CN109777499B - Refinery gas combined processing technology - Google Patents
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Abstract
The invention discloses a refinery gas combined processing technology, which comprises the following contents: (a) mixing wax oil raw oil and circulating oil with hydrogen in hydrogen dissolving equipment, then adding the mixture into a hydrotreating catalyst bed in a hydrogenation reactor to react under the condition of hydrogenation operation, and arranging gas dissolving equipment between adjacent catalyst beds; (b) mixing refinery gas and/or hydrogen and then entering gas dissolving equipment arranged between any adjacent catalyst bed layers; (c) mixing the hydrogenation reaction material flow obtained in the step (b) with refinery gas and hydrogen in a gas dissolving device, and then allowing the mixture to enter a hydrogenation catalyst bed layer in a supplementary hydrogenation reactor to react under the liquid phase hydrogenation operation condition; (d) separating the hydrogenation reaction effluent obtained in the step (c) into a gas phase and a liquid phase, and fractionating the separated liquid phase to obtain naphtha, diesel oil and hydrotreated heavy distillate oil; mixing part or all of the diesel oil and/or the hydrotreating heavy fraction obtained in the step (c) with hydrogen, allowing the mixture to enter a hydrocracking catalyst bed layer in a hydrocracking reactor for reaction, and fractionating the separated liquid in a fractionating tower to obtain naphtha, aviation kerosene, diesel oil and tail oil. The method can simultaneously hydrotreat refinery gas and produce high-quality hydrocracking products.
Description
Technical Field
The invention belongs to a hydrogenation process of an oil refining technology, relates to a refinery gas combined processing process, and particularly relates to a hydrogenation combined method for hydrotreating refinery gas and producing high-quality hydrocracking products.
Background
With the stricter environmental regulations, the quality requirement of motor fuel is higher and higher. The most outstanding characteristic of hydrocracking technology is that clean motor fuels such as clean diesel oil, high-quality aviation kerosene and the like without sulfur, low aromatic hydrocarbon and high cetane number, and high-quality petrochemical raw materials such as light naphtha, heavy naphtha, tail oil and the like can be directly produced from inferior and heavy raw materials. But also has the characteristics of high production flexibility, high liquid product yield and the like. With the upsizing of the hydrocracking device, the hydrocracking technology will be further developed and applied. From the viewpoint of processing flow, two-stage hydrocracking process was first developed and widely used. The two-stage hydrocracking technology mainly comprises a first-stage hydrocracking pretreatment reaction zone and a second-stage hydrocracking reaction zone, wherein in the first-stage hydrocracking pretreatment reaction zone, raw oil and hydrogen undergo reactions such as desulfurization, denitrification, deoxidation and olefin aromatic hydrocarbon hydrogenation saturation, the first-stage generated oil undergoes oil-gas separation, and liquid enters the second-stage hydrocracking reaction zone after being subjected to steam stripping and/or fractionation to undergo hydrocracking and olefin aromatic hydrocarbon hydrogenation saturation reactions, and a small amount of reactions such as hydrodesulfurization, denitrification, deoxidation and the like are continuously performed.
The liquid-phase wax oil hydrocracking technology can meet the requirement of clean diesel oil production under the condition of greatly reducing energy consumption. US6213835, US6428686 and CN103797093B disclose a hydrogenation process of pre-dissolved hydrogen, which all dissolve hydrogen in wax oil raw material to carry out hydrogenation reaction, and do not utilize the hydrogen left in the reaction, and separate and treat it separately.
Refinery gases generally include dry gases, liquefied gases, and the like, and have various paths for their use. The main application comprises that dry gas is hydrogenated and then used as a raw material for preparing ethylene by steam cracking, liquefied gas is hydrogenated and then used as a raw material for preparing ethylene by steam cracking, a raw material for synthesizing maleic anhydride, liquefied gas for vehicles and the like. In the existing refinery gas hydrogenation technology, CN201410271572.3 discloses a coking dry gas hydrogenation catalyst and a catalyst grading method. The method only solves the problem of controlling the reaction temperature during the hydrogenation of the coking dry gas, but the temperature rise in the reaction process is large. CN201010221244.4 discloses a method for preparing ethylene cracking material by hydrogenation of liquefied petroleum gas, which comprises two reactors, a cooling facility is arranged between the reactors, and CN201310628425.2 discloses a high-temperature hydrogenation purification process of liquefied petroleum gas, wherein olefin saturation and hydrogenation are performed by hydrogenation to remove impurities. As is well known, the hydrogenation reaction of unsaturated hydrocarbons such as olefin, diene, alkyne and the like is a strong exothermic reaction, the temperature rise in the gas hydrogenation process is very large, generally 100-200 ℃, the balance of the hydrogenation reaction is damaged along with the temperature rise, and the generation of carbon deposition is seriously increased, so that the service cycle of the catalyst is reduced.
