CN117821112A - Residuum hydrotreating method for improving desulfurization selectivity - Google Patents
Residuum hydrotreating method for improving desulfurization selectivity Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 22
- 230000023556 desulfurization Effects 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 16
- 238000004939 coking Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000003111 delayed effect Effects 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002283 diesel fuel Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000002485 combustion reaction Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 239000007791 liquid phase Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 230000036961 partial effect Effects 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000003223 protective agent Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 238000005194 fractionation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- -1 fatty acid ester Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000001593 sorbitan monooleate Substances 0.000 claims description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 2
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 2
- 239000001587 sorbitan monostearate Substances 0.000 claims description 2
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 2
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims 1
- 239000011593 sulfur Substances 0.000 abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 15
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
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Abstract
The invention relates to a residuum hydrotreatment method for improving desulfurization selectivity, after residuum enters a fixed bed residuum hydrogenation first reaction zone to react, the reaction effluent is uniformly mixed with water containing an emulsifying agent, and then enters a fixed bed residuum hydrogenation second reaction zone to contact with a residuum hydrogenation catalyst to react, gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil are obtained after separation in the fixed bed residuum hydrogenation second reaction zone, and the obtained hydrogenated tail oil is a ship-combustion blending component or a delayed coking raw material. The invention can reduce the sulfur content of the hydrogenated residual oil under the condition of keeping the carbon residue value of the hydrogenated residual oil unchanged, and can effectively reduce the hydrogen consumption.
Description
Technical Field
The invention relates to the technical field of residuum hydrotreatment, in particular to a residuum hydrotreatment method for improving desulfurization selectivity.
Background
At present, the heavy quality and the poor quality of crude oil in various places of the world are becoming serious, and the demand for high-quality light oil is increasing, so that the heavy oil processing and the full utilization are the main topics of interest in the oil refining industry. Residuum is the heaviest component in crude oil, has large average relative molecular mass, high boiling point, high viscosity and high polarity, and concentrates most of sulfur-containing, nitrogen-containing, oxygen-containing compounds and colloid in crude oil, and all asphaltenes and heavy metals, which are important points and difficulties in oil processing.
The quality of delayed coked petroleum coke products is greatly affected by the variety of crude oil processed by refineries, and about 70% of the petroleum coke worldwide is high sulfur, fuel grade petroleum coke. In recent years, the new law of environmental protection is continuously put on the way of the country, so that the environmental protection pressure is unprecedentedly increased, the use of high-sulfur petroleum coke as a high-pollution product is obviously limited, and the rigidity requirement of the fuel industry is changed to high-quality petroleum coke or alternative fuel. The demand of the downstream industry for low-sulfur petroleum coke will be greatly increased, the demand of high-sulfur petroleum coke will shrink, and the situation that the low-sulfur petroleum coke resources are tense and the high-sulfur petroleum coke productivity is surplus is expected to be formed.
In order to solve the problem of high sulfur coke, a fixed bed residual oil hydrogenation and delayed coking process route can be adopted, and the sulfur content of the delayed coking raw material is reduced through the fixed bed residual oil hydrogenation, so that the delayed coking can produce low sulfur coke. The ideal carbon residue value of the catalytic cracking raw material is lower and not higher than 15%, so that the selective desulfurization is realized when the delayed coking raw material is produced by a fixed bed residual oil hydrogenation process, namely, the hydrogenation conversion rate of the carbon residue is reduced as much as possible while the desulfurization rate reaches the requirement.
In addition, with the continuous aggravation of global environmental problems, environmental regulations are continuously put out at home and abroad to limit the sulfur mass fraction of marine fuel oil (hereinafter referred to as ship fuel). In the face of the stricter environmental regulations, it is generally believed that the use of low sulfur heavy fuel (meaning a residual fuel with a sulfur mass fraction of no more than 0.5% or no more than 0.1%) would be a major solution for the shipper, and the cost of the fuel would severely impact the shipper's choice of fueling sites. The main blending component of the low-sulfur heavy ship fuel is low-sulfur hydrogenated residual oil, so how to reduce the cost of the hydrogenated residual oil becomes a new challenge of the fixed bed residual oil hydrogenation process. The low sulfur heavy ship combustion has loose requirements on carbon residue value, so if the selective desulfurization can be realized, the hydrogen consumption of the process can be reduced, thereby effectively reducing the cost of hydrogenated residual oil.
