CN1233796C - Technology for hydrogenating treatment of synthetizing diesel oil - Google Patents
Technology for hydrogenating treatment of synthetizing diesel oil Download PDFInfo
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- CN1233796C CN1233796C CN 03133999 CN03133999A CN1233796C CN 1233796 C CN1233796 C CN 1233796C CN 03133999 CN03133999 CN 03133999 CN 03133999 A CN03133999 A CN 03133999A CN 1233796 C CN1233796 C CN 1233796C
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Abstract
The present invention discloses a hydrotreating method of synthetic diesel oil. Fischer-tropsch synthesis wax is cut so as to extract a light diesel oil component and a heavy diesel oil component; the heavy diesel oil component and hydrogen and a hydrogenation catalytic dewaxing catalyst have a contact reaction in a first catalyst bed; after the effluent which is not extracted is mixed with the light diesel oil component, the effluent directly enters a second catalyst bed; the effluent contacts the hydrogen and a hydrogenation isomerization catalyst to proceed with a catalytic reaction; the effluent after the reaction is cooled and enters a high-pressure separator; an extracted liquid product enters a fractionating system; after gas which comprises the hydrogen is purified, the gas returns to a reactor by circulating. The process of the present invention is a one-step process and has high operation flexibility; the operation parameter is adjusted according to the product requirements; therefore, diesel oil products of different specifications are produced; besides, the operation pressure is correspondingly low; consequently, the investment of devices is reduced, and the operation cost is reduced.
Description
Technical field
The present invention relates to a kind of hydroprocessing technique of combined diesel oil cut material, more particularly, is the hydroprocessing technique by the diesel oil distillate material of expense-holder synthetic wax production.
Background technology
Along with the appearance of 21 century world's derv fuel oil specification, the derv fuel oil cleaningization worldwide presents the trend of accelerated development.Stricter control is not only carried out to the sulphur in the diesel product in countries in the world at present, and also aromaticity content in the diesel oil and cetane value and density etc. has all been proposed strict requirement accordingly.Each company of great oil refining of the world all has the more Technology of the production 21 century fuel for cleaning vehicle of high technology content in exploitation under this background.When having renewal technology to occur frequently, pass through to take-hold in the palm synthetic method production charges-holder synthetic wax with coal resource, and then the technology of production diesel oil distillate is also in greatly developing at natural oil cut production clean fuel.Reason is that the diesel oil distillate of expense-holder synthetic wax production had not both had sulphur, nitrogen, does not also have aromatic hydrocarbons, and has than higher cetane value, and its cetane value generally is at least 60, is 70 preferably, better is about 74.This diesel oil distillate both can have been done the blend component of natural diesel oil distillate, also can directly do diesel product and use.Also there is deficiency in the diesel oil distillate of synthetic wax production of not going to undue expense-hold in the palm, because its composition is mainly normal paraffin, its condensation point is higher, and its range of application is reduced greatly, has weakened its market competitiveness exactly.Utilize the advantage of the diesel oil distillate that expense-holder synthetic wax produces, it is our every oil refining worker that the deficiency that solves it increases its rate of utilization, has also complied with the needs of world's sustainable development.
Summary of the invention
The hydroprocessing process that the purpose of this invention is to provide a kind of combined diesel oil cut is to enlarge the use range of this combined diesel oil cut.
Method provided by the invention is a kind of method that hydrogenation catalyst dewaxing and hydroisomerization dewax technology are combined.So-called catalytic dewaxing claims to face the hydrogen shape slective cracking again, i.e. the hydrocracking of carrying out on the catalyzer that the configuration diffusion is arranged; So-called isomerization dewaxing is by hydroisomerization and selective hydrogenation cracking, and by the low Technology of coagulating product of waxy oil production, the main chemical reactions of isomerization dewaxing is a hydroisomerizing.
