CN104927902A - Wax oil hydrotreating method - Google Patents
Wax oil hydrotreating method Download PDFInfo
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- CN104927902A CN104927902A CN201410108494.5A CN201410108494A CN104927902A CN 104927902 A CN104927902 A CN 104927902A CN 201410108494 A CN201410108494 A CN 201410108494A CN 104927902 A CN104927902 A CN 104927902A
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Abstract
The present invention provides a wax oil hydrotreating method comprising the following steps: hydrogen gas is sent into a wax oil raw material by pores with the average pore size in nanometer-size to obtain hydrogen-containing wax oil; and the hydrogen-containing wax oil is fed into a tubular reactor for contacting with a hydrogenation catalyst filled in the tubular reactor under conditions of liquid-phase hydrogenation processing. Even hydrogen oil ratio is lower, and space velocity is higher, sulfur and nitrogen in the wax oil can be effectively removed, part of aromatics are saturated, hydrogen-carbon atom ratio of the wax oil can be improved, and a high-quality catalytic cracker raw material can be obtained.
Description
Technical field
The present invention relates to a kind of wax oil hydrogenation treatment process.
Background technology
In recent years, along with the scarcity day by day of petroleum resources, crude oil heaviness, in poor quality trend are on the rise, and along with expanding economy, increasingly increase the demand of light-end products, therefore, the lighting of mink cell focus maximum, maximizing the benefits become the target that oil refining enterprise is pursued.
The Main Means of mink cell focus processing treatment has hydrocracking, catalytic cracking and delayed coking.Hydrocracking due to investment comparatively large, running cost is high, is difficult to processing coked waxy oil and residual oil limits its application, delayed coking due to liquid yield low, the factor application such as poor product quality are also restricted.Hydrocarbon Content by Catalytic Cracking Operation expense is low, and light oil yield is high, and gasoline product quality is good, can process the heavy inferior raw material such as wax oil and residual oil, thus obtain process application widely.
Along with China is more and more tighter to petrol and diesel oil target level of product quality, how to solve sulfur content of catalytic cracking gasoline high, catalytic cracking diesel oil sulphur and the problem that aromaticity content is high, cetane value is low become the focus of Recent study.Developed a lot of catalytic cracking catalyst, auxiliary agent and Technology at present, wherein the pre-hydrogen addition technology of catalytically cracked material becomes solution catalytic gasoline sulphur content high effective means.The pre-hydrogenation of catalytically cracked material not only reduces sulphur, nitrogen and aromaticity content, also helps raising catalytic cracking conversion, and increase catalytic cracking and gently receive, reduce content of sulfur in gasoline, gasoline olefin and diesel cetane-number also make moderate progress.
In the various methods of straight-run gas oil lighting, wax oil hydrogenation is a good operational path as the technique of catalytically cracked material.Wax oil is stripped of most of sulphur, nitrogen impurity after hydrotreatment, and saturated part aromatic hydrocarbons, improve hydrogen richness, and then the feed stock conversion of catalytic cracking can be improved, reduce coke yield, improve catalytic cracking yield of light oil, obtain the product of quality improvement, the sulphur content of the gasoline obtained is low, and gasoline olefin and diesel cetane-number also make moderate progress; Meanwhile, wax oil hydrogenation process also can by-product 15% low-sulfur diesel-oil, improves the diesel and gasoline ratio of refinery.Therefore wax oil hydrogenation process generates the oily technique as catalytically cracked material and also obtains general process application.
Wax tailings sulphur, nitrogen content are high, particularly basic n content is high, carbon residue is high, aromaticity content is high, directly entering catalytic cracking unit handling ease makes catalyzer lose catalytic activity, causes catalyzer serious inactivation, thus causes catalytic cracking unit yield of gasoline low, coke yield rises, and therefore wax tailings carries out weighted BMO spaces and is more necessary relative to other wax oil component.
CN1313379A discloses a kind of method of poor-quality raw material for catalytic cracking weighted BMO spaces; raw material contacts with Hydrobon catalyst with hydrogenation protecting agent, Hydrodemetalation catalyst by the method successively, hydrogen dividing potential drop be 5.0-10.0 MPa, temperature is 330-420 DEG C, hydrogen to oil volume ratio is 300-1000:1, liquid hourly space velocity is 0.2-1.2 hour
-1condition under with hydrogen reaction, reacted effluent is through refrigerated separation, and hydrogen-containing gas recycles, and product liquid enters fractionating system.Raw material sulphur, nitrogen and metal content after hydrogenation all reduce, and can directly use as catalytically cracked material.