CN105505449a relates to a hydrogen-donating coking method, which comprises adding a hydrogen-donating agent as a mixed feed to a coking raw material residual oil in a proportion of 0.1-30wt%, and carrying out coking reaction; the reaction temperature is 450-550 ℃, the reaction pressure is 0.1-0.8MPa, and the reaction residence time is 0.1-240min; the hydrogen donor is selected from hydrogenated catalytic cracking diesel oil or narrow fraction of hydrogenated catalytic cracking diesel oil; the distillation range is between 200 and 350 ℃. The method can improve the yield of coking liquid products and reduce the yield of coke.
CN102585897a relates to a method for the hydrogenation and lightening of heavy oil with low hydrogen content using hydrogen-donating hydrocarbon, which uses hydrogen-donating hydrocarbon stream rich in hydrogen-donating hydrocarbon in the hydrogenation and lightening process of heavy oil such as coal tar pitch, and has the effects of inhibiting condensation coking speed, improving the liquid product yield in the hydrogenation and lightening process of heavy oil of coal tar, improving product quality, reducing reaction temperature rise, and enhancing the operation stability and safety of the device.
Disclosure of Invention
The invention aims to solve the problem of low desulfurization selectivity of the residual oil raw material when the residual oil raw material is hydrogenated to produce coking raw material and heavy ship is combusted.
The residual oil hydrotreating method for improving desulfurization selectivity provided by the invention comprises the following steps:
(l) The residual oil enters a fixed bed residual oil hydrogenation first reaction zone, hydrogenation reaction is carried out under the action of hydrogen and a residual oil hydrogenation catalyst, reaction effluent of the fixed bed residual oil hydrogenation first reaction zone is uniformly mixed with water containing an emulsifying agent, the obtained mixture enters a fixed bed residual oil hydrogenation second reaction zone, and the mixture is contacted with the residual oil hydrogenation catalyst for reaction, wherein the weight ratio of the residual oil to the water is 100: 1-20, wherein the weight ratio of the emulsifier to the water is 0.5-10:100;
(2) The reaction effluent of the fixed bed residual oil hydrogenation second reaction zone obtained in the step (1) enters a hot high-pressure separator to be separated into a first gas phase stream and a first liquid phase stream; the obtained first gas phase material flow enters a cold high-pressure separator to be separated into a second gas phase material flow, a second liquid phase material flow and acid water;
(3) The first liquid phase material flow and the second liquid phase material flow enter a fractionating tower together for fractionation to obtain gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil, wherein the obtained hydrogenated tail oil is a ship combustion blending component or a delayed coking raw material.
The invention has no limitation on the residual oil raw material, and the atmospheric residual oil and/or vacuum residual oil can be treated.
The method of mixing the emulsifier-containing water with the reaction effluent of the fixed bed residuum hydrogenation first reaction zone is not limited in this invention, and any method that can be uniformly mixed is suitable for the present invention.
In another embodiment of the invention, the water containing the emulsifier is mixed with cold hydrogen and then enters the catalyst bed layer of the second reaction zone of the fixed bed residual oil hydrogenation together.
In one embodiment of the invention, the weight ratio of residuum to water is 100: 3-12, the weight ratio of the emulsifier to the water is 1.5-5:100.
The inventor of the present invention has found that the additional addition of water in the second reaction zone of fixed bed residuum hydrogenation can increase the selectivity of hydrodesulfurization of residuum, i.e., can reduce sulfur content under suitable reaction conditions while maintaining the carbon residue value of the product unchanged. Because the hydrogen partial pressure of the second reaction zone of the fixed bed residual oil hydrogenation is reduced after the added water is gasified, the inhibition effect on the hydrogenation conversion of the residual carbon is obvious, thereby improving the selectivity of the hydrodesulfurization. In addition, the invention prefers the addition amount of water, on one hand, the water amount is too small, the effect of improving the hydrodesulfurization selectivity is not obvious, and on the other hand, the adverse effect of the excessive addition amount of water on the strength of the fixed bed residual oil hydrogenation catalyst is avoided.
