CN115449397B - Viscosity reducing cracking device and viscosity reducing cracking method - Google Patents
Viscosity reducing cracking device and viscosity reducing cracking method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 104
- 238000005336 cracking Methods 0.000 title claims abstract description 58
- 239000002253 acid Substances 0.000 claims abstract description 442
- 230000009467 reduction Effects 0.000 claims abstract description 157
- 239000000463 material Substances 0.000 claims abstract description 74
- 238000001514 detection method Methods 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 56
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 38
- 239000003921 oil Substances 0.000 claims description 479
- 239000007788 liquid Substances 0.000 claims description 82
- 238000000926 separation method Methods 0.000 claims description 67
- 239000000203 mixture Substances 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000009835 boiling Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 description 129
- 238000006243 chemical reaction Methods 0.000 description 40
- 238000010438 heat treatment Methods 0.000 description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 9
- 239000005642 Oleic acid Substances 0.000 description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000004939 coking Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
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- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
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Abstract
The invention provides a viscosity reducing cracking device and a viscosity reducing cracking method. This visbreaking device includes: the viscosity reducing cracking unit is provided with a raw oil inlet and a viscosity reducing cracking residual oil outlet; the acid value detection unit of the raw oil is used for detecting the acid value of the raw oil; and an acid value detection unit of the visbreaking residual oil for detecting the acid value of the visbreaking residual oil. In the case of using the visbreaking device and the visbreaking method of the invention, the degree of back mixing of materials in the visbreaking device can be clearly reflected by measuring the acid values of the raw materials and visbreaking residues and calculating the acid value reduction rate. Accordingly, the structure and process of the visbreaker can be modified to ensure that the visbreaker operates at high severity, giving the best performance of the visbreaking process.
Description
Technical Field
The application relates to the technical field of petroleum processing, in particular to a viscosity reducing cracking device and a viscosity reducing cracking method.
Background
With the increasing world economy, the demand for petroleum is increasing, conventional petroleum resources have not met the needs of people, and heavy crude oil has become the main raw material in petroleum processing today. The visbreaking has the characteristics of mature technology, low investment, easy construction, low operation cost, low requirement on raw materials and the like, and plays an important role in the heavy oil processing technology.
The visbreaking process is one of the effective ways to lighten the heavy inferior oil. Visbreaking is a parallel sequential reaction process in which both cracking and condensation reactions are present. In practical production, it is desired to increase the cracking depth of the visbreaking process, however, increasing the cracking depth increases the reaction temperature or increases the reaction time, which increases the condensation reaction and causes coking, thereby causing problems such as equipment blockage and shortening the production cycle. In contrast, high viscosity reduction efficiency cannot be obtained at low reaction severity. In addition, the stability of the viscosity-reduced oil is reduced with the increase of the condensation reaction, so that the fuel oil is delaminated until precipitation affects the storage and transportation of the product. The problem to be solved is therefore to balance the relationship between normal operation of the device and increasing the severity of the reaction to produce more light oil.
In order to reduce the viscosity of residual oil, produce light distillate oil as much as possible, and keep the viscosity-reducing oil stable, the key problem is how to keep the materials in the viscosity-reducing reaction tower in a plug flow state, and reduce back mixing, because the materials have small severity and large severity along with the increase of the back mixing degree, the viscosity-reducing raw material reaction is enabled to be operated only under low severity to ensure the stability of the product and long-period running of the device, so the back mixing degree of the materials in the viscosity-reducing device reaction tower is the most critical factor for influencing the viscosity-reducing cracking, namely, the smaller the back mixing degree of the materials in the viscosity-reducing cracking reaction tower is, the larger the severity of the viscosity-reducing cracking can be on the same raw material under the premise of ensuring the quality of the product and long-period stable running of the device. Therefore, it is particularly important how to judge and measure the relative intensity of the back mixing of materials in the viscosity reduction reaction tower, and the structure and the process which can keep or popularize the degree of the back mixing of the materials in the reactor to be reduced are measured, so that the viscosity reduction cracking is ensured to operate under high severity, and the optimal efficiency of the viscosity reduction cracking process is exerted.
However, the prior art methods are not effective in assessing the degree of back mixing of the materials in the visbreaking reaction tower. Accordingly, there remains a need for an apparatus and method that clearly reflects the degree of back mixing of materials in an visbreaking reaction tower.
Disclosure of Invention
The application mainly aims to provide an anti-viscosity cracking device and an anti-viscosity cracking method, which are used for solving the problem that the back mixing degree of materials in an anti-viscosity cracking reaction tower cannot be effectively estimated in the prior art.
In order to achieve the above object, according to one aspect of the present application, there is provided an visbreaking apparatus comprising: the viscosity reducing cracking unit is provided with a raw oil inlet and a viscosity reducing cracking residual oil outlet; the acid value detection unit of the raw oil is used for detecting the acid value of the raw oil; and an acid value detection unit of the visbreaking residual oil for detecting the acid value of the visbreaking residual oil.
Further, in the above-mentioned visbreaking apparatus, the visbreaking unit is equipped with an automatic control device, a pressure controller and a temperature controller, the automatic control device being connected with the raw oil acid value detection unit, the visbreaking residuum acid value detection unit, the pressure controller and the temperature controller; and the automatic control equipment receives the acid value of the raw oil and the acid value of the visbreaking residual oil, calculates the acid value reduction rate, and adjusts the pressure controller and the temperature controller of the visbreaking unit in real time according to the acid value reduction rate.
Further, in the above-mentioned visbreaking device, the visbreaking device further includes a first raw oil supply unit and a second raw oil supply unit, and the raw oil inlets are respectively connected with the first raw oil supply unit and the second raw oil supply unit; the automatic control equipment is connected with the first raw oil supply unit and the second raw oil supply unit, receives the acid value of the visbreaking residual oil and the acid value of the raw oil, and adjusts the feeding amount of the first raw oil supply unit and/or the second raw oil supply unit in real time according to the acid value reduction rate.
Further, in the above-mentioned visbreaking device, the visbreaking device further includes: the gas-liquid separation unit is provided with a raw material inlet and a liquid separator outlet, the liquid separator outlet is connected with the raw material oil inlet of the viscosity-reducing cracking unit, and the gas-liquid separation unit is used for performing gas-liquid separation on the raw material oil to obtain a gaseous separator and a liquid separator, and the gaseous separator comprises water and light gas oil; and the automatic control equipment is connected with the acid value detection unit of the raw oil, the acid value detection unit of the visbreaking residual oil, the raw oil supply unit and the gas-liquid separation unit, receives the acid value of the visbreaking residual oil and the acid value of the raw oil, calculates the acid value reduction rate, and adjusts the feeding amount of the gas-liquid separation unit and/or the visbreaking unit and/or the temperature of the gas-liquid separation unit in real time according to the acid value reduction rate.