CN101007964A discloses a kind of method of hydrotreating producing fine quality catalytic cracking raw material, raw material oil-hydrogen mixture carries out hydro-upgrading reaction under the effect of hydrogenation catalyst, its resultant of reaction obtains naphtha fraction after refrigerated separation, diesel oil distillate and gas oil fraction, wherein, hydrogenation catalyst is by hydrogenation protecting agent, optional Hydrodemetalation catalyst and hydrotreating catalyst composition, with integer catalyzer volume for benchmark, wherein hydrogenation protecting agent, the admission space percentage ratio of Hydrodemetalation catalyst and hydrotreating catalyst is respectively 2-15 volume %, 0-30 volume % and 55-95 volume.
CN102344826A discloses a kind of combined hydrogenation method producing fcc raw material and fine-quality diesel oil.The method arranges the hydroconversion reaction zone of two parallel fill-outs, and a shared hydrogen gas system and a shared rear separation system, wherein the charging of the first hydroconversion reaction zone is wax oil raw material, and the charging of the second hydroconversion reaction zone is diesel raw material.The entrance hydrogen dividing potential drop in two reacted districts is 5.0-11.0MPa.
CN1896192A discloses a kind of wax oil hydrogenation process and catalytic cracking two-way combined process, wherein, wax oil and heavy catalytic cycle oil, catalytic cracking diesel oil enters hydrotreater together, hydrogenation reaction is carried out under hydrogen and hydrogenation catalyst exist, reaction product isolated obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenation tail oil, hydrogenation tail oil enters catalytic cracking unit, cracking reaction is carried out under catalytic cracking catalyst exists, dry gas is obtained after being separated, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, heavy catalytic cycle oil and slurry oil, catalytic cracking diesel oil and heavy catalytic cycle oil are circulated to hydrotreater.
Although adopt aforesaid method to urge wax oil to carry out hydrotreatment, qualified raw material can be provided for catalytic cracking; But aforesaid method is all adopt conventional trickle bed hydrogenation technique, needs recycle hydrogen and circulation device thereof, and air speed during the operation of device is low, cause facility investment and running cost higher.
Summary of the invention
The object of the invention is to overcome that existing wax oil hydrogenation treatment process exists needs recycle hydrogen and the technical problem run under low-speed of needs, a kind of wax oil hydrogenation treatment process is provided, the method is adopted to carry out hydrotreatment to wax oil, even if carry out at a high space velocity with lower hydrogen-oil ratio, also can obtain good hydrotreatment effect, be met wax oil after the hydrogenation as the requirement of catalytically cracked material.
The invention provides a kind of wax oil hydrogenation treatment process, the method comprises: sent in wax oil by the hole that mean pore size is nano-scale by hydrogen, obtain hydrogeneous wax oil; Described hydrogeneous wax oil is sent in tubular reactor, contacts with the hydrogenation catalyst be seated in described tubular reactor under liquid-phase hydrogenatin treatment condition.
Method of the present invention is adopted to process wax oil, even if with lower hydrogen-oil ratio also at a high space velocity, sulphur, the nitrogen in wax oil also effectively can be removed, and makes part aromatic saturation, the hydrogen-to-carbon ratio of wax oil after raising hydrogenation, thus obtain the catalytically cracked material of high-quality.
Method of the present invention is adopted to send in wax oil by hydrogen by the hole that mean pore size is nano-scale, can more hydrogen be dissolved in wax oil, undissolved hydrogen then can be highly dispersed in wax oil, can guarantee that hydrogenation reaction is carried out in the liquid phase like this, improve hydrogenation reaction speed, reduce the trend of catalyzer green coke, make the catalytic activity that catalyzer keeps higher, the work-ing life of extending catalyst, thus the stable operation cycle extending hydrogenation unit.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.
Fig. 1 is used for schematically illustrating a kind of preferred implementation of the component of adjacent fluid passage and gas passage in the gas liquid mixer that the present invention uses.
Fig. 2 is a kind of cross sectional representation of the component shown in Fig. 1.
Fig. 3 is the another kind of cross sectional representation of the component shown in Fig. 1.
Fig. 4 is the structural representation of the gas liquid mixer that the present invention uses.
Fig. 5 is a kind of embodiment of wax oil hydrogenation treatment process of the present invention.
Fig. 6 is the another kind of embodiment of wax oil hydrogenation treatment process of the present invention.
Fig. 7 is another embodiment of wax oil hydrogenation treatment process of the present invention.
Fig. 8 is for illustration of the annexation between gas liquid mixer and tubular reactor.
Description of reference numerals
1: gas liquid mixer 10: component
101: tube wall 102: passage
103: porous-film 11: gas inlet
12: liquid inlet 13: liquid exit
14: housing 2: hydrogen
3: wax oil 4: tubular reactor
5: ring flange 6: ring flange
7: ring flange 8: ring flange
9: wax oil after hydrogenation
Embodiment
The invention provides a kind of wax oil hydrogenation treatment process, the method comprises: sent in wax oil by the hole that mean pore size is nano-scale by hydrogen, obtain hydrogeneous wax oil; Described hydrogeneous wax oil is sent in tubular reactor, contacts with the hydrogenation catalyst be seated in described tubular reactor under liquid-phase hydrogenatin treatment condition.
