
3Weight ratio can be 0.02-0.06:0.12-0.16:0.01-0.02:0:003-0.02:1
In a preferred embodiment, the NiO:MoO of described Hydrobon catalyst
3: P
2O
5: TiO
2: Al
2O
3Weight ratio is further 0.035-0.05:0.135-0.15:0.012-0.018:0.005-0.015:1.
In hydrofining of the present invention and/or hydroisomerizing cracking system, described hydroisomerizing cracking catalyst contains NiO, WO
3And Al
2O
3, and NiO:WO
3: Al
2O
3Weight ratio is generally 0.02-0.09:0.15-0.25:1.
In a preferred embodiment, the NiO:WO of described hydroisomerizing cracking catalyst
3: Al
2O
3Weight ratio is 0.035-0.075:0.18-0.225:1.
In hydrofining of the present invention and/or hydroisomerizing cracking system, the heavy component in the refining product that obtains of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is the refining rear heavy distillate more than 370 ℃ of low temperature hydrogenation of Fischer-Tropsch synthesis oil.
The present invention carries out the aforementioned low temperature hydrogenation of Fischer-Tropsch synthesis oil of hydrorefined process using refining system to the low temperature Fischer-Tropsch synthesis oil, and it comprises the following steps successively:
The raw material that comprises the low temperature Fischer-Tropsch synthesis oil of heating or preheating is sent in described fixed-bed reactor, and under described Hydrobon catalyst effect, made described raw material carry out hydrofining reaction; With
The very wet of described hydrofining reaction product is partly sent into is mutually carried out fractionation in described separation column, thereby obtain various fraction products,
Wherein, the raw material that comprises the low temperature Fischer-Tropsch synthesis oil is entered in described fixed-bed reactor by bottom or the bottom of described fixed-bed reactor, and the refining reaction product of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is discharged by top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
The present invention makes with extra care and hydroisomerizing cracking system the aforementioned low temperature hydrogenation of Fischer-Tropsch synthesis oil of process using that the low temperature Fischer-Tropsch synthesis oil carries out hydrofining and hydroisomerizing cracking, and it comprises the following steps successively:
The raw material that comprises the low temperature Fischer-Tropsch synthesis oil of heating or preheating is sent in described fixed-bed reactor, and under described Hydrobon catalyst effect, made described raw material carry out hydrofining reaction;
Heavy component in the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil is sent in described slurry attitude bed or ebullated bed reactor after heating or preheating, and under the effect of described hydroisomerizing cracking catalyst, make described heavy component carry out the hydroisomerizing cracking reaction; With
With the very wet of described hydrofining reaction product mutually part and hydroisomerizing cracked reaction product send into and carry out fractionation in described separation column, thereby obtain various fraction products;
Wherein, the raw material that comprises the low temperature Fischer-Tropsch synthesis oil is entered in described fixed-bed reactor by bottom or the bottom of described fixed-bed reactor, and the refining reaction product of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is discharged by top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
Technique of the present invention is relied on aforementioned system implementation of the present invention, and the hydrofining reaction process adopts liquid-phase hydrogenatin and lower feeding manner, has overcome beds top " knot lid " problem that pressure drop is large; Whole temperature of reactor gradient is minimum, makes hydrogen concentration more reasonable along the reactor axial distribution; Simultaneously, the required hydrogen of hydrofining reaction process comes from the saturated dissolved hydrogen of liquid phase, thereby has saved circulating hydrogen compressor, has reduced plant investment and running cost, easy operation, and the cycle of operation extends.In addition, after hydrofining〉heavy distillate of the 370 ℃ slurry attitude bed of the isocracking/boiling bed hydrogenation isocracking reaction process that circulates can realize the full back-mixing of gas, liquid, solid three phase materials, the high pressure drop that can avoid fixed bed top coking to produce, the while can also guarantee the homogeneity of inside reactor temperature of reaction; Simultaneously, save the links such as injection of cold hydrogen, also helped the running period of extending catalyst.
In technique of the present invention, but independent operating between liquid-phase hydrogenatin refined unit and slurry attitude bed/boiling bed hydrogenation isocracking unit thus, can according to the market requirement, singly be opened partial devices and produce the products such as petroleum naphtha, diesel oil and Fischer-Tropsch wax.
In hydrofining of the present invention and/or hydroisomerizing cracking technique, the heavy component in the refining product that obtains of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is the refining rear heavy distillate more than 370 ℃ of low temperature hydrogenation of Fischer-Tropsch synthesis oil.
