CN110882674A - Coupling reaction separation and absorption supergravity sulfonate continuous production system and method - Google Patents
Coupling reaction separation and absorption supergravity sulfonate continuous production system and method Download PDFInfo
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- CN110882674A CN110882674A CN201910968932.8A CN201910968932A CN110882674A CN 110882674 A CN110882674 A CN 110882674A CN 201910968932 A CN201910968932 A CN 201910968932A CN 110882674 A CN110882674 A CN 110882674A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/28—Moving reactors, e.g. rotary drums
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
Abstract
The invention provides a system and a method for continuously producing hypergravity sulfonate by coupling reaction separation and absorption. According to the invention, the surfaces of the cutting raw oil of the supergravity device, which are liquid films and liquid drops, are set to be oleophobic structures, when the supergravity device works, the cutting of the raw oil can not cause the raw oil to be adhered to the surfaces of the cutting raw oil, so that when the supergravity device is applied, the problem that the local concentration is unbalanced because the raw oil is adhered to the surfaces of the cutting raw oil and the local concentration of the raw oil is higher near the surfaces of the cutting raw oil can not be caused, the problem that the sulfonation reaction time is too long because the raw oil is adhered to the surfaces of the cutting raw oil and the sulfur trioxide are too long in contact time can be avoided, the coking problem caused by too high local concentration, too strong reaction and too long reaction time in the petroleum sulfonation process can be effectively.
Description
Technical Field
The invention relates to the technical field of petroleum collection. And more particularly to a system and method for continuous production of supergravity sulfonate by coupling reaction separation and absorption.
Background
The sulfonate is a basic chemical for oil extraction, can improve the recovery ratio of tertiary oil recovery of an oil field by 7-28%, and the domestic market demand is estimated to be 150 ten thousand tons/year, but because the prior production process has the series problems of low utilization rate of a sulfonating agent, low sulfonation efficiency, three wastes, difficult continuous production, potential safety hazard and the like, the national productivity is less than 15 ten thousand tons/year, and the gap is huge. Therefore, the development of a green, safe and efficient sulfonate production technology is the key to realizing the stable yield of the oil field in China.
The sulfonate is produced mainly by liquid-phase kettle type sulfonation technology and gas-phase membrane type sulfonation technology. As the liquid phase sulfonation reaction is a rapid exothermic reaction, in the traditional stirred tank, due to the limitation of mixing and transfer, the distribution of reactants is uneven, side reactions are easy to occur, and the problems of over-sulfonation, coking, difficult amplification and the like exist. In addition, the liquid phase sulfonation needs to introduce an organic solvent, which causes the problems of long production process, high production cost, harsh production condition requirements and the like. The gas-phase membrane type sulfonation reaction process is favored because of simple and safe process. In the membrane reactor, however, the raw material flows from top to bottom along the reaction tube under the action of gravity and contacts with the gas-phase sulfur trioxide sulfonating agent in a parallel flow manner, the viscosity of the liquid phase increases in hundreds of times along with the reaction, the transfer in the liquid phase is limited, and the phenomena of over-sulfonation, coking and the like easily occur; meanwhile, because the utilization rate of the gas-phase sulfur trioxide is low, a large amount of waste acid and sulfite solution are generated in the post-treatment process. Only take the gas-phase membrane sulfonation production line of 5000 tons/year produced by Daqing refining company as an example, the production amount of waste acid and waste oil exceeds 4000 tons/year, because of reactor coking, the production needs to be stopped and cleaned once every 5 days, the continuous production is seriously influenced, and the potential safety hazard exists, thus limiting the popularization and the application of the process.
Aiming at the problems of over sulfonation, easy coking, large waste acid and waste oil discharge and the like in the industrial production process of sulfonate, a system and a method for continuously producing the hypergravity sulfonate by coupling reaction separation and absorption are urgently needed.
Disclosure of Invention
The invention provides a supergravity sulfonate continuous production system and a supergravity sulfonate continuous production method for coupling reaction separation and absorption, aiming at solving at least one of the problems of over-sulfonation, easy coking, large waste acid and waste oil discharge amount and the like in the industrial production process of the existing sulfonate.