In the present invention, described mean pore size is the mean pore size in the hole of nano-scale can be generally 1nm to 1000nm, is preferably 30nm to 1000nm, is more preferably 30nm to 800nm, more preferably 50nm to 500nm.Described mean pore size adopts scanning electron microscope method to measure.
From improving the dispersion mixing of hydrogen described wax oil further, and then hydrogen can the faster angle be more uniformly dispersed in described wax oil be set out, the ratio that the quantity in the hole that aperture is within the scope of 50-500nm accounts for total hole number is more than 95%, such as 95-98%.
Hydrogen can be injected in static wax oil, also hydrogen can be injected the wax oil being in flow state.Preferably hydrogen is injected the wax oil being in flow state, while transporting wax oil, hydrogen can be injected wax oil like this, thus obtain the production efficiency improved further.When hydrogen injection is in the wax oil of flow state, the injection speed of described hydrogen is v
1and with gh
-1m
-2(representing within the unit time, the total amount by the hydrogen in hole in unit surface) counts, and the flow velocity of described wax oil is v
2and with kgh
-1m
-2(quality of the wax oil in the representation unit time, unit section passed through) is counted, v
1/ v
2be preferably 0.000625-0.09, the hydrogen dispersing and dissolving effect improved further can be obtained like this.More preferably, v
1/ v
2=0.005-0.06(is as 0.005-0.01), the hydrogen dispersing and dissolving effect that can not only obtain like this, and higher production efficiency can be obtained.
Can adopt various method that hydrogen is injected described wax oil by the hole that mean pore size is nano-scale.
In the preferred embodiment of the present invention, hydrogen is injected in described wax oil by a kind of gas liquid mixer, described gas liquid mixer comprises at least one for holding the fluid passage of described wax oil and at least one is for holding the gas passage of described hydrogen, adjoined by a component between described fluid passage and described gas passage, described component at least part of for there being porose area, described have porose area to have hole that described mean pore size is nano-scale, the hole that described hydrogen is nano-scale by described mean pore size is injected in described wax oil.In the present invention, term " fluid passage " refers to the space that can hold wax oil; Term " gas passage " refers to the space that can hold hydrogen.
Described component at least part of for there being porose area, described in have porose area to extend along the length direction of described component.Preferably, described in have porose area cover whole component (that is, between described fluid passage and described gas passage by have described mean pore size be the hole of nano-scale component adjoin, described hydrogen is injected in described wax oil by described hole).Described have porose area to have hole that described mean pore size is nano-scale, with make hydrogen pass through described in there is the hole that mean pore size is nano-scale be injected in described wax oil.Described have the porosity of porose area to be preferably 5-75%, enough hydrogen can be disperseed better and be dissolved in wax oil like this.Describedly the porosity of porose area is had to be more preferably 10-45%(as 20-25%).Described porosity refers to that the volume of voids in porose area occupies the percentage ratio of the cumulative volume of porose area, adopts nitrogen adsorption methods to measure.
Described component can make to be contained in hydrogen in described gas passage and is the hole of nano-scale and the component entered in the wax oil be contained in described fluid passage by described mean pore size for various.In an example, described component is formed by porous material, and the mean pore size in hole is wherein nano-scale.In another example, (namely described component comprises matrix, tube wall) and attachment porous-film on the matrix, described matrix has through hole, on the surface contacted with the wax oil being contained in described fluid passage that described porous-film can be positioned at described matrix and/or be positioned on the surface contacted with the hydrogen being contained in described gas passage of described matrix.Preferably, described porous-film is positioned on the surface contacted with the wax oil being contained in described fluid passage of described matrix.The hole of to be previously described mean pore size be the hole in described porous-film nano-scale.The mean pore size of the through hole on described matrix is not particularly limited, as long as can by gas.Preferably, the mean pore size of the through hole on described matrix is 1nm to 1000 μm (as 50-200 μm).
The shape of described component can be selected according to the position relationship of fluid passage and gas passage, is as the criterion by this component is adjacent can make described fluid passage and described gas passage.
In one embodiment of the invention, described component is the pipeline with at least one passage.The tube wall of described pipeline has hole, and the mean pore size in described hole is previously described nano-scale.
