CN102051217A - Hydrogenation method for producing ultra-low sulfur clean diesel - Google Patents
Hydrogenation method for producing ultra-low sulfur clean diesel Download PDFInfo
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Abstract
The invention relates to a hydrogenation method for producing ultra-low sulfur clean diesel. The method comprises the following steps: mixing diesel fraction feed oil and hydrogen gas, then transferring the mixture into a reactor to contact with a hydrofining catalyst I and a hydrofining catalyst II to react sequentially, and separating and distilling the reaction outflow to obtain the diesel product, wherein the hydrofining catalyst I is a supported hydrofining catalyst using Co-Mo as the active metal component, and the hydrofining catalyst II is a bulk hydrofining catalyst. By adopting the method provided by the invention to process inferior diesel fractions under mild conditions, the low sulfur or ultra-low sulfur clean diesel product can be obtained. Compared with the prior art, when the hydrodesulphurization depths are same, the chemical hydrogen consumption in the hydrogenation process of the invention is 5wt%-10wt% lower than that of the prior art.
Description
Technical field
The invention belongs to a kind ofly in the method that has under the situation of hydrogen refining hydrocarbon ils, more particularly, is a kind of method of hydrotreating of production super low sulfur clean diesel.
Background technology
Increasingly stringent along with the world wide environmental requirement, people are also more and more harsher to the requirement of petroleum products quality, 3 big changes have taken place in most important sulphur content index in the diesel oil specification in less than 10 years, the specification of S＜500 μ g/g (Europe II) was implemented in Europe in 1996, further be reduced to S＜350 μ g/g (Europe III) in 2000, in January, 2005, the derv fuel oil sulphur content was reduced to less than 50 μ g/g (Europe IV).Automotive industry " strategic research plan " has been delivered in European national governments in 2005 and the representative of automotive industry circle in Brussels, proposition will allow European highway communication " safer, more less contamination and more competitive ", put into effect strict more fuel oil for vehicles standard-Ou V standard for this reason, the diesel oil sulphur content is reduced to below the 10 μ g/g, reach " no sulphur " requirement, and implemented in 2008.China's derv fuel oil standard is also in continuous strictness, and Europe II standard was implemented in the whole nation in 2005, and EUROIII Emission Standard is implemented in Beijing, and from 2008, EUROIII Emission Standard was implemented in the nationwide, and Europe IV standard will be implemented in big cities such as Beijing.From the development trend of domestic derv fuel oil standard, in the near future, big city derv fuel oil standards such as Beijing will integrate with Europe, reach Europe V standard, and sulphur content will be less than 10 μ g/g.
Producing the diesel oil that satisfies Europe IV emission standard at present can realize by a kind of main hydrogenating catalyst and conventional hydrogenation unit.Along with Europe V standard to the particularly strictness of sulphur content index of diesel oil index, under the routine operation condition, need pay higher cost by the Europe V standard of a kind of main hydrogenating catalyst or conventional hydrogenation flow process realization diesel oil sulphur content, this just need be under high operating severity, as low-speed, High Operating Temperature and hydrogen dividing potential drop, realize satisfying the production of Euro V emissions diesel oil, high operating severity certainly will increase production cost, and the design objective of conventional equipment does not reach this severity requirement.
Except that Fischer-Tropsch combined diesel oil and hydrocracking diesel oil, catalytic diesel oil, coker gas oil and visbreaking diesel oil all can not satisfy the requirement of clean diesel sulphur content, aromaticity content and cetane value, even straight-run diesel oil also has quite a few to be difficult to satisfy particularly ultra-low-sulphur diesel specification requirement of clean diesel.Therefore, produce clean diesel particularly during ultra-low-sulphur diesel, all diesel oil blending components all must deep hydrodesulfurizationof.The technological difficulties of producing clean diesel are particularly catalytic diesel oil, coker gas oil components of all diesel components, should improve cetane value again by deep desulfuration, and investment and production cost all can not be too high simultaneously.
