CN102051217B - Hydrogenation method for producing ultra-low sulfur clean diesel - Google Patents

Hydrogenation method for producing ultra-low sulfur clean diesel Download PDF

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CN102051217B
CN102051217B CN200910210325.1A CN200910210325A CN102051217B CN 102051217 B CN102051217 B CN 102051217B CN 200910210325 A CN200910210325 A CN 200910210325A CN 102051217 B CN102051217 B CN 102051217B
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vib
metal component
hydrobon catalyst
diesel
hydrogen
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CN102051217A (en
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陈若雷
王哲
高晓冬
张乐
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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

A kind of method of hydrotreating of producing ultra-low sulfur clean diesel
Technical field
The invention belongs to a kind of method of refining hydrocarbon ils in the situation that there is hydrogen, more particularly, is a kind of method of hydrotreating of producing ultra-low sulfur clean diesel.
Background technology
Along with the increasingly stringent of world wide environmental requirement, people are also more and more harsher to the requirement of petroleum product-quality, in diesel oil regulation there is 3 large changes in most important sulphur content index in less than 10 years, the specification of S < 500 μ g/g (Europe II) is implemented in Europe for 1996, within 2000, be further reduced to S < 350 μ g/g (Europe III), derv fuel oil sulphur content was reduced to and was less than 50 μ g/g (Europe IV) in January, 2005.Automotive industry " strategic research plan " has been delivered in European Countries government 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 stricter fuel oil for vehicles standard-Ou V standard for this reason, diesel oil sulphur content is reduced to below 10 μ g/g, reach " without sulphur " requirement, and implemented in 2008.China's derv fuel oil standard is also constantly strict, and within 2005, Europe II standard is implemented in the whole nation, and EUROIII Emission Standard is implemented in Beijing, and from 2008, EUROIII Emission Standard was implemented in nationwide, and Europe IV standard will be implemented in the big cities such as Beijing.From the development trend of domestic derv fuel oil standard, in the near future, the 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.
Production at present meets the diesel oil of Europe IV emission standard and can realize by a kind of main hydrogenating catalyst and conventional hydrogenation unit.Along with Europe V standard is to particularly sulphur content index strict of diesel oil index, the Europe V standard that realizes diesel oil sulphur content by a kind of main hydrogenating catalyst or conventional hydrogenation flow process under routine operation condition need to be paid higher cost, this just need to be under high operating severity, as low-speed, High Operating Temperature and hydrogen dividing potential drop, realize the production that meets 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 Fischer-Tropsch combined diesel oil and hydrocracking diesel oil, catalytic diesel oil, coker gas oil and visbreaking diesel oil all can not meet 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 meet particularly ultra-low-sulphur diesel specification requirement of clean diesel.Therefore, produce clean diesel particularly when 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 again cetane value by deep desulfuration, and investment and production cost all can not be too high simultaneously.
Produce low-sulfur, high hexadecane value clean diesel by existing technology, must, under original complete processing, improve the severity of operation.Conventionally the measure of taking comprises raising temperature of reaction, improves reactive hydrogen dividing potential drop and reduces air speed etc.But raising temperature of reaction, not only has a strong impact on catalyzer work-ing life, shortened the device cycle of operation, and aromatic saturation reaction is the reaction that is subject to thermodynamics equilibrium limit, when under certain reaction pressure, along with the rising of temperature of reaction, product aromaticity content can increase.And high hydrogen dividing potential drop has proposed more requirement to equipment, cause production cost significantly to rise; Reduce volume space velocity and mean reduction unit capacity.On the other hand, due to excessive hydrogenation, reactive hydrogen consumption is increased, elective reduction; Meanwhile, the oilness of product also declines 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 the problems such as running cost improves, the operational cycle shortens, the de-fragrant rate reduction of product, also can produce other classes as the problem of product oilness.Along with processing raw material to the continuous increase of heaviness future development and high-sulfur crude oil proportion, the intractability of diesel oil distillate is further increased, be difficult to reach the quality product requirement of clean diesel with conventional Hydrofining Technology.
US6217748 discloses a kind of processing method that adopts the method for cutting to reach deep hydrodesulfurizationof.This technique is divided into FOUR EASY STEPS, first under the effect of CoMo hydrogenation catalyst, raw material is carried out to hydrodesulfurization reaction, and exported product sulphur content is reduced to below 500ppm; Then taking 320~340 DEG C as cut point, product is divided into two portions; Add the catalyzer of a small amount of molecular sieve with Ni-Mo again and Co (Ni)-Mo catalyst combination is being carried out hydrogenation to heavy constituent under exacting terms relatively, heavy constituent after light constituent and the hydrogenation separating the most at last is mixed, and obtains the ultra-low-sulphur diesel product that sulphur content is less than 100ppm.The method adopts the catalyzer with acid and isomery performance that contains molecular sieve, can effectively reduce more unmanageable sulfocompound in heavy constituent.But the Catalysts for Reducing that contains molecular sieve diesel yield, increased chemical hydrogen consumption.