In another embodiment of the invention, described component is the pipeline with at least one passage, the inwall of the passage of described pipeline and/or the outer wall of pipeline are attached with porous-film, the tube wall of described pipeline has through hole, the hole of to be mean pore size be the hole on described porous-film nano-scale, is called film pipe by the component with this structure below.Particularly, as Figure 1-3, described component is the film pipe with at least one passage.Described film pipe has the pipeline of through hole as matrix on tube wall 101, and pipeline has at least one path 10 2, and the inwall of path 10 2 of pipeline and/or the outer wall of pipeline are attached with porous-film 103.The mean pore size of the through hole on tube wall is not particularly limited, as long as hydrogen can be made to pass through, can be usually 1nm to 1000 μm (as 50-200 μm); The hole of to be previously described mean pore size be the hole on described porous-film nano-scale.
In above-mentioned two kinds of embodiments, the quantity of the passage on described pipeline or described film pipe is preferably at least two, as 4-20 bar.
In actual mechanical process, described component be pipeline or film pipe time, described gas liquid mixer can also comprise housing, and the inside of described housing is provided with pipeline described at least one, Existential Space between the outer wall of described pipeline and the inwall of described housing.Particularly, as shown in Figure 4, component 10 can with housing 14 with the use of.That is, at least one component 10 is placed in housing 14, and makes Existential Space between the outer wall of component 10 and the inwall of housing 14.Passage on described component is as the described fluid passage for holding wax oil, and the space that the outer wall of described component and the inwall of described housing are formed is as the described gas passage for holding hydrogen; Or the passage on described component is as the described gas passage for holding hydrogen, and the space that the outer wall of described component and the inwall of described housing are formed is as the described fluid passage for holding wax oil.Preferably, the passage on described component is as the described fluid passage for holding wax oil, and the space that the outer wall of described component and the inwall of described housing are formed is as the described gas passage for holding hydrogen.
The filling ratio of described component in described housing can be generally 10-90%, as 50-70%.Described filling ratio refers to the percent value of the cubic capacity of the space that component occupies and housing.
Passage is on the members as the described fluid passage for holding wax oil, when the space that the outer wall of described component and the inwall of described housing are formed is as described gas passage for holding hydrogen, as shown in Figure 4, can gas inlet 11, liquid inlet 12 and liquid exit 13 be set on housing 14, the two ends of described fluid passage are communicated with liquid exit 13 with liquid inlet 12 respectively, and described gas passage is communicated with gas inlet 11.Hydrogen is sent in housing 14 by gas inlet 11, wax oil is sent in the passage of component 10, under the effect of pressure difference, hydrogen is entered in described wax oil by the hole on tube wall, thus obtains hydrogeneous wax oil.
The material forming described component can for inorganic materials (as inorganic ceramic), also can be organic materials, if formed described component material can not with hydrogen and wax oil generation chemical interaction.
The amount sending into the hydrogen in described wax oil can be selected according to the foreign matter content in described wax oil.In existing wax oil hydrogenation technique, the consumption of hydrogen is large, and the volume ratio of hydrogen and wax oil is generally more than 500.Hydrogen is sent in described wax oil by the hole of the nano-scale of mean pore size by method of the present invention, can make hydrogen high dispersing and be dissolved in described wax oil, thus provides enough hydrogen sources for hydrogenation reaction; Further, in method of the present invention, hydrogenation reaction is carried out in the liquid phase, reaction heat can be taken out of in time.Therefore, even if method of the present invention reduces the amounts of hydrogen sent in described wax oil, also can obtain good hydrotreatment effect, and reduce the trend of catalyzer green coke.According to the inventive method, the feeding amount of described hydrogen and the volume ratio (that is, hydrogen to oil volume ratio) of described wax oil can be 30-180, are preferably 90-150.
According to method of the present invention, preferably hydrogen is sent in the wax oil of heating, hydrogen can be made like this to dissolve better and be dispersed in wax oil, and be also conducive to transporting of wax oil.Preferably, hydrogen is sent into temperature and pressure be in hydrogenation temperature and hydrogenation pressure under wax oil in, the trend that hydrogen is overflowed from hydrogeneous wax oil can be reduced so further.Particularly, hydrogen can be sent into temperature and be 330-420 DEG C and pressure is that 4-20MPa(is as 10-20MPa) wax oil in.
Described tubular reactor refers to the reactor had compared with larger ratio of height to diameter.Particularly, the height of described tubular reactor and the ratio of internal diameter can be that 5-200:1(is as 10-20:1).The internal diameter of described tubular reactor can be conventional selection, such as, can be that 20-2000mm(is as 50-500mm).Compared with tank reactor, adopt tubular reactor can reduce the volume of reactor on the one hand, on the other hand when by previously described gas liquid mixer (be particularly pipeline or film pipe at described component), directly described gas liquid mixer is arranged on the material inlet pipeline of described tubular reactor, flexible operation and convenient.