CN201010221263.7 discloses a liquefied petroleum gas-coker gasoline hydrogenation combination process method, which is a combination method, but not a liquid phase hydrogenation method, the coker gasoline is firstly mixed with hydrogen to carry out fixed bed hydrogenation reaction, and a hydrogenation product and liquefied gas are mixed and enter another reactor, so that the problem of hydrogenation temperature rise of the liquefied gas is only solved.
In summary, in the prior art, the hydrotreating process of refinery gas is a gas phase reaction, the wax oil hydrogenation is a liquid phase reaction, and the reaction types of the two are completely different, so the combined method of the refinery gas hydrotreating and the wax oil liquid phase hydrocracking is rarely reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a combined processing technology. The method can simultaneously hydrotreat refinery gas and produce high-quality hydrocracking products. The utilization efficiency of hydrogen is improved on the premise of not influencing the quality of a hydrocracking product, the problem of temperature rise in the hydrotreating process of refinery gas is effectively solved, the equipment investment is reduced, and the operation energy consumption is reduced.
The invention relates to a refinery gas combined processing technology, which comprises the following contents:
(a) mixing wax oil raw oil and circulating oil with hydrogen in hydrogen dissolving equipment, and then adding the mixture into a hydrotreating catalyst bed in a hydrogenation reactor to react under the condition of hydrogenation operation, wherein the catalyst bed is provided with a plurality of layers, preferably 2-8 layers, and gas dissolving equipment is arranged between adjacent catalyst beds;
(b) mixing refinery gas and/or hydrogen, entering a gas dissolving device arranged between any adjacent catalyst bed layers, mixing the refinery gas and/or hydrogen with a reactant flow from the previous catalyst bed layer, and entering the next catalyst bed layer for reaction;
(c) mixing the hydrogenation reaction material flow obtained in the step (b) with refinery gas and hydrogen in a gas dissolving device, and then allowing the mixture to enter a hydrogenation catalyst bed layer in a supplementary hydrogenation reactor to react under the liquid phase hydrogenation operation condition;
(d) separating the hydrogenation reaction effluent obtained in the step (c) into a gas phase and a liquid phase, continuously separating the gas phase obtained by separation after removing hydrogen sulfide to obtain hydrogen and hydrotreated refinery gas, fractionating the liquid phase obtained by separation to obtain naphtha, diesel oil and hydrotreated heavy distillate oil, and returning part of the liquid phase obtained by separation of the high-pressure separator and/or part of the hydrogenation reaction effluent obtained in the step (b) and/or part of the hydrogenation reaction material flow obtained in the step (c) as circulating oil to a hydrogen dissolving device;
(d) mixing part or all of the diesel oil and/or the hydrotreated heavy fraction obtained in the step (c) with hydrogen, allowing the mixture to enter a hydrocracking catalyst bed layer in a hydrocracking reactor for reaction, separating reactant streams in a high-pressure separator, recycling the separated gas, and fractionating the separated liquid in a fractionating tower to obtain naphtha, aviation kerosene, diesel oil and tail oil.
(e) Mixing the hydrotreated heavy distillate oil and hydrogen, feeding the mixture into a catalyst bed layer in a hydrocracking reactor, reacting under the condition of hydrogenation operation, separating reactant flow in a high-pressure separator, recycling the separated gas, carrying out gas-liquid separation on the separated liquid in a low-pressure separator, and continuously fractionating the separated liquid in a fractionating tower to obtain various wax oil base oils.
In the above method, the wax oil raw oil used may include VGO, CGO, HGO, HLCO, DAO, etc. obtained from petroleum, coal tar, coal liquefied oil, etc., and may be a raw oil, a mixed raw oil composed of several raw materials, or light distillate oil blended with LCO, etc.
In the method, the hydrotreating operation condition is generally that the reaction pressure is 3.0-20.0 MPa, and the volume space velocity of the wax oil raw material oil is 0.2h-1~8.0h-1The average reaction temperature is 180-450 ℃, and the ratio of the circulating oil to the wax oil raw oil is 0.5: 1-10: 1; the preferable operation conditions are that the reaction pressure is 4.0 MPa-18.0 MPa, and the volume space velocity of the wax oil raw material oil is 0.5h-1~6.0h-1The average reaction temperature is 200-440 ℃, and the ratio of the circulating oil to the wax oil raw oil is 0.6: 1-8: 1.
In the above method, supplementThe hydrotreating operation conditions generally comprise a reaction pressure of 3.0-20.0 MPa and a volume space velocity of the wax oil raw material of 0.5h-1~40.0h-1The average reaction temperature is 180-450 ℃; the preferable operation conditions are that the reaction pressure is 4.0 MPa-18.0 MPa, and the volume space velocity of the wax oil raw material oil is 0.8h-1~30.0h-1The average reaction temperature is 200-440 ℃.