Produce low-sulfur, high hexadecane value clean diesel with existing technology, must under original complete processing, improve the severity of operation.Usually the measure of taking comprises the raising temperature of reaction, improves the reactive hydrogen dividing potential drop and reduces air speed etc.But the raising temperature of reaction not only has a strong impact on catalyzer work-ing life, and the device cycle of operation is shortened, and the aromatic hydrocarbons saturated reaction is the reaction that is subjected to thermodynamics equilibrium limit, when under certain reaction pressure, along with the rising of temperature of reaction, the product aromaticity content can increase.And high hydrogen dividing potential drop has proposed more requirement to equipment, causes production cost to rise significantly; Reduce volume space velocity and mean the reduction unit capacity.On the other hand, because the over-drastic hydrogenation makes the reactive hydrogen consumption increase, selectivity reduces; Simultaneously, the oilness of product also descends along with the increase of the hydrogenation degree of depth, causes engine scuffing serious.Therefore, concerning prior art, improve severity and not only can bring running cost raising, operational cycle shortening, product to take off problems such as fragrant rate reduction, also can produce the problem of other classes such as product oilness.Develop continuous increase with the high-sulfur crude oil proportion along with processing raw material to the heaviness direction, make the intractability of diesel oil distillate further increase, be difficult to reach the quality product requirement of clean diesel with conventional hydrofining technology.
US6217748 discloses the processing method that a kind of method that adopts cutting reaches deep hydrodesulfurizationof.This technology is divided into FOUR EASY STEPS, at first under the effect of CoMo hydrogenation catalyst raw material is carried out hydrodesulfurization reaction, and the exported product sulphur content is reduced to below the 500ppm; Be that cut point is divided into two portions with product with 320～340 ℃ then; Catalyzer and Co (the Ni)-Mo catalyst combination that adds small number of molecules sieve with Ni-Mo carried out hydrogenation to heavy constituent under the exacting terms relatively again, light constituent of telling the most at last and the heavy constituent behind the hydrogenation mix, and obtain the ultra-low-sulphur diesel product of sulphur content less than 100ppm.This method adopts the catalyzer with acid and isomery performance that contains molecular sieve, can effectively reduce more unmanageable sulfocompound in the heavy constituent.But the catalyzer that contains molecular sieve has reduced diesel yield, has increased chemical hydrogen consumption.
US5068025 discloses a kind of method of desulfurizing and dearomatizing diesel oil deeply, this method adopts the dual catalyst bed reactive system that two kinds of different non-precious metal catalysts are housed respectively, first bed loads the strong NiW catalyzer of a kind of hydrogenation performance, carries out the saturated of aromatic hydrocarbons, eliminates space steric effect; Second bed loads the good Co of a kind of desulfurization performance and/or Ni and Mo Hydrobon catalyst, carries out deep hydrodesulfurizationof and takes off aromatic hydrocarbons.This method can only adopt non-precious metal catalyst to realize that promptly deep hydrodesulfurizationof takes off the purpose of aromatic hydrocarbons.
US20020070147 discloses a kind of technology of utilizing novel Hydrobon catalyst to realize deep hydrodesulfurizationof.This technology utilization is a kind of to be contained Ni-Mo-P and through the novel hydrogenation desulfurization catalyst of thiol acid dipping, Middle East high-sulfur diesel oil is made with extra care, and produces the ultra-low-sulphur diesel product.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of hydrotreating of production super low sulfur clean diesel, to be solved when being prior art production super low sulfur clean diesel, operational condition harshness, problems such as hydrogen consumption height.
Method provided by the invention is: diesel oil distillate stock oil with enter reactor after hydrogen mixes, under the hydrofining reaction condition, with Hydrobon catalyst I and Hydrobon catalyst II contact reacts, its reaction effluent separates and fractionation, obtains diesel product successively; Described Hydrobon catalyst I is that activated metal component is the load hydrogenation catalyst for refining of cobalt-molybdenum, and described Hydrobon catalyst II is a body phase Hydrobon catalyst.
The admission space ratio of described Hydrobon catalyst I and Hydrobon catalyst II is 9: 1～2: 8.