Further, in the above-mentioned visbreaking apparatus, the visbreaking apparatus further includes a raw oil supply unit, and the visbreaking unit further includes: the first visbreaking unit is provided with a first raw oil inlet and a first visbreaking residual oil outlet; the second visbreaking unit is provided with a second raw oil inlet and a second visbreaking residual oil outlet, and the raw oil supply unit is respectively connected with the first raw oil inlet and the second raw oil inlet; the visbreaking residual acid value detection unit is used for detecting the acid value of visbreaking residual at the outlet of the first visbreaking residual and recording the acid value as a first acid value, and is used for detecting the acid value of visbreaking residual at the outlet of the second visbreaking residual and recording the acid value as a second acid value, wherein the visbreaking device is provided with an automatic control device, the automatic control device is connected with the raw oil supply unit, the raw oil acid value detection unit and the visbreaking residual acid value detection unit, the automatic control device receives the first acid value, the second acid value and the acid value of the raw oil, calculates the first acid value reduction rate and the second acid value reduction rate, and adjusts the feeding amount of the first visbreaking unit and/or the second visbreaking unit in real time according to the first acid value reduction rate and the second acid value reduction rate.
According to another aspect of the present invention, there is provided a visbreaking process comprising: step S1, detecting the acid value of raw oil; s2, performing visbreaking on raw oil to obtain visbroken generated oil, and fractionating the visbroken generated oil to obtain visbroken residual oil; and step S3, detecting the acid value of the visbreaking residual oil, and calculating the acid value reduction rate.
Further, the above visbreaking method further comprises: the pressure and/or temperature of the visbreaker is adjusted based on the acid number reduction rate.
Further, in the above visbreaking method, the raw oil in step S1 is a mixture of a plurality of raw oils, and the visbreaking method further includes adjusting the composition of the raw oil based on the acid value reduction rate.
Further, in the above-mentioned visbreaking method, the visbreaking method further includes: and (3) carrying out gas-liquid separation on the hot mixture before feeding the raw oil according to the acid value reduction rate to obtain a gaseous separated product and a liquid separated product, and carrying out viscosity reduction cracking on the liquid separated product.
Further, in the above-mentioned visbreaking method, the temperature of gas-liquid separation is adjusted according to the acid value reduction rate.
Further, in the visbreaking process described above, the gaseous separation comprises water and light gas oil.
Further, in the above-mentioned visbreaking method, step S2 includes visbreaking the raw oil under a first visbreaking condition to obtain a first visbroken product oil, fractionating the first visbroken product oil to obtain a first visbroken residue, and visbreaking the raw oil under a second visbreaking condition to obtain a second visbroken product oil, and fractionating the second visbroken product oil to obtain a second visbroken residue, wherein the first visbreaking condition is different from the second visbreaking condition; step S3, detecting the acid value of the first visbreaking residual oil and the acid value of the second visbreaking residual oil, calculating a first acid value reduction rate according to the acid value of the raw oil and the acid value of the first visbreaking residual oil, and calculating a second acid value reduction rate according to the acid value of the raw oil and the acid value of the second visbreaking residual oil; and wherein the visbreaking process further comprises: and S4, selecting the visbreaking conditions according to the first acid value reduction rate and the second acid value reduction rate.
Further, in the visbreaking method, visbreaking residual oil is visbreaking generated oil, and the visbreaking residual oil is distilled at a true boiling point to obtain the residual oil with the temperature of more than 430 ℃.
In the case of using the visbreaking device and the visbreaking method of the invention, the degree of back mixing of materials in the visbreaking device can be clearly reflected by measuring the acid values of the raw materials and visbreaking residues and calculating the acid value reduction rate. Accordingly, the structure and process of the visbreaker can be modified to ensure that the visbreaker operates at high severity, giving the best performance of the visbreaking process.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
From the foregoing background, it can be appreciated that the prior art methods are not effective in assessing the degree of back mixing of materials in an visbreaking reaction column. Aiming at the technical problems described above, the application provides a viscosity reducing cracking device and a viscosity reducing cracking method.
The inventors have found that the acid value of the visbreaking feedstock is mainly contributed by the petroleum acid contained therein. Petroleum acid is easy to decompose at the temperature of above 370 ℃, if the materials are not back mixed in the visbreaking reactor, the petroleum acid of visbreaking residual oil is easy to remove under the normal visbreaking condition, but if the materials are back mixed in the visbreaking process, the retention time of part of the materials in the visbreaking reactor is too short, the petroleum acid of part of the materials is not sufficiently decomposed, and the acid value of the visbreaking residual oil is still higher. Therefore, under the same visbreaking conditions, the acid values of visbreaking residues obtained by different back mixing degrees of materials in the visbreaking tower are different for the same high-acid visbreaking raw materials. While acid number detection techniques are relatively well-established in the art and it is therefore particularly feasible to utilize acid numbers to measure the degree of back mixing, in one exemplary embodiment of the present application there is provided an visbreaking apparatus comprising an visbreaking unit having a feedstock inlet and an visbroken residue outlet, a feedstock oleic acid number detection unit for detecting the acid number of the feedstock and an visbroken residue acid number detection unit for detecting the acid number of the visbroken residue.
In the case of using the visbreaker of the present application, the acid value of the raw oil is detected by the raw oil oleic acid value detecting unit before the raw oil enters the visbreaker. After entering an visbreaking device through a raw oil inlet, visbreaking generated oil is obtained through the visbreaking device, visbreaking generated oil is fractionated to obtain visbreaking residual oil and distillate oil, and an acid value detection unit of the visbreaking residual oil is utilized to detect the acid value of the visbreaking residual oil.
The viscosity reduction test raw material is high acid value residual oil with an acid value not less than 1.0 mgkOH/g; when the visbreaking test material is a low acid value residue having an acid value of less than 1.0mgkOH/g, a certain amount of a high acid value vacuum residue is added, the acid value of the mixed material is adjusted to not less than 1.0mgkOH/g, and then the test is conducted as a material.
The acid value of the raw oil for the viscosity-reducing test refers to the acid value of residual oil with the temperature of more than 430 ℃ obtained by distilling the raw oil with a true boiling point; the acid value of the visbreaking residual oil refers to the acid value of the residual oil with the temperature of more than 430 ℃ obtained by distillation of visbreaking generated oil with a true boiling point.
After detection by the raw material oleic acid value detecting unit and the visbroken residue acid value detecting unit, the raw material oleic acid value and the visbroken residue acid value can be obtained. The acid value reduction rate after the visbreaking of the raw material was calculated by:
Reduction rate of acid value= (acid value of raw oil-acid value of visbroken residue)/acid value of raw oil×100% (formula 1)
Through the formula, the acid value reduction rate can be calculated, the device can be used for measuring the acid value reduction rate of the visbreaking of the raw materials under the same operation condition in the visbreaking tower of the same visbreaking device, the acid value reduction rate is large, the back mixing degree of the materials in the visbreaking device (such as the visbreaking tower) is small, on the contrary, the acid value reduction rate is small, the back mixing degree of the materials in the visbreaking device is large, the acid value reduction rate is close, the back mixing degree of the two materials in the visbreaking device is equivalent, and the acid value reduction rate of the visbreaking of the raw materials under the same operation condition in the same visbreaking device can be clearly reflected by measuring the back mixing degree of the materials in the same visbreaking device.
Unlike the prior art devices which cannot effectively evaluate the degree of back mixing of materials in an visbreaking reaction tower, the device can clearly reflect the degree of back mixing of materials in the visbreaking device by measuring acid values of raw materials and visbreaking residues and calculating the acid value reduction rate. Accordingly, the structure and process of the visbreaker can be modified to ensure that the visbreaker operates at high severity, giving the best performance of the visbreaking process.