In certain embodiments, a coupled reaction separation and absorption hypergravity sulfonate continuous production system comprises a hypergravity sulfonation reaction unit and a tail gas absorption unit;
the hypergravity sulfonation reaction unit comprises a hypergravity sulfonation device and an aging device,
raw oil and sulfur trioxide gas can be introduced into the hypergravity sulfonation device to carry out sulfonation reaction, and the aging device is communicated with the hypergravity sulfonation device, so that a sulfonated crude product can be introduced into the aging device to be aged;
the tail gas absorption unit is used for absorbing sulfur-containing tail gas discharged when the hypergravity sulfonation reaction unit works;
the surface of the hypergravity sulfonation device used for cutting the raw oil into liquid films or liquid drops is of an oleophobic structure.
In certain embodiments, the supergravity sulfonation device is a stator-rotor supergravity reactor, the surfaces of the stator columns and the rotor columns of the stator-rotor supergravity reactor form an oleophobic structure; alternatively, the first and second electrodes may be,
the hypergravity sulfonation device is a packing type rotary packed bed, and the surface of the packing type rotary packed bed, which is contacted with the raw oil, forms an oleophobic structure.
In certain embodiments, the oleophobic structure is a depression having a plurality of micro-nano dimensions, the depression formed by laser etching on its surface; alternatively, the first and second electrodes may be,
the oleophobic structure is a material modification layer covered on the surface of the oleophobic structure, and the surface energy of the surface of the hypergravity sulfonation device used for cutting the raw oil into liquid films or liquid drops when the material modification layer is not covered is higher than that of the material modification layer.
In some embodiments, the depressions are pits or stripes.
In certain embodiments, the tail gas absorption unit comprises:
a sulfur trioxide absorption device, a sulfur dioxide absorption device and a chemical fertilizer generation device;
sulfur trioxide absorbing device can let in the sulfur trioxide in the alkylbenzene absorption tail gas, sulfur dioxide absorbing device can let in the sulfur dioxide in the ammonia oil absorption tail gas, the chemical fertilizer generates the device and utilizes the ammonium sulfate solution that forms behind the sulfur dioxide in the ammonia oil absorption tail gas generates the chemical fertilizer.
In certain embodiments, a continuous production process utilizing the above system comprises:
raw oil and sulfur trioxide gas are introduced into a hypergravity sulfonation device;
introducing a sulfonated crude product generated after reaction in a hypergravity sulfonation device into an aging device for aging reaction, wherein after the aging reaction, the sulfonated crude product forms a sulfonated product positioned on an upper layer and an unsulfonated finished product positioned on a lower layer;
pumping out the aged product after the preset time, adding alkali liquor for neutralization, cooling, collecting the aged sulfonated product, and pumping the unaged product into the aging device again;
and absorbing sulfur-containing tail gas discharged by the supergravity sulfonation reaction unit during working by using a tail gas absorption unit.
In certain embodiments, the absorbing sulfur-containing tail gas discharged from the supergravity sulfonation reaction unit during operation by using a tail gas absorption unit comprises:
absorbing sulfur trioxide in the tail gas by alkylbenzene through a sulfur trioxide absorption device;
absorbing sulfur dioxide in the tail gas by ammonia oil through a sulfur dioxide absorption device;
and (3) generating a chemical fertilizer by using an ammonium sulfate solution formed after the ammonia oil absorbs sulfur dioxide in the tail gas through a chemical fertilizer generating device.
In certain embodiments, a supergravity device, comprising:
a housing;
the liquid distributor is positioned in a reaction cavity formed by the shell and used for spraying the raw oil to the surface of the device used for cutting the raw oil into liquid films or liquid drops;
the cutting assembly is positioned in a reaction cavity formed by the shell and arranged around the liquid distributor, and comprises a surface used for cutting the raw oil into liquid films or liquid drops;
wherein, the surface for cutting the raw oil into liquid films or liquid drops is of an oleophobic structure.
In certain embodiments, the apparatus is a stator-rotor hypergravity reactor, the cutting assembly comprising a stator post and a rotor post of the stator-rotor hypergravity reactor; the surfaces of a stator column and a rotor column of the stator-rotor supergravity reactor form an oleophobic structure; alternatively, the first and second electrodes may be,
the device is a packed rotary packed bed, and the cutting assembly comprises the packing; and an oleophobic structure is formed on the surface of the filler contacted with the raw oil.