According to method of the present invention, hydrogeneous wax oil can be sent in tubular reactor in the mode upwards flowed, and also can send in tubular reactor in the mode flowed downward.Preferably, described hydrogeneous wax oil is sent in tubular reactor in the mode upwards flowed, like this in reaction process, to dissolve and the hydrogen be dispersed in wax oil substantially can not be assembled and forms large bubble overflowing, for hydrogenation reaction provides enough hydrogen sources, obtain good hydrotreatment effect, to go forward side by side the trend of a step-down low catalyst green coke, make the catalytic activity that catalyzer keeps higher, the work-ing life of further extending catalyst, thus extend the stable operation cycle of hydrogenation unit further.
The contact of described hydrogeneous wax oil and hydrogenation catalyst can be carried out under liquid-phase hydrogenatin treatment condition.Described liquid-phase hydrogenatin process refers to that external phase is under hydroprocessing conditions liquid phase, and whole or basic all gas phases as disperse phase dispersion in the liquid phase.Usually, temperature can be 330-420 DEG C; In gauge pressure, pressure can be that 4-20MPa(is as 10-20MPa).The air speed of described hydrogeneous wax oil also can be conventional selection.Method of the present invention, even if described hydrogeneous wax oil passes through described hydrogenation catalyst with higher air speed, also can obtain good hydrogenation effect.Therefore, in method of the present invention, the volume space velocity of hydrogeneous wax oil is preferably 0.5-5h
-1(as 2-4h
-1).
According to method of the present invention, the quantity of described tubular reactor can be 1, also can be more than 2.When the quantity of described tubular reactor is more than 2, described tubular reactor can, for being connected in series, can, for being connected in parallel, can also be also series connection and combination in parallel.Described be connected in series the hydrogenation referring to that previous tubular reactor exports after logistics be the charging of next tubular reactor; Described being connected in parallel refers to do not have material to exchange between tubular reactor.
At employing previously described gas liquid mixer, hydrogen being injected wax oil, to obtain hydrogeneous wax oil, and when hydrogeneous wax oil is sent into tubular reactor, described gas liquid mixer is r for exporting the internal diameter of hydrogeneous wax oil outlet
1, described reactor is r for inputting the internal diameter of the entrance of hydrogeneous wax oil
2, r
1/ r
2=0.6-1(is as 0.85-1).The internal diameter connecting the pipe of described outlet and described entrance is r
3, r
1/ r
3=0.85-1.5(is as 0.85-1).Hydrogeneous like this wax oil is more stable in transport process, can obtain better hydrogenation effect.
Method of the present invention can carry out hydrotreatment to the wax oil in various source.Usually, described wax oil is in air distillation process, the vacuum distillate of recovered temperature in 350-520 DEG C, can be one or more in straight-run gas oil, wax tailings, visbreaking wax oil and diasphaltene wax oil.
The various catalyzer with hydrogenation catalyst effect that described hydrogenation catalyst can be commonly used for wax oil hydrogenation field.Usually, described hydrogenation catalyst contains carrier and load group vib metal on the carrier and group VIII metal, and described group vib metal is preferably molybdenum and/or tungsten, and described group VIII metal is preferably cobalt and/or nickel.Described group vib metal and group VIII metal charge capacity on the carrier can be selected according to the kind of hydrogenation catalyst.Usually, with the total amount of described hydrogenation catalyst for benchmark and with oxide basis, the content of described group vib metal can be 1-15 % by weight, and the content of described group VIII metal can be 0.5-8 % by weight.Described carrier can be the various heat-resistant inorganic oxide being suitable for carrier as hydrogenation catalyst, such as silicon oxide and/or aluminum oxide.The carrier of described hydrogenation catalyst load can also there be conventional various auxiliary agents, no longer describe in detail herein.
According to the one of method of the present invention preferred embodiment shown in Fig. 5.In this embodiment, in gas liquid mixer 1, hydrogen 2 is injected wax oil 3, obtain hydrogeneous wax oil.Hydrogeneous wax oil enters in tubular reactor 4 and contacts with hydrogenation catalyst, thus carries out hydrogenation reaction, obtains wax oil 9 after hydrogenation.According to this embodiment, can arrange multiple tubular reactor, can, for being connected in series, can, for being connected in parallel, can also be also series connection and combination in parallel between multiple tubular reactor.When multiple tubular reactor is connected in series, along the flow direction of material, gas liquid mixer can be arranged on the inlet end of first tubular reactor; Also as shown in Figure 6, gas liquid mixer 1 can be set respectively at the inlet end of each tubular reactor 4.When multiple tubular reactor is connected in parallel, a gas liquid mixer only can be set, wax oil is mixed with hydrogen, then the hydrogeneous wax oil obtained be sent into respectively in the multiple tubular reactors be connected in parallel; Also as shown in Figure 7 gas liquid mixer 1 can be set respectively at the inlet end of each tubular reactor 4.