In hydrofining of the present invention and/or hydroisomerizing cracking technique, the operating parameters of described fixed-bed reactor is as follows: temperature of reaction: 250-350 ℃; Hydrogen dividing potential drop: 2-12MPa; Dissolved hydrogen/raw material (weight ratio): 0.0002-0.0012; Raw material cumulative volume air speed: 1.0-4.0/ hour; Cold hydrogen injection rate/raw material (weight ratio): 0.001-0.005.
In hydrofining of the present invention and/or hydroisomerizing cracking technique, the operating parameters of described slurry attitude bed or ebullated bed reactor is as follows: temperature of reaction: 320-400 ℃; Hydrogen dividing potential drop: 2-12MPa; Raw material cumulative volume air speed: 1.0-4.0/ hour; Hydrogen/heavy component (volume ratio) 800-1600; Empty tower gas velocity: 5-15 cel.
In hydrofining of the present invention and/or hydroisomerizing cracking technique, the described raw material that comprises the low temperature Fischer-Tropsch synthesis oil comprises light ends oil, heavy distillate and Fischer-Tropsch wax.
Fig. 2 is the schema of one embodiment of the invention.Now in conjunction with this accompanying drawing, the present invention is made exemplary illustration.Be understandable that, the explanation that this figure reaches for this figure does not all consist of any restriction to the present invention.
At first, the low temperature Fischer-Tropsch synthesis oil raw material that will comprise light ends oil I, heavy distillate II and Fischer-Tropsch wax III is pumped in hydrofining process furnace 2 by hydrofining fresh feed pump 1, cold hydrogen VI also is delivered in hydrofining process furnace 2 by pipeline, and mixes with low temperature Fischer-Tropsch synthesis oil raw material therein.Mass transport after Hybrid Heating is carried out hydrofining to the refining fixed-bed reactor 3 of liquid-phase hydrogenatin.Carry out gas-liquid separation through the mass transport that hydrofining obtains to the high separating tank 4 of hydrofining heat.The gas-phase product VII that is obtained by high separating tank 4 separation of hydrofining heat discharges (directly act as a fuel and use or reclaim) from the top of the high separating tank 4 of hydrofining heat, the liquid product that separation obtains is delivered to and carries out fractionation in product separation column 6.The heavy component that obtains in product separation column 6 is pumped to heating in hydroisomerizing cracking process furnace 9 by hydroisomerizing cracked charge pump 8, and simultaneously, cold hydrogen VI also is delivered in hydroisomerizing cracking process furnace 9 by pipeline, and mixes with wherein heavy component.Mass transport after Hybrid Heating is carried out the hydroisomerizing cracking to starching in attitude bed/boiling bed hydrogenation isocracking reactor 10.Carry out gas-liquid separation to the hydroisomerizing heat of cracking in high separating tank 11 through the mass transport that the hydroisomerizing cracking obtains.Separating by the high separating tank of the hydroisomerizing heat of cracking 11 liquid product that obtains is delivered to and carries out fractionation in product separation column 6; The gas gas-phase objects (comprising unreacted hydrogen) that separation obtains is delivered to hydroisomerizing cracking process furnace 9 through circulating hydrogen compressor 7 circulations from the top of the high separating tank 11 of the hydroisomerizing heat of cracking, therein with cold hydrogen and treat that the heavy component of hydroisomerizing cracking mixes, thus continuation hydroisomerizing cracking process.The liquid phase thing that separation obtains enters product separation column 6 through pipeline from the bottom of the high separating tank 11 of the hydroisomerizing heat of cracking, the liquid product of 6 pairs of hydrofinings of product separation column and hydroisomerizing cracking carries out fractionation, as required they are fractionated into petroleum naphtha IV and diesel oil V, and the heavy component for the treatment of the hydroisomerizing cracking.
By schema as seen, in unifining process, the hydrogen of reaction process consumption comes from the saturated dissolved hydrogen of liquid phase, without recycle hydrogen, has therefore saved the hydrofining circulating hydrogen compressor.But when hydroisomerizing cracking unit isolated operation or itself and the operation of hydrofining unit associations, just need the recycle hydrogen system, comprise circulating hydrogen compressor.
Below, by embodiment, the present invention is done more detailed description.
Embodiment 1
Adopt system shown in Figure 1 to carry out hydrofining and hydroisomerizing cracking to the low temperature Fischer-Tropsch synthesis oil.