Specifically, the diesel oil distillate stock oil that need carry out hydrogenating desulfurization with enter into the reactor that two kinds of Hydrobon catalysts are housed after hydrogen make-up and recycle hydrogen are mixed, the load hydrogenation catalyst for refining I that a kind of activated metal component is a cobalt-molybdenum is equipped with on reactor top, adopt the cobalt-molybdenum type catalyzer that non-thiophene-type sulfide, thiophene-based and the benzothiophene kind sulfides that is easy to desulfurization carried out direct hydrogenolysis desulfurization, directly the hydrogenolysis desulfurization is the less desulphurization reaction of hydrogen-consuming volume.According to the stock oil composition and property with to the different mass requirement of product, cobalt-molybdenum load hydrogenation catalyst for refining can be divided into one or several bed.The reactor lower part branch is equipped with a kind of body phase (non-loading type) Hydrobon catalyst II, adopt dibenzothiophene (DBT) class of bulk phase catalyst to more difficult desulfurization, especially the 4-methylbenzene thiophthene (4-MDBT), 4 that is difficult to most desulfurization, 6-dimethyl Dibenzothiophene (4,6-DMDBT) the DBT sulfides with the diethyl replacement carries out first hydrogenation, the hydrogenating desulfurization of back desulfurization, according to the stock oil composition and property with to the different mass requirement of product, body phase Hydrobon catalyst can be divided into one or several bed.Reaction such as stock oil and hydrogen carry out hydrogenating desulfurization, hydrodenitrification under the effect of Co-Mo load hydrogenation catalyst for refining I and body phase Hydrobon catalyst II, alkene is saturated and aromatic hydrocarbons is saturated.
Described hydrofining reaction condition is: 250～430 ℃ of temperature of reaction, preferred 280～400 ℃, hydrogen dividing potential drop 1.0～12.0MPa, preferred 2.0～10.0MPa, volume space velocity 0.1～9.0h during liquid
-1, preferred 0.3～6.0h
-1, hydrogen to oil volume ratio 100～1500Nm
3/ m
3, preferred 150～1000Nm
3/ m
3
The reaction effluent of gained is through after the heat exchange, enter high-pressure separator and light pressure separator successively and carry out gas-liquid separation, through the separating obtained hydrogen-rich gas most of Returning reactor top after circulating hydrogen compressor boosts of high-pressure separator, small part turns back to cold hydrogen box between bed as quenching hydrogen; Liquid phase stream through the light pressure separator gained enters fractionating system, obtains naphtha fraction, fine-quality diesel oil product after fractionation.
Described diesel oil distillate stock oil is selected from one or more in straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, the visbreaking diesel oil, and its boiling range scope is 180 ℃～400 ℃.
Described Hydrobon catalyst I contains a kind of carrier and the molybdenum and the cobalt that load on this carrier, with the catalyzer total amount is benchmark, it consists of: cobalt oxide 1～10 heavy %, molybdenum oxide is 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina, with described carrier is benchmark, and the content of the silicon oxide in the preferred silica-alumina is 2～45 heavy %, and the content of aluminum oxide is 55～98 heavy %; The content of further preferred silicon oxide is 5～40 heavy %, and the content of aluminum oxide is 60～95 heavy %, and described silica-alumina has the specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of preferred silica-alumina is 150～350m
2/ g, more preferably 180～300m
2/ g, the pore volume of preferred silica-alumina is 0.4～1ml/g, more preferably 0.5～0.8ml7g.
Described Hydrobon catalyst I contains to be selected from and contains in oxygen or the nitrogenous organism one or more, and preferred oxygen-containing organic compound is selected from one or more in organic alcohol, the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, the organic ammonium salt.For example, oxygenatedchemicals can be ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetate, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, in 2-CDTA, citric acid, tartrate, the oxysuccinic acid one or more, organic compounds containing nitrogen can be quadrol, EDTA and ammonium salt thereof.Described organism be 0.03-2 in the cobalt of oxide compound, the mol ratio of molybdenum sum, be preferably 0.08-1.5.
