CN111410989B - Atmospheric and vacuum carbon five alkali-free non-hydrodesulfurization device and method - Google Patents
Atmospheric and vacuum carbon five alkali-free non-hydrodesulfurization device and method Download PDFInfo
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- CN111410989B CN111410989B CN202010258017.2A CN202010258017A CN111410989B CN 111410989 B CN111410989 B CN 111410989B CN 202010258017 A CN202010258017 A CN 202010258017A CN 111410989 B CN111410989 B CN 111410989B
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses an atmospheric and vacuum carbon five alkali-free non-hydrodesulfurization device and a method, the device comprises a liquid membrane bed, the liquid membrane bed is connected with an extraction separation tank, the extraction separation tank is connected with an inlet of a dehydration coalescer, an outlet of the dehydration coalescer is connected with an inlet of a dehydration tower, an outlet of the dehydration tower is connected with an inlet of a mercaptan catalytic conversion tower, an outlet of the mercaptan catalytic conversion tower is connected with an inlet of a mixer, an outlet of a complex desulfurizer tank is connected with an inlet of the mixer through a metering pump, and an outlet of the mixer is connected with one side of the upper part of a desulfurization rectifying tower. According to the device and the method for the alkali-free non-hydrodesulfurization of the atmospheric and vacuum carbon five, the thioether removal rate is more than 99%, the mercaptan conversion rate is more than 99%, the higher-boiling-point morphological sulfur removal rate is more than 98%, the total sulfur of the atmospheric and vacuum carbon five can be removed to be below 5 mug/g, and no foul tail gas or waste alkali liquor is discharged.
Description
Technical Field
The invention relates to the technical field of petroleum refining, in particular to an alkali-free non-hydrodesulfurization device and method for atmospheric and vacuum carbon five.
Background
The main components of the carbon five products produced by the atmospheric and vacuum distillation device of oil refining enterprises comprise n-pentane, isopentane, neopentane, a small amount of carbon four carbon six carbon alkane and a small amount of carbon four carbon five carbon six carbon alkene, wherein the boiling point of the carbon four carbon five alkane alkene is approximately in a range of-10 to 50 ℃ under the normal pressure condition, and the forms of the atmospheric and vacuum carbon five sulphur mainly comprise methyl sulfide (the boiling point is 37.3 ℃), ethyl sulfide (the boiling point is 92 ℃), methyl mercaptan (the boiling point is 6 ℃), ethyl mercaptan (the boiling point is 36.2 ℃), propyl mercaptan (the boiling point is 67 ℃), butyl mercaptan (the boiling point is 98 ℃), disulfide (the boiling point is 109.6 ℃), thiophene (the boiling point is 84 ℃), thiophene derivatives and other forms of sulphur.
At present, most of sulfides in carbon five of an atmospheric and vacuum distillation device are desulfurized by a hydrodesulfurization method, but the hydrodesulfurization method has large investment and higher desulfurization cost; and aiming at the sulfur content of only dozens of mug/g carbon five, the desulfurization can be carried out by adopting an adsorbent desulfurization method.
Chinese patent CN103571524A (device and method for removing total sulfur in cracking carbon five) mainly removes hydrogen sulfide, carbonyl sulfur and carbon disulfide in carbon five (mainly unsaturated carbon five) in a cracking device.
The method disclosed in chinese patent CN1321725A is to utilize dissolved oxygen in liquefied gas or natural gas to directly convert mercaptan in the material into disulfide under the action of a special catalyst fixed bed, and then remove the disulfide by a rectification method, thereby achieving the purpose of removing mercaptan.
The method described in chinese patent CN1706549A and chinese patent CN1888022A is to inject one or two compounds of liquid tert-butyl hydroperoxide and di-tert-butyl hydroperoxide into petroleum product, and when the mixture passes through a special catalyst fixed bed, the tert-butyl hydroperoxide decomposes oxygen and converts mercaptan in the petroleum product into disulfide.
The above patents all adopt corresponding desulfurization technology for one or more forms of sulfur in liquid hydrocarbon or light oil, which can only remove forms of sulfur such as mercaptan, carbonyl sulfur and carbon disulfide in materials, but hardly remove sulfur ether, thiophenic sulfur and derivatives thereof in carbon five of atmospheric and vacuum distillation unit.