In one embodiment of the invention, the emulsifier in step (1) acts to homogenize the residue with the water; the emulsifier is a single surfactant or a mixture of the surfactant and other auxiliary agents, the elements composing the emulsifier are any one element of C, H and at least S, N, O, and the sum of the mass fractions of the S element and the N element is 0-10%, preferably 0-5% based on the mass of the emulsifier.
In the invention, the emulsifier can be commercial brand on the market, and can be single or mixed by a plurality of emulsifiers, but the contained elements can be limited to C, H, S, N, O, so as to ensure that new elements are not introduced into the system.
In a preferred case, the emulsifier comprises one or more of sorbitan monooleate, sorbitan monostearate, polyoxyethylene sorbitan fatty acid ester and alkylphenol polyoxyethylene.
In one embodiment of the invention, the process conditions of the fixed bed residuum hydrogenation first reaction zone are: hydrogen partial pressure 5.0-22.0 MPa, reaction temperature 330-450 deg.c and liquid hourly space velocity 0.5 hr -1～ 2.5h -1 Hydrogen-oil ratio is 350-1500;
the technological conditions of the second reaction zone of the fixed bed residual oil hydrogenation are as follows: hydrogen partial pressure 5.0-22.0 MPa, reaction temperature 330-450 deg.c and volume space velocity 0.5 hr -1 ～2.5h -1 Hydrogen-oil ratio is 350-1500.
In one embodiment of the invention, the hydrogenation protective agent and the hydrodemetallization agent are sequentially filled in the fixed bed residual oil hydrogenation first reaction zone, the hydrogenation desulfurization and carbon residue removal agent is filled in the fixed bed residual oil hydrogenation second reaction zone, the filling amount of the hydrogenation protective agent is 1-20% based on the whole volume of the residual oil hydrogenation catalyst, the filling amount of the hydrodemetallization agent is 20-60%, and the filling amount of the hydrodedesulfurization and carbon residue removal agent is 30-70%.
In one embodiment of the invention, each of the hydrogenation protecting agent, the hydrodemetallization agent and the hydrodesulphurization and carbon residue removing agent independently comprises a carrier and an active metal component loaded on the carrier, wherein the active metal component is at least one of metal elements of group VIB and/or group VIII, and the carrier is one or more of alumina, silica and amorphous silica-alumina;
in the hydrogenation protective agent, the total amount of the hydrogenation protective agent is taken as a reference, and the content of the active metal component is 1-12% by weight calculated by oxide;
in the hydrodemetallization agent, the content of the active metal component is 6-15 wt% in terms of oxide based on the total amount of the hydrodemetallization agent;
in the hydrodesulphurization and carbon residue removal agent, the content of the active metal component is 8-25 wt% based on the total amount of the hydrodesulphurization and carbon residue removal agent and calculated by oxide.
In the present invention, the hydrodesulfurization and carbon residue removal agent refers to a fixed bed residuum hydrogenation catalyst having both desulfurization and carbon residue removal functions, but the duty ratio of the respective functions is not limited. Hydrodesulfurization agents, hydrodecarbonization agents, or combinations of both conventionally used in fixed bed residuum hydrogenation techniques can be considered hydrodesulphurisation and carbon removal agents of the present invention.
In the invention, the reaction effluent obtained in the second reaction zone of fixed bed residual oil hydrogenation is subjected to gas-liquid separation, and the obtained liquid phase material flow enters a fractionating tower for fractionation. In one embodiment of the invention, the first liquid phase stream and the second liquid phase stream are subjected to gas-liquid separation in a low pressure separator before entering the fractionation column, and the liquid phase stream from which the low-pressure gas and the sour water are separated enters the fractionation column. The low pressure separator is one or more.
In one embodiment of the invention, the cold high-pressure separator in the step (2) separates the obtained acid water and the acid water separated by the low-pressure separator enters a water treatment unit for sewage treatment. In one embodiment of the invention, the resulting treated water may be recycled to step (1).