Described Hydrobon catalyst II contains at least a VIII family metal component, at least two kinds of group vib metal components and organic additive, wherein, the content of a kind of VIII family metal component, at least two kinds of group vib metal components and organic additive satisfies: mR:[VIIIx (VIB-1) y (VIB-2) z] O
2Wherein, represent a kind of group vib metal component with VIB-1, VIB-2 represents another kind of group vib metal component, and R represents at least a organic additive, and m represents every mole of [VIIIx (VIB-1) y (VIB-2) z] O
2In the mole number of contained organic additive, the span of m is 0.1～2, total amount with VIII family metal component, VIB-1 metal component and VIB-2 metal component is a benchmark, x, y, z represents VIII family metal component respectively, the VIB-1 metal component, the molar fraction of VIB-2 metal component, x, y, the span of z satisfies (y+z): x=10: 1～1: 10.
In described group VIII metal component chosen from Fe, cobalt, the nickel one or more, the group vib metal component is selected from least two kinds in chromium, molybdenum and the tungsten, described x, y, the span of z satisfies (y+z): x=5: 1～1: 5, and y: z=5: 1～1: 5.
Described organic additive is selected from the organic ammonium compound, one or more in sulfonate and the organophosphate.The organic ammonium compound is selected from tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, TPAOH, hexamethylenetetramine, Dodecyl trimethyl ammonium chloride; Sulfonate is selected from sodium laurylsulfonate, Sodium dodecylbenzene sulfonate.
Also containing binding agent among the Hydrobon catalyst II, is benchmark with the catalyzer, and the content of described binding agent is no more than 75 weight %.Described binding agent is selected from one or more in silicon oxide, aluminum oxide, the silica-alumina, and the content of preferred described binding agent is no more than 50 weight %.
The preparation method of described Hydrobon catalyst II is: with at least aly contain the compound of group VIII metal component, at least two kinds of compound, organic additive and water that contain different group vib metal components are mixed with mixed solution, the pH value that adopts acid or alkali to adjust mixed solution is 7～11, with described mixed solution place in the reactor in, temperature of reaction is a room temperature to 250 ℃, reaction times is 1～24 hour, filters afterwards and drying.
The used body phase Hydrobon catalyst II of the present invention compares with traditional load hydrogenation catalyst, and its active centre density is much higher, has conventional load type hydrogenation catalyst incomparable superelevation hydrogenating desulfurization, denitrogenation and arene saturating activity.
Advantage of the present invention is:
1, adopts method provided by the invention, owing to adopt loaded catalyst and body (non-loading type) catalyst combination loading mutually, for the sulfide that more easily removes in the raw material, can carry out direct desulfurization through the cobalt-molybdenum loaded catalyst earlier, because direct desulfurization is the less desulphurization reaction of hydrogen-consuming volume, can avoid the sulfide that is easy to remove hydrogenation reaction exceedingly, thereby reduce reactive chemistry hydrogen consumption.For the remaining difficult sulfide that removes, carry out desulfurization through bulk phase catalyst with high hydrodesulfurization activity, can obtain the clean diesel product of ultra-deep desulfurization.The present invention compares with prior art, when reaching the identical hydrogenating desulfurization degree of depth, the chemical hydrogen loss-rate prior art of hydrogenation process is hanged down 5 weight %～10 weight %, thereby has reduced tooling cost, reach energy-conservation, reduce hydrogen consumption, the effect that improves the economy of device.Compare with producing low-sulfur diesel-oil (sulphur content is less than 350 μ g/g), when producing ultra-low-sulphur diesel (sulphur content is less than 50 μ g/g), the amplitude that adopts existing hydrogen addition technology hydrogen consumption to increase is very big.Concerning the refinery, hydrogen accounts for very big cost, and technology of the present invention can effectively reduce the hydrogen consumption, thereby reduces the full scale plant tooling cost.
2, method flow provided by the invention is simple, working pressure is low, facility investment and process cost are all lower, the catalyst activity height, and activity stability is good, and the device cycle of operation is long.Both can be used in new device, and also can be used for building on the plant modification.
3, adaptability to raw material is good, can handle high-sulfur and do high diesel oil distillate, can be under demulcent operational condition comparatively, and the Europe IV standard or the Europe V standard of production super low sulfur, low nitrogen, low aromatic hydrocarbons or do not have the sulfur diesel product.