Disclosure of Invention
In view of the above technical problems in the related art, the present invention provides an apparatus and a method for normal pressure carbon five alkali-free non-hydrodesulfurization, which can overcome the above disadvantages in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
an alkali-free non-hydrodesulfurization device for atmospheric and vacuum carbon five comprises a liquid membrane bed, wherein the bottom of the liquid membrane bed is connected with the top of one end of an extraction separation tank, the bottom of the other end of the extraction separation tank is connected with one side of the upper part of the liquid membrane bed through a circulating pump, the top of the other end of the extraction separation tank is connected with an inlet of a dehydration coalescer through a pipeline, an outlet of the dehydration coalescer is connected with an inlet of a dehydration tower through a pipeline, an outlet of the dehydration tower is connected with an inlet of a mercaptan catalytic conversion tower through a pipeline, an outlet of the mercaptan catalytic conversion tower is connected with an inlet of a mixer through a pipeline, an outlet of a complex desulfurizer tank is connected with an inlet of the mixer through a metering pump, an outlet of the mixer is connected with one side of the upper part of a desulfurization rectification tower, and an outlet of the top of the desulfurization rectification tower is connected with an inlet of a material reflux tank of the top of the rectification tower through a material cooler, an outlet of the rectifying tower top material reflux tank is connected with one side of the upper part of the desulfurization rectifying tower through a rectifying tower top material reflux pump, an outlet of the bottom of the desulfurization rectifying tower is respectively connected with an inlet of a reboiler and an inlet of a rectifying tower bottom material cooler through pipelines, and an outlet of the reboiler is connected with one side of the lower part of the desulfurization rectifying tower through a pipeline;
the liquid film bed comprises a shell, and the top end of the shell is connected with an end enclosure through a flange; the top of the seal head is provided with a first inlet, one side of the seal head is provided with a second inlet, a distributor is arranged in the seal head, and an outlet of the circulating pump is connected with the distributor through the second inlet; the inner wall of the upper end of the shell is welded with two ends of the fiber bundle hanging beam, the fiber bundle hanging beam is fixedly connected with the fiber bundle, and the fiber bundle is uniformly distributed on the fiber bundle hanging beam;
the lower part of the mercaptan catalytic conversion tower is provided with a catalytic oxygen release bed layer, and the upper part of the mercaptan catalytic conversion tower is provided with a catalyst activated carbon bed layer.
Furthermore, a coalescence filter element is arranged in the dehydration coalescer, a solid adsorbent is arranged in the dehydration tower, and a rectifying tower sieve plate is arranged in the desulfurization rectifying tower.
Furthermore, the catalytic oxygen release bed layer is prepared by preparing balls, long strips or round rods from powdery sodium percarbonate, heavy metal oxide and bentonite binder and drying at 40-50 ℃.
Further, the content of sodium percarbonate in the catalytic oxygen release bed layer is 70-90wt%, the content of heavy metal oxide is 5-20wt%, the content of bentonite binder is 5-10wt%, and the heavy metal oxide is chromium oxide, manganese oxide, iron oxide, nickel oxide or copper oxide.
Further, the catalyst activated carbon bed layer is solid-supported caustic alkali and cobalt catalyst activated carbon.
Further, the caustic alkali is sodium hydroxide or potassium hydroxide, and the cobalt-based catalyst is sulfonated cobalt phthalocyanine, poly cobalt phthalocyanine or dinuclear cobalt phthalocyanine ammonium sulfonate.
Furthermore, each distribution hole of the distributor is provided with an atomizing nozzle, the fiber filaments in the fiber bundle are in a continuous corrugated shape, the wave height is 1-5mm, and the wavelength is 3-15 mm.