The inventive method comprises following implementation step:
A, expense-holder synthetic wax cutting and separating is gone out solar oil component and heavy gas oil component;
Isolated heavy gas oil component contacts with the hydrogenation catalyst dewaxing catalyst in first beds with hydrogen in B, the steps A, and reaction conditions is: hydrogen dividing potential drop 0.5～8.0MPa, best 1.0～6.0MPa; 300 ℃～450 ℃ of temperature, best 350 ℃～420 ℃; Liquid hourly space velocity 0.2h
-1～7.00h
-1, best 1.0h
-1～6.0h
-1Hydrogen-oil ratio 200～1000, best 300～800.
The effluent of C, first beds directly enters second beds again with after the solar oil component is mixed without separating, and contacts with hydroisomerisation catalysts with hydrogen and carries out catalyzed reaction.Reaction conditions is: hydrogen dividing potential drop 0.5～8.0MPa, best 1.0～6.0MPa; 320 ℃～450 ℃ of temperature, best 350 ℃～440 ℃; Liquid hourly space velocity 0.5h
-1～7.0h
-1, best 1.0h
-1～6.0h
-1Reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and hydrogen-containing gas loops back reactor after purifying.
In the steps A, the method that expense-holder synthetic wax cutting and separating is gone out solar oil component and heavy gas oil component is: expense-holder synthetic wax cutting and separating is gone out diesel oil distillate, and its flow process scope is 160 ℃～380 ℃, and cutting and separating is solar oil component and heavy gas oil component again; Or when expense-holder synthetic wax cutting and separating goes out diesel oil distillate, isolate solar oil component and heavy gas oil component.Wherein to distillate temperature a little be 280 ℃～340 ℃ to the boiling range of solar oil component 95%.
The series connection of first beds and second beds, can be in same fixed-bed reactor, also can be in two different fixed-bed reactor.The purpose of first beds mainly is that macromolecular normal paraffin is selected shape hydrocracking pour point depression; And the purpose of second beds mainly is that normal paraffin is carried out the hydroisomerizing pour point depression.
First beds can be different with second used hydrogenation catalyst of beds, also can be identical.The catalyzer of first beds filling is a loaded catalyst, with ZSM type molecular sieve, Y zeolite, γ-Al
2O
3Or contain SiO
2γ-Al
2O
3Deng in the cracking type carrier one or more is carrier; Loaded metal is VIB and group VIII base metal, and as Co, Mo, Ni and W etc., preferred Co or Ni do active metal component, and metal content (in oxide compound) is 1.0wt%～15.0wt%, preferred 1.0wt%～10.0wt%;
The catalyzer of second beds filling is a hydroisomerization catalyst, and carrier is Al
2O
3, halogen-containing Al
2O
3, in SAPO-11, ZSM-12, ZSM-35, MCM-2, MCM-41, ZSM-5 molecular sieve, ZSM-5 molecular sieve with small crystal grains, HBeta zeolite, the y-type zeolite one or more; So-called fine grain ZSM-5 type molecular sieve is meant that its size is less than 1 μ m.Auxiliary agent is TiO
2, SiO
2, ZrO
2, Al
2O
3, rare-earth oxide is (as La
2O
3) in waiting one or more.Loaded metal is a kind of or its various combination in the transition state base metals such as Co, Mo, Ni and W, also can be in the precious metals such as Pt, Re, Ir one or more, perhaps while load base metal and precious metal.Loading for transiting state metals such as Co, Mo, Ni and W by the metal oxide compound, is generally 0.5wt%～20.0wt%, preferred 1.0wt%～15.0wt%.This kind catalyzer should have stronger isomery function.
When this arts demand maximum is produced diesel product, the boiling range that expense-holder synthetic wax cutting and separating can be gone out diesel oil distillate suitably relaxes, can arrive 530 ℃ as final boiling point, but light constituent to cut apart separating ranges constant, the boiling range scope of heavy constituent widening and broaden just with diesel oil boiling range scope.
The invention has the advantages that: the present invention is the single hop flow process, has bigger flexibility of operation, can adjust operating parameters according to product requirement, produces the diesel product of different size, utilizes existing apparatus to carry out appropriate reconstruction and can implement; And working pressure is relatively low, thereby has reduced plant investment, has reduced process cost.
The inventive method can be used for various natural diesel oil hydroprocessing, is particularly useful for the hydrotreatment of the diesel oil distillate of expense-holder synthetic wax production.