In certain embodiments, the oleophobic structure is a depression having a plurality of micro-nano dimensions, the depression formed by laser etching on its surface; alternatively, the first and second electrodes may be,
the oleophobic structure is a material modification layer covered on the surface of the oleophobic structure, and the surface energy of the surface for cutting the raw oil into liquid films or liquid drops when the material modification layer is not covered is higher than that of the material modification layer.
The invention has the following beneficial effects:
the invention provides a system and a method for continuously producing hypergravity sulfonate by coupling reaction separation and absorption, the surface of the cutting raw oil of the hypergravity device, which is a liquid film and liquid drops, is set to be an oleophobic structure, thus, when the hypergravity device works, the raw oil is cut without causing the raw oil to adhere to the surface of the hypergravity device, thereby avoiding the problems that the local concentration of the raw oil is unbalanced because the raw oil is adhered to the surface of the device and the local concentration of the raw oil is higher as the distance from the surface is closer, and can avoid the problem that the sulfonation reaction time is too long due to the fact that the raw oil is adhered to the surface of the raw oil and the contact time with sulfur trioxide is too long, further effectively avoiding the coking problem caused by overlarge local concentration, over-strong reaction and overlong reaction time in the petroleum sulfonation process, thereby being suitable for continuous long-time production of petroleum sulfonation and the like which needs to be carried out by the participation of raw oil in the reaction.
Further, in a preferred technical scheme, the tail gas absorption unit in the continuous production system adopts a supergravity desulfurization device and a fertilizer generation device, and absorption liquid circulating in the supergravity device is ammonia oil solution, so that the absorption liquid can form ammonium sulfate solution after absorbing tail gas, and further can generate fertilizer required by industry and agriculture by combining with the fertilizer generation device, so that the whole continuous production system cannot generate any pollution.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a schematic structural diagram of a packed rotating bed as a supergravity device in an embodiment of the present invention.
Figure 2 shows one of the simplified schematic diagrams of the packing of figure 1.
Figure 3 shows a second simplified schematic of the packing of figure 1.
Fig. 4 shows a schematic diagram of the process of cutting raw oil into liquid drops or liquid films by filler through the filler.
Fig. 5 shows a schematic surface structure of the filler in the embodiment of the present invention.
FIG. 6 is a graph showing results of oleophobic structures in tests for oleophobic characterization in embodiments of the invention.
FIG. 7 shows a schematic configuration of a coupled reaction separation and absorption supergravity sulfonate continuous production system in an embodiment of the present invention.
FIG. 8 shows a schematic flow diagram of a process for the continuous production of a hypergravity sulfonate by coupled reaction separation and absorption in an embodiment of the invention.
Fig. 9 shows a detailed flowchart of step S4 in fig. 8.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
At present, such as preparation of sulfonate, etc., a liquid phase is raw oil or a mixture of raw oil and other reactants, taking preparation of sulfonate as an example, the current mature technologies include a liquid-phase kettle type sulfonation technology and a gas-phase membrane type sulfonation technology, the current sulfonation technology cannot solve the problems of over-sulfonation, etc., and in addition, the current sulfonation technology cannot be used for long-time continuous production due to the over-sulfonation problem. Further, no petroleum sulfonation system with near zero emission has emerged at present.
A first aspect of the present invention provides a supergravity apparatus comprising: a housing; the liquid distributor is positioned in a reaction cavity formed by the shell and used for spraying the raw oil to the surface of the device used for cutting the raw oil into liquid films or liquid drops; the cutting assembly is positioned in a reaction cavity formed by the shell and arranged around the liquid distributor, and comprises a surface used for cutting the raw oil into liquid films or liquid drops; wherein, the surface for cutting the raw oil into liquid films or liquid drops is of an oleophobic structure.