In the method, the hydrogenation active component in the hydrogenation catalyst is one or more of Co, Mo, W and Ni, the weight content of the hydrogenation active component is 5-70% in terms of oxide, the carrier of the hydrogenation catalyst is generally alumina, amorphous silicon aluminum, silicon oxide, titanium oxide and the like, and other auxiliary agents such as P, Si, B, Ti, Zr and the like can be simultaneously contained. The catalyst may be used commercially or may be prepared by methods known in the art. The hydrogenation active component is a catalyst in an oxidation state, and is subjected to conventional vulcanization treatment before use, so that the hydrogenation active component is converted into a vulcanization state. The commercial hydrogenation catalysts mainly comprise hydrogenation catalysts such as 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FF-46, FF-56, FH-98, FH-UDS and FZC-41 developed by the Fushu petrochemical research institute (FRIPP), hydrogenation catalysts such as HR-406, HR-416 and HR-448 of IFP company, hydrogenation catalysts such as ICR154, ICR174, ICR178 and ICR179 of CLG company, hydrogenation catalysts such as HC-P, HC-K UF-210/220 newly developed by UOP company, hydrogenation catalysts such as TK-525, TK-555 and TK-557 of Topsor company, KF-752, KF-756, KF-757, KF-840, KF-848, KF-901, KF-907 and the like hydrogenation catalysts of AKZO corporation.
In the method, preferably, the wax oil raw oil and the circulating oil are mixed and then mixed with hydrogen in a hydrogen dissolving device, and then enter a hydrogenation catalyst bed layer to react under the hydrotreating operation condition, and the hydrogenation catalyst passing through the reaction material firstly accounts for 30-80% of the volume of all the hydrogenation catalysts, preferably 35-75%, and most preferably 40-65%, and then the refinery gas is introduced.
In the method, the wax oil raw oil and the circulating oil are mixed and then enter from the top of the hydrogenation reactor, the mixed material flow in which the hydrogen and/or the hydrogen-refinery gas is dissolved can pass through the catalyst bed layer from top to bottom in a downward mode, the wax oil raw oil and the circulating oil are mixed and then can also enter from the bottom of the hydrogenation reactor, and the mixed material flow in which the hydrogen and/or the hydrogen-refinery gas is dissolved can pass through the catalyst bed layer from bottom to top in an upward mode.
In the above method, the previous catalyst bed or the next catalyst bed is based on the flowing direction of the reactant flow, and whether the hydrogenation reaction is an upflow type or a downflow type, the bed in the adjacent beds which is contacted with the reactant flow first is an upper bed and then is a lower bed.
In the method, the refinery gas may comprise one or more of dry gas, liquefied gas and the like. The source of the gas can be one or more of coking, catalytic cracking, thermal cracking, visbreaking and the like.
In the method, the dry gas and the liquefied gas in the refinery gas in the step (b) and the step (c) are independently mixed with hydrogen and then respectively enter gas dissolving equipment arranged between different adjacent catalyst bed layers.
One particularly preferred embodiment is as follows: the hydrogenation reactor is internally provided with three catalyst beds, gas dissolving equipment is arranged between adjacent catalyst beds, dry gas and hydrogen are mixed and then enter the gas dissolving equipment between the second catalyst bed and the third catalyst bed, liquefied gas and hydrogen are mixed and then enter the gas dissolving equipment between the beds of the supplementary hydrogenation reactor, and the dry gas entering the hydrogenation reactor accounts for 50-100% of the volume of all dry gas raw materials.
In the method, the volume ratio of the hydrogen introduced in the step (b) to the refinery gas is 2: 1-200: 1, preferably 5: 1-150: 1, and more preferably 10: 1-100: 1.
In the method, the hydrogenation reaction effluent is separated by a high-pressure separator and/or a low-pressure separator. The high-pressure separator is a conventional gas-liquid separator. The hydrogenation reaction flow is separated in a high-pressure separator to obtain gas and liquid. The low-pressure separator is a conventional gas-liquid separator. The liquid obtained by separation in the high-pressure separator is separated in the high-low pressure separator to obtain gas and liquid.
In the method, the fractionating system used for fractionating comprises a stripping tower and/or a fractionating tower. And the liquid obtained by separation in the low-pressure separator is subjected to steam stripping and/or fractionation in a fractionation system to obtain naphtha, diesel oil and hydrotreated heavy distillate oil.
In the above method, the gas separator used for gas separation is a conventional separator. And the gas obtained by separation in the high-pressure separator and the gas obtained by separation in the low-pressure separator are mixed and then separated in the gas separator to obtain hydrogen, dry gas, liquefied gas and the like, and if a liquid product exists, the gas directly enters a stripping tower and/or a fractionating tower.
In the above method, the gas separator used for gas separation is a conventional separator. The gas obtained by separation in the high-pressure separator and the gas obtained by separation in the low-pressure separator are mixed, hydrogen sulfide is removed, then hydrogen, dry gas, liquefied gas and the like are obtained by separation in the gas separator, and if liquid products exist, the gas directly enters a stripping tower and/or a fractionating tower.
In the method, in the step (d), the diesel oil and/or the hydrotreated heavy fraction is less than 5 mug/g, the nitrogen content is less than 5 mug/g, preferably the sulfur content is less than 3 mug/g, and the nitrogen content is less than 3 mug/g.