Embodiment
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Used Hydrobon catalyst I is that activated metal component is the load hydrogenation catalyst for refining of cobalt-molybdenum among the embodiment, Hydrobon catalyst II is a body phase Hydrobon catalyst, used Hydrobon catalyst III is that activated metal component is the load hydrogenation catalyst for refining of nickel-tungsten in the Comparative Examples, and its composition sees Table 1.
Table 1
Table 2
| Type of feed | Raw material A | Raw material B | Raw material C |
| Density (20 ℃), g/cm 3 | 0.8388 | 0.8640 | 0.8921 |
| Sulphur content, μ g/g | 7800 | 8300 | 7700 |
| Nitrogen content, μ g/g | 155 | 403 | 536 |
| Aromatic hydrocarbons, heavy % | 28.0 | 41.5 | 60.3 |
| Polycyclic aromatic hydrocarbons, heavy % | 11.0 | 21.5 | 35.1 |
| Boiling range ASTM D-86, ℃ | |||
| ?IBP | 193 | 185 | 177 |
| ?10％ | 233 | 221 | 210 |
| ?50％ | 283 | 278 | 267 |
| ?90％ | 347 | 347 | 343 |
| ?FBP | 377 | 378 | 374 |
Embodiment 1
A kind of Middle East high-sulfur straight(-run) diesel distillate is a raw material A, and its character sees Table 2.Raw material A with enter into the reactor that two kinds of Hydrobon catalysts are housed after hydrogen make-up and recycle hydrogen are mixed, reactor is divided into two beds, reactor top filling Hydrobon catalyst I, reactor lower part filling Hydrobon catalyst II, the filling ratio of two kinds of Hydrobon catalysts is 9: 1 (volume ratio).Raw material A is carried out the deep hydrodesulfurizationof reaction under the effect of two kinds of Hydrobon catalysts, reaction conditions is: 340 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 6.4MPa, volume space velocity 2.0h during liquid
-1, hydrogen to oil volume ratio 300Nm
3/ m
3Resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut, and reaction conditions and product main character are as shown in table 3.
Comparative Examples 1
This Comparative Examples adopts the raw material identical with embodiment 1, raw material A with enter into the reactor that Hydrobon catalyst III is housed after hydrogen make-up and recycle hydrogen are mixed, under it acts on, carry out deep hydrodesulfurizationof and react, reaction conditions is with embodiment 1.Resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.Reaction conditions and product main character are as shown in table 3.
Table 3
As can be seen from Table 1, the stock oil of embodiment 1 is a kind of high-sulfur straight(-run) diesel distillate, and sulphur content is 7800 μ g/g, and nitrogen content is 155 μ g/g, and polycyclic aromatic hydrocarbon content is 11 heavy %.As can be seen from Table 2, adopt the hydrogen addition technology of embodiment 1, the sulphur content of product is 9.5 μ g/g, polycyclic aromatic hydrocarbon content is 1.6 heavy %, total aromatic hydrocarbons and polycyclic aromatic hydrocarbons all have decline significantly, are the clean diesels that satisfies Euro V emissions, can be used as fine clean diesel blend component.Adopt the hydrogen addition technology of Comparative Examples 1 under identical processing condition, the sulphur content of the product that obtains is 50 μ g/g, and polycyclic aromatic hydrocarbon content is 2.0 heavy %.As 100, desulphurizing activated relatively, the relative denitrification activity that calculates embodiment 1 is respectively 305 and 152 with the desulfurization of Comparative Examples 1, denitrification activity.The chemical hydrogen consumption of embodiment 1 is 0.36 heavy %, and the chemical hydrogen consumption of Comparative Examples 1 is 0.40 heavy %, shows that the chemical hydrogen consumption of the chemical hydrogen loss-rate Comparative Examples 1 of embodiment 1 has reduced by 10%.As seen, adopt hydrogen addition technology of the present invention to compare, can obtain sulphur content, the product that meets the clean diesel standard that nitrogen content is lower, can reduce the chemical hydrogen consumption of reaction simultaneously with existing hydrogen addition technology.
