CN113698993B - Nigre acidification dephosphorization equipment and process - Google Patents
Nigre acidification dephosphorization equipment and process Download PDFInfo
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- CN113698993B CN113698993B CN202110964517.2A CN202110964517A CN113698993B CN 113698993 B CN113698993 B CN 113698993B CN 202110964517 A CN202110964517 A CN 202110964517A CN 113698993 B CN113698993 B CN 113698993B
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000020477 pH reduction Effects 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000004891 communication Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 11
- 150000007524 organic acids Chemical class 0.000 abstract description 7
- 238000006386 neutralization reaction Methods 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 238000006366 phosphorylation reaction Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000004519 grease Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 49
- 235000019198 oils Nutrition 0.000 description 49
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003225 biodiesel Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 235000021190 leftovers Nutrition 0.000 description 4
- 150000003904 phospholipids Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 small molecule organic acid Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000931143 Gleditsia sinensis Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
- C11B13/02—Recovery of fats, fatty oils or fatty acids from waste materials from soap stock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Abstract
The invention relates to the technical field of development and utilization of grease waste, in particular to soapstock acidification dephosphorization equipment and process. The process comprises the following steps: s1, mixing nigre and small molecular organic acid, and removing a water phase after neutralization reaction to obtain an oil phase; s2, mixing the oil phase with supercritical carbon dioxide for reaction, and removing carbon dioxide to obtain the low-phosphorylation oil. In the method, the nigre is neutralized by the small molecular organic acid to remove alkali in the nigre, and then is acidified by the carbon dioxide, so that the use of sulfuric acid in the traditional process is avoided, the dephosphorization rate of the nigre is greatly improved, and the phosphorus content in the prepared acidified oil is reduced.
Description
Technical Field
The invention relates to the technical field of development and utilization of grease waste, in particular to soapstock acidification dephosphorization equipment and process.
Background
With the development of economic globalization, petrochemical energy is continuously reduced, and environmental problems are also increasingly prominent. Biodiesel is the best product for replacing petroleum diesel by virtue of its excellent physicochemical properties. In the process of producing grease annually in China, a large amount of leftovers are produced, wherein the leftovers contain the Chinese honeylocust and the oil foot, and the acidified oil can be obtained through acidification treatment, so that the acidified oil is converted into the raw material for preparing the biodiesel, and therefore, the cost is greatly reduced by taking the cheap leftovers as the raw material for preparing the biodiesel.
The soapstock is the leftover generated in the alkali refining process of crude oil of edible vegetable oil processing enterprises, and the content of phospholipid in the soapstock is very high because the oilseed contains phospholipid. The conventional process for preparing acidified oil mostly uses sulfuric acid acidification method to reduce phospholipid content, such as the method for preparing acidified oil by using nigre disclosed in patent document with publication number of CN109554230A, which is characterized in that the preparation method comprises heating nigre to 88-92 ℃ and adding acid and acid water for primary acidification reaction, and separating to obtain primary acidified oil; heating the primary acidified oil to 88-92 ℃ and adding concentrated sulfuric acid to perform secondary acidification reaction, and separating to obtain acidified oil; wherein the acid water is acidified water obtained by separation after secondary acidification reaction. The acid in the primary acidification reaction is sulfuric acid with the mass fraction not lower than 70%; the concentrated sulfuric acid in the secondary acidification reaction is sulfuric acid with the mass fraction not less than 90%. The problem of high phospholipid content in the acidified oil produced by the method can lead to the easy emulsification of the subsequent treatment and utilization stages of the acidified oil. The method has the advantages of low yield of the obtained acidified oil, poor product quality, large acid and alkali consumption, high energy consumption, serious wastewater pollution and difficult treatment. With the rapid development of biodiesel industry, low-phosphorylating oils are becoming more and more popular in the market. In order to improve the quality of the acidified oil, it is highly desirable to improve existing equipment and processes so that acidic wastewater is minimized during the production of the acidified oil and the phosphorous content in the acidified oil can be reduced.
Disclosure of Invention
The invention aims to solve the problems and provides soapstock acidification dephosphorization equipment and process capable of effectively reducing the phosphorus content in the acidified oil.