In the above method, the hydrocracked raw oil may also include cycle oil used in the full-cycle or partial-cycle operation of the hydrocracking unit liquid, and the cycle oil may include one or more of the hydrocracked liquid products.
In the method, the hydrocracking operation condition is generally that the reaction pressure is 3.0-18.0 MPa, and the volume space velocity of the raw oil is 0.2h-1~6.0h-1The average reaction temperature is 180-450 ℃, and the volume ratio of hydrogen to oil is 300: 1-1500: 1; the preferable operation conditions are that the reaction pressure is 4.0 MPa-16.0 MPa, and the volume airspeed of the raw oil is 0.4h-1~5.0h-1The average reaction temperature is 200-440 ℃, and the volume ratio of hydrogen to oil is 400: 1-1200: 1.
In the above method, the hydrocracking catalyst is a conventional hydrocracking catalyst, and may be a noble metal hydrocracking catalyst or a non-noble metal hydrocracking catalyst. The carrier of the hydrocracking catalyst is alumina and molecular sieve, and the content of the molecular sieve is generally 5wt% -80 wt%. Commercial hydrocracking catalysts are mainly: HC-12, HC-14, HC-24, HC-39, etc. from UOP, FC-12, FC-16, FC-24, 3971, 3976, FC-26, ZHC-02, FC-28, etc. from FRIPP, and ICR126, ICR210, etc. from CHEVRON. Or noble metal catalysts, and the commercial hydrocracking catalysts mainly comprise: HC-28 and HC-35 by Union, and ICR207 and ICR209 by CHEVRON. Conventional hydrocracking pretreatment catalysts and hydrocracking catalysts may also be prepared according to techniques well known in the art.
In the method, the hydrocracking reaction effluent is separated by a high-pressure separator and/or a low-pressure separator. The high-pressure separator is a conventional gas-liquid separator. The hydrogenation reaction flow is separated in a high-pressure separator to obtain gas and liquid. The low-pressure separator is a conventional gas-liquid separator. The gas obtained by separation in the high-pressure separator is recycled after being pressurized by a compressor, and the liquid obtained by separation in the high-pressure separator is separated in the low-pressure separator to obtain the gas and the liquid.
In the method, the hydrocracking fractionation system comprises a fractionating tower. And the liquid obtained by separation in the low-pressure separator is fractionated in a fractionating system to obtain naphtha, aviation kerosene, diesel oil and tail oil.
Hydrogen dissolved in the wax oil liquid phase hydrogenation process is excessive, and a large amount of hydrogen can be dissolved in hydrogenation generated oil after the reaction is finished, so that the hydrogen is not used effectively, namely, the energy consumption is increased; in the process of gas hydrogenation, the temperature rise of a catalyst bed layer is large due to large reaction heat release, so that the temperature range of the hydrogenation reaction is large, the effect of the hydrogenation reaction is influenced, the generation of carbon deposition of the catalyst is accelerated, and the service cycle of the catalyst is shortened. Research results show that the refinery gas and the incompletely hydrotreated material of the wax oil have higher solubility and the refinery gas has higher saturation in a liquid phase, and the refinery gas can be effectively dissolved in the wax oil flow for hydrogenation reaction. In the wax oil liquid phase circulation hydrogenation device, a gas raw material and hydrogen are mixed and enter a plurality of catalyst bed layers behind the device, the aim of producing hydrogenation purified gas is achieved by utilizing higher reaction pressure, higher-activity hydrogenation catalyst and hydrogen atmosphere fused into a liquid phase, the utilization efficiency of the hydrogen is improved on the premise of not influencing the quality of wax oil products, the equipment investment is reduced overall, and the operation energy consumption is reduced.
In the prior art, the wax oil raw material can be used for producing clean wax oil by a liquid phase circulating hydrogenation method, the dry gas raw material is used for producing a dry gas product by a fixed bed hydrogenation method, and the liquefied gas raw material is used for producing a liquefied gas product by a fixed bed hydrogenation method. The gas has certain solubility in liquid, which is the principle of the development of wax oil liquid phase circulation hydrogenation technology, namely, the hydrogenation reaction is realized by utilizing hydrogen dissolved in wax oil, wherein the catalyst of the first bed layer plays the largest role, and a large amount of hydrodesulfurization reaction which easily occurs all occur in the bed layer. However, the dissolved hydrogen cannot be completely reacted, and a large amount of hydrogen can be remained in the reaction product, and usually 20% -70% of the dissolved hydrogen can be remained. The solubility of dry gas and liquefied gas as organic gas in wax oil is larger, and the dissolving amount of hydrogen can be increased in the presence of hydrogen. And the dissolved dry gas and liquefied gas are easy to generate hydrogenation reaction in the atmosphere of catalyst and hydrogen, thus realizing the purpose of producing clean gas. According to the invention, by fully utilizing the characteristic that the wax oil liquid phase circulation hydrogenation process needs to dissolve hydrogen, in order to reduce the influence of dissolved gas on the original wax oil hydrogenation as much as possible, the gas raw material mixed hydrogen enters the catalyst bed layer behind the first catalyst bed layer, the hydrogenation reaction of the gas is completed by utilizing the atmosphere of hydrogen and the catalyst, and the hydrogen can be more dissolved in the wax oil raw material to promote the hydrogenation reaction of the wax oil; or further mixing part of dry gas or all dry gas raw materials in the mixed gas with hydrogen to enter a second catalyst bed layer, wherein the main points are that the olefin content in the dry gas is low, the hydrogen consumption is low, the number of required active centers is small, the time of a reaction desorption process is short, the influence on the wax oil hydrogenation reaction is reduced to the minimum, and the gas with relatively high hydrogen consumption is introduced into a subsequent catalyst bed layer with relatively low hydrogen consumption in wax oil hydrogenation, so that the influence on the wax oil hydrogenation effect is reduced.