Please refer to the schematic structural diagram of the supergravity device shown in fig. 1, which includes a liquid distributor 1, a liquid distributor 2, a liquid outlet 3, a gas inlet 4, a filler 5, a housing 6, and a rotating motor 7. Wherein, liquid distributor 1 and liquid distributor 2 extend to in the cavity that the filler surrounds, set up the aperture on the liquid distributor, can spray liquid to on the filler, reaction solution is gone into the hypergravity device from two liquid distributors by the cutting on the filler into liquid drop or liquid film from this, reaction gas gets into the hypergravity device through gas inlet 4, and then with liquid intensive mixing, under the rotation of rotating electrical machines 7, drive the filler and rotate, thereby produce huge centrifugal force and make by the liquid drop or the liquid film of cutting throw away outside the filler, flow out through liquid outlet 3 again.
It should be noted that, when the reaction is required to be continued, the liquid flowing out from the liquid outlet 3 of the supergravity device is pumped into the supergravity device again through the liquid distributor to be circulated. When premixing is required, the liquid flowing out of the liquid outlet 3 by the supergravity device is not circulated, and the invention is not limited to this.
In addition, FIG. 1 shows a two-feed high gravity rotating packed bed with no pre-mixing zone between the liquid distributor 1 and the liquid distributor 2, i.e. before the two reactants enter the packing 5 inside, they are sprayed separately to the packing without pre-mixing, and mix and react in the packing.
Further, in other embodiments, only one of the liquid distributors 1 and 2 shown in fig. 1 may be provided, and only one of the reaction solutions needs to be pumped as required, for example, for the reaction of a single reaction solution and gas, so that the reaction solution may be pumped alternatively, or only one liquid distributor may be provided, but the present invention is not limited thereto.
In addition, the supergravity device in the present invention is not limited to a liquid-liquid reaction or a gas-liquid reaction, and it should be understood that, as to whether the supergravity reaction is a liquid-liquid reaction system or a gas-liquid reaction system, if the liquid therein is the feedstock oil with too high viscosity, no matter the liquid-liquid reaction system or the liquid-liquid reaction system, the core concept of the present invention is not affected.
The embodiment in fig. 1 is a super-gravity rotating packed bed, the cutting component is the packing 5 in the super-gravity rotating packed bed, and the surface for cutting the raw oil into liquid films or liquid drops is the surface of the packing 5. The filler 5 may be a wire mesh filler, or a filler such as polytetrafluoroethylene.
The following description will be made with reference to fig. 2 to 6.
Fig. 2 shows one of the simplified schematic diagrams of a packing, and fig. 3 shows a left side view of fig. 2. It will be appreciated that the packing 5 is stacked in layers. After the raw oil is sprayed to the inner cavity of the filler by the liquid distributor, the filler 5 rotates along with the rotating motor, so that the raw oil is cut layer by layer. As can be known by combining the figure 4, a plurality of small droplets are formed after the raw oil liquid is cut by the i-2 layers of fillers, part of the small droplets are converged into large droplets again in the gap between the i-1 th layer and the i-th layer, and the large droplets are cut into small droplets again through the i-th layer, so that the mass transfer effect of the whole system is improved through the cutting of a plurality of layers.
In this example, the surface of the filler in contact with the stock oil had an oil-repellent structure. When the supergravity device works, petroleum sulfonation is taken as an example, raw oil is not adhered to the surface of the cutting device by cutting, so that when the supergravity device is applied, the problem that the local concentration is unbalanced due to the fact that the raw oil is adhered to the surface of the cutting device, the problem that the local concentration of the raw oil is higher and closer to the surface of the cutting device is solved, the problem that the contact time of the raw oil and sulfur trioxide is too long and the sulfonation reaction time is too long due to the fact that the raw oil is adhered to the surface of the cutting device is solved, the coking problem caused by too large local concentration, too strong reaction and too long reaction time in the petroleum sulfonation process can be effectively solved, and the supergravity device can.
FIG. 5 illustrates a schematic representation of an oleophobic structure in an embodiment of the invention. The oleophobic structure in fig. 5 is a depression with multiple micro-nano dimensions, which is formed by laser etching on its surface. Generally, the depressions may be pits or stripes, and fig. 5 shows a structure in which the depressions are stripes, and more particularly, fig. 5 shows a grid structure. Wherein the dark fringe areas are corresponding depressions. The micro-nano scale indentation changes the roughness of the surface of the filler, so that the oleophobic performance of the bakelite surface is improved. In specific implementation, the width of the grid bars can be changed by changing factors such as the scanning times and speed set by the laser, and the oleophobic performance is further adjusted.