US5068025 discloses a kind of method of desulfurizing and dearomatizing diesel oil deeply, the method adopts the dual catalyst bed reactive system that two kinds of different non-precious metal catalysts are housed respectively, the first bed loads the NiW catalyzer that a kind of Hydrogenation is strong, carries out the saturated of aromatic hydrocarbons, eliminates space steric effect; The second bed loads Co and/or Ni and the Mo Hydrobon catalyst that a kind of desulfurization performance is good, carries out the de-aromatic hydrocarbons of deep hydrodesulfurizationof.The method can only adopt non-precious metal catalyst to realize the object of the de-aromatic hydrocarbons of deep hydrodesulfurizationof.
US20020070147 discloses a kind of technique of utilizing novel Hydrobon catalyst to realize deep hydrodesulfurizationof.A kind of Ni-Mo-P novel hydrogenation desulfurization catalyst through thiol acid dipping of containing of this technology utilization, refines Middle East high sulfur-containing diesel, produces ultra-low-sulphur diesel product.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of method of hydrotreating of producing ultra-low sulfur clean diesel, to be solved is that prior art is produced when ultra-low sulfur clean diesel, operational condition harshness, the problem such as hydrogen consumption is high.
Method provided by the invention is: diesel oil distillate stock oil enters reactor after mixing with hydrogen, under 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 body phase Hydrobon catalyst.
The admission space ratio of described Hydrobon catalyst I and Hydrobon catalyst II is 9: 1~2: 8.
Specifically, after mixing with hydrogen make-up and recycle hydrogen, the diesel oil distillate stock oil that need carry out hydrogenating desulfurization enters into the reactor that two kinds of Hydrobon catalysts are housed, reactor top is divided the load hydrogenation catalyst for refining I that a kind of activated metal component is cobalt-molybdenum is housed, adopt cobalt-molybdenum type catalyzer to carry out direct hydrogenolysis desulfurization to the non-thiophene-type sulfide, thiophene-based and the benzothiophene kind sulfides that are easy to desulfurization, directly hydrogenolysis desulfurization is the less desulphurization reaction of hydrogen-consuming volume.According to stock oil composition and property and the different mass requirement to product, cobalt-molybdenum load hydrogenation catalyst for refining can be divided into one or several bed.Reactor lower part divides a kind of body phase (non-loading type) Hydrobon catalyst II is housed, adopt dibenzothiophene (DBT) class of bulk phase catalyst to more difficult desulfurization, especially be difficult to most the 4-methylbenzene thiophthene (4-MDBT), 4 of desulfurization, 6-dimethyl Dibenzothiophene (4,6-DMDBT) carry out first hydrogenation with the DBT sulfides of diethyl replacement, the hydrogenating desulfurization of rear desulfurization, according to stock oil composition and property and the different mass requirement to product, body phase Hydrobon catalyst can be divided into one or several bed.Stock oil and hydrogen carry out the reactions such as hydrogenating desulfurization, hydrodenitrification, olefin saturated and aromatic saturation under the effect of Co-Mo load hydrogenation catalyst for refining I and body phase Hydrobon catalyst II.
Described hydrofining reaction condition is: 250~430 DEG C of temperature of reaction, preferably 280~400 DEG C, hydrogen dividing potential drop 1.0~12.0MPa, preferably 2.0~10.0MPa, volume space velocity 0.1~9.0h when liquid -1, preferably 0.3~6.0h -1, hydrogen to oil volume ratio 100~1500Nm 3/ m 3, preferably 150~1000Nm 3/ m 3.
The reaction effluent of gained is after heat exchange, enter successively high-pressure separator and light pressure separator 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 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, visbreaking diesel oil, and its boiling range scope is 180 DEG C~400 DEG C.
