CN114437809B - Liquid phase hydrogenation device and liquid phase hydrogenation method - Google Patents
Liquid phase hydrogenation device and liquid phase hydrogenation method Download PDFInfo
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- CN114437809B CN114437809B CN202011220871.6A CN202011220871A CN114437809B CN 114437809 B CN114437809 B CN 114437809B CN 202011220871 A CN202011220871 A CN 202011220871A CN 114437809 B CN114437809 B CN 114437809B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 102
- 239000007791 liquid phase Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 152
- 239000001257 hydrogen Substances 0.000 claims abstract description 152
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 143
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 25
- 230000023556 desulfurization Effects 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims description 46
- 238000004523 catalytic cracking Methods 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 21
- 230000001502 supplementing effect Effects 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 239000000295 fuel oil Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004939 coking Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 4
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000004891 communication Methods 0.000 abstract description 6
- 230000003009 desulfurizing effect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a liquid phase hydrogenation device and a liquid phase hydrogenation method, belonging to the field of petrochemical industry. In the liquid phase hydrogenation device, a feeding component, a tube pass of a heat exchanger, a heating furnace, a hydrogen mixer, a liquid phase hydrogenation reactor, a stripping tower, a pressure reducing valve, a gas phase outlet of a flash tank and an inlet of a desulfurization and denitrification tower are sequentially communicated through pipelines; the inlet of the desulfurizing and denitrifying tower is also communicated with the gas phase outlet of the stripping tower; the outlet of the compressed hydrogen inlet component is respectively communicated with the hydrogen mixer and the liquid phase hydrogenation reactor; the liquid phase outlet of the flash tank is in communication with the shell side of the heat exchanger. The device has lower cost and lower energy consumption, and can improve the hydrogenation reaction efficiency.
Description
Technical Field
The invention relates to the field of petroleum processing, in particular to a liquid phase hydrogenation device and a liquid phase hydrogenation method.
Background
At present, the quality requirements on light fuel oil such as gasoline, kerosene, diesel oil and the like are higher and higher, and at present, catalytic cracking (FCC for short) is generally adopted to convert heavy oil into light oil, however, catalytic cracking raw materials usually contain a large amount of sulfur, nitrogen and other impurities, and in order to obtain clean fuel oil meeting the environmental protection requirements by utilizing the catalytic cracking raw materials, the catalytic cracking raw materials are required to be subjected to hydrotreatment.
The related art provides a circulating liquid phase hydrogenation method, which is provided with two liquid phase hydrogenation reactors connected in series, and the part of the reaction generated oil is circulated back to the reactor bed layer for continuous hydrogenation treatment so as to strengthen the reaction depth.
In carrying out the invention, the present inventors have found that there are at least the following problems in the prior art:
the related art reserves a high-temperature and high-pressure liquid circulating oil system, and is provided with a more complex separation system, so that the investment of the device is higher.
Disclosure of Invention
In view of the above, the present invention provides a liquid phase hydrogenation apparatus and a liquid phase hydrogenation method, which can solve the above-mentioned technical problems.
Specifically, the method comprises the following technical scheme:
in one aspect, there is provided a liquid phase hydrogenation apparatus comprising: the device comprises a feeding component, a compressed hydrogen feeding component, a heat exchanger, a heating furnace, a hydrogen mixer, a liquid phase hydrogenation reactor, a stripping tower, a pressure reducing valve, a flash tank and a desulfurization and denitrification tower;
the feeding component, the tube side of the heat exchanger, the heating furnace, the hydrogen mixer, the liquid phase hydrogenation reactor, the stripping tower, the pressure reducing valve, the gas phase outlet of the flash tank and the inlet of the desulfurization and denitrification tower are sequentially communicated through pipelines;
the inlet of the desulfurization and denitrification tower is also communicated with the gas phase outlet of the stripping tower;
the outlet of the compressed hydrogen inlet component is respectively communicated with the hydrogen mixer and the liquid phase hydrogenation reactor;
the liquid phase outlet of the flash tank is in communication with the shell side of the heat exchanger.
In some possible implementations, the outlet of the inlet compressed hydrogen assembly is also in communication with a line between the feed assembly and the heat exchanger.
In some possible implementations, the feed assembly includes: the catalytic cracking raw material storage tank, the filter and the feed pump are communicated in sequence.
In some possible implementations, the inlet compressed hydrogen assembly includes: a hydrogen storage tank and a hydrogen compressor which are communicated in sequence.