The method further makes full use of the characteristic that a large amount of hydrogen is still dissolved in the oil generated by the wax oil liquid phase circulation hydrogenation process, and a supplementary hydrogenation reactor is arranged in the subsequent stage of the wax oil hydrogenation reactor, so that the refinery gas raw material is dissolved in the wax oil hydrogenation reaction material flow and enters a catalyst bed layer of the supplementary hydrogenation reactor, and the hydrogenation reaction of the gas is completed by utilizing the dissolved hydrogen and the catalyst atmosphere, thereby not only solving the problem of large temperature rise of the gas hydrogenation, but also using the hydrogen dissolved in the wax oil for the gas hydrogenation reaction and reducing the hydrogen consumption; or a plurality of catalyst beds are arranged in a further supplementary hydrogenation reactor, part of dry gas or all dry gas raw materials in the mixed gas and wax oil hydrogenation generated oil are mixed to enter the first catalyst bed, and the rest gas and/or hydrogen mixed mixture enters the subsequent catalyst bed. The combined method is generally characterized in that the gas hydrogenation process is completed on the premise of not influencing the quality of the hydrocracking product, the hydrocracking product and the gas product are obtained, and the two technologies are optimally combined, so that the equipment investment and the operation cost are saved.
Drawings
FIG. 1 is a flow chart of the combined process of the present invention.
Wherein: 1-raw oil, 2-raw oil pump, 3-cycle oil, 4-hydrogen dissolver, 5-fresh hydrogen, 6-gas raw material, 7-hydrotreating reactor, 8-vent valve, 9-hydrotreating reactant stream, 10-hydrotreating high-pressure separator, 11-hydrotreating low-pressure separator, 12-hydrotreating stripping/fractionating system, 13-stripping gas, 14-hydrotreating naphtha product, 15-hydrotreating diesel product, 16-hydrotreating heavy fraction oil, 17-hydrotreating high-pressure separator gas, 18-hydrotreating low-pressure separator gas, 19-gas separator, 20-hydrogen, 21-dry gas product, 22-liquefied gas product, 23-gas dissolver, 24-supplementary reactor, 25-make-up hydrogenation reaction material flow, 26-hydrocracking reactor, 27-hydrocracking reaction material flow, 28-hydrocracking high-pressure separator, 29-hydrocracking high-fraction gas, 30-recycle hydrogen compressor, 31-hydrocracking high-pressure separator liquid, 32-hydrocracking low-pressure separator, 33-hydrocracking low-fraction gas, 34-hydrocracking low-pressure separator liquid, 35-hydrocracking fractionating tower, 36-hydrocracking naphtha product, 37-hydrocracking aviation kerosene, 38-hydrocracking diesel oil and 39-hydrocracking tail oil.
Detailed Description
The flow and effect of the hydrogenation combination method of the present invention will be further illustrated with reference to the following examples, which should not be construed as limiting the process of the present invention.