In some embodiments of the present application, the visbreaking unit is equipped with an automatic control device, a pressure controller, and a temperature controller, the automatic control device being connected to the feedstock oil acid value detection unit, the visbreaking resid acid value detection unit, the pressure controller, and the temperature controller; and the automatic control equipment receives the acid value of the raw oil and the acid value of the visbreaking residual oil, calculates the acid value reduction rate, and adjusts the pressure controller and the temperature controller of the visbreaking unit in real time according to the acid value reduction rate. In this embodiment, the visbreaking apparatus performs the visbreaking reaction under the control of the automatic control apparatus. After the acid value of the raw oil and the acid value of the visbroken residue were measured, the reduction rate of the acid value was calculated by the formula (1). The automatic control equipment of the visbreaking equipment can adjust the temperature, the pressure, the reaction time and the like of the visbreaking equipment in real time according to the calculated acid value reduction rate. When the automatic control device detects that the acid value reduction rate is lower than a set value, the temperature, pressure and reaction time of the viscosity-reducing cracking unit are automatically adjusted, so that the reaction conditions of the viscosity-reducing cracking unit are changed, and the acid value of the viscosity-reducing cracked residual oil generated after the change of the reaction conditions is further measured, so that the acid value reduction rate is calculated. In the process of visbreaking, the automatic control equipment can regulate and control the conditions such as the temperature, the pressure, the reaction time and the like of visbreaking so as to ensure that the acid value reduction rate is in a controllable range for visbreaking. Under the process condition of the maximum acid value reduction rate, the materials in the viscosity-reducing cracking unit undergo back mixing to a smaller extent, so that the problem of excessive coking of the materials in the viscosity-reducing cracking unit is effectively avoided.
In other embodiments of the present application, the visbreaker apparatus further comprises a first feedstock supply unit and a second feedstock supply unit. The raw material oil inlet is respectively connected with the first raw material oil supply unit and the second raw material oil supply unit; the automatic control equipment is connected with the first raw oil supply unit and the second raw oil supply unit, receives the acid value of the visbreaking residual oil and the acid value of the raw oil, and adjusts the feeding amount of the first raw oil supply unit and/or the second raw oil supply unit in real time according to the acid value reduction rate. In this embodiment, both the first feedstock supply unit and the second feedstock supply unit are connected to the feedstock inlet of the visbreaker. The first feedstock and the second feedstock have different compositions. Before the raw oil enters the visbreaking device, the raw oil acid value detection unit may detect the acid values of the first raw oil and the second raw oil that will enter the raw oil inlet to obtain a first raw oil acid value and a second raw oil acid value, respectively, or after the first raw oil and the second raw oil are mixed, the raw oil acid value detection unit may detect the mixed raw oil to obtain a raw oil acid value.
By using the above-mentioned visbreaking device, the visbroken raw oil can be selected, for example, in one embodiment, first raw oil is fed into the visbreaking device, visbreaking is performed in the visbreaking device to generate a first visbroken residue, and then the acid value of the first visbroken residue is detected by the visbroken residue acid value detection unit. The feed of the first feedstock is then stopped and the visbreaker is fed using a second feedstock supply unit. After the visbreaking cracking is carried out in the visbreaking device to generate second visbreaking residual oil, the acid value of the second visbreaking residual oil is detected by the visbreaking residual oil acid value detection unit. The automatic control unit receives the acid value of the first feedstock oil and the acid value of the first visbreaking residual oil and calculates the reduction rate of the first acid value by the formula (1), and receives the acid value of the second feedstock oil and the acid value of the second visbreaking residual oil and calculates the reduction rate of the second acid value by the formula (1). And after the automatic control unit compares the reduction rate of the first acid value and the reduction rate of the second acid value, selecting raw oil with large acid value reduction rate to feed the visbreaking device.
With the above-described visbreaker, the composition of the visbroken mixed feedstock may be adjusted, such as in one embodiment, by feeding the first feedstock and the second feedstock to the visbreaker simultaneously. Before the mixed material enters the viscosity-reducing cracking device, the raw material oleic acid value detection unit detects the acid value of the mixed material to obtain the raw material oleic acid value. After the mixed raw oil is subjected to visbreaking in the visbreaking device to generate visbreaking residual oil, the acid value of the visbreaking residual oil is detected by the visbreaking residual oil acid value detection unit. The automatic control unit receives the acid value of the raw oil and the acid value of the visbreaking residual oil and calculates the reduction rate of the visbreaking acid value of the raw material according to the formula (1). The automatic control unit automatically adjusts the feed amount of the first raw material oil supply unit and/or the second raw material oil supply unit, thereby obtaining a plurality of groups of different acid value reduction rates. In the visbreaking process, the automatic control equipment can regulate and control the composition of the mixed raw oil fed into the visbreaking device so as to ensure that the acid value reduction rate is in a controllable range for visbreaking.
In other embodiments of the present application, the visbreaker apparatus further comprises: the gas-liquid separation unit is provided with a raw material inlet and a liquid separator outlet, the liquid separator outlet is connected with the raw material oil inlet of the visbreaking unit, and the gas-liquid separation unit is used for performing gas-liquid separation on the hot mixture before feeding the visbreaking unit to obtain a gaseous separator and a liquid separator, and the gaseous separator comprises water and light gas oil; and the automatic control equipment is connected with the acid value detection unit of the raw oil, the acid value detection unit of the visbreaking residual oil, the raw oil supply unit and the gas-liquid separation unit, receives the acid value of the visbreaking residual oil and the acid value of the raw oil, calculates the acid value reduction rate, and adjusts the feeding amount of the gas-liquid separation unit and/or the visbreaking unit and/or the temperature of the gas-liquid separation unit in real time according to the acid value reduction rate.
In these embodiments, the visbreaking apparatus of the present application includes a visbreaking unit, a feedstock acid value detection unit, a visbroken resid acid value detection unit, a gas-liquid separation unit, and a feedstock supply unit. The raw oil supply unit is directly connected with the viscosity reducing cracking unit, and can directly feed the raw oil to the viscosity reducing cracking device. The raw oil supply unit may also be connected to the visbreaking unit via a gas-liquid separation unit, so that the raw oil may be separated into a liquid separator and a gaseous separator containing water and light gas oil after gas-liquid separation via the gas-liquid separation unit. After gas-liquid separation, the liquid separation is fed to a visbreaking unit. Light gas oil components have been removed from the feedstock prior to visbreaking. In the subsequent visbreaking reaction, because the reaction system does not contain water and light gas oil components, the visbreaking reaction can be carried out under higher severity, and the problems of back mixing of materials caused by gas phase components such as water and light gas oil and excessive coking caused by partial material condensation are avoided. The raw material oleic acid value detection unit may detect an acid value of the raw material oil supplied from the raw material oil supply unit. The automatic control equipment is connected with the raw oil acid value detection unit, the viscosity-reducing cracking residual oil acid value detection unit, the raw oil supply unit and the gas-liquid separation unit, so that the temperature, pressure and other technological parameters of the gas-liquid separation unit can be adjusted in real time through the difference between the raw oil acid value and the viscosity-reducing cracking residual oil acid value.