The invention provides a soapstock acidification dephosphorization process, which comprises the following steps:
s1, mixing nigre and small molecular organic acid, and removing a water phase after neutralization reaction to obtain an oil phase;
s2, mixing the oil phase with supercritical carbon dioxide for reaction, and removing carbon dioxide to obtain the low-phosphorylation oil.
As a preferred aspect of the present invention, in step S1, the neutralization reaction is carried out at 160 to 210℃for 1 to 2 hours.
As a preferred aspect of the present invention, in the step S2, the oil phase is mixed with supercritical carbon dioxide to react for 2-4 hours.
As a preferred aspect of the present invention, the low-phosphorous acid oil has an acid value of 110 to 140mgKOH/g and a phosphorous content of less than 15mg/kg.
Preferably, the small molecule organic acid comprises one or more of formic acid, acetic acid and oxalic acid. Further preferably, the small molecule organic acid is formic acid.
As a preferred aspect of the present invention, step S2 further comprises the steps of: before removing carbon dioxide, introducing hydrogen into the system, raising the temperature to 160-210 ℃ again for reaction for 1-2h to obtain an oil body and a water body, separating the water body, and heating and deacidifying the rest oil body to obtain the low-phosphorylation oil.
Wherein, hydrogen can be used for carrying out hydrogenation hardening on the low-phosphate oil so as to obtain stearic acid with wider application. On the other hand, the acid can also react with carbon dioxide to generate formic acid, so that the acidification dephosphorization effect is further improved.
Another object of the present invention is to provide an apparatus for a soapstock acidification dephosphorization process, comprising an outer shell, an inner shell disposed within the outer shell, and a temperature control member disposed within the outer shell; the inner shell comprises an inner shell body with an opening at the top and an inner shell cover for covering the opening, wherein the inner shell body and the inner shell cover both comprise cylindrical inner shell side parts, the inner shell side parts of the inner shell body are provided with external threads, and the inner shell side parts of the inner shell cover are provided with internal threads in threaded connection with the external threads; the side part of the inner shell sequentially comprises a closed upper part, a middle part provided with a plurality of communication holes and a lower part provided with a plurality of centrifugal holes from the opening to the bottom of the inner shell, wherein the centrifugal holes are covered with an oil-water separation film; the side part of the inner shell cover comprises a sealing part which can be connected with the lower part and a communication part which can be connected with the middle part, and the communication part is provided with a through hole which can be communicated with the communication hole; the shell comprises an outer shell body and an outer shell cover, the outer shell cover is connected with the inner shell cover, the outer shell body and the outer shell cover both comprise shell side parts, and the shell side parts of the outer shell body are provided with vertical slots into which the shell side parts of the outer shell cover can be inserted; the bottom of the inner shell is connected with an output shaft of the motor, and the inner shell cover is in sliding connection with a vertical limit groove arranged on the inner wall of the outer shell through a connecting rod; the shell cover is provided with a carbon dioxide inlet, and a feeding port for feeding materials into the inner shell is arranged at the joint of the shell cover and the inner shell cover.
Preferably, the inner wall of the vertical slot is provided with a rubber sealing layer.
Preferably, the stirring roller is arranged in the inner shell, one end of the stirring roller is connected with the inner wall of the inner shell, and the other end of the stirring roller is suspended.
As a preferable aspect of the present invention, the outer case includes a fixed outer case and a movable outer case provided in the fixed outer case, the inner case being provided in the movable outer case; the fixed outer shell is provided with the vertical slot, and the movable outer shell is provided with the vertical limit slot; a filter block is filled between the movable outer shell and the fixed outer shell, the movable outer shell is provided with a guide-out hole, and the fixed outer shell is provided with a collecting hole.
As a preferable mode of the invention, the movable outer shell is provided with a mechanical cavity, a first rotating shaft and a second rotating shaft which are driven by a gear tooth chain structure are arranged in the mechanical cavity, and the first rotating shaft is close to the bottom of the movable outer shell relative to the second rotating shaft; the first rotating shaft is provided with a transmission gear, one end of a rack is inserted into the mechanical cavity and meshed with the transmission gear, and the other end of the rack can be inserted into a slot formed in the inner shell; the second rotating shaft is provided with a control block, one end of the control block is connected with the second rotating shaft, and the other end of the control block is inserted into the vertical limiting groove.