The specific implementation mode of the hydrogenation combination method is as follows: raw oil 1 and cycle oil 3 are mixed, the mixed material and hydrogen are mixed in a hydrogen dissolving device 4 and then enter a hydrotreating reactor 7, and pass through a first catalyst bed layer, hydrogen is dissolved in the effluent of the first catalyst bed layer, and pass through a second catalyst bed layer, hydrogen and a gas raw material 6 are dissolved in the effluent of the second catalyst bed layer, and pass through a third catalyst bed layer, a hydrotreating reaction material flow 9 and the gas raw material 6 are mixed in a gas dissolving device 23 and then enter a supplementary reactor 24, and pass through the first catalyst bed layer, the gas raw material 6 is dissolved in the effluent of the first catalyst bed layer, and pass through the second catalyst bed layer, a supplementary hydrotreating reaction material flow 25 enters a hydrotreating high-pressure separator 10, and is separated in the hydrotreating high-pressure separator 10 to obtain hydrotreating high-pressure separator gas 17 and liquid, the liquid enters a hydrotreating low-pressure separator 11, and is separated in the hydrotreating low-pressure separator 11 to obtain hydrotreating low-pressure separator gas 18 and liquid, the liquid and the liquid component separated by the gas separator 19 are mixed and then enter a hydrotreating stripping/fractionating system 12, and are fractionated in the fractionating system under the action of a stripping gas 13 to obtain a hydrotreating naphtha product 14, a hydrotreating diesel product 15 and hydrotreating heavy distillate oil 16, and the hydrotreating high-pressure separator gas 17 and the hydrotreating low-pressure separator gas 18 are mixed and then enter the gas separator 19, and are separated in the gas separator 19 to obtain hydrogen, dry gas and liquefied gas products. The cycle oil 3 can be obtained directly from the hydrotreating reaction stream 9 or can be obtained from the liquid separated in the hydrotreating high-pressure separator 10. The hydrotreated heavy fraction oil 16 and recycle hydrogen are mixed and enter a hydrocracking reactor 26, and pass through a hydrocracking catalyst bed layer, a hydrocracking reaction material flow 27 is subjected to gas-liquid separation in a hydrocracking high-pressure separator 28, a hydrocracking high-pressure gas 29 obtained through separation is subjected to pressurization through a recycle hydrogen compressor 30 and then is recycled, a hydrocracking high-pressure separator liquid 31 obtained through separation is continuously subjected to gas-liquid separation in a hydrocracking low-pressure separator 32, a hydrocracking low-pressure gas 33 is obtained through separation, a hydrocracking low-pressure separator liquid 34 obtained through separation is continuously fed into a hydrocracking fractionating tower 35 for fractionation, and a hydrocracking naphtha product 36, hydrocracking aviation kerosene 37, hydrocracking diesel oil 38 and hydrocracking tail oil 39 are obtained.
The following examples further illustrate specific aspects of the present invention. Experimental studies were conducted using FF-56 hydrotreating catalyst and FC-32 cracking catalyst developed and produced by FRIPP development.
TABLE 1 wax oil feedstock Primary Properties
| Wax oil feedstock | Raw oil 1 | Raw oil 2 |
| Density, g/cm3 | 0.913 | 0.924 |
| Range of distillation range, deg.C | 320~547 | 335~560 |
| Sulfur content, wt.% | 1.32 | 2.16 |
| Nitrogen content, wt% | 0.146 | 0.089 |
TABLE 2 gas feed principal Properties
| Gaseous feedstock | Dry gas | Liquefied gas | Mixed gas |
| Gas composition | |||
| H2 | 7.0 | 0 | 3.5 |
| CH4 | 12.6 | 0 | 2.9 |
| C2H6 | 55.3 | 0 | 27.1 |
| C2H4 | 5.6 | 0.1 | 4.6 |
| C3 H8 | 10.8 | 16.0 | 13.6 |
| C3 H6 | 2.7 | 6.5 | 4.5 |
| C3 H4 | 0 | 0 | 0 |
| C4 H10 | 5.3 | 34.5 | 20.5 |
| C4 H8 | 0.5 | 33.1 | 19.1 |
| C4 H6 | 0 | 1.2 | 0.5 |
| C5 + | 0.1 | 8.6 | 3.6 |
| CO | 0.005 | 0 | 0.002 |
| CO2 | 0.01 | 0 | 0.008 |
Table 3 examples process conditions and main product properties
| Process conditions | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Hydrogenation reactor operating conditions | |||||
| Raw oil | Raw oil 1 | Raw oil 1 | Raw oil 1 | Raw oil 2 | Raw oil 2 |
| Operating conditions of wax oil hydrogenation reactor | |||||
| Reaction pressure, MPa | 15.0 | 13.0 | 13.0 | 12.0 | 17.0 |
| Average reaction temperature,. degree.C | 380 | 370 | 370 | 375 | 385 |
| Volume space velocity of fresh raw oil, h-1 | 1.2 | 1.0 | 1.0 | 0.8 | 1.5 |
| Circulation ratio | 2:1 | 2.5:1 | 2.5:1 | 4:1 | 3:1 |
| Three-bed inlet gas feedstock | Dry gas | Dry gas | Dry gas | Liquefied gas | Mixed gas |
| Volume ratio of hydrogen and gas raw material dissolved in three-bed layer inlet | 80:20 | 80:20 | 80:20 | 95:5 | 80:20 |
| Make-up of hydrogenation reactor operating conditions | |||||
| Refinery gas feedstock at reactor inlet | Dry gas | Mixed gas | Dry gas | Liquefied gas | Mixed gas |
| Reaction pressure, MPa | 15.0 | 13.0 | 13.0 | 12.0 | 17.0 |