In the invention, a fractionating tower is used for separating and obtaining gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil. The obtained hydrogenated naphtha can be used as a raw material of a reforming device or an ethylene device, the obtained hydrogenated diesel is a blending component of a diesel product, the boiling point range of the obtained hydrogenated tail oil is more than 350 ℃, and the obtained hydrogenated tail oil is a ship combustion blending component or a delayed coking raw material.
The invention improves the desulfurization selectivity of the residual oil hydrogenation by adding water, can reduce the sulfur content of the hydrogenated residual oil under the condition of keeping the carbon residue value of the hydrogenated residual oil unchanged under proper conditions, can effectively reduce the hydrogen consumption, and provides high-quality raw materials for delayed coking or low-sulfur high-quality blending components for heavy marine fuel oil.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a residuum hydroprocessing process for enhanced desulfurization selectivity provided by the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings, without thereby limiting the invention.
FIG. 1 is a schematic diagram of one embodiment of a residuum hydroprocessing process of the present invention for increasing desulfurization selectivity. As shown in fig. 1, the residual oil from the pipeline 1 and the hydrogen from the pipeline 4 are mixed and then enter a fixed bed residual oil hydrogenation first reaction zone 2 together, hydrogenation reaction is carried out under the action of the hydrogen and the residual oil hydrogenation catalyst, the reaction effluent of the fixed bed residual oil hydrogenation first reaction zone 2 is pumped out through a pipeline 3 and is uniformly mixed with water containing an emulsifying agent from a pipeline 5, the obtained mixture enters a fixed bed residual oil hydrogenation second reaction zone 7 through a pipeline 6 and is contacted with the residual oil hydrogenation catalyst for reaction, and the reaction effluent of the obtained fixed bed residual oil hydrogenation second reaction zone 7 enters a hot high pressure separator through a pipeline 8 for separation 9 to carry out gas-liquid separation, thus obtaining a first gas phase stream and a first liquid phase stream. The first gaseous stream is passed via line 10 to a cold high pressure separator 11 for further gas-liquid separation to provide a second gaseous stream, a second liquid stream and sour water. The second gas-phase material flow is obtained to remove H 2 S is fed into a circulating hydrogen compressor 13 through a pipeline 12, is boosted and is mixed with new hydrogen from a pipeline 14, and is then fed into slag through a pipeline 4The oil is mixed. The resulting sour water separated by the cold high pressure separator 11 exits the apparatus via line 15. The first liquid stream from the hot high pressure separator 9 is mixed via line 16 with the second liquid stream from the cold high pressure separator 11 and passed via line 17 to a fractionation column 18 where it is separated to produce gas, hydrogenated naphtha, hydrogenated diesel and hydrogenated tail oil which are fed to the apparatus via lines 19, 20 and 21 respectively and which is withdrawn via line 22 as a marine blending component or delayed coker feedstock.
The invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
The residual oil hydrogenation tests of the examples and the comparative examples are carried out in a fixed bed double-tube reactor, wherein a hydrogenation protecting agent and a hydrodemetallization agent are filled in a first reactor (abbreviated as a first reaction), a hydrogenation desulfurization and carbon residue removal agent is filled in a second reactor (abbreviated as a second reaction), and the filling volume ratio of the hydrogenation protecting agent to the hydrodemetallization agent is 1:4:6, wherein the commodity name of the hydrodemetallization agent is RG-30B, the commodity name of the hydrodemetallization agent is RDM-32, the commodity name of the hydrodemetallization and carbon residue removal agent is RMS-30, and the hydrodemetallization and carbon residue removal agents are all manufactured by Bobo Ji Mao catalyst Co.