According to another aspect of the invention, a method for performing alkali-free non-hydrodesulfurization on atmospheric pressure carbon five by using the device comprises the following steps:
s1, pressure-feeding carbon five from an atmospheric and vacuum device into a liquid film bed from the top of the liquid film bed, filling a compound oxidant into an extraction separation tank, pressurizing by a circulating pump, feeding the carbon five into the liquid film bed from the top side of the liquid film bed, and oxidizing thioether in the carbon five into dimethyl sulfoxide by the compound oxidant and dissolving the dimethyl sulfoxide in the compound oxidant;
s2, the carbon five subjected to thioether removal enters a dehydration coalescer for coarse dehydration, and then enters a dehydration tower for fine dehydration, so that the water content in the carbon five is removed to be below 30 microgram/g;
s3, enabling the finely dehydrated carbon five to pass through a mercaptan catalytic conversion tower from bottom to top, firstly passing through a catalytic oxygen release bed layer, dissolving oxygen released by decomposing sodium percarbonate in the carbon five, then passing through a catalyst activated carbon bed layer, oxidizing mercaptan in the carbon five into disulfide under the catalytic action of a cobalt catalyst and caustic alkali, and dissolving the generated disulfide in the carbon five;
s4, injecting a complexing desulfurizer into carbon five containing disulfide through a metering pump, mixing the carbon five containing disulfide through a mixer, then entering a desulfurization rectifying tower, controlling the pressure at the top of the rectifying tower to be within the range of 0.05-0.2Mpa, heating the material part at the bottom of the tower back to the desulfurization rectifying tower through a reboiler, controlling the temperature at the bottom of the tower to be within the range of 100-140 ℃, controlling the reflux ratio at the top of the tower to be 0.3-1, the reflux temperature to be 40-50 ℃, the temperature at the top of the tower to be 60-80 ℃, controlling the total sulfur of the carbon five to be not more than 5 [ mu ] g/g, using a sulfur-containing waste agent at the bottom of the tower as an organic matter, and cooling the organic matter and then sending the organic matter out of the device.
Further, the compound oxidant is prepared by compounding a liquid oxidant and a cosolvent, the liquid oxidant is hydrogen peroxide or sodium hypochlorite, the cosolvent is one or more of methanol, ethanol, isopropanol, acetone, butanone, pyridine, dimethyl sulfoxide, dimethyl sulfone and sulfolane, and the content of the cosolvent in the compound oxidant is 0.5-3 wt%.
Further, the complex desulfurizer is a compound system of aromatic organic matters and a scorch retarder, and the content of the scorch retarder in the complex desulfurizer is 2-10 wt%.
The invention has the beneficial effects that: the device and the method for normal-pressure and reduced-pressure carbon five alkali-free non-hydrodesulfurization adopt a compound oxidant extraction technology to remove thioether, the extraction equipment preferably selects a liquid membrane bed, and the thioether removal rate is more than 99 percent; removing the water content in the carbon five to be below 30 microgram/g by adopting a coalescer and a solid adsorbent for two-stage dehydration so as to protect a subsequent mercaptan catalytic conversion fixed bed; converting mercaptan into disulfide by adopting a catalytic oxygen release bed layer and an immobilized caustic alkali and cobalt catalyst activated carbon bed layer combined fixed bed, wherein the conversion rate of the mercaptan is more than 99%; the method is characterized in that sulfur with higher boiling point forms such as disulfide, thiophenic sulfur and derivatives thereof is removed by rectifying a carbon five complexing desulfurizer, the removal rate of the sulfur with the higher boiling point forms is more than 98%, one or more steps in the combined process desulfurization steps can be selected according to the content of sulfur in materials, the sulfur form condition and the product desulfurization precision requirement, the total sulfur in the atmospheric and vacuum carbon five is removed to be below 5 mug/g, and no foul tail gas or waste alkali liquor is discharged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic diagram of a configuration of an atmospheric and vacuum carbon five alkali-free non-hydrodesulfurization unit according to an embodiment of the invention;
FIG. 2 is a schematic structural diagram of a liquid film bed according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a distributor according to an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a tow hitch beam according to an embodiment of the present invention;
in the figure: 1. the device comprises a liquid membrane bed, 2, a distributor, 3, a fiber bundle, 4, an extraction separation tank, 5, a circulating pump, 6, a dehydration coalescer, 7, a coalescing filter element, 8, a dehydration tower, 9, a solid adsorbent, 10, a mercaptan catalytic conversion tower, 11, a catalytic oxygen release bed layer, 12, a catalyst active carbon bed layer, 13, a mixer, 14, a complexing desulfurizer tank, 15, a metering pump, 16, a desulfurization rectification tower, 17, a rectification tower sieve plate, 18, a rectification tower top material cooler, 19, a rectification tower top material reflux tank, 20, a rectification tower top material reflux pump, 21, a reboiler, 22, a rectification tower bottom material cooler, 23, a shell, 24, a flange, 25, a seal head, 26, an inlet I, 27, an inlet II, 28, a fiber bundle hanging beam, 29 and an atomizing nozzle.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1