Can adopt and in various manners gas liquid mixer 1 is connected on entrance pipe, such as: a ring flange (Fig. 8 shows one of them ring flange 5) respectively can be set at the two ends of gas liquid mixer 1, be connected with the flangeseal on corresponding entrance pipe separately (as shown in Figure 8, the ring flange 5 of gas liquid mixer one end is tightly connected with the ring flange 6 on entrance pipe); The other end of entrance pipe is connected with the ring flange 8 of the inlet end of tubular reactor 4 by ring flange 7.
After the hydrogenation obtained by method of the present invention, wax oil is suitable for the raw material as catalytic cracking, and therefore method of the present invention is suitable for and the coupling of wax catalysis process.
Below in conjunction with embodiment and comparative example, the present invention is described in detail, but therefore do not limit the scope of the invention.
In following examples and comparative example, adopt scanning electron microscope method to measure mean pore size, pressure is all in gauge pressure.
Embodiment 1-3 is for illustration of method of the present invention.
Embodiment 1
The wax oil raw material used in the present embodiment is second line of distillation straight-run gas oil, and its character is listed in Table 1.
The present embodiment adopts the method shown in Fig. 5 to carry out hydrotreatment to wax oil.Wherein, the structure of gas liquid mixer as shown in Figure 4, the structure of the component for adjacent fluid passage and gas passage in gas liquid mixer is that the pipeline formed by porous material (is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, pipeline is evenly distributed with 19 passages, the internal diameter of each passage is 3.3mm, the mean pore size in the hole on tube wall is 50nm, and the ratio accounting for total hole number of the hole number that aperture is within the scope of 50-55nm is 98%, and the porosity of tube wall is 20%); Passage on pipeline is as fluid passage, and the space that the outer wall of pipeline and the inwall of housing are formed is as gas passage, and pipeline in the housing filling ratio is 60%.
Temperature and pressure in the fluid passage of gas liquid mixer is identical with hydrogenation reaction temperature and pressure.The ratio of the internal diameter of the internal diameter of the material outlet of gas liquid mixer and the material inlet of tubular reactor is 1, and the internal diameter of the material outlet of gas liquid mixer is 1 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular reactor that are connected gas liquid mixer.
Concrete operations are as follows: (wherein, the ratio of the flow velocity of hydrogen and the flow velocity of wax oil raw material is 0.006, and the flow velocity of hydrogen is with gh in wax oil raw material, to inject hydrogen by gas liquid mixer
-1m
-2meter, the flow velocity of wax oil raw material is with kgh
-1m
-2meter), obtain hydrogeneous wax oil.Hydrogeneous wax oil is sent into tubular fixed-bed reactor, and (internal diameter is 65mm; according to the flow direction of logistics in tubular reactor, according to the wax oil hydrogenation dearomatization catalyst of the wax oil hydrogenation metal remover that the volume ratio of 1:2:4:3 loads wax oil hydrogenation protective material that the trade mark is RG-20 successively, the trade mark is RDM-32, the trade mark to be the wax oil hydrogenation sweetening agent of RVS-420 and the trade mark be RDA-30.Wherein, wax oil hydrogenation protective material, wax oil hydrogenation metal remover, wax oil hydrogenation sweetening agent and wax oil hydrogenation dearomatization catalyst are all purchased from Sinopec catalyzer Chang Ling branch office; in tubular reactor, the filling aspect ratio of catalyzer is 14) in; contact with hydrogenation catalyst under the conditions shown in Table 1; obtain wax oil after hydrogenation, its character is listed in table 2.
Comparative example 1
The method identical with embodiment 1 is adopted to carry out hydrotreatment to wax oil raw material, unlike, component in gas liquid mixer is the pipeline formed by porous material, the mean pore size in the hole on the tube wall of this pipeline is 5 μm, porosity is 35%, and the ratio accounting for total hole in the hole that aperture is within the scope of 5-5.5 μm is that 95%(is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd).
After the hydrogenation obtained, wax oil properties is listed in table 2.
Comparative example 2
This comparative example adopts trickle bed hydrogenation technique to carry out hydrotreatment to stock oil; use fixed-bed reactor; according to the flow direction of logistics in reactor; according to the wax oil hydrogenation sweetening agent that the wax oil hydrogenation metal remover that the volume ratio of 1:2:4:3 loads wax oil hydrogenation protective material that the trade mark is RG-20 successively, the trade mark is RDM-32 and the trade mark are RVS-420, the trade mark is the wax oil hydrogenation dearomatization catalyst of RDA-30.Wherein, the filling aspect ratio of catalyzer is 4.
Concrete operations flow process is: stock oil and hydrogen are mixed in SV type static mixer (purchased from Shanghai Hu Long petrochemical industry project company limited).Sent at the top of the mixture obtained from fixed-bed reactor, contact, carry out hydrogenation reaction under the condition that table 1 is listed with hydrogenation catalyst, wax oil after obtaining hydrogenation from the bottom of fixed-bed reactor, its character is listed in table 2.