In some possible implementations, the outlet of the desulfurization and denitrification tower is in communication with the inlet of the hydrogen storage tank.
In some possible implementations, a protecting agent bed layer and at least one stage of refining catalyst bed layer are arranged in the liquid-phase hydrogenation reactor at intervals from bottom to top, and at least one hydrogen supplementing pipe is arranged between any two adjacent bed layers and is communicated with an outlet of the compressed hydrogen inlet component.
In some possible implementation manners, the hydrogen supplementing pipe is a circular ring pipe, and the gas outlet holes with the average pore diameter of 150-250 nm are uniformly distributed on the pipe wall of the hydrogen supplementing pipe.
In another aspect, a liquid phase hydrogenation process employing any one of the liquid phase hydrogenation apparatuses described above is also provided.
In some possible implementations, the liquid phase hydrogenation process includes:
the catalytic cracking raw material provided by the feeding component is heated by a tube side of a heat exchanger and a heating furnace in sequence, then enters a hydrogen mixer, and is mixed with compressed hydrogen entering the hydrogen mixer through a compressed hydrogen inlet component to obtain a hydrogen mixed raw material;
the hydrogen-mixed raw material enters a liquid-phase hydrogenation reactor to carry out hydrogenation reaction, and the reaction product enters a stripping tower to carry out stripping treatment so as to remove hydrogen sulfide and ammonia gas in the reaction product and obtain a stripping product;
and the stripping product is decompressed by a decompression valve, enters a flash tank for gas-liquid separation, enters a shell side of the heat exchanger for heat exchange and cooling, is discharged, and enters a desulfurizing and denitrifying tower for desulfurization and denitrification treatment with gas-phase product and gas-phase material flow from the stripping tower to obtain circulating hydrogen.
In some possible implementations, the liquid phase hydrogenation process further comprises: and returning the circulating hydrogen to the compressed hydrogen inlet assembly for recycling.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
the liquid phase hydrogenation device provided by the embodiment of the invention can be used in a liquid phase hydrogenation process, and when the liquid phase hydrogenation device is applied, the catalytic cracking raw material provided by the feeding component is heated by the tube pass of the heat exchanger and the heating furnace in sequence, and then enters the hydrogen mixer to be mixed with the compressed hydrogen entering the hydrogen mixer through the compressed hydrogen inlet component, so as to obtain the hydrogen mixing raw material. The hydrogen mixed raw material enters a liquid-phase hydrogenation reactor to carry out hydrogenation reaction, and the reaction product enters a stripping tower to carry out stripping treatment so as to remove hydrogen sulfide and ammonia gas in the reaction product, thus obtaining a stripping product. The stripped product is decompressed by a decompression valve, enters a flash tank for gas-liquid separation, the liquid phase product enters a shell side of a heat exchanger for heat exchange and cooling and is discharged, and the gas phase product and a gas phase material flow from the stripping tower enter a desulfurization and denitrification tower for desulfurization and denitrification treatment to obtain circulating hydrogen.
When the liquid phase hydrogenation device provided by the embodiment of the invention is used for liquid phase hydrogenation, a high-temperature high-pressure liquid circulating pump, a circulating hydrogen compressor system and a part of high-pressure separation system are eliminated, the device structure is simplified, and the cost is reduced. And a hydrogen mixer is used for dissolving sufficient hydrogen into the catalytic cracking raw material, so that the hydrogen dissolving amount of the catalytic cracking raw material and the mutual dissolving uniformity of the catalytic cracking raw material and the hydrogen are increased, and the hydrogenation reaction efficiency is improved. H formed by the reaction 2 S and NH 3 The impurities such as the impurities are effectively removed through the gas stripping tower, which is beneficial to improving the reaction depth of hydrofining. And in the reaction process, the heat exchanger is used for heat exchange, so that the reaction heat is effectively utilized, and the energy consumption is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a liquid phase hydrogenation apparatus according to an embodiment of the present invention.