As shown in FIG. 1, the apparatus for atmospheric and vacuum carbon-five alkali-free non-hydrodesulfurization according to the embodiment of the invention comprises a liquid membrane bed 1, wherein the bottom of the liquid membrane bed 1 is connected with the top of one end of an extraction separation tank 4, the bottom of the other end of the extraction separation tank 4 is connected with one side of the upper part of the liquid membrane bed 1 through a circulating pump 5, the top of the other end of the extraction separation tank 4 is connected with an inlet of a dehydration coalescer 6 through a pipeline, an outlet of the dehydration coalescer 6 is connected with an inlet of a dehydration tower 8 through a pipeline, an outlet of the dehydration tower 8 is connected with an inlet of a mercaptan catalytic conversion tower 10 through a pipeline, an outlet of the mercaptan catalytic conversion tower 10 is connected with an inlet of a mixer 13 through a pipeline, an outlet of a complex desulfurizer tank 14 is connected with an inlet of the mixer 13 through a metering pump 15, an outlet of the mixer 13 is connected with one side of the upper part of a desulfurization and rectification tower 16, the export at 16 tops of desulfurization rectifying column passes through rectifying column top material cooler 18 and 19 entry linkage of rectifying column top material reflux drum, the export of rectifying column top material reflux drum 19 pass through rectifying column top material reflux pump 20 with the upper portion one side of desulfurization rectifying column 16 is connected, the export of 16 bottoms of desulfurization rectifying column passes through the entry that the pipeline is connected reboiler 21 respectively, the entry of rectifying column bed charge cooler 22, the export of reboiler 21 pass through the pipeline with the lower part one side of desulfurization rectifying column 16 is connected. A coalescence filter element 7 is arranged in the dehydration coalescer 6, a solid adsorbent 9 is arranged in the dehydration tower 8, and a rectifying tower sieve plate 17 is arranged in the desulfurization rectifying tower 16.
As shown in fig. 2, the liquid film bed 1 comprises a shell 23, wherein the top end of the shell 23 is connected with a seal head 25 through a flange 24; the top of the seal head 25 is provided with a first inlet 26, one side of the seal head 25 is provided with a second inlet 27, the seal head 25 is internally provided with a distributor 2, and the outlet of the circulating pump 5 is connected with the distributor 2 through the second inlet 27; as shown in fig. 3, each distribution hole of the distributor 2 is correspondingly provided with an atomizing nozzle 29, as shown in fig. 4, the inner wall of the upper end of the housing 23 is welded to two ends of a fiber bundle hanging beam 28, the fiber bundle hanging beam 28 is fixedly connected with the fiber bundle 3, the fiber bundle 3 is uniformly distributed on the fiber bundle hanging beam 28, the fiber filaments in the fiber bundle 3 are in a continuous corrugated shape, the wave height is 1-5mm, and the wavelength is 3-15 mm. The fiber yarn is hydrophilic modified fiber yarn, the surface of the fiber yarn is treated by a hydrophilic modification technology, and the hydrophilic angle is required to be not more than 5 degrees.
The lower part of the mercaptan catalytic conversion tower 10 is provided with a catalytic oxygen release bed layer 11, and the upper part of the mercaptan catalytic conversion tower 10 is provided with a catalyst activated carbon bed layer 12. The catalytic oxygen release bed layer 11 is prepared by making powder sodium percarbonate, heavy metal oxide and bentonite binder into phi 10-15mm small balls or long strips or round rods with the diameter phi 3-5mm and the length 20-30mm, and baking at 40-50 ℃, wherein the adding proportion of the sodium percarbonate is preferably 70-90wt%, the heavy metal oxide is the oxide of chromium, manganese, iron, nickel, copper and other metals, the adding proportion of the heavy metal oxide is preferably 5-20wt%, and the bentonite is stickyThe addition ratio of the caking agent is preferably 5-10 wt%. The height of the single-layer catalytic oxygen release bed layer is not more than 2m, the height-diameter ratio of the bed layer is 2-4, and the space velocity of carbon five is 0.2-2h-1It is preferable. The catalyst activated carbon bed layer 12 is an immobilized caustic alkali and cobalt catalyst activated carbon, and can be regenerated by soaking in a caustic alkali aqueous solution in which a cobalt catalyst is dissolved for more than 24 hours, the caustic alkali is preferably sodium hydroxide or potassium hydroxide, and the cobalt catalyst is preferably high-quality sulfonated cobalt phthalocyanine, cobalt phthalocyanine or binuclear ammonium cobalt phthalocyanine sulfonate. The height of the single-layer catalyst active carbon bed layer is not more than 4m, the height-diameter ratio of the bed layer is 3-6, and the carbon five space velocity is 0.5-3h-1It is preferable.