Described Hydrobon catalyst I contains a kind of carrier and loads on molybdenum and the cobalt on this carrier, taking catalyzer total amount as benchmark, it consists of: the heavy % of cobalt oxide 1~10, molybdenum oxide is 10~50 heavy %, the heavy % of fluorine 1~10, the heavy % of phosphorus oxide 0.5~8, surplus is silica-alumina, taking described carrier as benchmark, the content of the silicon oxide in preferred silica-alumina is 2~45 heavy %, and the content of aluminum oxide is 55~98 heavy %; Further the content of preferential oxidation silicon is 5~40 heavy %, and the content of aluminum oxide is 60~95 heavy %.Described silica-alumina has specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of preferential oxidation silicon-aluminum oxide is 150~350m 2/ g, more preferably 180~300m 2/ g, the pore volume of preferential oxidation silicon-aluminum oxide is 0.4~1ml/g, more preferably 0.5~0.8ml/g.
Described Hydrobon catalyst I contains and is selected from containing one or more in oxygen or nitrogenous organism, and preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol, organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, organic ammonium salt.For example, oxygenatedchemicals can be ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartrate, oxysuccinic acid, organic compounds containing nitrogen can be quadrol, EDTA and ammonium salt thereof.Described organism as 0.03-2, is preferably 0.08-1.5 with the mol ratio taking the cobalt of oxide compound, molybdenum sum.
Described Hydrobon catalyst II contains at least one 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 meets: mR:[VIIIx (VIB-1) y (VIB-2) z] O 2; Wherein, 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 one 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, taking the total amount of VIII family metal component, VIB-1 metal component and VIB-2 metal component as benchmark, x, y, z represents respectively VIII family metal component, VIB-1 metal component, the molar fraction of VIB-2 metal component, x, y, the span of z meets (y+z): x=10: 1~1: 10.
One or more in described group VIII metal component chosen from Fe, cobalt, nickel, group vib metal component is selected from least two kinds in chromium, molybdenum and tungsten, described x, y, the span of z meets (y+z): x=5: 1~1: 5, and y: z=5: 1~1: 5.
Described organic additive is selected from organic ammonium compound, one or more in sulfonate and organophosphate.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.
In Hydrobon catalyst II, also contain binding agent, taking catalyzer as benchmark, the content of described binding agent is no more than 75 % by weight.Described binding agent is selected from one or more in silicon oxide, aluminum oxide, silica-alumina, and the content of preferred described binding agent is no more than 50 % by weight.
The preparation method of described Hydrobon catalyst II is: at least one compound containing group VIII metal component, at least two kinds of compound, organic additive and water containing different group vib metal components are mixed with to mixed solution, the pH value that adopts acid or alkali to adjust mixed solution is 7~11, by described mixed solution be placed in reactor in, temperature of reaction is room temperature to 250 DEG C, reaction times is 1~24 hour, filters afterwards and is dried.
The present invention body phase Hydrobon catalyst II used 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, adopt method provided by the invention, owing to adopting loaded catalyst and body phase (non-loading type) catalyst combination loading, for the sulfide more easily removing in raw material, can first carry out direct desulfurization through cobalt-molybdenum loaded catalyst, because direct desulfurization is the less desulphurization reaction of hydrogen-consuming volume, can avoid the exceedingly hydrogenation reaction of sulfide that is easy to remove, thereby reduce reactive chemistry hydrogen consumption.For the remaining more difficult sulfide removing, carry out desulfurization through the bulk phase catalyst with high hydrodesulfurization activity, can obtain the clean diesel product of ultra-deep desulfurization.The present invention compared with the existing technology, in the time reaching the identical hydrogenating desulfurization degree of depth, the chemical hydrogen consumption of hydrogenation process is than low 5 % by weight~10 % by weight of prior art, thereby reduced tooling cost, reach energy-conservation, reduce hydrogen consumption, the effect that improves the economy of device.Compared with producing low-sulfur diesel-oil (sulphur content is less than 350 μ g/g), while 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 large.Concerning refinery, hydrogen accounts for very large cost, and technology of the present invention can effectively reduce hydrogen consumption, thereby reduces full scale plant tooling cost.
2, method flow provided by the invention is simple, working pressure is low, facility investment and process cost all lower, catalyst activity is high, activity stability is good, device the cycle of operation long.Both can be used in new device, also can be used on built plant modification.
3, adaptability to raw material is good, can process high-sulfur and do high diesel oil distillate, can be under the operational condition comparatively relaxing, and the Europe IV standard of production super low sulfur, low nitrogen, low aromatic hydrocarbons or Europe V standard or without sulfur diesel product.
Embodiment
The following examples will, to method provided by the invention, be further described, but not thereby limiting the invention.
In embodiment, Hydrobon catalyst I used is that activated metal component is the load hydrogenation catalyst for refining of cobalt-molybdenum, Hydrobon catalyst II is body phase Hydrobon catalyst, in comparative example, Hydrobon catalyst III used is that activated metal component is the load hydrogenation catalyst for refining of nickel-tungsten, and its composition is in table 1.