Example 1
The properties of the residuum are shown in table 1. The residual oil and hydrogen enter a first reaction and are contacted with a hydrogenation protective agent and a hydrodemetallization agent in sequence to carry out hydrogenation reaction, the reaction effluent of the first reaction is uniformly mixed with water containing an emulsifying agent, and the obtained mixture enters a second reaction and is contacted with a hydrodesulphurization and carbon residue removal agent to carry out reaction. The reaction effluent enters a hot high-pressure separator to be separated into a first gas-phase material flow and a first liquid-phase material flow; the first gas phase material flow enters a cold high-pressure separator to be separated into a second gas phase material flow, a second liquid phase material flow and acid water; the first liquid-phase material flow and the second liquid-phase material flow enter a fractionating tower together for fractionation, and gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil are obtained. Wherein the weight ratio of residual oil to water is 100:3, the weight ratio of the emulsifier to the water is 1.5:100. The test conditions were: hydrogen partial pressure 15.0MPa, first reaction temperature 380 ℃, second reaction temperature 390 ℃ and hydrogen-oil ratio 700Nm 3 /m 3 Liquid time volume of residuumSpace velocity of 0.25h -1 . The properties of the resulting hydrogenated naphtha, hydrogenated diesel and hydrogenated residuum are shown in Table 2. The hydrogen consumption of this example was 1.33%.
Example 2
The residuum feedstock, emulsifier, process flow and test conditions employed in example 2 were the same as in example 1. Unlike example 1, the weight ratio of residuum a to water in example 2 was 100:5 and the weight ratio of emulsifier to water was 2.5:100. After the device was operated smoothly, samples of one hydrogenated residue were collected every 24 hours, 3 samples were collected in total, and the properties of the hydrogenated residue are shown in table 3.
Example 3
The procedure and test conditions used in example 3 were the same as those used in example 1. Unlike example 1, the weight ratio of residuum to water was 100:10 and the weight ratio of emulsifier to water was 4:100. The properties of the resulting hydrogenated residuum are shown in Table 3.
Comparative example 1
The residuum raw materials, emulsifiers, process flows and test conditions used in this comparative example were the same as in example 1. In comparison with example 1, the water containing the emulsifier in this comparative example was mixed with the residuum to be reacted under the following test conditions: hydrogen partial pressure 15.0MPa, first reaction temperature 380 ℃, second reaction temperature 390 ℃ and hydrogen-oil ratio 700Nm 3 /m 3 Space velocity of residual oil of 0.25h -1 . The properties of the resulting hydrogenated residuum are shown in Table 3.
Comparative example 2
The residuum feedstock, process flow and test conditions used in this comparative example were the same as in example 1. In comparison with example 1, the feed oil in this comparative example was only residuum, and the test conditions were: hydrogen partial pressure 15.0MPa, first reaction temperature 380 ℃, second reaction temperature 390 ℃ and hydrogen-oil ratio 700Nm 3 /m 3 The volume space velocity of the slag oil liquid is 0.25h -1 . The properties of the resulting hydrogenated residuum are shown in Table 3. The hydrogen consumption of this comparative example was 1.47%.
Comparative example 3
The residuum feedstock, process flow and test conditions used in this comparative example were the same as in example 2. In comparison with example 2, no emulsifier was added in this comparative example. The test conditions were: hydrogen partial pressure 15.0MPa, a first reaction temperature of 380 ℃, a second reaction temperature of 390 ℃, and a hydrogen-oil ratio of 700Nm 3 /m 3 The volume space velocity of the slag oil liquid is 0.25h -1 . Samples of one hydrogenated residue were collected every 24 hours, and a total of 3 were collected, and the properties of the obtained hydrogenated residue are shown in table 3.
Comparative example 4
The residuum raw materials, emulsifiers, process flows and test conditions used in this comparative example were the same as in example 2. The only difference compared to example 2 is that the weight ratio of residuum to water in this comparative example is 100:0.5. The test conditions were: hydrogen partial pressure 15.0MPa, first reaction temperature 380 ℃, second reaction temperature 390 ℃ and hydrogen-oil ratio 700Nm 3 /m 3 The volume space velocity of the slag oil liquid is 0.25h -1 . The properties of the resulting hydrogenated residuum are shown in Table 3.
Comparative example 5
The residuum raw materials, emulsifiers, process flows and test conditions used in this comparative example were the same as in example 2. The only difference compared to example 2 is that the weight ratio of residuum to water in this comparative example is 100:22. The test conditions were: hydrogen partial pressure 15.0MPa, first reaction temperature 380 ℃, second reaction temperature 390 ℃ and hydrogen-oil ratio 700Nm 3 /m 3 The volume space velocity of the slag oil liquid is 0.25h -1 . The properties of the resulting hydrogenated residuum are shown in Table 3.