Comparative example 3
The method identical with comparative example 2 is adopted to carry out hydrotreatment to wax oil, unlike, reaction conditions is as shown in table 1.After the hydrogenation obtained, wax oil properties is listed in table 2.
Table 1
| Reaction conditions | Embodiment 1 | Comparative example 2 | Comparative example 3 |
| Reaction pressure, MPa | 14.0 | 14.0 | 14.0 |
| Reaction velocity, h -1 | 1.6 | 1.6 | 0.8 |
| Temperature of reaction, DEG C | 370 | 370 | 370 |
| Hydrogen to oil volume ratio, V/V | 90 | 90 | 500 |
Table 2
Embodiment 2
Adopt the method identical with embodiment 1 to carry out hydrotreatment to wax oil raw material, difference is as follows.
(1) the wax oil raw material used in the present embodiment is coking wax slop, and its character is listed in table 4.
(2) component in gas liquid mixer is that film pipe as shown in Figure 3 (is purchased Tianyuan Genie et Environnement in Beijing; The mean pore size in the hole on matrix is 100 μm; The mean pore size in the hole on porous-film is 500nm, and on porous-film, the ratio accounting for total hole in the hole that aperture is within the scope of 500-550nm is 95%; The porosity of porous-film is 25%); Porous-film is positioned on the outer wall of film pipe; Be evenly distributed with 7 passages, the internal diameter of each fluid passage is 6mm; Using the passage on film pipe as fluid passage, the space formed by the inwall of the outer wall of film pipe and housing is as gas passage, and film pipe filling ratio is in the housing 50%.
(3) injection speed of hydrogen and the ratio of the velocity of flow of wax oil in fluid passage are 0.008.
(4) operational conditions of tubular reactor is listed in table 3.
The hydrogenation wax oil properties obtained is listed in table 4.
Table 3
| Reaction pressure, MPa | 16.0 |
| Reaction velocity, h -1 | 2.0 |
| Temperature of reaction, DEG C | 370 |
| Hydrogen to oil volume ratio, V/V | 150 |
Table 4
| Project | Coking wax slop raw material | Embodiment 2 |
| Density/kg/m 3 | 955.3 | 919.8 |
| Initial boiling point/DEG C | 327 | 315 |
| 10%/℃ | 464 | 438 |
| 30%/℃ | 487 | 479 |
| Less than 520 DEG C ends content/% by weight | 38.5 | 45.5 |
| Carbon/% by weight | 87.17 | 87.03 |
| Hydrogen/% by weight | 10.98 | 12.38 |
| Total sulfur/% by weight | 1.12 | 0.33 |
| Total nitrogen/% by weight | 0.73 | 0.26 |
| Alkali nitrogen/wppm | 1824 | 756 |
| Stable hydrocarbon/% by weight | 52.9 | 63.4 |
| Aromatic hydrocarbon/% by weight | 35.6 | 33.8 |
| Colloid/% by weight | 11.2 | 2.6 |
| Bituminous matter/% by weight | 0.3 | 0.2 |
| Carbon residue/% by weight | 3.2 | 1.0 |
| Metal/wppm | 17.2 | 1.5 |
Embodiment 3
Adopt the method identical with embodiment 1 to carry out hydrotreatment to wax oil raw material, difference is as follows.
(1) the wax oil raw material used in the present embodiment is visbreaking wax oil, and its character is listed in table 6.
(2) component in gas liquid mixer is that film pipe as shown in Figure 2 (is purchased Tianyuan Genie et Environnement in Beijing; The mean pore size in the hole on matrix is 100 μm; The mean pore size in the hole on porous-film is 250nm, and on porous-film, the ratio accounting for total hole in the hole that aperture is within the scope of 250-260nm is 95%; The porosity of porous-film is 25%); Porous-film is positioned on the inwall of film pipe; Be evenly distributed with 7 passages, the internal diameter of each fluid passage is 6mm; Using the passage on film pipe as fluid passage, the space formed by the inwall of the outer wall of film pipe and housing is as gas passage, and film pipe in the housing filling ratio is 65%.
(3) ratio of the internal diameter of the internal diameter of the material outlet of gas liquid mixer and the material inlet of tubular reactor is 0.85, and the internal diameter of the material outlet of gas liquid mixer is 1 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular reactor that are connected gas liquid mixer.
(4) injection speed of hydrogen and the ratio of the velocity of flow of wax oil in fluid passage are 0.008.
(5) operational conditions of tubular reactor is listed in table 5.
The hydrogenation wax oil properties obtained is listed in table 6.