Reference numerals denote:
1-a feeding assembly, wherein the feeding assembly comprises a feeding assembly,
101-a catalytic cracking raw material storage tank,
102-a filter, which is arranged on the surface of the substrate,
103-a feeding pump, wherein the feeding pump is provided with a feeding pump,
2-feeding the compressed hydrogen component,
201-a hydrogen storage tank,
a 202-one of the hydrogen gas compressor,
a 3-heat exchanger, wherein the heat exchanger is provided with a heat pipe,
a 4-heating furnace, wherein the heating furnace is provided with a heating chamber,
a 5-hydrogen mixer for mixing the hydrogen with the water,
a 6-liquid phase hydrogenation reactor,
a 7-stripping tower, wherein the stripping tower is provided with a plurality of stripping columns,
an 8-pressure-reducing valve for reducing the pressure of the air,
a 9-flash tank, wherein the flash tank is provided with a flash tank,
a 10-desulfurization and denitrification tower,
11-hydrogen supplementing pipe.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
In one aspect, an embodiment of the present invention provides a liquid phase hydrogenation apparatus, as shown in fig. 1, including: the device comprises a feeding component 1, a compressed hydrogen feeding component 2, a heat exchanger 3, a heating furnace 4, a hydrogen mixer 5, a liquid phase hydrogenation reactor 6, a stripping tower 7, a pressure reducing valve 8, a flash tank 9 and a desulfurization and denitrification tower 10. Wherein, the feeding component 1, the tube side of the heat exchanger 3, the heating furnace 4, the hydrogen mixer 5, the liquid phase hydrogenation reactor 6, the stripping tower 7, the pressure reducing valve 8, the gas phase outlet of the flash tank 9 and the inlet of the desulfurizing and denitriding tower 10 are sequentially communicated through pipelines; the inlet of the desulfurizing and denitrifying tower 10 is also communicated with the gas phase outlet of the stripping tower 7; the outlet of the compressed hydrogen inlet assembly 2 is respectively communicated with a hydrogen mixer 5 and a liquid phase hydrogenation reactor 6; the liquid phase outlet of the flash tank 9 communicates with the shell side of the heat exchanger 3.
The liquid phase hydrogenation device provided by the embodiment of the invention can be used in a liquid phase hydrogenation process, and when the liquid phase hydrogenation device is applied, the catalytic cracking raw material provided by the feeding component 1 is heated by the tube side of the heat exchanger 3 and the heating furnace 4 in sequence, then enters the hydrogen mixer 5, and is mixed with the compressed hydrogen entering the hydrogen mixer 5 through the compressed hydrogen inlet component 2, so as to obtain the hydrogen mixing raw material. The hydrogen-mixed raw material enters a liquid-phase hydrogenation reactor 6 for hydrogenation reaction, and the reaction product enters a stripping tower 7 for stripping treatment to remove hydrogen sulfide and ammonia gas in the reaction product, so as to obtain a stripped product. The stripped product is decompressed by a decompression valve 8, enters a flash tank 9 for gas-liquid separation, the liquid phase product enters the shell side of the heat exchanger 3 for heat exchange and cooling and is discharged, and the gas phase product and the gas phase material flow from the stripping tower 7 enter a desulfurization and denitrification tower 10 for desulfurization and denitrification treatment, so that the circulating hydrogen is obtained.
When the liquid phase hydrogenation device provided by the embodiment of the invention is used for liquid phase hydrogenation, a high-temperature high-pressure liquid circulating pump, a circulating hydrogen compressor 202 system and a part of high-pressure separation system are eliminated, the device structure is simplified, and the cost is reduced. Sufficient hydrogen is dissolved in the catalytic cracking raw material by using the hydrogen mixer 5, so that the hydrogen dissolution amount of the catalytic cracking raw material and the mutual dissolution uniformity of the catalytic cracking raw material and the hydrogen are increased, and the hydrogenation reaction efficiency is improved. H formed by the reaction 2 S and NH 3 The impurities such as the impurities are effectively removed through the gas stripping tower, which is beneficial to improving the reaction depth of hydrofining. And in the reaction process, the heat exchanger 3 is used for exchanging heat, so that the reaction heat is effectively utilized, and the energy consumption is reduced.
The liquid phase hydrogenation device provided by the embodiment of the invention is particularly suitable for liquid phase hydrogenation treatment of poor catalytic cracking raw materials.
The structure and function of each component included in the liquid phase hydrogenation apparatus provided in the embodiment of the present invention are described below:
in some possible implementations, as shown in fig. 1, the feed assembly 1 includes: a catalytic cracking raw material storage tank 101, a filter 102 and a feed pump 103 which are sequentially communicated.