As the preferable mode of the invention, the connecting rod comprises a hollow fixed sleeve and a movable rod inserted into the fixed sleeve, one end of the movable rod is inserted into the vertical limit groove, the other end of the movable rod is connected with the inner bottom of the fixed sleeve through a spring, an electromagnet is arranged at the inner bottom of the fixed sleeve, and the movable rod is an iron rod.
Preferably, the inner shell cover is connected with the outer shell cover through a connecting column, one end of the connecting column is fixedly connected with the inner shell cover, the other end of the connecting column is connected with the outer shell cover through a rotating bearing, and the inside of the connecting column is hollow so as to form the feeding hole.
The invention has the beneficial effects that:
1. in the application, the alkali in the soapstock is firstly removed by neutralizing the soapstock with the small molecular organic acid, and then the soapstock is acidified with carbon dioxide, so that the use of sulfuric acid in the traditional process is avoided, the dephosphorization rate of the soapstock is greatly improved, and the phosphorus content in the prepared acidified oil is reduced.
2. In the application, the soapstock is mixed with the supercritical carbon dioxide, and the supercritical carbon dioxide is used as a soapstock solvent, so that the dispersity of the soapstock in the equipment is improved, and the dephosphorization efficiency is improved.
3. In this application, set up motor drive pivoted inner shell, it both as the reaction vessel, as centrifugal device again, improved dephosphorization efficiency.
Drawings
FIG. 1 is a schematic diagram of an embodiment of a soapstock acidification dephosphorization apparatus;
FIG. 2 is a schematic diagram of another embodiment of a soapstock acidification dephosphorization apparatus;
FIG. 3 is a schematic diagram illustrating the operation of another embodiment of a soapstock acidification dephosphorization apparatus;
in the figure: a housing 1; an outer case 11, a fixed outer case 11a, a movable outer case 11b, a transmission gear 11b1, a control block 11b2; a housing cover 12, a carbon dioxide inlet 121, a feed port 122; an inner case 2; an inner housing 21, a communication hole 211, a centrifugal hole 212, a stirring roller 213, a slot 214; a housing cover 22, a through hole 221; a motor 3; a connecting rod 4, a fixed sleeve 41 and a movable rod 42.
Detailed Description
The following is a specific embodiment of the present invention, and the technical solution of the present invention is further described with reference to the accompanying drawings, but the present invention is not limited to these examples.
Example 1
A soapstock acidification dephosphorization process comprises the following steps:
s1, mixing nigre and small molecular organic acid, and carrying out neutralization reaction for 1-2 hours at 160-210 ℃ to obtain an oil phase and a water phase, and removing the water phase to obtain an oil phase;
s2, mixing the oil phase with supercritical carbon dioxide for 2-4 hours, and removing carbon dioxide to obtain the low-phosphate oil.
In order to perform the above process, the application also discloses a soapstock acidification dephosphorization device, as shown in fig. 1, which comprises an outer shell 1, an inner shell 2 arranged in the outer shell 1, and a temperature control piece arranged in the outer shell 1.
The inner shell 2 includes an inner shell 21 and an inner shell cover 22, wherein the inner shell 21 and the inner shell cover 22 are hollow cylinders with an opening bottom and a closed bottom, and therefore, the inner shell 21 and the inner shell cover 22 include cylindrical inner shell sides. The radius of the bottom surface of the inner housing cover 22 is slightly larger than the radius of the bottom surface of the inner housing 21, and according to the direction in fig. 1, the opening of the inner housing 21 is upward, and the opening of the inner housing cover 22 is downward. In this application, the inner shell side of the inner shell 21 and the inner shell side of the inner shell cover 22 are almost high, the inner shell side of the inner shell 21 is provided with external threads, and the inner shell side of the inner shell cover 22 is provided with internal threads screwed with the external threads, so that the inner shell cover 22 is screwed with the inner shell 21.