Table 1
Hydrobon catalyst I Hydrobon catalyst II Hydrobon catalyst III
Active ingredient, heavy % Cobalt oxide, 3.2 molybdenum oxides, 15 Tungsten oxide 99.999,21 molybdenum oxides, 14 nickel oxide, 35 Nickel oxide, 27 Tungsten oxide 99.999s, 3
Carrier, heavy % Silica-alumina, 71.8 Nothing Aluminum oxide, 66
Auxiliary agent, heavy % Fluorine, phosphorus, 10 Binding agent (aluminum oxide), 30 Fluorine, 4
Table 2
Type of feed Raw material A Raw material B Raw material C
Density (20 DEG C), 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, DEG C
?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 raw material A, and its character is in table 2.Raw material A enters into the reactor that two kinds of Hydrobon catalysts are housed after mixing with hydrogen make-up and recycle hydrogen, 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 deep hydrodesulfurizationof reaction under the effect of two kinds of Hydrobon catalysts, and reaction conditions is: 340 DEG C of temperature of reaction, reactive hydrogen dividing potential drop 6.4MPa, volume space velocity 2.0h when liquid -1, hydrogen to oil volume ratio 300Nm 3/ m 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, and reaction conditions and product main character are as shown in table 3.
Comparative example 1
This comparative example adopts the raw material identical with embodiment 1, and raw material A enters into the reactor that Hydrobon catalyst III is housed after mixing with hydrogen make-up and recycle hydrogen, under its effect, carries out deep hydrodesulfurizationof reaction, and 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 significantly decline, are the clean diesels that meets Euro V emissions, can be used as the clean diesel blend component of high-quality.Under identical processing condition, adopt the hydrogen addition technology of comparative example 1, the sulphur content of the product obtaining is 50 μ g/g, and polycyclic aromatic hydrocarbon content is 2.0 heavy %.Using the desulfurization of comparative example 1, denitrification activity as 100, relatively desulphurizing activated, the relative denitrification activity that calculates embodiment 1 is respectively 305 and 152.The chemical hydrogen consumption of embodiment 1 is 0.36 heavy %, and the chemical hydrogen consumption of comparative example 1 is 0.40 heavy %, shows that the chemical hydrogen consumption of embodiment 1 has reduced by 10% than the chemical hydrogen consumption of comparative example 1.Visible, adopt hydrogen addition technology of the present invention compared with existing hydrogen addition technology, can obtain sulphur content, the product that meets clean diesel standard that nitrogen content is lower, can reduce the chemical hydrogen consumption of reaction simultaneously.
Embodiment 2
A kind of Middle East high-sulfur straight(-run) diesel distillate with a kind of domestic catalytic cracking diesel oil cut by weight mixing at 1: 1, and the Medium diesel oil cut obtaining is raw material B, and its character is in table 2.Raw material B enters into the reactor that two kinds of Hydrobon catalysts are housed after mixing with hydrogen make-up and recycle hydrogen, 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 deep hydrodesulfurizationof reaction under the effect of two kinds of Hydrobon catalysts, and reaction conditions is: 355 DEG C of temperature of reaction, reactive hydrogen dividing potential drop 6.4MPa, volume space velocity 1.0h when liquid -1, hydrogen to oil volume ratio 300Nm 3/ m 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, and reaction conditions and product main character are as shown in table 4.
Comparative example 2
This comparative example adopts the raw material identical with embodiment 2, and raw material B enters into the reactor that Hydrobon catalyst III is housed after mixing with hydrogen make-up and recycle hydrogen, under its effect, carries out deep hydrodesulfurizationof reaction, and 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 significantly decline, are the clean diesel blend components of high-quality.Under identical processing condition, adopt the hydrogen addition technology of comparative example 2, the sulphur content of the product obtaining is 53 μ g/g, and polycyclic aromatic hydrocarbon content is 4.3 heavy %.Using the desulfurization of comparative example 2, denitrification activity as 100, relatively desulphurizing activated, the relative denitrification activity that calculates embodiment 2 is respectively 278 and 143.The chemical hydrogen consumption of embodiment 2 is 0.48 heavy %, and the chemical hydrogen consumption of comparative example 2 is 0.53 heavy %, shows that the chemical hydrogen consumption of embodiment 2 has reduced by 9.4% than the chemical hydrogen consumption of comparative example 2.Visible, adopt hydrogen addition technology of the present invention compared with existing hydrogen addition technology, can obtain sulphur content, the product that meets clean diesel standard that nitrogen content is lower, can reduce the chemical hydrogen consumption of reaction simultaneously.