| Average reaction temperature,. degree.C | 380 | 370 | 370 | 375 | 385 |
| Volume space velocity of fresh raw oil, h-1 | 20.0 | 15.0 | 15.0 | 10 | 16 |
| Two-bed inlet refinery gas raw material | — | Liquefied gas | Liquefied gas | Liquefied gas | Mixed gas |
| Volume ratio of hydrogen dissolved in inlet of two-bed layer to raw material of refinery gas | — | 95:5 | 95:5 | 100:0 | 95:5 |
| Hydrocracking process conditions | |||||
| Raw oil | Hydrotreating heavy distillate | Hydrotreating heavy distillate | Hydrotreating heavy distillate | Hydrotreating heavy distillate | Hydrotreating heavy distillate |
| Reaction pressure, MPa | 10.0 | 13.0 | 13.0 | 10.0 | 15.0 |
| Volumetric space velocity h-1 | 1.2 | 2.0 | 2.0 | 0.8 | 2.5 |
| Average reaction temperature,. degree.C | 330 | 340 | 340 | 325 | 345 |
| Volume ratio of hydrogen to oil | 1000 | 1200 | 1200 | 800 | 1000 |
| Dry gas product | |||||
| Olefin content, v% | 0 | 0 | 0 | 0 | 0 |
| Liquefied gas product | |||||
| Olefin content, v% | 0 | 0 | 0 | 0 | 0 |
| CO+CO2，µg/g | 0 | 0 | 0 | 0 | 0 |
| Naphtha product | |||||
| Sulphur content, μ g/g | 0.3 | 0.4 | 0.4 | 0.3 | 0.4 |
| Aviation kerosene product | |||||
| Smoke point, mm | 27 | 26 | 26 | 25 | 29 |
| Diesel oil product | |||||
| Density, g/cm3 | 0.813 | 0.821 | 0.821 | 0.830 | 0.825 |
| Sulphur content, μ g/g | 2 | 5 | 5 | 3 | 4 |
| Cetane number | 60 | 57 | 57 | 53 | 56 |
| Tail oil | |||||
| BMCI | 4.6 | 6.4 | 6.4 | 8.9 | 7.5 |
| Sulphur content, μ g/g | 0.5 | 0.6 | 0.6 | 0.3 | 0.2 |
It can be seen from the examples that wax oil feedstock and gas feedstock can be directly used to produce high quality hydrocracked products and clean gas products by the hydrocombination process of the present technology.
Claims (19)
1. The combined processing technology of refinery gas comprises the following contents:
(a) mixing wax oil raw oil and circulating oil with hydrogen in hydrogen dissolving equipment, and then adding the mixture into a hydrotreating catalyst bed in a hydrogenation reactor to react under the condition of hydrogenation operation, wherein the catalyst bed is arranged into 2-8 layers, and gas dissolving equipment is arranged between adjacent catalyst beds;
(b) mixing refinery gas and/or hydrogen, entering a gas dissolving device arranged between any adjacent catalyst bed layers, mixing the refinery gas and/or hydrogen with a reactant flow from the previous catalyst bed layer, and entering the next catalyst bed layer for reaction;
(c) mixing the hydrogenation reaction material flow obtained in the step (b) with refinery gas and hydrogen in a gas dissolving device, and then allowing the mixture to enter a hydrogenation catalyst bed layer in a supplementary hydrogenation reactor to react under the liquid phase hydrogenation operation condition;
(d) separating the hydrogenation reaction effluent obtained in the step (c) into a gas phase and a liquid phase, continuously separating the gas phase obtained by separation after removing hydrogen sulfide to obtain hydrogen and hydrotreated refinery gas, fractionating the liquid phase obtained by separation to obtain naphtha, diesel oil and hydrotreated heavy distillate oil, and returning part of the liquid phase obtained by separation of the high-pressure separator and/or part of the hydrogenation reaction effluent obtained in the step (b) and/or part of the hydrogenation reaction material flow obtained in the step (c) as circulating oil to a hydrogen dissolving device;
(e) mixing part or all of the diesel oil and/or the hydrotreated heavy fraction obtained in the step (d) with hydrogen, allowing the mixture to enter a hydrocracking catalyst bed layer in a hydrocracking reactor for reaction, separating reactant streams in a high-pressure separator, recycling the separated gas, and fractionating the separated liquid in a fractionating tower to obtain naphtha, aviation kerosene, diesel oil and tail oil.
2. The process according to claim 1, characterized in that: the wax oil raw material oil is one or more of VGO, CGO, HGO, HLCO, DAO, coal tar and coal liquefaction oil.
3. The process according to claim 1, characterized in that: the wax oil hydrotreating operation conditions are that the reaction pressure is 3.0 MPa-20.0 MPa, and the volume space velocity of the wax oil raw material oil is 0.2h-1~8.0h-1The average reaction temperature is 180-450 ℃, and the ratio of the circulating oil to the wax oil raw oil is 0.5: 1-10: 1.
4. The process according to claim 3, characterized in that: the wax oil hydrogenation operation conditions are that the reaction pressure is 4.0MPa to 18.0MPa, and the volume space velocity of the wax oil raw material oil is 0.5h-1~6.0h-1The average reaction temperature is 200-440 ℃, and the ratio of the circulating oil to the wax oil raw oil is 0.6: 1-8: 1.
5. The process according to claim 1, characterized in that: the supplementary hydrogenation operation conditions are that the reaction pressure is 3.0MPa to 20.0MPa, and the volume airspeed of the wax oil raw material oil is 0.5h-1~40.0h-1The average reaction temperature is 180-450 ℃.