Comparative example 6
The residuum raw materials, emulsifiers, process flows and test conditions used in this comparative example were the same as in example 2. The only difference compared to example 2 is that the weight ratio of emulsifier to water in this comparative example is 12:100. The test conditions were: hydrogen partial pressure 15.0MPa, first reaction temperature 380 ℃, second reaction temperature 390 ℃ and hydrogen-oil ratio 700Nm 3 /m 3 The volume space velocity of the slag oil liquid is 0.25h -1 . The properties of the resulting hydrogenated residuum are shown in Table 3.
Comparative example 7
The residuum raw materials, emulsifiers, process flows and test conditions used in this comparative example were the same as in example 2. The weight ratio of emulsifier to water in this comparative example was only 0.3:100, compared to example 2. The test conditions were: hydrogen partial pressure 15.0MPa, first reaction temperature 380 ℃, second reaction temperature 390 ℃ and hydrogen-oil ratio 700Nm 3 /m 3 The volume space velocity of the slag oil liquid is 0.25h -1 . The properties of the resulting hydrogenated residuum are shown in Table 3.
As can be seen from Table 3, the hydrogenated residues of examples 1 to 3 had sulfur contents of 0.23%, 0.24% (average value of three samples) and 0.24%, respectively, and carbon residue values of 6.81%, 6.97% (average value of three samples) and 7.00%, respectively. The sulfur content of the hydrogenated residuum was unchanged from comparative examples 1 and 2, but the carbon residue value was increased, indicating that the sulfur content could be reduced by controlling the operating conditions while maintaining the carbon residue value of the product unchanged. It can be seen from comparative examples 1 and 2 that the injection of water into the primary reaction also has the effect of increasing the hydrodesulphurisation selectivity, except that no water is directly injected into the secondary reaction.
As can be seen from Table 3, the carbon residue values of the three samples in example 2 are relatively stable, while the carbon residue values of the three hydrogenated residuum samples without emulsifier in comparative example 3 are relatively variable, indicating whether water and residuum can be uniformly mixed, which can affect the stability of product properties.
As can be seen from examples 2, 4 and 5, the addition of water does not achieve good technical effects within the range, and too little addition does not reflect the technical effects, and too much addition damages the catalyst structure, thereby also reducing the technical effects.
The invention defines desulfurization selectivity as the ratio of desulfurization rate to char conversion rate. As shown by a great deal of experimental study, the inventor of the present invention has shown that under the same reaction conditions, the absolute value of desulfurization selectivity of the same raw oil is increased by 0.06 at most through some conventional technical means, and further as can be seen from Table 3, the desulfurization selectivity is increased from 2.07 to 2.24, the absolute value is increased by 0.17, and the percentage is increased by 8.2% by comparing the desulfurization selectivity data of example 3 and comparative example 2. It can be seen that the desulfurization selectivity can be effectively improved by adding water.
TABLE 1 residuum feedstock Properties
| Density (20 ℃ C.) kg/m 3 | 956.6 |
| Viscosity (100 ℃ C.) mm 2 /s | 108.5 |
| CCR,wt％ | 10.99 |
| S,wt％ | 1.28 |
| N,ppm | 3300 |
| Ni+V,ppm | 90.6 |
TABLE 2 example 1 hydrogenation product Properties and yield
| Hydrogenated naphtha | Hydrogenated diesel oil | Hydrogenated residuum | |
| CCR,wt％ | - | - | 6.86 |
| S,wt％ | 50ppm | 200ppm | 0.23 |
| N,ppm | 80ppm | 300ppm | 2580 |
| Ni+V,ppm | - | - | 29.0 |
| Yield rate * ，wt％ | 1.95 | 8.08 | 89.32 |
* Based on residuum feed.