In one embodiment, the acid value of the raw oil is first detected using a raw oil acid value detection unit. And then feeding the raw oil into a viscosity reducing cracking device for viscosity reducing cracking to obtain viscosity reducing cracking generated oil. And after the residue is discharged out of the visbreaking device through a visbreaking residue outlet, detecting the acid value of the visbreaking residue through a residue visbreaking oleic acid value detection unit arranged at the visbreaking residue outlet. The automatic control equipment receives the acid value of the raw oil and the acid value of the visbreaking residual oil, and the reduction rate of the visbreaking acid value of the raw material is calculated by the formula (1). When the automatic control equipment detects that the reduction rate of the acid value of the raw material viscosity-reducing cracking is lower than a set value, the automatic control equipment adjusts the feeding amount of the raw material into the viscosity-reducing cracking unit, so that after partial or all of the raw material oil flowing out of the raw material oil supply unit is subjected to gas-liquid separation by the gas-liquid separation unit, liquid separation obtained after separation is fed into the viscosity-reducing cracking device. The automatic control equipment receives the acid value of the raw oil measured by the raw oil acid value detection unit in real time while adjusting the feeding amount, and adjusts the proportion of the raw oil subjected to gas-liquid separation in real time by combining the acid value of the visbreaking residual oil measured by the visbreaking residual oil acid value detection unit, so that the reduction rate of the visbreaking acid value of the raw material after visbreaking is ensured to meet the requirement.
In another embodiment, the visbreaking unit is first fed with a pre-feed hot mixture to a gas-liquid separation unit where the hot mixture is separated into a liquid fraction and a gaseous fraction comprising water and light gas oil. Then, feeding the liquid separation product into an visbreaking unit for visbreaking to obtain visbroken product oil. And after the visbreaking residual oil is discharged from the visbreaking residual oil outlet, detecting the acid value of the visbreaking residual oil by an visbreaking residual oil acid value detection unit, and detecting the acid value of the raw oil by the raw oil acid value detection unit. The automatic control equipment receives the acid value of the raw oil and the acid value of the visbroken residual oil, and the acid value reduction rate is obtained through the calculation of the formula (1). When the automatic control device detects that the rate of decrease in acid value is below a set point, the temperature and pressure of the gas-liquid separation unit will be automatically adjusted to thereby adjust the amount of water and light gas oil separated from the feed stream. In the process of visbreaking, the automatic control equipment can regulate and control the temperature and pressure conditions of visbreaking to ensure that the acid value reduction rate is in a controllable range for visbreaking.
In other embodiments of the present application, the visbreaking apparatus further comprises a feedstock supply unit, and the visbreaking unit further comprises a first visbreaking unit and a second visbreaking unit, wherein the first visbreaking unit has a first feedstock inlet and a first visbreaking resid outlet; the second visbreaking unit is provided with a second raw oil inlet and a second visbreaking residual oil outlet. The raw material oil supply unit is respectively connected with the first raw material oil inlet and the second raw material oil inlet; the visbreaking residual acid value detection unit is used for detecting the acid value of visbreaking residual at the outlet of the first visbreaking residual and recording the acid value as a first acid value, and is used for detecting the acid value of visbreaking residual at the outlet of the second visbreaking residual and recording the acid value as a second acid value, wherein the visbreaking device is provided with an automatic control device, the automatic control device is connected with the raw oil supply unit, the raw oil acid value detection unit and the visbreaking residual acid value detection unit, the automatic control device receives the first acid value, the second acid value and the acid value of the raw oil, calculates the first acid value reduction rate and the second acid value reduction rate, and adjusts the feeding amount of the first visbreaking unit and/or the second visbreaking unit in real time according to the first acid value reduction rate and the second acid value reduction rate.
In some embodiments, the acid value of the raw oil supplied from the raw oil supply unit is first detected using a raw oil acid value detection unit. The feedstock is then fed to the first and second visbreaking units via the first and second feedstock inlets, respectively. And after the visbreaking is carried out in the first visbreaking unit and the second visbreaking unit respectively, obtaining the first visbreaking residual oil and the second visbreaking residual oil. And then leading the first visbreaking residual oil and the second visbreaking residual oil out of the first visbreaking unit and the second visbreaking unit through the first visbreaking residual oil outlet and the second visbreaking residual oil outlet respectively. In this embodiment, the first visbreaking unit is different from the second visbreaking unit in the number of trays, the opening ratio of the trays, and the like. After the obtained first visbreaking residual oil and second visbreaking residual oil are led out, the acidity of the first visbreaking residual oil is detected by using an visbreaking residual oil acid value detection unit and is marked as a first acid value, and the acidity of the second visbreaking residual oil is marked as a second acid value. The first acid value reduction rate and the second acid value reduction rate were calculated using the formula 1 described previously, respectively. As a result of comparing the first acid value reduction rate with the second acid value reduction rate, a large acid value reduction rate indicates that the same raw material is less back-mixed in the visbreaking unit, and thus the visbreaking unit is more suitable for such raw material. In some embodiments, the automatic control device will automatically adjust the feed supply to the first and second visbreaking units based on the comparison of the first and second acid number reduction rates, thereby selecting visbreaking units that are more suitable for the feed used.
In another exemplary embodiment of the present application, there is provided an visbreaking process, comprising: step S1, detecting the acid value of raw oil; s2, performing visbreaking on raw oil to obtain visbroken generated oil, and fractionating the visbroken generated oil to obtain visbroken residual oil; and step S3, detecting the acid value of the visbreaking residual oil, and calculating the acid value reduction rate.
Unlike the prior art method, in the case of using the method of the present application, the acid value of the raw oil is detected before the raw oil is subjected to the visbreaking, and the acid value of the resulting visbroken residue is also detected after the visbreaking and fractionation are performed. After the acid value detection, the acid value decrease rate after the visbreaking of the raw material can be calculated by the following formula:
Reduction rate of acid value= (acid value of raw oil-acid value of visbroken residue)/acid value of raw oil×100% (formula 1)
Through the above formula, the acid value reduction rate can be calculated, and experience shows that the acid value reduction rate is large, so that the back mixing degree of materials in the visbreaking device (such as a visbreaking tower) is small, and conversely, the acid value reduction rate is small, so that the back mixing degree of materials in the visbreaking device is large, the acid value reduction rate is close, the back mixing degree of two materials in the visbreaking device is equivalent, and the back mixing degree of materials in the same visbreaking device can be clearly reflected through the reduction rate
In further embodiments, the visbreaking process of the present application further comprises adjusting the pressure, temperature, and/or reaction time of the visbreaking unit based on the acid number reduction rate. After the acid value reduction rate is calculated by the formula (1), the pressure, temperature and/or reaction time of the visbreaker may be adjusted individually or simultaneously. The acid value of the raw oil and the acid value of the residual oil were measured at different pressures, temperatures and/or reaction times, and the reduction rate of the acid value was calculated. In the visbreaking process, the temperature, pressure and/or reaction time conditions of visbreaking can be regulated to ensure that the acid value reduction rate is in a controllable range for visbreaking. Under the process condition of the maximum acid value reduction rate, the materials in the viscosity reducing cracking device undergo back mixing to a smaller extent, so that the problem of excessive coking of the materials in the viscosity reducing cracking unit is effectively avoided.