The method for carrying out the atmospheric and vacuum carbon five alkali-free non-hydrodesulfurization by using the device comprises the steps of extracting and removing thioether through a liquid film bed and a compound oxidant, finely dehydrating through a coalescer and a solid adsorbent, converting mercaptan into disulfide through a mercaptan catalytic conversion fixed bed, and rectifying and removing sulfur with a higher boiling point form through a carbon five complex desulfurizer, and specifically comprises the following steps:
s1, feeding carbon five from an atmospheric and vacuum device into a liquid membrane bed under the pressure of 0.3-3.0 MPa and the temperature of 10-50 ℃, feeding the carbon five into the liquid membrane bed from the top of the device under pressure, feeding a compound oxidant into an extraction separation tank, feeding the compound oxidant into the liquid membrane bed from the top of the device under the pressure of a circulating pump, uniformly distributing the compound oxidant on hydrophilic fiber bundles in the device through a distributor at the top of the liquid membrane bed, forming a water phase film with the thickness of micron on the outer surface of fiber filaments under the action of the surface tension of a polar oxidant, dispersing the carbon five into an oil phase film by a large number of extremely fine fiber filaments, contacting the oil phase and the water phase in the form of the liquid film, greatly increasing the contact area of the two phases, greatly shortening the distance of a single-phase inner solute from the inside to the surface of the liquid membrane, increasing the mass transfer efficiency of the two phases by orders of orders, and oxidizing thioether in the carbon five into dimethyl sulfoxide and dissolving the dimethyl sulfoxide in the oxidant. The effective components of the compound oxidant need to be replaced regularly after being consumed to a certain concentration.
S2, carrying trace water in the carbon five after the ether is removed, adopting hydrophilic modified polymer fiber yarns or a filter element as a coalescer of a coalescing filter element for coarse dehydration for protecting a subsequent mercaptan catalytic conversion filler, and then adopting anhydrous calcium chloride or a 4A molecular sieve for fine dehydration, wherein the water content in the carbon five is required to be removed to be below 30 microgram/g.
S3, enabling the finely dehydrated carbon five to pass through a mercaptan catalytic conversion fixed bed tower from bottom to top, enabling the carbon five to pass through a catalytic oxygen release bed layer made of sodium percarbonate and heavy metal oxides, dissolving oxygen released by decomposition of the sodium percarbonate in the carbon five, and when the carbon five passes through an active carbon bed layer of a solid-supported caustic alkali and a cobalt catalyst, oxidizing mercaptan of the carbon five into a disulfide under the catalytic action of the cobalt catalyst and the caustic alkali, and dissolving the generated disulfide in the carbon five.
S4, injecting a small amount of complexing desulfurizer into carbon five containing disulfide, thiophene and derivatives thereof through a metering pump, mixing the mixture by a mixer, then feeding the mixture into a sieve plate rectifying tower, controlling the pressure at the top of the rectifying tower to be in the range of 0.05-0.2Mpa (G), heating the material part at the bottom of the tower back to the rectifying tower through a reboiler, controlling the temperature at the bottom of the tower to be 100-140 ℃, the reflux ratio at the top of the tower to be 0.3-1, the reflux temperature to be 40-50 ℃ and the temperature at the top of the tower to be 60-80 ℃. The addition amount of the complexing desulfurizer is 200-2000 mug/g of the mass flow of the carbon five, the reflux ratio of the tower top can be reduced by increasing the addition amount of the complexing desulfurizer, the energy consumption and the operation cost of rectification desulfurization are reduced, the total sulfur removal rate of the carbon five can also be increased, and the total sulfur of the product carbon five is controlled not to exceed 5 mug/g. The sulfur-containing waste agent at the tower bottom is an organic matter, is cooled and then is sent out of the device, and can be mixed with gasoline or diesel oil for hydrodesulfurization treatment.