When in use, the catalytic cracking raw material is stored in a catalytic cracking raw material storage tank 101, filtered by a filter 102 to remove impurities therein, and then pumped to the tube side of the heat exchanger 3 by a feed pump 103 for preheating. The preheated catalytic cracking raw material enters a heating furnace 4 and is heated to a proper temperature.
In some possible implementations, as shown in fig. 1, the inlet compressed hydrogen assembly 2 includes: a hydrogen storage tank 201 and a hydrogen compressor 202 which are communicated in sequence. In application, hydrogen stored in the hydrogen storage tank 201 is compressed to a design pressure by the hydrogen compressor 202 and enters the hydrogen mixer 5.
In some possible implementations, the outlet into the compressed hydrogen assembly 2 is also in communication with a line between the feed assembly 1 and the heat exchanger 3.
That is, the hydrogen compressed by the hydrogen compressor 202 may also enter the pipeline between the feed assembly 1 and the heat exchanger 3 through an additional design branch pipeline, and preliminary hydrogen mixing may be performed before the catalytic cracking feedstock exchanges heat, so as to improve the hydrogen mixing effect.
The hydrogen mixer 5 is common in the art, and the hydrogen mixer 5 for liquid phase hydrogenation of hydrocarbon oil, as described in chinese patent CN210057917U, for example, is suitable for use in the present invention. In the embodiment of the invention, a first inlet, a second inlet and an outlet are arranged on the hydrogen mixer 5, wherein the first inlet of the hydrogen mixer 5 is connected with the outlet of the heating furnace 4 and is used for enabling the heated catalytic cracking raw material to enter the hydrogen mixer 5; the second inlet of the hydrogen mixer 5 is connected to the hydrogen compressor 202 of the compressed hydrogen inlet assembly 2 for allowing compressed hydrogen to enter the hydrogen mixer 5, so that the compressed hydrogen and the heated catalytic cracking feedstock are thoroughly mixed in the hydrogen mixer 5 to obtain a hydrogen-mixed feedstock, i.e. a saturated hydrogen oil mixture by thoroughly dissolving hydrogen.
Therefore, the embodiment of the invention increases the hydrogen dissolution amount of the catalytic cracking raw material through the hydrogen mixer 5, improves the mutual dissolution uniformity of the catalytic cracking raw material and hydrogen, improves the hydrogenation reaction efficiency, and reduces the energy consumption of the device and the investment cost of equipment.
In some possible implementations, the liquid-phase hydrogenation reactor 6 is internally provided with a protecting agent bed layer and at least one level of refining catalyst bed layer at intervals from bottom to top, and at least one hydrogen supplementing pipe 11 is arranged between any two adjacent bed layers, and the hydrogen supplementing pipe 11 is communicated with an outlet of the compressed hydrogen inlet assembly 2, namely, the hydrogen compressor 202.
Wherein the purification catalyst bed is provided with multiple stages, for example, two stages, three stages, four stages, etc., and the catalysts in each stage of purification catalyst bed may be the same or different.
When the catalyst is applied, the hydrogen-mixed raw material is fed from the bottom of the liquid-phase hydrogenation reactor 6, discharged from the top, and fully contacted with the protecting catalyst in the protecting agent bed and the refining catalyst in the refining catalyst bed through a plurality of beds arranged in the liquid-phase reactor, so as to perform liquid-phase hydrogenation reaction, thereby achieving the purposes of demetallization, carbon residue removal, desulfurization, denitrification and dearomatization.
The inside of the liquid-phase hydrogenation reactor 6 is respectively provided with a protective agent bed layer, a first-stage refined catalyst bed layer, a second-stage refined catalyst bed layer and a plurality of stages of refined catalyst bed layers from bottom to top.
The protecting catalyst filled in the protecting catalyst bed layer and the refining catalyst filled in the refining catalyst bed layer use commercial wax oil or heavy oil protecting catalyst and common hydrofining catalyst, and the catalysts adopt a grading filling mode.
For example, these catalysts generally comprise at least two of W, mo, ni, co as active components and alumina or titanium-containing alumina as a carrier, and the main physical properties of the carrier are required to satisfy the specific surface area>300m 2 /g, pore volume>0.45mL/g。
In some possible implementations, at least one hydrogen supplementing tube 11 is disposed between two adjacent catalyst beds, and two adjacent hydrogen supplementing tubes 11 are disposed in a vertically spaced relationship.