Take the synthetic full distillate oil of Shenhua coal based synthetic gas low temperature Fischer-Tropsch as raw material, its character sees Table 1.The liquid-phase hydrogenatin catalyst for refining is NiO-MoO
3-P
2O
5/ Al
2O
3, available from Shandong, Shandong catalyst plant, model is FF-26, wherein NiO is 3.5wt%, MoO
3Be 13.5wt%, P
2O
5Be 1.4wt%, TiO
2Be 1.4%; Bed/boiling bed hydrogenation isocracking catalyzer is NiO-WO to the slurry attitude
3/ Al
2O
3, available from Shandong, Shandong catalyst plant, model is FC-14, wherein NiO is 5wt%, WO
3Be 23wt%, the catalyzer specific nature is as shown in table 2.Fixed bed liquid-phase hydrogenatin is made with extra care and the operational condition of slurry attitude bed/boiling bed hydrogenation isocracking is listed in table 3, and one of product naphtha fraction character is listed in table 4, and one of product diesel oil distillate character is listed in table 5.
As shown in Figure 1, cut o'clock heating in the heavy component more than 370 ℃ is pumped to hydroisomerizing cracking process furnace 9 by hydroisomerizing cracked charge pump 8 in the product that will obtain in product separation column 6, it is delivered to together with hydrogen in slurry attitude bed/boiling bed hydrogenation isocracking reactor 10 and carries out the hydroisomerizing cracking afterwards.Liquid product obtains petroleum naphtha IV and diesel oil V through 6 fractionation of product separation column.
Table 1 low temperature Fischer-Tropsch synthesizes full distillate oil character
| Project | Numerical value |
| Density, g/cm 3 | 0.8092 |
| Oxygen level, wt%(is based on oily gross weight) | 0.48 |
| Sulphur content, μ g/g | <4 |
| Nitrogen content, μ g/g | <1 |
| Carbon content, wt% | 84.88 |
| Hydrogen richness, wt% | 14.64 |
| Boiling range (ASTM D-1160) | ? |
| The IBP/5%(initial boiling point) | 65/114 |
| 10%/30% | 142/279 |
| 50%/70% | 372/456 |
| 90%/95% | 560/650 |
Table 2 liquid-phase hydrogenatin catalyst for refining and slurry attitude bed/boiling bed hydrogenation isocracking catalyst property
| Project | Data |
| The liquid-phase hydrogenatin catalyst for refining | ? |
| Specific surface area, m 2/g | 180 |
| Specific pore volume, ml/g | 0.4 |
| MoO 3，wt% | 13.5 |
| NiO，wt% | 3.5 |
| P 2O 5，wt% | 1.4 |
| TiO 2，wt% | 1.2 |
| Crushing strength, N/cm | 180 |
| Packing density, g/cm 3 | 0.80 |
| Slurry attitude bed/boiling bed hydrogenation isocracking catalyzer | ? |
| Specific surface area, m 2/g | 180 |
| Specific pore volume, ml/g | 0.5 |
| NiO,wt% | 5.0 |
| WO
3, |
23 |
Table 3 hydrofining and hydroisomerizing cracking operational condition
| Project | Data |
| Fixed bed liquid-phase hydrogenatin refining reaction device | ? |
| The hydrogen dividing potential drop, Mpa | 6.4 |
| Temperature of reaction, ℃ | 265 |
| The cumulative volume air speed, h -1 | 2.0 |
| The stock oil dissolved hydrogen, wt%(is to stock oil) | 0.07 |
| Cold hydrogen injection rate, wt%(is to stock oil) | 0.23 |
| Slurry attitude bed/boiling bed hydrogenation isocracking reactor | ? |
| The hydrogen dividing potential drop, Mpa | 6.4 |
| Temperature of reaction, ℃ | 340 |
| Volume space velocity, h -1 | 2.0 |
| Hydrogen to oil volume ratio | 1200 |
| Empty tower gas velocity, cm/ |
10 |
Table 4 product naphtha fraction character
| Project | Numerical value |
| The boiling range scope | Initial boiling point-165 ℃ |
| Density, g/cm 3 | 0.7065 |
| Form wt% | ? |
| Normal paraffin | 47.8 |
| Isoparaffin | 44.0 |
| Naphthenic hydrocarbon | 8.2 |
Table 5 product diesel product character
| Project | Data |
| The boiling range scope | 150-350℃ |
| Density, g/cm 3 | 0.7586 |
| Condensation point, ℃ | -35 |
| Cold filter clogging temperature, ℃ | -31 |
| Cetane value | 75 |
| Oxidation stability, total insoluble substance mg/100ml | 0.5 |
| Flash-point, ℃ | 63.5 |
Adopt system shown in Figure 1 to carry out hydrofining to the low temperature Fischer-Tropsch synthesis oil, namely close down pulp bed in system shown in Figure 1/boiling bed hydrogenation isocracking unit.