In some embodiments of the present application, the feedstock of step S1 is a mixture of feedstock oils, and the visbreaking process of the present application further comprises adjusting the composition of the feedstock oil based on the acid value reduction rate. In one embodiment, the first feedstock may be mixed with the second feedstock prior to performing the visbreaking reaction, and the mixture may be subjected to the visbreaking reaction. And (3) detecting the acid value of the separated residual oil to obtain the acid value of the residual oil. The acid value reduction rate was calculated by mixing the acid value of the raw oil with the acid value of the residue. Based on the adjustment of the ratio of the first raw oil to the second raw oil, a plurality of sets of different acid value reduction rates are obtained. In the visbreaking process, the composition of the raw oil mixture subjected to visbreaking can be regulated so as to ensure that the acid value reduction rate is in a controllable range for visbreaking.
In other embodiments of the present application, the visbreaking process of the present application comprises subjecting a pre-feed hot mixture of feedstock oil to gas-liquid separation to obtain a gaseous separator and a liquid separator, and subjecting the liquid separator to visbreaking, based on the acid number reduction.
After the acid value of the raw oil and the acid value of the residual oil are measured, based on the acid value reduction rate, the hot mixture before the raw oil is fed may be first subjected to gas-liquid separation before the raw oil is subjected to visbreaking. Since water and light gas oils in the hot mix will cause severe back mixing in the visbreaking reaction, it is necessary to remove the water and light gas oils from the hot mix. In one embodiment, a portion or all of the hot mixture may be subjected to gas-liquid separation based on the rate of decrease in acid value. In some embodiments, after the gas-liquid separation, the liquid isolate is subjected to visbreaking. In other embodiments, after the gas-liquid separation, a portion of the feedstock oil that has not been subjected to the gas-liquid separation is mixed with the liquid separation and the mixture is visbroken. And carrying out gas-liquid separation on the raw oil with different proportions, measuring the acid value and calculating the reduction rate for a plurality of times, and obtaining the raw oil proportion with proper back mixing degree according to the comparison of the reduction rate.
In a further embodiment, the visbreaking process of the present application includes adjusting the temperature of the gas-liquid separation based on the acid value reduction rate. In embodiments in which gas-liquid separation is used to separate the entire hot mixture, the temperature of the gas-liquid separation may also be adjusted according to the acid value reduction rate. And (3) performing gas-liquid separation at the changed temperature to obtain liquid separated matters with different components. After visbreaking of the liquid separation, residuum is obtained. The acid value of the residue was measured, and the acid value decrease rate was calculated in combination with the acid value of the raw oil. The operations of temperature change, gas-liquid separation and visbreaking were repeated to obtain a plurality of values of the acid value reduction rate. And selecting a gas-liquid separation temperature capable of obtaining the maximum acid value reduction rate to perform gas-liquid separation, and then performing viscosity-reducing cracking. Under the process condition of the maximum acid value reduction rate, the materials in the viscosity-reducing cracking unit undergo back mixing to a smaller extent, so that the problem of excessive coking of the materials in the viscosity-reducing cracking unit is effectively avoided.
In a further embodiment of the application, the gaseous separation comprises water and light gas oil. Since gas-liquid separation separates the gaseous separation product containing water and light gas oil from the feedstock, the light gas oil and water components have been removed from the feedstock prior to visbreaking. In the subsequent visbreaking reaction, the reaction system does not contain light gas oil and water components, so that the visbreaking reaction can be carried out under higher severity, and the problem of excessive coking caused by material back mixing and material transitional reaction condensation due to the existence of water and light gas oil components is avoided. Therefore, in the visbreaking reaction, more severe reaction conditions can be adopted, so that the visbreaking of the heavy fuel oil components in the reaction is fully carried out, thereby improving the yield of the light distillate oil.
In some embodiments of the present application, step S2 includes subjecting the feedstock to visbreaking under first visbreaking conditions to obtain a first visbroken product oil, fractionating the first visbroken product oil to obtain a first visbroken residue, and subjecting the feedstock to visbreaking under second visbreaking conditions to obtain a second visbroken product oil, and fractionating the second visbroken product oil to obtain a second visbroken residue, wherein the first visbreaking conditions are different from the second visbreaking conditions. Step S3 comprises detecting the acid value of the first visbreaking residual oil and the acid value of the second visbreaking residual oil, calculating a first acid value reduction rate according to the acid value of the raw oil and the acid value of the first visbreaking residual oil, and calculating a second acid value reduction rate according to the acid value of the raw oil and the acid value of the second visbreaking residual oil. And the visbreaking process further comprises: and S4, selecting an visbreaking device according to the first acid value reduction rate and the second acid value reduction rate.
In the above examples, the acid numbers of the obtained visbroken residues were different due to the different visbreaking conditions employed. The first acid value reduction rate and the second acid value reduction rate were calculated by the formula 1 described previously, respectively. The comparison of the first acid value reduction rate and the second acid value reduction rate shows that a large acid value reduction rate indicates that the same feedstock is less backmixed under the visbreaking conditions, and thus the visbreaking conditions are more suitable for such feedstock. The visbreaking conditions in this example include the visbreaking apparatus used and the process conditions such as time, temperature and pressure for visbreaking.
In a preferred embodiment, the residuum obtained after visbreaking is a residuum obtained at a real boiling point distillation cut point at 410 ℃ to 430 ℃, and the acid value of the residuum obtained at the cut point can better reflect the back mixing condition in the visbreaking process, preferably, the residuum is a residuum obtained by cutting at 430 ℃.
In a further example, when the acid value of the raw oil is 1mgKOH/g or less, it is necessary to adjust the acid value of the raw oil to be more than 1mgKOH/g using a raw oil or residuum having a high acid value.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
The raw oil A and the raw oil B are used as raw oil, and the visbreaking reaction is respectively carried out under the same visbreaking condition.
The raw oil A is Liaohe super heavy oil, wherein the density of the raw oil at 20 ℃ is 1004.6kg/m 3, the kinematic viscosity at 100 ℃ is 905.6mm 2/s, the carbon residue is 13.72wt%, and the fraction content of the raw oil less than 165 ℃ is 0.01wt% and the fraction (residual oil) content of the raw oil greater than 350 ℃ is 91.1%. The residual oil yield is 75.03wt% at the temperature of more than 430 ℃.
Feedstock B is a vacuum residuum having a density of 986.2kg/m 3 at 20 ℃, a kinematic viscosity of 556.8mm 2/s at 100 ℃, a char of 11.77wt% and a residuum yield of 99.32wt% above 430 ℃.
The acid value of the raw oil A was first detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil A was 7.34mgKOH/g.
The raw oil A and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. The mixture was fed into a heating furnace (heating unit) for heating, wherein the outlet temperature of the heating furnace was 435 ℃. The heated material is fed into the visbreaking tower through a raw oil inlet arranged at the bottom of the visbreaking tower for visbreaking. The pressure of the visbreaking tower is 1.0MPa, and the retention time of the materials in the visbreaking device is 50 minutes. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbreaking residual oil is detected to be 3.2mgKOH/g by an visbreaking residual oil acid value detection unit.