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 enters into the reactor that two kinds of Hydrobon catalysts are housed after mixing with hydrogen make-up and recycle hydrogen, 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 deep hydrodesulfurizationof reaction under the effect of two kinds of Hydrobon catalysts, and reaction conditions is: 340 DEG C of temperature of reaction, reactive hydrogen dividing potential drop 6.4MPa, volume space velocity 2.0h when liquid -1, hydrogen to oil volume ratio 300Nm 3/ m 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, and reaction conditions and product main character are as shown in table 5.
Comparative example 3
This comparative example adopts the raw material identical with embodiment 3, and raw material C enters into the reactor that Hydrobon catalyst III is housed after mixing with hydrogen make-up and recycle hydrogen, under its effect, carries out deep hydrodesulfurizationof reaction, and 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 the clean diesel blend component of high-quality.Under identical processing condition, adopt the hydrogen addition technology of comparative example 3, the sulphur content of the product obtaining is 119 μ g/g, and polycyclic aromatic hydrocarbon content is 9.4 heavy %.Using the desulfurization of comparative example 3, denitrification activity as 100, relatively desulphurizing activated, the relative denitrification activity that calculates embodiment 2 is respectively 233 and 120.The chemical hydrogen consumption of embodiment 3 is 0.61 heavy %, and the chemical hydrogen consumption of comparative example 3 is 0.65 heavy %, shows that the chemical hydrogen consumption of embodiment 3 has reduced by 6% than the chemical hydrogen consumption of comparative example 3.Visible, adopt hydrogen addition technology of the present invention compared with existing hydrogen addition technology, can obtain sulphur content, the product that meets clean diesel standard that nitrogen content is lower, can reduce the chemical hydrogen consumption of reaction simultaneously.

Claims (9)

1. produce the method for hydrotreating of ultra-low sulfur clean diesel for one kind, it is characterized in that, diesel oil distillate stock oil enters reactor after mixing with hydrogen, under 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 contains a kind of carrier and loads on molybdenum and the cobalt on this carrier, taking Hydrobon catalyst I total amount as benchmark, it consists of: the heavy % of cobalt oxide 1~10, molybdenum oxide is 10~50 heavy %, the heavy % of fluorine 1~10, the heavy % of phosphorus oxide 0.5~8, surplus is silica-alumina, the pore volume of described silica-alumina is 0.4~1ml/g, described Hydrobon catalyst II is body phase Hydrobon catalyst, contain at least one VIII family metal component, at least two kinds of group vib metal components and organic additive
The preparation method of described Hydrobon catalyst II is: at least one compound containing group VIII metal component, at least two kinds of compound, organic additive and water containing different group vib metal components are mixed with to mixed solution, the pH value that adopts acid or alkali to adjust mixed solution is 7~11, described mixed solution is placed in reactor, temperature of reaction is room temperature to 250 DEG C, reaction times is 1~24 hour, filters afterwards and is dried.
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 DEG C of temperature of reaction, hydrogen dividing potential drop 1.0~12.0MPa, volume space velocity 0.1~9.0h when 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 DEG C of temperature of reaction, hydrogen dividing potential drop 2.0~10.0MPa, volume space velocity 0.3~6.0h when 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, visbreaking diesel oil, and its boiling range scope is 180 DEG C~400 DEG C.
6. in accordance with the method for claim 1, it is characterized in that, the content of a kind of VIII family metal component in described Hydrobon catalyst II, at least two kinds of group vib metal components and organic additive meets: mR:[VIIIx (VIB-1) y (VIB-2) z] O 2; Wherein, 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 one 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, taking the total amount of VIII family metal component, VIB-1 metal component and VIB-2 metal component as benchmark, x, y, z represents respectively VIII family metal component, VIB-1 metal component, the molar fraction of VIB-2 metal component, x, y, the span of z meets (y+z): x=10: 1~1: 10.
7. in accordance with the method for claim 6, it is characterized in that, one or more in group VIII metal component chosen from Fe, cobalt, nickel, group vib metal component is selected from least two kinds in chromium, molybdenum and tungsten, described x, y, the span of z meets (y+z): x=5: 1~1: 5, and y: z=5: 1~1: 5.
8. in accordance with the method for claim 6, it is characterized in that, described organic additive is selected from organic ammonium compound, one or more in sulfonate and organophosphate.
9. in accordance with the method for claim 6, it is characterized in that, in Hydrobon catalyst II, also contain binding agent, taking catalyzer as benchmark, the content of described binding agent is no more than 75 % by weight.
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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
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