Carry out liquid-phase hydrogenatin with the raw material identical with embodiment 1, the use liquid-phase hydrogenatin catalyst for refining identical with embodiment 1 and the employing liquid-phase hydrogenatin refined unit identical with embodiment 1 and operational condition refining, obtain petroleum naphtha, diesel oil and wax oil (or claiming tail oil) from the product separation column, its character sees Table 6.
The character of petroleum naphtha, diesel oil and wax oil after the synthetic full fraction oil hydrogenation refining of table 6 low temperature Fischer-Tropsch
The term that this specification sheets is used and form of presentation only are used as descriptive and nonrestrictive term and form of presentation, the feature that will represent and describe unintentionally when using these terms and form of presentation or any equivalent exclusion of its integral part.
Although represented and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize that in the situation that do not break away from principle of the present invention and spirit can be carried out any accommodation and improvement to these embodiments, protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (14)
1. low temperature hydrogenation of Fischer-Tropsch synthesis oil refining system comprises:
Fixed-bed reactor are used for the low temperature hydrogenation of Fischer-Tropsch synthesis oil refining, contain Hydrobon catalyst in described fixed bed; With
Separation column is used for fractionation by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil,
Wherein, the pan feeding entrance of described fixed-bed reactor is positioned at bottom or the bottom of described fixed-bed reactor; And the refining reacting product outlet of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is positioned at top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
2. a low temperature hydrogenation of Fischer-Tropsch synthesis oil is made with extra care and hydroisomerizing cracking system, comprising:
Fixed-bed reactor are used for the low temperature hydrogenation of Fischer-Tropsch synthesis oil refining, contain Hydrobon catalyst in described fixed bed;
Slurry attitude bed or ebullated bed reactor are used for the heavy component hydroisomerizing cracking by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil, and described slurry attitude bed or ebullated bed reactor contain the hydroisomerizing cracking catalyst; With
Separation column is used for fractionation by the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil and the product that obtained by the heavy component hydroisomerizing cracking of the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil;
Wherein, the pan feeding entrance of described fixed-bed reactor is positioned at bottom or the bottom of described fixed-bed reactor; And the refining reacting product outlet of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is positioned at top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
3. system according to claim 1 and 2, wherein, described Hydrobon catalyst contains NiO, MoO
3, P
2O
5, TiO
2And Al
2O
3, and NiO:MoO
3: P
2O
5: TiO
2: Al
2O
3Weight ratio is 0.02-0.06:0.12-0.16:0.01-0.02:0:003-0.02:1.
4. system according to claim 3, wherein, NiO:MoO
3: P
2O
5: TiO
2: Al
2O
3Weight ratio is 0.035-0.05:0.135-0.15:0.012-0.018:0:005-0.015:1.
5. system according to claim 2, wherein, described hydroisomerizing cracking catalyst contains NiO, WO
3And Al
2O
3, and NiO:WO
3: Al
2O
3Weight ratio is 0.02-0.09:0.15-0.25:1.
6. system according to claim 5, wherein, NiO:WO
3: Al
2O
3Weight ratio is 0.035-0.075:0.18-0.225:1.
7. according to claim 1,2 or 4-6 one of any described system, described system further comprises fresh feed pump, process furnace, high pressure hot separator and circulating hydrogen compressor.
According to claim 2 with one of any described system of 4-6, wherein, the heavy component in the refining product that obtains of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is the heavy distillate 370 ℃ or more of low temperature hydrogenation of Fischer-Tropsch synthesis oil after refining.