In an embodiment not shown in the drawings, the oleophobic structure can be obtained by means of surface modification, for example, the oleophobic structure is a material modification layer covered on the surface of the oleophobic structure, and the surface energy of the surface of the supergravity sulfonation device used for cutting the raw oil into liquid films or liquid drops when the material modification layer is not covered is higher than the surface energy of the material modification layer. The surface energy of the modified layer obtained in this way is low, and an oleophobic structure is formed, and certainly, in a reasonable range, the lower the surface energy is, the better the oleophobic performance is, and details are not given in the invention.
In other practical embodiments, it can be inferred from the above embodiments that if the supergravity device is a stator-rotor supergravity reactor, the corresponding cutting assemblies are the stator column and the rotor column, and in these embodiments, the surfaces of the stator column and the rotor column of the stator-rotor supergravity reactor form the oleophobic structure as shown above.
Characterization of the oleophobic structure can be performed by: dripping raw oil with a certain volume (6-12 μ L) on the surface of the oil tank, taking five different measuring points, measuring the contact angle of five oil drops on the surface of the oil tank by using a contact angle measuring instrument, reading the contact angle value, and taking the average value. For example, fig. 6 shows a photograph obtained by performing the above characterization test using a certain material oil, and it can be understood from fig. 6 that the oil-repellent structure formed on the surface can exert the oil-repellent effect.
The inventor of the invention discovers through long-term experimental demonstration and research that the problem of over-sulfonation can be solved by using the surface oleophobic treatment of the reactor, and the surface of the hypergravity device used for cutting the raw oil into liquid films or liquid drops is subjected to the oleophobic treatment to obtain the oleophobic structure, so that the adhesion phenomenon can not be caused when the high-viscosity raw oil is cut, the mass transfer can not be influenced, the local concentration is uniform, the over-sulfonation phenomenon can not be caused in petroleum sulfonation, and the influence of unbalanced local concentration can not be considered when the high-viscosity raw oil is used for a long time due to the fact that the adhesion phenomenon can not be caused, and the high-viscosity raw oil is suitable for a long-term continuous.
Based on the above inventive concept, the second aspect of the present invention provides a hypergravity sulfonate continuous production system for coupling reaction separation and absorption, which cannot perform continuous production currently using a hypergravity device due to high viscosity of the raw oil of sulfonate, and is prone to oversulfonation.
In some embodiments, a coupled reaction separation and absorption hypergravity sulfonate continuous production system, shown in connection with fig. 7, comprises a hypergravity sulfonation reaction unit and a tail gas absorption unit; the hypergravity sulfonation reaction unit comprises a hypergravity sulfonation device and an aging device, wherein raw oil and sulfur trioxide gas can be introduced into the hypergravity sulfonation device to carry out sulfonation reaction, and the aging device is communicated with the hypergravity sulfonation device so that a sulfonated crude product can be introduced into the aging device to age; the tail gas absorption unit is used for absorbing sulfur-containing tail gas discharged when the hypergravity sulfonation reaction unit works; the surface of the hypergravity sulfonation device used for cutting the raw oil into liquid films or liquid drops is of an oleophobic structure.