The inner shell side of the inner shell 21 sequentially comprises a closed upper part, a middle part provided with a plurality of communication holes 211 and a lower part provided with a plurality of centrifugal holes 212 from an opening to the bottom of the inner shell 21, wherein the centrifugal holes 212 are covered with an oil-water separation film, and only water and oil are allowed to pass through. When the inner case cover 22 is completely covered on the inner case 21, the inner case side portion of the inner case cover 22 includes a closing portion connected to the lower portion, a communicating portion connected to the middle portion, and another closing portion connected to the upper portion. The communication portion is provided with a through hole 221 that can communicate with the communication hole 211, and the through hole 221 communicates with the communication hole 211 only when the inner housing cover 22 and the inner housing 21 are screwed to the bottom.
In addition, in order to further improve the mixing uniformity, a stirring roller 213 is provided in the inner housing 21, and one end of the stirring roller 213 is connected to the inner wall of the inner housing 21 and the other end is suspended.
The outer shell 1 includes an outer shell 11 and an outer shell cover 12, and similarly to the inner shell 2, the outer shell 11 and the outer shell cover 12 are hollow cylinders with an open bottom and a closed bottom, but the bottom of the outer shell 1 may be any shape, such as a direction, a circle, etc., and in this embodiment, the bottom of the outer shell 1 is also circular. The outer shell 11 and the outer shell cover 12 each comprise an outer shell side, and the outer shell side of the outer shell 11 is provided with a vertical slot into which the outer shell side of the outer shell cover 12 can be inserted, unlike the connection of the inner shell 2. In order to ensure the sealing effect, the inner wall of the vertical slot is provided with a rubber sealing layer.
The inner housing 21 may be directly placed in the outer housing 11, or the bottom of the inner housing 21 may be connected to the bottom of the outer housing 11 through a rolling bearing. The outer housing cover 12 is connected to the inner housing cover 22. Then make motor 3 output shaft pass behind the bottom of shell 11 and be connected with the bottom of inner shell 21, simultaneously with the vertical spacing groove 112 sliding connection that inner shell cover 22 and outer shell 11 inner wall set up through connecting rod 4, just can be when motor 3 drive inner shell 21 pivoted, make inner shell cover 22 remove in the vertical direction, drive outer shell cover 12 and remove simultaneously to change the volume size in the shell 1.
In addition, to assist in feeding, the housing cover 12 is provided with a carbon dioxide inlet 121, and a connection of the outer housing cover 12 and the inner housing cover 22 is provided with a feed port 122 for feeding into the inner housing 21.
When in use, the method comprises the following steps:
s1, mixing nigre and small molecular organic acid, and carrying out neutralization reaction for 1-2 hours at 160-210 ℃ to obtain an oil phase and a water phase, and removing the water phase to obtain an oil phase; the small molecule organic acid in this embodiment is formic acid.
I.e. the air inside the device is first excluded: the communication hole 211 and the through hole 221 are maintained in communication, the carbon dioxide inlet 121 and the feed port 122 are opened, carbon dioxide is introduced into the apparatus through the carbon dioxide inlet 121, at this time, the feed port 122 serves as an exhaust port until air in the housing 1 is exhausted, and then the carbon dioxide inlet 121 is closed.
The motor 3 is then controlled to rotate the inner housing 21 a small turn so that the inner housing cover 22 moves upward a small distance so that the communication hole 211 and the through hole 221 are not communicated and the closing portion covers the centrifugal hole 212. And then, the soapstock and formic acid are introduced into the inner shell 2 through the feed inlet 122, the feed inlet 122 is closed, the temperature in the equipment is controlled to rise to 160-210 ℃ through a temperature control, and the reaction is carried out for 1-2 hours, so that an oil phase and a water phase are obtained.
Then, the motor 3 is controlled to drive the inner shell 21 to rotate, so that the inner shell cover 22 continues to move upwards and the outer shell cover 12 is driven to move upwards, the sealing part does not cover the centrifugal holes 212 any more, meanwhile, in the rotation process of the inner shell 21, water phase in the sealing part enters between the outer shell 11 and the inner shell 21 through the oil-water separation film on the centrifugal holes 212, and oil phase is left in the inner shell 2.
S2, mixing the oil phase with supercritical carbon dioxide for 2-4 hours, and removing carbon dioxide to obtain the low-phosphate oil.