Table 5
| Reaction pressure, MPa | 13.0 |
| Reaction velocity, h -1 | 3.0 |
| Temperature of reaction, DEG C | 385 |
| Hydrogen to oil volume ratio, V/V | 120 |
Table 6
| Project | Visbreaking wax oil raw material | Embodiment 3 |
| Density/kg/m 3 | 912.5 | 894.5 |
| Initial boiling point/DEG C | 229 | 204 |
| 10%/℃ | 367 | 337 |
| 50%/℃ | 409 | 385 |
| 95%/℃ | 446 | 439 |
| Carbon/% by weight | 86.57 | 86.75 |
| Hydrogen/% by weight | 11.73 | 12.81 |
| Total sulfur/% by weight | 0.95 | 0.23 |
| Total nitrogen/% by weight | 0.75 | 0.21 |
| Basic nitrogen/wppm | 3328 | 685 |
| Stable hydrocarbon/% by weight | 64.8 | 70.3 |
| Aromatic hydrocarbon/% by weight | 30.9 | 28.1 |
| Colloid/% by weight | 4.2 | 1.5 |
| Bituminous matter/% by weight | 0.1 | 0.1 |
| Carbon residue/% by weight | 0.8 | 0.2 |
| Metal/wppm | 7.5 | 1.1 |
The result of embodiment 1-3 confirms, adopt method of the present invention to carry out hydrotreatment to wax oil, even if carry out under high-speed with low hydrogen/gasoline ratio, also effectively can remove the sulphur in wax oil, nitrogen (comprising basic nitrogen), metal and carbon residue, saturated part aromatic hydrocarbons simultaneously, increases the hydrogen richness of wax oil.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a wax oil hydrogenation treatment process, the method comprises: sent in wax oil by the hole that mean pore size is nano-scale by hydrogen, obtain hydrogeneous wax oil; Described hydrogeneous wax oil is sent in tubular reactor, contacts with the hydrogenation catalyst be seated in described tubular reactor under liquid-phase hydrogenatin treatment condition.
2. method according to claim 1, wherein, described mean pore size is the mean pore size in the hole of nano-scale is 1-1000nm.
3. method according to claim 1, wherein, sends into temperature and is 330-420 DEG C and pressure is in the wax oil of 4-20MPa by hydrogen.
4. the method according to claim 1 or 3, wherein, the feeding amount of hydrogen and the volume ratio of described wax oil are 30-180.
5. according to the method in claim 1-3 described in any one, wherein, hydrogen is injected described wax oil by a kind of gas liquid mixer, thus obtain described hydrogeneous wax oil, described gas liquid mixer comprises at least one for holding the fluid passage of described wax oil and at least one is for holding the gas passage of described hydrogen, adjoined by a component between described fluid passage and described gas passage, described component at least part of for there being porose area, described have porose area to have hole that described mean pore size is nano-scale, the hole that described hydrogen is nano-scale by described mean pore size is injected in described wax oil.
6. method according to claim 5, wherein, described component is the pipeline with at least one passage, and the tube wall of described pipeline has through hole, the hole of described through hole to be mean pore size be nano-scale; Or the inwall of the passage of described pipeline and/or the outer wall of pipeline are attached with porous-film, and the tube wall of described pipeline has through hole, the hole of to be mean pore size be the hole on described porous-film nano-scale.
7. method according to claim 6, wherein, described gas liquid mixer also comprises housing, described housing has gas inlet, liquid inlet and liquid exit, the inside of described housing is provided with pipeline described at least one, Existential Space between the outer wall of described pipeline and the inwall of described housing, passage on described pipeline is as described fluid passage, the space that the outer wall of described pipeline and the inwall of described housing are formed is as described gas passage, the two ends of described fluid passage are communicated with described liquid exit with described liquid inlet respectively, described gas passage is communicated with described gas inlet.
8. method according to claim 5, wherein, described gas liquid mixer is arranged on the inlet end of described tubular reactor.
9. method according to claim 1, wherein, described wax oil is one or more in straight-run gas oil, wax tailings, visbreaking wax oil and diasphaltene wax oil.
10. method according to claim 1, wherein, the aspect ratio of described tubular reactor is 5-200:1.
11. methods according to claim 1, wherein, described liquid-phase hydrogenatin treatment condition comprise: temperature is 330-420 DEG C, and pressure is 4-20MPa, and the volume space velocity of described hydrogeneous wax oil is 0.5-5h
-1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110878221A (en) * | 2019-12-25 | 2020-03-13 | 陕西延长石油（集团）有限责任公司 | Process for producing low-sulfur marine fuel oil by external circulation type fixed wax oil bed hydrotreatment |
| CN114105846A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Hydrofining method and device of caprolactam |
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| CN114105846A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Hydrofining method and device of caprolactam |
| CN114105846B (en) * | 2020-08-31 | 2023-09-05 | 中国石油化工股份有限公司 | Hydrofining method and device for caprolactam |
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