Embodiment 2
A kind of Middle East high-sulfur straight(-run) diesel distillate mixes by weight 1: 1 with a kind of domestic catalytic cracking diesel oil cut, and the Medium diesel oil cut that obtains is raw material B, and its character sees Table 2.Raw material B with enter into the reactor that two kinds of Hydrobon catalysts are housed after hydrogen make-up and recycle hydrogen are mixed, reactor is divided into two beds, reactor top filling Hydrobon catalyst I, reactor lower part filling Hydrobon catalyst II, the filling ratio of two kinds of Hydrobon catalysts is 6: 4 (volume ratio).Raw material B carries out the deep hydrodesulfurizationof reaction under the effect of two kinds of Hydrobon catalysts, reaction conditions is: 355 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 6.4MPa, volume space velocity 1.0h during liquid
-1, hydrogen to oil volume ratio 300Nm
3/ m
3Resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut, and reaction conditions and product main character are as shown in table 4.
Comparative Examples 2
This Comparative Examples adopts the raw material identical with embodiment 2, raw material B with enter into the reactor that Hydrobon catalyst III is housed after hydrogen make-up and recycle hydrogen are mixed, under it acts on, carry out deep hydrodesulfurizationof and react, reaction conditions is with embodiment 2.Resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.Reaction conditions and product main character are as shown in table 4.
Table 4
As can be seen from Table 2, the stock oil of embodiment 2 is the Medium diesel oil cut of a kind of straight(-run) diesel distillate and catalytic cracking diesel oil cut, and sulphur content is 8300 μ g/g, and nitrogen content is 403 μ g/g, and polycyclic aromatic hydrocarbon content is 41.5 heavy %.As can be seen from Table 4, adopt the hydrogen addition technology of embodiment 2, the sulphur content of product is 15 μ g/g, and polycyclic aromatic hydrocarbon content is 3.2 heavy %, and total aromatic hydrocarbons and polycyclic aromatic hydrocarbons all have decline significantly, are fine clean diesel blend components.Adopt the hydrogen addition technology of Comparative Examples 2 under identical processing condition, the sulphur content of the product that obtains is 53 μ g/g, and polycyclic aromatic hydrocarbon content is 4.3 heavy %.As 100, desulphurizing activated relatively, the relative denitrification activity that calculates embodiment 2 is respectively 278 and 143 with the desulfurization of Comparative Examples 2, denitrification activity.The chemical hydrogen consumption of embodiment 2 is 0.48 heavy %, and the chemical hydrogen consumption of Comparative Examples 2 is 0.53 heavy %, shows that the chemical hydrogen consumption of the chemical hydrogen loss-rate Comparative Examples 2 of embodiment 2 has reduced by 9.4%.As seen, adopt hydrogen addition technology of the present invention to compare, can obtain sulphur content, the product that meets the clean diesel standard that nitrogen content is lower, can reduce the chemical hydrogen consumption of reaction simultaneously with existing hydrogen addition technology.
Embodiment 3
A kind of secondary processing catalytic cracking diesel oil cut is raw material C, its main character is as shown in table 2, raw material C with enter into the reactor that two kinds of Hydrobon catalysts are housed after hydrogen make-up and recycle hydrogen are mixed, reactor is divided into two beds, reactor top filling Hydrobon catalyst I, reactor lower part filling Hydrobon catalyst II,, the filling ratio of two kinds of hydrogenation catalysts is 3: 7 (volume ratio).Raw material C carries out the deep hydrodesulfurizationof reaction under the effect of two kinds of Hydrobon catalysts, reaction conditions is: 340 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 6.4MPa, volume space velocity 2.0h during liquid
-1, hydrogen to oil volume ratio 300Nm
3/ m
3Resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut, and reaction conditions and product main character are as shown in table 5.
Comparative Examples 3
This Comparative Examples adopts the raw material identical with embodiment 3, raw material C with enter into the reactor that Hydrobon catalyst III is housed after hydrogen make-up and recycle hydrogen are mixed, under it acts on, carry out deep hydrodesulfurizationof and react, reaction conditions is with embodiment 3.Resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.Reaction conditions and product main character are as shown in table 5.