Illustratively, the spacing between adjacent two hydrogen supply pipes 11 is 100mm to 200mm, for example, 100mm, 120mm, 150mm, 180mm, 190mm, etc., so that a more sufficient hydrogen mixing effect can be obtained.
In some possible implementation manners, the hydrogen supplementing tube 11 provided in the embodiments of the present invention is a circular tube, and air outlet holes with an average pore diameter of 150nm-250nm are uniformly distributed on the tube wall of the hydrogen supplementing tube 11, for example, the air outlet holes are circular holes, so as to form nano-scale micro-bubbles.
Through the structural design, the hydrogen can be supplemented at multiple points between the bed layers of the reactor, so that the timely supplementation of hydrogen consumed by the reaction can be realized, excessive hydrogen bubbles in the catalyst bed layer can be effectively avoided, and the influence of the hydrogen bubbles on the mass transfer of the hydrogen to the liquid phase hydrogenation reaction efficiency is avoided.
In the embodiment of the invention, the liquid phase material flow in the liquid phase hydrogenation reactor 6 adopts an uplink flow mode, a liquid level control system is omitted, the stable operation and running of a reaction and separation system are facilitated, and the liquid phase material flow in the liquid phase hydrogenation reactor 6 timely takes away the reaction heat, so that the temperature rise of the reaction system is small.
In some possible implementations, the outlet of the desulfurization and denitrification tower 10 is in communication with the inlet of the hydrogen storage tank 201, and the recycle hydrogen is returned to the compressed hydrogen assembly 2 for recycling.
The stripping tower 7 used in the embodiment of the invention is a hydrogenation stripping tower, and hydrogen is timely supplemented into the stripping tower 7 to improve the stripping effect.
On the other hand, the embodiment of the invention also provides a liquid phase hydrogenation method, which adopts any one of the liquid phase hydrogenation devices.
In some possible implementations, the liquid phase hydrogenation method provided by the embodiment of the invention includes:
the catalytic cracking raw material provided by the feeding component 1 is heated by a tube side of the heat exchanger 3 and the heating furnace 4 in sequence, then enters the hydrogen mixer 5, and is mixed with the compressed hydrogen entering the hydrogen mixer 5 through the compressed hydrogen inlet component 2, so as to obtain the hydrogen mixing raw material.
The hydrogen-mixed raw material enters a liquid-phase hydrogenation reactor 6 for hydrogenation reaction, and the reaction product enters a stripping tower 7 for stripping treatment to remove hydrogen sulfide and ammonia gas in the reaction product, so as to obtain a stripped product.
The stripped product is decompressed by a decompression valve 8, enters a flash tank 9 for gas-liquid separation, the liquid phase product enters the shell side of the heat exchanger 3 for heat exchange and cooling and is discharged, and the gas phase product and the gas phase material flow from the stripping tower 7 enter a desulfurization and denitrification tower 10 for desulfurization and denitrification treatment, so that the circulating hydrogen is obtained.
Catalytic cracking feedstocks contemplated in embodiments of the present invention include, but are not limited to: at least one of vacuum wax oil, coking wax oil, deasphalted oil and atmospheric residuum.
When the hydrogenation reaction is carried out in the liquid-phase hydrogenation reactor 6, the reaction temperature is 300℃to 390℃such as 300℃310℃320℃330℃340℃350℃360℃370℃380℃390 ℃.
When the hydrogenation reaction is carried out in the liquid-phase hydrogenation reactor 6, the reaction pressure is 6.0MPa to 12.0MPa, for example, 6.0MPa, 7.0MPa, 8.0MPa, 9.0MPa, 10.0MPa, 11.0MPa, 12.0MPa, etc.
When the hydrogenation reaction is carried out in the liquid-phase hydrogenation reactor 6, the volume space velocity is 0.5h -1 -2.0h -1 For example 0.5h -1 、0.7h -1 、0.9h -1 、1h -1 、1.5h -1 、1.8h -1 Etc.
In the case of the hydrogenation reaction in the liquid-phase hydrogenation reactor 6, the hydrogen-oil volume ratio is 20 to 100, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, etc.