6. The process according to claim 5, characterized in that: the supplementary hydrogenation operation conditions are that the reaction pressure is 4.0MPa to 18.0MPa, and the volume space velocity of the wax oil raw material oil is 0.8h-1~30.0h-1The average reaction temperature is 200-440 ℃.
7. The process according to claim 1, characterized in that: the hydrogenation active components of the hydrogenation catalyst used in the wax oil hydrotreating reactor and the hydrogenation active components used in the supplementary hydrogenation reactor are one or more of Co, Mo, W and Ni, the weight content of the hydrogenation active components is 5-70% by weight calculated by oxides, and the carrier of the hydrogenation catalyst is one or more of alumina, amorphous silicon aluminum, silicon oxide and titanium oxide.
8. The process according to claim 1, characterized in that: mixing the wax oil raw oil and the circulating oil, mixing the mixture with hydrogen in a hydrogen dissolving device, then entering a hydrogenation catalyst bed layer to react under the hydrogenation operation condition, and introducing refinery gas after the volume of the hydrogenation catalyst which is firstly passed by the reaction material accounts for 10-80% of the volume of all the hydrogenation catalysts in the hydrotreating reactor in the step (a).
9. The process according to claim 1, characterized in that: the refinery gas is one or more of dry gas and liquefied gas, and the gas is one or more of coking, catalytic cracking and thermal cracking reaction.
10. The process according to claim 9, characterized in that: three catalyst beds are arranged in the hydrogenation reactor, gas dissolving equipment is arranged between adjacent catalyst beds, dry gas and hydrogen are mixed and then enter the gas dissolving equipment between the second catalyst bed and the third catalyst bed, two catalyst beds are arranged in the supplementary hydrogenation reactor, and refinery gas at least containing liquefied gas and hydrogen are mixed and then enter the gas dissolving equipment between the supplementary hydrogenation reactor beds.
11. The process according to claim 10, characterized in that: the volume of the dry gas entering the hydrogenation reactor accounts for 50-100% of the volume of the whole dry gas raw material.
12. The process according to claim 1, characterized in that: when hydrogen and refinery gas are introduced simultaneously in the step (b) or the step (c), the volume ratio of the introduced hydrogen to the refinery gas is 2: 1-200: 1.
13. The process according to claim 1, characterized in that: and (d) in the step (d), the sulfur content in the diesel oil and/or the hydrotreated heavy fraction is less than 5 mug/g, and the nitrogen content is less than 5 mug/g.
14. The process according to claim 13, characterized in that: and (d) in the step (d), the sulfur content in the diesel oil and/or the hydrotreated heavy fraction is less than 3 mug/g, and the nitrogen content is less than 3 mug/g.
15. The process according to claim 1, characterized in that: the hydrocracking operation conditions are that the reaction pressure is 3.0MPa to 18.0MPa, and the volume airspeed of the raw oil is 0.2h-1~6.0h-1The average reaction temperature is 180-450 ℃, and the volume ratio of hydrogen to oil is 300: 1-1500: 1.
16. The process of claim 15, wherein: the hydrocracking operation conditions are that the reaction pressure is 4.0MPa to 16.0MPa, and the volume airspeed of the raw oil is 0.4h-1~5.0h-1The average reaction temperature is 200-440 ℃, and the volume ratio of hydrogen to oil is 400: 1-1200: 1.
17. The process according to claim 1, characterized in that: the hydrocracking catalyst is a noble metal hydrocracking catalyst or a non-noble metal hydrocracking catalyst, the carrier of the hydrocracking catalyst is alumina and a molecular sieve, and the content of the molecular sieve is 5wt% -80 wt%.
18. The process according to claim 1, characterized in that: and separating the hydrocracking reaction material flow in a high-pressure separator to obtain gas and liquid, pressurizing the gas obtained by separation in the high-pressure separator by a compressor and then recycling the gas, and separating the liquid obtained by separation in the high-pressure separator in a low-pressure separator to obtain the gas and the liquid.
19. The process of claim 18, wherein: and (4) fractionating the liquid obtained by separation in the low-pressure separator in a fractionating system to obtain naphtha, aviation kerosene, diesel oil and tail oil.
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| CN101880549A (en) * | 2009-05-06 | 2010-11-10 | 中国石油化工股份有限公司 | Hydrogenation method for liquefied gas fraction |
| CN102268293A (en) * | 2010-06-07 | 2011-12-07 | 中国石油化工集团公司 | Hydrogenation combined process |
| CN104560132A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for hydrotreatment of continuous liquid-phase wax oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101880549A (en) * | 2009-05-06 | 2010-11-10 | 中国石油化工股份有限公司 | Hydrogenation method for liquefied gas fraction |
| CN102268293A (en) * | 2010-06-07 | 2011-12-07 | 中国石油化工集团公司 | Hydrogenation combined process |
| CN104560132A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for hydrotreatment of continuous liquid-phase wax oil |
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