One kind with according to claim 1,3,4,6-7 one of any described system carries out hydrorefined technique to the low temperature Fischer-Tropsch synthesis oil, it comprises the following steps successively:
The raw material that comprises the low temperature Fischer-Tropsch synthesis oil of heating or preheating is sent in described fixed-bed reactor, and under described Hydrobon catalyst effect, made described raw material carry out hydrofining reaction; With
The very wet of described hydrofining reaction product is partly sent into is mutually carried out fractionation in described separation column, thereby obtain various fraction products,
Wherein, the raw material that comprises the low temperature Fischer-Tropsch synthesis oil is entered in described fixed-bed reactor by bottom or the bottom of described fixed-bed reactor, and the refining reaction product of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is discharged by top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
10. one kind is carried out the technique of hydrofining and hydroisomerizing cracking with according to claim 2-8 one of any described systems to the low temperature Fischer-Tropsch synthesis oil, and it comprises the following steps successively:
The raw material that comprises the low temperature Fischer-Tropsch synthesis oil of heating or preheating is sent in described fixed-bed reactor, and under described Hydrobon catalyst effect, made described raw material carry out hydrofining reaction;
Heavy component in the refining product that obtains of low temperature hydrogenation of Fischer-Tropsch synthesis oil is sent in described slurry attitude bed or ebullated bed reactor after heating or preheating, and under the effect of described hydroisomerizing cracking catalyst, make described heavy component carry out the hydroisomerizing cracking reaction; With
With the very wet of described hydrofining reaction product mutually part and hydroisomerizing cracked reaction product send into and carry out fractionation in described separation column, thereby obtain various fraction products,
Wherein, the raw material that comprises the low temperature Fischer-Tropsch synthesis oil is entered in described fixed-bed reactor by bottom or the bottom of described fixed-bed reactor, and the refining reaction product of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is discharged by top or the top of described fixed-bed reactor, and there is no excessive recycle hydrogen in described fixed-bed reactor, the required hydrogen of hydrofining reaction is only provided by the hydrogen that dissolves in the low temperature Fischer-Tropsch synthesis oil.
11. technique according to claim 10, wherein, the heavy component in the refining product that obtains of described low temperature hydrogenation of Fischer-Tropsch synthesis oil is the heavy distillate more than 370 ℃ after the low temperature hydrogenation of Fischer-Tropsch synthesis oil is made with extra care.
12. according to claim 9-11 one of any described techniques, wherein, the operating parameters of described fixed-bed reactor is as follows: temperature of reaction: 250-350 ℃; Hydrogen dividing potential drop: 2-12MPa; Dissolved hydrogen/raw material (weight ratio): 0.0002-0.0012; Raw material cumulative volume air speed: 1.0-4.0/ hour; Cold hydrogen injection rate/raw material (weight ratio): 0.001-0.005.
13. according to claim 10 or 11 described techniques, wherein, the operating parameters of described slurry attitude bed or ebullated bed reactor is as follows: temperature of reaction: 320-400 ℃; Hydrogen dividing potential drop: 2-12MPa; Raw material cumulative volume air speed: 1.0-4.0/ hour; Hydrogen/heavy component volume ratio 800-1600; Empty tower gas velocity: 5-15 cel.
14. according to claim 9,10 or 11 described techniques, wherein, the described raw material that comprises the low temperature Fischer-Tropsch synthesis oil comprises light ends oil, heavy distillate and Fischer-Tropsch wax.
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| CN106590732B (en) * | 2015-10-15 | 2019-04-09 | 神华集团有限责任公司 | A kind of method and system of Fischer-Tropsch synthesis oil low temperature liquid phase hydrofinishing |
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| CN105733673A (en) * | 2016-02-26 | 2016-07-06 | 武汉凯迪工程技术研究总院有限公司 | Device and method for producing environment-friendly type solvent oil from Fischer-Tropsch synthesis oil |
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| CN105733673B (en) * | 2016-02-26 | 2018-01-23 | 武汉凯迪工程技术研究总院有限公司 | Utilize the device and method of Fischer-Tropsch synthesis oil production environment-friendlysolvent solvent oil |
| WO2017161981A1 (en) * | 2016-03-25 | 2017-09-28 | 武汉凯迪工程技术研究总院有限公司 | System and method for producing low-condensation-point middle distillate using fischer-tropsch synthesized whole distillate |
| CN113563149A (en) * | 2021-06-16 | 2021-10-29 | 陕西未来能源化工有限公司 | Method for producing low-carbon olefin by steam cracking of coal-based Fischer-Tropsch synthetic oil |
| CN113563149B (en) * | 2021-06-16 | 2023-10-27 | 陕西未来能源化工有限公司 | Method for producing low-carbon olefin by steam cracking of coal-based Fischer-Tropsch synthesis oil product |
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