Following embodiment further specifies of the present invention, and it does not limit use range of the present invention.
Embodiment 1～6
The main hydrogenation effect of investigating hydrogenation technique of the present invention of this test.Diesel oil distillate with expense-holder synthetic wax production is an example.The main character of raw materials used oil sees Table 1 in this test.Hydrogenation reaction is all carried out in this test on the long run test device.Required catalyzer sees Table 2.Operational condition and the test-results thereof of each embodiment see Table 3.
Table 1 stock oil main character
| Density, g/cm 3 | Condensation point, ℃ | Cetane value | Boiling range, ℃ (5%～95%) |
| 0.843 | 45 | 67 | 170～378 |
Table 2 catalyzer physico-chemical property
| The first bed catalyzer | The second bed catalyzer | |
| Catalytic active component | Ni | Ni |
| Shape | Bar shaped | Bar shaped |
| Diameter, mm | 2.15 | 1.9 |
| Specific surface area, m 2/g | 438.4 | 453.5 |
| Pore volume, ml/g | 0.378 | 0.383 |
| Metal component (oxide compound meter), wt% NiO | 5.4 | 3.5 |
| Carrier | ZSM-5 | The HBeta zeolite |
The operational condition of each embodiment of table 3 and experimental result thereof
| Embodiment | 1 | 2 | 3 |
| Operational condition reaction pressure/MPa temperature of reaction/℃ first beds, second beds liquid hourly space velocity/h -1First beds, the second beds hydrogen to oil volume ratio | 2.0 350 370 2.0 2.0 300 | 3.0 370 390 4.0 4.0 400 | 3.5 390 420 6.0 6.0 500 |
| The solar oil cut point, T95/ ℃ | 285 | 285 | 285 |
| Full distillate oil character condensation point, ℃ cetane value | 1 63 | -7 59 | -21 55 |
Operational condition and the experimental result thereof of continuous each embodiment of table 3
| Embodiment | 4 | 5 | 6 |
| Operational condition reaction pressure/MPa temperature of reaction/℃ first beds, second beds liquid hourly space velocity/h -1First beds, the second beds hydrogen to oil volume ratio | 4.0 350 370 6.0 4.0 300 | 5.0 370 390 6.0 4.0 400 | 6.0 390 420 6.0 4.0 500 |
| Solar oil cut point/T95/ ℃ | 300 | 320 | 335 |
| Full distillate oil character condensation point, ℃ cetane value | 5 65 | -5 61 | -12 57 |
By table 3 as seen, take-hold in the palm diesel oil distillate that synthetic wax produces by hydrotreatment after, it is bigger that its condensation point reduces amplitude, but also by in the table as seen, along with the reduction of the diesel oil distillate condensation point of taking-holding in the palm synthetic wax production, its cetane value is also in decline.
Claims (12)
1, a kind of hydroprocessing process of combined diesel oil comprises the steps:
A, expense-holder synthetic wax cutting and separating is gone out solar oil component and heavy gas oil component;
Isolated heavy gas oil component contacts with the hydrogenation catalyst dewaxing catalyst in first beds with hydrogen in B, the steps A, and its reaction conditions is: hydrogen dividing potential drop 0.5～8.0MPa, 300 ℃～450 ℃ of temperature, liquid hourly space velocity 0.2h
-1～7.0h
-1, hydrogen-oil ratio 200～1000;
The effluent of C, first beds directly enters second beds again with after the solar oil component is mixed without separating, contact with hydroisomerisation catalysts with hydrogen and to carry out catalyzed reaction, its reaction conditions is: hydrogen dividing potential drop 0.5～8.0MPa, 320 ℃～450 ℃ of temperature, liquid hourly space velocity 0.5h
-1～7.0h
-1Reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and hydrogen-containing gas loops back reactor after purifying.
2, in accordance with the method for claim 1, it is characterized in that the method that in the steps A expense-holder synthetic wax cutting and separating is gone out solar oil component and heavy gas oil component is: expense-holder synthetic wax cutting and separating is gone out diesel oil distillate, its flow process scope is 160 ℃～380 ℃, and cutting and separating is solar oil component and heavy gas oil component again; Or when expense-holder synthetic wax cutting and separating goes out diesel oil distillate, isolate solar oil component and heavy gas oil component.