The acid value of the raw oil B was detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil B was 1.56mgKOH/g.
The raw oil B and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. The mixture was fed into a heating furnace (heating unit) for heating, wherein the outlet temperature of the heating furnace was 435 ℃. The heated material is fed into the visbreaking tower through a raw oil inlet arranged at the bottom of the visbreaking tower for visbreaking. The pressure of the visbreaking tower is 1.0MPa, and the retention time of the materials in the visbreaking device is 50 minutes. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbroken residue obtained by detection through the visbroken residue acid value detection unit is 0.18mgKOH/g.
The acid value reduction rates of the raw oil a and the raw oil B were calculated by the acid value reduction rate= (raw oil acid value-visbroken residue acid value)/raw oil acid value×100%.
The acid value reduction rate of the visbreaking of the raw material A is= (7.34-3.20)/7.34 multiplied by 100% = 56.4%.
The reduction rate of the acid value of the visbreaking of the raw material B is= (1.56-0.18)/1.56 multiplied by 100% = 88.5%.
Because the reduction rate of the visbreaking acid value of the raw material A is lower than that of the visbreaking acid value of the raw material B, the raw material B has smaller back mixing degree than the raw material A under the same visbreaking condition in the same visbreaking tower, and the materials react more uniformly in the visbreaking reaction tower.
Example 2
The feedstock oil a was used as a feedstock oil, and the visbreaking reactions were performed under different visbreaking conditions (method 1 and method 2), respectively.
The raw oil A is Liaohe super heavy oil, wherein the density of the raw oil at 20 ℃ is 1004.6kg/m 3, the kinematic viscosity at 100 ℃ is 905.6mm 2/s, the carbon residue is 13.72wt%, and the fraction content of the raw oil less than 165 ℃ is 0.01wt% and the fraction (residual oil) content of the raw oil greater than 350 ℃ is 91.1%. The residual oil yield is 75.03wt% at the temperature of more than 430 ℃.
Method 1:
the acid value of the raw oil A was first detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil A was 7.34mgKOH/g.
The raw oil A and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. The mixture was fed into a heating furnace (heating unit) for heating, wherein the outlet temperature of the heating furnace was 435 ℃. The heated material is fed into the visbreaking tower through a raw oil inlet arranged at the bottom of the visbreaking tower for visbreaking. The pressure of the visbreaking tower is 1.0MPa, and the retention time of the materials in the visbreaking device is 50 minutes. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbroken residue obtained by detection through the visbroken residue acid value detection unit is 3.20mgKOH/g. The toluene insoluble (coke) content of the visbreaking oil was determined to be 0.58wt%.
Method 2:
the acid value of the raw oil A was first detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil A was 7.34mgKOH/g.
The raw oil A and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. The mixture is fed into a heating furnace (heating unit) for heating, the heated material is led into a gas-liquid separation tank (gas-liquid separation unit), water and light gas oil are separated and flow out from the outlet at the top of the gas-liquid separation tank, the light gas oil is obtained through condensation, and the temperature of a liquid phase part is 435 ℃. The liquid phase part obtained by gas-liquid separation is fed into the visbreaking tower through a raw oil inlet arranged at the bottom of the visbreaking tower for visbreaking. The pressure of the visbreaking tower is 1.0MPa, and the retention time of the materials in the visbreaking device is 50 minutes. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbroken residue obtained by detection through the visbroken residue acid value detection unit is 0.28mgKOH/g. The toluene insoluble matter (coke) content of the oil blend of the visbreaking product oil and the light gas oil was determined to be 0.17wt%.
The acid value reduction rate of the visbroken resid was obtained by subjecting method 1 and method 2 to calculation of the acid value reduction rate= (acid value of the raw oil-acid value of the visbroken resid)/acid value of the raw oil x 100%.
The reduction rate of the visbreaking acid value of the method 1 is = (7.34-3.20)/7.34×100% = 55.85%.
Method 2 the reduction rate of the visbreaking acid value is = (7.38-0.28)/7.34×100% = 96.7%.
Because the reduction rate of the visbreaking acid value of the method 1 is lower than that of the method 2, the method 2 has smaller back mixing degree than the method 1 under the same visbreaking condition in the same visbreaking tower, and the materials react more uniformly in the visbreaking reaction tower.
As can be seen from the comparison of the toluene insoluble (coke) content of the two-process visbreaking product oil and the toluene insoluble (coke) content of the visbreaking product oil and the light gas oil mixed oil, the toluene insoluble (coke) content of the visbreaking product of method 2 is significantly reduced, the degree of back mixing is smaller, and the materials react more uniformly in the visbreaking reaction tower than that of the visbreaking product of method 1.
Example 3
The feedstock oil B was used as a feedstock oil, and the visbreaking reactions were performed under different visbreaking conditions (method 1 and method 2), respectively.
The raw oil B is vacuum residue, wherein the density of the raw oil at 20 ℃ is 986.2kg/m 3, the kinematic viscosity at 100 ℃ is 556.8mm 2/s, the carbon residue is 11.77wt%, and the residue yield is 99.32wt% at more than 430 ℃.
Method 1:
The acid value of the raw oil B was first detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil B was 1.56mgKOH/g.
The raw oil B and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. The mixture was fed into a heating furnace (heating unit) for heating, wherein the outlet temperature of the heating furnace was 435 ℃. The heated material is fed into the visbreaking tower through a raw oil inlet arranged at the bottom of the visbreaking tower for visbreaking. The pressure of the visbreaking tower is 1.0MPa, and the retention time of the materials in the visbreaking device is 50 minutes. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbroken residue obtained by detection through the visbroken residue acid value detection unit is 0.18mgKOH/g.
Method 2:
The acid value of the raw oil B was first detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil B was 1.56mgKOH/g.
The raw oil B and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. Feeding the mixture into a heating furnace (heating unit) for heating, introducing the heated material into a gas-liquid separation tank (gas-liquid separation unit), separating water and light gas oil from an outlet at the top of the gas-liquid separation tank, and condensing to obtain light gas oil; the liquid phase portion temperature was 435 ℃. The liquid phase part obtained by gas-liquid separation is fed into the visbreaking tower through a raw oil inlet arranged at the bottom of the visbreaking tower for visbreaking. The pressure of the visbreaking tower is 1.0MPa, and the retention time of the materials in the visbreaking device is 50 minutes. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbreaking residual oil is detected to be 0.04mgKOH/g by an visbreaking residual oil acid value detection unit.
The acid value reduction rate of the visbroken resid was obtained by subjecting method 1 and method 2 to calculation of the acid value reduction rate= (acid value of the raw oil-acid value of the visbroken resid)/acid value of the raw oil x 100%.
Method 1 the reduction rate of the visbreaking acid value is = (1.56-0.18)/1.56×100% = 88.5%.
Method 2 the reduction rate of the visbreaking acid value is = (1.56-0.04)/1.56×100% = 97.4%.
Because the reduction rate of the visbreaking acid value of the method 1 is lower than that of the method 2, the method 2 has smaller back mixing degree than the method 1 under the same visbreaking condition in the same visbreaking tower, and the materials react more uniformly in the visbreaking reaction tower.