The liquid phase hydrogenation method provided by the embodiment of the invention eliminates a high-temperature high-pressure liquid circulating pump, a circulating hydrogen compressor 202 system and a part of high-pressure separation system, simplifies the structure of the device and reduces the cost. Sufficient hydrogen is dissolved in the catalytic cracking raw material by using the hydrogen mixer 5, so that the hydrogen dissolution amount of the catalytic cracking raw material and the mutual dissolution uniformity of the catalytic cracking raw material and the hydrogen are increased, and the hydrogenation reaction efficiency is improved. H formed by the reaction 2 S and NH 3 The impurities such as the impurities are effectively removed through the gas stripping tower, which is beneficial to improving the reaction depth of hydrofining. And in the reaction process, the heat exchanger 3 is used for exchanging heat, so that the reaction heat is effectively utilized, and the energy consumption is reduced.
In the embodiment of the invention, the reaction product enters the stripping tower 7 for stripping treatment to obtain a stripping product, which is also called reaction generated oil, and the stripping product is decompressed by the decompression valve 8 without heat exchange and enters the high-temperature and low-pressure flash tank 9 for gas-liquid separation, thereby being beneficial to saving energy consumption and production cost.
In the embodiment of the invention, the liquid phase material flow in the liquid phase hydrogenation reactor 6 adopts an uplink flow mode, a liquid level control system is canceled, the stable operation and running of a reaction and separation system are facilitated, and the liquid phase material flow in the liquid phase hydrogenation reactor 6 timely takes away the reaction heat, so that the temperature rise of the reaction system is small; the multi-point supplement of hydrogen between the bed layers of the reactor not only can realize the timely supplement of hydrogen consumed by the reaction, but also can effectively avoid excessive hydrogen bubbles in the catalyst bed layer and avoid influencing the mass transfer of hydrogen due to the bubbles of the hydrogen so as to influence the liquid phase hydrogenation reaction efficiency.
Further, the recycle hydrogen discharged from the outlet of the desulfurization and denitrification tower 10 may be directly discharged from the apparatus, or may be returned to the compressed hydrogen inlet unit 2 for recycling.
Embodiments of the present invention will be further described by way of specific examples:
in the embodiments 1-3, different catalytic cracking raw materials are respectively subjected to liquid-phase hydrogenation treatment under the same process conditions by using a liquid-phase hydrogenation device shown in the attached figure 1.
Wherein, the catalytic cracking raw material used in the example 1 is 100% decompressed wax oil;
the catalytic cracking raw material used in the example 2 is coked wax oil mixed with coked-decompressed wax oil with the mass concentration of 10%;
the catalytic cracking feedstock used in example 3 was coker wax oil blended with a mass concentration of 30% coker-vacuum hybrid wax oil.
In the embodiments 3, 4 and 5 of the invention, coking wax oil mixed with coking-decompression wax oil with the mass concentration of 30% is used as a catalytic cracking raw material, and liquid phase hydrogenation treatment is respectively carried out under different process conditions by using a liquid phase hydrogenation device shown in the attached figure 1.
Wherein, the properties of the catalytic cracking feedstock for examples 1-5 are shown in the following Table 1:
TABLE 1
Examples 1-5 the process conditions used in carrying out the liquid phase hydroprocessing are shown in Table 2 below:
TABLE 2
Examples 1-5 the reaction products, i.e. the oils produced, after liquid phase hydrotreatment are tested for parameters see table 3:
TABLE 3 Table 3
As can be seen from tables 1, 2 and 3, the test results of the produced oil obtained by hydrogenating the catalytic cracking raw material by using the liquid phase hydrogenation device and the liquid phase hydrogenation method provided by the embodiment of the invention accord with the reaction rule of hydrofining to remove S, N impurities. When the reaction process conditions are constant, the density of the produced oil, the sulfur content and the nitrogen content in the produced oil are gradually increased along with the gradual poor quality of the catalytic cracking raw material, and if the severity of the reaction conditions is increased, the desulfurization and denitrification rates equivalent to those of the embodiment 1 can be achieved in the embodiments 2 and 3, but the corresponding energy consumption and the operation cost are increased.
In examples 3, 4 and 5, the density, sulfur content and nitrogen content in the produced oil gradually decreased with increasing reaction temperature when the feed oil was constant.