In one embodiment, the super-gravity sulfonation device is a rotary packed bed 11, the aging device is a gas-liquid separation tank 12, the rotary packed bed 11 is filled with gas-phase sulfur trioxide through a pipeline 13, raw oil is filled through a pipeline 14, a sulfonated crude product flows out of a liquid outlet below the rotary packed bed 11 after sulfonation reaction and enters the gas-liquid separation tank 12, the upper layer in the gas-liquid separation tank 12 is a sulfonated product, and the lower layer is an unaged finished product,
in a specific embodiment, the super-gravity sulfonation device is a rotary packed bed 11, the aging device is a gas-liquid separation tank 12, the rotary packed bed 11 is filled with gas-phase sulfur trioxide through a pipeline 13, raw oil is filled through a pipeline 14, and then the raw oil is fully mixed under the cutting of the filler to generate sulfonation reaction, a crude sulfonated product generated after the sulfonation reaction enters the gas-liquid separation tank 12 through a liquid outlet, in the embodiment, on one hand, gas-liquid separation can be performed, on the other hand, aging is performed, after a certain time of aging, the product which is not sulfonated is layered with the sulfonated product due to different densities, the product which is not aged is layered, the upper layer is the sulfonated product, the lower layer is the product which is not aged, the product which is not aged is pumped out again through a sulfonic acid pump 22, added with alkali liquor (from an alkali liquor tank 18) for neutralization, and then pressurized by a neutralization, the sulfonated product is extracted from the product tank 15, and the product which is not aged returns to the gas-liquid separation tank 12 to be aged continuously, so that the yield of the sulfonated product and the utilization rate of the raw materials are improved.
Experiments show that the oleophobic structure avoids the adhesion phenomenon caused by overhigh viscosity of raw oil, further avoids the phenomenon of uneven local concentration, and can avoid the over-sulfonation problem.
Based on the same inventive concept as the above, the hypergravity sulfonation device is a stator-rotor hypergravity reactor, and the surfaces of a stator column and a rotor column of the stator-rotor hypergravity reactor form an oleophobic structure; or the hypergravity sulfonation device is a packing type rotary packed bed, and the surface of the packing type rotary packed bed, which is contacted with the raw oil, forms an oleophobic structure.
Similarly, based on the same inventive concept as the above, the oleophobic structure is a recess with a plurality of micro-nano scales, and the recess is formed by etching on the surface of the recess by laser; or the oleophobic structure is a material modification layer covered on the surface of the oleophobic structure, and the surface energy of the surface of the hypergravity sulfonation device used for cutting the raw oil into liquid films or liquid drops when the material modification layer is not covered is higher than that of the material modification layer.
Further, the depressions are pits or strips.
In some casesIn a specific embodiment, the system comprises a sulfur trioxide absorption device 19 and an alkylbenzene storage tank 20, alkylbenzene in the alkylbenzene storage tank 20 is introduced into the sulfur trioxide absorption device 19, SO that SO in the sulfur-containing tail gas discharged by the rotating packed bed 11 can be removed3。
In addition, in order to achieve near-zero emission, the exhaust gas absorption unit of the present invention further includes: the absorption liquid rich liquid tank 16, wherein the absorption liquid in the absorption liquid rich liquid tank 16 is ammonia oil solution; the sulfur dioxide absorption device 21 can pump the absorption liquid and collect sulfur-containing tail gas discharged by the high-gravity sulfonation reaction unit during working, so that sulfur dioxide in the tail gas is absorbed by ammonia oil; and a fertilizer generating device (not shown in the figure) for generating a fertilizer by using an ammonium sulfate solution formed after the absorption liquid absorbs sulfur dioxide in the tail gas.
In some embodiments, the oil component in the tail gas may be removed by an electrostatic demister.
In some embodiments, the sulfur trioxide absorption device 19 and the sulfur dioxide absorption device 21 may also be supergravity reaction devices, and the supergravity reaction devices can greatly enhance the gas absorption efficiency, which is not repeated herein.
In this embodiment, ammonia oil and tail gas (sulfur dioxide) reaction generate ammonium sulfate, and ammonium sulfate passes through the chemical fertilizer and generates the device and form into the chemical fertilizer to make the emission of sulfur dioxide be almost zero on the one hand, and the waste liquid of production can not be extravagant, can be used for producing the chemical fertilizer, carry out secondary development and utilization to the pollution product, avoided the pollution to the environment.
Obviously, based on the same inventive concept as the supergravity device, those skilled in the art can know that, in the supergravity sulfonate continuous production system for coupling reaction separation and absorption according to the second aspect of the present invention, because the surface of the supergravity device for cutting the raw oil into liquid films or liquid drops is subjected to oleophobic treatment, an oleophobic structure is obtained, so that no adhesion phenomenon is caused when the high viscosity raw oil is cut, and further no mass transfer is affected, the local concentration is uniform, and no over sulfonation phenomenon is caused in petroleum sulfonation.