The control motor 3 rotates the inner housing 21 such that the inner housing cover 22 moves down and the outer housing cover 12 moves down, such that the communication hole 211 and the through hole 221 communicate, and such that the closing portion covers the centrifugal hole 212. And then introducing carbon dioxide into the equipment through the carbon dioxide inlet 121 until the pressure in the equipment reaches the critical pressure of the carbon dioxide, and simultaneously controlling the temperature in the equipment through a temperature control until the temperature reaches the critical temperature of the carbon dioxide, and keeping for 2-4h. Then the carbon dioxide inlet 121 and the feeding hole 122 are opened, after the inside of the device is released to normal pressure, the temperature in the device is controlled to rise, so that supercritical carbon dioxide is gasified and discharged, and the rest of the inner shell 21 is the low-phosphate oil.
The acid value of the obtained low-phosphate oil is 110-140mgKOH/g, the phosphorus content is less than 15mg/kg, and the yield of the low-phosphate oil is more than 95%. The obtained low-phosphate oil can be used as a raw material for producing hydrocarbon biodiesel (HOV).
In this embodiment, as shown in fig. 2, the outer casing 11 includes a fixed outer casing 11a and a movable outer casing 11b disposed in the fixed outer casing 11a, and the inner casing 21 is disposed in the movable outer casing 11 b. Similarly, the fixed outer casing 11a, the movable outer casing 11b and the casing cover 12 are hollow cylinders with one open surface and the other closed surface, the movable outer casing 11b is directly arranged in the fixed outer casing 11a, or the bottom surface of the movable outer casing 11b is connected with the bottom surface of the fixed outer casing 11a through a rotating bearing, and the inner casing 21 is directly arranged in the movable outer casing 11b, or the bottom surface of the inner casing 21 is connected with the bottom surface of the movable outer casing 11b through a rotating bearing. At this time, the fixed housing 11a is provided with a vertical slot 111, and the movable housing 11b is provided with a vertical limit slot 112. A filter block is filled between the movable outer shell 11b and the fixed outer shell 11a, the movable outer shell 11b is provided with a guiding-out hole, the fixed outer shell 11a is provided with a collecting hole, and the horizontal plane of the collecting hole is higher than that of the guiding-out hole. The water phase in the inner shell 21 enters between the movable outer shell 113 and the inner shell 21, and enters the collecting box to be collected after being removed by the filtering block under the action of the suction pump.
In addition, in this application, the rotation of the inner housing 21 drives the inner housing cover 22 to move upwards, and when the inner housing cover 22 moves to the top, the continuous rotation of the inner housing 21 is affected, which affects the centrifugal operation. Therefore, in this embodiment, the movable outer housing 11b is provided with a mechanical cavity, in which a first rotating shaft and a second rotating shaft driven by a gear tooth chain structure are disposed, and the first rotating shaft is close to the bottom of the movable outer housing 11b relative to the second rotating shaft; the first rotating shaft is provided with a transmission gear 11b1, one end of a rack 5 is inserted into the mechanical cavity and meshed with the transmission gear 11b1, and the other end of the rack can be inserted into a slot 214 formed in the inner shell 21; the second rotating shaft is provided with a control block 11b2, one end of the control block 11b2 is connected with the second rotating shaft, the other end of the control block 11b2 is inserted into the vertical limiting groove 112, and an opening for the control block 11b2 to rotate around the second rotating shaft is formed in the bottom of the vertical limiting groove 112. The horizontal plane of the second rotating shaft is higher than the horizontal plane of the lower part. The inner shell cover 22 is connected with the outer shell cover 12 through a connecting column, one end of the connecting column is fixedly connected with the inner shell cover 22, the other end of the connecting column is connected with the outer shell cover 12 through a rotating bearing, and the inside of the connecting column is hollow so as to form a feed inlet 122.
As shown in fig. 3, when the inner housing 21 rotates to enable the inner housing cover 22 to drive the connecting rod 4 to move below the control block 11b2, the connecting rod 4 continues to move upwards, so as to push the end of the control block 11b2 to rotate upwards, thereby driving the second rotating shaft to rotate and drive the first rotating shaft to rotate, and further driving the rack 5 to move towards the slot 214, so that the rack 5 is inserted into the slot 214, and the movable outer housing 11b is connected with the inner housing 21, so that the inner housing 21 drives the movable outer housing 11b and further drives the inner housing cover 22 to rotate together, thereby improving the centrifugal efficiency.