Example 4
The raw oil B and the raw oil C are used as raw oil, and the visbreaking reaction is respectively carried out under the same visbreaking condition.
Feedstock B is a vacuum residuum having a density of 986.2kg/m 3 at 20 ℃, a kinematic viscosity of 556.8mm 2/s at 100 ℃, a char of 11.77wt% and a residuum yield of 99.32wt% above 430 ℃.
Feedstock C is a vacuum residuum having a feedstock oil density of 932.6kg/m 3 at 20 ℃, a kinematic viscosity of 234.2mm 2/s at 100 ℃ and a char residue of 6.59 wt.%.
The acid value of the raw oil B was first detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil B was 1.56mgKOH/g.
The raw oil B and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. The mixture was fed into a heating furnace (heating unit) for heating, wherein the outlet temperature of the heating furnace was 435 ℃. The heated material is fed into the visbreaking tower through a raw oil inlet arranged at the bottom of the visbreaking tower for visbreaking. The pressure of the visbreaking tower is 1.0MPa, and the retention time of the materials in the visbreaking device is 50 minutes. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbroken residue obtained by detection through the visbroken residue acid value detection unit is 0.33mgKOH/g.
The acid value of the raw oil C was detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil C was 0.25mgKOH/g. Since the acid value of the raw oil C is 1mgKOH/g or less, a vacuum residue D having a density of 1062.9kg/m 3 at 20℃and a kinematic viscosity of 1234.8mm 2/s at 100℃, carbon residue of 16.36wt% and an acid value of 12.5mgKOH/g is added to the raw oil C. The obtained mixture of the raw oil C and the raw oil D is mixed high-acid residual oil. The acid value of the mixed high-acid residue was detected by using a raw material oleic acid value detection unit, and the acid value of the obtained mixed high-acid residue was 2.2mgKOH/g.
Mixing the high acid residuum with the water mixture to form a mixture wherein the weight ratio of water to feedstock is 0.5:100. The mixture was fed into a heating furnace (heating unit) for heating, wherein the outlet temperature of the heating furnace was 435 ℃. The heated material is fed into the visbreaking tower through a raw oil inlet arranged at the bottom of the visbreaking tower for visbreaking. The pressure of the visbreaking tower is 1.0MPa, and the retention time of the materials in the visbreaking device is 50 minutes. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbreaking residual oil is detected to be 0.95mgKOH/g by an visbreaking residual oil acid value detection unit.
The acid value reduction rates of the raw oil a and the raw oil B were calculated by the acid value reduction rate= (raw oil acid value-visbroken residue acid value)/raw oil acid value×100%.
The reduction rate of the acid value of the visbreaking of the raw material B is= (1.56-0.33)/1.56 multiplied by 100% = 78.8%.
The reduction rate of the visbreaking acid value of the mixed high acid sludge oil is = (2.2-0.95)/2.2X100% = 56.8%.
Because the reduction rate of the visbreaking acid value of the mixed high acid residue oil is lower than that of the raw material B, the raw material B has smaller back mixing degree than the mixed high acid residue oil under the same visbreaking condition in the same visbreaking tower, and the materials react more uniformly in the visbreaking reaction tower.
Example 5
The feedstock oil B was used as a feedstock oil, and the visbreaking reactions were performed under different visbreaking apparatuses (apparatus 1 and apparatus 2), respectively, in which apparatus 1 corresponds to method 1 and apparatus 2 corresponds to method 2.
Feedstock B is a vacuum residuum having a density of 986.2kg/m 3 at 20 ℃, a kinematic viscosity of 556.8mm 2/s at 100 ℃, a char of 11.77wt% and a residuum yield of 99.32wt% above 430 ℃.
Method 1:
The acid value of the raw oil B was first detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil B was 1.56mgKOH/g.
The raw oil B and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. The mixture was fed into a heating furnace (heating unit) for heating, wherein the outlet temperature of the heating furnace was 435 ℃. The heated material is fed into the visbreaking tower 1 through a raw oil inlet arranged at the bottom of the visbreaking tower 1 for visbreaking. The pressure of the visbreaking tower 1 is 1.0MPa, the retention time of materials in the visbreaking device is 50 minutes, three sieve plates are arranged in the visbreaking tower 1, and the aperture ratio of each sieve plate is 10%. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower 1. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbroken residue obtained by detection through the visbroken residue acid value detection unit is 0.83mgKOH/g.
Method 2:
The acid value of the raw oil B was first detected by using a raw oil acid value detecting unit, and the acid value of the obtained raw oil B was 1.56mgKOH/g.
The raw oil B and the water mixture are formed into a mixture, wherein the weight ratio of water to raw oil is 0.5:100. The mixture was fed into a heating furnace (heating unit) for heating, wherein the outlet temperature of the heating furnace was 435 ℃. The heated material is fed into the visbreaking tower 2 through a raw oil inlet arranged at the bottom of the visbreaking tower 2 for visbreaking. The pressure of the visbreaking tower 2 is 1.0MPa, the retention time of materials in the visbreaking device is 50 minutes, six sieve plates are arranged in the visbreaking tower 2, and the opening ratio of the sieve plates of the visbreaking tower is 10%, 12%, 15%, 16%, 18% and 20% from bottom to top. After the visbreaking treatment, visbreaking-produced oil is discharged through an outlet provided at the bottom of the visbreaking tower 2. The visbroken product oil is then fractionated through a fractionating column, wherein a visbroken resid having a cut greater than 430 ℃ is obtained at the bottom outlet of the fractionating column.
The acid value of the visbroken residue obtained by detection through the visbroken residue acid value detection unit is 0.42mgKOH/g.
The acid value reduction rate of the visbroken resid was obtained by subjecting method 1 and method 2 to calculation of the acid value reduction rate= (acid value of the raw oil-acid value of the visbroken resid)/acid value of the raw oil x 100%.
The reduction rate of the visbreaking acid value of the method 1 is = (1.56-0.83)/1.56×100% = 46.8%.
Method 2 the reduction rate of the visbreaking acid value is = (1.56-0.42)/1.56×100% = 73.1%.
Because the reduction rate of the visbreaking acid value of the method 1 is lower than that of the method 2, the method 2 has smaller back mixing degree than the method 1 under the same visbreaking condition in the same visbreaking tower, and the materials react more uniformly in the visbreaking reaction tower.