The compound oxidant is prepared by compounding a liquid oxidant and a cosolvent, the liquid oxidant is preferably hydrogen peroxide or sodium hypochlorite, the cosolvent is preferably one or more of methanol, ethanol, isopropanol, acetone, butanone, pyridine, dimethyl sulfoxide, dimethyl sulfone, sulfolane and the like, and the proportion of the cosolvent is preferably 0.5-3 wt%. The complex desulfurizer is a compound system of aromatic organic matters and a scorch retarder, and the addition proportion of the scorch retarder is preferably 2-10 wt%. The injection amount of the complexing desulfurizer to the carbon five is adjusted according to the total content of sulfur in a form with a higher boiling point in the carbon five, the injection amount is generally 2-5 times of the sulfur content, and when the sulfur content is lower, the injection amount is not lower than 200 mu g/g of the mass flow of the carbon five.
Example 2
A petrochemical company provides an atmospheric and vacuum device to produce five-carbon samples at the temperature of 15-20 ℃, the hydrogen sulfide content is less than 1 microgram/g, the mercaptan content is 50-100 microgram/g, the methyl sulfide content is 20-50 microgram/g, the disulfide content is 10-20 microgram/g, the sulfur content of thiophene and other forms is 50-100 microgram/g, the device of embodiment 1 is adopted to carry out a desulfurization experiment, and the total sulfur content of the five-carbon products is less than 3 microgram/g.
Example 3
The method comprises the steps of producing five carbon by an atmospheric and vacuum device of a petrochemical company, wherein the flow rate of the five carbon is 15-20t/h, the temperature is 30-40 ℃, the pressure is 0.5-0.7Mpa (G), the content of hydrogen sulfide is less than 5 mug/g, the content of mercaptan is 30-70 mug/g, the content of methyl sulfide is 10-30 mug/g, the content of disulfide is 20-50 mug/g, the content of thiophene and other forms of sulfur is 80-150 mug/g, a desulfurization experiment is carried out by adopting the device of embodiment 1, the flow rate of a compound oxidant is 0.8-1t/h, a hydrophilic modified high-molecular fiber filament inner core coalescer and a 4A molecular sieve are adopted for fine dehydration, the water content is about 20 mug/g, the five carbon is subjected to mercaptan catalytic conversion fixed bed and fine distillation desulfurization, the injection flow rate of a complex desulfurizer is 15-20kg/h, and the total sulfur of the five carbon is removed to 2-5 mug/g.
Example 4
The method comprises the steps of producing five carbon, five carbon flow rate of 20-30t/h, temperature of 30-40 ℃, pressure of 0.4-0.5Mpa (G), hydrogen sulfide content of less than 1 mug/g, mercaptan content of 10-30 mug/g, methyl sulfide content of 5-10 mug/g, disulfide content of 5-20 mug/g, and sulfur content of thiophene and other forms of 10-20 mug/g by a crude oil hydrogenation device and an atmospheric and vacuum distillation device of a petrochemical company, conducting a desulfurization experiment by adopting the device of embodiment 1, enabling the flow rate of a compound oxidant to be 0.6-1t/h, dehydrating by adopting a hydrophilic modification filter element coalescer and a 4A molecular sieve, enabling the water content to be about 25 mug/g, conducting catalytic conversion on a fixed bed by mercaptan and a rectification desulfurization, injecting a complex desulfurizer of 5-10kg/h, and enabling the total sulfur of the five carbon to be less than 3 mug/g.