Table 5
As can be seen from Table 2, the stock oil of embodiment 3 is a kind of catalytic cracking diesel oil cut, and sulphur content is 7700 μ g/g, and nitrogen content is 536 μ g/g, and polycyclic aromatic hydrocarbon content is 35.1 heavy %.As can be seen from Table 5, adopt the hydrogen addition technology of embodiment 3, the sulphur content of product is 45 μ g/g, and polycyclic aromatic hydrocarbon content is 7.7 heavy %, is fine clean diesel blend component.Adopt the hydrogen addition technology of Comparative Examples 3 under identical processing condition, the sulphur content of the product that obtains is 119 μ g/g, and polycyclic aromatic hydrocarbon content is 9.4 heavy %.As 100, desulphurizing activated relatively, the relative denitrification activity that calculates embodiment 2 is respectively 233 and 120 with the desulfurization of Comparative Examples 3, denitrification activity.The chemical hydrogen consumption of embodiment 3 is 0.61 heavy %, and the chemical hydrogen consumption of Comparative Examples 3 is 0.65 heavy %, shows that the chemical hydrogen consumption of the chemical hydrogen loss-rate Comparative Examples 3 of embodiment 3 has reduced by 6%.As seen, adopt hydrogen addition technology of the present invention to compare, can obtain sulphur content, the product that meets the clean diesel standard that nitrogen content is lower, can reduce the chemical hydrogen consumption of reaction simultaneously with existing hydrogen addition technology.
Claims (10)
1. method of hydrotreating of producing the super low sulfur clean diesel, it is characterized in that, diesel oil distillate stock oil with enter reactor after hydrogen mixes, under the hydrofining reaction condition, successively with Hydrobon catalyst I and Hydrobon catalyst II contact reacts, its reaction effluent separates and fractionation, obtains diesel product; Described Hydrobon catalyst I is that activated metal component is the load hydrogenation catalyst for refining of cobalt-molybdenum, and described Hydrobon catalyst II is a body phase Hydrobon catalyst.
2. in accordance with the method for claim 1, it is characterized in that the admission space ratio of described Hydrobon catalyst I and Hydrobon catalyst II is 9: 1～2: 8.
3. in accordance with the method for claim 1, it is characterized in that described hydrofining reaction condition is: 250～430 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0～12.0MPa, volume space velocity 0.1～9.0h during liquid
-1, hydrogen to oil volume ratio 100～1500Nm
3/ m
3
4. in accordance with the method for claim 3, it is characterized in that described hydrofining reaction condition is: 280～400 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～10.0MPa, volume space velocity 0.3～6.0h during liquid
-1, hydrogen to oil volume ratio 150～1000Nm
3/ m
3
5. in accordance with the method for claim 1, it is characterized in that described diesel oil distillate stock oil is selected from one or more in straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, the visbreaking diesel oil, its boiling range scope is 180 ℃～400 ℃.
6. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst I contains a kind of carrier and the molybdenum and the cobalt that load on this carrier, with the catalyzer total amount is benchmark, it consists of: cobalt oxide 1～10 heavy %, molybdenum oxide are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina.
7. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst II contains at least a VIII family metal component, at least two kinds of group vib metal components and organic additive, wherein, the content of a kind of VIII family metal component, at least two kinds of group vib metal components and organic additive satisfies: mR:[VIIIx (VIB-1) y (VIB-2) z] O
2Wherein, represent a kind of group vib metal component with VIB-1, VIB-2 represents another kind of group vib metal component, and R represents at least a organic additive, and m represents every mole of [VIIIx (VIB-1) y (VIB-2) z] O
2In the mole number of contained organic additive, the span of m is 0.1～2, total amount with VIII family metal component, VIB-1 metal component and VIB-2 metal component is a benchmark, x, y, z represents VIII family metal component respectively, the VIB-1 metal component, the molar fraction of VIB-2 metal component, x, y, the span of z satisfies (y+z): x=10: 1～1: 10.