In addition, the third aspect of the present invention further provides a method for continuously producing sulfonate by using the above system, specifically referring to fig. 8, the method includes:
and S1, introducing raw oil and sulfur trioxide gas into the hypergravity sulfonation device.
Specifically, raw oil is introduced into the hypergravity sulfonation device through a liquid distributor, sulfur trioxide gas is introduced through a gas inlet, and then the raw oil and the sulfur trioxide gas are fully mixed under the cutting of the filler to generate sulfonation reaction.
And S2, introducing the sulfonated crude product generated after the reaction in the hypergravity sulfonation device into an aging device for aging reaction.
The crude sulfonated product produced after the sulfonation reaction enters an aging device through a liquid outlet, in the embodiment, the aging device is a gas-liquid separation aging tank, on one hand, gas-liquid separation can be performed, on the other hand, aging is performed, after aging for a certain time, the product after the aging reaction is layered because the density of the product which is not sulfonated is different from that of the sulfonated product, the upper layer is the sulfonated product, and the lower layer is the product which is not aged.
And S3, pumping out the aged product after the preset time, adding alkali liquor for neutralization, cooling, collecting the aged sulfonated product, and pumping the unaged product into the aging device again.
And pumping the unaged product by a sulfonic acid pump, adding alkali liquor for neutralization, pressurizing by a neutralization circulating pump, cooling by a double-pipe heat exchanger, extracting the sulfonated product, and returning the unaged product to the aging tank for continuous aging, thereby improving the yield of the sulfonated product and the utilization rate of the raw materials.
And S4, absorbing the sulfur-containing tail gas discharged by the hypergravity sulfonation reaction unit during operation by using the tail gas absorption unit.
In some embodiments, as shown in fig. 9, the step S4 includes:
s41, absorbing sulfur trioxide in the tail gas by alkylbenzene through a sulfur trioxide absorption device;
s42, absorbing sulfur dioxide in the tail gas by ammonia oil through a sulfur dioxide absorption device;
and S43, generating the fertilizer by using an ammonium sulfate solution formed after the ammonia oil absorbs the sulfur dioxide in the tail gas through a fertilizer generating device.
In this embodiment, ammonia oil and tail gas (sulfur dioxide) reaction generate ammonium sulfate, and ammonium sulfate passes through the chemical fertilizer and generates the device and form into the chemical fertilizer to make the emission of sulfur dioxide be almost zero on the one hand, and the waste liquid of production can not be extravagant, can be used for producing the chemical fertilizer, carry out secondary development and utilization to the pollution product, avoided the pollution to the environment.
Obviously, based on the same inventive concept as the supergravity device, those skilled in the art can know that, in the supergravity sulfonate continuous production method based on coupling reaction separation and absorption of the third aspect of the present invention, because the surface of the supergravity device used for cutting the raw oil into liquid films or liquid drops is subjected to oleophobic treatment, an oleophobic structure is obtained, so that no adhesion phenomenon is caused during cutting of high viscosity raw oil, and further no mass transfer is influenced, the local concentration is uniform, and no over sulfonation phenomenon is caused during petroleum sulfonation, and no influence of unbalanced local concentration needs to be considered during long-time use due to no adhesion phenomenon, therefore, the method can be used for continuously producing sulfonate in large scale for a long time, has the advantage of high yield, and is suitable for industrial popularization.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to 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 scope of the claims of the present application.
Claims (10)
1. A hypergravity sulfonate continuous production system for coupling reaction separation and absorption is characterized by comprising a hypergravity sulfonation reaction unit and a tail gas absorption unit;
the hypergravity sulfonation reaction unit comprises a hypergravity sulfonation device and an aging device,
raw oil and sulfur trioxide gas can be introduced into the hypergravity sulfonation device to carry out sulfonation reaction, and the aging device is communicated with the hypergravity sulfonation device, so that a sulfonated crude product can be introduced into the aging device to be aged;
the tail gas absorption unit is used for absorbing sulfur-containing tail gas discharged when the hypergravity sulfonation reaction unit works;
the surface of the hypergravity sulfonation device used for cutting the raw oil into liquid films or liquid drops is of an oleophobic structure.