After the centrifugation is completed, if the inner shell cover 22 is required to move upwards continuously, the connecting rod 4 can be made to comprise a hollow fixed sleeve 41 and a movable rod 42 inserted into the fixed sleeve 41, one end of the movable rod 42 is inserted into a vertical limit groove 112, the other end of the movable rod is connected with the inner bottom of the fixed sleeve 41 through a spring, an electromagnet is arranged at the inner bottom of the fixed sleeve 41, and the movable rod 42 is an iron rod. By the adsorption of the electromagnet to the iron rod, the movable rod 42 is contracted, and the control block 11b2 is not propped against the control block 11b2 any more, so that the control block 11b2 can return to the recovery state, and the rack 5 is pulled out from the slot 214. Wherein the electromagnet needs to be energized, the inside of the inner housing cover 22 can also be made hollow to facilitate the arrangement of the electric wires. On this basis, heating wires may be provided in the inner cover 22 to serve as temperature control members.
Example 2
A soapstock acidification dephosphorization process comprises the following steps:
s1, mixing nigre and small molecular organic acid, and carrying out neutralization reaction for 1-2 hours at 160-210 ℃ to obtain an oil phase and a water phase, and removing the water phase to obtain an oil phase;
s2, mixing the oil phase with supercritical carbon dioxide for 2-4 hours, introducing hydrogen into the system, heating to 160-210 ℃ again for reacting for 1-2 hours to obtain an oil body and a water body, separating the water body, and heating the rest oil body to obtain the low-phosphorylation oil.
The apparatus used in this example was identical to that of example 1, except that: since the operations of synthesizing formic acid by hydrogenation of carbon dioxide and of hydrogenating and hardening fatty acids are required in the inner case 21, a catalyst is required, and Cu/ZrO is preferably used 2 -Al 2 O 3 Catalysts and nickel formate catalysts. The catalyst may be directly put into the inner housing 21 together with the soapstock, or may be placed in a groove formed in the stirring roller 213 as in the present embodiment.
The procedure for carrying out step S1 corresponds to example 1; in implementing step S2, the operation steps are:
the control motor 3 rotates the inner housing 21 such that the inner housing cover 22 moves down and the outer housing cover 12 moves down, such that the communication hole 211 and the through hole 221 communicate, and such that the closing portion covers the centrifugal hole 212. And then introducing carbon dioxide into the equipment through the carbon dioxide inlet 121 until the pressure in the equipment reaches the critical pressure of the carbon dioxide, and simultaneously controlling the temperature in the equipment through a temperature control until the temperature reaches the critical temperature of the carbon dioxide, and keeping for 2-4h.
The motor 3 is then controlled to rotate the inner housing 21 a small turn so that the inner housing cover 22 moves upward a small distance so that the communication hole 211 and the through hole 221 are not communicated, but so that the closing portion still covers the centrifugal hole 212. Hydrogen is introduced into the inner shell 21 through the feed inlet 122, so that the supercritical carbon dioxide hydrogenation is realized to synthesize formic acid, the fatty acid hydrogenation hardening is realized, and then the temperature in the equipment is controlled to be further increased to 160-210 ℃ for reaction for 1-2h, so that an oil body and a water body are obtained.
Then, the motor 3 is controlled to drive the inner shell 21 to rotate, so that the inner shell cover 22 moves upwards and the outer shell cover 12 moves upwards, the sealing part does not cover the centrifugal holes 212 any more, and water in the sealing part enters between the outer shell 11 and the inner shell 21 through the oil-water separation membrane on the centrifugal holes 212. After releasing the inside of the equipment to normal pressure, the temperature in the equipment is controlled to rise to remove acid, and the rest of the inner shell 21 is the low-phosphate oil.