8. in accordance with the method for claim 7, it is characterized in that, in group VIII metal component chosen from Fe, cobalt, the nickel one or more, the group vib metal component is selected from least two kinds in chromium, molybdenum and the tungsten, described x, y, the span of z satisfies (y+z): x=5: 1～1: 5, and y: z=5: 1～1: 5.
9. in accordance with the method for claim 7, it is characterized in that described organic additive is selected from the organic ammonium compound, one or more in sulfonate and the organophosphate.
10. in accordance with the method for claim 7, it is characterized in that, also contain binding agent among the Hydrobon catalyst II, is benchmark with the catalyzer, and the content of described binding agent is no more than 75 weight %.
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| CN200910210325.1A CN102051217B (en) | 2009-10-30 | 2009-10-30 | Hydrogenation method for producing ultra-low sulfur clean diesel |
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| CN102876374A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Inferior diesel oil hydrodesulfurization method |
| CN103059943A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing low freezing point diesel oil by coked gasoline and diesel oil |
| CN103059977A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing high-quality low-freezing diesel oil |
| CN103059976A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing high-quality low-freezing diesel oil |
| CN103224810A (en) * | 2012-01-31 | 2013-07-31 | 中国石油化工股份有限公司 | Hydrogenation method for producing diesel oil with low pour point |
| CN103773478A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing diesel oil with high quality and low freezing point |
| US8722564B2 (en) | 2010-06-01 | 2014-05-13 | Exxonmobil Research And Engineering Company | Hydroprocessing catalysts and their production |
| CN105435824A (en) * | 2014-09-25 | 2016-03-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition and application thereof |
| CN105498792A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst combination for hydrogenation treatment and application thereof |
| CN105498791A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition and application thereof |
| CN105542850A (en) * | 2014-10-28 | 2016-05-04 | 中国石油化工股份有限公司 | Method for producing ultra low sulfur diesel oil through hydrorefining |
| CN105623718A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Hydrogenation method for producing clean diesel oil |
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| US8722564B2 (en) | 2010-06-01 | 2014-05-13 | Exxonmobil Research And Engineering Company | Hydroprocessing catalysts and their production |
| US8722563B2 (en) | 2010-06-01 | 2014-05-13 | Exxonmobil Research And Engineering Company | Hydroprocessing catalysts and their production |
| CN102876374A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Inferior diesel oil hydrodesulfurization method |
| CN103059977B (en) * | 2011-10-19 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of method of producing high-grade low-freezing diesel oil |
| CN103059943A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing low freezing point diesel oil by coked gasoline and diesel oil |
| CN103059977A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing high-quality low-freezing diesel oil |
| CN103059976A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing high-quality low-freezing diesel oil |
| CN103059943B (en) * | 2011-10-19 | 2015-03-18 | 中国石油化工股份有限公司 | Method for producing low freezing point diesel oil by coked gasoline and diesel oil |
| CN103059976B (en) * | 2011-10-19 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of method of producing high-grade low-freezing diesel oil |
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| CN103773478A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing diesel oil with high quality and low freezing point |
| CN103773478B (en) * | 2012-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of method of producing high-grade low-freezing diesel oil |
| CN105435824A (en) * | 2014-09-25 | 2016-03-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition and application thereof |
| CN105498792A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst combination for hydrogenation treatment and application thereof |
| CN105498791A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition and application thereof |
| CN105435824B (en) * | 2014-09-25 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of hydrogenating catalyst composition and its application |
| CN105498791B (en) * | 2014-09-25 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of hydrogenating catalyst composition and its application |
| CN105498792B (en) * | 2014-09-25 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of catalyst combination and its application for hydrotreating |
| CN105542850A (en) * | 2014-10-28 | 2016-05-04 | 中国石油化工股份有限公司 | Method for producing ultra low sulfur diesel oil through hydrorefining |
| CN105623718A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Hydrogenation method for producing clean diesel oil |
| CN105542850B (en) * | 2014-10-28 | 2017-05-24 | 中国石油化工股份有限公司 | Method for producing ultra low sulfur diesel oil through hydrorefining |
| CN105623718B (en) * | 2014-10-28 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of method of hydrotreating for producing cleaning diesel oil |
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