In summary, according to the above technical solution of the present invention, by reacting a compound containing thioether, thiol, disulfide, the method comprises the steps of removing thioether from sulfur in forms of thiophene, thiophene derivatives and the like by adopting a compound oxidant extraction technology, finely dehydrating by using a coalescer and a solid adsorbent, converting mercaptan into disulfide by using a mercaptan catalytic conversion fixed bed, and removing the disulfide, the thiophene sulfur, the derivatives and other sulfur in forms of higher boiling points by using a carbon five complex desulfurizer through rectification, wherein the desulfurizing ether extraction equipment preferably selects a liquid membrane bed, the finely dehydrated solid adsorbent preferably selects spherical anhydrous calcium chloride or a 4A molecular sieve, the mercaptan catalytic conversion fixed bed consists of a catalytic oxygen release bed layer made of sodium percarbonate and heavy metal oxides and an upper layer and a lower layer of an active carbon bed layer of a solid-supported caustic alkali and cobalt catalyst, and the carbon five complex desulfurizer is a compound system of aromatic organic matters and a scorch retarder. One or more steps in the combined process desulfurization steps can be selected according to the sulfur content of the material, the sulfur form condition and the product desulfurization precision requirement, equipment selected for each desulfurization step can be designed to be single-stage or multi-stage, when equipment in a certain step is multi-stage, the equipment can be designed to be a combined process of series connection, parallel connection or series connection and parallel connection, the total sulfur of the atmospheric and vacuum carbon five can be removed to be below 5 mug/g, and no foul tail gas or waste alkali liquor is discharged.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The device for normal-pressure and reduced-pressure carbon-five alkali-free non-hydrodesulfurization is characterized by comprising a liquid membrane bed (1), wherein the bottom of the liquid membrane bed (1) is connected with the top of one end of an extraction separation tank (4), the bottom of the other end of the extraction separation tank (4) is connected with one side of the upper part of the liquid membrane bed (1) through a circulating pump (5), the top of the other end of the extraction separation tank (4) is connected with an inlet of a dehydration coalescer (6) through a pipeline, an outlet of the dehydration coalescer (6) is connected with an inlet of a dehydration tower (8) through a pipeline, an outlet of the dehydration tower (8) is connected with an inlet of a mercaptan catalytic conversion tower (10) through a pipeline, an outlet of the mercaptan catalytic conversion tower (10) is connected with an inlet of a mixer (13) through a pipeline, and an outlet of a complexing desulfurizer tank (14) is connected with an inlet of the mixer (13) through a metering pump (15), the outlet of the mixer (13) is connected with one side of the upper part of a desulfurization rectifying tower (16), the outlet of the top of the desulfurization rectifying tower (16) is connected with the inlet of a rectifying tower top material reflux tank (19) through a rectifying tower top material cooler (18), the outlet of the rectifying tower top material reflux tank (19) is connected with one side of the upper part of the desulfurization rectifying tower (16) through a rectifying tower top material reflux pump (20), the outlet of the bottom of the desulfurization rectifying tower (16) is respectively connected with the inlet of a reboiler (21) and the inlet of a rectifying tower bottom material cooler (22) through pipelines, and the outlet of the reboiler (21) is connected with one side of the lower part of the desulfurization rectifying tower (16) through a pipeline;
the liquid film bed (1) comprises a shell (23), and the top end of the shell (23) is connected with a seal head (25) through a flange (24); the top of the seal head (25) is provided with a first inlet (26), one side of the seal head (25) is provided with a second inlet (27), the seal head (25) is internally provided with a distributor (2), and an outlet of the circulating pump (5) is connected with the distributor (2) through the second inlet (27); the inner wall of the upper end of the shell (23) is welded with two ends of a fiber bundle hanging beam (28), the fiber bundle hanging beam (28) is fixedly connected with a fiber bundle (3), and the fiber bundle (3) is uniformly distributed on the fiber bundle hanging beam (28);
the lower part of the mercaptan catalytic conversion tower (10) is provided with a catalytic oxygen release bed layer (11), and the upper part of the mercaptan catalytic conversion tower (10) is provided with a catalyst activated carbon bed layer (12).
2. The device for the alkali-free non-hydrodesulfurization of carbon five under atmospheric and vacuum conditions as claimed in claim 1, wherein a coalescing filter element (7) is arranged in the dehydration coalescer (6), a solid adsorbent (9) is arranged in the dehydration tower (8), and a rectifying tower sieve plate (17) is arranged in the desulfurization rectifying tower (16).
3. The atmospheric and vacuum carbon penta alkali-free non-hydrodesulfurization device according to claim 1, characterized in that the catalytic oxygen release bed (11) is made of powdery sodium percarbonate, heavy metal oxides and bentonite binder into balls, strips or round rods, and is baked at 40-50 ℃.