3, according to claim 1 or 2 described methods, it is characterized in that separating of solar oil component and heavy gas oil component in the steps A, wherein to distillate temperature a little be 280 ℃～340 ℃ to the boiling range of solar oil component 95%.
4, in accordance with the method for claim 1, it is characterized in that the reaction conditions among the step B is: hydrogen dividing potential drop 1.0～6.0MPa, 350 ℃～420 ℃ of temperature, liquid hourly space velocity 1.0h
-1～6.0h
-1, hydrogen-oil ratio 300～800.
5, in accordance with the method for claim 1, it is characterized in that the reaction conditions among the step C is: hydrogen dividing potential drop 1.0～6.0MPa, 350 ℃～440 ℃ of temperature, liquid hourly space velocity 1.0h
-1～6.0h
-1
6, in accordance with the method for claim 1, it is characterized in that the catalyzer that first beds loads is a loaded catalyst: with ZSM type molecular sieve, Y zeolite, γ-Al
2O
3Or contain SiO
2γ-Al
2O
3In one or more be carrier, loaded metal is group vib and group VIII base metal, in metal oxide, the content of metal is 1.0wt%～15.0wt%.
7, in accordance with the method for claim 6, the metal that it is characterized in that load on the catalyzer of first beds filling is Co or Ni.
8, according to claim 6 or 7 described methods, it is characterized in that the amount of metal of load on the catalyzer of first beds filling, in metal oxide, be 1.0wt%～10.0wt%.
9, in accordance with the method for claim 1, the hydroisomerization catalyst that it is characterized in that second beds filling: carrier is Al
2O
3, halogen-containing Al
2O
3, in SAPO-11, ZSM-12, ZSM-35, MCM-2, MCM-41, ZSM-5 molecular sieve, ZSM-5 molecular sieve with small crystal grains, HBeta zeolite and the y-type zeolite one or more; The metal of load is one or more among Co, Mo, Ni, W, Pt, Re and the Ir.
10, in accordance with the method for claim 9, the metal that it is characterized in that the hydroisomerization catalyst load of second beds filling is one or more among Co, Mo, Ni and the W, and by the metal oxide compound, metal content is 0.5wt%～20.0wt%.
11,, it is characterized in that adding auxiliary agent TiO in the hydroisomerization catalyst of second beds filling according to claim 9 or 10 described methods
2, SiO
2, ZrO
2, Al
2O
3With in the rare-earth oxide one or more.
12, in accordance with the method for claim 10, it is characterized in that the hydroisomerization catalyst of second beds filling, by the metal oxide compound, metal content is 1.0wt%～15.0wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133999 CN1233796C (en) | 2003-09-15 | 2003-09-15 | Technology for hydrogenating treatment of synthetizing diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133999 CN1233796C (en) | 2003-09-15 | 2003-09-15 | Technology for hydrogenating treatment of synthetizing diesel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597854A CN1597854A (en) | 2005-03-23 |
| CN1233796C true CN1233796C (en) | 2005-12-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03133999 Expired - Lifetime CN1233796C (en) | 2003-09-15 | 2003-09-15 | Technology for hydrogenating treatment of synthetizing diesel oil |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7938953B2 (en) * | 2008-05-20 | 2011-05-10 | Institute Francais Du Petrole | Selective heavy gas oil recycle for optimal integration of heavy oil conversion and vacuum gas oil treating |
| WO2011112661A2 (en) * | 2010-03-09 | 2011-09-15 | Exxonmobil Research And Engineering Company | Hydroprocessing of diesel range biomolecules |
| US20120090223A1 (en) * | 2010-10-13 | 2012-04-19 | Uop Llc | Methods for producing diesel range materials having improved cold flow properties |
| CN114425428B (en) * | 2020-10-14 | 2023-10-31 | 中国石油化工股份有限公司 | Full fraction catalytic diesel hydrofining catalyst and preparation method and application thereof |
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