The water body is treated in the same manner as the water phase in embodiment 1, but the water body is mainly acid water and can be recycled after collection, so that the collection box can be preferably connected with the inner shell 2 through a flexible hose, for example, an opening is formed in the top of the inner shell cover 22 and is communicated with the collection box through the opening, so that the water body can be recycled.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (4)
1. An apparatus for performing a soapstock acidification dephosphorization process, characterized by: comprises an outer shell (1), an inner shell (2) arranged in the outer shell (1) and a temperature control piece arranged in the outer shell (1); the inner shell (2) comprises an inner shell (21) with an opening at the top and an inner shell cover (22) for covering the opening, the inner shell (21) and the inner shell cover (22) both comprise cylindrical inner shell side parts, the inner shell side parts of the inner shell (21) are provided with external threads, and the inner shell side parts of the inner shell cover (22) are provided with internal threads in threaded connection with the external threads; the side part of the inner shell (21) sequentially comprises a closed upper part, a middle part provided with a plurality of communication holes (211) and a lower part provided with a plurality of centrifugal holes (212) from the opening to the bottom of the inner shell (21), wherein the centrifugal holes (212) are covered with an oil-water separation film; the side part of the inner shell cover (22) comprises a closing part capable of being connected with the lower part and a communicating part capable of being connected with the middle part, and the communicating part is provided with a through hole (221) capable of communicating with the communicating hole (211); the shell (1) comprises an outer shell body (11) and an outer shell cover (12), the outer shell cover (12) is connected with the inner shell cover (22), the outer shell body (11) and the outer shell cover (12) both comprise outer shell side parts, and the outer shell side parts of the outer shell body (11) are provided with vertical slots (111) into which the outer shell side parts of the outer shell cover (12) can be inserted; the bottom of the inner shell (21) is connected with an output shaft of the motor (3), and the inner shell cover (22) is in sliding connection with a vertical limit groove (112) arranged on the inner wall of the outer shell (11) through a connecting rod (4); the outer shell cover (12) is provided with a carbon dioxide inlet (121), and a feeding hole (122) for feeding into the inner shell (2) is formed at the joint of the outer shell cover (12) and the inner shell cover (22);
the outer shell (11) comprises a fixed outer shell (11 a) and a movable outer shell (11 b) arranged in the fixed outer shell (11 a), and the inner shell (21) is arranged in the movable outer shell (11 b); the fixed outer shell (11 a) is provided with the vertical slot (111), and the movable outer shell (11 b) is provided with the vertical limit slot (112); a filter block is filled between the movable outer shell (11 b) and the fixed outer shell (11 a), the movable outer shell (11 b) is provided with a guide-out hole, and the fixed outer shell (11 a) is provided with a collecting hole;
the movable outer shell (11 b) is provided with a mechanical cavity, a first rotating shaft and a second rotating shaft which are driven by a gear tooth chain structure are arranged in the mechanical cavity, and the first rotating shaft is close to the bottom of the movable outer shell (11 b) relative to the second rotating shaft; the first rotating shaft is provided with a transmission gear (11 b 1), one end of a rack (5) is inserted into the mechanical cavity and meshed with the transmission gear (11 b 1), and the other end of the rack can be inserted into a slot (214) formed in the inner shell (21); the second rotating shaft is provided with a control block (11 b 2), one end of the control block (11 b 2) is connected with the second rotating shaft, and the other end of the control block is inserted into the vertical limiting groove (112).
2. An apparatus for performing a soapstock acidification dephosphorization process according to claim 1, characterized in that: the stirring device is characterized in that a stirring roller (213) is arranged in the inner shell (21), one end of the stirring roller (213) is connected with the inner wall of the inner shell (21), and the other end of the stirring roller is suspended.
3. An apparatus for performing a soapstock acidification dephosphorization process according to claim 1, characterized in that: the connecting rod (4) comprises a hollow fixed sleeve (41) and a movable rod (42) inserted into the fixed sleeve (41), one end of the movable rod (42) is inserted into the vertical limiting groove (112), the other end of the movable rod is connected with the inner bottom of the fixed sleeve (41) through a spring, an electromagnet is arranged at the inner bottom of the fixed sleeve (41), and the movable rod (42) is an iron rod.
4. An apparatus for performing a soapstock acidification dephosphorization process according to claim 1, characterized in that: the inner shell cover (22) is connected with the outer shell cover (12) through a connecting column, one end of the connecting column is fixedly connected with the inner shell cover (22), the other end of the connecting column is connected with the outer shell cover (12) through a rotating bearing, and the inside of the connecting column is hollow so as to form the feeding hole (122).
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