TABLE 3 residuum feedstock and hydrogenated residuum Properties
Claims (10)
1. A residuum hydroprocessing process for enhanced desulfurization selectivity comprising:
(l) The residual oil enters a fixed bed residual oil hydrogenation first reaction zone, hydrogenation reaction is carried out under the action of hydrogen and a residual oil hydrogenation catalyst, reaction effluent of the fixed bed residual oil hydrogenation first reaction zone is uniformly mixed with water containing an emulsifying agent, the obtained mixture enters a fixed bed residual oil hydrogenation second reaction zone, and the mixture is contacted with the residual oil hydrogenation catalyst for reaction, wherein the weight ratio of the residual oil to the water is 100: 1-20, wherein the weight ratio of the emulsifier to the water is 0.5-10:100;
(2) The reaction effluent of the fixed bed residual oil hydrogenation second reaction zone obtained in the step (1) enters a hot high-pressure separator to be separated into a first gas phase stream and a first liquid phase stream; the obtained first gas phase material flow enters a cold high-pressure separator to be separated into a second gas phase material flow, a second liquid phase material flow and acid water;
(3) The first liquid phase material flow and the second liquid phase material flow enter a fractionating tower together for fractionation to obtain gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated tail oil, wherein the obtained hydrogenated tail oil is a ship combustion blending component or a delayed coking raw material.
2. The method of claim 1, wherein the weight ratio of residuum to water is 100: 3-12, the weight ratio of the emulsifier to the water is 1.5-5:100.
3. The process of claim 1 wherein the emulsifier in step (1) is used to uniformly mix the residuum with water; the emulsifier is a single surfactant or a mixture of the surfactant and other auxiliary agents, the elements composing the emulsifier are any one element of C, H and at least S, N, O, and the sum of the mass fractions of the S element and the N element is 0-10%, preferably 0-5% based on the mass of the emulsifier.
4. A method according to claim 3, wherein the sum of the mass fractions of the S element and the N element is 0 to 5% based on the mass of the emulsifier.
5. A method according to claim 3, wherein the emulsifier comprises one or more of sorbitan monooleate, sorbitan monostearate, polyoxyethylene sorbitan fatty acid ester, alkylphenol ethoxylates.
6. The process of claim 1 wherein the process conditions in the fixed bed residuum hydrogenation first reaction zone are: hydrogen partial pressure 5.0-22.0 MPa, reaction temperature 330-450 deg.c and liquid hourly space velocity 0.5 hr -1～ 2.5h -1 Hydrogen-oil ratio is 350-1500;
the technological conditions of the second reaction zone of the fixed bed residual oil hydrogenation are as follows: hydrogen partial pressure 5.0-22.0 MPa, reaction temperature 330-450 deg.c and volume space velocity 0.5 hr -1 ～2.5h -1 Hydrogen-oil ratio is 350-1500.
7. The method according to claim 1, wherein the first reaction zone for hydrogenating the fixed bed residual oil is filled with a hydrogenation protecting agent and a hydrodemetallization agent in sequence, the second reaction zone for hydrogenating the fixed bed residual oil is filled with a hydrogenation desulfurizing and carbon removing agent, the filling amount of the hydrogenation protecting agent is 1-20%, the filling amount of the hydrodemetallization agent is 20-60% and the filling amount of the hydrodesulfation and carbon removing agent is 30-70% based on the whole volume of the residual oil hydrogenation catalyst.
8. The method according to claim 7, wherein each of the hydroprotectant, hydrodemetallization agent and hydrodesulphurisation carbon residue agent independently comprises a support and an active metal component supported on the support, the active metal component being selected from at least one of group VIB and/or group VIII metal elements, the support being one or more selected from alumina, silica and amorphous silica alumina;
in the hydrogenation protective agent, the total amount of the hydrogenation protective agent is taken as a reference, and the content of the active metal component is 1-12% by weight calculated by oxide;
in the hydrodemetallization agent, the content of the active metal component is 6-15 wt% in terms of oxide based on the total amount of the hydrodemetallization agent;
in the hydrodesulphurization and carbon residue removal agent, the content of the active metal component is 8-25 wt% based on the total amount of the hydrodesulphurization and carbon residue removal agent and calculated by oxide.
9. The process of claim 1 wherein the water containing the emulsifier is mixed with cold hydrogen before passing together between the catalyst beds in the fixed bed residuum hydrogenation second reaction zone.
10. The process of claim 1 wherein the first and second liquid phase streams are subjected to gas-liquid separation in a low pressure separator prior to entering the fractionation column, and the liquid phase stream separated from the low vapor fraction and the sour water enters the fractionation column.
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