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:
In the case of using the visbreaking apparatus and the visbreaking method of the present application, the degree of back mixing of the materials in the visbreaking tower can be clearly reflected by measurement of the acid values of the raw materials and the produced resid and calculation of the acid value reduction rate. And based on the acid value reduction rate, the structure and process parameters of the visbreaking tower can be adjusted to ensure that the visbreaking process is operated at high severity, thereby exerting the best performance of the visbreaking process.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. A method of assessing the degree of back mixing of materials in an visbreaker, the visbreaker comprising:
the viscosity reducing cracking unit is provided with a raw oil inlet and a viscosity reducing cracking residual oil outlet;
a raw oil acid value detection unit for detecting an acid value of the raw oil; and
An acid value detection unit of the visbreaking residual oil is used for detecting the acid value of the visbreaking residual oil,
The automatic control equipment is connected with the raw oil acid value detection unit, the visbreaking residual oil acid value detection unit, the pressure controller and the temperature controller; the automatic control device receives the acid value of the raw oil and the acid value of the visbreaking residual oil and calculates the acid value reduction rate, the automatic control device adjusts the pressure controller and the temperature controller of the visbreaking unit in real time according to the acid value reduction rate, and
The visbreaking device further comprises a first raw oil supply unit and a second raw oil supply unit, wherein the raw oil inlets are respectively connected with the first raw oil supply unit and the second raw oil supply unit; the automatic control equipment is connected with the first raw oil supply unit and the second raw oil supply unit, receives the acid value of the visbreaking residual oil and the acid value of the raw oil, adjusts the feeding amount of the first raw oil supply unit and/or the second raw oil supply unit in real time according to the acid value reduction rate,
Wherein the acid value decrease rate is calculated by the following formula:
Acid value reduction rate = (acid value of raw oil-acid value of visbreaking residual oil)/acid value of raw oil x 100% (1),
The high acid value reduction rate indicates that the back mixing degree of the materials in the viscosity reducing cracking device is small, the low acid value reduction rate indicates that the back mixing degree of the materials in the viscosity reducing cracking device is large,
And wherein the visbreaking residual oil is obtained by performing true boiling point distillation on visbreaking generated oil to obtain residual oil with the temperature of more than 430 ℃.
2. The method of claim 1, wherein the visbreaking unit further comprises:
the gas-liquid separation unit is provided with a raw material inlet and a liquid separator outlet, the liquid separator outlet is connected with the raw material oil inlet of the viscosity reducing cracking unit, and the gas-liquid separation unit is used for performing gas-liquid separation on the raw material oil to obtain a gaseous separator and a liquid separator, and the gaseous separator comprises water and light gas oil;
A raw oil supply unit connected with the raw oil inlet of the gas-liquid separation unit and the raw oil inlet of the visbreaking unit respectively,
The automatic control equipment is connected with the raw oil acid value detection unit, the visbreaking residual oil acid value detection unit, the raw oil supply unit and the gas-liquid separation unit, receives the acid value of the visbreaking residual oil and the acid value of the raw oil, calculates the acid value reduction rate, and adjusts the feeding amount of the gas-liquid separation unit and/or the visbreaking unit and/or the temperature of the gas-liquid separation unit in real time according to the acid value reduction rate.
3. The method of claim 1, wherein the visbreaking unit further comprises a feedstock supply unit, the visbreaking unit further comprising:
The first visbreaking unit is provided with a first raw oil inlet and a first visbreaking residual oil outlet;
The second visbreaking unit is provided with a second raw oil inlet and a second visbreaking residual oil outlet, and the raw oil supply unit is respectively connected with the first raw oil inlet and the second raw oil inlet;
The acid value detection unit of the visbreaking residual oil is used for detecting the acid value of the visbreaking residual oil at the outlet of the first visbreaking residual oil and recording the acid value as a first acid value, and is used for detecting the acid value of the visbreaking residual oil at the outlet of the second visbreaking residual oil and recording the acid value as a second acid value,
The automatic control device is connected with the raw oil supply unit, the raw oil acid value detection unit and the visbreaking residual oil acid value detection unit, receives the first acid value, the second acid value and the acid value of the raw oil, calculates a first acid value reduction rate and a second acid value reduction rate, and adjusts the feeding amount of the first visbreaking unit and/or the second visbreaking unit in real time according to the first acid value reduction rate and the second acid value reduction rate.
4. An visbreaking process comprising:
Step S1, detecting the acid value of raw oil;
S2, performing viscosity reduction cracking on the raw oil to obtain viscosity reduction cracking generated oil, and fractionating the viscosity reduction cracking generated oil to obtain viscosity reduction cracking residual oil; and
S3, detecting the acid value of the visbreaking residual oil, calculating the acid value reduction rate,
Wherein the pressure and/or temperature of the visbreaking is adjusted based on the acid value reduction rate; and the raw oil of the step S1 is a mixture of a plurality of raw oils, the visbreaking method further comprises adjusting the composition of the raw oil based on the acid value reduction rate,
Wherein the acid value decrease rate is calculated by the following formula:
Acid value reduction rate = (acid value of raw oil-acid value of visbreaking residual oil)/acid value of raw oil x 100% (1),
The high acid value reduction rate shows that the back mixing degree of the materials in the visbreaking is small, the low acid value reduction rate shows that the back mixing degree of the materials in the visbreaking is large,
And wherein the visbreaking residual oil is obtained by performing true boiling point distillation on the visbreaking generated oil to obtain residual oil with the temperature of more than 430 ℃.
5. The visbreaking process according to claim 4, further comprising:
And according to the acid value reduction rate, carrying out gas-liquid separation on the hot mixture before feeding the raw oil to obtain a gaseous separated product and a liquid separated product, and carrying out viscosity reduction cracking on the liquid separated product.
6. The visbreaking method according to claim 5, wherein the temperature of the gas-liquid separation is adjusted according to the acid value decrease rate.
7. The visbreaking process of claim 5, wherein the gaseous isolate comprises water and light gas oil.
8. The visbreaking process according to claim 4, wherein,
The step S2 comprises the steps of performing visbreaking on the raw oil under a first visbreaking condition to obtain first visbreaking product oil, fractionating the first visbreaking product oil to obtain first visbreaking residual oil, performing visbreaking on the raw oil under a second visbreaking condition to obtain second visbreaking product oil, and fractionating the second visbreaking product oil to obtain second visbreaking residual oil, wherein the first visbreaking condition is different from the second visbreaking condition;
The step S3 comprises detecting the acid value of the first visbreaking residual oil and the acid value of the second visbreaking residual oil, calculating a first acid value reduction rate according to the acid value of the raw oil and the acid value of the first visbreaking residual oil, and calculating a second acid value reduction rate according to the acid value of the raw oil and the acid value of the second visbreaking residual oil;
and wherein the visbreaking process further comprises: and S4, selecting visbreaking conditions according to the first acid value reduction rate and the second acid value reduction rate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200139A (en) * | 1995-10-20 | 1998-11-25 | 埃克森研究工程公司 | Viscosity reduction by heat soak-induced naphthenic acid decomposition in hydrocarbon oils |
| CN1814704A (en) * | 2005-01-31 | 2006-08-09 | 中国石油化工股份有限公司 | Method for deeply removing petroleum acids from acid-contained raw oil |
| CN206184388U (en) * | 2016-11-01 | 2017-05-24 | 中石化广州工程有限公司 | Raw oil proportion blending feeding system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200139A (en) * | 1995-10-20 | 1998-11-25 | 埃克森研究工程公司 | Viscosity reduction by heat soak-induced naphthenic acid decomposition in hydrocarbon oils |
| CN1814704A (en) * | 2005-01-31 | 2006-08-09 | 中国石油化工股份有限公司 | Method for deeply removing petroleum acids from acid-contained raw oil |
| CN206184388U (en) * | 2016-11-01 | 2017-05-24 | 中石化广州工程有限公司 | Raw oil proportion blending feeding system |
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