4. The atmospheric and vacuum carbon penta alkali-free non-hydrodesulfurization device according to claim 3, wherein the content of sodium percarbonate, heavy metal oxide and bentonite binder in the catalytic oxygen release bed (11) is 70-90wt%, 5-20wt% and 5-10wt%, and the heavy metal oxide is chromium oxide, manganese oxide, iron oxide, nickel oxide or copper oxide.
5. The atmospheric and vacuum carbon penta alkali-free non-hydrodesulfurization unit according to claim 1, wherein the catalyst activated carbon bed (12) is an immobilized caustic and cobalt catalyst activated carbon.
6. The apparatus according to claim 5, wherein the caustic alkali is sodium hydroxide or potassium hydroxide, and the cobalt-based catalyst is sulfonated cobalt phthalocyanine, cobalt phthalocyanine or dinuclear ammonium cobalt phthalocyanine sulfonate.
7. The device for the alkali-free and non-hydrodesulfurization of carbon five under atmospheric and vacuum conditions as claimed in claim 1, characterized in that each distribution hole of the distributor (2) is equipped with an atomizing nozzle (29), and the fiber filaments in the fiber bundle (3) are in a continuous corrugated shape, with a wave height of 1-5mm and a wave length of 3-15 mm.
8. A method for carrying out alkali-free non-hydrodesulfurization of atmospheric and vacuum carbon five by using the device of any one of claims 1 to 7, which is characterized by comprising the following steps:
s1, pressure-feeding carbon five from an atmospheric and vacuum device into a liquid film bed from the top of the liquid film bed, filling a compound oxidant into an extraction separation tank, pressurizing the carbon five by a circulating pump, feeding the carbon five into the liquid film bed from the top side of the liquid film bed, oxidizing thioether in the carbon five into dimethyl sulfoxide by the compound oxidant, dissolving the dimethyl sulfoxide in the compound oxidant, wherein the compound oxidant is formed by compounding a liquid oxidant and a cosolvent, the liquid oxidant is hydrogen peroxide or sodium hypochlorite, the cosolvent is one or more of methanol, ethanol, isopropanol, acetone, butanone, pyridine, dimethyl sulfoxide, dimethyl sulfone and sulfolane, and the cosolvent content in the compound oxidant is 0.5-3 wt%;
s2, the carbon five subjected to thioether removal enters a dehydration coalescer for coarse dehydration, and then enters a dehydration tower for fine dehydration, so that the water content in the carbon five is removed to be below 30 microgram/g;
s3, enabling the finely dehydrated carbon five to pass through a mercaptan catalytic conversion tower from bottom to top, firstly passing through a catalytic oxygen release bed layer, dissolving oxygen released by decomposing sodium percarbonate in the carbon five, then passing through a catalyst activated carbon bed layer, oxidizing mercaptan in the carbon five into disulfide under the catalytic action of a cobalt catalyst and caustic alkali, and dissolving the generated disulfide in the carbon five;
s4, injecting a complexing desulfurizer into carbon five containing disulfide through a metering pump, mixing the carbon five containing disulfide through a mixer, then feeding the mixture into a desulfurization rectifying tower, controlling the pressure at the top of the rectifying tower to be within the range of 0.05-0.2Mpa, heating the material part at the bottom of the tower to return to the desulfurization rectifying tower through a reboiler, controlling the temperature at the bottom of the tower to be within the range of 100-140 ℃, controlling the reflux ratio at the top of the tower to be 0.3-1, the reflux temperature to be 40-50 ℃, the temperature at the top of the tower to be 60-80 ℃, controlling the total sulfur content of the carbon five to be not more than 5 [ mu ] g/g, using sulfur-containing waste agents at the bottom of the tower as organic matters, cooling the organic matters, and then sending the organic matters out of the device, wherein the complexing desulfurizer is a compound system of aromatic organic matters and a scorch retarder, and the content of the scorch retarder in the complexing desulfurizer is 2-10 wt%.
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| CN103911177A (en) * | 2014-03-07 | 2014-07-09 | 武汉纺织大学 | Deep desulfurization method for saturated liquid hydrocarbon |
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