2. The continuous production system of claim 1, wherein the hypergravity sulfonation device is a stator-rotor hypergravity reactor, and surfaces of stator columns and rotor columns of the stator-rotor hypergravity reactor form an oleophobic structure; alternatively, the first and second electrodes may be,
the hypergravity sulfonation device is a packing type rotary packed bed, and the surface of the packing type rotary packed bed, which is contacted with the raw oil, forms an oleophobic structure.
3. The continuous production system according to claim 1, wherein the oleophobic structure is a depression having a plurality of micro-nano dimensions, the depression being formed by laser etching on a surface thereof; alternatively, the first and second electrodes may be,
the oleophobic structure is a material modification layer covered on the surface of the oleophobic structure, and the surface energy of the surface of the hypergravity sulfonation device used for cutting the raw oil into liquid films or liquid drops when the material modification layer is not covered is higher than that of the material modification layer.
4. The continuous production system of claim 3, wherein the indentations are cratered or striped.
5. The continuous production system of claim 1, wherein the tail gas absorption unit comprises:
a sulfur trioxide absorption device, a sulfur dioxide absorption device and a chemical fertilizer generation device;
sulfur trioxide absorbing device can let in the sulfur trioxide in the alkylbenzene absorption tail gas, sulfur dioxide absorbing device can let in the sulfur dioxide in the ammonia oil absorption tail gas, the chemical fertilizer generates the device and utilizes the ammonium sulfate solution that forms behind the sulfur dioxide in the ammonia oil absorption tail gas generates the chemical fertilizer.
6. A continuous production process using the system of any one of claims 1 to 5, comprising:
raw oil and sulfur trioxide gas are introduced into a hypergravity sulfonation device;
introducing a sulfonated crude product generated after reaction in the hypergravity sulfonation device into an aging device for aging reaction;
pumping out the aged product after the preset time, adding alkali liquor for neutralization, cooling, collecting the aged sulfonated product, and pumping the unaged product into the aging device again;
and absorbing sulfur-containing tail gas discharged by the supergravity sulfonation reaction unit during working by using a tail gas absorption unit.
7. The continuous production method according to claim 6, wherein the tail gas absorption unit is used for absorbing sulfur-containing tail gas discharged during the operation of the hypergravity sulfonation reaction unit, and comprises the following steps:
absorbing sulfur trioxide in the tail gas by alkylbenzene through a sulfur trioxide absorption device;
absorbing sulfur dioxide in the tail gas by ammonia oil through a sulfur dioxide absorption device;
and (3) generating a chemical fertilizer by using an ammonium sulfate solution formed after the ammonia oil absorbs sulfur dioxide in the tail gas through a chemical fertilizer generating device.
8. A hypergravity apparatus, comprising:
a housing;
the liquid distributor is positioned in a reaction cavity formed by the shell and used for spraying the raw oil to the surface of the device used for cutting the raw oil into liquid films or liquid drops;
the cutting assembly is positioned in a reaction cavity formed by the shell and arranged around the liquid distributor, and comprises a surface used for cutting the raw oil into liquid films or liquid drops;
wherein, the surface for cutting the raw oil into liquid films or liquid drops is of an oleophobic structure.
9. The apparatus of claim 8, wherein the apparatus is a stator-rotor hypergravity reactor, and the cutting assembly comprises a stator post and a rotor post of the stator-rotor hypergravity reactor; the surfaces of a stator column and a rotor column of the stator-rotor supergravity reactor form an oleophobic structure; alternatively, the first and second electrodes may be,
the device is a packed rotary packed bed, and the cutting assembly comprises the packing; and an oleophobic structure is formed on the surface of the filler contacted with the raw oil.
10. The device according to claim 8, wherein the oleophobic structure is a depression having a plurality of micro-nano dimensions, and the depression is formed by laser etching on the surface of the depression; alternatively, the first and second electrodes may be,
the oleophobic structure is a material modification layer covered on the surface of the oleophobic structure, and the surface energy of the surface for cutting the raw oil into liquid films or liquid drops when the material modification layer is not covered is higher than that of the material modification layer.
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Application publication date: 20200317 |