The foregoing description is only for the convenience of those skilled in the art to understand the technical solution of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A liquid phase hydrogenation method is characterized in that the liquid phase hydrogenation method is carried out by a liquid phase hydrogenation device, wherein,
the liquid phase hydrogenation device comprises: the device comprises a feeding component, a compressed hydrogen feeding component, a heat exchanger, a heating furnace, a hydrogen mixer, a liquid phase hydrogenation reactor, a stripping tower, a pressure reducing valve, a flash tank and a desulfurization and denitrification tower;
the feeding component, the tube side of the heat exchanger, the heating furnace, the hydrogen mixer, the liquid phase hydrogenation reactor, the stripping tower, the pressure reducing valve, the gas phase outlet of the flash tank and the inlet of the desulfurization and denitrification tower are sequentially communicated through pipelines;
the outlet of the compressed hydrogen inlet assembly and the feeding assembly are communicated with the same heat exchanger through pipelines;
the feed assembly includes: the catalytic cracking raw material storage tank, the filter and the feed pump are sequentially communicated;
the compressed hydrogen feed assembly comprises: a hydrogen storage tank and a hydrogen compressor which are communicated in sequence; the hydrogen mixer is provided with a first inlet, a second inlet and a hydrogen mixer outlet, wherein the first inlet is connected with the outlet of the heating furnace, the second inlet is connected with the hydrogen compressor, and the hydrogen mixer outlet is communicated with the bottom of the liquid-phase hydrogenation reactor; the inlet of the desulfurization and denitrification tower is also communicated with the gas phase outlet of the stripping tower;
the outlet of the desulfurization and denitrification tower is communicated with the inlet of the hydrogen storage tank; the outlet of the compressed hydrogen inlet component is respectively communicated with the hydrogen mixer and the liquid phase hydrogenation reactor;
the liquid phase outlet of the flash tank is communicated with the shell side of the heat exchanger;
the inside of the liquid-phase hydrogenation reactor is provided with a protective agent bed layer and more than one refined catalyst bed layer at intervals from bottom to top, wherein the protective agent bed layer is filled with commodity wax oil or heavy oil type protective catalyst, the refined catalyst bed layer is filled with hydrofining catalyst, the commodity wax oil or heavy oil type protective catalyst and the active components of the hydrofining catalyst comprise at least two of W, mo, ni, co, the carrier of the commodity wax oil or heavy oil type protective catalyst and the hydrofining catalyst is titanium-containing alumina, and the commodity wax oil or heavy oil type protective catalyst and the hydrofining catalyst adopt a graded filling mode so as to achieve the purposes of demetallization, carbon removal, desulfurization, denitrification and dearomatization;
at least one hydrogen supplementing pipe is arranged between any two adjacent beds, the two adjacent hydrogen supplementing pipes are arranged at intervals of 100mm-200mm up and down, and the hydrogen supplementing pipes are communicated with an outlet of the compressed hydrogen inlet assembly;
the hydrogen supplementing pipe is a circular pipe, and air outlet holes with the average pore diameter of 150-250 nm are uniformly distributed on the pipe wall of the hydrogen supplementing pipe so as to form nano-scale micro-bubbles;
the stripping tower is a hydrogenation stripping tower, and hydrogen is supplemented in the hydrogenation stripping tower at any time;
the method comprises the following steps:
the inferior catalytic cracking raw material provided by the feeding component is heated by a tube side of the heat exchanger and the heating furnace in sequence, then enters the hydrogen mixer, and is mixed with compressed hydrogen entering the hydrogen mixer through the compressed hydrogen component to obtain a hydrogen-mixed raw material; wherein the poor quality catalytic cracking raw material comprises: at least one of vacuum wax oil, coking wax oil, deasphalted oil and atmospheric residuum;
the hydrogen-mixed raw material enters the liquid-phase hydrogenation reactor to carry out hydrogenation reaction, and the reaction product enters the stripping tower to carry out stripping treatment so as to remove hydrogen sulfide and ammonia gas in the reaction product and obtain a stripping product;
wherein, when hydrogenation reaction is carried out in the liquid phase hydrogenation reactor, the reaction temperature is 300 ℃ to 310 ℃, the reaction pressure is 10.0MPa to 12.0MPa, and the volume space velocity is 1.8h -1 The volume ratio of hydrogen to oil is 20-90; and the stripping product is decompressed by the decompression valve, enters the flash tank for gas-liquid separation, the liquid phase product enters the shell side of the heat exchanger for heat exchange and cooling, and is discharged, and the gas phase product and the gas phase material flow from the stripping tower enter the desulfurization and denitrification tower for desulfurization and denitrification treatment, so that circulating hydrogen is obtained, and the circulating hydrogen is returned to the compressed hydrogen inlet component for recycling.
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